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Research Article

In situ reconstruction induced oxygen-deficient multiphase Cu based species hybridized with Ni single atoms as tandem platform for CO2 electroreduction

Juzhe Liu1, Yuheng Wang1, Pengpeng Mo1, Feng Yang1, Kaiqi Jiang1, Zhixiang Cheng1, Yuxuan Liu1, Zhiyi Sun2, Zheng Liu3,4( ), Yimei Zhang1( ), Wenxing Chen2( )
The Key Laboratory of Resources and Environmental System Optimization, Ministry of Education, College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, China
Energy & Catalysis Center, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
SEPA Key Laboratory of Eco-Industry, Chinese Research Academy of Environmental Sciences, Beijing 100012, China
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Graphical Abstract

To construct a robust tandem factory for multicarbons by CO2 electroreduction, we developed a single atom involved multivalent oxide-derived Cu composite material and found it inclined to reconstruct into oxygen-deficient Cu based species hybridized with atomically dispersed NiN4 units on the C matrix. The in situ formed tandem catalytic system exhibited high selectivity for ethanol. This work provides a promising construction strategy for tandem catalytic systems and deepens the understanding of catalytic properties of materials related to electrochemical self-reconstruction.

Abstract

Tandem catalysis, capable of decoupling individual steps, provides a feasible way to build a high-efficiency CO2 electro-conversion system for multicarbons (C2+). The construction of electrocatalytic materials is one of focusing issues. Herein, we fabricated a single atom involved multivalent oxide-derived Cu composite material and found it inclined to reconstruct into oxygen-deficient multiphase Cu based species hybridized with monatomic Ni on N doped C matrix. In this prototype, rapid CO generation and C−C coupling are successively achieved on NiN4 sites and surface amorphized Cu species with defects, resembling a micro-production line. In this way, the in situ formed tandem catalyst exhibited a high Faradaic efficiency (FE) of ~ 78% for C2+ products along with satisfactory durability over 50 h. Particularly, the reconstruction-induced amorphous layer with abundant asymmetric sites should be favorable to improve the ethanol selectivity (FE: 63%), which is about 10 times higher than that of the non-tandem Cu-based contrast material. This work offers a new approach for manipulating tandem catalyst systems towards enhancing C2+ products.

Keywords

tandem catalysissingle atomreconstructionamorphousCO2 reduction reaction

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References

[1]

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.
Crossref Google Scholar
[2]

Kong, X. D.; Zhao, J. K.; Xu, Z. F.; Wang, Z. Y.; Wu, Y. Y.; Shi, Y. H.; Li, H. L.; Ma, C. X.; Zeng, J.; Geng, Z. G. Dynamic metal–ligand coordination boosts CO2 electroreduction. J. Am. Chem. Soc. 2023, 145, 14903–14911.
Crossref Google Scholar
[3]

Wang, Y. C.; Wang, Q. C.; Wu, J.; Zhao, X.; Xiong, Y.; Luo, F. H.; Lei, Y. P. Asymmetric atomic sites make different: Recent progress in electrocatalytic CO2 reduction. Nano Energy 2022, 103, 107815.
Crossref Google Scholar
[4]

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.
Crossref Google Scholar
[5]

Su, J. J.; Liu, Y.; Song, Y.; Huang, L. B.; Guo, W. H.; Cao, X. H.; Dou, Y. B.; Cheng, L.; Li, G.; Hu, Q. S. et al. Recent development of nanomaterials for carbon dioxide electroreduction. SmartMat 2022, 3, 35–53.
Crossref Google Scholar
[6]

Ahmad, T.; Liu, S.; Sajid, M.; Li, K.; Ali, M.; Liu, L.; Chen, W. Electrochemical CO2 reduction to C2+ products using Cu-based electrocatalysts: A review. Nano Res. Energy 2022, 1, 9120021.
Crossref Google Scholar
[7]

Li, Z.; Wu, R.; Zhao, L.; Li, P. B.; Wei, X. X.; Wang, J. J.; Chen, J. S.; Zhang, T. R. Metal–support interactions in designing noble metal-based catalysts for electrochemical CO2 reduction: Recent advances and future perspectives. Nano Res. 2021, 14, 3795–3809.
Crossref Google Scholar
[8]

Yang, D. R.; Ni, B.; Wang, X. Heterogeneous catalysts with well-defined active metal sites toward CO2 electrocatalytic reduction. Adv. Energy Mater. 2020, 10, 2001142.
Crossref Google Scholar
[9]

Zhu, Y. T.; Cui, X. Y.; Liu, H. L.; Guo, Z. G.; Dang, Y. F.; Fan, Z. X.; Zhang, Z. C.; Hu, W. P. Tandem catalysis in electrochemical CO2 reduction reaction. Nano Res. 2021, 14, 4471–4486.
Crossref Google Scholar
[10]

Cao, B.; Li, F. Z.; Gu, J. Designing Cu-based tandem catalysts for CO2 electroreduction based on mass transport of CO intermediate. ACS Catal. 2022, 12, 9735–9752.
Crossref Google Scholar
[11]

Jiang, J. C.; Chen, J. C.; Zhao, M. D.; Yu, Q.; Wang, Y. G.; Li, J. Rational design of copper-based single-atom alloy catalysts for electrochemical CO2 reduction. Nano Res. 2022, 15, 7116–7123.
Crossref Google Scholar
[12]

Xia, T.; Wan, J. W.; Yu, R. B. Progress of the structure–property correlation of heteroatomic coordination structured carbon-based single-atom electrocatalysts. Chem. J. Chin. Univ. 2022, 43, 20220162.
Crossref Google Scholar
[13]

Tan, X. Y.; Yu, C.; Ren, Y. W.; Cui, S.; Li, W. B.; Qiu, J. S. Recent advances in innovative strategies for the CO2 electroreduction reaction. Energy Environ. Sci. 2021, 14, 765–780.
Crossref Google Scholar
[14]

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
[15]

Wang, X. L.; De Araújo, J. F.; Ju, W.; Bagger, A.; Schmies, H.; Kühl, S.; Rossmeisl, J.; Strasser, P. Mechanistic reaction pathways of enhanced ethylene yields during electroreduction of CO2-CO co-feeds on Cu and Cu-tandem electrocatalysts. Nat. Nanotechnol. 2019, 14, 1063–1070.
Crossref Google Scholar
[16]

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.
Crossref Google Scholar
[17]

Zhang, Y.; Li, P.; Zhao, C. M.; Zhou, G.; Zhou, F. Y.; Zhang, Q. T.; Su, C. L.; Wu, Y. E. Multicarbons generation factory: CuO/Ni single atoms tandem catalyst for boosting the productivity of CO2 electrocatalysis. Sci. Bull. 2022, 67, 1679–1687.
Crossref Google Scholar
[18]

Yan, T. T.; Wang, P.; Sun, W. Y. Single-site metal-organic framework and copper foil tandem catalyst for highly selective CO2 electroreduction to C2H4. Small 2023, 19, 2206070.
Crossref Google Scholar
[19]

Hu, X. S.; Li, J. Y.; Zhou, Z. Q.; Wen, L. Y. Tandem electroreduction of CO2 to programmable acetate and syngas via single-nickel-atom-encapsulated copper nanocatalysts. ACS Materials Lett. 2023, 5, 85–94.
Crossref Google Scholar
[20]

Lai, W. C.; Ma, Z. S.; Zhang, J. W.; Yuan, Y. L.; Qiao, Y.; Huang, H. W. Dynamic evolution of active sites in electrocatalytic CO2 reduction reaction: Fundamental understanding and recent progress. Adv. Funct. Mater. 2022, 32, 2111193.
Crossref Google Scholar
[21]

Shang, H. S.; Zhou, X. Y.; Dong, J. C.; Li, A.; Zhao, X.; Liu, Q. H.; Lin, Y.; Pei, J. J.; Li, Z.; Jiang, Z. L. et al. Engineering unsymmetrically coordinated Cu-S1N3 single atom sites with enhanced oxygen reduction activity. Nat. Commun. 2020, 11, 3049.
Crossref Google Scholar
[22]

Zhang, A.; Liang, Y. X.; Li, H. P.; Zhang, B. Y.; Liu, Z. H.; Chang, Q. X.; Zhang, H.; Zhu, C. F.; Geng, Z. G.; Zhu, W. G. et al. In-situ surface reconstruction of InN nanosheets for efficient CO2 electroreduction into formate. Nano Lett. 2020, 20, 8229–8235
Crossref Google Scholar
[23]

Xiong, Y.; Dong, J. C.; Huang, Z. Q.; Xin, P. Y.; Chen, W. X.; Wang, Y.; Li, Z.; Jin, Z.; Xing, W.; Zhuang, Z. B. et al. Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation. Nat. Nanotechnol. 2020, 15, 390–397.
Crossref Google Scholar
[24]

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
[25]

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 OM. Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proc. Natl. Acad. Sci. USA 2006, 103, 10186–10191.
Crossref Google Scholar
[26]

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
[27]

Han, L.; Tian, B. Q.; Gao, X. X.; Zhong, Y.; Wang, S. N.; Song, S. C.; Wang, Z. L.; Zhang, Y.; Kuang, Y.; Sun, X. M. Copper nanowire with enriched high-index facets for highly selective CO2 reduction. SmarMat 2022, 3, 142–150.
Crossref Google Scholar
[28]

Enayati, M. H.; Mohamed, F. A. Application of mechanical alloying/milling for synthesis of nanocrystalline and amorphous materials. Int. Mater. Rev. 2014, 59, 394–416.
Crossref Google Scholar
[29]

Xiong, W. F.; Li, H. F.; Wang, H. M.; Yi, J. D.; You, H. H.; Zhang, S. Y.; Hou, Y.; Cao, M. N.; Zhang, T.; Cao, R. Hollow mesoporous carbon sphere loaded Ni-N4 single-atom: Support structure study for CO2 electrocatalytic reduction catalyst. Small 2020, 16, 2003943.
Crossref Google Scholar
[30]

Li, H. D.; Han, Y.; Zhao, H.; Qi, W. J.; Zhang, D.; Yu, Y. D.; Cai, W. W.; Li, S. X.; Lai, J. P.; Huang, B. L. et al. Fast site-to-site electron transfer of high-entropy alloy nanocatalyst driving redox electrocatalysis. Nat. Commun. 2020, 11, 5437.
Crossref Google Scholar
[31]

Zheng, S. J.; Cheng, H.; Yu, J.; Bie, Q.; Chen, J. D.; Wang, F.; Wu, R.; Blackwood, D. J.; Chen, J. S. Three-dimensional ordered porous N-doped carbon-supported accessible Ni-N x active sites for efficient CO2 electroreduction. Rare Met. 2023, 42, 1800–1807.
Crossref Google Scholar
[32]

Zhou, J. S.; Song, H. H.; Ma, L. L.; Chen, X. H. Magnetite/graphene nanosheet composites: Interfacial interaction and its impact on the durable high-rate performance in lithium-ion batteries. RSC Adv. 2011, 1, 782–791.
Crossref Google Scholar
[33]

Qu, M.; Chen, Z.; Sun, Z. Y.; Zhou, D. N.; Xu, W. J.; Tang, H.; Gu, H. F.; Liang, T.; Hu, P. F.; Li, G. W. et al. Rational design of asymmetric atomic Ni-P1N3 active sites for promoting electrochemical CO2 reduction. Nano Res. 2023, 16, 2170–2176.
Crossref Google Scholar
[34]

Liang, S. Y.; Zhang, T. Y.; Zheng, Y.; Xue, T. S.; Wang, Z.; Wang, Q.; He, H. Maximizing the utilization of single-atom sites on carbon-based catalysts for efficient CO2 electroreduction with ultrahigh turnover frequency. Appl. Catal. B Environ. 2023, 333, 122801.
Crossref Google Scholar
[35]

Zhang, J. F.; Wang, Y.; Li, Z. Y.; Xia, S.; Cai, R.; Ma, L.; Zhang, T. Y.; Ackley, J.; Yang, S. Z.; Wu, Y. C. et al. Grain boundary-derived Cu+/Cu0 interfaces in CuO nanosheets for low overpotential carbon dioxide electroreduction to ethylene. Adv. Sci. (Weinh.) 2022, 9, 2200454.
Crossref Google Scholar
[36]

Chen, Y. X.; Guo, Y. H.; Hu, H. X.; Wang, S.; Lin, Y.; Huang, Y. C. Achieving low temperature formaldehyde oxidation: A case study of NaBH4 reduced cobalt oxide nanowires. Inorg. Chem. Commun. 2017, 82, 20–23.
Crossref Google Scholar
[37]

Gao, D. F.; Zegkinoglou, I.; Divins, N. J.; Scholten, F.; Sinev, I.; Grosse, P.; Cuenya, B. R. Plasma-activated copper nanocube catalysts for efficient carbon dioxide electroreduction to hydrocarbons and alcohols. ACS Nano 2017, 11, 4825–4831.
Crossref Google Scholar
[38]

Zhao, S.Y.; Liu, A. H.; Li, Y. H.; Wen, Y. Y.; Gao, X. Q.; Chen, Q. L. Boosting the electrocatalytic CO2 reduction reaction by nanostructured metal materials via defects engineering. Nanomaterials (Basel) 2022, 12, 2389.
Crossref Google Scholar
[39]

Liu, J. Z.; Nai, J. W.; You, T. T.; An, P. F.; Zhang, J.; Ma, G. S.; Niu, X. G.; Liang, C. Y.; Yang, S. H.; Guo, L. The flexibility of an amorphous cobalt hydroxide nanomaterial promotes the electrocatalysis of oxygen evolution reaction. Small 2018, 14, 1703514.
Crossref Google Scholar
[40]

Mu, S. J.; Lu, H. L.; Wu, Q. B.; Li, L.; Zhao, R. J.; Long, C.; Cui, C. H. Hydroxyl radicals dominate reoxidation of oxide-derived Cu in electrochemical CO2 reduction. Nat. Commun. 2022, 13, 3694.
Crossref Google Scholar
[41]

Liu, J. Z.; Guo, L. In situ self-reconstruction inducing amorphous species: A key to electrocatalysis. Matter 2021, 4, 2850–2873
Crossref Google Scholar
[42]

Gu, Z. X.; Yang, N.; Han, P.; Kuang, M.; Mei, B. B.; Jiang, Z.; Zhong, J.; Li, L.; Zheng, G. Oxygen vacancy tuning toward efficient electrocatalytic CO2 reduction to C2H4. Small Methods 2018, 3, 1800449.
Crossref Google Scholar
[43]

Periasamy, A. P.; Ravindranath, R.; Kumar, S. M. S.; Wu, W. P.; Jian, T. R.; Chang, H. T. Facet- and structure-dependent catalytic activity of cuprous oxide/polypyrrole particles towards the efficient reduction of carbon dioxide to methanol. Nanoscale 2018, 10, 11869–11880.
Crossref Google Scholar
[44]

Liu, J. Z.; Hu, Q.; Wang, Y.; Yang, Z.; Fan, X. Y.; Liu, L. M.; Guo, L. Achieving delafossite analog by in situ electrochemical self-reconstruction as an oxygen-evolving catalyst. Proc. Natl. Acad. Sci. USA 2020, 117, 21906–21913.
Crossref Google Scholar
[45]

Wang, H. Z.; Bi, X. Z.; Yan, Y. F.; Zhao, Y. Z.; Yang, Z. X.; Ning, H.; Wu, M. B. Efficient electrocatalytic reduction of CO2 to ethanol enhanced by spacing effect of Cu-Cu in Cu2− x Se nanosheets. Adv. Funct. Mater. 2023, 33, 2214946.
Crossref Google Scholar
[46]

Su, X. Z.; Jiang, Z. L.; Zhou, J.; Liu, H. J.; Zhou, D. N.; Shang, H. S.; Ni, X. M.; Peng, Z.; Yang, F.; Chen, W. X. et al. Complementary Operando spectroscopy identification of in-situ generated metastable charge-asymmetry Cu2-CuN3 clusters for CO2 reduction to ethanol. Nat. Commun. 2022, 13, 1322.
Crossref Google Scholar
[47]

Zhang, T. T.; Yuan, B. W.; Wang, W. L.; He, J.; Xiang, X. Tailoring *H intermediate coverage on the CuAl2O4/CuO catalyst for enhanced electrocatalytic CO2 reduction to ethanol. Angew. Chem., Int. Ed. 2023, 62, e202302096.
Crossref Google Scholar
[48]

Guo, C. Y.; Guo, Y. H.; Shi, Y. M.; Lan, X. N.; Wang, Y. T.; Yu, Y. F.; Zhang, B. Electrocatalytic reduction of CO2 to ethanol at close to theoretical potential via engineering abundant electron-donating Cu δ + species. Angew. Chem., Int. Ed. 2022, 61, e202205909.
Crossref Google Scholar
[49]

Chen, J. Y.; Wang, D. S.; Yang, X. X.; Cui, W. J.; Sang, X. H.; Zhao, Z. L.; Wang, L. G.; Li, Z. J.; Yang, B.; Lei, L. C. et al. Accelerated transfer and spillover of carbon monoxide through tandem catalysis for kinetics-boosted ethylene electrosynthesis. Angew. Chem., Int. Ed. 2023, 62, e202215406.
Crossref Google Scholar
Nano Research
Volume 17 Issue 5,
May 2024
Pages 3888-3894
DOI: 10.1007/s12274-023-6375-6
Cite this article:
Liu J, Wang Y, Mo P, et al. In situ reconstruction induced oxygen-deficient multiphase Cu based species hybridized with Ni single atoms as tandem platform for CO2 electroreduction. Nano Research, 2024, 17(5): 3888-3894. https://doi.org/10.1007/s12274-023-6375-6
Topics:
Electrolytic reduction

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Received: 28 October 2023
Revised: 14 November 2023
Accepted: 27 November 2023
Published: 29 December 2023
© Tsinghua University Press 2023
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