Synthesis of Porous Polymeric Catalysts for the Conversion of Carbon

Review Cite This: ACS Catal. 2018, 8, 9079−9102

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Synthesis of Porous Polymeric Catalysts for the Conversion of Carbon Dioxide Kuan Huang,*,† Jia-Yin Zhang,† Fujian Liu,*,‡ and Sheng Dai§,∥

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†

Key Laboratory of Poyang Lake Environment and Resource Utilization of Ministry of Education, School of Resources Environmental and Chemical Engineering, Nanchang University, Nanchang, Jiangxi 330031, China ‡ National Engineering Research Center for Chemical Fertilizer Catalyst (NERC−CFC), School of Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350116, China § Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United States ∥ Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States ABSTRACT: Because CO2 is the main greenhouse gas, its capture and catalytic conversion are thought to be significant issues to be solved at the current time. Given the thermodynamically stable and inert nature of CO2, it is highly desirable to develop advanced catalysts to facilitate the transformation of CO2 to other high-value-added chemicals under mild conditions. Within this regard, porous organic polymers (POPs), featuring large surface areas, high thermal stabilities, diverse building blocks, and tunable porous structures, are an ideal platform for the construction of heterogeneous catalysts for CO2 conversion. Incorporating active sites that are capable of activating CO2 and/or substrates into the frameworks of POPs can facilitate CO2 conversion. In this Review, the most recent advances in the design and synthesis of POP-based heterogeneous catalysts for the conversion of CO2 are summarized. We mainly focus on the synthetic strategies researchers have used for incorporating active sites into POP frameworks to prepare heterogeneous catalysts for CO2 conversion, including N-doping, metalation, and ionic functionalization. Problems remaining to be addressed in this field are analyzed, and future directions are outlined. KEYWORDS: porous organic polymers, heterogeneous catalysis, CO2 conversion, greenhouse gas, reusability amines,16−18 and alcohols.19−21 Figure 1 shows six representative pathways for CO2 conversion. Therefore, the integration of CO2 capture with CO2 conversion, by which energyintensive desorption and compression of CO2 are avoided and high-value-added chemicals are obtained, is very promising from the viewpoints of modern chemistry and economics. However, it remains a great challenge to transform CO2 to other chemicals under mild conditions because of the thermodynamically stable and inert nature of CO2. To overcome this problem, various advanced catalysts, both homogeneous and heterogeneous, have been developed in the past decade to facilitate CO2 conversion. Homogeneous catalysts include metal complexes, 22−25 ionic liquids (ILs),26−29 N-heterocyclic carbenes (NHCs),30−33 superbases,34−36 and frustrated Lewis pairs (FLPs).37−40 Heterogeneous catalysts include porous carbons,41−43 porous silicas, 4 4 − 4 7 zeolites, 4 8 , 4 9 metal−organic frameworks (MOFs),50−53 and porous organic polymers (POPs).54−56 Compared with homogeneous catalysts, heterogeneous cata-

1. INTRODUCTION The continual consumption of fossil fuels since the Industrial Revolution has caused the atmospheric concentration of CO2 to increase by 25% over the past century.1 CO2 is one of the most important greenhouse gases, and its accumulation in the atmosphere may cause multiple disastrous climatic and environmental effects, for example, global warming and sea level rise. There is high demand for controlling CO2 emissions resulting from the combustion of fossil fuels in industrial activities. In this context, there are proposals for CO2 capture, which typically is realized by absorption in liquids or adsorption on solids.2−4 The captured CO2 is then stripped out by a temperature and/or pressure swing, followed by compression and storage. However, the application of CO2 capture technologies in industry is quite limited because of the high costs of capture. It is estimated that $59.10 is spent for each ton of CO2 captured by the amine-scrubbing process in a typical coal-fired power plant.5 The high cost of CO2 capture arises mainly from the intensive energy required for CO2 desorption and compression. On the other hand, CO2 is a cheap, renewable, nontoxic C1 feedstock for the production of a wide range of high-valueadded chemicals, such as organic carbonates,6,7 formamides,8−10 carboxylic acids,11,12 urea-derivates,13−15 alkyl© 2018 American Chemical Society

Received: June 3, 2018 Revised: August 15, 2018 Published: August 20, 2018 9079

DOI: 10.1021/acscatal.8b02151 ACS Catal. 2018, 8, 9079−9102

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ACS Catalysis

In this Review, the most recent advances in the design and synthesis of POP-based heterogeneous catalysts for CO2 conversion are summarized. We mainly focus on the synthetic strategies researchers use to incorporate active sites into POP frameworks to prepare heterogeneous catalysts for CO2 conversion. In the first part, we introduce the incorporation of active sites that are capable of activating CO2, mainly focusing on the synthesis of N-doped POPs. In the second part, we introduce the incorporation of active sites that are capable of activating substrates, mainly focusing on the synthesis of metalated and ionic-functionalized POPs. Finally, we summarize the state-of-the-art routes such as electrochemical and photocatalytic CO2 conversion. We also analyze the problems remaining to be addressed in this field and discuss future directions of research.

2. SYNTHESIS OF POPS AND THEIR APPLICATIONS IN CO2 CONVERSIONS 2.1. POPs Activating CO2. Considering the Lewis acidic nature of the CO2 molecule, it is within expectations that basic sites are capable of activating CO2. Actually, the activation of CO2 by most homogeneous catalysts, such as NHCs and superbases, is realized through the acid−base interaction between CO2 and basic sites.30−36 Basic sites play two roles in activating CO2: (1) making the CO2 molecules much denser around them than in the gas phase and (2) changing the electron distribution in CO2 molecules. Therefore, the incorporation of basic sites into the frameworks of POPs is believed to be a promising strategy to prepare POPs that are capable of activating CO2. Roeser et al.55 reported the use of covalent triazine frameworks (CTFs) as catalysts for the conversion of CO2 under solvent- and metal-free conditions. Figure 2 shows the idealized chemical structures of two CTFs (CTF-1 and CTFP), which were synthesized by trimerization of corresponding dicyano-compounds under ionothermal conditions. To obtain the amorphous high-surface-area analogues (CTF-1-HSA or CTF-P-HSA), they were prepared from the same monomer but at a higher reaction temperature. Triazine and pyridine units, which could selectively bind with CO2 through Lewis base-acid interaction, were the active sites in CTFs for

Figure 1. Representative pathways for CO2 conversion.

lysts show obvious superiority in catalyst recycling and thus have become a frontier field in modern catalysis research. Among the heterogeneous catalysts mentioned, POPs are particularly attractive because of their unique features such as large surface areas, high thermal stabilities, diverse building blocks, and tunable porous structures.57−59 They are regarded as an ideal platform for the construction of heterogeneous catalysts for CO2 conversion. To endow POPs with the ability to catalyze CO2 conversion, active sites that are capable of activating CO2 and/or substrates should be incorporated into their frameworks. For example, nitrogen species with Lewis basicity can help densify CO2 in the inner pores of POPs, activating it for subsequent conversion; metal ions with strong coordination ability and halide anions with high nucleophilicity can help activate substrates for complexing with CO2. Based on these principles, different POPs embedded with one or more kinds of active sites can be rationally designed and synthesized for catalytic CO2 conversion. To date, significant progress has been achieved in this field, and thus, a timely and comprehensive review is needed.

Figure 2. Chemical structures of CTF-1 (left) and CTF-P (right). 9080


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Figure 3. Schematic representation of the synthesis of sterically embedded NP-imine, NP-imidazolium, and NP-NHC starting from sterically hindered aromatic tetraamine. Reprinted with permission from ref 66. Copyright 2015 American Chemical Society.

triazine, melamine, triazole, tetrazole, amide, and imide have been successfully prepared.61,62 However, most of these basic sites are nitrogen species, the basicity of which is not strong enough to effectively activate CO2. Jiang et al.63 screened the binding energy of various nitrogen species with CO2 by ab initio calculations and found that the values were located in the range of −10.7 ∼ −21.2 kJ/mol. These values were less exothermic than the binding energy of NHCs and superbases with CO2 (90.0% were achieved after 48 h at 70 °C and 0.1 MPa. Obviously, the catalytic activities of ionic-functionalized POPs with abundant large mesopores for CO 2 conversion were superior to those with only micropores or small mesopores. Based on the results discussed above, ionic-functionalized POPs with simultaneous hydroxyl/carboxyl groups and enriched porosity should be a fascinating option for the catalytic conversion of CO2. He et al.111 synthesized highly ordered mesoporous polymer-supported imidazolium-based ILs by chloromethylation of the FDU-15 mesoporous polymer, followed by functionalization with imidazole and quaternization with halogen-substituted alcohols or carboxylic acids (Figure 26). The same group also demonstrated the direct synthesis of ordered imidazolyl-functionalized mesoporous polymers (IM-MPs) sing an imidazolyl-functionalized resol for cross-linking with formaldehyde. The presynthesized IMMPs were then quaternized with bromoethane to give ionicfunctionalized POPs.112 Using a different route, Zhang et al.113 synthesized imidazolium salt-modified porous hyper-crosslinked polymers (POM-IMs) by the Friedel−Crafts alkylation reaction of benzyl halide monomers containing hydroxyl

Friedel−Crafts alkylation reaction of 2-phenylimidazoline with α,α′-dichloro-p-xylene (DCX) or α,α′-dibromo-p-xylene (DBX) (Figure 23). Gao et al.105 described the synthesis of covalent organic frameworks (COFs) immobilized with ILs by the polycondensation reaction of 4,4′,4′′,4′′′-(pyrene-1,3,6,8tetrayl) tetraaniline (PyTTA) with 2,5-dihydroxyterephthalaldehyde (DHPA) and 1,4-phthalaldehyde (PA), followed by the Williamson ether reaction of the phenol groups with (2bromoethyl)triethylammonium bromide, as shown in Figure 24. Coskun et al.106 described the synthesis of charged covalent triazine frameworks (cCTFs) by ionothermal trimerization of cyanophenyl-substituted viologen dication as a monomer (Figure 25). However, these ionic-functionalized POPs did not show an obvious improvement in catalytic activity for CO2 conversion in comparison with T-IM and PCPs because of their predominant micropores (0−2 nm) or small mesopores (2−5 nm). These were not beneficial for the diffusion of reactants in the inner pores. Free radical polymerization under solvothermal conditions has proved to be an advanced technique to synthesize ionicfunctionalized POPs with large mesopores without the assistance of any template. Park et al.107 and Bordiga et al.108 prepared nonionic POPs with mesoporous structures by first copolymerizing 1-vinylimidazole (1-VIm) and DVB and then quaternizing the nonionic POPs containing imidazole units to produce ionic-functionalized POPs with average pore sizes of 5−8 nm. The synthesized ionic-functionalized POPs effectively catalyzed the cycloaddition of CO2 to epoxides at 110 °C and 1.34 MPa, with epoxide conversions of up to 92% after 6 h. Ma et al.109 prepared PIPs by self-polymerization of quaternized phosphonium salts tethered with three vinyl groups. The synthesized PIPs exhibited excellent activity for catalyzing the 9091


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Figure 24. Synthesis of [Et4NBr]X%-Py-COFs with the ionization of channel walls through the Williamson ether reaction of [HO]X%-Py-COFs with (2-bromoethyl)triethylammonium bromide. The [HO]X%-Py-COFs were synthesized via the condensation of PyTTA with DHPA and PA at various molar ratios. Reprinted with permission from ref 105. Copyright 2016 Royal Society of Chemistry.

groups with dichloroethane, followed by quaternization with 1methylimidazole (Figure 27). As an alternative, Yang et al.114 used free radical polymerization under solvothermal conditions to synthesize ionic-functionalized POPs. Taking the synthesis of IL-based porous polymers functionalized with intermolecular hydroxyl groups as an example (Figure 28), the solvothermal copolymerization of 1-butyl-3-vinylimidazolium bromide, (4-vinylphenyl)methanol, and divinylbenzene (DVB) resulted in the targeted ionic-functionalized POPs. When SBA15 was used as the support for copolymerization, ionicfunctionalized POPs with higher hydroxyl contents and BET surface areas were obtained. The catalytic activity of these ionic-functionalized POPs for CO2 conversion was determined by the content of the hydroxyl groups and the porosity. More recently, the combination of polyILs with porous supports has been further utilized to design highly efficient catalysts for CO2 conversion to useful chemicals.115−118 For instance, Jiang and co-workers incorporated imidazoliumbased polyILs into a MOF, and the resultant composite catalysts showed excellent activities for the selective capture and conversion of CO2. Their excellent activities should be attributed to the synergistic effect among the good CO2

enrichment capacity, the Lewis acid sites in MOF, as well as the Lewis base sites in polyILs.115 Yang and co-workers reported catalysts based on porphyrin-based porous polymers and thermal-responsive ILs, which exhibited excellent activities for catalyzing CO2 cycloaddition reaction.116 For a clear comparison, the sample information, reaction conditions, and activities of some typical POP-based catalysts designed for CO2 conversion are summarized in Table 1. 2.2.3. Multifunctionalized POPs. In the conversion of CO2 catalyzed by metalated POPs, cocatalysts such as halide salts are commonly used. However, the recycling of cocatalysts is an important issue. It has been demonstrated that both metal ions and halide anions can be incorporated into POP frameworks by taking advantage of the diverse building blocks and synthetic methods of POPs. Based on these achievements, multifunctionalized POPs in which metal ions and halide anions are integrated into the same polymeric chain are proposed as heterogeneous catalysts for CO2 conversion. The cooperative functions of metal ions and halide anions underlie the powerful ability of multifunctionalized POPs to catalyze the CO2 conversion without the assistance of any other cocatalysts. 9092


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Figure 25. Synthetic route for the preparation of charged covalent triazine frameworks (cCTFs). Reprinted with permission from ref 106. Copyright 2017 American Chemical Society.

TOFs of up to 15600 h−1 at 120 °C and 3.0 MPa and TONs of up to 2400 after 24 h at 25 °C and 0.1 MPa for the cycloaddition of CO2 to epoxides. Inspired by this work, other multifunctionalized POPs were also designed and synthesized. Cao et al.122 synthesized a bifunctional cationic POP (Al-CPOP) by quaternizationinduced hypercross-linking of metalated salen containing chloromethyl groups with 2,4,6-tris(imidazol-1-yl)-1,3,5-striazine (TIST), as shown in Figure 30. Al-POP effectively catalyzed the cycloaddition of CO2 to epoxides at 120 °C and 0.1 MPa with epoxide conversions of up to 99% after 24 h. Ji et al.123 synthesized metallosalen-based ionic porous polymers (DVB@ISA and DVB@ISZ) by free radical copolymerization of metalated salens containing vinylimidazolium-based ILs with DVB under solvothermal conditions (Figure 31). DVB@ ISA and DVB@ISZ were able to effectively catalyze the cycloaddition of CO2 to epoxides at 60 °C and 1.0 MPa, with epoxide conversions of up to 99% after 24 h. The same group synthesized charged metalloporphyrin polymers (Al-iPOPs) by the Yamamoto−Ullmann coupling reaction of 5,10,15,20tetrakis(4-bromophenyl)porphyrin-aluminum(III) chloride

Ding et al.119 reported the first example of using multifunctionalized POPs for catalyzing CO2 conversion. As shown in Figure 29, phosphonium salt and ZnX2−PPh3 integrated hierarchical POPs were synthesized by free radical copolymerization of phosphonium salts tethered with three vinyl groups and tertiary phosphine tethered with three vinyl groups under solvothermal conditions. This was followed by metalation with metal ions. The ratios of phosphonium salt to ZnX2−PPh3 were tuned by adjusting the ratios of monomers. The catalytic activity of synthesized multifunctionalized POPs for cycloaddition of CO2 to epoxides was among the highest of the heterogeneous catalystsinitial TOFs of up to 3985 h−1 at 120 °C and 3.0 MPa. The same group also synthesized analogous multifunctionalized POPs by free radical copolymerization of imidazolium salts tethered with two vinyl groups and tertiary phosphine tethered with three vinyl groups under solvothermal conditions. This was followed by metalation with metal ions,120 or free radical copolymerization of phosphonium salts tethered with three vinyl groups and metalated porphyrins tethered with four vinyl groups under solvothermal conditions.121 The latter samples offered extraordinary initial 9093


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Figure 26. Schematic illustration for preparing a series of FDU-15 mesoporous polymer-supported imidazolium-based ionic liquids: (a) FDUHEIMBr, (b) FDU-CMIMBr, (c) FDU-DHPIMBr, and (d) FDU-EIMB. Reprinted with permission from ref 111. Copyright 2014 Royal Society of Chemistry.

Figure 27. Synthesis of supported imidazolium salts and the typical structure of POM-IM. Reprinted with permission from ref 113. Copyright 2015 Royal Society of Chemistry.

(Al-TBPP) with brominated ILs, as shown in Figure 32.124 AliPOPs effectively catalyzed the cycloaddition of CO2 to epoxides at 25 °C and 1.0 MPa, with epoxide conversions of up to 99% after 8 h. In general, it is highly desirable to use nontoxic solvents for the synthesis of catalysts to eliminate the potential impacts of solvents on the environment. To this end, our group recently developed a hydrothermal technology for the synthesis of ionic-functionalized POPs.125 As shown in Figure 33, the free radical self-polymerization of 1-(4-vinylbenzyl)-1,3,5,7-tetraazaadamantan-1-ium chloridea monomer prepared by quaternization of hexamethylenetetramine (HMTA) with 4vinylbenzyl chloride (VBC)in aqueous solution under high temperature induced the decomposition of the HMTA unit

into ammonia and formaldehyde. The ammonia and formaldehyde produced then induced the cross-linking of benzene rings via “resol chemistry” to produce N-doped mesomacroporous organic polymers (N-MMOPs) containing IL moieties. The presynthesized N-MMOPs were further metalated with metal ions to give multifunctionalized POPs (Zn@N-MMOPs and Co@N-MMOPs). The Zn@N-MMOPs and Co@N-MMOPs showed competitive activity for catalyzing the cycloaddition of CO2 to propylene oxide at 25 °C and 1.0 MPa in the presence of TBAB as a cocatalyst, with carbonate yields of up to 97.5% after 48 h. Although cocatalyst was required in the conversion of CO2 catalyzed by Zn@NMMOPs and Co@N-MMOPs because of their limited number of ionic sites, this approach did represent a significant advance 9094


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Figure 28. Illustration of the synthesis of (A) porous polymers functionalized with both ionic liquid and intermolecular hydroxyl group and (B) hybrid SBA-[VxOHy]R materials. Reprinted with permission from ref 114. Copyright 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Table 1. Activities of Different Catalysts for CO2 Conversion catalysts

reactions

cocatalysts

CO2 (MPa)

temp (°C)

time (h)

yield (%) or TOF (h−1)

refs

CTF-1-HSA NP-NHC Zn-CMP Co-MON Zn@SBMMP Al-CMP Bp-Zn@MA M(Por)OP M/POP-TPP HUST-1-Co TB-MOP-Ru Zn/HAzo-POPs Zn/HAzo-POPs Co@N-OMPs cross-linked ionic polymers PS-HEIMX T-IM ionic-functionalized POPs PIPs PILs ZnX2−PPh3 the latter samples Al-POP DVB@ISA Al-iPOPs Zn@N-MMOPs PPS⊂COF-TpBpy-Cu

cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition hydrogenation cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition cycloaddition

TBAB TBAC TBAB PPNCl TBAB KI TBAB TBAB Ph3P TBAB TBAB TBAB TBAB TBAB -

0.69 0.1 3.0 3.0 2.0 3.0 1.0 1.0 0.1 0.1 12 3.0 0.1 1.0 5.0 2.5 1.0 1.34 0.1 0.1 3.0 3.0 0.1 1.0 1.0 1.0 0.1

130 120 120 60 60 100 100 120 25 25 40 100 25 100 140 120 150 110 100 70 120 120 120 60 25 25 40

4 24 / / 4 / / / 24 30 12 / 48 / 3 4 10 6 3 48 / 24 24 24 8 48 24

100 98 11600 155 97 364 1580 2124 95.6 >94.0 2254 (TON) 3330 >99 168.6 98 98 87 92 99 >90 3985 15600 99 99 99 >97.5 95

56 66 71 73 74 74 76 78 80 81 88 89 89 91 94 95 101 108 109 110 119 121 122 123 124 125 126

highly flexible linear polymers to address this issue. As shown in Figure 34, the metal ions and halide anions were not appended to the same polymeric chain. Instead, the metal ions were anchored on the rigid framework of a COF, and the halide anions were anchored on the chains of a linear ionic polymer with high flexibility. The linear ionic polymer was formed in the pores of a COF bearing 2,2′-bipyridine units by in situ free radical polymerization of phosphonium salt tethered with a vinyl group. The resultant ionic polymerCOF composite (PPS⊂COF-TpBpy) was then metalated with Cu2+ by the coordination reaction of 2,2′-bipyridine units with Cu2+ to give multifunctionalized POPs (PPS⊂COF-TpBpyCu). PPS⊂COF-TpBpy-Cu retained the crystallinity and

in the facile and green synthesis of multifunctionalized POPs with promising applications in catalytic CO2 conversion. Another significant advance in the synthesis of multifunctionalized POPs for catalyzing CO2 conversion was achieved by Ma et al.126 In the above-mentioned multifunctionalized POPs, the two kinds of active sites (metal ions and halide anions) that are capable of activating substrates are spatially separated by the rigid frameworks. It is actually difficult for the metal ions and halide anions to cooperate with each other in catalyzing CO2 conversion, thus limiting the catalytic activity of those multifunctionalized POPs. Ma et al. proposed the concept of heterogeneous concerted catalysis between active sites on the porous materials and the use of 9095


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electrochemical and photocatalytic conversion of CO2 could be performed under rather mild condition, and valuable products such as formic acid, methanol, ethanol, CH4, CO, and aldehydes could be obtained by using these state-of-the-art routes. However, the electrochemical and photocatalytic conversion of CO2 usually employ nonpolymeric nanocatalysts. For instance, Xie and co-workers successfully developed partially oxidized atomic cobalt layer electrocatalysts, which exhibit excellent activities for the electroreduction of CO2 to liquid fuels such as formic acid.127 Fan and co-workers successfully synthesized Z-scheme Ag3PO4/gC3N4 composited photocatalysts, which could catalyze the conversion of CO2 into useful chemicals such as methanol, CH4 and CO.128 The excellent activities of Ag3PO4/g-C3N4 composites should be attributed to the efficient separation of photoexcited electron holes in the composites. Besides the above-mentioned results, there are many other pioneering works focusing on the electrochemical and photocatalytic conversion of CO2, and many important progresses have been achieved.129−132

3. OUTLOOK Although significant progress has been achieved in the design and synthesis of POPs for catalytic CO2 conversion, two important issues still must be addressed in this field. (1) The major source of CO2 emissions is flue gas, the combustion product of fossil fuels. In flue gas, CO2 concentrations are low (i.e., 10−15 v/v%).133 Considerable research works have been concerned for the treating of diluted CO2 streams in these years. How to catalyze the conversion of CO2 from a dilute source especially for the CO2 derived from flue gas and air, is a significant issue in the field. Most POP-based heterogeneous catalysts reported to date are effective only under elevated pressure (0.1−6.0 MPa) because these POPs are only capable of effectively activating either CO2 or substrates. For example, NHC-functionalized POPs are capable of effectively activating CO2 but cannot effectively activate substrates; metalated and ionicfunctionalized POPs can effectively activate substrates, but not CO2. Therefore, a future direction is to design and synthesize multifunctionalized POPs that are capable of activating CO2 and substrates simultaneously. On the other hand, there exist many other components in flue gas, such as steam and oxygen,133 which may influence the stabilities and catalytic activities of POPs. In fact, rationally adjusting surface wettability, controlling compositions, and enhancing cross-linking degree of the networks of POPs could effectively improve their hydrothermal stabilities and water-tolerant properties under harsh reaction conditions.134 It is urgent to thoroughly investigate the stabilities and catalytic activities of POPs in the presence of steam and oxygen at high adsorption and reaction temperatures. In particular, the underlying mechanisms for the degradation of POPs should be investigated, with the assistance of experimental and theoretical tools, to provide guidance for the design and synthesis of POP-based heterogeneous catalysts with enhanced stabilities under industrial conditions. (2) The development of POP-based heterogeneous catalysts relies greatly on the versatile building blocks and

Figure 29. Preparation procedure for 1P+X−&1PPh3@POPs and the corresponding 1P+X−&ZnX2−1PPh3@POP. Reprinted with permission from ref 119. Copyright 2016 Royal Society of Chemistry.

Figure 30. Synthesis of Al-CPOP.

nanoporosity of the COF, exhibiting high thermal stability and accessibility of reactants to active sites. It was found that PPS⊂COF-TpBpy-Cu showed excellent activity for catalyzing the cycloaddition of CO2 to epoxides at 40 °C and 0.1 MPa, with carbonate yields of up to 95% after 24 h. 2.3. Other Advanced Routes for the Conversion of CO2. Besides the chemical conversion of CO2, other routes such as electrochemical and photocatalytic conversion of CO2 are also hot topics, having received considerable attentions in these years. Compared with chemical conversion of CO2, 9096


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Figure 31. Synthesis of metallosalen-based ionic POPs. Reprinted with permission from ref 123. Copyright 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Figure 32. Synthesis of Al-POP, Al-iPOP-1, and Al-iPOP-2. [Ni(cod)2] = bis(1,5-cyclooctadiene)-nickel(0).

However, simpler methods are still greatly needed. Mechanochemical synthesis is an advanced technology developed in recent years.135 In mechanochemical synthesis, chemical reactions are accelerated by mechanical force and/or instantaneous frictional heat. Therefore, chemical reactions proceed in a solid state, avoiding the use of large amounts of solvents. Thus, the solubility of monomers in solvents is no longer a limitation for the design and synthesis of POPs. Mechanochemical synthesis has been widely applied in the preparation of a wide range of porous materials and has proved to be a powerful tool for fast, scalable production.136 Therefore, it is suggested that mechanochemical synthesis be extended to the preparation of POP-based heterogeneous catalysts for CO2 conversion.

4. CONCLUSIONS The most recent advances in the design and synthesis of POPbased heterogeneous catalysts for CO2 conversion are summarized in this Review. The development of N-doped, metalated, and ionic-functionalized POPs for catalytic conversion of CO2 is examined in detail, with an emphasis on synthetic strategies researchers have used to incorporate active sites into POP frameworks. POPs have been demonstrated to be an ideal platform for the construction of heterogeneous catalysts for CO2 conversion owing to their tunable structures and high activity. Future work in this field should pay special attention to the design and synthesis of

Figure 33. Synthetic route for nitrogen-functionalized meso-macroporous organic polymers (N-MMOPs). Reprinted with permission from ref 125. Copyright 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

synthetic strategies of POPs. However, the construction of most POPs requires expensive monomers and/or complex synthetic routes, making it unfavorable for industrial applications of POPs. Solvent-free91 and hydrothermal89,122 technologies represent significant advances in the facile and green synthesis of POPs. 9097


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Figure 34. (a) Concept of heterogeneous concerted catalysis between active sites on porous materials with the use of highly flexible linear polymers and (b) schematic of PPS⊂COF-TpBpy-Cu synthesis and structures of COF-TpBpy and PPS⊂COF-TpBpy-Cu. Reprinted with permission from ref 126. Copyright 2016 American Chemical Society. (4) MacDowell, N.; Florin, N.; Buchard, A.; Hallett, J.; Galindo, A.; Jackson, G.; Adjiman, C. S.; Williams, C. K.; Shah, N.; Fennell, P. An overview of CO2 capture technologies. Energy Environ. Sci. 2010, 3, 1645−1669. (5) Rao, A. B.; Rubin, E. S. A technical, economic, and environmental assessment of amine-based CO2 capture technology for power plant greenhouse gas control. Environ. Sci. Technol. 2002, 36, 4467−4475. (6) North, M.; Pasquale, R.; Young, C. Synthesis of cyclic carbonates from epoxides and CO2. Green Chem. 2010, 12, 1514−1539. (7) Darensbourg, D. J.; Holtcamp, M. W. Catalysts for the reactions of epoxides and carbon dioxide. Coord. Chem. Rev. 1996, 153, 155− 174. (8) Liu, J.; Guo, C.; Zhang, Z.; Jiang, T.; Liu, H.; Song, J.; Fan, H.; Han, B. Synthesis of dimethylformamide from CO2, H2 and dimethylamine over Cu/ZnO. Chem. Commun. 2010, 46, 5770−5572. (9) Bi, Q. Y.; Lin, J. D.; Liu, Y. M.; Xie, S. H.; He, H. Y.; Cao, Y. Partially reduced iridium oxide clusters dispersed on titania as efficient catalysts for facile synthesis of dimethylformamide from CO2, H2 and dimethylamine. Chem. Commun. 2014, 50, 9138−9140. (10) Cui, X.; Zhang, Y.; Deng, Y.; Shi, F. Amine formylation via carbon dioxide recycling catalyzed by a simple and efficient heterogeneous palladium catalyst. Chem. Commun. 2014, 50, 189− 191. (11) Federsel, C.; Jackstell, R.; Beller, M. State-of-the-art catalysts for hydrogenation of carbon dioxide. Angew. Chem., Int. Ed. 2010, 49, 6254−6257. (12) Zhang, Z.; Xie, Y.; Li, W.; Hu, S.; Song, J.; Jiang, T.; Han, B. Hydrogenation of carbon dioxide is promoted by a task-specific ionic liquid. Angew. Chem., Int. Ed. 2008, 47, 1127−1129. (13) Shi, F.; Deng, Y.; SiMa, T.; Peng, J.; Gu, Y.; Qiao, B. Alternatives to phosgene and carbon monoxide: synthesis of symmetric urea derivatives with carbon dioxide in ionic liquids. Angew. Chem., Int. Ed. 2003, 42, 3257−3260. (14) Jiang, T.; Ma, X.; Zhou, Y.; Liang, S.; Zhang, J.; Han, B. Solvent-free synthesis of substituted ureas from CO2 and amines with a functional ionic liquid as the catalyst. Green Chem. 2008, 10, 465− 469. (15) Li, J.; Guo, X.; Wang, L.; Ma, X.; Zhang, Q.; Shi, F.; Deng, Y. Co(acac)3/BMMImCl as a base-free catalyst system for clean syntheses of N,N′-disubstituted ureas from amines and CO2. Sci. China Chem. 2010, 53, 1534−1540. (16) Beydoun, K.; vom Stein, T.; Klankermayer, J.; Leitner, W. Ruthenium-catalyzed direct methylation of primary and secondary aromatic amines using carbon dioxide and molecular hydrogen. Angew. Chem., Int. Ed. 2013, 52, 9554−9557.

POPs capable of effectively catalyzing the conversion of CO2 from dilute sources, with enhanced stabilities under industrial conditions, which are easily synthesized from low-cost reagents by simple methods. The establishment of structure−property relationships for the catalytic activity of POPs is also an urgent task to provide guidance for the rational design and synthesis of catalysts. Overall, the application of POP-based heterogeneous catalysts for CO2 conversion is still in its infancy, and extensive work is required to promote the industrial application of POPs for catalytic CO2 conversion.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail for K.H.: [email protected]. *E-mail for F.L.: [email protected]. ORCID

Kuan Huang: 0000-0003-1905-3017 Fujian Liu: 0000-0002-6694-582X Sheng Dai: 0000-0002-8046-3931 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS F.L. acknowledges the financial support of the National Natural Science Foundation of China (Nos. 21573150 and 21203122), Natural Science Foundation of Zhejiang Province (LY15B030002). K.H. acknowledges sponsorship from the Natural Science Foundation of Jiangxi Province (No.20171BAB203019) and Nanchang University. S.D. was supported by U.S. Department of Energy, Office of Science, Chemical Sciences, Geosciences and Biosciences Division.

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Synthesis of Porous Polymeric Catalysts for the Conversion of Carbon

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