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Vol. 14 (2022)

Atomically Dispersed Fe-Co Bimetallic Catalysts for the Promoted Electroreduction of Carbon Dioxide

https://doi.org/10.1007/s40820-021-00746-9
Zhangsen Chen
Institut National de la Recherche Scientifique-Énergie Matériaux et Télécommunications, Varennes, QC J3X 1P7, Canada
Gaixia Zhang
Institut National de la Recherche Scientifique-Énergie Matériaux et Télécommunications, Varennes, QC J3X 1P7, Canada
Yuren Wen
School of Materials Science and Engineering, University of Science and Technology, 100083 Beijing, People’s Republic of China
Ning Chen
Canadian Light Source, University of Saskatchewan, Saskatoon, SK S7N 2V3, Canada
Weifeng Chen
Canadian Light Source, University of Saskatchewan, Saskatoon, SK S7N 2V3, Canada
Tom Regier
Canadian Light Source, University of Saskatchewan, Saskatoon, SK S7N 2V3, Canada
James Dynes
Canadian Light Source, University of Saskatchewan, Saskatoon, SK S7N 2V3, Canada
Yi Zheng
Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou 350116, People’s Republic of China
Shuhui Sun
Institut National de la Recherche Scientifique-Énergie Matériaux et Télécommunications, Varennes, QC J3X 1P7, Canada

Corresponding Author: Shuhui Sun

shuhui@emt.inrs.ca

Nano-Micro Letters, Vol. 14 (2022), Article Number: 25

Abstract

The electroreduction reaction of CO2 (ECO2RR) requires high-performance catalysts to convert CO2 into useful chemicals. Transition metal-based atomically dispersed catalysts are promising for the high selectivity and activity in ECO2RR. This work presents a series of atomically dispersed Co, Fe bimetallic catalysts by carbonizing the Fe-introduced Co-zeolitic-imidazolate-framework (C–Fe–Co–ZIF) for the syngas generation from ECO2RR. The synergistic effect of the bimetallic catalyst promotes CO production. Compared to the pure C–Co–ZIF, C–Fe–Co–ZIF facilitates CO production with a CO Faradaic efficiency (FE) boost of 10%, with optimal FECO of 51.9%, FEH2 of 42.4% at − 0.55 V, and CO current density of 8.0 mA cm−2 at − 0.7 V versus reversible hydrogen electrode (RHE). The H2/CO ratio is tunable from 0.8 to 4.2 in a wide potential window of − 0.35 to − 0.8 V versus RHE. The total FECO+H2 maintains as high as 93% over 10 h. The proper adding amount of Fe could increase the number of active sites and create mild distortions for the nanoscopic environments of Co and Fe, which is essential for the enhancement of the CO production in ECO2RR. The positive impacts of Cu–Co and Ni–Co bimetallic catalysts demonstrate the versatility and potential application of the bimetallic strategy for ECO2RR.


Highlights:


1 X-ray photoelectron spectroscopy results confirmed the increased number of M–N sites in the bimetallic Fe–Co catalyst.
2 Synchrotron-based X-ray absorption fine structure demonstrated that the interaction in the coordination environments of the different transition metal sites facilitated the CO production in electroreduction reaction of CO2 (ECO2RR).
3 This bimetallic strategy has also been extended to fabricate other catalysts such as Cu–Co and Ni–Co, which also exhibited enhanced performance for ECO2RR.

Keywords

CO2 reduction Electrocatalysis Syngas production Cobalt Iron Bimetallic catalysts
Chen, Zhangsen, Gaixia Zhang, Yuren Wen, Ning Chen, Weifeng Chen, Tom Regier, James Dynes, Yi Zheng, and Shuhui Sun. 2021. “Atomically Dispersed Fe-Co Bimetallic Catalysts for the Promoted Electroreduction of Carbon Dioxide”. Nano-Micro Letters 14 (December):25. https://doi.org/10.1007/s40820-021-00746-9.
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References
  1. Z.S. Chen, G.X. Zhang, J. Prakash, Y. Zheng, S.H. Sun, Rational design of novel catalysts with atomic layer deposition for the reduction of carbon dioxide. Adv. Energy Mater. 9(37), 1900889 (2019). https://doi.org/10.1002/aenm.201900889
  2. Z. Chen, G. Zhang, L. Du, Y. Zheng, L. Sun et al., Nanostructured cobalt-based electrocatalysts for CO2 reduction: Recent progress, challenges, and perspectives. Small 16(52), e2004158 (2020). https://doi.org/10.1002/smll.202004158
  3. Y. Zhang, X. Su, L. Li, H. Qi, C. Yang et al., Ru/TiO2 catalysts with size-dependent metal/support interaction for tunable reactivity in Fischer-Tropsch synthesis. ACS Catal. 10(21), 12967–12975 (2020). https://doi.org/10.1021/acscatal.0c02780
  4. V. Andrei, B. Reuillard, E. Reisner, Bias-free solar syngas production by integrating a molecular cobalt catalyst with perovskite-BiVO4 tandems. Nat. Mater. 19, 189–194 (2019). https://doi.org/10.1038/s41563-019-0501-6
  5. J. Kang, S. He, W. Zhou, Z. Shen, Y. Li et al., Single-pass transformation of syngas into ethanol with high selectivity by triple tandem catalysis. Nat. Commun. 11(1), 827 (2020). https://doi.org/10.1038/s41467-020-14672-8
  6. B. Zhang, B. Zhang, Y. Jiang, T. Ma, H. Pan et al., Single-atom electrocatalysts for multi-electron reduction of CO2. Small 17(36), e2101443 (2021). https://doi.org/10.1002/smll.202101443
  7. S. Zhu, E.P. Delmo, T. Li, X. Qin, J. Tian et al., Recent advances in catalyst structure and composition engineering strategies for regulating CO2 electrochemical reduction. Adv. Mater. (2021). https://doi.org/10.1002/adma.202005484
  8. X. Wang, Z. Chen, X. Zhao, T. Yao, W. Chen et al., Regulation of coordination number over single Co sites: triggering the efficient electroreduction of CO2. Angew. Chem. Int. Ed. 57(7), 1944–1948 (2018). https://doi.org/10.1002/anie.201712451
  9. 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
  10. H.B. Yang, S.F. Hung, S. Liu, K. Yuan, S. Miao et al., Atomically dispersed Ni(I) as the active site for electrochemical CO2 reduction. Nat. Energy 3(2), 140–147 (2018). https://doi.org/10.1038/s41560-017-0078-8
  11. C. Zhang, S. Yang, J. Wu, M. Liu, S. Yazdi et al., Electrochemical CO2 reduction with atomic iron-dispersed on nitrogen-doped graphene. Adv. Energy Mater. 8(19), 1703487 (2018). https://doi.org/10.1002/aenm.201703487
  12. J. Gu, C.S. Hsu, L. Bai, H.M. Chen, X. Hu, Atomically dispersed Fe3+ sites catalyze efficient CO2 electroreduction to CO. Science 364(6445), 1091–1094 (2019). https://doi.org/10.1126/science.aaw7515
  13. X. Wang, Z. Wang, Y. Bai, L. Tan, Y. Xu et al., Tuning the selectivity of photoreduction of CO2 to syngas over Pd/layered double hydroxide nanosheets under visible-light up to 600 nm. J. Energy Chem. 46, 1–7 (2020). https://doi.org/10.1016/j.jechem.2019.10.004
  14. W. Zhou, K. Cheng, J. Kang, C. Zhou, V. Subramanian et al., New horizon in C1 chemistry: breaking the selectivity limitation in transformation of syngas and hydrogenation of CO2 into hydrocarbon chemicals and fuels. Chem. Soc. Rev. 48(12), 3193–3228 (2019). https://doi.org/10.1039/c8cs00502h
  15. J. Long, H. Zhang, J. Ming, J. Zhao, Q. Gu et al., High-rate, tunable syngas production with artificial photosynthetic cells. Angew. Chem. Int. Ed. 58(23), 7718–7722 (2019). https://doi.org/10.1002/anie.201902361
  16. S.J. Shen, C. Han, B. Wang, Y.A. Du, Y.D. Wang, Dual active sites-dependent syngas proportions from aqueous CO2 electroreduction. Appl. Catal. B Environ. 279, 119380 (2020). https://doi.org/10.1016/j.apcatb.2020.119380
  17. M. Wu, G. Zhang, Y. Hu, J. Wang, T. Sun et al., Graphitic-shell encapsulated FeNi alloy/nitride nanocrystals on biomass-derived N-doped carbon as an efficient electrocatalyst for rechargeable Zn-air battery. Carbon Energy 3(1), 176–187 (2020). https://doi.org/10.1002/cey2.52
  18. M. Wu, G. Zhang, N. Chen, W. Chen, J. Qiao et al., A self-supported electrode as a high-performance binder- and carbon-free cathode for rechargeable hybrid zinc batteries. Energy Stor. Mater. 24, 272–280 (2020). https://doi.org/10.1016/j.ensm.2019.08.009
  19. C.H. Wu, C. Liu, D. Su, H.L. Xin, H.T. Fang et al., Bimetallic synergy in cobalt–palladium nanocatalysts for CO oxidation. Nat. Catal. 2(1), 78–85 (2018). https://doi.org/10.1038/s41929-018-0190-6
  20. Z. Kou, X. Li, T. Wang, Y. Ma, W. Zang et al., Fundamentals, on-going advances and challenges of electrochemical carbon dioxide reduction. Electrochem. Energy Rev. (2021). https://doi.org/10.1007/s41918-021-00096-5
  21. Y. Liu, D. Tian, A.N. Biswas, Z. Xie, S. Hwang et al., Transition metal nitrides as promising catalyst supports for tuning CO/H2 syngas production from electrochemical CO2 reduction. Angew. Chem. Int. Ed. 59(28), 11345–11348 (2020). https://doi.org/10.1002/anie.202003625
  22. M.B. Ross, Y. Li, P.D. Luna, D. Kim, E.H. Sargent et al., Electrocatalytic rate alignment enhances syngas generation. Joule 3(1), 257–264 (2019). https://doi.org/10.1016/j.joule.2018.09.013
  23. Q. He, D. Liu, J.H. Lee, Y. Liu, Z. Xie et al., Electrochemical conversion of CO2 to syngas with controllable CO/H2 ratios over CO and Ni single-atom catalysts. Angew. Chem. Int. Ed. 59(8), 3033–3037 (2019). https://doi.org/10.1002/anie.201912719
  24. S.H. Yin, J. Yang, Y. Han, G. Li, L.Y. Wan et al., Construction of highly active metal-containing nanoparticles and FeCo-N4 composite sites for the acidic oxygen reduction reaction. Angew. Chem. Int. Ed. 132(49), 22160–22163 (2020). https://doi.org/10.1002/ange.202010013
  25. Sarveena, J.M. Vargas, D.K. Shukla, C.T. Meneses, P.M. Zelis et al., Synthesis, phase composition mossbauer and magnetic characterization of iron oxide nanoparticles. Phys. Chem. Chem. Phys. 18(14), 9561–9568 (2016). https://doi.org/10.1039/c5cp07698f
  26. G. Zhang, X. Yang, M. Dubois, M. Herraiz, R. Chenitz et al., Non-PGM electrocatalysts for PEM fuel cells: effect of fluorination on the activity and stability of a highly active NC_Ar + NH3 catalyst. Energy Environ. Sci. 12(10), 3015–3037 (2019). https://doi.org/10.1039/c9ee00867e
  27. Y. Pan, R. Lin, Y. Chen, S. Liu, W. Zhu 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. 140(12), 4218–4221 (2018). https://doi.org/10.1021/jacs.8b00814
  28. T. Schiros, D. Nordlund, L. Palova, D. Prezzi, L. Zhao et al., Connecting dopant bond type with electronic structure in N-doped graphene. Nano Lett. 12(8), 4025–4031 (2012). https://doi.org/10.1021/nl301409h
  29. L. Jin, B. Liu, P. Wang, H. Yao, L.A. Achola et al., Ultrasmall Au nanocatalysts supported on nitrided carbon for electrocatalytic CO2 reduction: the role of the carbon support in high selectivity. Nanoscale 10(30), 14678–14686 (2018). https://doi.org/10.1039/c8nr04322a
  30. A. Roy, D. Hursán, K. Artyushkova, P. Atanassov, C. Janáky et al., Nanostructured metal-N-C electrocatalysts for CO2 reduction and hydrogen evolution reactions. Appl. Catal. B 232, 512–520 (2018). https://doi.org/10.1016/j.apcatb.2018.03.093
  31. Z. Chen, X. Zhang, W. Liu, M. Jiao, K. Mou et al., Amination strategy to boost CO2 electroreduction current density of M-N/C single-atom catalysts to industrial application level. Energy Environ. Sci. 14(4), 2349–2356 (2021). https://doi.org/10.1039/d0ee04052e
  32. L. Lin, H. Li, C. Yan, H. Li, R. Si et al., Synergistic catalysis over iron-nitrogen sites anchored with cobalt phthalocyanine for efficient CO2 electroreduction. Adv. Mater. 31(41), e1903470 (2019). https://doi.org/10.1002/adma.201903470
  33. 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
  34. V.V. Mesilov, V.R. Galakhov, A.F. Gubkin, E.A. Sherstobitova, G.S. Zakharova et al., X-ray diffraction and X-ray spectroscopy studies of cobalt-doped anatase TiO2: Co nanopowders. J. Phys. Chem. C 121(43), 24235–24244 (2017). https://doi.org/10.1021/acs.jpcc.7b05873
  35. X. Yang, M. Wang, M.J. Zachman, H. Zhou, Y. He et al., Binary atomically dispersed metal-site catalysts with core−shell nanostructures for O2 and CO2 reduction reactions. Small Sci. (2021). https://doi.org/10.1002/smsc.202100046
  36. W.T. Chen, C.W. Hsu, J.F. Lee, C.W. Pao, I.J. Hsu, Theoretical analysis of Fe k-edge XANES on iron pentacarbonyl. ACS Omega 5(10), 4991–5000 (2020). https://doi.org/10.1021/acsomega.9b03887
  37. H. Dong, L. Zhang, L. Li, W. Deng, C. Hu et al., Abundant Ce3+ ions in Au-CeOx nanosheets to enhance CO2 electroreduction performance. Small 15(17), e1900289 (2019). https://doi.org/10.1002/smll.201900289
  38. G.W. Woyessa, J.B. Cruz, M. Rameez, C.H. Hung, Nanocomposite catalyst of graphitic carbon nitride and Cu/Fe mixed metal oxide for electrochemical CO2 reduction to CO. Appl. Catal. B 291, 120052 (2021). https://doi.org/10.1016/j.apcatb.2021.120052
  39. J. Wang, S. Kattel, C.J. Hawxhurst, J.H. Lee, B.M. Tackett et al., Enhancing activity and reducing cost for electrochemical reduction of CO2 by supporting palladium on metal carbides. Angew. Chem. Int. Ed. 58(19), 6271–6275 (2019). https://doi.org/10.1002/anie.201900781
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