Synthesis of Porous Polymeric Catalysts for the Conversion of Carbon Dioxide

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.

Facile synthesis of crystalline viologen-based porous ionic polymers with hydrogen-bonded water for efficient catalytic CO2 fixation under ambient conditions

“…6,7 In particular, ionic moieties of halogen-based PIPs have strong dipole quadrupole interactions with CO 2 , which endow intrinsic CO 2 -philicity for PIPs, while the specic halogen anions can be used as active nucleophiles for catalytic conversion of CO 2 . 8,9 Further, a lot of ionic liquids (ILs) or IL-like structures in the solid polymers have intrinsic hydrophilicity, which can chemically absorb water molecules nearby ionic moieties via hydrogen bond interactions between water and halogen anions (such as Cl À and Br À ). [10][11][12][13] It was reported that a suitable amount of water can be regarded as hydrogen bond donors (HBD) co-catalysts for enhancing the coupling of CO 2 /epoxide by forming H-bonds with the oxygen atom of epoxides.…”

Imidazolium‐Functionalized Ionic Hypercrosslinked Porous Polymers for Efficient Synthesis of Cyclic Carbonates from Simulated Flue Gas

“…Carbon dioxide (CO 2 ) is a typical greenhouse gas responsible for global warming, and, moreover, an easily available and renewable C 1 feedstock for synthetic chemistry . From this point of view, chemical CO 2 fixation into high value‐added chemicals is of great potential to alleviate the continuously worsening environmental concerns and dwindling of resources such as fossil fuels . In this context, CO 2 cycloaddition with high‐energy compounds such as epoxides has attracted growing attention because of the ability to overcome the thermodynamic barrier of inert CO 2 , and the products, such as cyclic carbonates, are valuable solvents and intermediates in industry .…”

“…Azo‐polymer‐supported ZnBr 2 exhibited a synergistic effect between metal salt and support in the cycloaddition of CO 2 /N 2 mixtures with various epoxides by using the organic nucleophile TBAB and ethanol as solvent . Compared with the homogeneous analogues, heterogeneous catalysts are advantageous for facile operation, separation, and recycling . However, additives are usually involved in many systems for the capture and conversion of diluted CO 2 by coupling with epoxides .…”

Constructing Mononuclear Palladium Catalysts by Precoordination/Solvothermal Polymerization: Recyclable Catalyst for Regioselective Oxidative Heck Reactions

“…Porous organic polymers (POPs) have remained a perennial focus as an intriguing platform for incorporating homogeneous metal/ligand catalytic systems into heterogeneous supports . In our previous work, we demonstrated the advantages of phosphorus‐doped (P‐doped) POPs in catalytic regioselective and chemoselective reactions, and as an effective metal support for a single‐site catalyst.…”