Review Solar Driver Matal Halide Perovskite For Photocatalysis

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Review
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Solar-Driven Metal Halide Perovskite

Photocatalysis: Design, Stability, and
Performance
Haowei Huang, Bapi Pradhan, Johan Hofkens, Maarten B. J. Roeffaers,* and Julian A. Steele*
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ABSTRACT: The development of green, sustainable, and economical chemical processes

represents a cornerstone challenge within chemistry today. Semiconductor heterogeneous
photocatalysis is currently utilized within a wide variety of societally impactful processes,
spanning reactions such as hydrogen production and CO2 conversion, to the organic
transformation of raw materials for value-added chemicals. Metal halide perovskites (MHPs)
have recently emerged as a new promising class of cheap and easy to make photocatalytic
semiconductors, though their unstable ionically bound crystal structure has thus far
restricted widespread application. In this Review, we examine the issues hampering MHP-
based photocatalysis and highlight the general approaches being taken to achieve promising
and stable photocatalytic reaction environments. Specifically, we outline the adoption of (1)
halogen acid solutions (i.e., HX; X = I or Br) for hydrogen evolution reactions, (2) relatively
low-polarity solvents for CO2 photoreduction and organic transformations, and (3) the
encapsulation of perovskites for CO2 reduction and water splitting. Further, we detail the
measures being taken to arrive at intrinsically stable photocatalytic materials, removing the
need for atypical environments. With each technology offering unique sets of benefits and challenges, we conclude by outlining
potentially promising opportunities and directions for metal halide perovskite-based photocatalysis research moving forward.
poor photoreduction potential,8 respectively. It follows that a
L ike the natural and efficient energy conversion exhibited

by photosynthesis, photocatalysis presents an effective
way for man-made solar-to-chemical energy conver-
sion.1,2 The first report of UV-driven photocatalytic hydrogen
production on TiO2 in 19723 has since motivated decades of
strong desire to develop new semiconductor photocatalysts with
suitable properties continues to motivate intense materials
exploration and research within the field.
Metal halide perovskite (MHP) semiconductors have
scientific exploration and development, leading to several recently emerged as promising optoelectronic materials for
applications important for human society; from energy applications spanning efficient solar cells and LEDs, to lasers and
conversion (e.g., water splitting, CO2 reduction) and chemical photodetector devices.21 MHPs are ionic crystals with the
transformations, to the remediation of organic pollutants. general chemical formula ABX3. Here A is a monovalent cation
Reactions driven by photocatalytic materials generally follow (MA: CH3NH3+, FA: CH(NH2)2+ and Cs+); B represents a
three separate processes: (i) absorption of photons to generate divalent metal cation (Pb2+, Sn2+, or Cu2+), and X is a halogen
electron and hole pairs, (ii) charge separation and migration to anion (Cl−, Br−, or I−).22 The successful application of MHPs
reaction sites on the photocatalyst surface, and (iii) chemical within optoelectronic devices is driven mainly by their low
oxidation and reduction at the surface mediated by the production costs and easy solution processing;22 tunable, direct
photogenerated holes and electrons, respectively.4 bandgap;23,24 long carrier diffusion lengths;25 high carrier
An ideal photocatalytic material should embody several mobility;26 and unusual tolerance to defects.27 Compared to
desirable physical traits, namely, broad and strong light
absorption, efficient charge separation, long operational Received: January 8, 2020
stability, and the appropriate redox ability for target reactions.5 Accepted: March 6, 2020
In reality, however, most photocatalysts are far from perfect. For Published: March 6, 2020
example, pristine TiO2, graphitic carbon nitride (g-C3N4), and
BiVO4 have their own shortcomings such as wide bandgap,6
rapid recombination of photogenerated charge carriers,7 and
© 2020 American Chemical Society https://dx.doi.org/10.1021/acsenergylett.0c00058

1107 ACS Energy Lett. 2020, 5, 1107−1123
ACS Energy Letters http://pubs.acs.org/journal/aelccp Review
Figure 1. Band edge positions of conventional photocatalysts and different MHPs relative to reversible hydrogen electrode (RHE).6−16 For
comparison, the redox potential of some common half-reactions are also presented.17−20
Figure 2. Top: Illustration of the vulnerability of MHP surfaces during photocatalytic reactions, when exposed to polar solvents (e.g., DMSO)
and water.31−33 Polar molecules undergo rapid intramolecular exchange with the organic cation, causing the immediate degradation of the
perovskite chemical structure. Water molecules degrade MHPs in a stepwise fashion, where initially a monohydrate perovskite structure is
formed which later decomposes into nonperovskite structures, through different intermediates. Reproduced with permission from ref 31.
Copyright 2015 The American Association for the Advancement of Science. Reproduced from refs 32 and 33. Copyright 2016 American
Chemical Society. Bottom: Three main routes toward creating stable reaction environments when employing MHPs as a photocatalyst:
saturated haloacid solutions stabilize MHPs by establishing a dynamic ionic equilibrium between the dissolved ionic species and the solid
perovskites; nonpolar or relatively low-polarity solvent dispersion reduces the degradation pathways; and encapsulation via capping agents or
shelling prevents direct contact with polar solvents or reaction products.
more traditional photocatalysts, MHPs exhibit relatively narrow achieve water oxidation, because of their relatively positive
bandgap energies as shown in Figure 1, enabling the absorption valence band maximum (VBM). For hydroxyl radical formation,
of lower-energy solar photons. which is often involved in dye degradation, the required
Based on the reaction thermodynamics, a suitable match is potential is above the VBM of MHPs, making them an
required between the electronic band structure of a semi- unsuitable candidate.
conductor and reaction redox potential. The potentials of typical Considering the (photo)physical properties exhibited by
photocatalytic half-reaction involved in water splitting, CO2 MHPs, they seemingly satisfy several of the important
reduction, aerobic organic transformation, and dye degradation requirements for good photocatalytic reactions as shown in
are shown in Figure 1.20 Here, the relative position of the MHP Figure 1. Indeed, the first report of MHP-based photocatalysis
conduction band (CB) and valence band (VB) are depicted appeared as recently as December 2016, where Nam and co-
alongside these redox potentials. Based on their comparison, workers28 outlined a strategy for photocatalytic-driven HI
Figure 1 highlights the excellent reduction ability of MHPs; that splitting using MAPbI3, exploiting the dynamic equilibrium of
is, the relative position of their CB is typically negative enough the dissolution and reprecipitation of MAPbI3 in saturated HI
for H2 generation, CO2 reduction, superoxide radical generation. aqueous solutions. This particular approach proved effective, as
Additionally, some members of the MHP family (namely the Cl- the ionic lattice of MHPs is highly unstable under more typical
based materials and all-inorganic CsPbBr3) can in theory also photocatalytic reaction conditions. For example, H2O splitting,
1108 https://dx.doi.org/10.1021/acsenergylett.0c00058
ACS Energy Lett. 2020, 5, 1107−1123
CO2 and N2 reduction, and dye degradation all require water or grain boundaries.33 This is a direct consequence of the surface
a polar solvent, which facilitate degradation pathways undergoing rapid hydration upon exposure to moisture, relative
detrimental for long-term use (Figure 2).29,30 Furthermore, for to the shielded interior. Furthermore, light absorption in MHPs
some radical-based reactions, like dye degradation, water or initiates a halide-to-metal charge-transfer process which reduces
polar solvents are prerequisite for the formation of the radical the charge density at the X sites, thereby weakening the
species that drive the reaction forward. Within this context, it is CH3NH3···X hydrogen bonding interactions and causing an
the relatively reactive and unstable nature of ionic MHP crystals increased rate of degradation upon illumination under a humid
which has thus far limited their application as a photocatalyst. In atmosphere.42
this Review, the current prospects of effectively applying MHPs As shown in Figure 2, when MHPs are exposed to polar
in photocatalysis are discussed. We provide a critical analysis of solvents like dimethyl sulfoxide (DMSO), the perovskite
the instability issues hampering progress in this new branch of structure also degrades to form coordination compounds, such
scientific research and highlight proven strategies allowing for as PbI2(DMSO)2, MAI-PbI2-DMSO via van der Waals
stable reaction environments. Finally, a brief perspective on the interactions.31,43,44 Rapid intramolecular exchange between
future challenges and possibilities of this promising new DMSO and FAI in FAPbI3 causes immediate decomposition
technology are described. of the perovskite structure. Solution-processed perovskite thin
Instability Constraints in MHP Photocatalysts. The structural films possess much more prominent defects when they are
and optoelectronic properties of MHPs change significantly fabricated from a polar coordinating solvent (e.g., DMF, DMSO,
upon phase transitions, thermal stress, ambient air exposure γ-butyrolactone), relative to the noncoordinating polar solvents
(oxygen and moisture), and illumination (UV light). The ionic (e.g., acetonitrile).45 This arises from the tendency of
interactions binding the charged components of MHP crystals coordinating solvents to get intercalated more easily during
render them vulnerable to structural modifications at its surface the perovskite film formation.
when coming into contact with polar additives. This particular The photostability of MHPs in the presence of ambient
feature within MHPs defines the limited scope of photocatalytic oxygen (O2) is also low. Reports have shown that iodide-based
reactions for which these semiconductors have been effectively
perovskites (i.e., MAPbI3) break down under simulated solar
applied. As shown in Figure 2, MHPs tend to decompose
irradiation (AM 1.5G) and O2 exposure.46,47 This process is
relatively quickly into a PbX2 (X = I, Br, Cl) precipitate, Cs+/
mediated by the rapid generation of iodide vacancies upon
MA+/FA+ cations, and halide anion when exposed to polar
photoexcitation, which offers a pathway for oxygen to be
molecules. The volatile nature of hygroscopic amine salts, the
MA+, FA+ cations contained in hybrid organic−inorganic introduced into the MHPs crystal lattice. Molecular oxygen
MHPs, leads to moisture instability.34−39 Also in Figure 2, reacts with photogenerated electrons at the iodide vacancy sites,
water interacts with the crystal via hydrogen bonding to hydrate producing reactive superoxide species which subsequently react
the surface, yielding a polycrystalline nonperovskite structural with MA cation, resulting in water, methane gas, and lead iodide
coating and grain boundaries.33 as the decomposition products.47,48
The quantitative and systematic investigation of the humidity- The lattice of MHP semiconductors is increasingly being
induced structural and chemical degradation mechanism of considered as soft in nature because of the occurrence of several
MAPbI3 has been performed by ultrafast transient absorption structural and chemical dynamic effects. Ultimately, the soft
spectroscopy and kinetics studies,35 in situ grazing incidence X- nature exhibited by MHP crystals renders their surfaces prone to
ray diffraction,36 and via ab initio molecular dynamics structural modification and degradation as discussed above. The
simulations.37 The absorbed water molecules easily penetrate replacement of A site organic cations with inorganic Cs+,
the MHPs structure and form intermediate monohydrate and resulting in the formation of all-inorganic chemical structure,
dihydrate structures by reacting with the [PbX6]4− octahedral substantially increases resistance to humidity and photo-
units.32 This is followed by rapid material breakdown through stability.49,50 The ionization energy of Cs compared to MA
hydrolyzation (eqs 1−4):30,35−39 can explain the higher chemical stability of the all-inorganic
perovskites.51 For example, CsPbBr3 nanocrystals are found to
CH3NH3PbI3 + H 2O → CH3NH3PbI3· H 2O (1) be substantially more stable in polar solvents, e.g., isopropyl
4CH3NH3PbI3 + 2H 2O → (CH3NH3)4 PbI6 · 2H 2O + 3PbI 2 alcohol, ethyl acetate, methyl acetate, acetonitrile, which is
encouraging for a vast number of photoredox catalysis
(2)
reactions.52
CH3NH3PbI3·H 2O → PbI 2 + CH3NH3I + H 2O (3) The instability issues outlined above have motivated the
development of several approaches aimed toward realizing
CH3NH3I → CH3NH 2 + HI (4) stable photocatalytic environments, which are summarized at
The hydrogen bond between the organic and inorganic units is the bottom of Figure 2: (i) placing MHPs in saturated halo acid
one of the key features in stabilizing the perovskite structure and solutions for solar-driven water splitting,28,53−61 (ii) minimizing
is compromised through this process; water forms two new types direct contact with highly polar environments via targeted low-
of hydrogen bonds, a strong one with the lattice halides and polarity solvents and solutions,62−80 and (iii) encapsulating
another one weakly with the organic cations.30,40,41 Notably, the MHP nanocrystals to screen them from polar molecules.81−95
interaction between MA and H2O is not established until the Efforts are also being made toward realizing MHPs which are
monohydrate phase transition, where the two become locked.32 intrinsically stabilized against exposure to polar solvents.
In polycrystalline thin films, the monohydrate phase formation Currently, some all-inorganic MHPs have proven to be stable
occurs independently of the film thickness because of the rapid in polar solvents.96−102 In what follows we outline the current
transport of water molecules across grain boundaries.32 Even in state of play for each of these approaches, highlighting their
bulk MAPbI3 single crystals, aging under ambient conditions successes and pitfalls and the features which ultimately govern
shows prominent surface restructuring with the formation of their realistic potential.
ACS Energy Lett. 2020, 5, 1107−1123
Figure 3. (A) MAPbI3 in aqueous HI solutions at different concentrations, (B) scheme representing the equilibrium between MAPbI3
dissolution and recrystallization in a saturated HI solution, (C) band diagram of the MAPbI3 powder for the HI splitting photocatalytic reaction,
and (D) stable photocatalytic H2 evolution in the saturated solution for 160 h.28 Reproduced with permission from ref 28. Copyright 2017
Springer Nature. (E) Reaction mechanism for MAPbBr3 with Pt/Ta2O5 and PEDOT:PSS as the electron- and hole-transporting motifs,
respectively, for photocatalytic HBr splitting reaction, and the corresponding energy level diagrams of MAPbBr3, Ta2O5, and PEDOT:PSS.56
Reproduced from ref 56. Copyright 2019 American Chemical Society. (F) Scheme of charge transfer in photoelectrochemical HI splitting cell of
MAPbI3/TNA(TiO2 nanorod array)/c-TiO2/FTO (F doped SnO2) photoelectrode as the band alignment, and (G) the H2 evolution on this cell
for 5 h.58 Reproduced with permission from ref 58. Copyright 2019 Elsevier.
Saturated Haloacid Solutions. Because MHPs are water-soluble MAPbI3. The Pt/TiO2-MAPbI3 photocatalyst powders, based
ionic compounds, utilizing the precipitation−solubility equili- on micrometer-sized MAPbI3 displayed a nearly 90-fold
brium between the perovskite phase and the soluble ionic enhancement for H2 generation (ca. 7.3 mmol/g/h,) from
species is a creative approach to solve the stability problem. Nam aqueous HI solution compared to the parent Pt/MAPbI3 (ca.
et al.28 first introduced the photocatalytic H2 production in 830 μmol/g/h) system. The introduction of TiO2 not only
methylammonium lead iodide (MAPbI3) saturated hydrogen improved the extraction of electrons from MAPbI3 via suitable
iodide (HI) acid aqueous solution using MAPbI3 perovskite band alignment but also acted to stabilize the Pt cocatalyst. The
polycrystalline powders. As shown in Figure 3A,B, in a saturated approach of Huang et al.53 was similar, in that they modified
HI solution, micrometer-sized MAPbI3 particles dissolve to MAPbI3 bulk microcrystals with reduced graphene oxide (rGO)
form methylammonium cations and PbIx complex anions, with to efficiently extract electrons from the MAPbI3 light absorber,
an equal amount of MAPbI3 particles recrystallizing in parallel. as well as provide H2 release sites. The combined MAPbI3/rGO
The MAPbI3 phase would be largely modulated by the I− and H+ system exhibited an H2 evolution rate of 939 μmol/g/h, which is
ion concentrations in the aqueous solution. In a relatively high 67 times greater than that of pure MAPbI3. After 200 h of
ion concentration regime (>3.16 mol/L HI solution), together irradiation, the composite material remained stable and did not
with a lower iodide concentration (i.e., [I−] ≤ [H+], whereby display decreased photocatalytic activity.53 Zhao et al. also used
HClO4 is added), the MAPbI3 perovskite phase remained stable. rGO to extract the photogenerated electrons, this time from a
Figure 3C presents the reaction mechanism for photocatalytic lead-free “double perovskite” (A 2I BI BIII X 6 architecture)
HI splitting on MAPbI3. Upon irradiating with visible light (λ ≥ Cs2AgBiBr6 bulk photocatalyst. In saturated HBr and H3PO2
475 nm), these mixtures produced roughly 26 μmol of H2 in 9 h solution, a 48.9 μmol/g/h H2 release rate was achieved on
using MAPbI3 as a photocatalyst, with the photogenerated holes Cs2AgBiBr6/rGO composite with visible light irradiation, which
driving the I− to I3− oxidation. In addition, as a good reducing is 80 times greaterer than that of pure Cs2AgBiBr6.61 Chen et al.
agent of I3− to I−, H3PO2 was added to maintain the I− similarly modified MAPbI3 bulk microcrystals for photocatalytic
concentration. Because of the dynamic equilibrium between applications, though with black phosphorus (BP).59 The BP/
the MAPbI3 powders and the ionic species in the saturated MAPbI3 system offered an impressive H2 evolution rate of 3472
solution, MAPbI3 remained stable for 160 h under continuous μmol/h/g in HI solution. Widening the fundamental bandgap
irradiation, without any compromise to the activity as shown in with bromine atoms at the halide sites, Li et al. demonstrated
Figure 3D. Furthermore, the deposition of Pt on the MAPbI3 that MAPbBr3 bulk microcrystals can be used for steady
(i.e., Pt/MAPbI3) increased the hydrogen evolution rate to 57 photocatalytic H2 production in saturated MAPbBr3 aqueous
μmol/g/h, resulting in a solar-to-chemical conversion efficiency HBr solution upon visible light irradiation.56 Their perovskite
(the ratio of solar light converted to chemical energy) of 0.81%. semiconductors were further modified with PEDOT:PSS
In the Pt/MAPbI3 sample, as the MAPbI3 particles dissolve and (poly(3,4-ethylenedioxythiophene) polystyrenesulfonate) and
reprecipitate, the change in contact between MAPbI3 and Pt is Ta2O5 as cocatalysts, preparing PEDOT:PSS/MAPbBr3/Ta2O5.
unclear. As described in Figure 3E, because of band alignment of
In a similar fashion, Li et al.57 improved the photocatalytic PEDOT:PSS and Ta2O5 with MAPbBr3, these additives acted as
activity of Pt/MAPbI3 by inserting TiO2 between Pt and hole and electron transporting layers, respectively, for efficient
ACS Energy Lett. 2020, 5, 1107−1123
photogenerated charge separation. Notably, in comparison to X3− takes priority over H2O oxidation. Thus, additional reducing
the pure MAPbBr3, ca. 52 times enhancement of the hydrogen agents such as H3PO2 need to be consumed to reduce X3− back
evolution rate was achieved with the hybrid material, and an to X−, however, this ultimately limits the added value of this
apparent quantum efficiency (AQE = Nelectron/Nphoton) of ca. reaction.103 Furthermore, the strong acidity of HX will prevent
16.4% was reported for 420 nm excitation. However, the the selection of certain cocatalysts which are unstable in such
photocatalytic activity of this hybrid material decreased environments.
gradually within a 4 h time experiment. The instability of this
system comes from the agglomeration of PEDOT:PSS in the Under such environmental conditions,
reaction solution, thus affecting the interfacial charge transfer
between MAPbBr3 and PEDOT:PSS. Finding a more suitable the relatively weak dipole moment of
hole transport material to replace PEDOT:PSS could give rise to the solvent does not readily coordinate
the high efficiency and stable photocatalytic production of H2. with the MHP crystal to dissociate them
Huang et al. introduced iodine into hybrid MAPbBr3 and all- into complexes of the composing ionic
inorganic CsPbBr3 bulk microcrystals (i.e., MAPbBr3−xIx54 and
CsPbBr3−xIx55) to form bandgap funnel structures via the graded species.
distribution of I atoms. In saturated HBr/HI mixed acid
solution, both the MAPbBr3−xIx/Pt and CsPbBr3−xIx/Pt photo-
catalysts exhibited decent H2 evolution under visible light Low-Polarity Solvents for CO2 Reduction. The ionic nature of
irradiation, reaching 2604.8 μmol/g/h and 1120 μmol/g/h, MHPs makes them especially sensitive to degradation by polar
respectively. Furthermore, both samples displayed a high molecules; hence, low-polarity solvents can be employed to
stability during the 50 h of testing. A similar strategy was create stable photocatalytic reaction conditions. Under such
followed for lead-free perovskite MA3Bi2I9 with a lamellar environmental conditions, the relatively weak dipole moment of
structure, as the system reaches a precipitation−solubility the solvent does not readily coordinate with the MHP crystal, to
equilibrium in saturated HI solution.60 The photocatalytic rate dissociate them into complexes of the composing ionic species.
for H2 evolution on Pt/MA3Bi2I9, with Pt as cocatalyst, is nearly This strategy was utilized by both Kuang et al.62 and Sun et al.,71
170 μmol/g/h in saturated HI solution. After 70 h of cycling, no employing all-inorganic CsPbBr3 quantum dots (QDs) for
decrease in H2 evolution rate was observed for this catalyst. photocatalytic CO2 reduction; note that due in contrast to the
The band engineering strategy for MHPs stabilized within a micrometer-sized crystals utilized in haloacids this approach also
halogen acid solution was further developed by Liu et al., with works for MHP nanocrystals and QDs. In Sun’s paper, the low-
the photocatalyst being deployed in a solar-driven photo- polarity solvent used was ethyl acetate mixed with trace amounts
electrochemical (PEC) cell for H2 evolution in Figure 3F.58 The of water as hole scavengers (volume ratio: 300:1) (see Figure
cell consisted of a MAPbI3−TiO2 nanorod array (TNA) as the 4A).71 Within 8 h of simulated solar light irradiation, 34, 12, and
photoanode, achieving efficient and stable H2 evolution in HI 0.8 μmol/g of CO, CH4, and H2, respectively, were generated;
solution (57 wt % HI aqueous solution saturated with MAPbI3 note that water acts as hole scavenger thus generating oxygen,
powder). The amount of evolved H2 on different PEC cells at but also water splitting into hydrogen is competing with the CO2
0.14 V vs Ag/AgCl is shown in Figure 3G, in comparison to reduction reaction. The reaction processes can be summarized
MAPbI3/c-TiO2/FTO and MAPbI3/TNA/FTO, the MAPbI3/ as eqs 5−8:
TNA/c-TiO2/FTO PEC cell exhibits the highest hydrogen 2H 2O → O2 + 4H− + 4e− (5)
evolution rate of 33.3 μmol/cm2/h under solar illumination, and
+ −
this during 5 h of experiment. 2H + 2e → H 2 (6)
CO2 + 2e− + 2H+ → CO + H 2O (7)

Because of the precipitation−solubility
equilibrium, MHPs remain stable in the CO2 + 8e− + 8H+ → CH4 + 2H 2O (8)
saturated HX acid solution, and addi- The CsPbBr3 QDs displayed a good structural stability under
tionally it can circumvent PbX2 precip- these conditions and maintained the surface morphology and
itation and suppresses the formation of crystalline structure during the reaction.71 In Kuang’s work, with
the hydrated MHP phase. 12 h of constant illumination, 49.5, 22.9, and 1.07 μmol/g of
CO, CH4, and H2 are produced on the CsPbBr3 QDs.59 To
further boost the performance, as depicted in Figure 4B, the
As summarized in Table 1, these promising examples CsPbBr3 QDs were modified by the addition of graphene oxide
demonstrate that saturated aqueous halogen acid solutions (GO) which is capable of efficient electron extraction and
offer a suitable reaction medium for MHP-based photocatalytic transport.62 The generated CsPbBr3/GO composite had a ca.
hydrogen evolution. Because of the precipitation−solubility 25% enhanced electron consumption rated (357.4 μmol/g) in
equilibrium, MHPs remain stable in the saturated HX acid comparison to pristine CsPbBr3 material (284.7 μmol/g) as is
solution, and additionally it can circumvent PbX2 precipitation shown in Figure 4C. In this latter example, pure ethyl acetate
and suppresses the formation of the hydrated MHP phase. without addition of water was used as the reaction medium. The
Analogous to the approach taken within the field of photovoltaic nature of the hole scavenger in this system is unclear.
solar cells, introducing heterogeneous interfaces (or even This concept was expanded in the work of Xu et al., where
compositional grading within the MHP) can tune the energetics CsPbBr3 QDs/graphitic carbon nitride (g-C3N4) composites
of the photocatalyst system for greatly improved charge were engineered for efficient CO2 photoreduction. It was found
separation and reaction activity. However, within the HX acid that the presence of g-C3N4 improves the electron extraction via
solution, X− acts as a sacrificial agent and the oxidation of X− to type-II bandgap alignment and the chemical bond formed
ACS Energy Lett. 2020, 5, 1107−1123
Table 1. Summary of Reported Photocatalytic Hydrogen Generation Activity from Haloacid (HX) Solution Using MHP-Based
Systems
activity
photocatalyst solution light source (μmol/g/h) measured time for stability (h) ref
MAPbI3 HI solution visible light (λ ≥ 475 nm) 33 160 28
Pt/TiO2-MAPbI3 HI solution visible light (λ ≥ 420 nm), 200 mW/cm2 7300 12 57
MAPbI3/rGO HI solution visible light (λ ≥ 420 nm), 300 W 939 200 53
Cs2AgBiBr6 HBr solution visible light (λ ≥ 420 nm), 300 W 48.9 120 61
Black Phosphorus/MAPbI3 HI solution visible light (λ ≥ 420 nm), 300 mW/cm2 3472 200 59
PEDOT:PSS/MAPbBr3/Ta2O5 HBr solution visible light (λ ≥ 420 nm), 150 mW/cm2 650 4 56
MAPbBr3−xIx/Pt HBr/HI mix solution visible light (λ ≥ 420 nm), 300 W 2604.8 50 54
CsPbBr3−xIx/Pt HBr/HI mix solution visible light (λ ≥ 420 nm), 300 W 1120 50 55
MA3Bi2I9/Pt HI solution visible light (λ ≥ 400 nm), 300 W 170 70 60
Figure 4. (A) CsPbBr3 for the photocatalytic CO2 reduction in a 300/1 ethyl acetate/water mixture. Reproduced with permission from ref 71.
Copyright 2017 John Wiley and Sons. (B) Scheme of the CsPbBr3 with graphene oxide for photocatalysis CO2 reduction in ethyl acetate and (C)
the yield of products in this reaction system.62 Reproduced from ref 62. Copyright 2017 American Chemical Society. (D) Band alignment of the
composite photocatalyst CsPbBr3 QDs/g-C3N4 for photocatalysis CO2 reduction in acetonitrile and ethyl acetate and (E) the CO generation for
three consecutive runs of 2 h each in acetonitrile/water and ethyl acetate/water system on this composite.69 Reproduced with permission from
ref 69. Copyright 2018 John Wiley and Sons. (F) Time course of CO and CH4 evolutions via CO2 reduction by Cs2AgBiBr6 NCs in ethyl
acetate.72 Reproduced with permission from ref 72. Copyright 2018 John Wiley and Sons.
between MHPs and g-C3N4, as shown in Figure 4D. In this work, photogenerated charge separation in CsPbBr3 nanoparticles.
both acetonitrile and ethyl acetate solvents with trace amounts The MXene-MHP photocatalyst yielded CO and CH 4
of water (volume ratio: 300:1) were employed, yielding CO with production rates of 32.15 and 14.64 μmol/g/h, respectively, in
the formation rates of 148.9 and 70 μmol/g/h, respectively.69 pure ethyl acetate solution.73
Furthermore, Figure 4E presents that with 3 successive cycles of Partial bromide substitution by chloride in CsPbBr3 to form
catalysis (6 h in total), only 10.3% and 2.4% activity was lost in CsPbBr3−xClx QDs was used by Su et al. to generate MHPs with
the acetonitrile/water and ethyl acetate/water systems, improved stability for the CO2 reduction.70 However, the
respectively. The enhanced stability can be attributed to the increased Cl content reduces the visible light response. This
surface passivation of CsPbBr3 by g-C3N4, through the shows the need for finding a balance between stability and
interaction between the amino group on the edges of heptazine activity/photoresponse within a chosen MHP photocatalyst
in g-C3N4 and Br− in CsPbBr3 QDs. Building on this work, through well-informed materials engineering.
Zhang et al. coupled CsPbBr3 to g-C3N4 containing titanium- Moving away from Pb-based MHPs to lead-free perovskites,
oxide species, to prepare CsPbBr3/TiO-g-C3N4, which exhibits Kuang et al. showed CO2 reduction over Cs2AgBiBr6 NCs under
improved activity on CO2 reduction in an ethyl acetate/water solar illumination in pure ethyl acetate.72 The stable evolution of
system, in comparison to CsPbBr3/g-C3N4. Here titanium-oxide CO and CH4 on Cs2AgBiBr6 NCs under simulated solar light
species helped to speed up the charge separation and acted as irradiation is shown in Figure 4F. After 6 h of irradiation, 5.5 and
reaction sites to improve the surface reaction.75 In a similar 0.65 μmol/g of CO and CH4 are generated on Cs2AgBiBr6,
fashion, the good charge conductivity of two-dimensional respectively, with no H2 side product detected.
layered Ti3C2Tx (Tx: fluorine, oxygen, and hydroxyl groups) CO2 reduction in low-polarity solvents with or without trace
MXene material was exploited by Liu et al. to accelerate the amounts of water as electron donor expands the potential
ACS Energy Lett. 2020, 5, 1107−1123
Table 2. Summary of the Reported Photocatalytic CO2 Reduction Performance of MHPs under Various Illumination Conditions
products and activities measured time for
photocatalyst solution light source (μmol/g/h) stability (h) ref
CsPbBr3 QDs ethyl acetate/ 300 W Xe lamp, AM 1.5G filter CO(4.25), CH4(1.5), 8 71
water H2(0.1)
CsPbBr3QDs/GO ethyl acetate 300 W Xe lamp, AM 1.5G filter, 150 mW/cm2 CO(4.89), CH4(2.47), 12 62
H2 (0.13)
CsPbBr3QDs/g-C3N4 ethyl acetate/ 300 W Xe lamp 420 nm cutoff filter CO(70) 6 69
water
acetonitrile/water CO(148.9)
CsPbBr3/TiO-g-C3N4 ethyl acetate/ 300 W Xe lamp, 400 nm cutoff filter, CO(12.9) 10 75
water 100 mW/cm2
CsPbBr3/MXene ethyl acetate 300 W Xe lamp 420 nm cutoff filter CO(32.15), CH4 12 73
(14.64)
CsPbBr3−xClx QDs ethyl acetate 300 W Xe lamp, AM 1.5 filter, 200 mW/cm2 CO(85), CH4 (12) 8 70
Cs2AgBiBr6 ethyl acetate 300 W Xe lamp, AM 1.5G filter, 150 mW/cm2 CO(0.92), CH4 (0.11) 6 72
CsPbBr3@TiO2 ethyl acetate/ 300 W Xe lamp, AM 1.5G filter, 150 mW/cm2 CO(3.9), CH4 (6.72), 30 81
isopropanol H2 (1.46)
MAPbI3@Fe-MOF ethyl acetate/ 300 W Xe lamp, 400 nm cutoff filter, CO(4.16), CH4 (13) 80 83
water 100 mW/cm2
Co2%@CsPbBr3/Cs4PbBr6 water 300 W Xe lamp, 400 nm cutoff filter, CO(11.95) 20 92
100 mW/cm2
CsPbBr3@ZIF-67 water vapor 100 W Xe lamp, AM 1.5G filter, 150 mW/cm2 CO(0.77), CH4 (3.51) 18 84
CsPbBr3NC/ZnO nanowire/ water vapor A 150 W Xe lamp, AM 1.5G and 420 nm cutoff CO(0.85), CH4 (6.29) 16 96
macroporous graphene filter, 150 mW/cm2
Cs2SnI6/SnS2 water and 150 mW/cm2 visible light, 400 nm long pass CH4 (6.09) 9 97
methanol vapor filter
Cs3Bi2I9 water vapor UV lamp, 80.38 μW/cm2 CO(7.76), CH4 (1.49) 10 98
Figure 5. (A) Schematic of the FAPbBr3/TiO2 using for photocatalytic benzyl alcohol oxidation, and recycle test of photocatalytic oxidation of
benzyl alcohol over pure FAPbBr3 and 15%FAPbBr3/TiO2 hybrids.63 Reproduced from ref 63. Copyright 2018 American Chemical Society. (B)
Photocatalytic polymerization of TerEDOT by CsPbI3 QDs under visible light illumination.67 Reproduced from ref 67. Copyright 2017
American Chemical Society. (C) Photocatalytic α-alkylation of aldehydes by Cs/MAPbBr3 in organic solvents.66 Reproduced from ref 66.
Copyright 2019 American Chemical Society. (D) Crystal structures and photocatalytic activity of 2D (HDA)2MI4(M = Pb, Sn) for indoline-2-
carboxylic acid decarboxylation in 25 h.80 Reproduced with permission from ref 80. Copyright 2019 John Wiley and Sons.
application of MHP photocatalysts, as summarized in Table 2. In O2. Nonetheless, employing a largely apolar environment, even
most reports, MHPs still face a poor product selectivity as CO with the inclusion of trace amounts of targeted polar molecules,
and CH4 are typically generated simultaneously, and addition- is a promising route toward long-term activity and stability.
ally water splitting generating H2 is competing for the generated Low-Polarity Solvents for Organic Transformations. Next to the
photoelectrons while the holes are scavenged by water forming photoreduction of CO2 for the generation of solar fuels, recent
ACS Energy Lett. 2020, 5, 1107−1123
efforts have focused on organic transformations within low- enhance hydroxyl radical generation on its surface.76 After that,
polarity solvents for solar-driven MHPs photocatalysis. Sudan Red III reacts with these two kinds of radicals to generate
Roeffaers et al.63 reported the use of MHPs as photocatalysts nontoxic products. Upon visible light irradiation, 71% Sudan
for benzylic alcohols oxidation in a nonpolar toluene solution, as Red III was degraded by CsPb(Br1−xClx)3-Au within 6 h, which
shown in Figure 5A. In this study, pure FAPbBr3 microparticles is 3 times higher than the CsPb(Br1−xClx)3 case (ca. 20% of
and nanoparticles were proven to be efficient photocatalysts Sudan Red III degradation). Here, the role of Au NCs is in
under solar excitation; within 8 h of irradiation, FAPbBr3 contrast to the widely employed nonplasma Au-nanoparticle
microparticles exhibited a conversion rate of roughly 15% with decorated photocatalysts,104,105 where Au extracts electrons
near 100% selectively (0.1 mmol of benzyl alcohol in 2.5 mL of from the semiconductors and acts both as an electron reservoir
toluene, 10 mg of catalyst). More importantly, after 5 reaction and a reduction site.
cycles (40 h in total) the FAPbBr3 photocatalyst displayed no Beyond photocatalytic organic transformations in toluene,
decrease in activity. Again, the activity of the MHP photocatalyst other low-polarity solvents like dichloromethane (DCM),
can be improved by selecting a suitable cocatalyst and re- tetrahydrofuran (THF), dioxane, and hexane have been used
engineering the band structure of the system. For instance, for MHP-based photocatalytic organic transformations. Wu et
modifying FAPbBr3 into a FAPbBr3/TiO2 hybrid nanomaterial al.68 achieved S−H bond activation using CsPbX3 (where X =
by in situ antisolvent growth realized the highest conversion rate Cl, Br, and I) NCs in DCM. Interestingly, this work also realized
of benzyl alcohol when optimized (ca. 63% conversion, with 15 C−H activation by evaluating phosphorylation of N-aryl
wt % FAPbBr3 in FAPbBr3/TiO2 composite), being 4 times tetrahydroisoquinoline derivatives in both toluene and THF
greater than the pristine MHP case. However, after TiO2 was solvent. As seen in Figure 5C, Yan et al. demonstrated that
incorporated, the increased activity comes at the cost of MAPbBr3 and CsPbBr3 nanocrystals could selectively form C−
compromising the stability of the photocatalyst, which is mainly C bond in α-alkylation of aldehydes in DCM, THF, and dioxane,
attributable to a breakdown of FAPbBr3 following aldehyde and via photocatalysis.66 A large turnover number (TON) of over
water generation. Similar results were obtained by Tüysüz et al., 52 000 is achieved in the perovskite-based photocatalytic α-
where they have prepared CsPbBr3/TiO2 for benzylic alcohol alkylation of aldehydes, under visible light illumination. This
oxidation in toluene.79 large TON is encouraging for this particular application and can
Also other organic transformations have been explored on potentially provide a path toward the commercialization of
MHP photocatalysts. For instance, as shown in Figure 5B, perovskite photocatalysis in the future. Follow up work by Yan
Tüysüz et al. found that CsPbI3 QDs can promote the and co-workers showed that not only C−C bond formation but
polymerization of 2,2′,5′,2″-ter-3,4-ethylenedioxythiophene also a series of organic transformation, C−O and C−N bond-
(TerEDOT) to poly(3,4-ethylenedioxythiophene) (PEDOT) formation, can be achieved on the CsPbBr3 photocatalyst.65 In
in dry toluene under visible light illumination.67 In fact, the ethyl acetate, CsPbBr3 can achieve C−N bond formations via
generated PEDOT further stabilizes the cubic perovskite phase direct N-heterocyclizations forming pyrazoles and pyrroles,
of CsPbI3 QDs by encapsulating the perovskites and shielding it upon irradiating with blue light. With a Ni cocatalyst, C−O
from the environment. The direct functionalization of saturated bond formation via aryl-esterification was realized on CsPbBr3 in
C−H bonds to form high value-added chemicals is another THF, upon irradiating with blue light. In addition, CsPbBr3QDs
challenging topic in modern chemistry. Roeffaers et al. recently can drive the MBT (2-mercaptobenzothiazole) oxidation in
used FAPbBr3 bulk microcrystals to photoactivate the C(sp3)-H hexane by photocatalysis and photoelectrocatalysis.74 Recently,
bond in aromatic hydrocarbons and to form the corresponding Gualdrón-Reyes and co-workers prepared CsPbBr3/I3−x nano-
alcohols and aldehydes.64 Similar to tailoring the energetics particles via both hot injection (H-I-CsPbBr3/I3−x) and anion
within solar cells, the addition of an electron-transfer layer exchange (A-E-CsPbBr3/I3−x) methods, to investigate the
(TiO2) and hole-transfer layer (NiOx) allowed for optimizing influential role of the surface chemical states in the photo-
the conversion efficiency of the MHP photocatalyst, by oxidation of β-naphthol in hexane.77 The two different
improving charge separation properties. This TiO2/FAPbBr3/ preparation methods arrived at CsPbBr3/I3−x nanoparticles
NiOx system achieved C(sp3)-H bond activation in toluene with with different iodide vacancy (VI) concentrations on the surface,
high selectivity and high conversion rates of benzaldehyde with a larger VI population found in A-E-CsPbBr3/I3−x. As a
generation from toluene (3800 μmol/g/h).64 Very recently, result, A-E-CsPbBr3/I3−x formed superoxide radicals, •O2−,
Tüysüz et al. confined Cs3Bi2Br9 nanoparticles (2−5 nm) inside species involved in the photodegradation of organic compounds.
large ordered channels of mesoporous silica SAB-15 and used The VI sites were found to provide key surface chemical states to
this composite for aliphatic and aromatic C−H bond activation, produce •O2−. On the other hand, the VB is shifted to more
to develop corresponding aldehydes and ketones.78 This study negative values and the bandgap is narrowed in H-I-CsPbBr3/
demonstrates that well-dispersed MHP nanoparticles offer a I3−x by increasing the iodide content.
better electron−hole separation and an improved contact with As shown in Figure 5D, Soo et al. synthesized 2D Pb and Sn
reaction substrates. halide perovskite microcrystals with the long-chain alkyl group
Besides the selective oxidation of organics to value-added 1 -hexadecyl am moni um (HDA): (HDA) 2 Pb I 4 and
products in toluene, the complete mineralization of organics to (HDA)2SnI4.80 These MHPs exhibited photocatalytic activity
CO2 and H2O using MHP photocatalysts has also been in decarboxylation and dehydrogenation of indoline-2-carbox-
investigated. Huang et al. synthesized CsPb(Br1−xClx)3-Au ylic acids in DCM. Figure 5D presents the stable performance of
NCs for the Sudan Red III degradation in toluene.76 When these materials during a 25 h “on−off” irradiation study.
the CsPb(Br1−xClx)3-Au NCs system is photoexcited, there is an However, if the two Pb- and Sn-based perovskites are compared,
inner electron field between Au and the perovskite enhancing the Sn-based structures exhibit inferior stability due to the self-
the charge separation. The dissolved O2 can be trapped by the oxidation of Sn2+ to Sn4+.
photoelectrons on CsPb(Br1−xClx)3 to produce superoxide This collection of recently reported results using MHPs as
anion radicals (•O2−), and Au NCs can act as hole reservoirs to photocatalyst in low-polarity solvents demonstrates their
ACS Energy Lett. 2020, 5, 1107−1123
potential in a wide range of photocatalytic reactions, including polar solvent which indeed enhances the stability of the MHP
CO2 reduction, selective organic transformations for value- photocatalyst.
added products, and organic pollutant degradation. The reduced On the other hand, encapsulation is not merely limited to the
polarity of the created environment results in a relatively low synthesis of individual core−shell photocatalyst structures, as
solubility for MHPs which preserves the original structure rather shown in Figure 6A,C. The small size of MHP QDs allows
than relying on a precipitation−solubility equilibrium as was trapping porous structures such as metal−organic frameworks
discussed for aqueous conditions. Under these conditions, MHP (MOFs). CsPbBr3 QDs trapped in the ZIF-type MOFs (ZIF-67,
nanoparticles and QDs can be used to drive photocatalytic ZIF-8) showed a steady CO2 photoreduction in an ethyl acetate
reactions rather than micrometer-sized MHPs in water, further and water mixture.84 Figure 6E presents a schematic of the
optimizing the accessible surface area. synthesized CsPbBr3@ZIF hybrids by directly growing ZIF
around CsPbBr3 QDs. The catalytic stability of CsPbBr3@ZIF
A straightforward stabilization method was also tested by a recycling photocatalytic reaction. After
cycling 6 times (18 h in total), no obvious decay was obtained in
consists of encapsulating the MHP by a Figure 6F, indicating the good protective function of the ZIF
protective layer inside core−shell par- shell. Very recently, Lu et al. incorporated iodide-based
ticles. perovskite MAPbI3 into Fe-MOF, which exhibited an impressive
activity on CO2 reduction in an ethyl acetate/water solution
(over 80 h: CO, 4.16 μmol/g/h; CH4, 13 μmol/g/h).83 Ghosh
Encapsulation. A straightforward stabilization method consists et al. incorporated a Br-based perovskite into the ZIF-8 pore
of encapsulating the MHP by a protective layer inside core−shell structure to prepare a composite photocatalyst, MA(OA)-
particles. The protective layer prevents direct contact between PbBr3@ZIF-8 (OA is n-octylammonium).86 OA, a long alkyl
the MHP and destabilizing polar molecules. Care should be chain ammonium cation, was used as a capping ligand to
taken that the shell material does not block the light from stabilize the MHP nanoparticles and control the crystallization
reaching the MHP. Kuang and co-workers used amorphous process for the formation of colloidal NPs inside the MOF.86
TiO2 as the encapsulating material to generate CsPbBr3@TiO2 This material presents outstanding chemical stability under a
core−shell structures.81 Figure 6A shows the TEM picture of variety of conditions which would normally be detrimental for
this core−shell structure in which the CsPbBr3 nanocrystal was the MHPs, such as water immersion, UV light irradiation, and
capped by amorphous TiO2. This photocatalyst was used for high-temperature (100 and 140 °C) heating. Furthermore, they
CO2 reduction in ethyl acetate/water under solar light exhibit promising activity and stability toward photocatalytic
irradiation, exhibiting better activity than bare CsPbBr3 because organic dye (methyl orange) degradation in water.86 Although
of improved electron transfer from CsPbBr3 to TiO2. Most the photogenerated holes found in the VB of MA(OA)PbBr3
importantly, this core−shell structure shows impressive stability cannot directly oxidize H2O, the electrons in the CB will react
improvement, retaining over 90% of its initial photocatalytic with O2 to generate superoxide radicals (•O2−) which react with
activity after 15 h of use. Even after 30 h of constant simulated H2O to produce the hydroxyl radicals.
solar light illumination, the encapsulated material still possessed Alternatively, adding hydrophobic ligands to coat the NC
comparable photocatalytic activity, as shown in Figure 6B. surface is another effective method toward creating a waterproof
Recently, Wu et al. covered CsPbBr3 microparticles with porous “shell” on the MHP crystal exterior. Lu et al. adopted this
graphitic carbon nitride (p-g-C3N4) and used it for malachite approach with their CsPbBr3/Cs4PbBr6 nanocrystals and used
green degradation in polar isopropanol. This catalyst exhibited a the highly hydrophobic ligand hexafluorobutyl methacrylate.92
stable activity during 10 cycles (∼4.7 h in total), as p-g-C3N4 The resultant MHP-based system possessed an outstanding
acted to protect the CsPbBr3 surface.94 The core−shell structure tolerance to H2O; after 100 h of storage in water, 90% of the PL
was also shown to help stabilize the MHP not only in low- intensity of this MHP component was retained. Further doping
polarity solvents but also in a high-polarity solvent like water. the photocatalyst with Co (generating Co2%@CsPbBr3/
Zheng et al. also prepared anatase-coated CsPbBr3 nano- Cs4PbBr6) allowed for a CO yield of roughly 240 μmol/g in
particles for photocatalytic applications; Figure 6C displays a 20 h via CO2 reduction, in pure water. Similarly, larger
TEM micrograph of the core−shell system.82 The tight TiO2 hydrophobic organic spacer cations (A-site cation, such as 2-
shell was prepared via a two-step process, which starts from a phenylethylammonium (PEA) or n-butylammonium (n-BA))
simple wet chemical hydrolysis of titanium butoxide in relative have been used to form lower-dimensional 2D or quasi-2D layer
humidity (RH) of 30%, to form a TiOx layer outside the perovskites.106 The addition of these A-site cations has been
CsPbBr3 NC at 25 °C. Next, a 300 °C heating step promotes the found to benefit the overall material stability in polar
formation of the tight TiO2 (a-TiO2). Compared to pristine environments, by acting as a protecting layer against moisture
CsPbBr3 NCs, the core/shell CsPbBr3/a-TiO2 NCs present a attack. These improvements to stability have been widely
higher photocurrent and a smaller resistance in 0.1 m Na2SO4 demonstrated for MHP-based solar cells and LEDs and offer a
aqueous solution due to the formation of type II band alignment promising direction toward developing more stable MHP
in the CsPbBr3/a-TiO2 core/shell heterostructure. On the other photocatalysts in the future.
hand, the CsPbBr3/a-TiO2 composite was relatively stable and Coating MHPs with hole and electron transport layers (HTL
was able to be stored in water for more than 12 weeks in the dark and ETL, respectively) and electrodes in PEC devices also
without leading to any phase change or chemical decomposition. prevents direct contact with polar solvents, providing another
Furthermore, within 8 h of irradiation, as shown in Figure 6D, effective route toward long-term stabilization. Currently, there
the photocurrent of core/shell NCs does not show any are two different directions for this particular approach: (1)
reduction, indicating excellent PEC stability in water. A implementing an MHP solar cell−electrode (photoelectrode)
protective layer on the outside of MHPs, especially a tight system, with the MHP PV separated completely from the
crystallized shell, could decrease the direct contact from the electrode and electrolyte; (2) MHP photoelectrode, with the
ACS Energy Lett. 2020, 5, 1107−1123
Figure 6. (A) TEM images of amorphous TiO2-encapsulated CsPbBr3 nanocrystal and (B) time course of photocatalytic CO2 reduction in ethyl
acetate with isopropanol traces upon solar light irradiation.81 Reproduced with permission from ref 81. Copyright 2018 John Wiley and Sons.
(C) TEM image of anatase TiO2-coated CsPbBr3/TiO2 core/shell NCs and (D) controlled potential electrolysis of the CsPbBr3/TiO2 NCs
electrode in neutral water within 8 h.82 Reproduced with permission from ref 82. Copyright 2018 John Wiley and Sons. (E) Schematic of
CsPbBr3@ZIF-67 formation and the charge transfer in this material and (F) its application for CO2 photoreduction in ethyl acetate solution.84
Reproduced from ref 84. Copyright 2018 American Chemical Society. (G) Perovskite water-splitting solar cell and (H) current density−time
curve of the device without external bias under solar light illumination.90 Reproduced with permission from ref 90. Copyright 2014 The
American Association for the Advancement of Science. (I) Structure diagram of FTO/PEDOT:PSS/perovskite/PCBM/PEIE:Ag photocathode
for water reduction and (J) the photocathode stability test by light-chopped chronoamperometry.91 Reproduced with permission from ref 91.
Copyright 2016 Springer Nature. (K) Schematic diagram of TiO2|CsPbBr3|m-c|GS photoanode and (L) its long-term stability of TiO2|CsPbBr3|
m-c|GS70 for water oxidation with solar light irradiation.94 Reproduced with permission from ref 94. Copyright 2019 Springer Nature.
MHP integrated into the electrode. Grätzel and co-workers were water splitting current reached 10 mA/cm2, which corresponds
the first to construct an MHP-based solar cell-electrode to a 12.3% solar-to-hydrogen efficiency. Kamat et al. and
(photoelectrode) system, for the application of water splitting Mathews et al. proposed MHP-based solar cell ensembles with
in an alkaline electrolyte. Here, they combined a perovskite BiVO4 and Fe2O3 photoanodes, respectively, for the same water-
tandem solar cell and a bifunctional NiFe layered double splitting reactions.87,89 Using these photoanodes, a single-
hydroxide (i.e., origin of both water oxidation and reduction),
with the perovskite placed out of the solution to keep it stable, as junction MAPbI3 solar cell can achieve water splitting, as holes in
shown in Figure 6G.90 Under solar light irradiation, this device these photoanodes can mediate water oxidation. Specifically, the
offered relatively impressive water-splitting performance; Figure BiVO4-MAPbI3 and Fe2O3-MAPbI3 exhibited solar-to-hydro-
6H shows the “on−off” current density−time curve of the device gen conversion efficiencies of 2.5% and 2.4% at neutral pH,
without external bias for water splitting in which the unbiased respectively.
ACS Energy Lett. 2020, 5, 1107−1123
Figure 7. (A) Scheme of CO2 photoreduction with water vapor on Bi-based perovskite photocatalysts and (B) the CH4 generation for 10 h.98
Reproduced from ref 98. Copyright 2019 American Chemical Society. (C) Scheme of the photodegradation crystal violet on the CsSnBr3 and
(D) stability test for the photodegradation of crystal violet in 5 cycles.99 Reproduced with permission from ref 99. Copyright 2018 John Wiley
and Sons. (E) Scheme of the photodegradation of RhB on the Cs2AgBiBr6 and photographs of RhB at different irradiation times and (F)
recycling test of photocatalytic RhB degradation upon visible-light irradiation.100 Reproduced with permission from ref 100. Copyright 2019
John Wiley and Sons.
Meanwhile, some researchers appropriately integrated MHPs grated an MHP-photoelectrode with BiVO4 photoanode to
into the electrode to prepare an MHP photoelectrode for the prepare a tandem device for syngas production.93 Under bias-
PEC reaction. In 2015, Zheng et al. reported the first MAPbI3- free operation, this tandem device, which consists of BiVO4,
photoelectrode for water splitting.88 In this work, a Ni layer was FAMA0.22Cs0.07Pb1.32I3.27Br0.66, and cobalt catalyst on carbon
coated onto MAPbI3 both as a physical passivation barrier and as nanotubes (CoMTPP@CNT), offers the production rates of H2
a hole transport layer. However, after 15−20 min of continuous and CO of 0.58 ± 0.33 and 0.18 ± 0.16 μmol/cm2/h in CO2
tests, the photocurrent of this photoelectrode experienced a saturated water, respectively. In this tandem device, FA-
sharp decrease. Reisner et al. further adopted a solar cell-like MA0.22Cs0.07Pb1.32I3.27Br0.66 and BiVO4 harvest solar light to
structure to develop a metal-encapsulated perovskite photo- generate carriers, with holes remaining in the BiVO4 for water
cathode, FTO/PEDOT:PSS/MAPbI3/PCBM([6,6]-phenyl- oxidation and electrons moving to CoMTPP@CNT for CO2
C61-butyric acid methyl ester)/PEIE(ethoxylated polyethyleni- and H2O reduction. The selectivity of products on CoMTPP@
mine):Ag, for PEC hydrogen evolution in an aqueous CNT can be controlled by the pH of the electrolyte. More H2
medium.91 As shown in Figure 6I, the perovskite solar cell was found to be released in acidic solutions; relatively low
provides the photocathode and two additional protective layers, production was observed in alkaline conditions, and neutral pH
composed of Ag and an eutectic alloy (InBiSn), were deposited favored more CO2 reduction. Furthermore, in comparison to a
to fully cover the solar cell. These two protective layers not only single-component photocatalyst, such as a MAPbBr3, a mixed
form a water-resistant metal-encapsulated photocathode and compound FAMA0.22Cs0.07Pb1.32I3.27Br0.66 system presents a
protect the perovskite but also transfer the photogenerated better efficiency and stability.107
electrons to the surface to react with water. This photocathode Overall, on the basis of the discussion above, MHP film
can be stored in water for 6 h without any decomposition. systems achieve “steady” PEC energy conversion in aqueous
Furthermore, as shown in Figure 6J, the photocathode retained conditions via several methods, including MHP solar cells
more than 80% of the initial photocurrent after continuous coupled with electrocatalyst and photoelectrocatalyst, and
illumination for 1.5 h. Recently, Poli et al. used graphite sheets protective layers fully covering to form an MHP photoelectrode.
(GSs) as a protective layer to create a TiO2/CsPbBr3/carbon/ In these systems, MHP, as a harvester of light to absorb solar
GS photoanode, as shown in Figure 6K. A 25 μm thick deposit of light and generate carriers, was isolated from the aqueous
GS offers a more compact seal to stop water from reaching the solution. As a result, the stability of MHP would be effectively
perovskite. Furthermore, the GS is superhydrophobic, which improved. These PEC systems offer an efficient method for the
also enhances the water-resistance of this photoanode. Under utilization of solar energy by halide perovskites in aqueous
solar illumination, the system remained stable for 30 h in the solutions.
aqueous electrolyte with above 2 mA/cm2 photocurrent at 1.23 Realizing Intrinsic MHP Stability. The approaches outlined
VRHE.94 above, while offering varying degrees of success under rather
In 2019, Reisner et al. expanded the reaction scope when regimented conditions, fail to offer a path toward widespread
using MHP-photoelectrodes for CO2 reduction. They inte- adoption. As has been highlighted throughout, this failure stems
ACS Energy Lett. 2020, 5, 1107−1123
from the instability of MHPs when exposed to inherently provides the dominant species involved in RhB degradation. As
reactive environments. Clearly, developing MHPs which can shown in Figure 7F, the material maintained its photoactivity
intrinsically endure common photocatalytic conditions, and and comparable stability in ethanol following 6 h of irradiation
importantly display long-term photocatalytic performance, (5 cycles), although a little bit of AgBr generated as water
represents an ideal scenario. In comparison to hybrid molecules might lead to partial dissolution of the Cs2AgBiBr6
organic−inorganic perovskites, all-inorganic perovskites are crystal. Similarly, Tüysüz et al. synthesized lead-free perovskite
more stable because of their higher formation energy, lower Cs3Bi2Br9 submicrometer/nanoparticles and used them for the
configurational entropy, nonvolatility, and lower hygroscopic ring-opening reaction of epoxides in isopropanol.101 In
nature.109 Owing to the elimination of weakly bonded organic Cs3Bi2Br9, Lewis acid Bi sites adsorbed and activated epoxides.
components in the crystal structure, all-inorganic perovskites Upon light irradiation, holes and electrons generated in
exhibit relatively higher resilience against environmental Cs3Bi2Br9 reacted with alcohols and O2 to form alcohol anions
triggers. Recently, some all-inorganic perovskites have been and superoxide radicals, respectively. Alcohol anions and alcohol
used with success for reactions employing water vapor. Kuang et radicals generated by the reaction between superoxide radicals
al. prepared CsPbBr3 NC/MRGO (macroporous graphene and alcohols would serve as nucleophiles to react with activated
oxide) composite, though they further modified the system by epoxides and form ether. Upon visible light irradiation, 99%
adding hierarchical branched ZnO nanowires (BZNW), styrene oxide was converted by Cs3Bi2Br9 after 6 h of irradiation.
generating CsPbBr3/BZNW/MRGO composite, for photo- Furthermore, with 3 cycles (18 h in total), Cs3Bi2Br9 still
catalytic CO2 reduction in the presence of water vapor. exhibited a decent activity (retaining 80% of its initial
Compared to both pristine CsPbBr3 NCs and CsPbBr3/ photocatalytic activity).
MRGO, the addition of the ZnO nanowires enhanced the The high humidity tolerance of all-inorganic MHPs makes
photoelectron consumption rate to >50 μmol/g/h.96 Further- them ideal materials for the photocatalytic CO2 reduction in the
more, during 4 cycles or 16 h of simulated solar illumination, the presence of high-polarity solvent vapors. Furthermore, the
CH4 generation remained steady without any apparent decrease. photodegradation of organic pollutants has proved that some all-
Then, Kuang et al. also explored the stability of lead-free MHP inorganic MHPs remain stable in high-polarity conditions.
photocatalyst when exposed to polar molecules. With methyl These discussed results open opportunities to apply these
alcohol and water vapor, a lead-free Cs2SnI6 perovskite materials to perform chemical conversions involving polar
nanocrystal combined with SnS2 nanosheets achieved the CO2 solvents or molecules, even water splitting without the need of
to CH4 (6.09 μmol/g/h) reduction. This hybrid system haloacids, biomass reforming, and N2 reduction.
provided a stable photocatalytic activity over 3 successful Summary and Prospects. MHP semiconductors are well-
reaction cycles (9 h in total).97 Similarly, Diau et al. prepared documented to exhibit remarkable optical properties, leading
Rb3Bi2I9, Cs3Bi2I9, and MA3Bi2I9 with an ultrasonication top- to a wide variety of useful optoelectronic applications (i.e., solar
down method, arriving at materials which can remain stable for 7 cells, LEDs, photodetectors, etc.). Recently, in light of their
days under 70% humidity.98 These perovskites were then used interesting photophysics, MHPs were repurposed for photo-
for CO2 photoreduction with water vapor. As shown in Figure catalytic reactions and solar-to-chemical energy conversion.
7A, CO2 and H2O can be adsorbed on the perovskite surface and However, the intrinsically poor stability of their ionic crystal
form different intermediate species, including dioxycarbon structure represents a major technical hurdle. The instability of
anion bridge carbonate, monodentate carbonate, and bidentate MHPs, and finding ways around it, has imposed the largest limit
carbonate. The time-dependent evolution of CH4 on these on the scope of heterogeneous photocatalytic reactions they can
perovskites under light irradiation is shown in Figure 7B, in be effectively applied to.
which the production of CH4 increases steadily for 10 h. More In this Review, we have examined the recent progress made in
surprisingly, in 2018, Navas et al. prepared CsSnBr3 micro- the field of MHP-based photocatalysis, focusing on the
particles for photocatalytic dye degradation in water solution.99 instability issues currently holding back progress. To overcome
As the CsSnBr3 VB (1.9 eV vs RHE) is more positive than the material instabilities, several “stable” MHP-based photocatalytic
redox potential of OH−/•OH,108 the generated hydroxyl systems have been designed and realized, including H2
radicals degraded the violet dye as shown in Figure 7C. generation from saturated halo acid solutions, CO2 reduction
Meanwhile, as shown in Figure 7D, within 5 cycles (15 h in and organic synthesis in low-polarity solvents, encapsulation and
total) in 2.0 mg/L crystal violet dye aqueous solution, there was capping of MHPs for CO2 reduction and photoelectrochemical
no compromise in the photoactivity. water splitting, and CO2 reduction and dye degradation on all-
On the other hand, researchers have also explored all- inorganic MHPs with suitable polar solvents. Prospects to
inorganic MHP photocatalysts for steady operation in alcohols. intrinsically improve the crystal stability by designing novel
For example, Fan et al. prepared CsPbBr3 nanoparticles for composite perovskites have also been demonstrated. On the
tetracycline hydrochloride (TC-HCl, antibiotic) degradation in basis of the current knowledge and material limitations, several
ethanol.102 Upon visible light irradiation, 76% TC-HCl could be promising paths toward improving both the stability and
degraded in 30 min. Within 4 cycles of experiments for a total of efficiency of MHP-based photocatalysis can be identified:
120 min, CsPbBr3 still maintained nearly 90% of its initial 1. Improving the long-term catalytic cycling and opera-
activity. The partial activity loss can be attributed to the loss of tional stability of MHPs. While conducting reactions in halo
photocatalyst material during recovery between consecutive acid and low-polarity solutions has been proven effective for
cycles. Relying on the relatively higher chemical robustness of several reactions, such approaches are not universal in nature.
Cs2AgBiBr6, Xu et al. demonstrated microparticles of this To enhance resistance to material degradation pathways,
material suitable for photocatalytic reaction in ethanol.100 In synthesizing core−shell structures (e.g., oxide capping layers)
Figure 7E, with continuous irradiation, ca. ∼98% Rhodamine B with near-perfect coverage will help to limit contact between the
(RhB) was degraded by Cs2AgBiBr6 photocatalyst within 2 h. In MHPs and any polar solvent. MHP-based solar cells have
this reaction, the efficient production of superoxide radicals recently made progress with the instability issues associated with
ACS Energy Lett. 2020, 5, 1107−1123
operation under ambient conditions, achieving reliable oper- the high value-added organic synthesis. Further, aiming for high
ation times exceeding more than 1000 h. This was achieved by specificity and stereoselectivity is a promising direction for
engineering stable device architectures. Thus, employing top MHP-based photoredox catalysis.
and bottom HTL and ETL materials to fully cover MHPs by 4. Enhancing the redox ability of MHP-based photo-
spin coating, CVD, or ALD offers a promising method to obtain catalysis. The relatively narrow bandgaps of MHPs will
MHP photocatalysts with long-term stability. Furthermore, inevitably bring about weak redox abilities and, specifically
HTL and ETL would facilitate charge carrier separation and related to the VB edge, poor oxidation abilities. Some oxidation
transportation in MHPs. Increasing the valence charges of the reactions, like water oxidation (1.23 eV vs RHE for H2O/O2) or
dopant ions (doping of trivalent ions at the B site; e.g. Sb3+ in volatile organic compound mineralization (1.67 eV vs RHE for
CsPbI3) to increase the interaction between the ions and the OH−/•OH), will challenge the oxidation ability of the small
crystal frame might give rise to intrinsically more stable bandgap MHP. By combination with other semiconductors with
perovskite structure without the need for additional function- a more positive VB to build heterostructure (generating a Z-
alization. The partial or full substitution for Pb in MHP with scheme), an alternate pathway to achieve broad light absorption
other metals has been widely explored for solar cells, LEDs, and and strong redox ability is possible. Alternatively, by developing
other optoelectronic devices.110,111 Such compositional mod- the MHP-based PEC reaction system (via encapsulating the
ification can enhance the stability of MHP devices and does not perovskite layer in a solar cell architecture), the applied voltage
necessarily compromise the optoelectronic performance. can enhance the redox ability of the MHP to achieve a broad
Further exploration of this strategy for photocatalytic reaction scope.
applications is highly promising. Recent advances have shown The general performance and stability of MHP-based
that the perovskite microstructure can be stabilized under water photocatalysts are currently far from optimal, limiting their
for more than six months by controlling the lead hydroxide ability to address society’s energy and environmental concerns
peripheral layer in octahedral perovskite geometry under both effectively. The current state of the art demonstrates that this
acidic and basic media at ambient conditions without any emerging technology does hold promise, driven by similar
additional capping ligands.112 These water-stable perovskites motives of other popular MHP-based optoelectronic applica-
can be directly explored for solar water splitting under neutral, tions: easy, low-cost materials processing coupled with
acidic, and basic conditions. In brief, there is room for interesting photophysical properties. The field of MHP-based
significantly improving the stability and lifetime of MHP- photocatalysis is still in a relatively early stage of discovery, and
based photocatalysts, in comparison to traditional photo- this Review is intended to serve as a general guiding tool toward
catalysts, such as TiO2 and perovskite oxides ABO3 (e.g., finding optimal photocatalytic performance and stability.
SrTiO3, NaTaO3 or NaNbO3).
2. Improving the activity of H2 generation and CO2
reduction on MHP-based photocatalysts. To date, the highest
■ AUTHOR INFORMATION
Corresponding Authors
photocatalytic H2 generation is achieved on Pt/TiO2 (1.97 mol/ Maarten B. J. Roeffaers − cMACS, Department of Microbial and
g/h),113 and the highest CO2 reduction rate is realized on Molecular Systems, KU Leuven, 3001 Leuven, Belgium;
Au3Cu@SrTiO3/TiO2 (3.77 mmol/g/h (CO), with a side Email: maarten.roeffaers@kuleuven.be
production of hydrocarbon (725.4 μmol/g/h)).114 However, to Julian A. Steele − cMACS, Department of Microbial and
date the greatest H2 generation rate and CO2 reduction rate Molecular Systems, KU Leuven, 3001 Leuven, Belgium;
achieved for MHPs-based photocatalyst are about 7.3 mmol/g/ orcid.org/0000-0001-7982-4413; Email: julian.steele@
h and 148.9 μmol/g/h (CO) on BP/MAPbI359 and CsPbBr3/ kuleuven.be
C3N4,69 respectively, as shown in Tables 1 and 2. There are
several clear ways to further enhance the activity of MHPs Authors
photocatalysis for H2 generation and CO2 reduction: Co- Haowei Huang − cMACS, Department of Microbial and
catalysts (Pt, Au, Ag, CoO, MoS2 etc.) can be added to Molecular Systems, KU Leuven, 3001 Leuven, Belgium
accelerate the surface reaction rate; nanostructure morphologies Bapi Pradhan − Department of Chemistry, KU Leuven, 3001
with more exposed surfaces (e.g., nanosheets, nanoplatelets) Heverlee, Belgium; orcid.org/0000-0002-6202-7343
and facets can be synthesized to increase the surface area and Johan Hofkens − Department of Chemistry, KU Leuven, 3001
density of reaction sites; novel heterojunctions can be formed to Heverlee, Belgium; orcid.org/0000-0002-9101-0567
enhance the charge separation. Complete contact information is available at:
3. Expanding the scope of organic transformations and https://pubs.acs.org/10.1021/acsenergylett.0c00058
develop new key chemical reactions. Several organic trans-
formations have been reported to date, such as benzyl alcohol Notes
oxidation and C−H, C−O, and C−N bond activations. Unlike The authors declare no competing financial interest.
H2 generation and CO2 reduction, MHPs offer an impressive Biographies
activity on organic transformations (TON over 52 000 for α-
alkylation of aldehydes on CsPbBr3,65 32 900 μmol/g/h of Haowei Huang received his masters degrees from Fuzhou University
acetophenone generation rate on Cs3Bi2Br9-based photo- (China) and University of York (U.K.). At the end of 2016, he joined
catalyst78). However, the reported organic transformations the group of Prof. Roeffaers (KU Leuven, Belgium) as a Ph.D. student
with MHP photocatalysts are narrow, in comparison to known (Marie Curie ESR) with financial support from Marie Sklodowska-
heterogeneous and homogeneous photocatalytic organic syn- Curie innovation program where he is mainly working on perovskites
thesis by other semiconductor photocatalysts115 or molecule photocatalysis.
photoredox catalysts.116,117 Expanding the photoredox reaction Bapi Pradhan received his M.Sc. in chemistry from Indian Institute of
scope of MHPs by combining them with other molecule Technology, Bombay, and Ph.D. degree from Indian Association for the
catalysts, such as Ir, Ru, and Ni complexes, can be promising for Cultivation of Science. Currently, he is working as a postdoc at KU
ACS Energy Lett. 2020, 5, 1107−1123
Leuven in the group of Prof. Hofkens on the optoelectronic applications (9) Elumalai, N. K.; Mahmud, M. A.; Wang, D.; Uddin, A. Perovskite
of metal halide perovskites. Solar Cells: Progress and Advancements. Energies 2016, 9, 861.
(10) Wu, Y.; Chen, W.; Chen, G.; Liu, L.; He, Z.; Liu, R. The Impact of
Johan Hofkens graduated from the Laboratory of Photochemistry and Hybrid Compositional Film/Structure on Organic−Inorganic Perov-
Spectroscopy, KU Leuven (Belgium), in 1993 studying TICT-states in skite Solar Cells. Nanomaterials 2018, 8, 356.
organic molecules by time-resolved fluorescence measurements. After a (11) Tamirat, A. G.; Rick, J.; Dubale, A. A.; Su, W.-N.; Hwang, B.-J.
postdoctoral stay (1994−1995) with Prof. Masuhara at Osaka Using hematite for photoelectrochemical water splitting: a review of
University (Japan) on the development of optical trapping and with current progress and challenges. Nanoscale Horiz. 2016, 1, 243−267.
the late Prof. Barbara at University of Minneapolis (United States) on (12) Hendon, C. H.; Tiana, D.; Fontecave, M.; Sanchez, C.; D’arras,
single-molecule spectroscopy, he returned to the KU Leuven were he L.; Sassoye, C.; Rozes, L.; Mellot-Draznieks, C.; Walsh, A. Engineering
started the single-molecule group, focusing on the development of the Optical Response of the Titanium-MIL-125 Metal−Organic
optical microscopy tools to study challenging topics at the boundary of Framework through Ligand Functionalization. J. Am. Chem. Soc.
chemistry, biology, and physics. 2013, 135, 10942−10945.
(13) Jiang, Y.; Cho, S.-Y.; Shim, M. Light-emitting diodes of colloidal
Maarten B. J. Roeffaers graduated from the Centre for Surface
quantum dots and nanorod heterostructures for future emissive
Chemistry and Catalysis, KU Leuven (Belgium), in 2008 studying displays. J. Mater. Chem. C 2018, 6, 2618−2634.
zeolite catalysis with fluorescence microscopy. After a postdoctoral stay (14) Kibria, M. G.; Mi, Z. Artificial photosynthesis using metal/
(2009−2010) with Prof. Xie at Harvard University (United States) on nonmetal-nitride semiconductors: current status, prospects, and
the development and use of coherent Raman microscopy, he returned challenges. J. Mater. Chem. A 2016, 4, 2801−2820.
to the KU Leuven. In 2010, he started his own research group (www. (15) Wang, Y.; Zhang, Z.; Zhang, L.; Luo, Z.; Shen, J.; Lin, H.; Long,
roeffaers-lab.org) focusing on the development of optical microscopy J.; Wu, J. C. S.; Fu, X.; Wang, X.; Li, C. Visible-Light Driven Overall
tools to study heterogeneous catalysis and optically active materials Conversion of CO2 and H2O to CH4 and O2 on 3D-SiC@2D-MoS2
such as Ag-zeolites and metal-halide perovskites. Heterostructure. J. Am. Chem. Soc. 2018, 140, 14595−14598.
(16) Xie, S.; Zhang, Q.; Liu, G.; Wang, Y. Photocatalytic and
Julian A. Steele received his Ph.D. in solid-state physics from The
photoelectrocatalytic reduction of CO2 using heterogeneous catalysts
Institute for Superconducting and Electronic Materials, University of
with controlled nanostructures. Chem. Commun. 2016, 52, 35−39.
Wollongong, in 2016 and then joined the group of Prof. Roeffaers (KU (17) Wu, J.; Huang, Y.; Ye, W.; Li, Y. CO2 Reduction: From the
Leuven) as a postdoctoral researcher with financial support from the Electrochemical to Photochemical Approach. Adv. Sci. 2017, 4,
Belgium government (FWO), where his work focuses on nanoscale 1700194.
optical materials. (18) Xiao, X.; Jiang, J.; Zhang, L. Selective oxidation of benzyl alcohol
■
into benzaldehyde over semiconductors under visible light: The case of
ACKNOWLEDGMENTS Bi12O17Cl2 nanobelts. Appl. Catal., B 2013, 142−143, 487.
(19) Kong, D.; Zheng, Y.; Kobielusz, M.; Wang, Y.; Bai, Z.; Macyk, W.;
The authors acknowledge financial support from the Research Wang, X.; Tang, J. Recent advances in visible light-driven water
Foundation - Flanders (FWO) through a postdoctoral fellow- oxidation and reduction in suspension systems. Mater. Today 2018, 21,
ship to J.A.S. (FWO Grant No. 12Y7218N) and research 897−924.
projects to J.H. and M.B.J.R (FWO Grant Nos. G098319N and (20) Li, X.; Yu, J.; Jaroniec, M. Hierarchical photocatalysts. Chem. Soc.
ZW15_09-GOH6316), the European Union (Horizon 2020) Rev. 2016, 45, 2603−2636.
Marie Sklodowska-Curie innovation program (Grant No. (21) Stranks, S. D.; Snaith, H. J. Metal-halide perovskites for
722591 and a Ph.D. fellowship to H.H.), the KU Leuven photovoltaic and light-emitting devices. Nat. Nanotechnol. 2015, 10,
Research Fund (C14/15/053 and C14/19/079), and the 391−402.
Flemish government through long term structural funding (22) Ha, S.-T.; Su, R.; Xing, J.; Zhang, Q.; Xiong, Q. Metal halide
Methusalem (CASAS2, Meth/15/04). perovskite nanomaterials: synthesis and applications. Chem. Sci. 2017,
■
8, 2522−2536.
(23) Brenner, T. M.; Egger, D. A.; Kronik, L.; Hodes, G.; Cahen, D.
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Solar-Driven Metal Halide Perovskite

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ABSTRACT: The development of green, sustainable, and economical chemical processes

poor photoreduction potential,8 respectively. It follows that a

L ike the natural and eﬃcient energy conversion exhibited

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsenergylett.0c00058

CO2 + 2e− + 2H+ → CO + H 2O (7)

quantum dots: A new efficient photocatalyst for degrading antibiotic

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