Systematic review of covalent organic frameworks for photocatalytic/electrocatalytic CO₂ reduction: From structural engineering to mechanistic insights

Abstract

The rapid increase in atmospheric CO₂ levels driven by fossil fuel combustion has exacerbated environmental crises worldwide. Efficient CO₂ capture and conversion have therefore become indispensable toward achieving carbon neutrality. Photocatalytic/electrocatalytic CO₂ reduction reactions (peCO₂RR) powered by renewable energy is a promising strategy for converting CO₂ into high-value chemicals and fuels. However, this process is hindered by the intrinsic limitations of traditional catalysts. As emerging crystalline porous polymers, covalent organic frameworks (COFs) offer distinct advantages for the peCO₂RR, including tunable topological structures, atomically precise active site design, large specific surface areas, and excellent chemical stabilities, which address the inherent limitations of conventional catalytic materials. This review systematically summarizes recent advances in COF-based peCO₂RR by exploring the intrinsic correlation between structural engineering and catalytic performance. Herein, we discuss the precise design of two-dimensional (2D)/three-dimensional (3D) crystalline pore structures, green synthetic strategies, and diverse functionalization routes. A comprehensive analysis of multimodal catalytic mechanisms, including photocatalysis, electrocatalysis, and their synergistic effects, is provided. Furthermore, we focus on the orientation of synthesis towards C1 and C2 products and clarify the core structural factors responsible for governing the product selectivity. The critical roles of theoretical simulations and in-situ /operando characterization techniques in uncovering catalytic pathways and the evolution of intermediates are also highlighted. Finally, we discuss the key challenges presented by COF-based systems in terms of their structural robustness, catalytic selectivity, scalable preparation, and device integration, and propose targeted prospects for rational design and practical applications. By moving beyond traditional laboratory metrics, this review aims to establish a comprehensive structure–property–performance roadmap that offers fundamental design principles to bridge the gap between molecular-level engineering and industrial-scale applications, thereby accelerating the deployment of COF-based technologies in the drive toward global carbon neutrality.

Keywords

carbon neutrality / photo/electrocatalytic / covalent organic frameworks / product selectivity / structure–property–performance

References

[1] X. Zhao, X.X. Jia, H.Y. Li, et al., Efficient degradation of Health-threatening organic pollutants in water by atomically dispersed Cobalt-Activated peroxymonosulfate, Chem. Eng. J., 450(2022), art. No. 138098.

[2] Guo XX, Zhang HR, Su Y, Zhou YT. Recent trends in CO₂ reduction through various catalytic methods to achieve carbon-neutral goals: A comprehensive bibliometric analysis. Front. Energy, 2025, 194500.

[3] J. He, X.D. Wang, P.J. Feng, et al., Isostructural phase transition-induced piezoelectricity in all-inorganic perovskite CsPb-Br₃ for catalytic CO₂ reduction, Appl. Catal. B: Environ. Energy, 355(2024), art. No. 124186.

[4] Li CJ, He J, Cai TL, et al. Surface oxygen vacancies of BiOBr regulating piezoelectricity for enhancing efficiency and selectivity of photocatalytic CO₂ reduction. Chin. J. Catal., 2025, 74: 130.

[5] H. Li, C.L. Gao, G. Yang, et al., Enhanced photocatalytic CO₂ reduction of Bi₂WO₆-BiOCl heterostructure with coherent interface for charge utilization, Chin. Chem. Lett., 36(2025), No. 9, art. No. 110547.

[6] Liang Q, Fan JS, Ding JW, et al. Concerted proton-coupled electron transfer by Mo⁵⁺/Mo⁶⁺ reversible transformation for CO₂ photoreduction with nearly 100% CH₄ selectivity. ACS Catal., 2024, 142217191.

[7] Tao HC, Jia TB, Zhang LN, et al. Tandem effect at snowflake-like cuprous sulphide interfaces for highly selective conversion of carbon dioxide to formate by electrochemical reduction. J. Colloid Interface Sci., 2024, 655: 909.

[8] Guo C, Gao SS, Li J, et al. P-tuned FeN₂ binuclear sites for boosted CO₂ electro-reduction. J. Energy Chem., 2025, 101: 816.

[9] T.B. Jia, L.L. Wang, Z.H. Zhu, et al., Modulating the degree of O vacancy defects to achieve selective control of electrochemical CO₂ reduction products, Chin. Chem. Lett., 35(2024), No. 5, art. No. 108692.

[10] X. Jiang, R. Chen, Y.X. Chen, and C.Z. Lu, Research progress of photoelectrochemical conversion of CO₂ to C₂₊ products, Chem. Synth., 4(2024), art. No. 46.

[11] Wang XY, Jan S, Wang ZY, Jin XB. Solid Bi₂O₃-derived nanostructured metallic bismuth with high formate selectivity for the electrocatalytic reduction of CO₂. Int. J. Miner., Metall. Mater., 2024, 314803.

[12] Q.Y. Yan, W. Wen, L.W. Qiang, et al., Advanced progress in constructing carbon-coated metal materials for electrocatalytic CO₂ reduction, J. Alloy. Compd., 1003(2024), art. No. 175705.

[13] Li JL, Zhang W, Peng YD, et al. MOFs-based single/dual-atom catalysts: Atomically active sites engineering for efficient CO₂ reduction. Chem. Synth., 2025, 5469.

[14] T.B. Jia, L.L. Wang, L.N. Zhang, et al., Engineering vacancy and hydrophobicity of spherical coral-like CuO catalyst for effective electrochemical CO₂ reduction to ethylene, Surf. Interfaces, 38(2023), art. No. 102841.

[15] Rodriguez AG, Chen ZY, Pant D, Dendooven J. Effect of catalyst ink preparation on formate production from CO₂ electroreduction using Sn as electrocatalyst. Int. J. Miner., Metall. Mater., 2025, 3292270.

[16] M.H. Liu, G.J. Liu, Q. Xu, and G. Zeng, Decorating pore environment via cationic units of covalent organic frameworks for enhancing CO₂ reduction reaction, Chem. Synth., 5(2025), art. No. 17.

[17] Wei RJ, Luo X, Ning GH, Li D. Covalent metal-organic frameworks: Fusion of covalent organic frameworks and metal-organic frameworks. Acc. Chem. Res., 2025, 585746.

[18] L.J. Wang, S.Q. Wu, and J.L. Zhang, Spin polarization effect enhances photocatalytic CO₂ reduction, Chem. Synth., 5(2025), art. No. 46.

[19] S. Raghav, J. Raghav, M.A. Muhammad, M.B. Singh, P. Jain, and D. Kumar, Recent advancements in synthesis and applications of covalent organic frameworks, Appl. Mater. Today, 44(2025), art. No. 102694.

[20] Côté AP, Benin AI, Ockwig NW, O’Keeffe M, Matzger AJ, Yaghi OM. Porous, crystalline, covalent organic frameworks. Science, 2005, 31057511166.

[21] El-Kaderi HM, Hunt JR, Mendoza-Cortés JL, et al. Designed synthesis of 3D covalent organic frameworks. Science, 2007, 3165822268.

[22] DeBlase CR, Silberstein KE, Truong TT, Abruña HD, Dichtel WR. β-ketoenamine-linked covalent organic frameworks capable of pseudocapacitive energy storage. J. Am. Chem. Soc., 2013, 1354516821.

[23] A. Nagai, Z.Q. Guo, X. Feng, et al., Pore surface engineering in covalent organic frameworks, Nat. Commun., 2(2011), art. No. 536.

[24] Zhuang XD, Zhao WX, Zhang F, et al. A two-dimensional conjugated polymer framework with fully sp²-bonded carbon skeleton. Polym. Chem., 2016, 7254176.

[25] Sick T, Hufnagel AG, Kampmann J, et al. Oriented Films of conjugated 2D covalent organic frameworks as photocathodes for water splitting. J. Am. Chem. Soc., 2018, 14062085.

[26] Zhang B, Wei MF, Mao HY, et al. Crystalline dioxin linked covalent organic frameworks from irreversible reactions. J. Am. Chem. Soc., 2018, 1404012715.

[27] Guan XY, Li H, Ma YC, et al. Chemically stable polyarylether-based covalent organic frameworks. Nat. Chem., 2019, 116587.

[28] F.L. Zhang, X.M. Ma, X.Y. Dong, X. Miao, and X.J. Lang, Inserting acetylene into an olefin-linked covalent organic framework for boosting the selective photocatalytic aerobic oxidation of sulfides, Chem. Eng. J., 451(2023), art. No. 138802.

[29] H.J. Hu, X.D. Sun, H. Li, et al., Construction of 2D/2D Pd metallene/COFs system with strong internal electric field for outstanding solar energy photocatalysis, Small, 21(2025), No. 2, art. No. 2407117.

[30] Ritchie LK, Trewin A, Reguera-Galan A, Hasell T, Cooper AI. Synthesis of COF-5 using microwave irradiation and conventional solvothermal routes. Microporous Mesoporous Mater., 2010, 1321–2132.

[31] Xu H, Tao SS, Jiang DL. Proton conduction in crystalline and porous covalent organic frameworks. Nat. Mater., 2016, 15: 722.

[32] X. Li, S.X. Yang, F.L. Zhang, L.Y. Zheng, and X.J. Lang, Facile synthesis of 2D covalent organic frameworks for cooperative photocatalysis with TEMPO: The selective aerobic oxidation of benzyl amines, Appl. Catal. B, 303(2022), art. No. 120846.

[33] Xie ZP, Yang XB, Zhang P, et al. Vinylene-linked covalent organic frameworks with manipulated electronic structures for efficient solar-driven photocatalytic hydrogen production. Chin. J. Catal., 2023, 47: 171.

[34] Li CZ, Ma YH, Liu HR, et al. Asymmetric photocatalysis over robust covalent organic frameworks with tetrahydroquinoline linkage. Chin. J. Catal., 2020, 4181288.

[35] Hu YX, Abazari R, Sanati S, et al. A dual-purpose Ce (III)-organic framework with amine groups and open metal sites: Third-order nonlinear optical activity and catalytic CO₂ fixation. ACS Appl. Mater. Interfaces, 2023, 153137300.

[36] X.Z. Deng, Y. Ke, J.W. Ding, et al., Construction of ZnO@CDs@Co₃O₄ sandwich heterostructure with multi-interfacial electron-transfer toward enhanced photocatalytic CO₂ reduction, Chin. Chem. Lett., 35(2024), No. 4, art. No. 109064.

[37] S.Q. Jia, M.K. Dong, Q.G. Zhu, X.C. Kang, H.H. Wu, and B.X. Han, Electrochemical conversion of CO₂ via C–X bond formation: Recent progress and perspective, Chem. Synth., 4(2024), art. No. 60.

[38] Bai XJ, Liu RJ, Zhu BW, et al. Advancements in controlling COFs structure for enhanced crystallization properties and self-generated photocatalytic hydrogen peroxide. CrystEngComm, 2024, 26243143.

[39] Zheng LP, Fang C, Chen ZH, et al. Advancing CO₂ conversion: integrated use of dual active catalytic sites in flexible, porous polymeric porphyrin and ionic liquid composite networks. Chem. Synth., 2026, 6112.

[40] H.P. Wang, X. Wang, Y.P. Jiang, et al., Application of COF materials in carbon dioxide electrocatalytic reduction, Chem. Rec., 25(2025), No. 5, art. No. e202400244.

[41] Zhang WY, Liu SW, Sun QH, Tian N, Wu ZF. Synthesis of covalent organic framework materials and their application in the field of sensing. Nano Res., 2024, 171162.

[42] A. Ebadi Amooghin, H. Sanaeepur, M. Ghomi, R. Luque, H. Garcia, and B.L. Chen, Flexible–robust MOFs/HOFs for challenging gas separations, Coord. Chem. Rev., 505(2024), art. No. 215660.

[43] Y.T. Zhou, R. Abazari, J. Chen, et al., Bimetallic metal–organic frameworks and MOF-derived composites: Recent progress on electro- and photoelectrocatalytic applications, Coord. Chem. Rev., 451(2022), art. No. 214264.

[44] K.M. Li, Y.L. Su, S.H. Sun, et al., Efficient crystallization of conjugated microporous polymers to boost photocatalytic CO₂ reduction, Carbon Energy, 7(2025), No. 9, art. No. e70025.

[45] Wang ZF, Zhang YS, Liu JJ, Chen Y, Cheng P, Zhang ZJ. Flux synthesis of two-dimensional covalent organic frameworks. Nat. Protoc., 2024, 19123489.

[46] Y.H. Mo, Y.L. Chen, H.F. Zhang, et al., Ether-oxygen based covalent organic frameworks: A new cognitive guide, Coord. Chem. Rev., 556(2026), art. No. 217632.

[47] N. Huang, P. Wang, and D.L. Jiang, Covalent organic frameworks: A materials platform for structural and functional designs, Nat. Rev. Mater., 1(2016), No. 10, art. No. 16068.

[48] C.S. Diercks and O.M. Yaghi, The atom, the molecule, and the covalent organic framework, Science, 355(2017), No. 6328, art. No. eaal1585.

[49] Yang X, Xie Z, Zhang T, et al. Direct pore engineering of 2D imine covalent organic frameworks via sub-stoichiometric synthesis. Sci. China Chem., 2022, 65: 190.

[50] Geng KY, He T, Liu RY, et al. Covalent organic frameworks: Design, synthesis, and functions. Chem. Rev., 2020, 120168814.

[51] Feng X, Liang XF, Li XX, et al. Improving the response of 2D COFs to the surface doping strategies through rational design of their chemical structure. Sci. China Mater., 2024, 67103272.

[52] Lu M, Zhang M, Liu CG, et al. Stable dioxin-linked metallophthalocyanine covalent organic frameworks (COFs) as photo-coupled electrocatalysts for CO2 reduction. Angew. Chem. Int. Ed., 2021, 6094864.

[53] S. Patial, V. Soni, A. Kumar, et al., Rational design, structure properties, and synthesis strategies of dual-pore covalent organic frameworks (COFs) for potent applications: A review, Environ. Res., 218(2023), art. No. 114982.

[54] S. Xue, X.F. Ma, Y.F. Wang, et al., Advanced development of three-dimensional covalent organic frameworks: Valency design, functionalization, and applications, Coord. Chem. Rev., 504(2024), art. No. 215659.

[55] Wu MM, Shan Z, Wang JJ, et al. Three-dimensional covalent organic frameworks based on a π-conjugated tetrahedral node. Chem. Commun., 2021, 578010379.

[56] H.R. Abuzeid, A.F.M. EL-Mahdy, and S.W. Kuo, Covalent organic frameworks: Design principles, synthetic strategies, and diverse applications, Giant, 6(2021), art. No. 100054.

[57] R. Shah, S. Ali, F. Raziq, et al., Exploration of metal organic frameworks and covalent organic frameworks for energy-related applications, Coord. Chem. Rev., 477(2023), art. No. 214968.

[58] Zhao XJ, Pachfule P, Thomas A. Covalent organic frameworks (COFs) for electrochemical applications. Chem. Soc. Rev., 2021, 50126871.

[59] Fang QR, Wang JH, Gu S, et al. 3D porous crystalline polyimide covalent organic frameworks for drug delivery. J. Am. Chem. Soc., 2015, 137268352.

[60] Ma WD, Zheng Q, He YT, et al. Size-controllable synthesis of uniform spherical covalent organic frameworks at room temperature for highly efficient and selective enrichment of hydrophobic peptides. J. Am. Chem. Soc., 2019, 1414518271.

[61] Zou CC, Li QQ, Hua YY, Zhou BH, Duan JG, Jin WQ. Mechanical synthesis of COF nanosheet cluster and its mixed matrix membrane for efficient CO2 removal. ACS Appl. Mater. Interfaces, 2017, 93429093.

[62] W.M. Zhang, Z.Y. Wang, and L. Zhang, Interface-assisted synthesized covalent organic framework film for efficient extraction of microcystins in aquatic organisms, Talanta, 282(2025), art. No. 127051.

[63] Peng P, Shi L, Huo F, et al. In situ charge exfoliated soluble covalent organic framework directly used for Zn-air flow battery. ACS Nano, 2019, 131878.

[64] Zhao YB, Guo L, Gándara F, et al. A synthetic route for crystals of woven structures, uniform nanocrystals, and thin films of imine covalent organic frameworks. J. Am. Chem. Soc., 2017, 1393713166.

[65] S. Kim, C. Park, M. Lee, et al., Rapid photochemical synthesis of sea-urchin-shaped hierarchical porous COF - 5 and its lithography-free patterned growth, Adv. Funct. Mater., 27(2017), No. 32, art. No. 1700925.

[66] C. Harrod, Z. Alsudairy, Q. Zheng, et al., Sustainable synthesis of palladium-immobilized covalent organic frameworks: A one-step sonochemical strategy, Adv. Sustainable Syst., 9(2025), No. 2, art. No. 2400700.

[67] Zhang XZ, Xue SH, Yan YJ, Liu SJ, Ye Q, Zhou F. Mechanochemical synthesis of thiadiazole functionalized COF as oil-based lubricant additive for reducing friction and wear. Langmuir, 2024, 4084373.

[68] P. Borah, S. Roy, and M. Ahmaruzzaman, The fusion of metalorganic framework (MOF) and covalent organic framework (COF): A synergistic leap toward bridging boundaries in catalytic, sensing, and biomedical frontiers, Adv. Colloid Interface Sci., 344(2025), art. No. 103613.

[69] Côté AP, El-Kaderi HM, Furukawa H, Hunt JR, Yaghi OM. Reticular synthesis of microporous and mesoporous 2D covalent organic frameworks. J. Am. Chem. Soc., 2007, 1294312914.

[70] B.C. Zhang, H. Zheng, K.M. Yang, et al., Bottom-up synthesis of a sulfhydryl-modified heteroporous covalent organic framework for ultrafast removal of trace Hg(II) from water, Chemosphere, 360(2024), art. No. 142410.

[71] W.J. Zhao, C.Y. Yu, J. Zhao, et al., 3D hydrazone-functionalized covalent organic frameworks as pH-triggered rotary switches, Small, 17(2021), No. 41, art. No. 2102630.

[72] Gu YY, Wang JX, Tang QQ, et al. Insights into substituent effects on the fundamental photocatalytic processes of covalent organic frameworks toward H₂ evolution and H₂O₂ production reactions. ACS Catal., 2024, 141511262.

[73] Bunck DN, Dichtel WR. Postsynthetic functionalization of 3D covalent organic frameworks. Chem. Commun., 2013, 49242457.

[74] Liu Y, Chi HB, Tan YF, Chen ZG, He Y. Guest-induced structural torsion in single covalent organic frameworks for enhanced photocatalysis. Nano Lett., 2025, 252911365.

[75] Lin S, Diercks CS, Zhang YB, et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO₂ reduction in water. Science, 2015, 34962531208.

[76] C.I. Yeo, Y.S. Tan, H.T.A. Awan, et al., A review on the advancements in covalent organic frameworks for photocatalytic reduction of carbon dioxide, Coord. Chem. Rev., 521(2024), art. No. 216167.

[77] X.B. Yang, Q. Xu, W. Wei, and G.F. Zeng, Linkage chemistry of covalent organic frameworks in photocatalysis and electrocatalysis, Angew. Chem. Int. Ed., 64(2025), No. 23, art. No. e202504355.

[78] N. Mushtaq, A. Ahmad, X.S. Wang, U. Khan, and J.K. Gao, MOFs/COFs hybrids as next-generation materials for electrocatalytic CO₂ reduction reaction, Chem. Eng. J., 486(2024), art. No. 150098.

[79] Li XJ, Yu XH, Yu Q. Research progress on electrochemical CO₂ reduction for Cu-based single-atom catalysts. Sci. China Mater., 2023, 66103765.

[80] Rahman MZ, Kibria MG, Mullins CB. Metal-free photocatalysts for hydrogen evolution. Chem. Soc. Rev., 2020, 4961887.

[81] Chen YX, Luo X, Zhang JJ, et al. Bandgap engineering of covalent organic frameworks for boosting photocatalytic hydrogen evolution from water. J. Mater. Chem. A, 2022, 104624620.

[82] Q. Yang, M.L. Luo, K.W. Liu, H.M. Cao, and H.J. Yan, Covalent organic frameworks for photocatalytic applications, Appl. Catal. B, 276(2020), art. No. 119174.

[83] Chen Q, Wang YJ, Luo GS. Photoenzymatic CO₂ reduction dominated by collaborative matching of linkage and linker in covalent organic frameworks. J. Am. Chem. Soc., 2024, 1461586.

[84] Yin Y, Zhang Y, Zhou X, et al. Ultrahigh-surface area covalent organic frameworks for methane adsorption. Science, 2024, 3866722693.

[85] Yu BQ, Tao Y, Yao X, et al. Single-crystalline 3D covalent organic frameworks with exceptionally high specific surface areas and gas storage capacities. J. Am. Chem. Soc., 2024, 1464228932.

[86] Chen RF, Shi JL, Ma Y, Lin GQ, Lang XJ, Wang C. Designed synthesis of a 2D porphyrin-based sp² carbon-conjugated covalent organic framework for heterogeneous photocatalysis. Angew. Chem. Int. Ed., 2019, 58196430.

[87] Shi T, Wang H, Li L, et al. Enhanced photostability in protonated covalent organic frameworks for singlet oxygen generation. Matter, 2022, 531004.

[88] H.L. Jia, B.H. Zhu, X.Y. Zhi, et al., Terephthalaldehyde-based covalent organic frameworks as photocatalysts for CO₂ reduction under visible light, FlatChem, 38(2023), art. No. 100492.

[89] M.F. Yu, W. Chen, Q.Q. Lin, et al., Electrostatic confinement-induced excited charge transfer in ionic covalent organic framework promoting CO₂ reduction, Angew. Chem. Int. Ed., 64(2025), No. 6, art. No. e202418422.

[90] A.M. Huang, T. Zhou, J.J. Zhang, et al., Competing CO and HCOOH pathways in CO₂ electroreduction, ChemCatChem, 16(2024), No. 17, art. No. e202400504.

[91] W.J. Li, F. Ma, B.M. Aramburu-Trošelj, J.W. Wang, and G.F. Ouyang, Molecular hybrid photocatalysts for CO₂ photoreduction by hybridization of molecular catalysts and photoactive covalent organic frameworks—A review, Chem. Eur. J., 31(2025), No. 31, art. No. e202404388.

[92] Zhang XL, Liang XM, Xu DH, Jiang WJ, Li LC. Study on the structural properties and CO2 reduction mechanism of Cu13 nanoparticles supported on carbon nanotubes and defective graphene. New J. Chem., 2025, 494820817.

[93] Y. Li, L.Y. Wang, D.Q. Fan, Z.L. Li, C.X. Zhao, and X.F. Yang, Enhanced photocatalytic reduction of CO2 to complete CO mediated by donor–acceptor covalent organic frameworks, Energy Environ. Mater., 9(2026), No. 2, art. No. e70150.

[94] Lei K, Wang D, Ye LQ, et al. A metal-free donor–acceptor covalent organic framework photocatalyst for visible-light-driven reduction of CO₂ with H₂O. ChemSusChem, 2020, 1371725.

[95] Lv HW, Sa RJ, Li PY, Yuan DQ, Wang XC, Wang RH. Metalloporphyrin-based covalent organic frameworks composed of the electron donor-acceptor dyads for visible-light-driven selective CO₂ reduction. Sci. China Chem., 2020, 6391289.

[96] Rahimi FA, Dey S, Verma P, Maji TK. Photocatalytic CO2 reduction based on a Re(I)-integrated conjugated micro-porous polymer: Role of a sacrificial electron donor in product selectivity and efficiency. ACS Catal., 2023, 1395969.

[97] W. Geng, Y.Y. Xiong, C.X. Chen, et al., Ternary metalation in a copper-covalent organic framework for tandem photocatalytic CO₂ reduction with high selectivity, Angew. Chem. Int. Ed., 64(2025), No. 25, art. No. e202505546.

[98] Fu YH, Zhu XL, Huang L, Zhang XC, Zhang FM, Zhu WD. Azine-based covalent organic frameworks as metalfree visible light photocatalysts for CO₂ reduction with H₂O. Appl. Catal. B, 2018, 239: 46.

[99] Sarkar M, Chakrabortty P, Sengupta M, Kothari AC, Islam MS, Islam SM. Light-mediated sustainable conversion of carbon dioxide to valuable methanol by highly efficient covalent organic framework g-C3N4 composites as a reusable photocatalyst. Ind. Eng. Chem. Res., 2024, 63135573.

[100] Yadav RK, Kumar A, Park NJ, Kong KJ, Baeg JO. A highly efficient covalent organic framework film photocatalyst for selective solar fuel production from CO₂. J. Mater. Chem. A, 2016, 4249413.

[101] W. Che, S.L. Zhao, W.J. Byun, et al., From carbon nitrides to COFs: Opportunities and prospects in photocatalytic CO₂ reduction, Adv. Mater., 37(2025), No. 45, art. No. e06961.

[102] L.T. Ren, X.N. Yang, X. Sun, Y.L. Wang, H.Q. Li, and Y.P. Yuan, Cascaded *CO-*COH intermediates on a nonmetallic plasmonic photocatalyst for CO₂-to-C₂H₆ with 90.6 % selectivity, Angew. Chem., 63(2024), No. 30, art. No. e202404660.

[103] M.P. Kou, W. Liu, Y.Y. Wang, et al., Photocatalytic CO₂ conversion over single-atom MoN2 sites of covalent organic framework, Appl. Catal. B, 291(2021), art. No. 120146.

[104] Huang XY, Xie XJ, Chen YZ, Song T. Modulating order–disorder structures in covalent organic frameworks for photocatalytic CO₂ reduction to propylene. ACS Appl. Polym. Mater., 2025, 7128176.

[105] X.Y. Huang, Y.Z. Chen, X.J. Xie, and T. Song, Covalent organic frameworks with tunable bridge positions for photocatalytic CO₂ reduction to propylene under visible light illumination, Small, 21(2025), No. 6, art. No. 2408817.

[106] F.W. Dagnaw, K. Harrath, T. Zheng, et al., Molecularly woven cationic covalent organic frameworks for highly selective electrocatalytic conversion of CO₂ to CO, Adv. Sci., 11(2024), No. 42, art. No. 2408152.

[107] Luo CY, Zhou Y, Guo YL, Li XM, Li RJ, Peng TY. Cobalt phthalocyanine-based covalent organic framework with bimetallic synergistic effect for efficient photocatalytic CO₂ reduction. ACS Sustainable Chem. Eng., 2024, 125218691.

[108] Liu MH, Zhao XY, Yang S, et al. Modulating the density of catalytic sites in multiple-component covalent organic frameworks for electrocatalytic carbon dioxide reduction. ACS Appl. Mater. Interfaces, 2023, 153744384.

[109] T. Xie, S. Chen, Y. Yue, T. Sheng, N. Huang, and Y.J. Xiong, Biomimetic phthalocyanine-based covalent organic frameworks with tunable pendant groups for electrocatalytic CO₂ reduction, Angew. Chem. Int. Ed., 63(2024), No. 43, art. No. e202411188.

[110] M.H. Liu, S. Yang, Y.B. Fu, et al., Ladder type covalent organic frameworks constructed with natural units for the oxygen and carbon dioxide reduction reactions, Chem. Eng. J., 488(2024), art. No. 150812.

[111] Liu M, Wang YR, Ding HM, et al. Self-assembly of anthraquinone covalent organic frameworks as 1D superstructures for highly efficient CO₂ electroreduction to CH₄. Sci. Bull., 2021, 66161659.

[112] H. Dong, M. Lu, Y. Wang, et al., Covalently anchoring covalent organic framework on carbon nanotubes for highly efficient electrocatalytic CO2 reduction, Appl. Catal. B, 303(2022), art. No. 120897.

[113] M. Zhang, M. Lu, M.Y. Yang, et al., Ultrafine Cu nanoclusters confined within covalent organic frameworks for efficient electroreduction of CO₂ to CH₄ by synergistic strategy, eScience, 3(2023), No. 3, art. No. 100116.

[114] Bhat SS, Rasool A, Dar MA. Single-atom-functionalized covalent organic frameworks for efficient CO₂ conversion: Electronic structure insights from first-principles simulations. J. Phys. Chem. C, 2025, 1293917512

[115] X.B. Yang, X.W. Li, Q.Z. An, et al., Altering electronic states of Cu sites in covalent organic frameworks for synthesis of formate via CO₂ reduction, Chem. Eng. J., 497(2024), art. No. 154636.

[116] S. Ali, R. Iqbal, F. Wahid, et al., Cobalt coordinated two-dimensional covalent organic framework a sustainable and robust electrocatalyst for selective CO2 electrochemical conversion to formic acid, Fuel Process. Technol., 237(2022), art. No. 107451.

[117] R.Z. Yang, L. Xia, W.L. Jiang, et al., Cu-based tandem architectures for CO2 electrolysis to multicarbon products, Adv. Energy Mater., 15(2025), No. 22, art. No. 2405964.

[118] Mao MJ, Zhang MD, Meng DL, et al. Imidazolium-functionalized cationic covalent triazine frameworks stabilized copper nanoparticles for enhanced CO₂ electroreduction. ChemCatChem, 2020, 12133530.

[119] Y. Xiao, J. Lu, K.A. Chen, Y.L. Cao, C.T. Gong, and F.S. Ke, Linkage engineering in covalent organic frameworks for metal-free electrocatalytic C₂H₄ production from CO₂, Angew. Chem. Int. Ed., 63(2024), No. 26, art. No. e202404738.

[120] Y.L. Yang, Q. Li, P. Liu, et al., Subtle tuning of catalytic well effect in phthalocyanine covalent organic frameworks for selective CO₂ electroreduction into C₂H₄, Adv. Mater., 37(2025), No. 4, art. No. 2415799.

[121] Singh A, Barman S, Rahimi FA, et al. Atomically dispersed Co²⁺ in a redox-active COF for electrochemical CO₂ reduction to ethanol: Unravelling mechanistic insight through operando studies. Energy Environ. Sci., 2024, 1762315.

[122] T.X. Wang, L.L. Guo, H. Pei, et al., Electron-rich pincer ligand-coupled cobalt porphyrin polymer with single-atom sites for efficient (photo)electrocatalytic CO₂ reduction at ultralow overpotential, Small, 17(2021), No. 45, art. No. 2102957.

[123] Wu QJ, Si DH, Ye S, Dong YL, Cao R, Huang YB. Photocoupled electroreduction of CO₂ over photosensitizerdecorated covalent organic frameworks. J. Am. Chem. Soc., 2023, 1453619856.

[124] Yang CH, Liu H, Yang Y, et al. Synergy of electron-deficient and photosensitive groups in 3D covalent organic frameworks for metal-free photocoupled electrocatalytic CO₂ reduction. CCS Chem., 2026, 831495.

[125] Wan WR, Meng FH, Chen S, et al. Triazine-COF@Silicon nanowire mimicking plant leaf to enhance photoelectrocatalytic CO₂ reduction to C²⁺ chemicals. Green Energy Environ., 2025, 102422.

[126] van Rysselberghe P. Polarographic reduction of carbon dioxide. II. Polymerization and adsorption at the dropping mercury cathode¹. J. Am. Chem. Soc., 1946, 68102047.

[127] Teeter TE, van Rysselberghe P. Reduction of carbon dioxide on mercury cathodes. J. Chem. Phys., 1954, 224759.

[128] Hori Y, Kikuchi K, Murata A, Suzuki S. Production of methane and ethylene in electrochemical reduction of carbon dioxide at copper electrode in aqueous hydrogencarbonate solution. Chem. Lett., 1986, 156897.

[129] Todorova M, Wippermann S, Neugebauer J. First-principles approaches and concepts to simulate electrochemical interfaces. Nat. Rev. Chem., 2026, 102133.

[130] Wang H, Wang Y, Wang J, et al. Multiscale insights of interfacial transport and kinetics in acidic CO₂ electroreduction. Sci. Bull., 2026, 713598.

[131] Sun QD, Yue X, Yu LK, et al. Well-defined Co₂ dual-atom catalyst breaks scaling relations of oxygen reduction reaction. J. Am. Chem. Soc., 2024, 1465135295.

[132] Cai ZQ, Hu GJ, Li XX, Feng YS. Photocatalytic oxidation of tetrahydro furfuryl alcohol over bimetallic synergistic Pd-Sm-Porphyrin Metal–organic framework under visible light. Inorg. Chem., 2025, 643015518.

[133] M.D. Zhang, J.R. Huang, W. Shi, P.Q. Liao, and X.M. Chen, Self - accelerating effect in a covalent-organic framework with imidazole groups boosts electroreduction of CO₂ to CO, Angew. Chem. Int. Ed., 62(2023), No. 42, art. No. e202308195.

[134] F. Chai, S.H. Luo, and C.Y. Deng, Research progress on covalent organic frameworks in zinc-air batteries: From rational design to performance optimization, J. Alloy. Compd., 1056(2026), art. No. 186503.

[135] S.Q. Cheng, X. Sun, J.X. Ran, et al., Tuning asymmetric isomers in one-dimensional covalent organic frameworks to enhance oxygen reduction activity, Angew. Chem. Int. Ed., 64(2025), No. 52, art. No. e20336.

[136] M.H. Xu, L. Huang, F.W. Zhang, et al., Copper-silver bimetallic metal-covalent organic frameworks with unique intermediate interlayer transfer effects for enhanced electrocatalytic CO₂ to ethylene conversion, Angew. Chem. Int. Ed., 65(2026), No. 3, art. No. e20496.

[137] S. Kerraj, A. Arif, Y. Rachdi, et al., Exploring the optoelectronic and photovoltaic properties of Ru-arene complexes: DFT and TD-DFT insights into DSSC performance, J. Organomet. Chem., 1034(2025), art. No. 123650.

[138] Q.H. Qu, Y.Q. Jiang, L.Y. Cheng, et al., Screening and preparation of functionalized TpBD-COFs for CO2 capture, Chem. Eng. Sci., 301(2025), art. No. 120702.

[139] Liu GJ, Li XW, Liu MH, et al. Capture-intensified electrocatalytic reduction of postcombustion CO₂ in transporting and catalytic channels of covalent organic frameworks. ACS Catal., 2024, 141411076.

[140] T.T. Sun, H. Zhang, Y. Wang, et al., Covalent organic frameworks anchoring single-atom Pt for three-phase interface-assisted photocatalytic overall water splitting, Angew. Chem. Int. Ed., 64(2025), No. 46, art. No. e202515397.

[141] Q. Wang, W.J. Yuan, Y.H. Zhang, X.Y. Chi, D.P. Qi, and X.L. Zhang, Tailoring the structural design of covalent organic frameworks for enhanced photocatalytic carbon dioxide reduction: A review, Renewable Sustainable Energy Rev., 217(2025), art. No. 115754.

[142] Wang JZ, Liu XH, Wang GS, et al. Interfacial coordination engineering of CuCOF/CNTs hybrids for selective electrocatalytic CO₂ reduction. J. Energy Chem., 2026, 115: 437.

[143] D.R. Chen, J. Liu, Y.J. Yuan, et al., Electrocatalytic CO₂ reduction to ethylene in an acid-fed membrane electrode assembly at 10 A, Nat. Commun., 16(2025), art. No. 10783.

[144] Tan YJ, Sun CL, Han GK, et al. Neutral electrosynthesis of methane from diluted CO2 on dense Cu sites embedded covalent organic frameworks. J. Am. Chem. Soc., 2026, 14833327.

[145] Y.S. Yang, J.L. Zhang, Z.H. Tan, et al., Highly selective production of C2+ oxygenates from CO2 in strongly acidic condition by rough Ag–Cu electrocatalyst, Angew. Chem. Int. Ed., 63(2024), No. 47, art. No. e202408873.

[146] Hu YM, Sengupta B, Long H, et al. Molecular recognition with resolution below 0.2 angstroms through thermoregulatory oscillations in covalent organic frameworks. Science, 2024, 38467031441.

[147] Q. Wang, J.J. Chen, H.H. Pan, et al., Modulating active center microenvironment in phthalocyanine-based covalent organic frameworks for enhanced electrocatalytic CO₂ to CH₃OH, Adv. Mater., 37(2025), No. 21, art. No. 2502644.

[148] R. Bu, S.Q. Jia, Y.H. Pei, et al., Stretchable asymmetric dualatom Cu(I) electrocatalyst for enhanced CO₂ reduction to C2+ products, Chem Catal., 5(2025), No. 6, art. No. 101327.

[149] Q.L. Wu, H.Y. Zou, X. Mao, et al., Unveiling the dynamic active site of defective carbon-based electrocatalysts for hydrogen peroxide production, Nat. Commun., 14(2023), art. No. 6275.

[150] L.J. Yuan, Z.Y. Miao, X.L. Sui, et al., Janus effect of FeCo dual atom catalyst with Co as active center in acidic oxygen reduction reaction, Nat. Commun., 16(2025), art. No. 7198.

[151] Z. Fang, C.J. Wang, C.Y. Li, et al., Improved selectivity of CH₄/CO₂ within 1D channel of COFs realized by pore wall functionalization strategy, Nano Res., 19(2026), No. 3, art. No. 94908269.

[152] R.T. Wang, X.K. Yang, J.P. Zhang, et al., In-situ characterization technologies and theoretical calculations in carbon dioxide reduction: In-depth understanding of reaction mechanisms and rational design of electrocatalysts, Coord. Chem. Rev., 533(2025), art. No. 216541.

[153] H.Z. Zhang, C. Zhu, R.L. Liu, et al., Insight into the behavior of interstitial electrons in CuZn alloy-functionalized covalent organic framework catalysts for enhanced CO₂ electroreduction, Angew. Chem. Int. Ed., 65(2026), No. 4, art. No. e17420.

[154] Fang MW, Miao X, Huang ZH, et al. Anionic ionomer: Released surface-immobilized cations and an established hydrophobic microenvironment for efficient and durable CO₂-to-ethylene electrosynthesis at high current over one month. J. Am. Chem. Soc., 2024, 1463927060.

[155] Mohata S, Majumder P, Banerjee R. Design and structure-function interplay in covalent organic frameworks for photocatalytic CO₂ reduction. Chem. Soc. Rev., 2025, 54126062.

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