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Research Article

Axial coordination regulation of MOF-based single-atom Ni catalysts by halogen atoms for enhanced CO2 electroreduction

Jia-Xin Peng1, Weijie Yang2, Zhenhe Jia2, Long Jiao1( ), Hai-Long Jiang1( )
Department of Chemistry, University of Science and Technology of China, Hefei 230026, China
Department of Power Engineering, School of Energy, Power and Mechanical Engineering, North China Electric Power University, Baoding 071003, China
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Graphical Abstract

A series of single-atom Ni catalysts with different axial coordination halogen atoms are successfully constructed. They demonstrate enhanced CO selectivity with the increase of Ni electronic states regulated by the halogen species in electrocatalytic CO2 reduction.

Abstract

Single-atom catalysts (SACs), with the utmost atom utilization, have attracted extensive interests for various catalytic applications. The coordination environment of SACs has been recognized to play a vital role in catalysis while their precise regulation at atomic level remains an immense challenge. Herein, a post metal halide modification (PMHM) strategy has been developed to construct Ni-N4 sites with axially coordinated halogen atoms, named Ni1-N-C (X) (X = Cl, Br, and I), on pre-synthetic nitrogen-doped carbon derived from metal–organic frameworks. The axial halogen atoms with distinct electronegativity can break the symmetric charge distribution of planar Ni-N4 sites and regulate the electronic states of central Ni atoms in Ni1-N-C (X) (X = Cl, Br, and I). Significantly, the Ni1-N-C (Cl) catalyst, decorated with the most electronegative Cl atoms, exhibits Faradaic efficiency of CO up to 94.7% in electrocatalytic CO2 reduction, outperforming Ni1-N-C (Br) and Ni1-N-C (I) catalysts. Moreover, Ni1-N-C (Cl) also presents superb performance in Zn-CO2 battery with ultrahigh CO selectivity and great durability. Theoretical calculations reveal that the axially coordinated Cl atom remarkably facilitates *COOH intermediate formation on single-atom Ni sites, thereby boosting the CO2 reduction performance of Ni1-N-C (Cl). This work offers a facile strategy to tailor the axial coordination environments of SACs at atomic level and manifests the crucial role of axial coordination microenvironments in catalysis.

Keywords

metal–organic frameworkssingle-atom catalystsCO2 electroreductionaxial coordination environment

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References

[1]

Wang, A. Q.; Li, J.; Zhang, T. Heterogeneous single-atom catalysis. Nat. Rev. Chem. 2018, 2, 65–81.
Crossref Google Scholar
[2]

Chen, Y. J.; 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.
Crossref Google Scholar
[3]

Liu, L. C.; Corma, A. Metal catalysts for heterogeneous catalysis: From single atoms to nanoclusters and nanoparticles. Chem. Rev. 2018, 118, 4981–5079.
Crossref Google Scholar
[4]

Fei, H. L.; Dong, J. C.; Chen, D. L.; Hu, T. D.; Duan, X. D.; Shakir, I.; Huang, Y.; Duan, X. F. Single atom electrocatalysts supported on graphene or graphene-like carbons. Chem. Soc. Rev. 2019, 48, 5207–5241.
Crossref Google Scholar
[5]

Zhu, C. Z.; Fu, S. F.; Shi, Q. R.; Du, D.; Lin, Y. H. Single-atom electrocatalysts. Angew. Chem., Int. Ed. 2017, 56, 13944–13960.
Crossref Google Scholar
[6]

Li, X. N.; Yang, X. F.; Huang, Y. Q.; Zhang, T.; Liu, B. Supported noble-metal single atoms for heterogeneous catalysis. Adv. Mater. 2019, 31, 1902031.
Crossref Google Scholar
[7]

Yi, J. D.; Xu, R.; Wu. Q.; Zhang, T.; Zang, K. T.; Luo, J.; Liang, Y. L.; Huang, Y. B.; Cao, R. Atomically dispersed iron-nitrogen active sites within porphyrinic triazine-based frameworks for oxygen reduction reaction in both alkaline and acidic media. ACS Energy Lett. 2018, 3, 883–889.
Crossref Google Scholar
[8]

Yang, S. X.; Yu, Y. H.; Dou, M. L.; Zhang, Z. P.; Dai, L. M.; Wang, F. Two-dimensional conjugated aromatic networks as high-site-density and single-atom electrocatalysts for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2019, 58, 14724–14730.
Crossref Google Scholar
[9]

Zhang, J.; Wang, Y. X.; Yang, C. J.; Chen, S. A.; Li, Z. J.; Cheng, Y.; Wang, H. N.; Xiang, Y.; Lu, S. F.; Wang, S. Y. Elucidating the electro-catalytic oxidation of hydrazine over carbon nanotube-based transition metal single atom catalysts. Nano Res. 2021, 14, 4650–4657.
Crossref Google Scholar
[10]

Lin, L. L.; Yu, Q. L.; Peng, M.; Li, A. W.; Yao, S. Y.; Tian, S. H.; Liu, X.; Li, A.; Jiang, Z.; Gao, R. et al. Atomically dispersed Ni/α-MoC catalyst for hydrogen production from methanol/water. J. Am. Chem. Soc. 2021, 143, 309–317.
Crossref Google Scholar
[11]

Qi, K.; Chhowalla, M.; Voiry, D. Single atom is not alone: Metal–support interactions in single-atom catalysis. Mater. Today 2020, 40, 173–192.
Crossref Google Scholar
[12]

Qin, R. X.; Liu, K. L.; Wu, Q. Y.; Zheng, N. F. Surface coordination chemistry of atomically dispersed metal catalysts. Chem. Rev. 2020, 120, 11810–11899.
Crossref Google Scholar
[13]

Li, X. Y.; Rong, H. P.; Zhang, J. T.; Wang, D. S.; Li, Y. D. Modulating the local coordination environment of single-atom catalysts for enhanced catalytic performance. Nano Res. 2020, 13, 1842–1855.
Crossref Google Scholar
[14]

Zhu, Y. Z.; Sokolowski, J.; Song, X. C.; He, Y. H.; Mei, Y.; Wu, G. Engineering local coordination environments of atomically dispersed and heteroatom-coordinated single metal site electrocatalysts for clean energy-conversion. Adv. Energy Mater. 2020, 10, 1902844.
Crossref Google Scholar
[15]

Yang, Q.; Jia, Y.; Wei, F. F.; Zhuang, L. Z.; Yang, D. J.; Liu, J. Z.; Wang, X.; Lin, S.; Yuan, P.; Yao, X. D. Understanding the activity of Co-N4−xCx in atomic metal catalysts for oxygen reduction catalysis. Angew. Chem., Int. Ed. 2020, 59, 6122–6127.
Crossref Google Scholar
[16]

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.
Crossref Google Scholar
[17]

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.
Crossref Google Scholar
[18]

Daiyan, R.; Zhu, X. F.; Tong, Z. Z.; Gong, L. L.; Razmjou, A.; Liu, R. S.; Xia, Z. H.; Lu, X. Y.; Dai, L. M.; Amal, R. Transforming active sites in nickel-nitrogen-carbon catalysts for efficient electrochemical CO2 reduction to CO. Nano Energy 2020, 78, 105213.
Crossref Google Scholar
[19]

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.
Crossref Google Scholar
[20]

Wang, Y.; Zheng, X. B.; Wang, D. S. Design concept for electrocatalysts. Nano Res. 2022, 15, 1730–1752.
Crossref Google Scholar
[21]

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. 2022, 1, 100013.
Crossref Google Scholar
[22]

Tang, C.; Chen, L.; Li, H. J.; Li, L. Q.; Jiao, Y.; Zheng, Y.; Xu, H. L.; Davey, K.; Qiao, S. Z. Tailoring acidic oxygen reduction selectivity on single-atom catalysts via modification of first and second coordination spheres. J. Am. Chem. Soc. 2021, 143, 7819–7827.
Crossref Google Scholar
[23]

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.
Crossref Google Scholar
[24]

Yang, H. Z.; Shi, R.; Shang, L.; Zhang, T. R. Recent advancements of porphyrin-like single-atom catalysts: Synthesis and applications. Small Struct. 2021, 2, 2100007.
Crossref Google Scholar
[25]

Huang, M.; Deng, B. W.; Zhao, X. L.; Zhang, Z. Y.; Li, F.; Li, K. L.; Cui, Z. H.; Kong, L. X.; Lu, J. M; Dong, F. et. al. Template-sacrificing synthesis of well-defined asymmetrically coordinated single-atom catalysts for highly efficient CO2 electrocatalytic reduction. ACS Nano 2022, 16, 2110–2119.
Crossref Google Scholar
[26]

Jing, H. Y.; Liu, W.; Zhao, Z. Y.; Zhang, J. W.; Zhu, C.; Shi, Y. T.; Wang, D. S.; Li, Y. D. Electronics and coordination engineering of atomic cobalt trapped by oxygen-driven defects for efficient cathode in solar cells. Nano Energy 2021, 89, 106365.
Crossref Google Scholar
[27]

Jing, H. Y.; Zhao, Z. Y.; Zhang, J. W.; Zhu, C.; Liu, W.; Li, N. N.; Hao, C.; Shi, Y. T.; Wang, D. S. Atomic evolution of metal–organic frameworks into Co–N3 coupling vacancies by cooperative cascade protection strategy for promoting triiodide reduction. J. Phys. Chem. C 2021, 125, 6147–6156.
Crossref Google Scholar
[28]

Zhi, Q. J.; Jiang, R.; Liu, W. P.; Sun, T. T.; Wang, K.; Jiang, J. Z. Atomic CoN3S1 sites for boosting oxygen reduction reaction via an atomic exchange strategy. Nano Res. 2022, 15, 1803–1808.
Crossref Google Scholar
[29]

Gong, Y. N.; Jiao, L.; Qian, Y. Y.; Pan, C. Y.; Zheng, L. R.; Cai, X. C.; Liu, B.; Yu, S. H.; Jiang, H. L. Regulating the coordination environment of MOF-templated single-atom nickel electrocatalysts for boosting CO2 reduction. Angew. Chem., Int. Ed. 2020, 59, 2705–2709.
Crossref Google Scholar
[30]

Pan, Y.; Chen, Y. J.; Wu, K. L.; Chen, Z.; Liu, S. J.; Cao, X.; Cheong, W. C.; Meng, T.; Luo, J.; Zheng, L. R. et al. Regulating the coordination structure of single-atom Fe-NxCy catalytic sites for benzene oxidation. Nat. Commun. 2019, 10, 4290.
Crossref Google Scholar
[31]

Zhao, C. X.; Li, B. Q.; Liu, J. N.; Zhang, Q. Intrinsic electrocatalytic activity regulation of M-N-C single-atom catalysts for the oxygen reduction reaction. Angew. Chem., Int. Ed. 2021, 60, 4448–4463.
Crossref Google Scholar
[32]

Wang, X. Y.; Wang, Y.; Sang, X. H.; Zheng, W. Z.; Zhang, S. H.; Shuai, L.; Yang, B.; Li, Z. J.; Chen, J. M.; Lei, L. C. et al. Dynamic activation of adsorbed intermediates via axial traction for the promoted electrochemical CO2 reduction. Angew. Chem., Int. Ed. 2021, 60, 4192–4198.
Crossref Google Scholar
[33]

Chen, Z. Q.; Huang, A. J.; Yu, K.; Cui, T. T.; Zhuang, Z. W.; Liu, S. J.; Li, J. Z.; Tu, R. Y.; Sun, K. A.; Tan, X. et al. Fe1N4-O1 site with axial Fe-O coordination for highly selective CO2 reduction over a wide potential range. Energy Environ. Sci. 2021, 14, 3430–3437.
Crossref Google Scholar
[34]

Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The chemistry and applications of metal–organic frameworks. Science, 2013, 341, 1230444.
Crossref Google Scholar
[35]

Zhou, H. C. J.; Kitagawa, S. Metal–organic frameworks (MOFs). Chem. Soc. Rev. 2014, 43, 5415–5418.
Crossref Google Scholar
[36]

Islamoglu, T.; Goswami, S.; Li, Z. Y.; Howarth, A. J.; Farha, O. K.; Hupp, J. T. Postsynthetic tuning of metal–organic frameworks for targeted applications. Acc. Chem. Res. 2017, 50, 805–813.
Crossref Google Scholar
[37]

Cai, G. R.; Yan, P.; Zhang, L. L.; Zhou, H. C.; Jiang, H. L. Metal–organic framework-based hierarchically porous materials: Synthesis and applications. Chem. Rev. 2021, 121, 12278–12326.
Crossref Google Scholar
[38]

Lin, R. B.; Xiang, S. C.; Zhou, W.; Chen, B. L. Microporous metal–organic framework materials for gas separation. Chem 2020, 6, 337–363.
Crossref Google Scholar
[39]

Qiu, T. J.; Liang, Z. B.; Guo, W. H.; Tabassum, H.; Gao, S.; Zou, R. Q. Metal–organic framework-based materials for energy conversion and storage. ACS Energy Lett. 2020, 5, 520–532.
Crossref Google Scholar
[40]

Li, X. R.; Yang, X. C.; Xue, H. G.; Pang, H.; Xu, Q. Metal–organic frameworks as a platform for clean energy applications. EnergyChem 2020, 2, 100027.
Crossref Google Scholar
[41]

Chen, Y. Z.; Zhang, R.; Jiao, L.; Jiang, H. L. Metal–organic framework-derived porous materials for catalysis. Coord. Chem. Rev. 2018, 362, 1–23.
Crossref Google Scholar
[42]

Zhao, S. L.; Tan, C. H.; He, C. T.; An, P. F.; Xie, F.; Jiang, S.; Zhu, Y. F.; Wu, K. H.; Zhang, B. W.; Li, H. J. et al. Structural transformation of highly active metal–organic framework electrocatalysts during the oxygen evolution reaction. Nat. Energy 2020, 5, 881–890.
Crossref Google Scholar
[43]

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.
Crossref Google Scholar
[44]

Wei, Y. S.; Zhang, M.; Zou, R. Q.; Xu. Q. Metal–organic framework-based catalysts with single metal sites. Chem. Rev. 2020, 120, 12089–12174.
Crossref Google Scholar
[45]

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.
Crossref Google Scholar
[46]

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.
Crossref Google Scholar
[47]

Stavretis, S. E.; Atanasov, M.; Podlesnyak, A. A.; Hunter, S. C.; Neese, F.; Xue, Z. L. Magnetic transitions in iron porphyrin halides by inelastic neutron scattering and ab initio studies of zero-field splittings. Inorg. Chem. 2015, 54, 9790–9801.
Crossref Google Scholar
[48]

Huang, X. C.; Lin, Y. Y.; Zhang, J. P.; Chen, X. M. Ligand-directed strategy for zeolite-type metal–organic frameworks: Zinc(Ⅱ) imidazolates with unusual zeolitic topologies. Angew. Chem., Int. Ed. 2006, 45, 1557–1559.
Crossref Google Scholar
[49]

Park, K. S.; Ni, Z.; Côté, A. P.; Choi, J. Y.; Huang, R. D.; Uribe-Romo, F. J.; Chae, H. K.; O’Keeffe, M.; Yaghi, O. M. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proc. Natl. Acad. Sci. USA. 2006, 103, 10186–10191.
Crossref Google Scholar
[50]

Matienzo, J.; Yin, L. I.; Grim, S. O.; Swartz, W. E. Jr. X-ray photoelectron spectroscopy of nickel compounds. Inorg. Chem. 1973, 12, 2762–2769.
Crossref Google Scholar
[51]

Jiao, L.; Zhu, J. T.; Zhang, Y.; Yang, W. J.; Zhou, S. Y.; Li, A. W.; Xie, C. F.; Zheng, X. S.; Zhou, W.; Yu, S. H. et al. Non-bonding interaction of neighboring Fe and Ni single-atom pairs on MOF-derived N-doped carbon for enhanced CO2 electroreduction. J. Am. Chem. Soc. 2021, 143, 19417–19424.
Crossref Google Scholar
[52]

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.
Crossref Google Scholar
[53]

Zhang, Y. H.; Tang, Z. R.; Fu, X. Z.; Xu, Y. J. Nanocomposite of Ag-AgBr-TiO2 as a photoactive and durable catalyst for degradation of volatile organic compounds in the gas phase. Appl. Catal. B 2011, 106, 445–452.
Crossref Google Scholar
[54]

Fan, Q.; Huang, J. W.; Dong, N. N.; Hong, S.; Yan, C.; Liu, Y. C.; Qiu, J. S.; Wang, J.; Sun, Z. Y. Liquid exfoliation of two-dimensional PbI2 nanosheets for ultrafast photonics. ACS Photonics 2019, 6, 1051–1057.
Crossref Google Scholar
[55]

Xie, J. F.; Zhou, Z.; Wang, Y. B. Metal-CO2 batteries at the crossroad to practical energy storage and CO2 recycle. Adv. Funct. Mater. 2020, 30, 1908285.
Crossref Google Scholar
[56]

Liu, M.; Pang, Y. J.; Zhang, B.; Luna, P. D.; Voznyy, O.; Xu, J. X.; Zheng, X. L.; Dinh, C. T.; Fan, F. J.; Cao, C. H. et al. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration. Nature 2016, 537, 382–386.
Crossref Google Scholar
[57]

Sun, S. N.; Li, N.; Liu, J.; Ji, W. X.; Dong, L. Z.; Wang, Y. R.; Lan Y. Q. Identification of the activity source of CO2 electroreduction by strategic catalytic site distribution in stable supramolecular structure system. Natl. Sci. Rev. 2021, 8, nwaa195.
Crossref Google Scholar
[58]

Zheng, T. T.; Jiang, K.; Wang, H. T. Recent advances in electrochemical CO2-to-CO conversion on heterogeneous catalysts. Adv. Mater. 2018, 30, 1802066.
Crossref Google Scholar
Nano Research
Volume 15 Issue 12,
December 2022
Pages 10063-10069
DOI: 10.1007/s12274-022-4467-3
Cite this article:
Peng J-X, Yang W, Jia Z, et al. Axial coordination regulation of MOF-based single-atom Ni catalysts by halogen atoms for enhanced CO2 electroreduction. Nano Research, 2022, 15(12): 10063-10069. https://doi.org/10.1007/s12274-022-4467-3
Topics:
Electrocatalysts
Part of a topical collection:
NR45 Awards in Nanocatalysis, 2022

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Received: 31 March 2022
Revised: 20 April 2022
Accepted: 21 April 2022
Published: 21 June 2022
© Tsinghua University Press 2022
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