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A Short Review of Catalysis

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A short review of catalysis for CO2 conversion

Article  in  Catalysis Today · November 2009


DOI: 10.1016/j.cattod.2009.08.015

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Catalysis Today 148 (2009) 221–231

Contents lists available at ScienceDirect

Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

A short review of catalysis for CO2 conversion


Jun Ma a,b, Nannan Sun a,b, Xuelan Zhang a,b, Ning Zhao a, Fukui Xiao a, Wei Wei a,*, Yuhan Sun a,*
a
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, PR China
b
Graduate School of the Chinese Academy of Sciences, Beijing, 100049, PR China

A R T I C L E I N F O A B S T R A C T

Article history: To be the abundant natural feedstock, CO2 chemical utilization has attracted the great interest in recent
Available online 6 October 2009 years. The key point to CO2 conversion is the activation of either CO2 or co-reactant at different
conditions. To bear this in mind, our strategy is to activate CO2 either with the presence of electron-rich
Keywords: chemicals or by hydrogen, and to convert CO2 with a coupling reaction in some case. In this way, catalytic
Carbon dioxide conversion conversion of CO2 has been carried out by different methodology at our lab, including CO2 reforming of
CO2 reforming methane to syngas production over bifunctional catalysis, CO2 hydrogenation for methanol synthesis by
Methanol
nano-structured catalyst, and synthesis of carbonates from sub- or super-critical CO2 with a coupling of
Dimethyl carbonate
Cyclic carbonate
in situ water removal reaction or bifunctional catalyst system. Herein, this brief review presents the
recent progress of catalytic CO2 conversion and aims to shed a light into the chemical fixation of CO2.
ß 2009 Elsevier B.V. All rights reserved.

CO2 is a cheap, nontoxic and abundant C1 feedstock and its tion. This brief review is therefore intended to provide an overview
chemical utilization is a challenge and important topic. Thus, any of the research progress on those topics.
efficient reactions using CO2 as a reagent have positive ramifications
on efforts towards carbon management. However, CO2 is a 1. CO2 reforming of CH4
thermodynamically stable compound, and then its reduction
requires high energy substances or electroreductive processes. Such CH4 and CO2 are relatively inexpensive due to their natural
an inert property of CO2, together with the lower reactivity in various abundance; hence, conversion of these two molecules to higher-
reactions, is probably the major reasons why currently the toxic value compounds is of great interest. The reaction between CO2
carbon monoxide, as a C1 building unit for many processes, is used and CH4 to produce synthesis gas (i.e., CO + H2) can be used in
mostly in industry. Although a number of organic syntheses using chemical energy transmission systems or utilized in the Fischer–
carbon dioxide are known, only a few were applied in industry, the Tropsch reaction to produce liquids. Reforming with CO2, rather
main processes being the syntheses of urea and its derivatives, and than H2O, could be employed in areas where water is not available
the production of organic carbonates, where phosgene (COCl2) is to form syngas with lower H2/CO ratios.
increasingly being replaced by CO2 as the C1 building unit. Another
important CO2 consumer is the electrochemical Kolbe–Schmitt CO2 þ CH4 ¼ 2CO þ 2H2 ; DH298 K ¼ 247:3 kJ=mol (1)
process for the production of salicylic acid.
The potential of homogeneous catalysis for CO2 fixation has Numerous researches have been devoted to the catalytic
been discussed in recent reviews [1–3]. Valuable chemicals performance of noble metals such as Rh, Ru, Pd, Pt and Ir towards
including the production of carbonates [4], carbamates [5], CO2 reforming of CH4 [10–15]. It is generally accepted that Rh and
urethanes [6], lactones [7], pyrones [8], and formic acid and its Ru showed both high activity and stability in CH4 dry reforming,
derivatives [9] could be synthesized by homogeneous catalysts. while Pd, Pt and Ir were less active and more prone to deactivation.
Heterogeneous catalysis can offer several technical advantages Typically, the catalyst activity were in the order of: Rh  Ru > Ir, Pt
such as stability, separation, handling and reuse of the catalyst and and Pd. The nature of support may have some influences on the
reactor design. Despite CO2 activation by heterogeneous catalytic activity of noble metals. Rezaei et al. studied a series of noble metal
routes were still limited, efforts have been made towards the catalysts supported on alumina-stabilized magnesia for the
synthesis of dimethyl carbonate, cyclic carbonates, and synthetic production of synthesis gas from methane and carbon dioxide.
gas (CO, H2) as well as methanol synthesis from CO2 hydrogena- The catalyst activity were in the order of: Rh  Ru > Ir > Pt > Pd
[10]. Nielsen et al. found that for MgO supported catalyst, the
activity for CO2 reforming was in the order of Ru, Rh > Ir > Ni, Pd,
* Corresponding author. Pt [11]. Erdohelyi’s study indicated that the activity toward the CH4
E-mail address: weiwei@sxicc.ac.cn (W. Wei). dissociation varied in the order of Rh/Al2O3 > Rh/TiO2 > Rh/

0920-5861/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.cattod.2009.08.015
222 J. Ma et al. / Catalysis Today 148 (2009) 221–231

Scheme 1. Concept design of stable Ni-based catalyst.

SiO2 > Rh/MgO [13]. However, considering the aspects of high cost stability showed a ‘‘confine effect’’ to prevent Ni particles from
and limited availability of noble metals, it is more practical, from sintering and crystalline growth, which was very important for the
the industrial standpoint, to develop non-noble metal catalysts catalytic stability towards CO2 reforming of CH4. H2-TPR of the
which exhibited both high activity and stability. catalyst indicated a main reduction peak at 883 K with a shoulder
Ni-based catalysts have been widely investigated [6,16–19] due at 723 K (see Fig. 2) which could be attributed to the reduction of
both to their similar activity and relatively low price when NiO particles interacted strongly and weakly with ZrO2, respec-
compared with noble metals. However, Ni-based catalysts were tively. The large peak at the high temperature suggested that most
readily deactivated by carbon deposition and sintering. Thus, more of the NiO in the catalyst interacted strongly with ZrO2 support.
effort were devoted towards development of a stable Ni-based
catalyst with high activity. Liu et al. employed MCM-41 as support
and prepared a Ni/MCM-41 catalyst by different method, it is
proved that the loading amounts of Ni and preparation method
have great influence on the catalytic stability [17]. Methane dry
reforming was carried out by Liu et al. over 7 wt.% Ni/SiC
monolithic foam catalyst. The catalyst exhibited excellent activity
and stability during 100 h [18]. By using CeO2 and ZrO2 as
modifiers, Corthals et al. improved the catalytic performance of a
Ni/MgAl2O4 catalyst. The doubly promoted NiCeO2ZrO2/MgAl2O4
catalyst within a certain composition ranges have higher stability
than singly promoted ones [19].
Al2O3, MgO, CaO were used as support to prepare Ni-based
catalysts for CH4 reforming reaction. It should be noticed that the
support with Lewis basic site might promote the carbon-resistant
ability of the catalyst for the strong adsorption capacity of CO2.
Furthermore, strong interaction might promote the dispersion of Ni
on the support, while much stronger interaction would decrease the
reducibility of Ni and thus the active sites Ni0 on the catalyst surface. Fig. 1. Pore distribution and absorption isotherms of Ni–CaO–ZrO2 nanocomposites.
Besides, it was suggested that the formation of filamentous carbon
was significantly influenced by the metal particle size and preceded
mostly over the metal particles larger than 7 nm, which implied that
the support might affect the catalytic stability of the catalyst [16].
Keep those mentioned above in mind, a novel catalyst, Ni–CaO–
ZrO2 nanocomposite, was designed for the CO2 reforming of
methane at our lab (see Scheme 1). Such a catalyst system with
high surface area and high thermal stability was synthesized via a
facile sol–gel process. Mesoporous ZrO2 was employed as the
substrate (see Scheme 1a), which has good oxygen storage capacity
and high hydrothermal stability. In this case, Ni particle was
effectively confined by the mesoporous framework and ZrO2 was
partially reduced with the formation of oxygen vacancies on the
catalyst surface (see Scheme 1b). Introduction of Ca2+ gave rise to
strong basicity of the catalyst as well as the stabilization effect to
the oxygen vacancies. As a result, coke elimination capacity was
improved on such a catalyst system, and the thermodynamically
favored carbon deposition process during reaction was also
suppressed by the small Ni particles.
In the present catalyst, most pores had a diameter of smaller
than 15 nm (see Fig. 1), such a porous structure with high thermal Fig. 2. TPR pattern of Ni–CaO–ZrO2 nanocomposites.
J. Ma et al. / Catalysis Today 148 (2009) 221–231 223

In the process of CO2 hydrogenation, the major reaction is the


methanol formation, while reverse water-gas-shift reaction
composes of the side reactions [23]:

Methanol formation
CO2 þ 3H2 ¼ CH3 OH þ H2 O; DH298 K ¼ 90:70 kJ=mol
Reverse water-gas-shift reaction
CO2 þ H2 ¼ CO þ H2 O; DH298 K ¼ 41:19 kJ=mol

The methanol formation is an exothermal reaction with


reduction of reaction molecule number. Thus, the decrease of
temperature and the rise of pressure should favor for the reaction
from thermodynamical analysis. However, considering the reac-
tion rate and the chemically inert nature of CO2, the enhancement
of reaction temperature (>513 K) facilitates CO2 activation and
then the methanol formation. The reverse water-gas shift reaction
Fig. 3. XRD patterns of fresh and used Ni–CaO–ZrO2 catalyst.
causes extra consumption of hydrogen and a reduction of
methanol formation. Meanwhile, the large amount of water form
as a by-product, from both methanol synthesis and the reverse
water-gas shift side reaction, also had an inhibitory effect on the
active metal during the reaction [24,25], leading to the deactiva-
tion of the catalyst. Besides, other hydrogenated products such as
higher alcohols and hydrocarbons are usually associated with
methanol formation. Therefore, methanol synthesis from CO2
hydrogenation requires a more selective catalyst to avoid the
formation of undesired by-products.
Highly efficient catalyst is the key for methanol synthesis via
CO2 hydrogenation. Up to now, the exploitation of the catalyst is
still not fully satisfactory for industrial application due to the
lacking of the necessary knowledge in catalyst designing for the
control of relevant catalytic properties and the mechanistic
understanding of CO2 hydrogenation. Although some kinetic
experiments with the aid of isotope-labeled CO and spectroscopy
[26–28] have demonstrated that methanol was produced by
hydrogenation of CO2 rather than CO, the commonly used ternary
Cu–Zn–Al oxide catalyst at 5.0–10.0 MPa and 473–523 K for CO
hydrogenation was not so active for hydrogenation of pure CO2
Fig. 4. Catalytic performance of Ni–CaO–ZrO2 catalyst (973 K [29]. Most catalyst used in CO2 hydrogenation was the modified
GHSV = 6000 ml h1 g1 CH4/CO2 = 1). methanol catalyst for CO hydrogenation and the research
addressed the chemical composition, supports, additives, different
This could improve the dispersion of NiO and promoted the preparation methods/conditions and morphology.
resistance to sintering under reaction conditions. The XRD patterns The majority of the catalysts for CO2 hydrogenation contained
of the catalyst before and after reaction indicated no apparent Cu and Zn as the main components together with different
change and growth in the NiO (or Ni) and CaO crystalline phase modifiers (Zr, Ga, Si, Al, B, Cr, Ce, V, Ti, etc.) [30–33]. Liaw and Chen
(see Fig. 3 a: Before b: after). This could be attributed to the [30] obtained ultrafine Cu/ZnO-based catalysts using a reduction
formation of a Ni–Ca–Zr–O ‘‘nano-composite’’ which justified the method in which the dispersion and stability of copper could be
interplanar distance of ZrO2 lattice and consequently, responsible improved by doping Cr, Zr and Th. Saito [31] reported that Al or Zr
for the strong interactions between Ni and ZrO2. As a result, the Ni– improves the dispersion of copper particles while Ga or Cr
CaO–ZrO2 catalyst showed both high catalytic activity and stability increases the specific activity per unit Cu surface area of the
in CO2 reforming of CH4 (see Fig. 4). The conversion appeared catalyst. And their further studies found that the Cu/ZnO-based
higher for CO2 than that of CH4, which could be attributed to the multi-component catalysts such as Cu/ZnO/ZrO2/Al2O3 and Cu/
occurrence of RWGS reaction. ZnO/ZrO2/Al2O3/Ga2O3 were highly active for methanol synthesis
from CO2 and H2. The addition of a small amount of colloidal silica
2. CO2 hydrogenation to methanol to the multi-component catalysts greatly improved their long-
term stability during methanol synthesis from CO2 and H2. Nitta
Carbon dioxide is a kind of potential carbon raw material and et al. [32] implied that the proper addition of certain amounts of
also one of the air pollutants [20]. In the past decades, the potential ZnO to the Cu/ZrO2 catalyst could greatly enhance its activity.
use of CO2, as an alternative feedstock replacing CO in the Arena [33] found that the Cu–ZnO/ZrO2 prepared by reverse co-
methanol production has received attention as an effective way of precipitation under ultrasound irradiation exhibited a significant
CO2 utilization. Under proper conditions, methanol made from improvement in the total surface area of the metal phase, and then
atmospheric CO2 by its reaction with hydrogen is regarded as the the enhanced CO2 conversion and methanol yield. Yang et al. [22]
‘‘most economic way’’ to mitigate the greenhouse effect which is studied the properties of the ZrO2-doped CuZnO catalyst prepared
caused by the substantial rise of CO2 concentration in the by precipitation method. XRD characterization confirmed that the
atmosphere [21,22]. active phase of copper in CuZnO catalyst prepared by co-
224 J. Ma et al. / Catalysis Today 148 (2009) 221–231

precipitation was well crystallized. The presence of ZrO2 led to a production with 25.9% of CO2 conversion and 72.9% of methanol
high copper dispersion, which was distinctive from CuZnO. Though selectivity at the low temperature of 443 K and pressure of 5 MPa
the activity for carbon monoxide hydrogenation was little lower using alcohol as solvent. Tsubaki et al. studied a new pathway for
than that of CuZnO catalyst. ZrO2-doped CuZnO catalyst showed CO2 hydrogenation to methanol over copper catalyst. In this novel
much higher activity and selectivity towards methanol synthesis process, alcohol, acted as both solvent and a catalytic liquid
in carbon dioxide hydrogenation. medium, changed the pathway of low temperature reaction.
In the noble metal-based catalysts, the supported Pd catalysts Conversion of CO2 reached 25.9% with a methanol selectivity of
are the most commonly used catalyst, which exhibit considerable 72.9% [29].
activity and selectivity for hydrogenation of CO2 to methanol, and Catalytic conversion of CO2 hydrogenation into methanol is an
the supports has significant effect on the performance of the attractive way to protect the global environment. Although many
catalyst. Edwin et al. [34] investigated the effect of the supports efforts have been made to facilitate the technology progress of
such as SiO2, Al2O3, ThO2, La2O3 on the catalytic performance of the methanol synthesis from CO2 hydrogenation, the highly efficient
supported Pd catalysts. The experiment showed that methanol process to enhance the CO2 conversion is still pursued due to the
selectivity can reach above 89% at 623 K and 12 MPa on the Pd/ thermodynamically stable nature of CO2 molecule. The catalyst
La2O3, while methane was the major product when Pd supported stability, catalyst sensitivities to impurities, catalyst intensity and
on the acidic supports. Fan et al. [35] reported that Pd/CeO2 reaction performance under scale-up conditions are needed to
possesses higher activity and longer lifetime after the catalyst was investigate in detail. Besides, the mechanism for methanol
reduced by H2 at 773 K. Recently, Liang et al. [36] developed a type synthesis via CO2 hydrogenation is not fully understood. The
of Pd–ZnO catalysts supported on multi-walled carbon nanotubes future shall emphasize the further developing highly efficient
(MWCNTs), which showed the excellent performance for CO2 catalyst and integrated process technology to meet the economic
hydrogenation to methanol. Under reaction conditions of 3.0 MPa efficiency for mitigation of global warming gases and sustainable
and 523 K, the observed turnover-frequency of CO2 hydrogenation development of carbon market demands.
reached 1.15  102 s1 over the 16% Pd0.1Zn1/CNTs(h-type).
PtW/SiO2 catalyst also reported to be used in CO2 hydrogenation. 3. Synthesis of dimethyl carbonate from CO2 and methanol
Under the conditions of 473 K, 3 MPa and H2/CO2 ratio of 3,
methanol selectivity can reach 92.2% with CO2 conversion of 2.6%
[37].
Transitional metal carbides are a type of metal-derived
compounds with the incorporation of carbon in the metal lattice.
They have the physico-chemical properties of high melting point Dimethyl carbonate (DMC) was widely used in industry [42–
and hardness, high thermal and mechanical stability as well as 44]. Synthesis of DMC directly from CO2 and methanol was
excellent catalytic performance for hydrogenation, which are favorable not only for reduction of greenhouse gas emissions but
similar to those of Pt, Rh and other noble metals [38,39]. Thus, the also for development of new carbon resource. Typically, synthesis
metal carbides can be used as potential substitutes for noble metal of DMC from CO2 and methanol was conducted in an autoclave. Lee
catalysts. Compared with metal sulfides, metal carbides possess et al. investigated the catalytic performance of supported copper
superior hydrogen adsorption, activation and transfer capabilities, catalyst and found that the reaction temperature and pressure had
and then they have potential application in CO2 hydrogenation great influence on the DMC yield [45]. Kizlink et al. found that
reactions. Sn(IV) and Ti(IV) alkoxides was effective for DMC synthesis from
From a view of practice, a highly active, selective and poisoning- CO2 and methanol using metal acetates as support [46–48]. Fang
resistant catalyst for methanol synthesis is desirable. Some et al. reported that MCO3 (Here, the letter M means alkaline metal)
researchers attempted to use transition metal carbides for was superior for DMC formation, moreover, CH3I played a key role
methanol synthesis via CO2 hydrogenation. Different carbides in the reaction [49]. Fang et al. found that Mg powder showed
were tested for CO2 hydrogenation, the results indicated that Mo2C better performance than Ca powder, while Al powder showed no
and Fe3C showed high CO2 conversion and good methanol activity toward the reaction. The DMC yield reached to the
selectivity, while TaC and SiC were almost inactive [40]. Such maximum at the reaction pressure of 7.5 MPa which was related
results seemed that metal carbides catalysts need to be further with the supercritical state of CO2 [50]. Cao et al. also found DMC
improved for the application for methanol synthesis via CO2 yield reached to the maximum near the critical pressure of CO2
hydrogenation. over K2CO3 and CH3I. The possible reaction mechanism was as
Besides the exploration of the catalyst with excellent perfor- follows: methanol was decomposed to CH3O- and H+ by K2CO3
mance, the innovation of reactor and process technology is another followed by CO2 insertion to form [CH3O–(CO)O]–, which reacted
important aspect for obtaining the higher yield and better with CH3I and H+ to form DMC and HI. CH3I was recovered via
selectivity toward methanol with the reducing proportion of by- reaction of HI and methanol [51]. The catalytic activities of the
products in CO2 hydrogenation. The methanol productivity is organotin alkoxides were very low due to the decomposition of the
usually low using the traditional on-stage catalyst bed in the fixed- catalysts by the side-product water. Toshiyasu et al. indicated that
bed gas phase tubular reactor. Rahimpour [41] proposed a two- the yield and selectivity of DMC enhanced by the increase of CO2
stage catalyst bed concept for conversion of carbon dioxide into pressure taking R2Sn(OMe)2 as the homogenous catalyst under the
methanol. Compared with a conventional single catalyst bed critic condition. However, R2Sn(OMe)2 was unstable in the moist
system, two-stage bed system showed the extremely favorable environment, which could hydrolyze with the by-product water.
temperature profile along the reactor tube length, causing a higher Thus, some typical dehydrating agents, such as dimethyl acetal and
level of catalyst activity and a longer catalyst life time. Also, trimethyl ortho ester, to consume the water were used in this
favorable temperature profile of catalyst bed plus high level of reaction system. And the DMC yield could reach as high as 70%
catalyst activity in gas-cooled reactor of two-stage bed system, [52,53]. Furthermore, the reaction mechanism and structure of
results in more production rate in this system. Other researchers R2Sn(OMe)2 were also discussed in detail [54].
[29] employed a novel low-temperature route in a semi-bath Bell et al. deduced the adsorption configuration of CO2, DMC
autoclave reactor for the efficient conversion of CO2 into methanol. and methanol through Raman spectra. The mechanism for the
This process realized a very high catalytic activity of methanol reaction of methanol and CO2 was elucidated in Scheme 2 [55,56].
J. Ma et al. / Catalysis Today 148 (2009) 221–231 225

Scheme 2. Mechanism for the reaction of methanol and CO2.

Jiang et al. has reported the zirconia supported Kiggin unit 12- reaction pressure and showed a maximum for DMC yield at the
tungstophosphoric acid/zirconia (H3PW12O40/ZrO2), which was pressure of 9.3 MPa. The concentration of methanol showed an
prepared via sol–gel technique, promoted the formation of DMC obvious influence on both the yield and selectivity of DMC. Nickel
from CO2 and methanol effectively under mild condition. The acetate appeared to be the precursor of the catalyst. The formation
results shown that with the amount of H3PW12O40 on the catalysts mechanism of dimethyl carbonate in supercritical phase was
in the range of 0–50 mg the DMC formation increased almost proposed in Scheme 3 [59].
linearly. And the mechanistic studies indicated that acid–base
bifunctional catalysis is essential in selective DMC synthesis. 4. Reaction of CO2 and propylene glycol (PG)
Compared with ZrO2, the H3PW12O40/ZrO2 catalysts has weak
Brønsted acid sites, uniquely, which were more effective than Cyclic carbonate can be used to produce chain carbonate via
Lewis acid sites for CH3OH activation [57]. transesterification which is a widely used method for carbonate
Wu has reported direct synthesis DMC from gaseous methanol synthesis [60,61]. In particular, five-membered ring carbonate,
and CO2 over the modified V2O5 catalysts, such as H3PO4/V2O5 and propylene carbonate (PC) are used as the feed of one of the main
Cu–Ni/VSO. In the H3PO4/V2O5 catalysts, the direct interaction process for dimethyl carbonate (DMC) synthesis, with 1,2-
between V and P formed weak Brønsted acid sites, which were propanediol (1,2-PG) as by-product. Thus, if 1,2-PG could be
more effective for the CH3OH activation. The crystal phase of further used to produce PC with CO2, not only 1,2-PG but also CO2
H3PO4/V2O5 was influenced by the composition of P/V, signifi- would be recycled, which could be considered as a new green
cantly, and with P/V = 0.15–0.50 it was in bicrystal phase technology.
(orthorhombic/tetragonal) showed effective activation of both
CO2 and CH3OH [58].
At our lab, direct synthesis of dimethyl carbonate from CO2 and
methanol was carried out at near supercritical conditions using
nickel acetate as the catalyst. It was demonstrated that DMC could
be produced as the unique product at such low temperature as
305 K and the yield was 12 times higher than that at non-
supercritical conditions. The synthesis was sensitive to the Tomishige et al. [62,63] found that over CeO2–ZrO2 catalysts,
cyclic carbonates such as ethylene carbonate (EC) and 1,2-PC were
selectively synthesized via the reactions of CO2 with ethylene
glycol and PG, respectively. No polycarbonate and ethers
(diethylene glycol and dipropylene glycol) were detected under
the optimum reaction conditions. The 1,2-PG conversion was 2%,
and was much dependent on the composition and calcination
temperature of the catalysts. On the basis of the catalyst
characterization, it was suggested that the active sites could be
weak acid–base sites which were present on the plain surface of
the catalysts calcined at high temperatures. On the other hand,
catalyst calcined at high temperature exhibited low activity due to
very low surface area. Du et al. [64] evaluated the catalytic
Scheme 3. Plausible mechanisms of dimethyl carbonate formation. performance of Sn compound in this reaction and found that the
226 J. Ma et al. / Catalysis Today 148 (2009) 221–231

Scheme 4. Possible mechanism of ammonium carbonate formation.

selectivity of PC was 99.9%, but the yield of PC was only 3.4%. They synthesis. Moreover, the reaction mechanisms were studied and
presumed that dibutyltin oxide reacted with 1,2-PG to give 4- proposed over different catalysts.
methyl-2,2-dibutyl-1,3,2-dioxastannolane, then the Sn–O bond in
4-methyl-2,2-dibutyl-1,3,2-dioxastannolane was easily inserted 5. Synthesis of cyclic carbonate from CO2 and epoxide
by CO2 to form a cyclic tin carbonate, and finally a subsequent
intramolecular nucleophilic attack of alkoxy group on the carbonyl The synthesis of cyclic carbonate via cycloaddition of CO2 to
carbon atom caused the formation of PC and regeneration of epoxide is one of effective routes of CO2 chemical fixation. Cyclic
dibutyltin oxide. carbonates were widely used as excellent aprotic polar solvents,
Although the selectivity of PC was high, the conversion of 1,2- electrolytes in secondary batteries, precursors for polycarbonates
PG was less over the above mentioned catalysts. Water, the by- and other polymeric materials, and intermediates in the production
product, was concluded to limit the equilibrium. More recently, of pharmaceuticals and fine chemicals like dialkyl carbonates,
CH3CN was reported as an available dehydrater in the carbonyla- glycols, carbamates, pyrimidines, purines, etc. The catalysts devel-
tion of 1,2-PG. Wang et al. utilized zinc acetate [65] to catalyze the opment as well as the reaction mechanisms had been reported over
reaction of CO2 and 1,2-PG to synthesis PC in the presence of alkali metal halides [71–74], organic bases [75–77], metal oxides
acetonitrile. With the acetonitrile hydrolysis, the conversion of 1,2- [78–81], zeolite [82,83], titanosilicates [84], smectites [85,86], and
PG and the yield of PC increased obviously. They suggested that for metal complexes [87–96] for synthesis of cyclic carbonates from CO2
zinc acetate, it turned to ZnO by the reaction with PG and then ZnO and epoxides. The synthesis of cyclic carbonates from CO2 and
reacted with both CO2 and NH3 to form (NH3)ZnCO3, and a possible epoxides has been applied in industrial scales; however, the activity,
mechanism for the synthesis of PC from CO2 and PG over zinc stability and recovery of the catalysts still remain to be improved.
acetate catalyst was elucidated [66]. In recent years, significant progress has been made in the
However, in this reaction system acetic acid from the hydrolysis application of ionic liquids as catalysts and alternative solvents in
of CH3CN could react with 1,2-PG to produce PG-2-acetate, which organic synthesis due to their unique advantages of negligible
resulted in the drop of the selectivity. At our lab, ammonia and vapor pressure. The use of ionic liquid as reaction media and/or
different amido compounds were chosen as the source of ammonia catalysts for clean catalytic transformations would indicate
to balance the side reactions for the improvement of PC selectivity profound effects on the reaction rate and product selectivity. It
[67]. And the results showed ammonium carbonate was probably the was also reported that CO2 could significantly dissolve into the
best reagents according to the following mechanism (see Scheme 4). ionic liquid phase, which therefore made the reactions of CO2
We also reported different catalysts for the carbonylation of possible and suitable [97,98]. Under these circumstances, the use
1,2-PG with carbon dioxide in the present of CH3CN. For alkali of ionic liquids would be attractive for synthesis of cyclic carbonate
carbonates catalysts, with the strengthening of alkaline the from CO2 and epoxide.
catalyst activity was enhanced, and Cs2CO3 possessed the best Deng et al. firstly reported the synthesis of cyclic carbonate over
catalytic activity than other alkali carbonates [67]. For organic ionic liquids 1-butyl-3-imidazolium tetrafluoroborate ([C4-
bases, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) showed best mim]BF4) [99]. They also found that either cation or anion affects
catalytic effects than others [68]. In the reaction PG was activated the activity of the ionic liquid. The activity for propylene carbonate
via being looted one hydroxyl H by the N atom of TBD, followed by synthesis decreased in the order of imidazolium > pyridinium and
the electrophilic attack of CO2 on the hydroxyl O atom giving rise to of BF4 > Cl > PF6. Kawanami et al. [100] investigated the cyclic
an ‘‘ion pair’’. Then, with the proton migrated to the other hydroxyl carbonates synthesis over various 1-alkyl-3-methylimidazolium
group of PG, the oxygen of the bonded CO2 nucleophilicly attacked salts ([Cn-mim]X) under scCO2 and found that both anion and the
the hydroxyl-losing carbon in PG to afford PC and water, and the length of alkyl chain in the cation were important for the catalytic
catalyst TBD was recovered. The essence of TBD catalysis lay in its performance. The carbonate yield increased with the increasing of
capability to act as a proton bridge with the synergistic action of its the alkyl chain length (from C2 to C8) which might be attributed to
N atoms. Further studies showed the catalytic activity of zinc salts the higher solubility of both the epoxide and CO2 in the ionic liquid
[69] catalysts were higher than those of organic base and inorganic having longer alkyl chain under the same pressure and tempera-
base mentioned above. It was found that zinc salts and transition ture. Moreover, influence of CO2 pressure on the yield also
metal halides were only the precursor of catalysts. The real depended on the alkyl chain length, e.g. for [C8-mim]BF4, with the
catalysts were coordination compounds, which was generated by CO2 pressure reduced from 14 MPa to a subcritical pressure of
the coordination of transition metal atom with acetamide 6 MPa, a remarkable decrease of the yield was also observed.
molecules. Zinc oxide modified with potassium salt as catalysts It was also found that the presence of Lewis acidic compounds
were prepared and used to effectively synthesis PC via the reaction as cocatalysts greatly enhanced the activity of ionic liquid for the
of 1,2-PG with CO2 in the presence of acetonitrile [70]. Among the cyclic carbonate synthesis. Kim et al. [101] showed that with the
catalysts, KI/ZnO showed the highest catalytic activity for PC addition of ZnBr2, the catalytic activities of ionic liquid [C4-
J. Ma et al. / Catalysis Today 148 (2009) 221–231 227

mimi]Cl or [C4-mim]Br for the reactions of CO2 with ethylene


oxide and propylene oxide can surprisingly be improved, although
zinc bromide alone showed no activity for the reactions. It might be
due to the in situ formation of bis(1-butyl-3-methylimidazolium)
zinc tetrahalides from ZnBr2 and [C4-mim]Cl or [C4-mim]Br.
For conversion of styrene oxide to styrene carbonate, high
reaction temperature, long reaction time, high CO2 pressure, and/
or solvent were required to obtain satisfied styrene carbonate yield
due to the less reactivity of b-carbon atom compared with
propylene oxide and ethylene oxide. Recently, Arai et al. found that
the catalyst system comprised of ZnBr2 and an ionic liquid [C4-
mim]Cl, could afford 93% yield with 100% selectivity for styrene Scheme 5. The preparation of [Amim]OH/SiO2.
carbonate at 353 K for 1 h [102] instead of the lower activity for
ZnBr2 and [C4-mim]Cl. They also found that the type of metal
cations in metal halides which acted as co-catalyst had strong A mixture of [Bmim]OH (30 mmol)and silica powder (20 g,
effect on the carbonate yield. The type of anion as well as the length pretreated at 300 8C for 6 h) in toluene (100 ml) was refluxed for
of alkyl chain on the imidazolium cation had strong effects on the 16 h at 90 8C. After being fully stirred, the volatile components of
conversion and selectivity. Besides, the [C4-mim]Cl/ZnBr2 ratio the mixture were removed on a rotary evaporator. Then, the
also affected the carbonate yield. resulting material was dried in vacuum at 80 8C for 12 h. Finally, a
Several research groups studied the reaction mechanisms for red powder was obtained which was denoted as [Bmim]OH/SiO2.
the synthesis of cyclic carbonate from epoxide and CO2 and As the same way, the GILs [Bmim]BF4/SiO2, [Bmim]Cl–AlCl3/
proposed that both Lewis base for the activation of CO2 and Lewis SiO2, [Bmim]Cl–ZnCl2/SiO2 were also prepared, respectively.
acid for the activation of epoxide were demanded in the reaction The structure of the grafted ionic liquids (GILs) characterized by
despite the different catalyst systems [79,80,92,94,97,103]. Ionic various physico-chemical measurements such as element analysis,
liquids could also act as solvents in the reaction of CO2 and epoxide, BET, FTIR.
e.g. Garcia et al. [104] have reported that [C4-mim]PF6 was a The content of nitrogen, carbon, and hydrogen for porous silica
suitable reaction media for the CO2 cycloaddition to epoxide support and the GILs were measured by elemental analysis
catalyzed over chromium salen complex. The catalyst could be (Table 1). The results showed that there was no nitrogen and
recovered and reused by liquid–liquid extraction of the substrate carbon in the porous silica which suggested that nitrogen and
and the products after the reaction. Zhang et al. prepared a series of carbon in grafted sample came from the ionic liquids instead of the
hydroxyl-functionalized ionic liquids (HFILs) which showed support. Considering that only [Bmim]OH contained N element, so
efficient reactivity and reusability toward the coupling of epoxide the weight percent of [Bmim]OH could be obtained according to
and CO2 without any additional co-catalyst and organic solvent. that of N. The grafted amount of [Bmim]OH was about 11.2%,
OH groups in the catalyst or reaction media were crucial for the which was equivalent to 1.4 mmol of imidazolium salt per gram of
reaction to proceed smoothly due to its cooperation function of catalyst.
ring-opening of epoxide. Highest activity and selectivity were IR is known to be useful for detecting functional group in the
achieved in the presence of 1-(2-hydroxyl-ethyl)-3-methylimida- molecular. The FTIR spectrums for the novel hydroxyl ionic liquid
zolium bromide (HEMIMB) [105]. [Bmim]Cl–AlCl3/SiO2, [Bmim]Cl–ZnCl2/SiO2, [Bmim]BF4/SiO2 and
Although ionic liquid had showed a high performance for the [Bmim]OH/SiO2 were recorded in KBr disks and paraffin oil coats
reaction of carbon dioxide and epoxide, the heterogeneous catalyst because paraffin oil coats could exclude the influence of
system still remained a challenge due to the ease of separation and hydrophilic character and IR absorption of KBr (see Fig. 5). The
the possibility to use a fixed-bed reactor. Recently, a novel method to peaks in the region 3000–2700 cm1 were account for aliphatic C–
immobilize ionic liquid onto solid supports was proposed and used H stretching frequency and the peak at 3200 and 3800 cm1 were
for the hydroformylation [106], hydrogenation [107] and Friedel– assigned to the hydroxyl band, respectively. In addition, methylic
Crafts alkylation reaction [108]. Xiao et al. found that the supported C–H transmutative peak at 1398 cm1 and 1468 cm1, as well as
[C3-mim]Br/SiO2-zinc chloride catalyst system exhibited a high the peak at 1570 cm1 and 1647 cm1 ascribed to imidazole
activity and selectivity for the synthesis of cyclic carbonates from absorbs and C5 5N stretching vibration were observed. These bands
carbon dioxide and epoxides under mild conditions in a high TOF indicated that ionic liquid groups had been successfully grafted on
without any additional co-solvents [109]. Takahashi et al. demon- the support of silica gel.
strated that phosphonium halides covalently bound to SiO2 exhibit N2 adsorption–desorption isotherms for the [Bmim]OH/SiO2
excellent catalytic activities for synthesizing propylene carbonate and SiO2 (Fig. 6) displayed type IV isotherms with clear hysteresis
from propylene oxide and CO2. The pseudo-first order rate constant loops according to the IUPAC. This indicated that the samples kept
of the catalyst normalized to phosphorus atom is about 300 times the mesoporous nature after grafting of ionic liquid groups. The
larger than that of the corresponding homogeneous catalyst [110]. specific surface areas of the samples were also calculated by BET
Wang et al. prepared silica-supported [C4-mim]+[BF4] and found method. It was found that the surface area and pore volume of the
that the as-prepared catalyst was effective for cyclic carbonate grafted samples decreased in comparison with pure silica (see
synthesis under supercritical carbon dioxide conditions. High cyclic Table 2). This could be attributed to the grafting of ionic liquid
carbonate yield together with excellent selectivity was achieved groups into the mesopore. The N2 adsorption–desorption iso-
[111]. Zhu et al. prepared the ionic liquid choline chloride/urea
supported on molecular sieves for the reactions of CO2 and epoxides Table 1
and found that this biodegradable and green catalyst was very active The element analysis of the samples.

and selective, and choline chloride and urea showed a synergetic Sample wt.% nC/nN Norg (mmol g1)
effect in promoting these reactions [112].
N C H
In our work, a series of new catalysts grafted ionic liquid 1-
Silica gel – – 0.73
butyl-3-methylimidazolium hydroxide [Bmim]X/SiO2 were pre-
[Bmim]OH/SiO2 1.96 5.83 1.14 2.97 1.4
pared for CO2 cycloaddition (see Scheme 5).
228 J. Ma et al. / Catalysis Today 148 (2009) 221–231

Fig. 5. The infrared spectra of GILs with different [Bmim]OH immobilized on silica gel.

main loss weight peaks. The first peak involved in the outer layer
water desorption; the second peak accounted for decomposition of
GILs; and the last one could be assigned to condensation of silanol
group. It can be seen that the sample was stable under 250 8C.
In the present work, the catalytic performance of catalysts was
investigated under the identical conditions (see Table 3). Grafted
ionic liquids [Amim]OH/SiO2 possessed the best catalytic perfor-
mance.
A series of catalytic cycles were conducted to investigate the
reusability of the catalyst. In each cycle, the catalyst was separated
by simple filtration and then used for the next reaction directly.
The results listed in Table 4 indicated that the catalyst could be
reused for up to four times.

6. Synthesis of cyclic carbonate in the presence of


ammonium salt

Quaternary ammonium salts may also catalyze CO2 fixation


Fig. 6. Nitrogen adsorption–desorption isotherms of the samples.
into cyclic carbonate. It was reported that inactive substrate
styrene oxide and polymerization sensitive oxirane glycidyl
therms of all the samples all showed a large break of relative methacrylate oxirane could convert to the corresponding cyclic
pressure in 0.6–0.9 which indicating that the ordered pore was carbonates with satisfied yields by using molten tert-butylammo-
kept after the grafting of ILs. nium bromide (TBAB) and/or tetrabutylammonium iodide (TBAI)
Thermogravimetry (TG) and differential thermal analysis (DTA) as solvent and catalyst [113]. TBAI showed higher activity than
of the sample were employed to clarify the thermal stability of the TBAB because of the difference in the nucleophilicity of the halide
grafted ionic liquid. As shown in Fig. 7, gradual weight loss was ions. The reaction rate depended greatly on the structure of the
observed from about 50 8C to approximately 600 8C, with three cation as well as the nucleophilicity of anion. Significant difference
on reactivity among imidazolium, thiazole, pyridinium and
tetraalkyl ammonium salts were observed. The effective activity
Table 2 of the tetraalkylammonium salt might come from the bulkiness of
The BET results of the samples.
the tetrahedral ammonium ion, which forces the halide ion away
Sample SBET/(m2 g1) Vp/(cm3 g1) dp/nm from the cation easier, resulting in less electrostatic interaction
Porous silica 310.88 0.86 11.38 between anion and cation and consequently in more nucleophi-
[Bmim]Cl–AlCl3/SiO2 254.62 0.73 10.76 licity of the anion. Lewis acid could enhance the activity of
[Bmim]Cl–ZnCl2/SiO2 277.46 0.84 11.20 ammonium salt. Kossev et al. [114] observed that calcium chloride
[Bmim]BF4/SiO2 254.46 0.81 11.31
promoted the reaction between CO2 and epoxides catalyzed over
[Bmim]OH/SiO2 240.82 0.67 10.70
tetraalkylammonium or phosphonium halides. Arai et al. also
found that a catalyst system consisting of ZnBr2/TBAB is active for
the CO2 cycloaddition [115], which quantitatively produces
Table 3
Catalytic performance of the samples. styrene carbonate from styrene oxide at 353 K for 1 h. Such
synergistic effect also occurs by the combination of metal complex
Catalysts PO conversion (%) PC selectivity (%)

Silica gel – –
[Bmim]Cl 99.8 98.2 Table 4
[Bmim]Cl/SiO2 97.2 98.6 Catalyst recycle studies in cycloaddition of CO2.
[Bmim]Cl–AlCl3/SiO2 90.1 99.7
Reused no. PO conversion (%)
[Bmim]Cl–ZnCl2/SiO2 98.0 98.6
[Bmim]BF4 94.9 97.5 1 99.1
[Bmim]BF4/SiO2 93.2 99.0 2 97.3
[Bmim]OH 100 99.9 3 94.6
[Bmim]OH/SiO2 99.1 100 4 89.0
J. Ma et al. / Catalysis Today 148 (2009) 221–231 229

Fig. 7. TGA for the [Bmim]Cl–AlCl3/SiO2, [Bmim]Cl–ZnCl2/SiO2, [Bmim]BF4/SiO2 and [Bmim]OH/SiO2.

and onium salt. Researches [115–119] also found that a coupled conditions had a great influence on the performance. With
catalyst system of the tetradentate Schiff base aluminium complex amine-functionalized silica, CO2 could be activated by amine
(SalenAlCl) and tetraalkylammonium halide were active toward groups, which might be beneficial for the insertion of CO2 into the
the reaction of CO2 and epoxide. Various cyclic carbonates could be C–O bond of epoxides via nucleophilic attack. On the other hand,
produced from corresponding epoxides even at room temperature high CO2 concentration hardly reduced the conversion of
with good yields, although the long reaction time was needed propylene oxide which was different from the conventional
[117]. The possible mechanism might involve the ring-opening mechanism reported in literature. Thus, the activation of
insertion of epoxide into Al–Cl bond followed by insertion of CO2 propylene oxide seemed different from the pathway of the
into Al–O bond of the resulting alkoxy complex. The ammonium conventional mechanism, and the hydroxyls such as the silanols
halide was supposed to contribute to the activation of epoxide. on the support surface perhaps involved in the activation of
At our lab, amine-functionalized silica catalysts (NH2/SiO2, epoxide by H-bond formation On condition that such hypothesis
NH(CH2)2NH2/SiO2 and 1,5,7-triazabicyclo[4,4,0]dec-5-ene/SiO2 was reasonable, the epoxides activated by H-bond formation were
(TBD/SiO2)) were prepared by ultrasonic technique under mild readily ring-opened in view of nucleophilic attack of even poorly
conditions. Such hybrid solid bases showed high catalytic activity nucleophilic reagents. The synergistic effect was sufficient to
towards CO2 coupling with propylene oxide. The reaction promote the insertion of CO2 to epoxides to form linear carbonates,

Scheme 6. Possible mechanism for cycloaddition of CO2 to an epoxide on TBD/SiO2.


230 J. Ma et al. / Catalysis Today 148 (2009) 221–231

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