Preparation and Potential Application of Perovskites Adsorbents Wastewater Treatment

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A review on the preparation, characterization and potential application of perovskites

as adsorbents for wastewater treatment
Zaharaddeen N. Garba, Weiming Zhou, Mingxi Zhang, Zhanhui Yuan
PII: S0045-6535(19)32714-6
DOI: https://doi.org/10.1016/j.chemosphere.2019.125474
Reference: CHEM 125474
To appear in: ECSN
Received Date: 30 April 2019

Revised Date: 11 November 2019
Accepted Date: 24 November 2019
Please cite this article as: Garba, Z.N., Zhou, W., Zhang, M., Yuan, Z., A review on the preparation,
characterization and potential application of perovskites as adsorbents for wastewater treatment,
Chemosphere (2019), doi: https://doi.org/10.1016/j.chemosphere.2019.125474.
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Credit Author Statement
Zaharaddeen N. Garba: Original draft; Writing – review & editing
Weiming Zhou: Figures drawing
Mingxi Zhang: Supervision
Zhanhui Yuan: Funding acquisition; Supervision and editing
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GRAPHICAL ABSTRACT:
A review on the preparation, characterization and potential application of perovskites
as adsorbents for wastewater treatment
Zaharaddeen N. Garbaa,b, Weiming Zhoua, Mingxi Zhanga, Zhanhui Yuana*
a
College of Materials Science and Engineering, Fujian Agriculture and Forestry University,
China
b
Department of Chemistry, Ahmadu Bello University Zaria, Nigeria
* Corresponding author. Tel.: +8613950268166
E-mail addresses: zhanhuiyuan@fafu.edu.cn (Zhanhui Yuan),
dinigetso2000@gmail.com (Zaharaddeen N. Garba)

1 A review on the preparation, characterization and potential application of
2 perovskites as adsorbents for wastewater treatment
3 Zaharaddeen N. Garbaa,b, Weiming Zhoua, Mingxi Zhanga, Zhanhui Yuana*
a
4 College of Materials Science and Engineering, Fujian Agriculture and Forestry
5 University, China
b
6 Department of Chemistry, Ahmadu Bello University Zaria, Nigeria
10
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12
13
14
15
16
17
18
19
20
21 * Corresponding author. Tel.: +8613950268166
22 E-mail addresses: zhanhuiyuan@fafu.edu.cn (Zhanhui Yuan),
23 dinigetso2000@gmail.com (Zaharaddeen N. Garba)
24
1
25 ABSTRACT:
26 Perovskite are among the popular materials utilized in many areas of modern
27 industrialization because of their low price, high stability, excellent oxidation activity,
28 adsorptive, catalytic, optical, magnetic, electronic and ferroelectric properties. Over
29 the years, widespread usage of perovskite nanoparticles has been reported due to its
30 various applications which include an environmental catalyst, fuel cells, chemical
31 sensors, magnetic materials, oxygen permeable membranes and adsorbents for
32 wastewater treatment. Various synthetic methods such as the sol-gel method, proteic
33 method, Pechini method, combustion, co-precipitation, and chelating precursor
34 method have been applied in producing perovskites. Therefore, this review assembles
35 the current knowledge on the processes involved in the preparation of perovskites,
36 their characterizations and potential applications in wastewater treatment. Challenges
37 and future opportunities of perovskite-based materials are discussed as well as
38 obstacles against their extensive uses. Conclusions have also been drawn proposing a
39 few suggestions for future research.
40 Keywords: Perovskite; Nanoparticles; Preparation; Characterization; Wastewater
41 treatment.
42 List of abbreviations
43 Abbreviation Description
44 4CP 4-chlorophenol
45 ACF Active carbon fibers
46 CA Uncast perovskites
47 CrI Crystallinity index
48 CWPO Catalytic wet peroxide oxidation

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49 DSCs Dye-sensitized solar cells
50 EDTA Ethylenediaminetetraacetic acid
51 EFM Environmental fate modeling
52 EG Ethylene glycol
53 ESR Electron spin resonance
54 FTIR Fourier transform infrared
55 I200 Maximum intensity of the peak
56 Iam Intensity of diffraction of the non-crystalline material
57 L Size of the crystallite (nm),
58 k Scherrer constant,
59 X-ray wavelength
60 Full width at half maximum of lattice plane reflection in radian
61 Corresponding Bragg angle (reflection angle)
62 DSC Differential scanning calorimetry
63 DB-53 Direct blue 53
64 DTA Differential thermal analysis
65 ABO3 Perovskite-type oxides
66 MB Methylene blue
67 MO Methyl orange
68 RhB Rhodamine B
69 CR Congo red
70 AR Alizarin red
71 LFO-ACFs Perovskite oxide decorated active carbon fibers

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72 PMS Peroxymonosulfate
73 XPS X-ray photoelectron spectroscopy
74 PSCs Perovskite solar cells
75 LCNO Lanthanum-calcium perovskite-type nanopowders
76 LCVD Laser-assisted chemical vapor deposition
77 LED Light-emitting diodes
78 NC Nanocast perovskites
79 NPs Nanoparticles
80 PEG-200 Polyethylene glycol
81 PLA Perovskite lanthanum aluminate
82 PVA Polyvinyl alcohol
83 PVB Polyvinyl butyral
84 PW12 Keggin-type phosphotungstic acid
85 RB5 Reactive blue 5
86 RF F to Bi atomic ratio
87 SEM Scanning electron microscope
88 SFMO Sr2FexMo2−xO6 double perovskite oxides
89 SSA Specific surface area
90 SSR Solid-state reaction
91 TEM Transmission electron microscopy

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92 TGA Thermogravimetric analysis
93 TOC Total organic carbon
94 TPR Temperature-programmed reduction
95 XRD X-ray diffraction
96 1. Introduction
97 Tackling the problems of modern civilization as well as growing industrial activities
98 with minimal costs, high efficiency of production as well as low environmental
99 impacts are becoming very vital (Lima et al., 2006; Soares et al., 2007). Efforts need
100 to be put into the search for new materials such as catalysts and adsorbents with
101 industrial applications in order to achieve high purity, product homogeneity, and
102 relatively low processing temperatures. Recently, nanomaterials have attracted the
103 attention of researchers owing to their exceptional properties and promising
104 applications in various nanotechnology fields (Arshadi et al., 2011; Karimi-Maleh et
105 al., 2014; Zhou et al., 2017). These applications include adsorbent and photocatalysis
106 (Chakraborty et al., 2017; Chen and Chen, 2011; De Luca et al., 2018; Gupta et al.,
107 2015; Mabuza et al., 2017; Wang et al., 2017; Zhang et al., 2011; Zhuang et al.,
108 2014), sensors (Karimi-Maleh et al., 2014; Zhou et al., 2017), catalysts for CO2
109 conversion, dry reforming and syngas production (Barison et al., 2017; Candamano et
110 al., 2015; Frontera et al., 2017; Frontera et al., 2018; Macario et al., 2019) nanofibrous
111 membrane for UV resistant (Xu et al., 2017), nano-lubricant additives (Ali et al.,
112 2016) and electrode materials (Dasgupta et al., 2016; Huang et al., 2017a; Li et al.,
113 2017; Li and Chen, 2017).
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114 Perovskites are ceramic materials that belong to the class of mixed oxides with a
115 general formula of ABO3. A represents an alkaline earth metal with B representing d-
116 block transition elements. In general, mechanical resistance is provided to the
117 perovskites by the metals occupying A position whereas the metals occupying
118 position B improves on the redox process reactivity (Grabowska, 2016; Zhu et al.,
119 2014). Perovskite-type nanomaterials show a promising application in the field of
120 catalytic and fundamental research due to their structural stability, high activity and
121 resistance to poisons (Markova-Velichkova et al., 2013; Nur Afifah, 2016).
122 Due to their versatile nature, several researchers have reported the preparation of
123 these perovskites nanomaterials (Afzal et al., 2017; Choi and Moon, 2009; Gallego et
124 al., 2013; Makhloufi et al., 2019; Markandeya et al., 2011; Meiqing et al., 2013;
125 Wang et al., 2016b) exhibiting optical, magnetic, thermal, electric, catalytic and
126 adsorptive properties (Algueró et al., 2012; Bengtsson et al., 2018; Gupta and Suhas,
127 2009; Moure and Peña, 2015; Shetkar and Salker, 2010; Yang et al., 2018b).
128 Perovskites halides were also explored for photodetectors, low-threshold lasers, and
129 LEDs (Laquai, 2014).
130 Various synthetic methods such as the sol-gel, proteic, Pechini, combustion, co-
131 precipitation and chelating precursors methods have been reported for perovskites
132 preparation (Algueró et al., 2012; Moure and Peña, 2015; Shetkar and Salker, 2010).
133 Finding suitable economic precursors and producing adsorbents with high adsorption
134 performance for wastewater treatment continue to be challenging. Adsorption has
135 been reported as the most commonly used method among various water purification
136 and recycling technologies (Adetokun et al., 2019; Ali and Gupta, 2007; Cheng et al.,
137 2018; Garba and Afidah, 2014b, 2015b; Garba and Afidah, 2016). Many studies have
138 been carried out (El-Haouti et al., 2018; Kamble et al., 2017) using various adsorbents
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139 such as agricultural wastes (Garba et al., 2016a; Garba et al., 2019b; Garba et al.,
140 2016b), kerolites (Gonzalez-Pradas et al., 2003), zeolites (Alvarez-Ayuso et al., 2003;
141 Cheng et al., 2018; Jiang et al., 2018; Rakic et al., 2010), bentonite-chitosan
142 composite (Dehghani et al., 2018), protonated cross-linked chitosan (Huang et al.,
143 2017), dead macrofungi (Maurya et al., 2006), ultrafiltration membranes (Sumisha et
144 al., 2015), modified electrolytic manganese residue (Jiancheng et al., 2018),
145 microcrystalline cellulose based materials (Garba et al., 2019c; Hussin et al., 2016;
146 Jiao et al., 2017), ultrasonic graphene materials (Soltani & Lee, 2016), halloysite
147 nanotubes (Zango et al., 2016) and activated carbon materials (Adetokun et al., 2019;
148 Afidah & Garba, 2016; Cooney et al., 1983; Garba & Afida, 2015; Garba & Afidah,
149 2014a; Garba & Afidah, 2014b; Garba et al., 2014; Garba et al., 2019a; Gupta et al.,
150 2011; Labaran et al., 2019).
151 Several physical characteristics of adsorbents such as surface area, porosity, size
152 distribution, density, and surface charge were reported to have a major influence on
153 the adsorption process. Thus, so much effort has been put to the development of novel
154 alternative adsorbents with high adsorptive capacity as well as adsorption
155 optimization. In this regard, more attention has recently been paid to various
156 processes of nanotechnology (Van der Bruggen et al., 1998; Yazdanbakhsh et al.,
157 2011). One advantage of NPs over ordinary sorbents is the ability to offer a
158 significantly higher surface area-to-volume ratio as well as short diffusion route
159 which results in rapid extraction dynamics and high extraction efficiencies (Afkhami
160 and Moosavi, 2010). Therefore, fewer amounts of these NPs give satisfactory results.
161 For that reason, perovskite-type NPs are among the novel and promising adsorbents
162 employed for the adsorption of various analytes such as dyes, volatile organic
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163 compounds (VOC), and pesticides (Santos et al., 2018; Tavakkoli and Yazdanbakhsh,
164 2013).
165 There is an increasing interest in research on perovskites (Fig. S1) with many review
166 articles giving deep insight into the structure and various applications of perovskites
167 NPs (Adnan et al., 2018; Chroneos et al., 2010; Fu et al., 2017; Hossain et al., 2019;
168 Lombardo and Ulla, 1998; Petrović et al., 2015; Shahbazi and Wang, 2016; Yang et
169 al., 2018a; Zhu et al., 2014; Zhu and Thomas, 2009). To the best of our knowledge,
170 no such work was devoted to the perovskites application as adsorbents for the
171 removal of dyes and heavy metals from wastewater despite the increasing interest in
172 this area. The present review, therefore, focuses more on revising and providing the
173 basic knowledge on the different procedures employed in the preparation,
174 characterizations, and applications of perovskites NPs as adsorbents in wastewater
175 treatment.
176 2. Properties and applications of Perovskites
177 Perovskite is a common name for oxides with the structural formula ABO3 or A2BO4
178 which originate from CaTiO3, (Zhu et al., 2014). Gustav Rose in the 1830s was the
179 first to describe perovskite as a mineral, named after Russian mineralogist A. Von
180 Perovskji (Adnan et al., 2018). A significant amount of work has been dedicated to
181 the structural, physical and chemical properties of perovskite in order to derive
182 materials for modern applications since the 1940s. The perovskite materials were also
183 reported to have a general formula of ABX3 or A2BX4, with A and B denoting cations
184 while X indicates an anion group holding A and B together through ionic bond. A has
185 larger ionic radius than B. Adnan and co-workers reported the structure of perovskite
186 nanomaterials to be viewed as follows: A and B are located on the edge and center of
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187 an octahedron respectively (Fig. S2) with cationic radii (rA > 0.09 nm and rB > 0.051
188 nm). Oxygen or non-oxygen materials such as fluorine (-F) or methyl (-CH3)
189 constitute the anion X (Adnan et al., 2018).
190 The A2BO4 oxides are occasionally called perovskite-like oxides which involved
191 alternated ABO3 and AO layers. For simplicity, the term perovskites were used in
192 naming both ABO3 and A2BO4 oxides in this review. They are materials with high
193 structural stability as well as the ability to substitute both A- and/or B-site with a
194 foreign cation that has distinct oxidation state or radius (Pena and Fierro, 2001; Zhu et
195 al., 2014). Thus, allowing easy control of the B-site cation oxidation state and the
196 content of oxygen vacancy when desired foreign cation is used. This offered a feasible
197 and convenient way of correlating physicochemical properties that may heighten the
198 adsorptive capabilities of the perovskites material. To date, most of the perovskites
199 materials reported in the literature have shown numerous technological applications,
200 high stability, and variations in structural properties. It is very impressive for the
201 perovskites structure to be altered suitable for specific applications, e.g. the distorted
202 form and reduced symmetry of some perovskites are significant due to interesting
203 electric and magnetic properties (Hossain et al., 2019). The properties and
204 applications of perovskites particles are summarized in Table 1.
205 Afzal et al. (2017) synthesized of mesoporous perovskites (NC-LaMnO3 and NC-
206 LaFeO3) by using the nanocasting technique. They employed SBA-15 as a template
207 for producing the nanocast perovskites which are applied in TOC removal and
208 catalytic ozonation of 2-chlorophenol. Upon comparison with uncast duplicate
209 perovskites (CA-LaMnO3 and CA-LaFeO3) as well as Mn3O4 and Fe2O3 that are
210 prepared by conventional citric acid assisted route, the nanocast perovskites show
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211 high specific surface area and large pore dimensions than the uncast perovskites.
212 Those properties enhanced the catalytic activity of the nanocast perovskites in terms
213 of TOC removal which followed the order: NC-LaMnO3 > NC-LaFeO3 > CA-
214 LaMnO3 > CA-LaFeO3 > Mn3O4 > Fe2O3 > O3. Moreover, the open porous structure
215 of the nanocast perovskites, as well as high surface area, were believed to be
216 responsible for enhancing the catalytic activity by surface reaction and easy access of
217 reactants to the active sites. The mechanism of catalytic ozonation is depicted in Fig 1
218 with the NC-LaMnO3 surface providing the adsorption sites for O3 and its activation,
219 whereas manganese serves as the active site for the transfer of electrons.
220 Yu et al. (2017) employed a solvothermal-calcination process to synthesize series of
221 fluorinated Bi2MoO6 crystals by varying the F to Bi atomic ratio (RF = 0.10, 0.15,
222 0.20, 0.25, 0.30). They reported a decrease in crystal size, an increase in crystallinity
223 and induced lattice shrinkage due to the substitution of F− anions for the host O2−
224 anions. Moreover, the separation of photoexcited electron-hole pairs was largely
225 boosted due to the possible withdrawal of photoexcited electrons by the oxygen
226 vacancies in F-Bi2MoO6 and F− adsorbed over the catalyst surface. Significant
227 photocatalytic performance was shown by F0.20-Bi2MoO6 in the removal of phenol, 4-
228 chlorophenol, bisphenol A and Rhodamine B dye. They also reported ESR and
229 radicals trapping confirming that holes are responsible for the degradation of the
230 target organic pollutants (Yu et al., 2017). The possible photocatalytic reaction
231 mechanism of F-Bi2MoO6 is proposed in Fig. S3.
232 Yazdanbakhsh et al. (2011) employed sol-gel method to fabricate perovskite-type
233 nanoparticles (La0.5Ca0.5NiO3−δ) in the presence of nitrate–metal–ethylene glycol (EG)
234 polymerized complex. They reported the nanoparticles to show excellent adsorption
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235 efficiency towards RB5 dye in aqueous solution. They also reported that the
236 nanoparticles do not have the ability to act as pure photocatalyst so the degradation of
237 RB5 dye followed only an adsorption process. However, they emphasized that
238 catalytic performance under solar energy leads to better results than UV irradiation in
239 the dark (Yazdanbakhsh et al., 2011). Jamali and co-workers also reported an
240 efficient, straightforward and time-saving microwave-assisted synthesis of LaFeO3
241 nanoparticles. They obtained high crystallinity perovskite particles with a narrow
242 band gap energy (2.12 eV) and mesoporous structure which showed great oxygen
243 adsorption/desorption ability (Jamali et al., 2017). They used gaseous and aqueous
244 reactants to assess the LaFeO3 photocatalytic activity. They further carried out studies
245 on the surface charge density and radical scavengers to introduce the possible
246 mechanism for the degradation of dye with the results showing hydroxyl radicals as
247 the main active species in the photodegradation reaction. Overall, the simplicity and
248 effectiveness of their synthesis method coupled with the high photocatalytic activity
249 under ambient light irradiation suggested the methodology to be a promising approach
250 for the synthesis of metal oxides.
251 3. Different perovskite preparation methods
252 Perovskite materials were previously reported to be prepared by the traditional SSR;
253 however, the resulting materials were mostly impure and heterogeneous. Other
254 shortcomings include the sensitivity of the materials to temperature changes, synthesis
255 method as well as the amount of starting materials involved. To overcome these
256 defects, several methods such as the glycine-nitrate route (Vidal et al., 2015), the sol-
257 gel method (Feldhoff et al., 2008) and the freeze-drying method (Ho Lee et al., 2004)
258 have been introduced. Recently, many researchers reported the incorporation of
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259 perovskite materials into thin films and integrated nanostructures via contemporary
260 preparation methods such as the chemical conversion hydrothermal process (Mao et
261 al., 2003), LCVD (Manawi et al., 2018), the sol-gel method (Li et al., 2011) and facile
262 thermal treatments (Liu et al., 2013).
263 3.1. Sol-gel method
264 Sol-gel method is one of the most widely used methods for the preparation of
265 perovskite nanoparticles. Yazdanbakhsh et al. (2011) employed nitrate–metal–
266 ethylene glycol (EG) polymerized complex in the fabrication of perovskite-type
267 La0.5Ca0.5NiO3−δ (LCNO) nanopowders by the method. Their method accelerated
268 polyesterification reactions between CA and EG to form a dry gel. Finally,
269 La0.5Ca0.5NiO3−δ nanoparticles were obtained by thermal treatment of the precursors at
270 two different temperatures 650 °C and 750 °C for 9 h in air (Yazdanbakhsh et al.,
271 2011). The prepared perovskite nanoparticle effectively removed high concentrations
272 of RB5 dye molecules. In another development, Markandeya et al. (2011) reported
273 the preparation of SFMO of different compositions by sol-gel method with x = 0.8,
274 0.9, 1.0, 1.1, 1.2, 1.3, 1.4 and 1.5 wt. %. They used the stoichiometric amounts of
275 Sr(NO3)2, Fe(NO3)2·9H2O and H2MoO4 to obtain the SFMO nanopowders. The
276 maximum degree of Fe/Mo ordering (ƞmax) of SFMO was calculated and compared
277 with magnetic and transport properties. They found a strong correlation between 3
278 parameters ƞmax, Ms and MR (%) with all of them showing a maximum at x = 1.0 wt.
279 % which decreases as x deviates from 1.0 in SFMO. They also discovered different
280 resistivity behavior between x≤1.2 wt.% and x > 1.2 wt.% samples of the material.
281 Semiconductor-metal transition temperature was found to be maximum at x = 1.0 wt.
282 % (Markandeya et al., 2011).
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283 Soongprasit et al. (2012) also reported the preparation of perovskite nanoparticles
284 using the sol-gel method, but their method employed the use of hybrid metal ions and
285 PVA to obtain La1-xCexNiO3 perovskite-type catalyst powder with PVA acting as
286 gelating agent. They assigned the metal ion to PVA monomer molar ratio at 1:1 and
287 the product formed was calcined at 800 oC. The metal ion incorporated into the
288 complex precursors with alkoxide improved the elemental dispersion and also
289 prevented agglomeration of the obtained catalyst which is strongly related to activity
290 and stability on syngas generation. The introduction of Ce into the obtained La1-
291 xCexNiO3 nanoparticle showed improved reducibility of the perovskite catalyst having
292 smaller particle sizes, and greater specific surface area. Additionally, carbon filament
293 was also found on used La0.8Ce0.2NiO3 and La0.6Ce0.4NiO3 which had a little effect on
294 the activity of the catalyst. Moreover, catalysts showed favorable stability because no
295 deactivation was observed during the 180 mins of the test. The experimental set up for
296 steam reforming of toluene as a model compound was carried out as illustrated in Fig.
297 2 (Soongprasit et al., 2012).
298 In another development, Benaicha and Omari (2018) reported the successful synthesis
299 of LaFe1-xCuxO3 powders by sol-gel method with x ranging from 0 to 0.4. In their
300 method, they employed metal nitrate salts as cation precursors with methanol as the
301 solvent. The obtained precursors were ground into powders and then annealed at
302 different annealing temperatures ranging between 450 oC to 850 oC in the air for 6 h at
303 a heating rate of 5 oC min-1. The oxide perovskite structure formed was reported to
304 possess a single cubic phase after heating at about 750 oC in the air for 6 h. The
305 microstructure and morphology of the compounds exhibited that the copper content
306 affects the surface area that leads the material compact with decreasing of pores.
307 Compared to all studied compositions, LaFe0.7Cu0.3O3 electrode exhibited
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308 significantly greater electroactivity with the electrochemical measurements showing
309 that the catalytic activity was influenced by copper doping (Benaicha and Omari,
310 2018).
311 Meiqing et al. (2013) reported the synthesis of La1–xCaxMnO3 catalysts by citrate sol-
312 gel method. They employed La(NO3)3·6H2O, Mn(NO3)2 and Ca(NO3)2·4H2O as
313 precursors with citric acid used as the complexing agent. After continuous stirring,
314 they kept the solution at 80 ºC for 2 h. Water was then evaporated until the solution
315 became a viscous gel. The gel was dried at 90 ºC for 12 h and then calcined at 700 ºC
316 for 5 h. They reported significant improvement in NO catalytic oxidation activity by
317 Ca doping especially for lower temperature activity (Meiqing et al., 2013). They also
318 observed that monodentate nitrates influenced the oxidation of NO resulting in the
319 formation of NO2. Based on the TPR and activated oxygen measurements they carried
320 out, the reducibility of Mn4+ ions and reactivity of activated oxygen were reported to
321 be favorable for the catalytic performances of NO oxidation. (Erdenee et al., 2017)
322 also reported the preparation of La1−xCexCoO3 ( = 0, 0.2, 0.4) and La1−xCexMnO3 (
323 = 0, 0.2) perovskite-type oxides by sol-gel process. They reported all the synthesized
324 samples to have shown well crystalline perovskite structure, 8–22nm crystallite sizes,
325 and SSA with 2–27 m2 g-1. The Ce substitution enhanced the structural transformation
326 of LaCoO3 from rhombohedral into cubic with no change in lattice geometry for
327 LaMnO3. Substitution with cerium ( = 0.2) also showed smaller crystallite size,
328 higher SSA and the highest reducibility as well as catalytic activity for LaCoO3.
329 Based on their confirmation, the present sol-gel method can be used for perovskite-
330 type oxides with different compositions.
331 In another development, Garcia-Muñoz et al. (2019) reported the synthesis of a series
332 of novel Ti-substituted LaFeO3 materials with varying titanium contents by
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333 employing a sol-gel method where they partially substituted La with Ti using
334 commercial TiO2 as titanium precursor. They employed it as a catalyst in the
335 photoassisted CWPO for the removal of 4CP in water. In their method, iron nitrate
336 nonahydrate and lanthanum nitrate hexahydrate were dissolved in distilled water with
337 the metallic ions undergoing complexation after subsequent addition of citric acid at
338 70 g L-1, corresponding to a stoichiometric molar ratio in respect of the metallic ions.
339 Controlled amounts of TiO2 Aeroxide P25 were further introduced into the aqueous
340 sol directly under stirring with the resulting suspensions maintained at 80 °C for 2
341 days (2 °C min-1 heating rate) to induce the complete gel formation. The calcination
342 of the dried gel was performed using a heating cycle as reported by (Gosavi and
343 Biniwale, 2010). The stoichiometric reaction leading to the formation of the LaFeO3
344 perovskite structure without considering the titania phase, was reported as follows (Qi
345 et al., 2003).
346 ( ) 6 + ( ) 9 + → + 6 +
347 3 + (1)
348 The reference materials were synthesized as non-modified lanthanum ferrite powders
349 by following the same protocol without any addition of titania, at a similar calcination
350 temperature of 600–800 °C. The Ti-substituted LaFeO3 acted as a good heterogeneous
351 photo-Fenton catalyst and photocatalyst with higher (total) and faster TOC removal
352 achieved on the catalyst calcined at 800 oC at neutral pH over 5 cycles of reuse with
353 stable efficiency and a limited Fe leaching, lower than 0.1 % of its total content.
354 3.2. Proteic method
355 Another method reported for the preparation of perovskites is the proteic method.
356 Santos et al. (2012) reported the synthesis of LaNiO3 perovskites via the modified
357 proteic gel method and studied the catalytic activity of LaNiO3 and LaNiO3/Al2O3 in
15
358 the syngas (CO + H2) production, providing strong support for the utilization of
359 collagen (a low-cost, non-toxic organic material) as a very good chelating agent in the
360 structural formation of LaNiO3 material. They reported the formation of rhombohedral
361 perovskite structure in all samples with some showing secondary phases, except the
362 sample with a metal/collagen ratio of 1.0:1.0 which formed a single-phase material.
363 They also observed that the methane conversion was approximately 46 % with the
364 selectivity to syngas of 79.3 % (CO) and 52.4 % (H2). In both cases, a low selectivity
365 to CO2 was corroborated using LaNiO3 and LaNiO3/Al2O3 catalysts (Santos et al.,
366 2012). In another development, soy protein was also reported to be employed as a
367 complexing agent in the preparation of LaNiO3 and LaMnO3 (Santos et al., 2018).
368 They reported coordination between the metal ions and precursor of the perovskite
369 phase containing amino and carboxilate groups from the soy protein. When
370 manganese was used at B site of the perovskite structure, LaMnO3 material with
371 higher crystallinity was reported to be synthesized by the proposed method with
372 calcination at 900 °C. They further reported the manganese-based perovskite samples
373 to have only one perovskite phase, whilst secondary phases also were observed with
374 respect to the nickel-based samples (Santos et al., 2018). Another advantage of the
375 proposed modified proteic method when compared with other conventional methods
376 is the high yield of materials with higher specific surface area values with the
377 produced perovskite samples reported to have the potential of removing significant
378 amount of CR from aqueous media (Santos et al., 2018). The perovskite samples used
379 on the adsorption tests in the liquid phase was also recovered after calcination at 900
380 °C for 2 h. At this temperature, the dye was degraded while the perovskite structure
381 remained intact and preserved.
382 3.3. Combustion method

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383 Combustion method is another important method for the preparation of perovskites as
384 reported by Shetkar and Salker (2010) where they reported the preparation of
385 SrMnO3, SmMnO3 and NdMnO3 nanoparticles. They dissolved the stoichiometric
386 quantity of strontium nitrate or the respective rare earth oxide in minimum quantity of
387 1:1 nitric acid and distilled water, respectively. Further careful heating involved the
388 exothermic combustion of the substrate, leading to the formation of residue and
389 subsequently the formation of monophasic compound after combustion process
390 (Shetkar and Salker, 2010). The residue was further mixed, grounded and finally
391 calcined in a muffle furnace at 700 oC for 10 h to ensure that no traces of un-reacted
392 particles remain in the mixture. The prepared perovskites by combustion method were
393 reported to be good catalysts for CO oxidation, giving better surface areas and finer
394 particles than the ceramic method. The authors reported good efficiency for NdMnO3
395 in the oxidation of CO. On the other hand, the authors reported lower activity for
396 SrMnO3 which was attributed to only one unpaired electron, its hexagonal structure,
397 and comparatively low surface area. All the catalysts were also revealed to have
398 semiconducting behavior, low energy band gap and higher magnetic moments
399 (Shetkar and Salker, 2010).
400 In another development, Silva et al. (2011) also employed the combustion method in
401 the synthesis of a series of LaNi1−xCoxO3 compounds with x=0, 0.2 and 0.4, utilizing
402 urea as a propellant in the partial oxidation of methane. They determined the
403 stoichiometric amount of the propellant by calculation based on the valencies of
404 oxidizing and reducing elements, as determined by the propellant chemistry
405 (Ringuedé et al., 2001). They reported the substitution of Ni by Co to have big
406 influence on the structural, textural and reductive properties of the perovskites with
407 the doped samples depicting lower specific surface area. Apart from the perovskite
17
408 structure, they also reported the presence of small formation of secondary phases
409 (NiO and La(OH)3). The substitution also caused an upsurge in the reduction
410 temperature, which was attributed to the metal-metal interactions during the reduction
411 process (Silva et al., 2011). The doped catalysts presented lower activity at high
412 temperatures, showing that Co atoms have a lower ability for methane activation.
413 Perovskites are known to be highly stable and able to stabilize the metal particles in
414 the well-dispersed state, for that, the synthesized perovskites were considered
415 promising catalyst for the partial oxidation of methane reaction.
416 Gallego et al. (2006) also reported the preparation of LaNiO3 and La2NiO4 type
417 perovskites by a self-combustion method which were used as catalyst precursors for
418 the CO2 reforming of CH4 reaction at 700 oC with glycine used as ignition promoter.
419 They reported the best catalytic performances to be attained using La2NiO4 after
420 reduction under hydrogen at 700 oC without carbon deposition when methane and
421 carbon dioxide conversion reached 80 and 90 % respectively. Nickel particles (7 nm)
422 were formed due to the reduction of La2NiO4, smaller than the particles obtained by
423 reduction of LaNiO3 (15 nm) with the presence of such small particles responsible for
424 the high activity (Gallego et al., 2006). The perovskite La2NiO4 used without
425 reductive treatment prior to the reaction leads to an important carbon deposition
426 resulting mainly from methane decomposition. The species Ni/La2O3 and Ni/La2NiO4
427 allowed the CO2 reforming of CH4 and carbon formation respectively (Gallego et al.,
428 2006). LaNiO3 and LaFeO3 were also reported to be prepared by a self-combustion
429 method where glycine (H2NCH2CO2H) utilized as ignition promoter was added to an
430 aqueous solution of metal nitrates with the appropriate stoichiometry (Gallego et al.,
431 2013). The authors obtained a glassy green gel after slowly evaporating the resulting
432 solution. The gel was then heated to around 250 oC, the temperature at which the
18
433 ignition reaction occurs producing a powdered precursor which still contains carbon
434 residues. The perovskite structure was formed by eliminating all of the remaining
435 carbon after calcination at 700 oC for 8 h (Gallego et al., 2013). The perovskite
436 LaFeO3 was reduced in situ under ethanol at 900 oC leading to the formation of Feo
437 and Fe3C, responsible for the growth of twisted carbon nanofibers. (Gallego et al.,
438 2013). They proposed a mechanism involving the role of the two species as shown in
439 Fig S4. Using LaNiO3, the authors reported a maximum yield of carbon materials at
440 low temperature due to the presence of dense carbon like nanofibers while at higher
441 temperatures, they reported the production of multiwalled carbon nanotubes (Gallego
442 et al., 2013).
443 Other researchers also reported the synthesis of nanocrystalline NdFeO3 perovskite
444 oxide for As(V) adsorption by using the combustion method in PVA and
445 corresponding metal nitrate precursors under optimum conditions: a solution with a
446 pH of 2, a metal/PVA molar ratio of 1:3, and a calcination temperature of 600 °C
447 (Luu et al., 2016). Upon heating the gel, crystallization occurred at a relatively low
448 temperature of 600 °C. pHpzc of the NdFeO3 adsorbent occurred at pH 6.5 in 0.01 M
449 NaCl and the presence of As (V) of 10 mg L-1 shifted to low pH values (about 4),
450 while the zeta potential became more negative in the pH range of 5–9, which
451 confirmed the evidence of inner-sphere surface complex formation (Luu et al., 2016).
452 The used adsorbent was effectively regenerated by 0.5 M NaOH solution for repeated
453 use without any significant capacity loss.
454 3.4. Pechini method
455 A pechini method in comparison to other physical methods is a technique that allows
456 for superior stoichiometric control, reproducibility and homogeneity. Fernandes et al.
457 (2002) reported the preparation of LaNiO3 powders from polymeric precursors by this
19
458 method, investigating the effect of the preparation procedure and calcination
459 parameters. The material was annealed at temperatures ranging between 300 to 800
o
460 C under flowing oxygen or in the air, leading to the formation of black crystalline
461 ceramic powder. On studying the thermal decomposition of the polymeric precursors,
462 the authors revealed that the LaNiO3 phase nucleated following the full
463 decomposition of organic matter and the formation of an intermediate phase
464 (Fernandes et al., 2002). In another research, Su et al. (2014) also reported the
465 synthesis of perovskite-type oxide; LaNiO3 and La1-xCexNiO3 (x ≤0.5) with catalytic
466 property by the Pechini method following a series of steps as presented in Fig. S5.
467 They employed the produced catalysts for carbon dioxide reforming of methane to
468 form synthesis gas (H2 + CO). During the reaction, they utilized the corresponding
469 metal nitrates as the starting materials for generating an aqueous solution with the
470 appropriate stoichiometry. They added citric acid to the mixed aqueous solution of the
471 metal nitrates in a designated proportion so as to make the molar ratio of citric acid to
472 the total metal cations to be 4:1. Ethylene glycol was then added to the mixed aqueous
473 solution to control the molar ratio of citric acid to ethylene glycol at 1:1. The mixed
474 aqueous solution was then heated and stirred in a water bath to start the process of sol
475 formation and the transformation of sol into a gel. A green gel was eventually formed
476 which was dried at 110 oC for 24 h, and then heat treated at 350 oC for 30 mins in air,
477 and finally calcined in air at 700 oC for 2 h. Concerning the CO2 reforming of
478 methane over La1-xCexNiO3 catalysts with Ce substitution (x=0.1), they revealed that
479 cerium provided more oxygen atoms than LaNiO3 and exhibits good stability,
480 yielding high conversions of CH4 and CO2 (93 % and 92 %, respectively, at 800 oC).
481 They also reported a lower Ce content in the perovskite structure to results in to
482 higher catalytic activity and inhibited carbon formation. Partially substituted
20
483 perovskite La1-xCexNiO3 with x=0.1 was also reported to be highly active in the
484 production of valuable syngas during the dry reformation of methane (Su et al., 2014).
485 3.5. Co-precipitation method
486 Co-precipitation is synonymous to simultaneous precipitation of a normally soluble
487 component with a macro-component from the same solution by the formation of
488 mixed crystals by adsorption, occlusion or mechanical entrapment. Successful
489 preparation of La1-xCexNiO3 mixed oxide catalysts by co-precipitation method was
490 reported by Cui et al. (2009). They synthesized their catalysts by dissolving the
491 corresponding nitrates: La(NO3)3.6H2O, Ce(NO3)3.6H2O and Ni(NO3)2.6H2O in
492 distilled water. They altered the ratio between the metal salts based on the desired
493 La/Ce molar ratio: La1-xCexNiO3 where x = 0, 0.1, 0.3, or 0.7. The precipitation was
494 carried out by adding ammonium hydrogen carbonate solution to the nitrate solution
495 during rigorous mixing. (Cui et al., 2009). The authors reported partially Ce
496 substituted La0.3Ce0.7NiO3 mixed oxide to show high activity and stability in the
497 glycerol steam reforming. The activity was noted to be analogous to that of a noble
498 metal (Pt) with the La0.3Ce0.7NiO3 remaining stable during the initial 10 h test for the
499 reforming reaction (Cui et al., 2009). The efficient operation and high stability of this
500 non-noble, inexpensive catalyst La0.3Ce0.7NiO3 was confirmed by unchanged catalyst
501 surface area (BET) during operation and low carbon deposition after reaction.
502 Gosavi and Biniwale (2010) also employed the co-precipitation method to synthesize
503 pure phase LaFeO3 perovskite with improved surface area. They prepared the aqueous
504 solutions of lanthanum nitrate and iron nitrate separately before being mixed together
505 in a 1:1 molar ratio. The prepared solution was then dropped slowly into 50 %
506 ammonia solution which leads to the formation of a precipitate. After complete
507 precipitation, the resultant brown precipitate was aged for 24 h, dried and then
21
508 calcinated. Reactions for the co-precipitation method were described as given below
509 (Li et al., 2004)
510 ( ) + ( ) + → ( ) + ( ) + (2)
511 ( ) + ( ) → (3)
512 In another development, Silva and Soares (2009) investigated how the synthesis of
513 perovskite-type oxides LaBO3 (B= Co, Ni, Mn) by oxidant co-precipitation affected
514 its catalytic activity in total oxidation of propane and CO. Here they used three metal
515 salts (Co(NO3)2.6H2O for LaCoO3, MnCl2.4H2O for LaMnO3 and Ni(NO3)2.6H2O for
516 LaNiO3) mixed with aqueous solution of lanthanum nitrate. They also used the inert
517 atmosphere to minimize carbonate contamination in the final product. They examined
518 co-precipitation of a stoichiometric Co/La, Mn/La, and Ni/La mixed hydroxide, in
519 which simultaneous oxidation of Co (II), Mn (III) and Ni (II) was induced by co-
520 addition of an oxidizing agent. High- area samples were reported to be obtained by
521 this method only after dehydrating the hydroxide gel in a controlled manner by
522 washing with a water-miscible non-aqueous solvent (Silva and Soares, 2009). They
523 revealed LaCoO3 to possess the highest specific surface area hence presented more
524 efficiency to oxidation reactions when compared to LaMnO3 and LaNiO3. (Silva and
525 Soares, 2009).
526 3.6. Other perovskite preparation methods
527 The synthesis of LaNixCo1-xO3 perovskites was reported by Silva et al. (2010) using
528 complex precursor methods. In their preparation, they employed nickel and/or cobalt
529 nitrates, lanthanum nitrate, ethylene glycol, citric acid, and EDTA as starting source
530 materials. They reported no notable changes in the lattice parameters due to the
531 replacement of Ni by Co. They further reported that perovskites prepared by this
532 method show more strength, little particle size and large surface area, higher than 100
22
533 m2 g-1 though showing similar structure when compared to the same powders prepared
534 by other methods. Wang and co-workers took another approach by employing a
535 conventional solid-state reaction method for the synthesis of Er2O3 doped KNbO3
536 smart ferroelectric ceramics where they investigated the effect of Er3+ doping on the
537 luminescence behavior of perovskite structure ceramics. The raw materials used in
538 their method include K2CO3, Nb2O5, and Er2O3 which were mixed for 24 h according
539 to a predetermined ratio with the addition of alcohol. The mixed raw materials were
540 dried and then calcined, re-milled and then granulated with PVB, then finally pressed
541 into pellets and sintered. The result show a decrease in the ratio of green and red
542 emission intensity with the increasing content of Er2O3 (Wang et al., 2016b).
543 Meanwhile, they reported KNbO3-0.75 % Er2O3 to give the most enhanced up-
544 conversion behavior, hinting that the Er3+ doped KNbO3 have an important role to
545 play in many fields as a multifunctional material considering the admirable
546 ferroelectric and piezoelectric properties of the KNbO3 matrix.
547 Another researcher explored various routes of synthesizing lanthanum phosphate sols
548 (LaPO4) for fiber coating (Chen, 1997). He investigated several of these reaction
549 routes in his study and the experimental details of each route were as follows:
550 Method A
551 The first method involved using an equal molar ratio of LaCl and H3PO4
552 + ! → ! +3 (4)
553 He reacted an approximate amount of phosphoric acid solution with lanthanum
554 chloride which formed white precipitates. The precipitates were washed with water
555 three times and dried at room temperature (Chen, 1997).
556 Method B
23
557 This method involved the neutral reaction of lanthanum nitrate with ammonium
558 phosphate at room temperature (reaction 4) to form the lanthanum phosphate
559 precipitates. Large and high purity LaPO4 crystals were reported to be produced by
560 this reaction (Chen, 1997; Jarosewich and Boatner, 1991) though the method has
561 some demerits which include the cumbersomeness and various by-products.
562 ! + → ! + (5)
563 [#$ 2( ) ]+ 6 → 2( ) +3 (6)
564 ( ) + ! → ! + + 2 (7)
565 The ammonium phosphate was gradually prepared by mixing phosphoric acid,
566 ammonium hydroxide, and water until a pH of 7&8 was reached. It was then cooled
567 to allow ! to crystallize and then vacuum filtered (Chen, 1997).
568 Method C
569 This method involved a direct and clean reaction between phosphoric acid and
570 lanthanum oxide with no by-products other than water.
571 + 2 ! → 2! +3 (8)
572 The reaction was vigorous and exothermic due to the hygroscopic nature of
573 lanthanum oxide (Roy and McKinstry, 1953). He reported the formation of large
574 precipitates at the reaction site, and then gradually broke into fine particles. Traces of
575 excess H3PO4 were removed by washing the samples three times with water.
576 Method D
577 The synthesis of LaPO4 by the reaction of La(OH)3 and H3PO4 has been studied and is
578 reproducible
579 ( ) + ! → ! +3 (9)
580 Here the lanthanum phosphate sol was prepared by mixing the approximate amount of
581 H3PO4 and ( ) . The ratio between phosphate and lanthanum in the reaction
24
582 mixture was very crucial in terms of the final lanthanum phosphate formed (Botto and
583 Baran, 1979). An experiment was carried out to confirm the formation of LaP3O9
584 according to the following reaction equation
585 ( ) + 3 ! → ! ' +6
586 (10)
587 In this case, the sol was prepared with a molar ratio of 1:3 instead of 1:1 (Chen,
588 1997). He then went ahead to carry out coating experiments on sapphire fibers using
589 various sol concentrations. Based upon the dip coating technique used in the study,
590 the average coating thicknesses were reported to be 60 and 150 nm for the sol
591 concentrations of 0.01 and 0.05 M LaPO4, respectively (Chen, 1997). The XRD
592 analysis of the coated fiber surface confirmed that the coating was LaPO4.
593 Another straightforward, efficient and time-saving method that was also employed by
594 Jamali et al. (2017) for the synthesis of LaFeO3 nanostructured perovskite-type oxide
595 was microwave-assisted synthesis. Here they dissolved appropriate amounts of
596 Fe(NO3)2·9H2O and La(NO3)3·6H2O in deionized water at room temperature under
597 constant magnetic stirring for almost 1 h. Afterward, they transfer the solution to a
598 microwave appliance and kept under microwave exposure (850 W) until a red-brick
599 powder was obtained (Baghbanzadeh et al., 2011; Jamali et al., 2017). The powder
600 was washed thoroughly with deionized water to remove any excess residue. It was
601 then transferred to an oven and kept for 2 h at 80 oC, the obtained powder was used as
602 a photocatalyst against organic reactants in gaseous and aqueous phases. They
603 reported the formation of a perovskite material with a narrow band gap energy value
604 of 2.12 eV, high crystallinity, great oxygen adsorption/ desorption ability and
605 mesoporous structure.
25
606 Citrate precursor method was also explored as reported by de Lima et al. (2008) in the
607 preparation of perovskite-type oxides such as La1-xCaxNiO3 (x = 0.0, 0.05, 0.1, 0.3,
608 0.5 and 0.8). They modified the original citrate method reported by (Lima et al., 2006)
609 as follows: A concentrated solution of citric acid was prepared and added to a solution
610 of the precursor of the B-site cation (Ni(NO3)2.6H2O with an excess of ethylene
611 glycol, and the mixture was kept at 60 oC for 1 h under constant stirring. Then,
612 solutions of lanthanum and calcium nitrates were added, the whole remaining at 60 oC
613 for 1 h more. The resulting solution was slowly evaporated at 110 oC for 48 h until a
614 spongy material was obtained. This citrate precursor was crushed and decomposed at
615 550 oC for 3 h and finally calcined at 900 oC for 10 h to obtain the final mixed oxide.
616 Then they carried out the catalytic experiments in the reforming of CH4 with CO2 in a
617 tubular reactor at 750 oC and atmospheric pressure.
618 Afzal et al. (2017) reported the synthesis of mesoporous nanocast perovskites (NC-
619 LaMnO3 and NC-LaFeO3) by nanocasting technique. They synthesized their nanocast
620 perovskite-based on the original procedure developed by (Nair et al., 2014). In this
621 method, commercial SBA-15 was employed as a template. The SBA-15 was stirred in
622 deionized water to make a suspension. Equimolar solutions were formed by adding
623 La(NO3)3·6H2O, Mn(NO3)2 and/or Fe(NO3)3·9H2O to citric acid dissolved in ethanol
624 for each perovskite preparation followed by stirring, drying and calcinations to
625 remove the organic constituents. Finally, the silica template was removed by stirring it
626 3–4 times in NaOH aqueous solution at room temperature. Ultimately, the product
627 was washed with water and ethanol repeatedly until it becomes neutral
628 (approximately pH 7) and dried overnight at 80 oC. The final product was then
629 applied for TOC removal and catalytic ozonation of 2-chlorophenol.
26
630 Levasseur and Kaliaguine (2009) reported another synthesis method called reactive
631 grinding which leads to the production of high specific surfaced area perovskite-type
632 mixed oxides (La1-yCeyCo1-xFexO3). They prepared five samples of perovskite-type
633 materials (LaCoO3, LaCo0.8Fe0.2O3, LaCo0.6Fe0.4O3, LaFeO3, and La0.9Ce0.1CoO3)
634 synthesized by grinding the single oxides. The precursors were first calcined and then
635 introduced into a laboratory grinder for a first grinding under O2. After this step, the
636 perovskite phase was obtained but a second grinding was performed in order to
637 increase the specific surface area (Kaliaguine et al., 2001). NaCl or ZnO was then
638 introduced as an additive in a weight ratio perovskite/additive = 1. The obtained
639 powder was repeatedly washed with diluted NH4NO3 (if the additive was ZnO) or
640 with water (if the additive was NaCl) in both cases in order to leach the additive from
641 the sample. Finally, the produced perovskites were tested for their catalytic activity in
642 VOC oxidation which was enhanced by introducing cerium and weakened by iron in
643 the lattice.
644 In another development, Yu et al., (2017) prepared a series of fluorinated Bi2MoO6
645 crystals with a different atomic ratio of F to Bi (RF = 0.10, 0.15, 0.20, 0.25, 0.30) by a
646 method called solvothermal-calcination process. The preparation was carried out
647 under sonication by first dissolving the specific amount of Bi(NO3)3·5H2O in ethylene
648 glycol. Then under magnetically stirring, a certain amount of (NH4)6Mo7O24·4H2O
649 and a stoichiometric amount of NaF (with the molar ratio of F to Mo at 0.10, 0.15,
650 0.20, 0.25, 0.30, respectively) were added and the pH value of ethylene glycol
651 solution was adjusted to 7.0. After stirring for 30 mins, the solution was placed in a
652 Teflon-lined stainless autoclave and heated to 160 oC which was maintained for 10 h.
653 The obtained powder was collected, washed several times with distilled water and
654 dried at 110 oC for 12 h. Finally, the powder was placed in a furnace and calcined at
27
655 400 oC for 2 h to obtain the FR-Bi2MoO6 (R: atomic ratio of F to Mo, R = 0.10, 0.15,
656 0.20, 0.25, 0.30, respectively). Recently, (Lu et al., 2019) also used the facile
657 solvothermal method to successfully synthesize cubic perovskite (CaTiO3) which was
658 utilized in the sequestration of U(VI) from aqueous solutions. In their experiment,
659 they adopted the methods reported by (Yang et al., 2010; Yang et al., 2008) where the
660 typical amount of Ca(NO3)2 was dissolved into PEG-200 under ultrasonic conditions.
661 Afterward, Ti(OC4H9)4 solution was added drop-wise into the above mixture followed
662 by NaOH addition under vigorous magnetic stirring. Subsequently, the suspension
663 was heated at 180 °C for 15 h. The perovskite was obtained by washing it with
664 acetone, dilute acetic acid and distilled water several times followed by centrifugation
665 at 6000 rpm for 30 mins.
666 4. Characterization of Perovskites
667 In order to study the structure and properties of perovskites, various complementary
668 techniques such as SEM and TEM, FTIR absorption spectroscopy, XRD, TGA and
669 TPR have been employed by many researchers.
670 4.1. Electron microscopy analysis
671 SEM is the most widely used technique in examining surface morphology of samples,
672 forming images in a three-dimensional structure that is crucial for sample analysis.
673 SEM possess the ability to scan bulky images better with a greater view consisting of
674 a shadow-relief effect of both secondary and backscattered electron contrast, as well
675 as produce a good image of the 3D structure (Aloulou et al., 2018; Goldstein et al.,
676 2012; Luykx et al., 2008). TEM on the other hand is a unique and powerful nanoscale
677 imaging technique which gives a better sample image at higher resolution (Wang,
678 2000). It has the ability to control the sample surface morphology and size distribution
679 but time-consuming analysis process. SEM has an advantage over TEM as it scans a
28
680 larger amount of sample once at greater resolution and higher magnification (Luykx et
681 al., 2008). The surface morphology of perovskites (ABO3) from different elements in
682 A position (La, Sr, Sm, and Nd) and B position (Fe, Ni, Zn, Co and Mn) as shown in
683 Table S1 (Afzal et al., 2017; Deng et al., 2019; Luu et al., 2016; Shetkar and Salker,
684 2010; Tavakkoli and Yazdanbakhsh, 2013; Yazdanbakhsh et al., 2011). Based on the
685 SEM images reported by Yazdanbaksh and co-workers, the surface porosity was clear
686 and the particles seem not to have grown with uniform sizes. Evident of rough
687 looking surface almost fully covered with the particles grown on it was also clear
688 from their SEM. They also reported the TEM image of their sample calcined at 750
689 °C to consist particles in the range of about 15 to 40 nm in size, clearly indicating that
690 the perovskites consist of agglomerates smaller than 70 nm (Yazdanbakhsh et al.,
691 2011). In agreement with above revelation, Tavakkoli and Yazdanbakhsh (2013)
692 reported that their LFCO1 samples are not well-distributed revealing over 80% of the
693 samples to be at the nanoscale and it seems that the nanoparticles were not grown
694 with uniform size. They also reported rough and nearly fully covered surface with
695 particle size distribution in the range 50–400 nm. In another development, Deng and
696 co-workers reported the growth of LaFeO3 perovskite crystals on the surface of the
697 active carbon fibers (ACF) (Deng et al., 2019). However, Luu et al. (2016) reported
698 their sample morphology to have homogeneous agglomerates of nano-sized
699 crystallines showing uniform grain size distribution and a fine powder size in the
700 nanoscale range, between 30 and 50 nm. The images from their TEM analysis
701 revealed the micrograph image of their NdFeO3 nanoparticles at 100 nm and 20 nm
702 scale (Luu et al., 2016). They reported sphere-like NdFeO3 monodispersed particles
703 with 20 nm as the approximate average size which agreed well with those calculated
704 (21 nm) by the Scherrer equation from the XRD data of their sample. Such
29
705 consistency was attributed to the fact that the NdFeO3 nanoparticles were single
706 crystalline (Luu et al., 2016). TEM technique was employed by fewer researchers due
707 to cost of analysis and more time consuming compared to SEM.
708 4.2. Fourier transform infrared spectroscopy
709 Another particularly reliable, rapid, sensitive and powerful characterization technique
710 is FTIR. In this modern era, FTIR has been used more in-depth in monitoring the
711 chemical structure and functional groups of various perovskites as compiled in Table
712 S2. A broad absorption band observed in the region of 3000–3600 cm−1 in the FTIR
713 spectra, are observed in almost all the perovskite particles analyzed indicating the
714 presence of OH stretching vibrations (Afzal et al., 2017; Erdenee et al., 2017;
715 Fernandes et al., 2002; Lu et al., 2019; Luu et al., 2016; Mahmoudi et al., 2019;
716 Makhloufi et al., 2019; Santos et al., 2018; Wang et al., 2011). Broadband between
717 3667 and 2998 cm−1 for LaMnO3 and LaNiO3 samples were reported and attributed to
718 O-H stretching from water molecule (Aquino et al., 2012; Santos et al., 2018). After
719 calcination, Santos et al. (2018) reported the disappearance of a doublet assigned to
720 the stretching of N-H bonds in primary amines (2925 and 2968 cm−1) from the
721 precursor, attributing it to the thermal decomposition of the parts of organic material
722 contained in the precursors. They also reported the presence of important bands
723 corresponding to the stretching vibrations of the metal-oxygen bond at 643 and 410
724 cm−1 for the manganese-based samples and at 685 and 655 cm−1 for the nickel-based
725 materials with the intensity of these bands is lower for LaNiO3-type materials, than
726 for LaMnO3-type materials. That inferred better interaction of Mn2+ with the ligand
727 leading to the formation of the perovskite phase.
728 Wang et al. (2019) also characterized their microwave induced templated-double
729 perovskite (LaCo1-xCuxO3@PMMA) using the FT-IR technique. They reported a
30
730 broad absorption peak at about 3150 cm-1 which was assigned to the O-H stretching
731 vibration. The band attributed to the stretching vibration of -COOH was reported at
732 1400 cm−1 depicting the presence of surface hydroxyl on the metal oxide surface
733 (Wang et al., 2018). They also reported the presence of rhombohedral perovskite-type
734 structure based on the absorption bands that appeared at around 415 and 595 cm−1
735 (Yao et al., 2016). Fingerprint bands at 668 and 480 cm-1 were also attributed to the
736 Co-O stretching vibration in octahedral CoO6 group and Cu-O stretching respectively
737 (Ma et al., 2011; Sharmila et al., 2018). Upon an increase in the Cu-substitution ratio,
738 the Cu-O characteristic peak shifted from 465 to 500 cm−1 attributed to the change in
739 charge density of the B cation in the perovskite, impacting their catalytic activity
740 (Wang et al., 2019). Other researchers from their various studies also revealed the
741 presence of bands between 600–500 cm−1 corresponding to formation of the
742 perovskite structure/phase (Afzal et al., 2017; Benaicha and Omari, 2018; Erdenee et
743 al., 2017; Lu et al., 2019; Mahmoudi et al., 2019; Makhloufi et al., 2019; Parhi and
744 Manivannan, 2008; Wang et al., 2011; Yazdanbakhsh et al., 2010).
745 4.3. X-ray diffraction
746 Another commonly used technique for the characterization and identification of
747 crystalline solids based on their atomic-scale structure is X-ray diffraction (XRD)
748 pattern (Luykx et al., 2008; Petkov, 2008). Apart from that, XRD is also a versatile
749 technique in providing in-depth information on the crystallographic structure and
750 chemical composition of materials as well as revealing the presence of both
751 amorphous and crystalline phases (Candamano et al., 2014). X-rays have wavelengths
752 in a systematic order of a few angstroms which is same as the interatomic distances
753 which cause diffraction to occur in crystalline solids (Luykx et al., 2008) displaying
754 the diffraction pattern inform of numerous sharp spots known as Bragg diffraction
31
755 peaks. Height ratio between the intensity of crystalline peak and total intensity of non-
756 crystalline peak are used in calculating crystallinity index using below the equation as
757 reported by (Segal et al., 1959):
*++, - *./
758 $( =
*++,
759 (11)
760 where crystallinity index is denoted as CrI, I200 stand for maximum intensity of the
761 peak with Iam signifying intensity of diffraction of the non-crystalline material. The
762 crystallite sizes are calculated using the Scherrer equation (Barrett and Massalski,
763 1996; Luu et al., 2016) as follows :
01
764 = 2 345 6
765 (12)
766 where L is the size of the crystallite (nm), k is the Scherrer constant, is the X-ray
767 wavelength, is the full width at half maximum of lattice plane reflection in radian,
768 and is the corresponding Bragg angle (reflection angle).
769 Various studies demonstrated peaks that characterized perovskite structure with single
770 phase and orthorhombic structure (Bradha et al., 2015; Deng et al., 2019; Luu et al.,
771 2016; Makhloufi et al., 2019; Meiqing et al., 2013; Santos et al., 2018; Shetkar and
772 Salker, 2010) with other researchers also reporting rhombohedral structure
773 (Mahmoudi et al., 2019; Silva et al., 2010). Jamali et al. (2017) reported an
774 orthorhombic LaFeO3 crystal unit produced by microwave-assisted synthesis with no
775 peaks attributed to any impurity which was in good agreement with Phokha et al.
776 (2014) who produced their perovskite through polymerized complex method, thus
777 proving both synthesis methods to serve as easy and efficient methods of producing
32
778 crystalline LaFeO3 nanoparticles. Mahmoudi et al. (2019) reported sharp peaks for
779 rhombohedral structured LaCoO3 without any impurity diffraction peaks, indicating
780 that single-phase perovskite-type LaCoO3 was obtained. The sharp reflections are
781 associated with the high crystallinity of the compound. The average crystallite size of
782 LaCoO3 was further calculated to be 57 nm (fundamental) and 58 nm (Williamson-
783 Hall) methods (Mahmoudi et al., 2019). In another development, Silva and Soares
784 (2009) prepared three perovskites catalysts, revealing two of them (LaNiO3 and
785 LaCoO3) to show rhombohedral structure while LaMnO3 presented orthorhombic
786 structure. In the catalysts LaCoO3 and LaNiO3, there was a peak representing
787 lanthanum oxide (La2O3), which indicated a cationic excess. LaNiO3, on the other
788 hand, shows a peak which confirmed the presence of NiO (Silva and Soares, 2009).
789 But LaMnO3 doesn’t show La2O3 peak; which was attributed to the fact that that this
790 oxide presented cationic vacancies coming with an excess of negative species of
791 oxygen.
792 4.4. Thermal analysis
793 Both TGA and DSC are commonly used in investigating the thermal and degradation
794 properties of samples. Generally, the TGA curves of perovskites show two
795 degradation stages, which indicate the weight loss of the sample. The first stage
796 corresponds to the release of hydration water at the region between 25 and 115 oC.
797 The second stage concerns the decompositions of amino acid fragments in the range
798 of 250–450 oC (Aquino et al., 2012; Giolito et al., 2004). Silva and co-workers
799 reported the thermal decomposition of their LaNixCo1-xO3 perovskites to take place in
800 two steps, stabilizing at temperatures high than 1100 oC. They attributed the mass loss
801 in the first step which was observed between 30-140 oC to various simultaneous
33
802 decomposition reactions of the residual material in the synthesis process (Silva et al.,
803 2010). The samples showed another decomposition (second step) above 850 oC which
804 was attributed to the decomposition of carbonate compounds formed.
805 Santos et al. (2018) employed thermogravimetric analysis in the synthesis of
806 perovskite materials using soy protein as a complexing agent in order to provide
807 information related to the decomposition processes of soy protein, and also form the
808 basis for choosing the calcination temperatures for their precursor powders. They
809 reported mass losses of about 8.6, 64.6 and 2.8 % from 24 to 114 oC, 225 to 580 °C
810 and 580 to 900 °C respectively which were attributed to the decomposition products
811 being residually eliminated. The thermal decomposition process of LaFe0.9Co0.1O3
812 (LFCO) was reported by Tavakkoli and Yazdanbakhsh (2013). They revealed the total
813 weight loss of the sample to be about 67 % with the decomposition process divided
814 into three distinct steps. The first weight loss occurred during the heating step from
815 room temperature to 180 oC (24 %) resulting from the dehydration and decomposition
816 of nitrates. The second step involved about 13 % weight loss from 180 oC to about
817 350 oC which was attributed to the decomposition of chemically bound groups. They
818 reported about 30 % mass loss for the third step from 350 to 650 oC which was
819 attributed to the combustion or oxidation of the chelate complex along with the
820 forming of metal oxides. They reported no further weight loss at a temperature above
821 650 oC which informed the formation of nanocrystalline LFCO as the decomposition
822 product. Hence, about 700 oC was plausibly concluded as the optimum calcination
823 temperature.
824 Other researchers also reported the decomposition process of LaFe0.8Cu0.2O3 to take
825 place in three steps (25-250 oC, 250-550 oC, 550-820 oC). The mass loss for the first
o
826 step (25-250 C) was attributed to water desorption and organic substances
34
827 decomposition (methanol, citric acid) which was also reflected by two exothermic
828 peaks at 190 and 220 oC (Shabbir et al., 2006). The second mass loss between 250-
829 550 oC was attributed to the burning of the remaining organic materials accompanied
830 by the evolution of CO2 and H2O gases as well as the formation of a metal carbonate
831 (Banerjee et al., 2015). The mass loss in the third step between 720-820 oC which was
832 probably attributed to the formation of LaFe0.8Cu0.2O3 oxide was associated with two
833 exothermic peaks at 745 °C and 806 °C as seen in DTA curve (Brunckova et al.,
834 2016). In another development, (Bradha et al., 2015) reported the mass loss profile of
835 their La0.8A0.2TiO3.5–δ (A=Ba, Sr, Ca) nano perovskite samples occurring in several
836 steps. They reported the first stage to be in the range between room temperature to
837 200 ºC which was attributed to the removal of adsorbed and structural water from the
838 sample with mass loss. The second stage was reported between 200 and 400 ºC which
839 was accompanied by an exothermic peak on the DTA curve with the mass loss
840 ascribed to the decomposition of nitrates and citrate complexes. They reported the
841 third stage to be in the range of 400–600 ºC, with mass loss representing the loss of
842 organics and carbon dioxide from metal oxides. It was also represented by an
843 exothermic peak at the DTA curve. The fourth stage was in the range of 600–1000 oC
844 with mass loss accredited to the oxygen loss and formation of LaTiO3.5–δ perovskite
845 phase and the structural variation in TiO6 octahedron under higher calcination
846 temperatures (Bradha et al., 2015). All the samples were then calcined at 800 ºC for 2
847 h based on those results.
848 4.5. Temperature-programmed reduction
849 Another technique employed by researchers in characterizing perovskite oxides is
850 TPR. The technique is usually applied in obtaining information about reducibility of
851 the studied samples as well as to identify the reduction temperature. Guo et al. (2003)
35
852 reported the reduction of four perovskite-type precursors (LaNiO3, La2NiO4, LaCoO3,
853 and La2CoO4) to take place in two steps: the first in the range between 350–500 oC
854 and the second one in the range of 500–700 oC. They revealed the Co-based
855 perovskites to be more stable under reducing atmosphere than Ni-based perovskites.
856 That was attributed to the reason for low reforming activity over Co-based perovskite
857 catalysts. Silva and Soares reported the presence of a peak in their TPR profile for
858 LaMnO3 which as ascribed to the d-oxygen, non-stoichiometric reduction and
859 consequently, reduction of Mn+3 as agreed by Tejuca et al. (1989). They also reported
860 two peaks for LaNiO3, a small shoulder near 451 °C corresponding to La2Ni2O5
861 formation, which resulted into Ni3+ to Ni2+ reduction, and the second peak (600 °C)
862 attributed to the reduction of Ni2+ to Ni0. That transformation was according to below
863 reactions, indicating the presence of both NiO and the perovskite phase (Vidyasagar
864 et al., 1985)
865 27 + 2 → 7 8 +2
866 (13)
867 7 + → 7 9 +
868 (14)
869 7 8 + 2 → 27 9 + + 2
870 (15)
871 The TPR profiles of LaNiO3 and La2NiO4 were also reported by other researchers
872 with the reduction of LaNiO3 shown to take place in three steps (Batiot-Dupeyrat et
873 al., 2003; Gallego et al., 2006).
874 47 + 2 → 7 ;9 + 7 9 + 2
875 (16)
36
876 7 ;9 + 3 → 7 + 27 9 + + 3
877 (17)
878 7 + → 7 9 + +
879 (18)
880 Thus, during the LaNiO3 reduction, the perovskite La2NiO4 was formed as an
881 intermediary, which was then completely reduced into metallic nickel and lanthanum
882 oxide at 610 oC. They further reported TPR profile of La2NiO4 to show two main
883 peaks with the first peak assigned to the reduction of amorphous NiO according to
884 Ruckenstein and Hu (1996) while the high-temperature peak between 520 and 680 oC
885 was attributed to the reduction of the perovskite phase. Thus, the complete reduction
886 of La2NiO4 was inferred to require a higher temperature (680 oC) than for the
887 complete reduction of LaNiO3 (610 oC).
888 5. Current applications of perovskites as adsorbents
889 Adsorption process which utilized effective adsorbents appears to be one the most
890 promising, economically and technically easy methods for the removal of
891 contaminants from wastewater (Luu et al., 2016). Many researchers devoted much
892 effort in the development of adsorbents that possess both high adsorption capacity as
893 well as cost-effectiveness (Adnan et al., 2018; Alidadi et al., 2018; Bazrchi et al.,
894 2018; Bengtsson et al., 2018; El-Naggar et al., 2018; Gan et al., 2019; Gan et al.,
895 2018; Garba et al., 2019c; Martison and Reddy, 2009; Marwani and Bakhsh, 2017;
896 Mekatel et al., 2015; Pena et al., 2005; Türk and Alp, 2014). Perovskite-type oxides
897 (ABO3) were among the novel and promising adsorbents reported for the adsorption
898 of various analytes such as dyes, volatile organic compounds, pesticides and heavy
37
899 metal ions (Luu et al., 2016; Santos et al., 2018; Song et al., 2008; Yazdanbakhsh et
900 al., 2011) as compiled in Table 2.
901 Yazdanbakhsh et al. (2011) reported the successful synthesis of nanocrystalline
902 La0.5Ca0.5NiO3 powders as promising surface material capable of azo dye removal
903 from wastewater over a wide concentration range. They studied how significant
904 adsorption parameters such as pH of solution, catalyst dosage, contact time as well as
905 initial dye concentration influenced the adsorption process. Their results revealed the
906 effectiveness of La0.5Ca0.5NiO3 powders in the removal of high concentrations of RB5
907 dye molecules. Also, the RB5 percentage removal obtained in the 10th minute of
908 stirring was 100 % using 0.03 g LCNO at pH 2. Equilibrium and kinetic data
909 modeling also revealed Langmuir isotherm and pseudo-second-order kinetic equation
910 as the best models respectively in describing the RB5 adsorption on to the LCNO.
911 (Wang et al., 2016a) also reported the synthesis of novel three-dimensional spherical
912 porous-Bi2WO6 microcrystals via a facile hydrothermal method thereby investigating
913 its adsorption properties on various contaminants. Their experimental results revealed
914 pseudo-second-order kinetic to be the best model in explaining the adsorption kinetic
915 of MB on the 3D surface of the porous-Bi2WO6 microcrystals. The Langmuir
916 isotherm data revealed monolayer adsorption capacity of MB to be 60.28 mg g-1,
917 which was higher than that of RhB, CR, AR and phenol. The adsorbent microcrystals
918 exhibited excellent preferential adsorption ability for MB and inferior adsorptivity for
919 RhB and CR which was attributed to the pore size, large surface-to-volume ratio of
920 3D porous-Bi2WO6 and the charge of exposed face.
921 Another investigation revealed the capability of nanocrystalline Fe3-xLaxO4 ferrite in
922 the adsorption of Congo red. The researchers tried to increase the adsorption capacity
38
923 by adulterating a small quantity of La3+ ions (x = 0, 0.01, 0.05, 0.10) into the
924 magnetite. Upon comparison with the pure magnetite, La3+-doped magnetite exhibited
925 better adsorption capability. Furthermore, Fe2.95La0.05O4 among the La3+-doped
926 products which possessed the largest Ms value owes the largest adsorption capacity.
927 The magnetite ability to remove CR was improved not by increasing the specific area
928 but by deforming the crystal structure via doped-La3+ ions (Wang et al., 2011).
929 Fe3-xLaxO4 nanoparticles also exhibited higher adsorption capacities for CR when they
930 were compared with many other adsorbents from literature. They also revealed
931 Langmuir adsorption isotherm as the best model that described the equilibrium
932 adsorption data with the kinetic model indicating the reliance of adsorption
933 mechanism on the adsorbate and adsorbent (Wang et al., 2011). The Fe3-xLaxO4
934 nanoparticles were revealed as excellent adsorbents due to their high adsorption,
935 desorption as well as recovery efficiency.
936 In another development, Mahmoudi et al., (2019) reported the synthesis of perovskite-
937 type LaCoO3 nanomaterials by a simple method. The prepared LaCoO3 nanomaterials
938 were then coated with silica which was used for the synthesis of LaCoO3@SiO2/PW12
939 hybrid nanomaterials. They employed both materials in the removal of organic dyes
940 (MB and MO) from aqueous solution. They reported the developed hybrid
941 nanomaterials to reveal higher MB adsorption efficiency than that of the bare LaCoO3
942 nanomaterial. Moreover, good reusability of the hybrid nanomaterial was found
943 without any decrease of adsorption after three cycles. It was clear based on their
944 findings that the hybrid materials have a promising future in the adsorption and
945 removal of dye pollutant from solutions. Deng et al. (2019) also reported the
946 successful synthesis of LaFeO3 perovskite oxide decorated active carbon fibers based
947 on cotton fabric waste through sol-gel loading and thermal treatment. The results
39
948 suggested a negligible effect of solution pH on the adsorption performance with
949 maximum adsorption capacity of 182.6 mg g-1 at 293 K. The adsorption kinetics
950 obeyed pseudo-second-order model with excellent regeneration of LFO-ACF realized
951 through an easy pyrolysis method. They suggested the valence states of La (III) and
952 Fe (III) as well as the existence of a large quantity of adsorbed hydroxyl groups to
953 promote interactions between RhB and LFO-ACF by electrostatic interaction,
954 hydrogen bonding, π-π stacking and cation-π interaction (Deng et al., 2019). An
955 elution of solvent was avoided in the recycling experiment through easy pyrolysis
956 with the regenerated LFO-ACF depicting excellent removal ability for RhB dye,
957 implying a good future application. The whole interactions of cationic and
958 zwitterionic RhB on the surface of LFO-ACF were illustrated in Fig. 3.
959 Wei et al. (2019) reported CuFe2O4 with peroxymonosulfate as an effective, fast and
960 efficient adsorbent for the removal of As(III) from water. They reported CuFe2O4 to
961 have less affinity for arsenic than CuFe2O4/PMS. The adsorption capacity for As on
962 CuFe2O4/PMS was 63.9 mg g-1, greater than that of As(III) (36.9 mg g-1) or As(V)
963 (45.4 mg g-1) on CuFe2O4 alone. In trying to understand the adsorption mechanism,
964 the surface hydroxyl groups (-OH) on metal oxide adsorbents was reported to be
965 crucial for arsenic adsorption with three possible innersphere arsenic complexes (Fig.
966 S6): bidentate binuclear, bidentate mononuclear and monodentate mononuclear
967 complexes (Arai et al., 2001; Manning and Goldberg, 1997). They further reported the
968 stoichiometric ratio of 1:2 and 2:1 with respect to surface hydroxyl between fresh
969 CuFe2O4 and the CuFe2O4 saturated with arsenic for a monodentate surface complex
970 and bidentate complex respectively (Wei et al., 2019).
971 Table S3 depicted the fitted data for O 1s XPS spectra of CuFe2O4 before or after
972 adsorbing arsenic. There was an upsurge in the ratio of OH−/O2− for CuFe2O4 from
40
973 20.9 % to 38.1 %, 31.0 % and 33.0 % after adsorbing As(III), As(V) and As(III)/PMS,
974 respectively. The arsenic adsorption was confirmed to be through the formation of
975 monodentate mononuclear complex based on an increase in OH-/O2- ratio (Goh et al.,
976 2009; Zhang et al., 2005). The larger value of OH−/O2− after As (III) adsorption upon
977 comparison with those after As(V) adsorption portrayed that monodentate
978 mononuclear complex was more significant in As(III) adsorption. The higher
979 proportion of OH−/O2− for As(III)/PMS adsorption than As(V) adsorption indicated
980 that the adsorbed As(III) maintained the monodentate mononuclear complex after
981 oxidation. Obviously, the monodentate mononuclear complex mechanism can
982 effectively increase the utilization of adsorption sites (Fig. S6a).
983 Farhadi and Mahmoudi (2019) reported the synthesis of perovskite-type
984 LaNiO3 nanoparticles by an auto-combustion method and coated with a SiO2 shell.
985 Then, silica-coated LaNiO3 nanoparticles were used as an active support of Keggin-
986 type phosphotungstic acid for the synthesis of
987 novel LaNiO3@SiO2/PW12 hybrid nanomaterial. The LaNiO3@SiO2/PW12 material
988 was tested as adsorbent for the removal of cationic dyes (MB and RhB) as well as
989 anionic MO dye from aqueous solutions. The results of the adsorption measurements
990 demonstrated that the LaNiO3@SiO2/PW12 hybrid exhibited superior performance to
991 pristine LaNiO3, suggesting that PW12 polyoxometalate play a critical role in the
992 adsorption performance improvement. Furthermore, selective adsorption of the
993 LaNiO3@SiO2/PW12 nanohybrid was investigated towards MB/RhB, MB/MO,
994 MO/RhB and MB/MO/RhB mixed dye solutions. The hybrid showed rapid and
995 selective adsorption for cationic MB and RhB dyes from mixed dye solutions (Farhadi
996 and Mahmoudi, 2019). Another added advantage shown by the hybrid material is easy
997 separation from the aqueous solutions which was recycled three times retaining its
41
998 adsorption ability. Based on the results of their study, the hybrid nanomaterial can be
999 concluded to be an efficient adsorbent for tackling water contaminated with cationic
1000 dyes.
1001 In another development, Manjunatha et al. (2019) utilized PLA as an adsorbent for the
1002 removal of fluoride and DB-53 contaminants. Mathematical modelling of kinetics and
1003 isotherms were computed using equations which revealed pseudo-second-order
1004 kinetic and Halsey isotherm equilibrium models as the best fit with maximum
1005 Langmuir adsorption capacity of 40.8 mg g-1 (fluoride) and 71.4 mg g-1 (DB-53),
1006 suggesting nature of the adsorption process to be physisorption (Manjunatha et al.,
1007 2019). From the obtained results, PLA was categorized as an effective adsorbent for
1008 fluoride and DB-53 dye for ground and industrial wastewater.
1009 6. Comparison between perovskites and other adsorbents
1010 The comparison in terms of performance of perovskite materials with other
1011 adsorbents for the removal of water contaminants is shown in Table 3. The
1012 comparison results clearly show a very good performance by the perovskite materials
1013 when compared with other established adsorbents used for the adsorption of various
1014 adsorbates. Perovskite materials as adsorbents are renewable, effective, economical,
1015 environment friendly and sustainable materials as compared to other adsorbents.
1016 7. Benefit analysis
1017 7.1. Estimating the costs of perovskites
1018 Perovskites are more popular and widely used in solar cell applications, so
1019 understanding the economic analysis of perovskite solar modules will go a long way
1020 in educating us about the economic viability of these materials as adsorbents. Due to
1021 high power conversion efficiencies and easy fabrication, PSCs are considered as
42
1022 promising candidates for the next generation of solar cells (Cai et al., 2017). Cai and
1023 her co-workers carried out a cost analysis on the production of two representative
1024 examples of PSCs: one was produced from cheap materials as a moderate-efficiency
1025 module A, while the other was a high-efficiency module B begotten from costly
1026 materials, reporting the costs of both modules to be lower than those of other
1027 photovoltaic technologies. The structures of modules A and B (which were assembled
1028 with series connections) are depicted in Fig. S7. The cells in module A were
1029 fabricated based on a mesoporous structure (Fig. S7a) by employing a series of simple
1030 techniques that relied on screen printing (denoted as humble process) to produce
1031 moderately efficient modules as high as 15 % (Chen et al., 2015). However, the cells
1032 in module B (Fig. S7b) were based on a precise structure, composed of several layers
1033 of high-quality thin films to which end up producing highly efficient modules ≈20%
1034 (Nie et al., 2015; Wu et al., 2015).
1035 A series of finely controlled processes, production of patterns with lasers and vacuum
1036 evaporation to produce metal electrodes were required for their fabrication. The
1037 upsurge in manufacturing cost was attributed to the high precision of the fabrication
1038 processes. (Cai et al., 2017) reported an expected improvement in the accuracy of the
1039 boundary due to the precision as well as narrowness of the etching produced by lasers
1040 which lead to a relatively large active area (0.95 m2 in one piece of 1 m2 module B).
1041 Fig. S7c shows the costs of modules of Module A and Module B at 1st year, 5th year
1042 and amortizing capital cost over 5 years. The module cost can be divided by the cost
1043 of materials, overhead cost, and capital cost. The capital costs of DSCs fabricated
1044 using the printing process together with thin-film silicon solar cells, were used for the
1045 calculation of the capital costs for Module A and B with the quantity of materials that
1046 were used also employed in estimating the cost of materials. The overhead cost was
43
1047 estimated based on reasonable assumption. The first year recorded a relatively high
1048 module cost which was attributed to the big depreciation rate (50 %) of capital
1049 investment. For Module A and B, the calculated capital costs in the first year were
1050 0.110 and 0.160 US$/W respectively (Cai et al., 2017). The low initial capital cost of
1051 Module A was attributed to the capital investment associated with using cheap
1052 printing facilities, which were lower than that of the high-vacuum machines used in
1053 Module B. However, there was rapid decrease in capital cost due to depreciation, with
1054 the result being a monotonic decrease of the total module cost during the first 5 years.
1055 After that time, the module cost was determined mainly by overhead and materials
1056 costs due to the contribution of capital cost to total cost becoming very low (Cai et al.,
1057 2017).
1058 As research on the potential values of perovskites is still on and its market is not
1059 mature enough, there is always the possibility of price variability in the perovskite
1060 prices in the future, which will be helpful to researchers in obtaining a comprehensive
1061 price and cost data of perovskites employed as adsorbents.
1062 6.1. The environmental impacts of perovskites
1063 Despite the economical importance, environmental impacts of perovskites are even
1064 more important. Scientists raised alarm on environmental concerns especially with
1065 lead-based perovskite solar cells in large-scale applications (Espinosa et al., 2015;
1066 Zhang, 2015). One such concern is that any slight contamination from damaged solar
1067 cells will likely cause major health and environmental problems due to this material
1068 being soluble in water coupled with the high toxicity of lead (Babayigit, 2016;
1069 Benmessaoud, 2016). In their attempt to address such concern, researchers proposed
1070 tin-based perovskite solar cells as an alternative to the toxic and environmentally
1071 threatening lead-based perovskites. This proposed tin-based perovskite solar cell is a
44
1072 special type of perovskite solar cell, where tin is used as a substitute for the toxic lead,
1073 having a tin-based perovskite structure of ASnX3, where 'A' is a 1+ cation and 'X' is a
1074 monovalent halogen anion. Maximum solar cell efficiencies were reported for various
1075 tin-based perovskite compounds such as 2.02 % for CsSnI3 (Kumar, 2014), 5.73 % for
1076 CH3NH3SnIBr2 (Hao, 2014), 6.4 % for methylammonium tin iodide (CH3NH3SnI3)
1077 (Noel, 2014), and 9 % for formamidinium tin triiodide (FASnI3) (Shao et al.,
1078 2018). The methylammonium tin iodide (CH3NH3SnI3) has a band gap of 1.2–1.3 eV
1079 (Hao, 2014; Noel, 2014). There are relatively few publications about tin-based
1080 perovskite solar cells in comparison to their counterpart, lead-based perovskite solar
1081 cells. One drawback of these new materials is the instability of the 2+ oxidation
1082 state of tin (Sn2+) especially in methylammonium tin iodide (CH3NH3SnI3), which can
1083 be easily oxidized to the more stable Sn4+ (Lee, 2016) leading to a process called self
1084 doping (Takahashi, 2011) where the Sn4+ acts as a p-dopant leading to the reduction
1085 in the solar cell efficiency. For that reason, tin-based perovskite solar cells are still
1086 being research upon
1087 EFM was also explored by scientists in an attempt at evaluating the exposed lead
1088 containing compounds in PSCs as well as their impacts on humans and the
1089 environment in general (Yoo et al., 2019). Fire (PbO) and flooding (PbI2) were two
1090 major accidental situations the scientists considered as plausible scenarios that involve
1091 the environment and exposure to compounds. As a result, water systems were
1092 concluded as the most vulnerable to lead toxicity when lead-containing compounds
1093 are discharged from PSCs (Yoo et al., 2019). Therefore, the regulatory standards for
1094 PSC generators should be established to fulfill both environmental and human safety
1095 limits. This could be accomplished by selecting the most conservative results from
1096 various environmental fate evaluation methods.
45
1097 7. Conclusion and future perspectives
1098 In this review, we reported a comprehensive state-of-art of several aspects of
1099 perovskites materials, which is crucial for further understanding of these
1100 nanoparticles. Here, we mainly focus on the properties, synthesis methods,
1101 characterization and potential application of perovskites as adsorbents for wastewater
1102 treatment. However, for the better understanding of the properties of these ABO3-
1103 materials and their role in adsorption processes, development of novel synthesis
1104 methods is very much needed. Additionally, perovskite oxides have not yet been
1105 applied as commercial adsorbents; therefore, in the future, there is a need for
1106 researchers to pay much attention to obtaining more efficient adsorbents for industrial
1107 use. Moreover, perovskite adsorption mechanisms and relationships among the
1108 structure, surface character, and adsorptive activity have not been well investigated
1109 and understood. Synthetic wastewater is usually used for adsorption studies by many
1110 researchers so examining the perovskite-based adsorbents is very crucial in a more
1111 realistic condition such as real wastewater containing various pollutants. Another
1112 important thing to consider is that most researchers tend to ignore the lifecycle of the
1113 adsorbents, so it is highly recommended that studying adsorption/desorption cycles be
1114 given utmost importance. Other vital issues that should be taken seriously include
1115 proper disposal of the adsorbents stuffed with pollutants and cost evaluation of
1116 fabricating modified adsorbents for targeted applications. There is also the need for
1117 future work to focus on reducing the mobility of various pollutants in soil
1118 environments by studying the application of these perovskite materials as adsorbents
1119 in pilot scale processes as well as soil amendments. There are still many challenges
1120 such as lacking sufficient stability towards long term applications and instability that
1121 also need addressing despite the significant progress achieved in perovskite
46
1122 nanostructures. These flaws may cause an obstacle on the path towards
1123 commercializing the perovskite use in the future. Therefore, there is a need for more
1124 dedication to improving the stability (such as photostability, thermal stability,
1125 moisture stability, and chemical stability) to catch up with the rapidly increasing
1126 efforts on their synthesis and properties for various applications. Upon comparison
1127 with other competing adsorbent materials, perovskites proved to be very good in
1128 removing dyes and heavy metals so their application needs to be expanded so that
1129 they can cover other water and wastewater contaminants. Considering the current
1130 engineering trend of practice-reduce, reuse and recycle; materials with properties of
1131 perovskites may garner more research attention and owing to their potentials become
1132 the next uprising materials of the future.
1133 Acknowledgments
1134 The authors would like to humbly acknowledge the international funding provided by
1135 Fujian Agriculture and Forestry University (KXB16001A) and the Department of
1136 Science and Technology of Fujian Province (2017H6003), P.R. China.
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70
Figure captions
Fig. 1. Schematic representation of catalytic ozonation mechanism (Afzal et al., 2017 ).
Fig. 2. Experimental set up for steam reforming of toluene (Soongprasit et al., 2012).
Fig. 3. Possible adsorption mechanism of RhB dye on LFO-ACF (Deng et al., 2019).
Table 1. Summary of the properties and potential applications of some perovskite materials
Perovskite materials Preparation method Properties Potential applications References
La0.5Ca0.5NiO3 Sol-gel method Good crystallinity with hexagonal Adsorptive and photocatalytic (Yazdanbakhsh et al., 2011)
perovskite structure activity against RB 5
La1-xCexNiO3 Sol-gel method Homogeneous structure and low Steam reforming of toluene (Soongprasit et al., 2012)
agglomeration
LaFe0.9Co0.1O3 (LFCO1) Sol–gel method Good crystallinity with orthorhombic Efficient removal of a vitavax (Tavakkoli & Yazdanbakhsh,
and LaFe0.1Co0.9O3 and hexagonal structure for LFCO1 pesticide from aqueous solutions 2013)
(LFCO2) and LFCO2 respectively
LaFe1-XCuXO3 Sol-gel method Single phase of cubic perovskite with Electrode material (Benaicha & Omari, 2018)
low specific area
LaNi1-xCoxO3 Sol-gel method Good crystallization of the perovskite Catalyst for the dry reforming of (Valderrama et al., 2008)
phase with conversions and CH4 over solid solution
selectivities close to thermodynamic
equilibrium (~100%).
La1−xCexBO3 Sol-gel method Well crystalline perovskite structure, Catalytic activities in the (Erdenee et al., 2017)
(B = Mn and Co) 8–22nm crystallite sizes. Ce dehydrogenation of propane
substitution promoted the structural
transformation for LaCoO3 from
rhombohedral into cubic and for
LaMnO3 no change in lattice geometry
La(1–x)AxTiO3.5–δ Sol-gel method Irregular morphology and Photocatalytic oxidation of CR (Bradha et al., 2015)
orthorhombic crytals dye
Fibrous LaFeO3 Sol-gel method Fibrous shape of the raw cotton fibres Adsorbent for the removal of RhB (Deng et al., 2019)
with negative electric potentials dye
LaFeO3 Sol-gel method Orthombic and polycrystalline Catalytic degradation of diclofenac (Rao et al., 2019)
structure
La1–xCaxMnO3 Sol-gel citrate method Well-crystallized perovskite-type NO catalytic oxidation activity (Meiqing et al., 2013)
structure without any detectable
1
secondary phases with crystal structure
belonging to rhombohedral system
LaNiO3 Sol-gel citrate method Constituted by the aggregation of A catalyst for the green technology (Palas et al., 2018)
cornered particles with various shapes applications of azo dye removal
and sizes which form a heterogeneous
structure. The catalyst texture also has
full cavities and crevices
LaNi1-xRhxO3 Citrate sol-gel Highly homogeneous and crystalline Catalyst for dry reforming of (Rivas et al., 2008)
method and co- solids methane
precipitation
La1-xCaxNiO3 Modified citrate method Perovskite and spinel-type structure Catalyst for the dry reforming of (de Lima et al., 2008)
methane
LaNiO3 and Modified proteic High crystallinity and surface area Removal of the congo red dye by (Santos et al., 2018)
LaMnO3 method adsorption from liquid phase
SrMnO3, SmMnO3 and Combustion Method Hexagonal and orthorhombic Catalysts for CO combustion (Shetkar & Salker, 2010)
NdMnO3, structures, semi-conductor nature
LaNi1-xCoxO3 Combustion method Highly stable, lower specific surface Catalyst for the partial oxidation of (Silva et al., 2011)
area and small formation of secondary methane (POM).
phases
NdFeO3 Combustion method High surface area and innersphere Adsorption of hazardous arsenate (Luu et al., 2016)
surface complex formation from aqueous solution
LaNiO3 and La2NiO4 Self-combustion method Perovskite structure with a Catalyst for CO2 reforming (Gallego et al., 2006)
rhombohedral symmetry tetragonal
structure
LaNiO3 and Self-combustion Clearly perovskite phase, low surface Catalyst precursors (Gallego et al., 2013)
LaFeO3 method. area and difficult to reduce
LaNiO3 Pechini method Monophase material with highly- - (Fernandes et al., 2002)
crystalline particles
La1-xCexFe0.7Ni0.3O3 Pechini method Large surface area and small crystallite Catalysts for steam reforming of (Choi & Moon, 2009)
size, higher hydrogen yield as well as methane
slower deactivation rates than those
2
exhibited by a commercial catalyst
LaBO3 (B= Co, Ni, Mn) Co-precipitation Hexagonal, rhombohedral or Application in CO and propane (Silva & Soares, 2009)
tetragonal distortions LaMnO3 combustion
presents a cationic vacancies and
generation for known oxygen
excess
La1-xCexNiO3 Co-precipitation High activity and stability, unchanged Catalyst for the steam reforming of (Cui et al., 2009)
method. catalyst surface area (BET) during glycerol (1,2,3-propantriol)
operation and low carbon deposition
after reaction
Cr-doped SrTiO3 One-pot solvothermal about 100 nm in size and 20 nm in Removal of Cr (VI) in water by (Yang et al., 2019)
method thickness possessing a mesopore visible-light photocatalytic
3.0 nm in size reduction
Fluorinated Bi2MoO6 Solvothermal- Induced lattice shrinkage, decrease in Photocatalytic (Yu et al., 2017)
calcination process crystal size and an increase in removal of water organic
crystallinity pollutants
LaMO3 (M = Mn, Fe) Nanocasting technique High surface area mesoporous TOC removal and catalytic (Afzal et al., 2017)
nanocast ozonation of 2-chlorophenol
La1-yCeyCo1-xFexO3 Reactive grinding Rhombohedral and orthorhombic Catalysts for the oxidation of (Levasseur & Kaliaguine,
crystal structures volatile organic compounds 2009)
Fluorinated Bi2MoO6 Solvothermal- Induced lattice shrinkage, decrease in Photocatalytic (Yu et al., 2017)
calcination process crystal size and an increase in removal of water organic
crystallinity pollutants
LaFeO3 Microwave-assisted High crystallinity, narrow band gap Photocatalytic activity against (Jamali et al., 2017)
synthesis energy and mesoporous structure organic reactants in gaseous and
aqueous phases
NiTiO3 Rapid one-step Rhombohedral crystal structure with Cool colorants for building (Moghtada et al., 2017)
sonochemical method uniform crystal size and agglomerated
nature
NiTiO3 Wet chemical method Crystallized in a hexagonal symmetry O2 evolution under visible light (Boudjellal et al., 2018)
with octahedral coordination
3
Bi4Ti3O12 - Ferroelectric with high curie High-temperature actuators, (Alexe et al., 1998)
temperature gigabit memory applications
BaTiO3 - Piezoelectricity, Ferroelectricity, high Embedded capacitance and (Cho et al., 2004)
dielectric constant multilayer ceramic capacitors
BiFeO3 - Small optical gap, high curie Magnetic field detectors, (Choi et al., 2009)
temperature memories, switchable ferroelectric
diode and photovoltaic
applications
LaAlO3 - Host materials for rare-earth Laser, in vivo imaging (Katayama et al., 2014)
luminescent ions,
Cesium Lead Halide - Optoelectronic, highly luminescent Photovoltaic and light-emitting (Bekenstein et al., 2015)
diodes
Hybrid halide perovskite - Optoelectronic, ionic transport Solar cell devices, light-emitting (Zhao & Zhu, 2016)
diodes, photodetectors, transistors
4
Table 2. Compilation of various perovskite materials utilized as adsorbents in wastewater treatment at various adsorption conditions
Adsorbents Adsorbates Adsorption variables Highlights References

pH Temperature Initial Contact
(K) adsorbate time
concentration (mins)
(mg L-1)
Rh B 2-12 293-323 10-400 - • The adsorption performance of LFO- (Deng et al., 2019)
Fibrous LaFeO3 ACF for RhB was nearly not affected
by solution pH
(LFO-ACF) • Zeta potential indicated that the whole
electric potentials of LFO-ACF were
negative in the pH range of 2.0–12.0
enhancing the electrostatic attraction
between RhB molecules and the
adsorbent
• Maximum adsorption capacity fitted by
the Langmuir isothermal model was
182.6 mg g-1 at 293 K
• The adsorption kinetics followed
pseudo-second-order model
• The valence state of La(Ⅲ) and Fe(Ⅲ)
in LFO-ACF and the existence of a
large quantity of adsorbed hydroxyl
groups suggested the adsorption
mechanism to involve interactions
between RhB and LFO-ACF by
electrostatic interaction, hydrogen
bonding, π-π stacking and cation-π
interaction
5
• Regeneration of LFO-ACF was well
realized through an easy pyrolysis
method.
LaFe0.9Co0.1O3 (LFCO1) Vitavax - 288-318 200 30-40 • The LCFOs can remove vitavax (Tavakkoli &
and adsorbent from aqueous solution with a Yazdanbakhsh, 2013)
very high adsorption capacity
LaFe0.1Co0.9O3 (LFCO2)
• The adsorption process follows first-
order kinetics and the Langmuir
adsorption isotherm model
• In addition, it was found that the
percentage removal of vitavax by
LFCO2 is less than that for LFCO1 at
the same conditions
• The thermodynamic study suggested
feasible and spontaneous the
adsorption of vitavax onto the LFCOs
LaNiO3 and LaMnO3 CR - - 50 10-120 • The perovskites containing Mn2+ (Santos et al., 2018)
calcined at 900 oC exhibited higher CR
adsorption eⅢciency (63 %) than Ni2+
ones (34).
• Kinetic adsorption data obeyed pseudo-
second order model.
• The perovskite samples were
recovered after calcinations at 900 °C
during 2 were the dye was degraded but
the perovskite structure preserved.
NdFeO3 As (V) 2-10 286-323 5-10 5-200 • Arsenate adsorption by NdFeO3 (Luu et al., 2016)
showed high adsorption capacity at pH
levels between 4 and 7
• Maximum As(V) adsorption capacity
was 126.58 mg g-1, higher than most
6
arsenate adsorbents reported in the
literature
• Kinetic and equilibrium data of
reaction under the experimental
conditions are best described by a
pseudo second-
order and Langmuir isotherm
respectively
• The thermodynamic studies suggested
endothermic and spontaneous
adsorption process which took place
with increasing entropy
La0.5Ca0.5NiO3−δ RB5 1-13 - 50-250 1-36 • The RB5 removal efficiency decreased (Yazdanbakhsh et al., 2011)
with increasing solution pH
(LCNO)
• LCNO exhibited good dye removal
efficiency at acidic pH (pH = 2)
• Adsorption kinetic and equilibrium data
followed pseudo-second-order and
Langmuir models
• Maximum adsorption capacity (‫ݍ‬௠௔௫ )
is 36.23 mg g-1
• In general, experimental results of the
photocatalytic activity also revealed
that dye removal can be achieved by
the adsorption process and LCNO
perovskite nanocatalyst indicated
favorable adsorption behavior in a dark
condition for the removal of RB5 dye
Bi2WO6 Rh B 1-12 298 20-70 5-50 • Bi2WO6 microcrystal exhibited higher (Wang et al., 2016)
MB adsorptivity for MB than that of RhB
CR and CR
AR and
7
Phenol • The kinetics and equilibrium adsorption
obey pseudo-second-order and
Langmuir models
• Maximum adsorption capacity (‫ݍ‬௠௔௫ )
for MB is 60.28 mg g-1, higher than that
of RhB, CR, AR and phenol
• The preferential adsorption ability for
MB was attributed to pore size, large
surface-to-volume ratio and the charge
of exposed face
Fe3-xLaxO4 CR - 286 30-100 0-90 • The adsorption capacity of Fe3-xLaxO4 (Wang et al., 2011)
for CR shows an improvement not by
increasing the specific area but by
deforming the crystal structure via
doped- La3+ ions
• Upon comparison with many other
adsorbents, Fe3-xLaxO4 showed high
adsorption capacity for CR
• Analysis of adsorption isotherm shows
that the adsorption experiment accord
with Langmuir model
• Again, adsorption kinetic model
indicates that the adsorption
mechanism
depends on the adsorbate and adsorbent
• In a word, the Fe3-xLaxO4 was excellent
adsorbent because of high adsorption,
desorption and recovery efficiency
• Doping La3+ ions was a good method
of enhancing the CR adsorption
efficiency in a wastewater treatment
8
process
Ni0.5Zn0.5Fe2O4 CR - 298 100-500 10-160 • The adsorption kinetics and adsorption (Liu et al., 2015)
isotherm of CR onto Ni0.5Zn0.5Fe2O4
calcined at 400 °C for 2 h with a
heating rate of 3 °C min-1 and absolute
alcohol of 15 mL were investigated at
room temperature
• The kinetic data related to the
adsorption of CR from aqueous
solutions was in good agreement with
the pseudo-second-order kinetic model
• Temkin isotherm model was the best to
describe the equilibrium adsorption
data at room temperature
• According to the theory of the Temkin
model, the surface of Ni0.5Zn0.5Fe2O4
is heterogeneous, and the binding
strength decreased with CR
occupation on the surface sites
• Adsorption mechanism revealed an
interaction of Ni0.5Zn0.5Fe2O4 with CR
adsorbate of CR, and the adsorption
may be a hybrid of monolayer and
multilayer adsorbing mechanisms
LaCoO3@SiO2/PW12 MB 2-10 298-328 15-45 0.5-240 • This novel LaCoO3@SiO2/PW12 hybrid (Mahmoudi et al., 2019)
nanomaterial displayed enhanced
adsorption ability for MB cationic dye
when compared with bare LaCoO3
perovskite with the reason attributed to
enhanced electrostatic attraction
interactions
9
• The maximum adsorption capacity
increases partially as: 21.14, 31.25,
33.22 and 34.48 mg g-1 at 25, 35,
45 and 55 oC respectively ascribed to
the fast diffuse rate of MB at higher
temperatures
• The experimental results demonstrated
an endothermic MB adsorption process
onto LaCoO3@SiO2/PW12
• Good reusability of the hybrid
nanomaterial was found without any
decrease of adsorption after three
cycles clearly showing it to be a
promising green adsorbent for
removing organic pollutants in water
CoFe2O4 CR - 293 50-120 0-180 • The adsorption capability of the as- (Ding et al., 2015)
synthesized CoFe2O4 for CR was
shown to enhance the adsorption
capability for CR with adding ethanol
as the mixing solution
• The maximum adsorption capacity for
CR was 190.5 mg g-1with the process
obeying pseudo-second-order model.
• The adsorption mechanism revealed
that the composition of ethanol/water
mixed solution has great effects on the
microstructure and magnetic properties
as well as adsorption capacity of CR
dye by the as-synthesized CoFe2O4
samples
CuFe2O4 and CuFe2O4 As (III) 3-9 283-313 0-20 0-40 • The adsorption capacity for As on (Wei et al., 2019)
with peroxymonosulfate CuFe2O4/PMS reached up to 63.9
10
(CuFe2O4/PMS) mg/g, which is much higher than that
of As(III) (36.9 mg g-1 or As(V) (45.4
mg g-1) on CuFe2O4 alone
• The process can work effectively over
a wide range of pH values and
temperatures
• Coexisting ions such as sulfate,
carbonate, silicate and humic acid
have an insignificant effect on As(III)
removal
• This process can achieve fast removal
of As(III) from water to meet the
drinking water standard (Co(As(III)) =
1415 µg L-1; CuFe2O4 = 0.2 g L-1;
PMS = 100 µM, t = 15 min)
• Additionally, the CuFe2O4/PMS
system can work effectively in a
broad range of geochemical
conditions.
• Furthermore, CuFe2O4 can be easily
separated for regeneration and reuse.
• In summary, the established process
is highly feasible for the remediation
of As(III)-contaminated water under
ambient conditions.
MFe2O4 CR - 291 50-150 0-180 • The cations distribution of MFe2O4 was (Wang et al., 2012a)
(M = Mn, Fe, Co, Ni) revealed as the most crucial factor in
deciding their adsorption capacity
• All the nanocrystals possess good soft-
magnetism, especially, CoFe2O4
showed higher saturation
11
magnetization of 86.1 emu g-1 as well
as the outstanding adsorption capacity
for CR
• The maximum adsorption capacity of
CoFe2O4 for CR was 244.5 mg g-1
• Acetone was proved to be an effective
desorption agent for the desorption of
MFe2O4 nanoparticles loaded by CR.
• Electrostatic absorption was conceived
as the main adsorption mechanism
• MFe2O4 nanoparticles exhibited a
clearly ferromagnetic behaviour under
applied magnetic field, which allowed
their high-efficient magnetic separation
from wastewater.
La0.1Sr0.9Co0.9Fe0.1O3−δ O2/N2 - - - - • The sorbent material has a large (Xu et al., 2018)
oxygen adsorption capacity, a
relatively high adsorption and
desorption rate and an infinitely large
oxygen selectivity over nitrogen or
other non-oxygen species due its
unique oxygen storage property
• Under optimum conditions, oxygen
purity of 98.21 %, recovery of 74.05 %
and productivity of 1.22 mmols-1kg-1
were achieved which were higher than
the reported values form previous
studies
• The LSCF1991 pellets have good
mechanical properties
XFe2O4-BiFeO3 (X = Cr, Toxic Trace 6 303 1.0 • Magnetite-perovskite was (Nie et al., 2018)
Mn, Fe, Co or Ni) Metals
12
biosynthesized by via microbial
Fe3+→Fe2+ reduction using Shewanella
(Shewanella oneidensis MR-1 and
Shewanella putrefaciens CN32)
• The average adsorption intensities of
nine toxic trace metals (Cr3+, Mn2+,
Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Pb2+, and
Hg2+) in Freundlich mode were 8.29–
10.79 multiples higher than that in
Langmuir mode
• The fluorescence quenching is
attributed to the orbital hybridization of
molecular oxygen activation and trace
metal (M) ions, which weakens the
X2+-O-Fe3+-O-(Fe3+) coupling orbital
• In addition Shewanella putrefaciens
CN32 created more oxygen vacancies
to modify Ni↓-Fe↓-O↑ d*-p hybridized
orbitals for enhancing the local spin-
orbit coupling with Cd-4d10
• This design idea can be extended to
other direct biosynthetic magnetite-
perovskite as highly efficient toxic
trace metal removal agents
13
Table 3 A comparisons of adsorption capacities at various conditions between the perovskites and other competitive materials
Adsorbent Adsorbates Adsorption variables Adsorption capacity References

-1
(mg g )
pH Temperature Initial Contact time
(K) adsorbate (Mins)
concentration
(mg L-1)
Bi2WO6 MB 1-12 298 20-70 5-50 60.28 (Wang et al., 2016)
LaCoO3@SiO2/PW12 MB 2-10 298-328 15-45 0.5-240 31.25 (Mahmoudi et al., 2019)
MFe2O4 (M = Mn, Fe, Co, Ni) CR - 291 50-150 0-180 244.5 (Wang et al., 2012a)
CoFe2O4 CR - 293 50-120 0-180 190.5 (Ding et al., 2015)
LFO-ACF RhB 2-12 293-323 10-400 - 182.6 (Deng et al., 2019)
La0.5Ca0.5NiO3−δ RB5 1-13 - 50-250 1-36 36.23 (Yazdanbakhsh et al., 2011)
CuFe2O4/PMS As(III) 3-9 283-313 0-20 0-40 63.9 (Wei et al., 2019)
NdFeO3 As(V) 2-10 286-323 5-10 5-200 126.58 (Luu et al., 2016)
Immobilized MCC MB 4-12 300 5-100 0-150 12.85 (Tan et al., 2018)
Commercial MCC MB 2-10 298-318 1-15 0-18 4.95 (Tan et al., 2016)
Carbon nanotube MB 6 298 10-50 0-140 59.7 (Wang et al., 2012b)
Ilmenite FeTiO3 MB - - 0.5-8 0-150 71.9 (Chen, 2011)
Immobilized Scenedesmus RB21 2 303 25–200 30-300 45.70 (Ergene et al., 2009)
quadricauda
14
MCC crosslinked with Cd (II) 2-6 293-323 10-85 0-40 14.89 (Cao et al., 2017)
tetrafluoroterephthalonitrile
Modified plantain peels Cd (II) 4.36 303 120 180 70.92 (Garba et al., 2016b)
Bacillus laterosporus Cd (II) 3-9 293-313 10-50 0-180 85.47 (Kulkarni et al., 2014)
(MTCC1628)
MCC crosslinked with Cu (II) 2-6 293-323 10-85 0-40 17.94 (Cao et al., 2017)
tetrafluoroterephthalonitrile
Defatted papaya seed Cu (II) - 303 150 120 17.29 (Garba et al., 2016a)
Polyflavonoid tannins Cu (II) 2-8 - 5-200 180 8.78 (Oo et al., 2009)
Amidoximated poly-(AN + Cu (II) 5.5 298 - - 76.82 (Singha & Guleria, 2014)
MAA)-g-cellulosic okra fibers
Cellulose-g-acrylic acid Cu (II) 5.0 303 - - 170 (Hajeeth et al., 2013)
copolymer
Defatted papaya seed Pb (II) - 303 150 120 53.02 (Garba et al., 2016a)
15
16
Fig. 1.
1
Fig. 2.
2
Fig. 3.
3
HIGHLIGHTS
• There is an increasing interest in research on perovskites as adsorbents.
• Various methods of perovskites preparation and characterizations were discussed.
• Potentials of perovskites as adsorbents for wastewater treatment are presented and
discussed.
• Conclusions have been drawn from the literature reviewed and future perspectives
were proposed
1
AUTHOR DECLARATION TEMPLATE
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We confirm that we have given due consideration to the protection of intellectual property associated with
this work and that there are no impediments to publication, including the timing of publication, with
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We understand that the Corresponding Author is the sole contact for the Editorial process (including
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Signed by all authors as follows:
1. Zaharaddeen N. Garba
2. Weiming Zhou
3. Mingxi Zhang
4. Zhanhui Yuan

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A review on the preparation, characterization and potential application of perovskites

Zaharaddeen N. Garba, Weiming Zhou, Mingxi Zhang, Zhanhui Yuan

To appear in: ECSN

Received Date: 30 April 2019

© 2019 Published by Elsevier Ltd.

Zaharaddeen N. Garba: Original draft; Writing – review & editing

Weiming Zhou: Figures drawing

Mingxi Zhang: Supervision

Zhanhui Yuan: Funding acquisition; Supervision and editing

A review on the preparation, characterization and potential application of perovskites

as adsorbents for wastewater treatment

Zaharaddeen N. Garbaa,b, Weiming Zhoua, Mingxi Zhanga, Zhanhui Yuana*

* Corresponding author. Tel.: +8613950268166

E-mail addresses: zhanhuiyuan@fafu.edu.cn (Zhanhui Yuan),

dinigetso2000@gmail.com (Zaharaddeen N. Garba)

2 perovskites as adsorbents for wastewater treatment

3 Zaharaddeen N. Garbaa,b, Weiming Zhoua, Mingxi Zhanga, Zhanhui Yuana*

21 * Corresponding author. Tel.: +8613950268166

22 E-mail addresses: zhanhuiyuan@fafu.edu.cn (Zhanhui Yuan),

23 dinigetso2000@gmail.com (Zaharaddeen N. Garba)

28 adsorptive, catalytic, optical, magnetic, electronic and ferroelectric properties. Over

30 various applications which include an environmental catalyst, fuel cells, chemical

31 sensors, magnetic materials, oxygen permeable membranes and adsorbents for

33 method, Pechini method, combustion, co-precipitation, and chelating precursor

35 the current knowledge on the processes involved in the preparation of perovskites,

36 their characterizations and potential applications in wastewater treatment. Challenges

37 and future opportunities of perovskite-based materials are discussed as well as

39 few suggestions for future research.

40 Keywords: Perovskite; Nanoparticles; Preparation; Characterization; Wastewater

45 ACF Active carbon fibers

47 CrI Crystallinity index

48 CWPO Catalytic wet peroxide oxidation

50 EDTA Ethylenediaminetetraacetic acid

51 EFM Environmental fate modeling

53 ESR Electron spin resonance

54 FTIR Fourier transform infrared

55 I200 Maximum intensity of the peak

56 Iam Intensity of diffraction of the non-crystalline material

57 L Size of the crystallite (nm),

60 Full width at half maximum of lattice plane reflection in radian

61 Corresponding Bragg angle (reflection angle)

62 DSC Differential scanning calorimetry

63 DB-53 Direct blue 53

64 DTA Differential thermal analysis

65 ABO3 Perovskite-type oxides

71 LFO-ACFs Perovskite oxide decorated active carbon fibers

73 XPS X-ray photoelectron spectroscopy

74 PSCs Perovskite solar cells

75 LCNO Lanthanum-calcium perovskite-type nanopowders

76 LCVD Laser-assisted chemical vapor deposition

77 LED Light-emitting diodes

80 PEG-200 Polyethylene glycol

81 PLA Perovskite lanthanum aluminate

82 PVA Polyvinyl alcohol

83 PVB Polyvinyl butyral

84 PW12 Keggin-type phosphotungstic acid

85 RB5 Reactive blue 5

87 SEM Scanning electron microscope

346 ( ) 6 + ( ) 9 + → + 6 +

347 3 + (1)