English

Ultrathin Nitrogenated Carbon Nanosheets with Single-Atom Nickel as an Efficient Catalyst for Electrochemical CO₂ Reduction

• Xiaoxiong Huang ^{1, 2,} ,
• Yingjie Ma ^{1, ,} ,
• Linjie Zhi ^{1, 2, ,}

• 1.

  CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing 100190, China

• 2.

  University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Yingjie Ma, mayj@nanoctr.cn Linjie Zhi, zhilj@nanoctr.cn

• Received Date: 19 November 2020
  Accepted Date: 13 December 2020
  Revised Date: 12 December 2020
  Available Online: 15 February 2022
• Fund Project:

Abstract: The gradual increase of CO₂ concentration in the atmosphere is believed to have a profound impact on the global climate and environment. To address this issue, strategies toward effective CO₂ conversion have been developed. As one of the most available strategies, the CO₂ electrochemical reduction approach is particularly attractive because the required energy can be supplied from renewable sources such as solar energy. Electrochemical reduction of CO₂ to chemical feedstocks offers a promising strategy for mitigating CO₂ emissions from anthropogenic activities; however, a critical challenge for this approach is to develop effective electrocatalysts with ultrahigh activity and selectivity. Herein, we report the facile synthesis of a highly efficient and stable atomically isolated nickel catalyst supported by ultrathin nitrogenated carbon nanosheets (Ni-N-C) for CO₂ reduction through pyrolysis of Ni-doped metal-organic frameworks (MOFs) and dicyandiamide (DCDA). MOFs are crystalline and assembled by metal-containing nodes and organic linkers, which have a large specific surface area, tunable pore size and porosity, and highly dispersed unsaturated metal centers. Thus, Ni-doped MOFs were chosen as the precursors to endow Ni-N-C with a porous carbon structure and nickel ions. The nitrogen in Ni-N-C came from DCDA, which acts as the active site to anchor nickel ions. Because of the porous structure and numerous nitrogen sites, the Ni content of Ni-N-C was as high as 7.77% (w). There were two types of nickel ion-containing structures, including Ni⁺-N-C and Ni²⁺-N-C. The structure transformation of the Ni⁺-N-C species from the initial Ni²⁺ (Ni-MOF) was achieved by pyrolysis, and the ratio of Ni⁺ and Ni²⁺ varied with the pyrolysis temperature. Compared to other Ni-N-C prepared at other temperatures, Ni-N-C-800 contained more Ni⁺-N-C species that possessed the optimum *CO binding energy and thus boosted the CO desorption and evolution rate, thereby exhibiting higher CO Faradaic efficiency (FE) up to 94.6% at -0.9 V (vs. the reversible hydrogen electrode, RHE) in 0.1 mol·L^-1 KHCO₃. In addition, it has been found that the rate of CO formation on the Ni-N-C-800 electrode relies on the electrolyte concentration. With the optimal electrolyte concentration, the Ni-N-C-800 electrode achieved a superior Faraday efficiency of > 90% for CO over a wide potential range of -0.77 to -1.07 V (vs. RHE) and displayed a CO FE as high as 97.9% with a current density of 12.6 mA·cm^-2 at -0.77 V (vs. RHE) in 0.5 mol·L^-1 KHCO₃. After testing at -0.77 V for 12 h, the Ni-N-C-800 electrode maintained a CO FE of approximately 95%, indicating superior long-term stability. We believe that this study will contribute to the design and synthesis of highly catalytically active atomically dispersed monovalent metal sites for metal-N-C catalysts.

Key words:
• Single-atom nickel
•  /  Nitrogenated two-dimensional carbon matrix
•  /  Ni-N-C catalyst
•  /  Pyrolysis
•  /  CO₂ reduction
•  /  Electrocatalysis
•  /  Carbon monoxide

• 1. [1]

     Qiao, J.; Liu, Y.; Hong, F.; Zhang, J. Chem. Soc. Rev. 2014, 45, 631. doi: 10.1002/chin.201417263

  2. [2]

     白晓芳, 陈为, 王白银, 冯光辉, 魏伟, 焦正, 孙予罕. 物理化学学报, 2017, 33, 2388. doi: 10.3866/PKU.WHXB201706131Bai, X. F.; Chen, W.; Wang, B. Y.; Feng, G. H.; Wei, W.; Jiao, Z.; Sun, Y. H. Acta Phys. -Chim. Sin. 2017, 33, 2388. doi: 10.3866/PKU.WHXB201706131

  3. [3]

     Zheng, T.; Jiang, K.; Wang, H. Adv. Mater. 2018, 30, 1802066. doi: 10.1002/adma.201802066

  4. [4]

     Tran-Phu, T.; Daiyan, R.; Fusco, Z.; Ma, Z.; Amal, R.; Tricoli, A. Adv. Funct. Mater. 2020, 30, 1906478. doi: 10.1002/adfm.201906478

  5. [5]

     Li, F.; Thevenon, A.; Rosas-Hernández, A.; Wang, Z.; Li, Y.; Gabardo, C. M.; Ozden, A.; Dinh, C. T.; Li, J.; Wang, Y.; et al. Nature 2020, 577, 509. doi: 10.1038/s41586-019-1782-2

  6. [6]

     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. Nat. Catal. 2018, 1, 764. doi: 10.1038/s41929-018-0139-9

  7. [7]

     Tee, S. Y.; Win, K. Y.; Teo, W. S.; Koh, L. D.; Liu, S.; Teng, C. P.; Han, M. Y. Adv. Sci. 2017, 4, 1600337. doi: 10.1002/advs.201600337

  8. [8]

     Hoffert, M. I.; Caldeira, K.; Benford, G.; Criswell, D. R.; Green, C.; Herzog, H.; Jain, A. K.; Kheshgi, H. S.; Lackner, K. S.; Lewis, J. S.; et al. Science 2002, 298, 981. doi: 10.1126/science.1072357

  9. [9]

     Zhang, Y. -J.; Sethuraman, V.; Michalsky, R.; Peterson, A. A. ACS Catal. 2014, 4, 3742. doi: 10.1021/cs5012298

  10. [10]

      Zhang, W.; Hu, Y.; Ma, L.; Zhu, G.; Wang, Y.; Xue, X.; Chen, R.; Yang, S.; Jin, Z. Adv. Sci. 2018, 5, 1700275. doi: 10.1002/advs.201700275

  11. [11]

      Chang, X.; Wang, T.; Zhao, Z. J.; Yang, P.; Greeley, J.; Mu, R.; Zhang, G.; Gong, Z.; Luo, Z.; Chen, J.; et al. Angew. Chem. Int. Ed. 2018, 57, 15415. doi: 10.1002/anie.201805256

  12. [12]

      Zhu, W.; Michalsky, R.; Metin, O. N.; Lv, H.; Guo, S.; Wright, C. J.; Sun, X.; Peterson, A. A.; Sun, S. J. Am. Chem. Soc. 2013, 135, 16833. doi: 10.1021/ja409445p

  13. [13]

      Liu, S. B.; Tao, H. B.; Zeng, L.; Liu, Q.; Xu, Z. H.; Liu, Q. X.; Luo, J. -L. J. Am. Chem. Soc. 2017, 139, 2160. doi: 10.1021/jacs.6b12103

  14. [14]

      Liu, S.; Xiao, J.; Lu, X. F.; Wang, J.; Wang, X.; Lou, X. W. Angew. Chem. Int. Ed. 2019, 58, 8499. doi: 10.1002/anie.201903613

  15. [15]

      García, J.; Jiménez, C.; Martínez, F.; Camarillo, R.; Rincón, J. J. Catal. 2018, 367, 72. doi: 10.1016/j.jcat.2018.08.017

  16. [16]

      金惠东, 熊力堃, 张想, 连跃彬, 陈思, 陆永涛, 邓昭, 彭扬. 物理化学学报, 2021, 37, 2006017. doi: 10.3866/PKU.WHXB202006017Jin, H. D.; Xiong, L. K.; Zhang, X.; Lian, Y. B.; Chen, S.; Lu, Y. T.; Deng, Z.; Peng, Y. Acta Phys. -Chim. Sin. 2021, 37, 2006017. doi: 10.3866/PKU.WHXB202006017

  17. [17]

      Jiang, K.; Sandberg, R. B.; Akey, A. J.; Liu, X.; Bell, D. C.; Nørskov, J. K.; Chan, K.; Wang, H. Nat. Catal. 2018, 1, 111. doi: 10.1038/s41929-017-0009-x

  18. [18]

      Lee, S.; Park, G.; Lee, J. ACS Catal. 2017, 7, 8594. doi: 10.1021/acscatal.7b02822

  19. [19]

      Bushuyev, O. S.; De Luna, P.; Dinh, C. T.; Tao, L.; Saur, G.; van de Lagemaat, J.; Kelley, S. O.; Sargent, E. H. Joule 2018, 2, 825. doi: 10.1016/j.joule.2017.09.003

  20. [20]

      Ye, R. P.; Ding, J.; Gong, W.; Argyle, M. D.; Yao, Y. G. Nat. Commun. 2019, 10, 5698. doi: 10.1038/s41467-019-13638-9

  21. [21]

      Zhou, W.; Cheng, K.; Kang, J. C.; Zhou, C.; Subramanian, V.; Zhang, Q. H.; Wang, Y. Chem. Soc. Rev. 2019, 48. doi: 10.1039/C8CS00502H

  22. [22]

      Yang, X. -F.; Wang, A. Q.; Qiao, B. T.; Li, J.; Liu, J. Y. Acc. Chem. Res. 2013, 46, 1740. doi: 10.1021/ar300361m

  23. [23]

      Qiao, B.; Wang, A.; Yang, X.; Allard, L. F.; Jiang, Z.; Cui, Y.; Liu, J.; Li, J.; Zhang, T. Nat. Chem. 2011, 3, 634. doi: 10.1038/nchem.1095

  24. [24]

      Ju, W.; Bagger, A.; Hao, G. -P.; Varela, A. S.; Sinev, I.; Bon, V.; Cuenya, B. R.; Kaskel, S.; Rossmeisl, J.; Strasser, P. Nat. Commun. 2017, 8, 944. doi: 10.1038/s41467-017-01035-z

  25. [25]

      Jiao, L.; Yang, W. J.; Wan, G.; Zhang, R.; Zheng, X. S.; Zhou, H.; Yu, S. H.; Jiang, H. L. Angew. Chem. Int. Ed. 2020, 59, 2. doi: 10.1002/anie.202008787

  26. [26]

      Zhang, X.; Wu, Z.; Zhang, X.; Li, L.; Li, Y.; Xu, H.; Li, X.; Yu, X.; Zhang, Z.; Liang, Y.; et al. Nat. Commun. 2017, 8, 14675. doi: 10.1038/ncomms14675

  27. [27]

      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. Adv. Mater. 2019, 31, 1903470. doi: 10.1002/adma.201903470

  28. [28]

      Gu, J.; Hsu, C. S.; Bai, L.; Chen, H. M.; Hu, X. Science 2019, 364, 1091. doi: 10.1126/science.aaw7515

  29. [29]

      Zhang, H.; Li, J.; Xi, S.; Du, Y.; Wang, J. Angew. Chem. Int. Ed. 2019, 131, 42. doi: 10.1002/ange.201906079

  30. [30]

      Zhang, X.; Wang, Y.; Gu, M.; Wang, M.; Zhang, Z. S.; Pan, W. Y.; Jiang, Z.; Zheng, H. Z.; Lucero, M.; Wang, H. L.; et al. Nat. Energy 2020, 5, 684. doi: 10.1038/s41560-020-0667-9

  31. [31]

      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. Nat. Energy 2018, 3, 140. doi: 10.1038/s41560-017-0078-8

  32. [32]

      Yan, Y.; Gu, P.; Zheng, S. S.; Zheng, M. B.; Pang, H.; Xue, H. G. J. Mater. Chem. A 2016, 4, 19078. doi: 10.1 039/c6ta08331e

  33. [33]

      Li, F.; Han, G. -F.; Noh, H. -J.; Kim, S. -J.; Lu, Y. L.; Jeong, H. Y.; Fu, Z. P.; Baek, J. -B. Energy Environ. Sci. 2018, 11, 2263. doi: 10.1039/C8EE01169A

  34. [34]

      Miao, X.; Qu, D.; Yang, D.; Nie, B.; Zhao, Y.; Fan, H.; Su, Z. Adv. Mater. 2018, 30, 1704740. doi: 10.1002/adma.201704740

  35. [35]

      Zhao, Y.; Liang, J.; Wang, C.; Ma, J.; Wallace, G. G. Adv. Energy Mater. 2018, 8, 1702524.1. doi: 10.1002/aenm.201702524

  36. [36]

      Wen, C. F.; Mao, F. X.; Liu, Y. W.; Zhang, X. Y.; Fu, H. Q.; Zheng, L. R.; Liu, P. F.; Yang, H. G. ACS Catal. 2020, 10, 1086. doi: 10.1021/acscatal.9b02978

  37. [37]

      He, S.; Ji, D.; Zhang, J.; Novello, P.; Liu, J. J. Phys. Chem. B 2020, 3, 511. doi: 10.1021/acs.jpcb.9b09730

  38. [38]

      Lu, C.; Yang, J.; Wei, S.; Bi, S.; Xia, Y.; Chen, M.; Hou, Y.; Qiu, M.; Yuan, C.; Su, Y.; et al. Adv. Funct. Mater. 2019, 29, 1806884. doi: 10.1002/adfm.201806884

  39. [39]

      Sa, Y. J.; Jung, H.; Shin, D.; Jeong, H. Y.; Ringe, S.; Kim, H.; Hwang, Y. J.; Joo, S. H. ACS Catal. 2020, 10, 10920. doi: 10.1021/acscatal.0c02325

  40. [40]

      Gabardo, C. M.; Seifitokaldani, A.; Edwards, J. P.; Dinh, C. T.; Burdyny, T.; Kibria, M. G.; O'Brien, C. P.; Sargent, E. H.; Sinton, D. Energy Environ. Sci. 2018, 11, 2531. doi: 10.1039/C8EE01684D

  41. [41]

      Gao, F. -Y.; Bao, R. -C.; Gao, M. -R.; Yu, S. -H. J. Mater. Chem. A 2020, 8, 15458. doi: 10.1039/D0TA03525D

  42. [42]

      Seifitokaldani, A.; Gabardo, C. M.; Burdyny, T.; Dinh, C. T.; Edwards, J. P.; Kibria, M. G.; Bushuyev, O. S.; Kelley, S. O.; Sinton, D.; Sargent, E. H. J. Am. Chem. Soc. 2018, 140, 3833. doi: 10.1021/jacs.7b13542

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