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Vol. 17 (2025)

Single-Point Linkage Engineering in Conjugated Phthalocyanine-Based Covalent Organic Frameworks for Electrochemical CO2 Reduction

https://doi.org/10.1007/s40820-025-01754-9
Wenchang Chen
Department of Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, People’s Republic of China
Yi Zhang
Department of Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, People’s Republic of China
Mingyu Yang
Department of Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, People’s Republic of China
Chao Yang
Department of Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, People’s Republic of China
Zheng Meng
Department of Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, People’s Republic of China

Corresponding Author: Zheng Meng

zhengmeng@ustc.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 252

Abstract

The utilization of covalent organic frameworks (COFs) holds great potential for achieving tailorable tuning of catalytic performance through bottom-up modulation of the reticular structure. In this work, we show that a single-point structural alteration in the linkage within a nickel phthalocyanine (NiPc)-based series effectively modulates the catalytic performance of the COFs in electrochemical CO2 reduction reaction (CO2RR). A NiPc-based COF series with three members which possess the same NiPc unit but different linkages, including piperazine, dioxin, and dithiine, have been constructed by nucleophilic aromatic substitution reaction between octafluorophthalocyanine nickel and tetrasubstituted benzene linkers with different bridging groups. Among these COFs, the dioxin-linked COF showed the best activity of CO2RR with a current density of CO (jCO) =  − 27.99 mA cm−2 at − 1.0 V (versus reversible hydrogen electrode, RHE), while the COF with piperazine linkage demonstrated an excellent selectivity of Faradaic efficiency for CO (FECO) up to 90.7% at a pretty low overpotential of 0.39 V. In addition, both a high FECO value close to 100% and a reasonable jCO of − 8.20 mA cm–2 at the potential of − 0.8 V (versus RHE) were obtained by the piperazine-linked COF, making it one of the most competitive candidates among COF-based materials. Mechanistic studies exhibited that single-point structural alteration could tailor the electron density in Ni sites and alter the interaction between the active sites and the key intermediates adsorbed and desorbed, thereby tuning the electrochemical performance during CO2RR process.


Highlights:
1 Three novel covalent organic frameworks (COFs) composed of nickel phthalocyanine units and different linkages, including dioxin, piperazine, and dithiine, were successfully constructed.
2 It was found that only a single-point structural variation of the linkage in the COFs could effectively modulate their performance in CO2 reduction reaction, where the piperazine-linked COF achieved a pretty high Faradaic efficiency for CO of 90.7% at a critically low overpotential of 0.39 V.
3 Theoretical calculations indicated that the COF with dioxin linkage stabilized the *COOH intermediate more effectively than the other two NiPc-based COFs.

Keywords

Conjugated covalent organic frameworks Linkage engineering Single heteroatom tuning CO2 electroreduction
Chen, Wenchang, Yi Zhang, Mingyu Yang, Chao Yang, and Zheng Meng. 2025. “Single-Point Linkage Engineering in Conjugated Phthalocyanine-Based Covalent Organic Frameworks for Electrochemical CO2 Reduction”. Nano-Micro Letters 17 (May):252. https://doi.org/10.1007/s40820-025-01754-9.
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References
  1. M. Aresta, A. Dibenedetto, A. Angelini, Catalysis for the valorization of exhaust carbon: from CO2 to chemicals, materials, and fuels technological use of CO2. Chem. Rev. 114(3), 1709–1742 (2014). https://doi.org/10.1021/cr4002758
  2. Z. Sun, T. Ma, H. Tao, Q. Fan, B. Han, Fundamentals and challenges of electrochemical CO2 reduction using two-dimensional materials. Chem 3(4), 560–587 (2017). https://doi.org/10.1016/j.chempr.2017.09.009
  3. C. Costentin, G. Passard, M. Robert, J.-M. Savéant, Ultraefficient homogeneous catalyst for the CO2-to-CO electrochemical conversion. Proc. Natl. Acad. Sci. 111, 14990–14994 (2014). https://doi.org/10.1073/pnas.1416697111
  4. A.J. Göttle, M.T.M. Koper, Determinant role of electrogenerated reactive nucleophilic species on selectivity during reduction of CO2 catalyzed by metalloporphyrins. J. Am. Chem. Soc. 140(14), 4826–4834 (2018). https://doi.org/10.1021/jacs.7b11267
  5. A.B. Sorokin, Phthalocyanine metal complexes in catalysis. Chem. Rev. 113(10), 8152–8191 (2013). https://doi.org/10.1021/cr4000072
  6. J.-M. Savéant, Molecular catalysis of electrochemical reactions mechanistic aspects. Chem. Rev. 108(7), 2348–2378 (2008). https://doi.org/10.1021/cr068079z
  7. J. Hawecker, J.-M. Lehn, R. Ziessel, Electrocatalytic reduction of carbon dioxide mediated by Re(bipy)(CO)3Cl (bipy = 2, 2’-bipyridine). J. Chem. Soc. Chem. Commun. 6, 328–330 (1984). https://doi.org/10.1039/c39840000328
  8. C. Costentin, S. Drouet, M. Robert, J.-M. Savéant, A local proton source enhances CO2 electroreduction to CO by a molecular Fe catalyst. Science 338(6103), 90–94 (2012). https://doi.org/10.1126/science.1224581
  9. C.S. Diercks, Y. Liu, K.E. Cordova, O.M. Yaghi, The role of reticular chemistry in the design of CO2 reduction catalysts. Nat. Mater. 17(4), 301–307 (2018). https://doi.org/10.1038/s41563-018-0033-5
  10. M. Ding, R.W. Flaig, H.-L. Jiang, O.M. Yaghi, Carbon capture and conversion using metal-organic frameworks and MOF-based materials. Chem. Soc. Rev. 48(10), 2783–2828 (2019). https://doi.org/10.1039/c8cs00829a
  11. Z.W. Seh, J. Kibsgaard, C.F. Dickens, I. Chorkendorff, J.K. Nørskov et al., Combining theory and experiment in electrocatalysis: insights into materials design. Science 355(6321), eaaad4998 (2017). https://doi.org/10.1126/science.aad4998
  12. F. Li, L. Chen, G.P. Knowles, D.R. MacFarlane, J. Zhang, Hierarchical mesoporous SnO2 nanosheets on carbon cloth: a robust and flexible electrocatalyst for CO2 reduction with high efficiency and selectivity. Angew. Chem. Int. Ed. 56(2), 505–509 (2017). https://doi.org/10.1002/anie.201608279
  13. N. Sreekanth, M.A. Nazrulla, T.V. Vineesh, K. Sailaja, K.L. Phani, Metal-free boron-doped graphene for selective electroreduction of carbon dioxide to formic acid/formate. Chem. Commun. 51(89), 16061–16064 (2015). https://doi.org/10.1039/c5cc06051f
  14. J.J. Leung, J.A. Vigil, J. Warnan, E. Edwardes Moore, E. Reisner, Rational design of polymers for selective CO2 reduction catalysis. Angew. Chem. Int. Ed. 58(23), 7697–7701 (2019). https://doi.org/10.1002/anie.201902218
  15. D. Azaiza-Dabbah, C. Vogt, F. Wang, A. Masip-Sánchez, C. de Graaf et al., Molecular transition metal oxide electrocatalysts for the reversible carbon dioxide-carbon monoxide transformation. Angew. Chem. Int. Ed. 61(5), e202112915 (2022). https://doi.org/10.1002/anie.202112915
  16. S.-Y. Ding, W. Wang, Covalent organic frameworks (COFs): from design to applications. Chem. Soc. Rev. 42(2), 548–568 (2013). https://doi.org/10.1039/C2CS35072F
  17. S. Lin, C.S. Diercks, Y.-B. Zhang, N. Kornienko, E.M. Nichols et al., Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 349(6253), 1208–1213 (2015). https://doi.org/10.1126/science.aac8343
  18. J. Jiang, Y. Zhao, O.M. Yaghi, Covalent chemistry beyond molecules. J. Am. Chem. Soc. 138(10), 3255–3265 (2016). https://doi.org/10.1021/jacs.5b10666
  19. Y. Xue, Y. Guo, H. Cui, Z. Zhou, Catalyst design for electrochemical reduction of CO2 to multicarbon products. Small Methods 5(10), e2100736 (2021). https://doi.org/10.1002/smtd.202100736
  20. J. Qiao, Y. Liu, F. Hong, J. Zhang, A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. Chem. Soc. Rev. 43(2), 631–675 (2014). https://doi.org/10.1039/c3cs60323g
  21. M. Liu, S. Yang, X. Yang, C.X. Cui, G. Liu et al., Post-synthetic modification of covalent organic frameworks for CO2 electroreduction. Nat. Commun. 14(1), 3800 (2023). https://doi.org/10.1038/s41467-023-39544-9
  22. Y. Zhang, X. Zhang, L. Jiao, Z. Meng, H.-L. Jiang, Conductive covalent organic frameworks of polymetallophthalocyanines as a tunable platform for electrocatalysis. J. Am. Chem. Soc. 145(44), 24230–24239 (2023). https://doi.org/10.1021/jacs.3c08594
  23. Y. Yue, H. Li, H. Chen, N. Huang, Piperazine-linked covalent organic frameworks with high electrical conductivity. J. Am. Chem. Soc. 144(7), 2873–2878 (2022). https://doi.org/10.1021/jacs.1c13012
  24. Z. Tian, Q. Zhang, T. Liu, Y. Chen, M. Antonietti, Emerging two-dimensional carbonaceous materials for electrocatalytic energy conversions: rational design of active structures through high-temperature chemistry. ACS Nano 18(8), 6111–6129 (2024). https://doi.org/10.1021/acsnano.3c12198
  25. C.S. Diercks, S. Lin, N. Kornienko, E.A. Kapustin, E.M. Nichols et al., Reticular electronic tuning of porphyrin active sites in covalent organic frameworks for electrocatalytic carbon dioxide reduction. J. Am. Chem. Soc. 140(3), 1116–1122 (2018). https://doi.org/10.1021/jacs.7b11940
  26. M. Wang, K. Torbensen, D. Salvatore, S. Ren, D. Joulié et al., CO2 electrochemical catalytic reduction with a highly active cobalt phthalocyanine. Nat. Commun. 10(1), 3602 (2019). https://doi.org/10.1038/s41467-019-11542-w
  27. M. Lu, M. Zhang, C.-G. Liu, J. Liu, L.-J. Shang et al., Stable dioxin-linked metallophthalocyanine covalent organic frameworks (COFs) as photo-coupled electrocatalysts for CO2 reduction. Angew. Chem. Int. Ed. 60(9), 4864–4871 (2021). https://doi.org/10.1002/anie.202011722
  28. B. Han, X. Ding, B. Yu, H. Wu, W. Zhou et al., Two-dimensional covalent organic frameworks with cobalt(II)-phthalocyanine sites for efficient electrocatalytic carbon dioxide reduction. J. Am. Chem. Soc. 143(18), 7104–7113 (2021). https://doi.org/10.1021/jacs.1c02145
  29. S. Huang, K. Chen, T.-T. Li, Porphyrin and phthalocyanine based covalent organic frameworks for electrocatalysis. Coord. Chem. Rev. 464, 214563 (2022). https://doi.org/10.1016/j.ccr.2022.214563
  30. X. Yang, X. Li, M. Liu, S. Yang, Q. Xu et al., Quantitative construction of boronic-ester linkages in covalent organic frameworks for the carbon dioxide reduction. Angew. Chem. Int. Ed. 63, e202317785 (2024). https://doi.org/10.1002/anie.202317785
  31. T. Xie, S. Chen, Y. Yue, T. Sheng, N. Huang et al., Biomimetic phthalocyanine-based covalent organic frameworks with tunable pendant groups for electrocatalytic CO2 reduction. Angew. Chem. Int. Ed. 63(43), e202411188 (2024). https://doi.org/10.1002/anie.202411188
  32. S. Haldar, M. Wang, P. Bhauriyal, A. Hazra, A.H. Khan et al., Porous dithiine-linked covalent organic framework as a dynamic platform for covalent polysulfide anchoring in lithium-sulfur battery cathodes. J. Am. Chem. Soc. 144(20), 9101–9112 (2022). https://doi.org/10.1021/jacs.2c02346
  33. Q. Zhi, R. Jiang, X. Yang, Y. Jin, D. Qi et al., Dithiine-linked metalphthalocyanine framework with undulated layers for highly efficient and stable H2O2 electroproduction. Nat. Commun. 15(1), 678 (2024). https://doi.org/10.1038/s41467-024-44899-8
  34. Y. Wang, J. Chen, C. Jiang, N. Ding, C. Wang et al., Tetra-β-nitro-substituted phthalocyanines: a new organic electrode material for lithium batteries. J. Solid State Electrochem. 21(4), 947–954 (2017). https://doi.org/10.1007/s10008-016-3419-9
  35. X. Chen, M. Zeng, J. Yang, N. Hu, X. Duan et al., Two-dimensional bimetallic phthalocyanine covalent-organic-framework-based chemiresistive gas sensor for ppb-level NO2 detection. Nanomaterials 13(10), 1660 (2023). https://doi.org/10.3390/nano13101660
  36. Z. Meng, J. Luo, W. Li, K.A. Mirica, Hierarchical tuning of the performance of electrochemical carbon dioxide reduction using conductive two-dimensional metallophthalocyanine based metal-organic frameworks. J. Am. Chem. Soc. 142(52), 21656–21669 (2020). https://doi.org/10.1021/jacs.0c07041
  37. X. Yang, X. Li, M. Liu, S. Yang, Q. Niu et al., Modulating electrochemical CO2 reduction performance via sulfur-containing linkages engineering in metallophthalocyanine based covalent organic frameworks. ACS Mater. Lett. 5(6), 1611–1618 (2023). https://doi.org/10.1021/acsmaterialslett.3c00168
  38. Z. Meng, A. Aykanat, K.A. Mirica, Welding metallophthalocyanines into bimetallic molecular meshes for ultrasensitive, low-power chemiresistive detection of gases. J. Am. Chem. Soc. 141(5), 2046–2053 (2019). https://doi.org/10.1021/jacs.8b11257
  39. L. Wei, K. Zhang, R. Zhao, L. Zhang, Y. Zhang et al., Modulating redox transition kinetics by anion regulation in Ni−Fe−X (X = O, S, Se, N, and P) electrocatalyst for efficient water oxidation. Nano Res. 17(6), 4720–4728 (2024). https://doi.org/10.1007/s12274-023-6400-9
  40. S. Ye, Probing electronic structures of transition metal complexes using electron paramagnetic resonance spectroscopy. Magn. Reson. Lett. 3(1), 43–60 (2023). https://doi.org/10.1016/j.mrl.2022.06.002
  41. A. Aykanat, Z. Meng, G. Benedetto, K.A. Mirica, Molecular engineering of multifunctional metallophthalocyanine-containing framework materials. Chem. Mater. 32(13), 5372–5409 (2020). https://doi.org/10.1021/acs.chemmater.9b05289
  42. J. Lee, O.K. Farha, J. Roberts, K.A. Scheidt, S.T. Nguyen et al., Metal–organic framework materials as catalysts. Chem. Soc. Rev. 38(5), 1450 (2009). https://doi.org/10.1039/b807080f
  43. L. Ye, J. Liu, Y. Gao, C. Gong, M. Addicoat et al., Highly oriented MOF thin film-based electrocatalytic device for the reduction of CO2 to CO exhibiting high faradaic efficiency. J. Mater. Chem. A 4(40), 15320–15326 (2016). https://doi.org/10.1039/C6TA04801C
  44. R. Matheu, E. Gutierrez-Puebla, M. Ángeles Monge, C.S. Diercks, J. Kang et al., Three-dimensional phthalocyanine metal-catecholates for high electrochemical carbon dioxide reduction. J. Am. Chem. Soc. 141(43), 17081–17085 (2019). https://doi.org/10.1021/jacs.9b09298
  45. H. Zhong, M. Ghorbani-Asl, K.H. Ly, J. Zhang, J. Ge et al., Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks. Nat. Commun. 11(1), 1409 (2020). https://doi.org/10.1038/s41467-020-15141-y
  46. N. Huang, K.H. Lee, Y. Yue, X. Xu, S. Irle et al., A stable and conductive metallophthalocyanine framework for electrocatalytic carbon dioxide reduction in water. Angew. Chem. Int. Ed. 59(38), 16587–16593 (2020). https://doi.org/10.1002/anie.202005274
  47. H.-J. Zhu, M. Lu, Y.-R. Wang, S.-J. Yao, M. Zhang et al., Efficient electron transmission in covalent organic framework nanosheets for highly active electrocatalytic carbon dioxide reduction. Nat. Commun. 11, 497 (2020). https://doi.org/10.1038/s41467-019-14237-4
  48. S. Wan, F. Gándara, A. Asano, H. Furukawa, A. Saeki et al., Covalent organic frameworks with high charge carrier mobility. Chem. Mater. 23(18), 4094–4097 (2011). https://doi.org/10.1021/cm201140r
  49. J. Shen, R. Kortlever, R. Kas, Y.Y. Birdja, O. Diaz-Morales et al., Electrocatalytic reduction of carbon dioxide to carbon monoxide and methane at an immobilized cobalt protoporphyrin. Nat. Commun. 6, 8177 (2015). https://doi.org/10.1038/ncomms9177
  50. Z. Weng, J. Jiang, Y. Wu, Z. Wu, X. Guo et al., Electrochemical CO2 reduction to hydrocarbons on a heterogeneous molecular Cu catalyst in aqueous solution. J. Am. Chem. Soc. 138(26), 8076–8079 (2016). https://doi.org/10.1021/jacs.6b04746
  51. Z. Zhang, J. Xiao, X.-J. Chen, S. Yu, L. Yu et al., Reaction mechanisms of well-defined metal-N4 sites in electrocatalytic CO2 reduction. Angew. Chem. Int. Ed. 57(50), 16339–16342 (2018). https://doi.org/10.1002/anie.201808593
  52. W.W. Kramer, C.L. McCrory, Polymer coordination promotes selective CO2 reduction by cobalt phthalocyanine. Chem. Sci. 7(4), 2506–2515 (2016). https://doi.org/10.1039/c5sc04015a
  53. N. Han, Y. Wang, L. Ma, J. Wen, J. Li et al., Supported cobalt polyphthalocyanine for high-performance electrocatalytic CO2 reduction. Chem 3(4), 652–664 (2017). https://doi.org/10.1016/j.chempr.2017.08.002
  54. X.-M. Hu, M.H. Rønne, S.U. Pedersen, T. Skrydstrup, K. Daasbjerg, Enhanced catalytic activity of cobalt porphyrin in CO2 electroreduction upon immobilization on carbon materials. Angew. Chem. Int. Ed. 56, 6468–6472 (2017). https://doi.org/10.1002/anie.201701104
  55. Y. Wu, Z. Jiang, X. Lu, Y. Liang, H. Wang, Domino electroreduction of CO2 to methanol on a molecular catalyst. Nature 575(7784), 639–642 (2019). https://doi.org/10.1038/s41586-019-1760-8
  56. Y. Yue, P. Cai, K. Xu, H. Li, H. Chen et al., Stable bimetallic polyphthalocyanine covalent organic frameworks as superior electrocatalysts. J. Am. Chem. Soc. 143(43), 18052–18060 (2021). https://doi.org/10.1021/jacs.1c06238
  57. J. Yuan, S. Chen, Y. Zhang, R. Li, J. Zhang et al., Structural regulation of coupled phthalocyanine–porphyrin covalent organic frameworks to highly active and selective electrocatalytic CO2 reduction. Adv. Mater. 34(30), 2203139 (2022). https://doi.org/10.1002/adma.202203139
  58. S. Aoi, K. Mase, K. Ohkubo, S. Fukuzumi, Selective electrochemical reduction of CO2 to CO with a cobalt chlorin complex adsorbed on multi-walled carbon nanotubes in water. Chem. Commun. 51(50), 10226–10228 (2015). https://doi.org/10.1039/C5CC03340C
  59. Y. Cao, S. Chen, S. Bo, W. Fan, J. Li et al., Single atom Bi decorated copper alloy enables C–C coupling for electrocatalytic reduction of CO2 into C2+ products. Angew. Chem. Int. Ed. 62(30), e202303048 (2023). https://doi.org/10.1002/anie.202303048
  60. W. Ren, X. Tan, W. Yang, C. Jia, S. Xu et al., Isolated diatomic Ni-Fe metal-nitrogen sites for synergistic electroreduction of CO2. Angew. Chem. Int. Ed. 58(21), 6972–6976 (2019). https://doi.org/10.1002/anie.201901575
  61. A. Rendón-Calle, S. Builes, F. Calle-Vallejo, A brief review of the computational modeling of CO2 electroreduction on Cu electrodes. Curr. Opin. Electrochem. 9, 158–165 (2018). https://doi.org/10.1016/j.coelec.2018.03.012
  62. J. Li, H. Zeng, X. Dong, Y. Ding, S. Hu et al., Selective CO2 electrolysis to CO using isolated antimony alloyed copper. Nat. Commun. 14(1), 340 (2023). https://doi.org/10.1038/s41467-023-35960-z
  63. L. Wang, Y. Kong, H. Cai, J. Sun, X. Jiang et al., Modulation of d-band electron enables efficient CO2 electroreduction towards CO on Ni nanops. J. Mater. Chem. A 12(27), 16403–16409 (2024). https://doi.org/10.1039/D4TA02800G
  64. J.K. Nørskov, T. Bligaard, J. Rossmeisl, C.H. Christensen, Towards the computational design of solid catalysts. Nat. Chem. 1(1), 37–46 (2009). https://doi.org/10.1038/nchem.121
  65. Y. Yao, X. Wei, H. Zhou et al., Regulating the d-band center of metal–organic frameworks for efficient nitrate reduction reaction and zinc-nitrate battery. ACS Catal. 14(21), 16205–16213 (2024). https://doi.org/10.1021/acscatal.4c04340
  66. X. Zhang, Y. Wang, M. Gu, M. Wang, Z. Zhang et al., Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction. Nat. Energy 5(9), 684–692 (2020). https://doi.org/10.1038/s41560-020-0667-9
  67. K. Chen, M. Cao, Y. Lin, J. Fu, H. Liao et al., Ligand engineering in nickel phthalocyanine to boost the electrocatalytic reduction of CO2. Adv. Funct. Mater. 32(10), 2111322 (2022). https://doi.org/10.1002/adfm.202111322
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