Decorating pore environment via cationic units of covalent organic frameworks for enhancing CO₂ reduction reaction

Abstract

The conversion performance for electrocatalytic CO₂ reduction reaction (CO₂RR) relies on the affinity of CO₂ molecules. Ionic covalent organic frameworks (COFs) are promising platforms for CO₂RR due to the accessible catalytic sites in the skeleton, high CO₂ combination ability and the electronic conductivity. However, most ionic COFs are constructed via pre-functionalization of the monomers or post-modification of the skeleton, encountering incomplete loading or uneven distribution of the active sites. In this work, a cationic porphyrin-based COF using the (3-carboxypropyl)trimethylammonium and Co-porphyrin units is developed through the sub-stoichiometric bottom-up synthesis method to fine-tune the pore environment for modulating the binding ability of CO₂. Compared to base COFs, the cationic COFs exhibit improved electronic conductivity, high CO₂ adsorption uptakes and enhanced reducibility, further improving the electrocatalytic CO₂RR performance. Notably, the cationic COF achieves a high CO selectivity of 93% and a partial current density of 24.6 mA·cm^-2. This work not only offers considerable insights for improving the catalytic performance of COFs through the cationic groups but also provides a stoichiometry method to modulate the pore environment.

Keywords

Covalent organic frameworks / CO₂ reduction reaction / modification strategy / cationic skeleton / CO₂ adsorption

References

[1] Chen Q,Zhou Y.Electrocatalytic CO₂ reduction to C₂₊ products in flow cells.Adv Mater2024;36:e2303902

[2] Lai W,Zhang J,Huang H.Design strategies for markedly enhancing energy efficiency in the electrocatalytic CO₂ reduction reaction.Energy Environ Sci2022;15:3603-29

[3] Li X,Jaroniec M.Cocatalysts for selective photoreduction of CO₂ into solar fuels.Chem Rev2019;119:3962-4179

[4] Lu M,Liu J.Covalent organic framework based functional materials: important catalysts for efficient CO₂ utilization.Angew Chem Int Ed Engl2022;61:e202200003

[5] Ma W,Wang W,Zhang Q.Electrocatalytic reduction of CO₂ and CO to multi-carbon compounds over Cu-based catalysts.Chem Soc Rev2021;50:12897-914

[6] Xiao C.Architectural design for enhanced C₂ product selectivity in electrochemical CO₂ reduction using Cu-based catalysts: a review.ACS Nano2021;15:7975-8000

[7] Xie C,Kim D,Yang P.Surface and interface control in nanoparticle catalysis.Chem Rev2020;120:1184-249

[8] Yang PP.Enrichment of reactants and intermediates for electrocatalytic CO₂ reduction.Chem Soc Rev2023;52:4343-80

[9] Zhang X,Li H.Insight into heterogeneous electrocatalyst design understanding for the reduction of carbon dioxide.Adv Energy Mater2022;12:2201461

[10] Zhang Z,Chen Z.Membrane electrode assembly for electrocatalytic CO₂ reduction: principle and application.Angew Chem Int Ed Engl2023;62:e202302789

[11] Guo L,Li M,Song Y.Covalent organic frameworks for fluorescent sensing: recent developments and future challenges.Coord Chem Rev2021;440:213957

[12] Haug WK,Wolfson ER.The luminescent and photophysical properties of covalent organic frameworks.Chem Soc Rev2020;49:839-64

[13] Jin E,Xu Q.Two-dimensional sp² carbon-conjugated covalent organic frameworks.Science2017;357:673-6

[14] Li Z,Wang H.Three-dimensional covalent organic framework with ceq topology.J Am Chem Soc2021;143:92-6

[15] Weng W.Chiral covalent organic framework films with enhanced photoelectrical performances.J Am Chem Soc2024;146:13201-9

[16] Liu L,Tong Y.Imidazole-linked fully conjugated covalent organic framework for high-performance sodium-ion battery.CCS Chem2024;6:1255-63

[17] Sun C,Wang B.Covalent organic frameworks for extracting water from air.Angew Chem Int Ed Engl2023;62:e202303378

[18] Xu X,Xu K,Chen H.Pore partition in two-dimensional covalent organic frameworks.Nat Commun2023;14:3360 PMCID:PMC10250421

[19] Yaghi OM.Reticular chemistry in all dimensions.ACS Cent Sci2019;5:1295-300 PMCID:PMC6820066

[20] Zhou T,Huang X.PEG-stabilized coaxial stacking of two-dimensional covalent organic frameworks for enhanced photocatalytic hydrogen evolution.Nat Commun2021;12:3934 PMCID:PMC8225615

[21] Li Z,Ma S.Three-component donor-π-acceptor covalent-organic frameworks for boosting photocatalytic hydrogen evolution.J Am Chem Soc2023:8364-74

[22] Lin Z,Weng W,Guo J.Photostimulated covalent linkage transformation isomerizing covalent organic frameworks for improved photocatalytic performances.Small2024;20:e2307138

[23] Liu M,Bi S.Dimensionally-controlled interlayer spaces of covalent organic frameworks for the oxygen evolution reaction.Chem Eng J2024;479:147682

[24] Zhang Y,Jiao L,Jiang HL.Conductive covalent organic frameworks of polymetallophthalocyanines as a tunable platform for electrocatalysis.J Am Chem Soc2023;145:24230-9

[25] Zhu HJ,Wang YR.Efficient electron transmission in covalent organic framework nanosheets for highly active electrocatalytic carbon dioxide reduction.Nat Commun2020;11:497 PMCID:PMC6981265

[26] Pan Y,Nairan A.Constructing FeNiPt@C trifunctional catalyst by high spin-induced water oxidation activity for Zn-Air battery and anion exchange membrane water electrolyzer.Adv Sci2024;11:e2308205 PMCID:PMC11109642

[27] Lin S,Zhang YB.Covalent organic frameworks comprising cobalt porphyrins for catalytic CO₂ reduction in water.Science2015;349:1208-13

[28] Han B,Chen B.Maximizing electroactive sites in a three-dimensional covalent organic framework for significantly improved carbon dioxide reduction electrocatalysis.Angew Chem Int Ed Engl2022;61:e202114244

[29] Yue Y,Xu K.Stable bimetallic polyphthalocyanine covalent organic frameworks as superior electrocatalysts.J Am Chem Soc2021;143:18052-60

[30] Liu M,Zeng G.Ionic covalent organic frameworks in adsorption and catalysis.Angew Chem Int Ed Engl2024;63:e202404886

[31] Zhang Q,Shao P.Covalent organic framework-based porous ionomers for high-performance fuel cells.Science2022;378:181-6

[32] Zhang M,Li RH.Green synthesis of bifunctional phthalocyanine-porphyrin cofs in water for efficient electrocatalytic CO₂ reduction coupled with methanol oxidation.Natl Sci Rev2023;10:nwad226 PMCID:PMC10561706

[33] Song Y,Dou Y.Atomically thin, ionic-covalent organic nanosheets for stable, high-performance carbon dioxide electroreduction.Adv Mater2022;34:e2110496

[34] Baker Cortés BD,Küster K.Structural transformation of surface-confined porphyrin networks by addition of Co atoms.Chemistry2021;27:12430-6 PMCID:PMC8456947

[35] Yao N,Jia H.Intermolecular energy gap-induced formation of high-valent cobalt species in CoOOH surface layer on cobalt sulfides for efficient water oxidation.Angew Chem Int Ed Engl2022;61:e202117178

[36] Yang D,He T.Visible-light-switched electron transfer over single porphyrin-metal atom center for highly selective electroreduction of carbon dioxide.Nat Commun2019;10:3844 PMCID:PMC6710284

[37] Huang Q,Li XF.Demystifying the roles of single metal site and cluster in CO₂ reduction via light and electric dual-responsive polyoxometalate-based metal-organic frameworks.Sci Adv2022;8:eadd5598 PMCID:PMC9733922

[38] Li N,Wu QJ,Huang YB.Boosting electrocatalytic CO₂ reduction with conjugated bimetallic Co/Zn polyphthalocyanine frameworks.CCS Chem2023;5:1130-43

[39] Liu M. Rational design of functional covalent organic frameworks for the oxygen and Carbon Dioxide reduction reactions. PhD thesis, University of Nottingham Ningbo China (UNNC), 2024. Available from: https://research.nottingham.edu.cn/en/studentTheses/rational-design-of-functional-covalent-organic-frameworks-for-the. [Last accessed on 9 Aug 2024]