Skip to main content
SpringerLink
Log in

Recent advances in the rational design of single-atom catalysts for electrochemical CO2 reduction

  • Review Article
  • Published:
Nano Research Aims and scope Submit manuscript

Abstract

Electrochemical CO2 reduction (CO2R) represents a sustainable way to store intermittent renewable energies and produce carbon-neutral fuels, yet the energy efficiency remains a huge bottleneck owning to its sluggish kinetics and complex reaction pathways. Highly active, selective, and robust electrocatalysts are strongly demanded to accelerate CO2 conversion and deploy this technology to practical applications. In this review, we focus on single-atom catalysts (SACs), a unique category of electrocatalysts with atomically dispersed metal active sites, which have shown distinctive performances in CO2R and offer an ideal platform for in-depth mechanistic studies at the atomic level. Despite various SACs with attractive CO2R performances have been reported, the relationship between electronic/geometric structure of SACs and the corresponding electrocatalytic performance still needs to be discussed with caution. Here we take a broad overview on the recent progress in understanding the structure-function correlation of SACs in CO2R, with the purpose of providing deep insights and guiding the future rational design of SACs. First, we provide the fundamental understandings of CO2R on SACs, following different reaction pathways. Then, we describe the progresses in the development of well-defined SACs and the mechanistic studies on the influences from particular structural parameters, such as first-shell and second-sphere coordination, conductive supports and interface with a secondary catalyst. Finally, some perspectives are highlighted on the path towards efficient CO2R on SACs.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Caldeira, K.; Wickett, M. E. Anthropogenic carbon and ocean pH. Nature 2003, 425, 365.

    Article  CAS  Google Scholar 

  2. Chu, S.; Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 2012, 488, 294–303.

    Article  CAS  Google Scholar 

  3. Shakun, J. D.; Clark, P. U.; He, F.; Marcott, S. A.; Mix, A. C.; Liu, Z. Y.; Otto-Bliesner, B.; Schmittner, A.; Bard, E. Global warming preceded by increasing carbon dioxide concentrations during the last deglaciation. Nature 2012, 484, 49–54.

    Article  CAS  Google Scholar 

  4. Kondratenko, E. V.; Mul, G.; Baltrusaitis, J.; Larrazábal, G. O.; Pérez-Ramírez, J. Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes. Energy Environ. Sci. 2013, 6, 3112–3135.

    Article  CAS  Google Scholar 

  5. Nitopi, S.; Bertheussen, E.; Scott, S. B.; Liu, X. Y.; Engstfeld, A. K.; Horch, S.; Seger, B.; Stephens, I. E. L.; Chan, K.; Hahn, C. et al. Progress and perspectives of electrochemical CO2 reduction on copper in aqueous electrolyte. Chem. Rev. 2019, 119, 7610–7672.

    Article  CAS  Google Scholar 

  6. Ross, M. B.; De Luna, P.; Li, Y. F.; Dinh, C. T.; Kim, D.; Yang, P.; Sargent, E. H. Designing materials for electrochemical carbon dioxide recycling. Nat. Catal. 2019, 2, 648–658.

    Article  CAS  Google Scholar 

  7. Grim, R. G.; Huang, Z.; Guarnieri, M. T.; Ferrell III, J. R.; Tao, L.; Schaidle, J. A. Transforming the carbon economy: Challenges and opportunities in the convergence of low-cost electricity and reductive CO2 utilization. Energy Environ. Sci. 2020, 13, 472–494.

    Article  CAS  Google Scholar 

  8. Kulkarni, A. P.; Hos, T.; Landau, M. V.; Fini, D.; Giddey, S.; Herskowitz, M. Techno-economic analysis of a sustainable process for converting CO2 and H2O to feedstock for fuels and chemicals. Sustainable Energy Fuels 2021, 5, 486–500.

    Article  CAS  Google Scholar 

  9. Sharifian, R.; Wagterveld, R. M.; Digdaya, I. A.; Xiang, C.; Vermaas, D. A. Electrochemical carbon dioxide capture to close the carbon cycle. Energy Environ. Sci. 2021, 14, 781–814.

    Article  CAS  Google Scholar 

  10. Chen, C.; Khosrowabadi Kotyk, J. F.; Sheehan, S. W. Progress toward commercial application of electrochemical carbon dioxide reduction. Chem 2018, 4, 2571–2586.

    Article  CAS  Google Scholar 

  11. Kortlever, R.; Shen, J.; Schouten, K. J. P.; Calle-Vallejo, F.; Koper, M. T. M. Catalysts and reaction pathways for the electrochemical reduction of carbon dioxide. J. Phys. Chem. Lett. 2015, 6, 4073–4082.

    Article  CAS  Google Scholar 

  12. Qiao, J. L.; Liu, Y. Y.; Hong, F.; Zhang, J. J. A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels. Chem. Soc. Rev. 2014, 43, 631–675.

    Article  CAS  Google Scholar 

  13. Ringe, S.; Clark, E. L.; Resasco, J.; Walton, A.; Seger, B.; Bell, A. T.; Chan, K. Understanding cation effects in electrochemical CO2 reduction. Energy Environ. Sci. 2019, 12, 3001–3014.

    Article  CAS  Google Scholar 

  14. Yoshio, H.; Katsuhei, K.; Shin, S. Production of CO and CH4 in electrochemical reduction of CO2 at metal electrodes in aqueous hydrogencarbonate solution. Chem. Lett. 1985, 14, 1695–1698.

    Article  Google Scholar 

  15. Birdja, Y. Y.; Pérez-Gallent, E.; Figueiredo, M. C.; Göttle, A. J.; Calle-Vallejo, F.; Koper, M. T. M. Advances and challenges in understanding the electrocatalytic conversion of carbon dioxide to fuels. Nat. Energy 2019, 4, 732–745.

    Article  CAS  Google Scholar 

  16. Benson, E. E.; Kubiak, C. P.; Sathrum, A. J.; Smieja, J. M. Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels. Chem. Soc. Rev. 2009, 38, 89–99.

    Article  CAS  Google Scholar 

  17. Franco, F.; Rettenmaier, C.; Jeon, H. S.; Roldan Cuenya, B. Transition metal-based catalysts for the electrochemical CO2 reduction: From atoms and molecules to nanostructured materials. Chem. Soc. Rev. 2020, 49, 6884–6946.

    Article  CAS  Google Scholar 

  18. Raciti, D.; Wang, C. Recent advances in CO2 reduction electrocatalysis on copper. ACS Energy Lett. 2018, 3, 1545–1556.

    Article  CAS  Google Scholar 

  19. Vasileff, A.; Xu, C. C.; Jiao, Y.; Zheng, Y.; Qiao, S. Z. Surface and interface engineering in copper-based bimetallic materials for selective CO2 electroreduction. Chem 2018, 4, 1809–1831.

    Article  CAS  Google Scholar 

  20. Zhang, S.; Fan, Q.; Xia, R.; Meyer, T. J. CO2 reduction: From homogeneous to heterogeneous electrocatalysis. Acc. Chem. Res. 2020, 53, 255–264.

    Article  CAS  Google Scholar 

  21. Wang, Y. C.; Xu, L.; Zhan, L. S.; Yang, P. Y.; Tang, S. H.; Liu, M. J.; Zhao, X.; Xiong, Y.; Chen, Z. Y.; Lei, Y. P. Electron accumulation enables Bi efficient CO2 reduction for formate production to boost clean Zn−CO2 batteries. Nano Energy 2022, 92, 106780.

    Article  CAS  Google Scholar 

  22. Wang, A. Q.; Li, J.; Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2018, 2, 65–81.

    Article  CAS  Google Scholar 

  23. Zhang, L. L.; Ren, Y. J.; Liu, W. G.; Wang, A. Q.; Zhang, T. Single-atom catalyst: A rising star for green synthesis of fine chemicals. Natl. Sci. Rev. 2018, 5, 653–672.

    Article  CAS  Google Scholar 

  24. Zhang, F. F.; Zhu, Y. L.; Lin, Q.; Zhang, L.; Zhang, X. W.; Wang, H. Y. Noble-metal single-atoms in thermocatalysis, electrocatalysis, and photocatalysis. Energy Environ. Sci. 2021, 14, 2954–3009.

    Article  CAS  Google Scholar 

  25. Zhang, L. L.; Zhou, M. X.; Wang, A. Q.; Zhang, T. Selective hydrogenation over supported metal catalysts: From nanoparticles to single atoms. Chem. Rev. 2020, 120, 683–733.

    Article  CAS  Google Scholar 

  26. Zhao, D.; Zhuang, Z. W.; Cao, X.; Zhang, C.; Peng, Q.; Chen, C.; Li, Y. D. Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation. Chem. Soc. Rev. 2020, 49, 2215–2264.

    Article  CAS  Google Scholar 

  27. Ji, S. F.; Chen, Y. J.; Wang, X. L.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Chemical synthesis of single atomic site catalysts. Chem. Rev. 2020, 120, 11900–11955.

    Article  CAS  Google Scholar 

  28. Li, Z.; Ji, S. F.; Liu, Y. W.; Cao, X.; Tian, S. B.; Chen, Y. J.; Niu, Z. Q.; Li, Y. D. Well-defined materials for heterogeneous catalysis: From nanoparticles to isolated single-atom sites. Chem. Rev. 2020, 120, 623–682.

    Article  CAS  Google Scholar 

  29. Qiao, B. T.; Wang, A. Q.; Yang, X. F.; Allard, L. F.; Jiang, Z.; Cui, Y. T.; Liu, J. Y.; Li, J.; Zhang, T. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 2011, 3, 634–641.

    Article  CAS  Google Scholar 

  30. Lang, R.; Du, X. R.; Huang, Y. K.; Jiang, X. Z.; Zhang, Q.; Guo, Y. L.; Liu, K. P.; Qiao, B. T.; Wang, A. Q.; Zhang, T. Single-atom catalysts based on the metal-oxide interaction. Chem. Rev. 2020, 120, 11986–12043.

    Article  CAS  Google Scholar 

  31. Li, X. N.; Yang, X. F.; Zhang, J. M.; Huang, Y. Q.; Liu, B. In situ/operando techniques for characterization of single-atom catalysts. ACS Catal. 2019, 9, 2521–2531.

    Article  CAS  Google Scholar 

  32. Ye, C. L.; Zhang, N. Q.; Wang, D. S.; Li, Y. F. Single atomic site catalysts: Synthesis, characterization, and applications. Chem. Commun. 2020, 56, 7687–7697.

    Article  CAS  Google Scholar 

  33. Tian, S. B.; Gong, W. B.; Chen, W. X.; Lin, N.; Zhu, Y. Q.; Feng, Q. C.; Xu, Q.; Fu, Q.; Chen, C.; Luo, J. et al. Regulating the catalytic performance of single-atomic-site Ir catalyst for biomass conversion by metal-support interactions. ACS Catal. 2019, 9, 5223–5230.

    Article  CAS  Google Scholar 

  34. Tian, S. B.; Wang, Z. Y.; Gong, W. B.; Chen, W. X.; Feng, Q. C.; Xu, Q.; Chen, C.; Chen, C.; Peng, Q.; Gu, L. et al. Temperature-controlled selectivity of hydrogenation and hydrodeoxygenation in the conversion of biomass molecule by the Ru1/mpg-C3N4 catalyst. J. Am. Chem. Soc. 2018, 140, 11161–11164.

    Article  CAS  Google Scholar 

  35. Wei, S. J.; Li, A.; Liu, J. C.; Li, Z.; Chen, W. X.; Gong, Y.; Zhang, Q. H.; Cheong, W. C.; Wang, Y.; Zheng, L. R. et al. Direct observation of noble metal nanoparticles transforming to thermally stable single atoms. Nat. Nanotechnol. 2018, 13, 856–861.

    Article  CAS  Google Scholar 

  36. Ye, X.; Yang, C. Y.; Pan, X. L.; Ma, J. G.; Zhang, Y. R.; Ren, Y. J.; Liu, X. Y.; Li, L.; Huang, Y. Q. Highly selective hydrogenation of CO2 to ethanol via designed bifunctional Ir1−In2O3 single-atom catalyst. J. Am. Chem. Soc. 2020, 142, 19001–19005.

    Article  CAS  Google Scholar 

  37. Liu, H.; Li, X. X.; Ma, Z. H.; Sun, M. Z.; Li, M. G.; Zhang, Z. Y.; Zhang, L.; Tang, Z. B.; Yao, Y.; Huang, B. L. et al. Atomically dispersed Cu catalyst for efficient chemoselective hydrogenation reaction. Nano Lett. 2021, 21, 10284–10291.

    Article  CAS  Google Scholar 

  38. Liu, Y.; Liu, J. C.; Li, T. H.; Duan, Z. H.; Zhang, T. Y.; Yan, M.; Li, W. L.; Xiao, H.; Wang, Y. G.; Chang, C. R. et al. Unravelling the enigma of nonoxidative conversion of methane on iron single-atom catalysts. Angew. Chem., Int. Ed. 2020, 59, 18586–18590.

    Article  CAS  Google Scholar 

  39. Sun, X. H.; Olivos-Suarez, A. I.; Osadchii, D.; Romero, M. J. V.; Kapteijn, F.; Gascon, J. Single cobalt sites in mesoporous N-doped carbon matrix for selective catalytic hydrogenation of nitroarenes. J. Catal. 2018, 357, 20–28.

    Article  CAS  Google Scholar 

  40. Yang, J. R.; Zeng, D. Q.; Zhang, Q. G.; Cui, R. F.; Hassan, M.; Dong, L. Q.; Li, J.; He, Y. L. Single Mn atom anchored on N-doped porous carbon as highly efficient Fenton-like catalyst for the degradation of organic contaminants. Appl. Catal. B:Environ. 2020, 279, 119363.

    Article  CAS  Google Scholar 

  41. Zuo, Z. J.; Liu, S. Z.; Wang, Z. C.; Liu, C.; Huang, W.; Huang, J.; Liu, P. Dry reforming of methane on single-site Ni/MgO catalysts: Importance of site confinement. ACS Catal. 2018, 8, 9821–9835.

    Article  CAS  Google Scholar 

  42. Fu, J. H.; Dong, J. H.; Si, R.; Sun, K. J.; Zhang, J. Y.; Li, M. R.; Yu, N. N.; Zhang, B. S.; Humphrey, M. G.; Fu, Q. et al. Synergistic effects for enhanced catalysis in a dual single-atom catalyst. ACS Catal. 2021, 11, 1952–1961.

    Article  CAS  Google Scholar 

  43. Gu, X. K.; Qiao, B. T.; Huang, C. Q.; Ding, W. C.; Sun, K. J.; Zhan, E. S.; Zhang, T.; Liu, J. Y.; Li, W. X. Supported single Pt1/Au1 atoms for methanol steam reforming. ACS Catal. 2014, 9, 3886–3890.

    Article  CAS  Google Scholar 

  44. Sun, G. D.; Zhao, Z. J.; Mu, R. T.; Zha, S. J.; Li, L. L.; Chen, S.; Zang, K. T.; Luo, J.; Li, Z. L.; Purdy, S. C. et al. Breaking the scaling relationship via thermally stable Pt/Cu single atom alloys for catalytic dehydrogenation. Nat. Commun. 2018, 9, 4454.

    Article  CAS  Google Scholar 

  45. Tang, Y.; Wei, Y. C.; Wang, Z. Y.; Zhang, S. R.; Li, Y. T.; Nguyen, L.; Li, Y. X.; Zhou, Y.; Shen, W. J.; Tao, F. F. et al. Synergy of single-atom Ni1 and Ru1 sites on CeO2 for dry reforming of CH4. J. Am. Chem. Soc. 2019, 141, 7283–7293.

    Article  CAS  Google Scholar 

  46. Zhou, P.; Hou, X. G.; Chao, Y. G.; Yang, W. X.; Zhang, W. Y.; Mu, Z. J.; Lai, J. P.; Lv, F.; Yang, K.; Liu, Y. X. et al. Synergetic interaction between neighboring platinum and ruthenium monomers boosts CO oxidation. Chem. Sci. 2019, 10, 5898–5905.

    Article  CAS  Google Scholar 

  47. Chen, Y.; Ji, S. F.; Chen, C.; Peng, Q.; Wang, D. S.; Li, Y. D. Single-atom catalysts: Synthetic strategies and electrochemical applications. Joule 2018, 2, 1242–1264.

    Article  CAS  Google Scholar 

  48. Lu, B. Z.; Liu, Q. M.; Chen, S. W. Electrocatalysis of single-atom sites: Impacts of atomic coordination. ACS Catal. 2020, 10, 7584–7618.

    Article  CAS  Google Scholar 

  49. Nguyen, T. N.; Salehi, M.; Van Le, Q.; Seifitokaldani, A.; Dinh, C. T. Fundamentals of electrochemical CO2 reduction on single-metal-atom catalysts. ACS Catal. 2020, 10, 10068–10095.

    Article  Google Scholar 

  50. Ou, H. H.; Wang, D. S.; Li, Y. D. How to select effective electrocatalysts: Nano or single atom? Nano Select 2021, 2, 492–511.

    Article  CAS  Google Scholar 

  51. Peng, Y.; Lu, B. Z.; Chen, S. W. Carbon-supported single atom catalysts for electrochemical energy conversion and storage. Adv. Mater. 2018, 30, 1801995.

    Article  CAS  Google Scholar 

  52. Wang, Y. X.; Su, H. Y.; He, Y. H.; Li, L. G.; Zhu, S. Q.; Shen, H.; Xie, P. F.; Fu, X. B.; Zhou, G. Y.; Feng, C. et al. Advanced electrocatalysts with single-metal-atom active sites. Chem. Rev. 2020, 120, 12217–12314.

    Article  CAS  Google Scholar 

  53. Zhang, H. B.; Cheng, W. R.; Luan, D. Y.; Lou, X. W. Atomically dispersed reactive centers for electrocatalytic CO2 reduction and water splitting. Angew. Chem., Int. Ed. 2021, 60, 13177–13196.

    Article  CAS  Google Scholar 

  54. Zhang, Q. Q.; Guan, J. Q. Single-atom catalysts for electrocatalytic applications. Adv. Funct. Mater. 2020, 30, 2000768.

    Article  CAS  Google Scholar 

  55. Liu, M. M.; Wang, L. L.; Zhao, K. N.; Shi, S. S.; Shao, Q. S.; Zhang, L.; Sun, X. L.; Zhao, Y. F.; Zhang, J. J. Atomically dispersed metal catalysts for the oxygen reduction reaction: Synthesis, characterization, reaction mechanisms and electrochemical energy applications. Energy Environ. Sci. 2019, 12, 2890–2923.

    Article  CAS  Google Scholar 

  56. Jing, H. Y.; Zhu, P.; Zheng, X. B.; Zhang, Z. D.; Wang, D. S.; Li, Y. D. Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis. Adv. Powder Mater., in press, https://doi.org/10.1016/j.apmate.2021.10.004.

  57. Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.

    Article  CAS  Google Scholar 

  58. Wang, Y. C.; Liu, Y.; Liu, W.; Wu, J.; Li, Q.; Feng, Q. G.; Chen, Z. Y.; Xiong, X.; Wang, D. S.; Lei, Y. P. Regulating the coordination structure of metal single atoms for efficient electrocatalytic CO2 reduction. Energy Environ. Sci. 2020, 13, 4609–4624.

    Article  CAS  Google Scholar 

  59. Zhou, D. N.; Li, X. Y.; Shang, H. S.; Qin, F. J.; Chen, W. X. Atomic regulation of metal-organic framework derived carbon-based single-atom catalysts for the electrochemical CO2 reduction reaction. J. Mater. Chem. A 2021, 9, 23382–23418.

    Article  CAS  Google Scholar 

  60. Lu, X. L.; Rong, X.; Zhang, C.; Lu, T. B. Carbon-based single-atom catalysts for CO2 electroreduction: Progress and optimization strategies. J. Mater. Chem. A 2020, 8, 10695–10708.

    Article  CAS  Google Scholar 

  61. Peterson, A. A.; Abild-Pedersen, F.; Studt, F.; Rossmeisl, J.; Nørskov, J. K. How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels. Energy Environ. Sci. 2010, 3, 1311–1315.

    Article  CAS  Google Scholar 

  62. Wang, Y. F.; Chen, Z.; Han, P.; Du, Y. H.; Gu, Z. X.; Xu, X.; Zheng, G. F. Single-atomic Cu with multiple oxygen vacancies on ceria for electrocatalytic CO2 reduction to CH4. ACS Catal. 2018, 8, 7113–7119.

    Article  CAS  Google Scholar 

  63. Zhang, Y.; Dong, L.-Z.; Li, S.; Huang, X.; Chang, J.-N.; Wang, J.-H.; Zhou, J.; Li, S.-L.; Lan, Y.-Q. Coordination environment dependent selectivity of single-site-Cu enriched crystalline porous catalysts in CO2 reduction to CH4. Nature Commun. 2021, 12, 6390.

    Article  CAS  Google Scholar 

  64. Wang, G. X.; Chen, J. X.; Ding, Y. C.; Cai, P. W.; Yi, L. C.; Li, Y.; Tu, C. Y.; Hou, Y.; Wen, Z. H.; Dai, L. M. Electrocatalysis for CO2 conversion: From fundamentals to value-added products. Chem. Soc. Rev. 2021, 50, 4993–5061.

    Article  CAS  Google Scholar 

  65. Zhao, K.; Quan, X. Carbon-based materials for electrochemical reduction of CO2 to C2+ oxygenates: Recent progress and remaining challenges. ACS Catal. 2021, 11, 2076–2097.

    Article  CAS  Google Scholar 

  66. Landers, A. T.; Fields, M.; Torelli, D. A.; Xiao, J. P.; Hellstern, T. R.; Francis, S. A.; Tsai, C.; Kibsgaard, J.; Lewis, N. S.; Chan, K. et al. The predominance of hydrogen evolution on transition metal sulfides and phosphides under CO2 reduction conditions: An experimental and theoretical study. ACS Energy Lett. 2018, 3, 1450–1457.

    Article  CAS  Google Scholar 

  67. Goyal, A.; Marcandalli, G.; Mints, V. A.; Koper, M. T. M. Competition between CO2 reduction and hydrogen evolution on a gold electrode under well-defined mass transport conditions. J. Am. Chem. Soc. 2020, 142, 4154–4161.

    Article  CAS  Google Scholar 

  68. Kimura, K. W.; Casebolt, R.; Cimada DaSilva, J.; Kauffman, E.; Kim, J.; Dunbar, T. A.; Pollock, C. J.; Suntivich, J.; Hanrath, T. Selective electrochemical CO2 reduction during pulsed potential stems from dynamic interface. ACS Catal. 2020, 10, 8632–8639.

    Article  CAS  Google Scholar 

  69. Gattrell, M.; Gupta, N.; Co, A. A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper. J. Electroanal. Chem. 2006, 594, 1–19.

    Article  CAS  Google Scholar 

  70. Baruch, M. F.; Pander III, J. E.; White, J. L.; Bocarsly, A. B. Mechanistic insights into the reduction of CO2 on tin electrodes using in situ ATR-IR spectroscopy. ACS Catal. 2011, 5, 3148–3156.

    Article  CAS  Google Scholar 

  71. Gao, D. F.; Zhou, H.; Cai, F.; Wang, D. N.; Hu, Y. F.; Jiang, B.; Cai, W. B.; Chen, X. Q.; Si, R.; Yang, F. et al. Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles. Nano Res. 2017, 10, 2181–2191.

    Article  CAS  Google Scholar 

  72. Zhao, Y. R.; Chang, X. X.; Malkani, A. S.; Yang, X.; Thompson, L.; Jiao, F.; Xu, B. J. Speciation of Cu surfaces during the electrochemical CO reduction reaction. J. Am. Chem. Soc. 2020, 142, 9735–9743.

    CAS  Google Scholar 

  73. Surdhar, P. S.; Mezyk, S. P.; Armstrong, D. A. Reduction potential of the carboxyl radical anion in aqueous solutions. J. Phys. Chem. 1989, 93, 3360–3363.

    Article  CAS  Google Scholar 

  74. Rosen, B. A.; Salehi-Khojin, A.; Thorson, M. R.; Zhu, W.; Whipple, D. T.; Kenis, P. J. A.; Masel, R. I. Ionic liquid-mediated selective conversion of CO2 to CO at low overpotentials. Science 2011, 334, 643–644.

    Article  CAS  Google Scholar 

  75. Sun, Z. Y.; Ma, T.; Tao, H. C.; Fan, Q.; Han, B. X. Fundamentals and challenges of electrochemical CO2 reduction using two-dimensional materials. Chem 2017, 3, 560–587.

    Article  CAS  Google Scholar 

  76. Rosen, J.; Hutchings, G. S.; Lu, Q.; Rivera, S.; Zhou, Y.; Vlachos, D. G.; Jiao, F. Mechanistic insights into the electrochemical reduction of CO2 to CO on nanostructured Ag surfaces. ACS Catal. 2011, 5, 4293–4299.

    Article  CAS  Google Scholar 

  77. Ju, W.; Bagger, A.; Hao, G. P.; Varela, A. S.; Sinev, I.; Bon, V.; Roldan Cuenya, B.; Kaskel, S.; Rossmeisl, J.; Strasser, P. Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2. Nat. Commun. 2017, 8, 944.

    Article  CAS  Google Scholar 

  78. Todorova, T. K.; Schreiber, M. W.; Fontecave, M. Mechanistic understanding of CO2 reduction reaction (CO2RR) toward multicarbon products by heterogeneous copper-based catalysts. ACS Catal. 2020, 10, 1754–1768.

    Article  CAS  Google Scholar 

  79. Vijay, S.; Ju, W.; Brückner, S.; Tsang, S. C.; Strasser, P.; Chan, K. Unified mechanistic understanding of CO2 reduction to CO on transition metal and single atom catalysts. Nat. Catal. 2021, 4, 1024–1031.

    Article  CAS  Google Scholar 

  80. Smith, B. D.; Irish, D. E.; Kedzierzawski, P.; Augustynski, J. A surface enhanced roman scattering study of the intermediate and poisoning species formed during the electrochemical reduction of CO2 on copper. J. Electrochem. Soc. 1997, 144, 4288–4296.

    Article  CAS  Google Scholar 

  81. Qin, X. P.; Zhu, S. Q.; Xiao, F.; Zhang, L. L.; Shao, M. H. Active sites on heterogeneous single-iron-atom electrocatalysts in CO2 reduction reaction. ACS Energy Lett. 2019, 4, 1778–1783.

    Article  CAS  Google Scholar 

  82. Fan, Q.; Hou, P. F.; Choi, C.; Wu, T. S.; Hong, S.; Li, F.; Soo, Y. L.; Kang, P.; Jung, Y.; Sun, Z. Y. Activation of Ni particles into single Ni-N atoms for efficient electrochemical reduction of CO2. Adv. Energy Mater. 2020, 10, 1903068.

    Article  CAS  Google Scholar 

  83. Meshitsuka, S.; Ichikawa, M.; Tamaru, K. Electrocatalysis by metal phthalocyanines in the reduction of carbon dioxide. J. Chem. Soc., Chem. Commun. 1974, 158–159.

  84. Kazuya, H.; Katsuhiro, T.; Hideo, S.; Shinobu, T. Electrocatalytic behavior of tetrasulfonated metal phthalocyanines in the reduction of carbon dioxide. Chem. Lett. 1977, 6, 1137–1140.

    Article  Google Scholar 

  85. Katsuhiro, T.; Kazuya, H.; Hideo, S.; Shinobu, T. Electrocatalytic behavior of metal porphyrins in the reduction of carbon dioxide. Chem. Lett. 1979, 8, 305–308.

    Article  Google Scholar 

  86. Fisher, B. J.; Eisenberg, R. Electrocatalytic reduction of carbon dioxide by using macrocycles of nickel and cobalt. J. Am. Chem. Soc. 1980, 102, 7361–7363.

    Article  CAS  Google Scholar 

  87. Lin, S.; Diercks, C. S.; Zhang, Y. B.; Kornienko, N.; Nichols, E. M.; Zhao, Y. B.; Paris, A. R.; Kim, D.; Yang, P. D.; Yaghi, O. M. et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 2011, 349, 1208–1213.

    Article  CAS  Google Scholar 

  88. Chen, B. T.; Li, B. R.; Tian, Z. Q.; Liu, W. B.; Liu, W. P.; Sun, W. W.; Wang, K.; Chen, L.; Jiang, J. Z. Enhancement of mass transfer for facilitating industrial-level CO2 electroreduction on atomic Ni−N4 sites. Adv. Energy Mater. 2021, 11, 2102152.

    Article  CAS  Google Scholar 

  89. Ni, W. P.; Liu, Z. X.; Zhang, Y.; Ma, C.; Deng, H. Q.; Zhang, S. G.; Wang, S. Y. Electroreduction of carbon dioxide driven by the intrinsic defects in the carbon plane of a single Fe−N4 site. Adv. Mater. 2021, 33, 2003238.

    Article  CAS  Google Scholar 

  90. Li, X. G.; Xi, S. B.; Sun, L. B.; Dou, S.; Huang, Z. F.; Su, T.; Wang, X. Isolated FeN4 sites for efficient electrocatalytic CO2 reduction. Adv. Sci. 2020, 7, 2001545.

    Article  CAS  Google Scholar 

  91. Grasemann, M.; Laurenczy, G. Formic acid as a hydrogen source-recent developments and future trends. Energy Environ. Sci. 2012, 5, 8171–8181.

    Article  CAS  Google Scholar 

  92. Pan, Z. W. H.; Wang, K.; Ye, K. H.; Wang, Y.; Su, H. Y.; Hu, B. H.; Xiao, J.; Yu, T. W.; Wang, Y.; Song, S. Q. Intermediate adsorption states switch to selectively catalyze electrochemical CO2 reduction. ACS Catal. 2020, 10, 3871–3880.

    Article  CAS  Google Scholar 

  93. Li, L.; Ozden, A.; Guo, S. Y.; García de Arquer, F. P.; Wang, C. H.; Zhang, M. Z.; Zhang, J.; Jiang, H. Y.; Wang, W.; Dong, H. et al. Stable, active CO2 reduction to formate via redox-modulated stabilization of active sites. Nat. Commun. 2021, 12, 5223.

    Article  CAS  Google Scholar 

  94. Huang, P. C.; Cheng, M.; Zhang, H. H.; Zuo, M.; Xiao, C.; Xie, Y. Single Mo atom realized enhanced CO2 electro-reduction into formate on N-doped graphene. Nano Energy 2019, 61, 428–434.

    Article  CAS  Google Scholar 

  95. Shang, H. S.; Wang, T.; Pei, J. J.; Jiang, Z. L.; Zhou, D. N.; Wang, Y.; Li, H. J.; Dong, J. C.; Zhuang, Z. B.; Chen, W. X. et al. Design of a single-atom indiumδ+-N4 interface for efficient electroreduction of CO2 to formate. Angew. Chem., Int. Ed. 2020, 59, 22465–22469.

    Article  CAS  Google Scholar 

  96. Zu, X. L.; Li, X. D.; Liu, W.; Sun, Y. F.; Xu, J. Q.; Yao, T.; Yan, W. S.; Gao, S.; Wang, C. M.; Wei, S. Q. et al. Efficient and robust carbon dioxide electroreduction enabled by atomically dispersed Snδ+ sites. Adv. Mater. 2019, 31, 1808135.

    Article  CAS  Google Scholar 

  97. Jiang, Z. L.; Wang, T.; Pei, J. J.; Shang, H. S.; Zhou, D. N.; Li, H. J.; Dong, J. C.; Wang, Y.; Cao, R.; Zhuang, Z. B. et al. Discovery of main group single Sb−N4 active sites for CO2 electroreduction to formate with high efficiency. Energy Environ. Sci. 2020, 13, 2856–2863.

    Article  CAS  Google Scholar 

  98. Peterson, A. A.; Nørskov, J. K. Activity descriptors for CO2 electroreduction to methane on transition-metal catalysts. J. Phys. Chem. Lett. 2012, 3, 251–258.

    Article  CAS  Google Scholar 

  99. Kuhl, K. P.; Hatsukade, T.; Cave, E. R.; Abram, D. N.; Kibsgaard, J.; Jaramillo, T. F. Electrocatalytic conversion of carbon dioxide to methane and methanol on transition metal surfaces. J. Am. Chem. Soc. 2014, 136, 14107–14113.

    Article  CAS  Google Scholar 

  100. Nie, X. W.; Esopi, M. R.; Janik, M. J.; Asthagiri, A. Selectivity of CO2 reduction on copper electrodes: The role of the kinetics of elementary steps. Angew. Chem., Int. Ed. 2013, 52, 2459–2462.

    Article  CAS  Google Scholar 

  101. Kuhl, K. P.; Cave, E. R.; Abram, D. N.; Jaramillo, T. F. New insights into the electrochemical reduction of carbon dioxide on metallic copper surfaces. Energy Environ. Sci. 2012, 5, 7050–7059.

    Article  CAS  Google Scholar 

  102. Gao, D. F.; Arán-Ais, R. M.; Jeon, H. S.; Roldan Cuenya, B. Rational catalyst and electrolyte design for CO2 electroreduction towards multicarbon products. Nat. Catal. 2019, 2, 198–210.

    Article  CAS  Google Scholar 

  103. Monteiro, M. C. O.; Dattila, F.; Hagedoorn, B.; García-Muelas, R.; López, N.; Koper, M. T. M. Absence of CO2 electroreduction on copper, gold and silver electrodes without metal cations in solution. Nat. Catal. 2021, 4, 654–662.

    Article  CAS  Google Scholar 

  104. Cai, Y. M.; Fu, J. J.; Zhou, Y.; Chang, Y. C.; Min, Q. H.; Zhu, J. J.; Lin, Y. H.; Zhu, W. L. Insights on forming N, O-coordinated Cu single-atom catalysts for electrochemical reduction CO2 to methane. Nat. Commun. 2021, 12, 586.

    Article  CAS  Google Scholar 

  105. Han, L. L.; Song, S. J.; Liu, M. J.; Yao, S. Y.; Liang, Z. X.; Cheng, H.; Ren, Z. H.; Liu, W.; Lin, R. Q.; Qi, G. C. et al. Stable and efficient single-atom Zn catalyst for CO2 reduction to CH4. J. Am. Chem. Soc. 2020, 142, 12563–12567.

    Article  CAS  Google Scholar 

  106. Yang, H. P.; Wu, Y.; Li, G. D.; Lin, Q.; Hu, Q.; Zhang, Q. L.; Liu, J. H.; He, C. X. Scalable production of efficient single-atom copper decorated carbon membranes for CO2 electroreduction to methanol. J. Am. Chem. Soc. 2019, 141, 12717–12723.

    Article  CAS  Google Scholar 

  107. Guan, A. X.; Chen, Z.; Quan, Y. L.; Peng, C.; Wang, Z. Q.; Sham, T. K.; Yang, C.; Ji, Y. L.; Qian, L. P.; Xu, X. et al. Boosting CO2 electroreduction to CH4 via tuning neighboring single-copper sites. ACS Energy Lett. 2020, 5, 1044–1053.

    Article  CAS  Google Scholar 

  108. Zhao, K.; Nie, X. W.; Wang, H. Z.; Chen, S.; Quan, X.; Yu, H. T.; Choi, W.; Zhang, G. H.; Kim, B.; Chen, J. G. Selective electroreduction of CO2 to acetone by single copper atoms anchored on N-doped porous carbon. Nat. Commun. 2020, 11, 2455.

    Article  CAS  Google Scholar 

  109. Karapinar, D.; Huan, N. T.; Ranjbar Sahraie, N.; Li, J. K.; Wakerley, D.; Touati, N.; Zanna, S.; Taverna, D.; Galvão Tizei, L. H.; Zitolo, A. et al. Electroreduction of CO2 on single-site copper-nitrogen-doped carbon material: Selective formation of ethanol and reversible restructuration of the metal sites. Angew. Chem., Int. Ed. 2019, 58, 15098–15103.

    Article  CAS  Google Scholar 

  110. Xu, H. P.; Rebollar, D.; He, H. Y.; Chong, L. N.; Liu, Y. Z.; Liu, C.; Sun, C. J.; Li, T.; Muntean, J. V.; Winans, R. E. et al. Highly selective electrocatalytic CO2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper. Nat. Energy 2020, 5, 623–632.

    Article  CAS  Google Scholar 

  111. Back, S.; Lim, J.; Kim, N. Y.; Kim, Y. H.; Jung, Y. Single-atom catalysts for CO2 electroreduction with significant activity and selectivity improvements. Chem. Sci. 2017, 8, 1090–1096.

    Article  CAS  Google Scholar 

  112. Huan, T. N.; Ranjbar, N.; Rousse, G.; Sougrati, M.; Zitolo, A.; Mougel, V.; Jaouen, F.; Fontecave, M. Electrochemical reduction of CO2 catalyzed by Fe-N-C materials: A structure-selectivity study. ACS Catal. 2017, 7, 1520–1525.

    Article  CAS  Google Scholar 

  113. Zhang, N. Q.; Zhang, X. X.; Tao, L.; Jiang, P.; Ye, C. L.; Lin, R.; Huang, Z. W.; Li, A.; Pang, D. W.; Yan, H. et al. Silver singleatom catalyst for efficient electrochemical CO2 reduction synthesized from thermal transformation and surface reconstruction. Angew. Chem., Int. Ed. 2021, 60, 6170–6176.

    Article  CAS  Google Scholar 

  114. Bagger, A.; Ju, W.; Varela, A. S.; Strasser, P.; Rossmeisl, J. Single site porphyrine-like structures advantages over metals for selective electrochemical CO2 reduction. Catal. Today 2017, 288, 74–78.

    Article  CAS  Google Scholar 

  115. Chen, W. X.; Pei, J. J.; He, C. T.; Wan, J. W.; Ren, H. L.; Zhu, Y. Q.; Wang, Y.; Dong, J. C.; Tian, S. B.; Cheong, W. C. et al. Rational design of single molybdenum atoms anchored on N-doped carbon for effective hydrogen evolution reaction. Angew. Chem., Int. Ed. 2017, 56, 16086–16090.

    Article  CAS  Google Scholar 

  116. Chen, W. X.; Pei, J. J.; He, C. T.; Wan, J. W.; Ren, H. L.; Wang, Y.; Dong, J. C.; Wu, K. L.; Cheong, W. C.; Mao, J. J. et al. Single tungsten atoms supported on MOF-derived N-doped carbon for robust electrochemical hydrogen evolution. Adv. Mater. 2018, 30, 1800396.

    Article  CAS  Google Scholar 

  117. Zhang, H. B.; Yu, L.; Chen, T.; Zhou, W.; Lou, X. W. Surface modulation of hierarchical MoS2 nanosheets by Ni single atoms for enhanced electrocatalytic hydrogen evolution. Adv. Funct. Mater. 2018, 28, 1807086.

    Article  CAS  Google Scholar 

  118. Shah, K.; Dai, R. Y.; Mateen, M.; Hassan, Z.; Zhuang, Z. W.; Liu, C. H.; Israr, M.; Cheong, W. C.; Hu, B. T.; Tu, R. Y. et al. Cobalt single atom incorporated in ruthenium oxide sphere: A robust bifunctional electrocatalyst for HER and OER. Angew. Chem., Int. Ed. 2022, 61, e202114951.

    Article  CAS  Google Scholar 

  119. Varela, A. S.; Ju, W.; Bagger, A.; Franco, P.; Rossmeisl, J.; Strasser, P. Electrochemical reduction of CO2 on metal-nitrogen-doped carbon catalysts. ACS Catal. 2019, 9, 7270–7284.

    Article  CAS  Google Scholar 

  120. Li, X. G.; Bi, W. T.; Chen, M. L.; Sun, Y. X.; Ju, H. X.; Yan, W. S.; Zhu, J. F.; Wu, X. J.; Chu, W. S.; Wu, C. Z. et al. Exclusive Ni−N4 sites realize near-unity CO selectivity for electrochemical CO2 reduction. J. Am. Chem. Soc. 2017, 139, 14889–14892.

    Article  CAS  Google Scholar 

  121. Han, N.; Wang, Y.; Ma, L.; Wen, J. G.; Li, J.; Zheng, H. C.; Nie, K. Q.; Wang, X. X.; Zhao, F. P.; Li, Y. G. et al. Supported cobalt polyphthalocyanine for high-performance electrocatalytic CO2 reduction. Chem 2017, 3, 652–664.

    Article  CAS  Google Scholar 

  122. Lin, L.; Li, H. B.; Wang, Y.; Li, H. F.; Wei, P. F.; Nan, B.; Si, R.; Wang, G. X.; Bao, X. H. Temperature-dependent CO2 electroreduction over Fe−N−C and Ni−N−C single-atom catalysts. Angew. Chem., Int. Ed. 2021, 60, 26582–26586.

    Article  CAS  Google Scholar 

  123. Wang, Y.; You, L. M.; Zhou, K. Origin of the N-coordinated singleatom Ni sites in heterogeneous electrocatalysts for CO2 reduction reaction. Chem. Sci. 2021, 12, 14065–14073.

    Article  CAS  Google Scholar 

  124. Gu, J.; Hsu, C. S.; Bai, L. C.; Chen, H. M.; Hu, X. L. Atomically dispersed Fe3+ sites catalyze efficient CO2 electroreduction to CO. Science 2019, 364, 1091–1094.

    Article  CAS  Google Scholar 

  125. Wang, X. Q.; Chen, Z.; Zhao, X. Y.; Yao, T.; Chen, W. X.; You, R.; Zhao, C. M.; Wu, G.; Wang, J.; Huang, W. X. et al. Regulation of coordination number over single Co sites: Triggering the efficient electroreduction of CO2. Angew. Chem., Int. Ed. 2018, 57, 1944–1948.

    Article  CAS  Google Scholar 

  126. Rong, X.; Wang, H. J.; Lu, X. L.; Si, R.; Lu, T. B. Controlled synthesis of a vacancy-defect single-atom catalyst for boosting CO2 electroreduction. Angew. Chem., Int. Ed. 2020, 59, 1961–1965.

    Article  CAS  Google Scholar 

  127. Yan, C. C.; Li, H. B.; Ye, Y. F.; Wu, H. H.; Cai, F.; Si, R.; Xiao, J. P.; Miao, S.; Xie, S. H.; Yang, F. et al. Coordinatively unsaturated nickel-nitrogen sites towards selective and high-rate CO2 electroreduction. Energy Environ. Sci. 2018, 11, 1204–1210.

    Article  CAS  Google Scholar 

  128. Yang, H. B.; Hung, S. F.; Liu, S.; Yuan, K. D.; Miao, S.; Zhang, L. P.; Huang, X.; Wang, H. Y.; Cai, W. Z.; Chen, R. et al. Atomically dispersed Ni(I) as the active site for electrochemical CO2 reduction. Nat. Energy 2018, 3, 140–147.

    Article  CAS  Google Scholar 

  129. Kim, H.; Shin, D.; Yang, W.; Won, D. H.; Oh, H. S.; Chung, M. W.; Jeong, D.; Kim, S. H.; Chae, K. H.; Ryu, J. Y. et al. Identification of single-atom Ni site active toward electrochemical CO2 conversion to CO. J. Am. Chem. Soc. 2021, 143, 925–933.

    Article  CAS  Google Scholar 

  130. Hossain, D.; Huang, Y. F.; Yu, T. H.; Goddard III, W. A.; Luo, Z. T. Reaction mechanism and kinetics for CO2 reduction on nickel single atom catalysts from quantum mechanics. Nat. Commun. 2020, 11, 2256.

    Article  CAS  Google Scholar 

  131. Kramer, W. W.; McCrory, C. C. L. Polymer coordination promotes selective CO2 reduction by cobalt phthalocyanine. Chem. Sci. 2016, 7, 2506–2515.

    Article  CAS  Google Scholar 

  132. Pan, Y.; Lin, R.; Chen, Y. J.; Liu, S. J.; Zhu, W.; Cao, X.; Chen, W. X.; Wu, K. L.; Cheong, W. C.; Wang, Y. et al. Design of single-atom Co−N5 catalytic site: A robust electrocatalyst for CO2 reduction with nearly 100% CO selectivity and remarkable stability. J. Am. Chem. Soc. 2018, 140, 4218–4221.

    Article  CAS  Google Scholar 

  133. Zhang, B. X.; Zhang, J. L.; Shi, J. B.; Tan, D. X.; Liu, L. F.; Zhang, F. Y.; Lu, C.; Su, Z. Z.; Tan, X. N.; Cheng, X. Y. et al. Manganese acting as a high-performance heterogeneous electrocatalyst in carbon dioxide reduction. Nat. Commun. 2019, 10, 2980.

    Article  CAS  Google Scholar 

  134. Zee, D. Z.; Nippe, M.; King, A. E.; Chang, C. J.; Long, J. R. Tuning second coordination sphere interactions in polypyridyl-iron complexes to achieve selective electrocatalytic reduction of carbon dioxide to carbon monoxide. Inorg. Chem. 2020, 59, 5206–5217.

    Article  CAS  Google Scholar 

  135. Nichols, A. W.; Hooe, S. L.; Kuehner, J. S.; Dickie, D. A.; Machan, C. W. Electrocatalytic CO2 reduction to formate with molecular Fe(III) complexes containing pendent proton relays. Inorg. Chem. 2020, 59, 5854–5864.

    Article  CAS  Google Scholar 

  136. Azcarate, I.; Costentin, C.; Robert, M.; Savéant, J. M. Through-space charge interaction substituent effects in molecular catalysis leading to the design of the most efficient catalyst of CO2-to-CO electrochemical conversion. J. Am. Chem. Soc. 2016, 138, 16639–16644.

    Article  CAS  Google Scholar 

  137. Tang, J. K.; Zhu, C. Y.; Jiang, T. W.; Wei, L.; Wang, H.; Yu, K.; Yang, C. L.; Zhang, Y. B.; Chen, C.; Li, Z. T. et al. Anion exchange-induced single-molecule dispersion of cobalt porphyrins in a cationic porous organic polymer for enhanced electrochemical CO2 reduction via secondary-coordination sphere interactions. J. Mater. Chem. A 2020, 8, 18677–18686.

    Article  CAS  Google Scholar 

  138. Weng, Z.; Jiang, J. B.; Wu, Y. S.; Wu, Z. S.; Guo, X. T.; Materna, K. L.; Liu, W.; Batista, V. S.; Brudvig, G. W.; Wang, H. L. Electrochemical CO2 reduction to hydrocarbons on a heterogeneous molecular Cu catalyst in aqueous solution. J. Am. Chem. Soc. 2016, 138, 8076–8079.

    Article  CAS  Google Scholar 

  139. Wu, Y. S.; Jiang, Z.; Lu, X.; Liang, Y. Y.; Wang, H. L. Domino electroreduction of CO2 to methanol on a molecular catalyst. Nature 2019, 575, 639–642.

    Article  CAS  Google Scholar 

  140. Chen, S. H.; Li, W. H.; Jiang, W. J.; Yang, J. R.; Zhu, J. X.; Wang, L. Q.; Ou, H. H.; Zhuang, Z. C.; Chen, M. Z.; Sun, X. H. et al. MOF encapsulating N-heterocyclic carbene-ligated copper single-atom site catalyst towards efficient methane electrosynthesis. Angew. Chem., Int. Ed. 2022, 61, e202114450.

    CAS  Google Scholar 

  141. Sun, X. H.; Tuo, Y. X.; Ye, C. L.; Chen, C.; Lu, Q.; Li, G. N.; Jiang, P.; Chen, S. H.; Zhu, P.; Ma, M. et al. Phosphorus induced electron localization of single iron sites for boosted CO2 electroreduction reaction. Angew. Chem., Int. Ed. 2021, 60, 23614–23618.

    Article  CAS  Google Scholar 

  142. Zhang, X.; Wu, Z. S.; Zhang, X.; Li, L. W.; Li, Y. Y.; Xu, H. M.; Li, X. X.; Yu, X. L.; Zhang, Z. S.; Liang, Y. Y. et al. Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures. Nat. Commun. 2017, 8, 14675.

    Article  Google Scholar 

  143. Liang, F. X.; Zhang, J.; Hu, Z. W.; Ma, C.; Ni, W. P.; Zhang, Y.; Zhang, S. G. Intrinsic defect-rich graphene coupled cobalt phthalocyanine for robust electrochemical reduction of carbon dioxide. ACS Appl. Mater. Interfaces 2021, 13, 25523–25532.

    Article  CAS  Google Scholar 

  144. Zhang, C.; Li, Y. L. Graphdiyne based atomic catalyst: An emerging star for energy conversion. Chem. Res. Chin. Univ. 2021, 37, 1149–1157.

    Article  CAS  Google Scholar 

  145. Liu, X.; Wang, Z. X.; Tian, Y.; Zhao, J. X. Graphdiyne-supported single iron atom: A promising electrocatalyst for carbon dioxide electroreduction into methane and ethanol. J. Phys. Chem. C 2020, 124, 3722–3730.

    Article  CAS  Google Scholar 

  146. Gu, H. L.; Zhong, L. X.; Shi, G. S.; Li, J. Q.; Yu, K.; Li, J.; Zhang, S.; Zhu, C. Y.; Chen, S. H.; Yang, C. L. et al. Graphdiyne/graphene heterostructure: A universal 2D scaffold anchoring monodispersed transition-metal phthalocyanines for selective and durable CO2 electroreduction. J. Am. Chem. Soc. 2021, 143, 8679–8688.

    Article  CAS  Google Scholar 

  147. Wang, J.; Huang, X.; Xi, S. B.; Xu, H.; Wang, X. Axial modification of cobalt complexes on heterogeneous surface with enhanced electron transfer for carbon dioxide reduction. Angew. Chem., Int. Ed. 2020, 59, 19162–19167.

    Article  CAS  Google Scholar 

  148. Huang, N.; Lee, K. H.; Yue, Y.; Xu, X. Y.; Irle, S.; Jiang, Q. H.; Jiang, D. L. A stable and conductive metallophthalocyanine framework for electrocatalytic carbon dioxide reduction in water. Angew. Chem., Int. Ed. 2020, 59, 16587–16593.

    Article  CAS  Google Scholar 

  149. Zhong, H. X.; Ghorbani-Asl, M.; Ly, K. H.; Zhang, J. C.; Ge, J.; Wang, M. C.; Liao, Z. Q.; Makarov, D.; Zschech, E.; Brunner, E. et al. Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks. Nat. Commun. 2020, 11, 1409.

    Article  CAS  Google Scholar 

  150. Wen, C. F.; Mao, F. X.; Liu, Y. W.; Zhang, X. Y.; Fu, H. Q.; Zheng, L. R.; Liu, P. F.; Yang, H. G. Nitrogen-stabilized low-valent Ni motifs for efficient CO2 electrocatalysis. ACS Catal. 2020, 10, 1086–1093.

    Article  CAS  Google Scholar 

  151. Lin, L.; Liu, T. F.; Xiao, J. P.; Li, H. F.; Wei, P. F.; Gao, D. F.; Nan, B.; Si, R.; Wang, G. X.; Bao, X. H. Enhancing CO2 electroreduction to methane with a cobalt phthalocyanine and zinc-nitrogen-carbon tandem catalyst. Angew. Chem., Int. Ed. 2020, 59, 22408–22413.

    Article  CAS  Google Scholar 

  152. Lin, L.; Li, H. B.; Yan, C. C.; Li, H. F.; Si, R.; Li, M. R.; Xiao, J. P.; Wang, G. X.; Bao, X. H. Synergistic catalysis over iron-nitrogen sites anchored with cobalt phthalocyanine for efficient CO2 electroreduction. Adv. Mater. 2019, 31, 1903470.

    Article  CAS  Google Scholar 

  153. Meng, D. L.; Zhang, M. D.; Si, D. H.; Mao, M. J.; Hou, Y.; Huang, Y. B.; Cao, R. Highly selective tandem electroreduction of CO2 to ethylene over atomically isolated nickel-nitrogen site/copper nanoparticle catalysts. Angew. Chem., Int. Ed. 2021, 60, 25485–25492.

    Article  CAS  Google Scholar 

  154. Li, F. W.; Li, Y. C.; Wang, Z. Y.; Li, J.; Nam, D. H.; Lum, Y. W.; Luo, M. C.; Wang, X.; Ozden, A.; Hung, S. F. et al. Cooperative CO2-to-ethanol conversion via enriched intermediates at molecule-metal catalyst interfaces. Nat. Catal. 2020, 3, 75–82.

    Article  CAS  Google Scholar 

  155. Zhang, N. Q.; Zhang, X. X.; Kang, Y. K.; Ye, C. L.; Jin, R.; Yan, H.; Lin, R.; Yang, J. R.; Xu, Q.; Wang, Y. et al. A supported Pd2 dual-atom site catalyst for efficient electrochemical CO2 reduction. Angew. Chem., Int. Ed. 2021, 60, 13388–13393.

    Article  CAS  Google Scholar 

  156. Zhang, H. C.; Chang, X. X.; Chen, J. G.; Goddard III, W. A.; Xu, B. J.; Cheng, M. J.; Lu, Q. Computational and experimental demonstrations of one-pot tandem catalysis for electrochemical carbon dioxide reduction to methane. Nat. Commun. 2019, 10, 3340.

    Article  CAS  Google Scholar 

  157. Ren, D.; Ang, B. S. H.; Yeo, B. S. Tuning the selectivity of carbon dioxide electroreduction toward ethanol on oxide-derived CuxZn catalysts. ACS Catal. 2016, 6, 8239–8247.

    Article  CAS  Google Scholar 

  158. Morales-Guio, C. G.; Cave, E. R.; Nitopi, S. A.; Feaster, J. T.; Wang, L.; Kuhl, K. P.; Jackson, A.; Johnson, N. C.; Abram, D. N.; Hatsukade, T. et al. Improved CO2 reduction activity towards C2+ alcohols on a tandem gold on copper electrocatalyst. Nat. Catal. 2018, 1, 764–771.

    Article  CAS  Google Scholar 

  159. Jouny, M.; Luc, W.; Jiao, F. High-rate electroreduction of carbon monoxide to multi-carbon products. Nat. Catal. 2018, 1, 748–755.

    Article  CAS  Google Scholar 

  160. Hou, Y.; Huang, Y. B.; Liang, Y. L.; Chai, G. L.; Yi, J. D.; Zhang, T.; Zang, K. T.; Luo, J.; Xu, R.; Lin, H. et al. Unraveling the reactivity and selectivity of atomically isolated metal-nitrogen sites anchored on porphyrinic triazine frameworks for electroreduction of CO2. CCS Chem. 2019, 1, 384–395.

    Article  CAS  Google Scholar 

  161. Gao, D. F.; Liu, T. F.; Wang, G. X.; Bao, X. H. Structure sensitivity in single-atom catalysis toward CO2 electroreduction. ACS Energy Lett. 2021, 6, 713–727.

    Article  CAS  Google Scholar 

  162. Zou, Y. Q.; Wang, S. Y. An investigation of active sites for electrochemical CO2 reduction reactions: From in situ characterization to rational design. Adv. Sci. 2021, 8, 2003579.

    Article  CAS  Google Scholar 

  163. Nguyen, T. N.; Dinh, C. T. Gas diffusion electrode design for electrochemical carbon dioxide reduction. Chem. Soc. Rev. 2020, 49, 7488–7504.

    Article  CAS  Google Scholar 

  164. García de Arquer, F. P.; Dinh, C. T.; Ozden, A.; Wicks, J.; McCallum, C.; Kirmani, A. R.; Nam, D. H.; Gabardo, C.; Seifitokaldani, A.; Wang, X. et al. CO2 electrolysis to multicarbon products at activities greater than 1 A·cm−2. Science 2020, 367, 661–666.

    Article  CAS  Google Scholar 

  165. Ma, W. C.; Xie, S. J.; Liu, T. T.; Fan, Q. Y.; Ye, J. Y.; Sun, F. F.; Jiang, Z.; Zhang, Q. H.; Cheng, J.; Wang, Y. Electrocatalytic reduction of CO2 to ethylene and ethanol through hydrogen-assisted C−C coupling over fluorine-modified copper. Nat. Catal. 2020, 3, 478–487.

    Article  CAS  Google Scholar 

Download references

Acknowledgment

This research was supported by the National Natural Science Foundation of China (Nos. 21872039 and 22072030) and Science and Technology Commission of Shanghai Municipality (Nos. 18JC1411700 and 19DZ2270100).

Author information

Authors and Affiliations

  1. Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200438, China

    Huoliang Gu, Jing Wu & Liming Zhang

Authors
  1. Huoliang Gu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jing Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Liming Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Liming Zhang.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gu, H., Wu, J. & Zhang, L. Recent advances in the rational design of single-atom catalysts for electrochemical CO2 reduction. Nano Res. 15, 9747–9763 (2022). https://doi.org/10.1007/s12274-022-4270-1

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12274-022-4270-1

Keywords

Search

Navigation