Journal Home > Volume 17 , Issue 5
Nano Research 2024, 17(5): 3911-3918 https://doi.org/10.1007/s12274-023-6386-3
Research Article | Issue | Published: 12 January 2024

Asymmetrically coordinated single atom Cu catalyst with unsaturated C–Cu–N structure for CO2 reduction to CO

Show Author's Information Zheng Liu1,2,  Yuxuan Liu3,  Jingqiao Zhang1,2,  Ting Cao1,2,  Zhiyi Sun4,  Juzhe Liu3( ),  Huishan Shang4( )
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
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
School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China
Keywords:
MXene, CO2 reduction, Ti3C2Tx, atomic regulation, cooper single atom
Topics:
Electrocatalysts
Cite this article:
Liu Z, Liu Y, Zhang J, et al. Asymmetrically coordinated single atom Cu catalyst with unsaturated C–Cu–N structure for CO2 reduction to CO. Nano Research, 2024, 17(5): 3911-3918. https://doi.org/10.1007/s12274-023-6386-3
Download citation
EndNote(RIS)
BibTeX

528

Views

83

Downloads

Citations

0

Crossref

0

WoS

0

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

Single atom catalysts (SACs) play a crucial role in energy catalysis due to their distinct coordination environment and high atomic utilization efficiency. This study focuses on the synthesis of a monatomic Cu catalyst with Cu–N1C1 coordination anchored to N-doped Ti3C2Tx MXene (Cu SA@N-Ti3C2Tx) to achieve efficient reduction of CO2 to CO. Detailed characterization, including morphology and multispectral analysis, confirmed the uniform distribution of asymmetrically coordinated Cu atoms in unsaturated C–Cu–N bridge fragments on Ti3C2Tx. The Cu SA@N-Ti3C2Tx catalyst exhibited an excellent CO selectivity with Faraday efficiency of 97.4% at −0.58 V vs. reversible hydrogen electrode (RHE) and satisfactory durability. The in situ X-ray absorption fine structure (XAFS) results confirmed that the carbon dioxide reduction reaction (CO2RR) product distribution is mainly affected by potential-dependent valence change of Cu species. These findings highlight the extensive potential of tuning coordination structure of MXene-based single-atom catalysts for CO2 reduction reactions.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Asymmetrically coordinated single atom Cu catalyst with unsaturated C–Cu–N structure for CO2 reduction to CO

Show Author's information Zheng Liu1,2, Yuxuan Liu3, Jingqiao Zhang1,2, Ting Cao1,2, Zhiyi Sun4, Juzhe Liu3( ), Huishan Shang4( )
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
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
School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China

Abstract

Single atom catalysts (SACs) play a crucial role in energy catalysis due to their distinct coordination environment and high atomic utilization efficiency. This study focuses on the synthesis of a monatomic Cu catalyst with Cu–N1C1 coordination anchored to N-doped Ti3C2Tx MXene (Cu SA@N-Ti3C2Tx) to achieve efficient reduction of CO2 to CO. Detailed characterization, including morphology and multispectral analysis, confirmed the uniform distribution of asymmetrically coordinated Cu atoms in unsaturated C–Cu–N bridge fragments on Ti3C2Tx. The Cu SA@N-Ti3C2Tx catalyst exhibited an excellent CO selectivity with Faraday efficiency of 97.4% at −0.58 V vs. reversible hydrogen electrode (RHE) and satisfactory durability. The in situ X-ray absorption fine structure (XAFS) results confirmed that the carbon dioxide reduction reaction (CO2RR) product distribution is mainly affected by potential-dependent valence change of Cu species. These findings highlight the extensive potential of tuning coordination structure of MXene-based single-atom catalysts for CO2 reduction reactions.

Keywords: MXene, CO2 reduction, Ti3C2Tx, atomic regulation, cooper single atom

References(56)

[1]

Choi, C.; Cai, J.; Lee, C.; Lee, H. M.; Xu, M. J.; Huang, Y. Intimate atomic Cu−Ag interfaces for high CO2RR selectivity towards CH4 at low over potential. Nano Res. 2021, 14, 3497–3501.
DOI Google Scholar
[2]

Eilert, A.; Roberts, F. S.; Friebel, D.; Nilsson, A. Formation of copper catalysts for CO2 reduction with high ethylene/methane product ratio investigated with in situ X-ray absorption spectroscopy. J. Phys. Chem. Lett. 2016, 7, 1466–1470.
DOI Google Scholar
[3]

He, M. Y.; Sun, Y. H.; Han, B. X. Green carbon science: Efficient carbon resource processing, utilization, and recycling towards carbon neutrality. Angew. Chem., Int. Ed. 2022, 61, e202112835.
DOI Google Scholar
[4]

Kong, S. Y.; Lv, X. M.; Wang, X.; Liu, Z. Z.; Li, Z. C.; Jia, B. Q.; Sun, D.; Yang, C.; Liu, L. J.; Guan, A. X. et al. Delocalization state-induced selective bond breaking for efficient methanol electrosynthesis from CO2. Nat. Catal. 2023, 6, 6–15.
DOI Google Scholar
[5]

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.
DOI Google Scholar
[6]

Wang, J. J.; Li, X. P.; Cui, B. F.; Zhang, Z.; Hu, X. F.; Ding, J.; Deng, Y. D.; Han, X. P.; Hu, W. B. A review of non-noble metal-based electrocatalysts for CO2 electroreduction. Rare Met. 2021, 40, 3019–3037.
DOI Google Scholar
[7]

Seger, B.; Laursen, A. B.; Vesborg, P. C. K.; Pedersen, T.; Hansen, O.; Dahl, S.; Chorkendorff, I. Hydrogen production using a molybdenum sulfide catalyst on a titanium-protected n+p-silicon photocathode. Angew. Chem. 2012, 124, 9262–9265.
DOI Google Scholar
[8]
Zhang, H.; Wan, F.; Li, X. G.; Chen, X. H.; Xiong, X. L.; Xi, B. J. Ultrafine PtMo nanocrystals confined on N-doped carbon toward efficient pH-universal hydrogen evolution reaction. Adv. Funct. Mater., in press, DOI: 10.1002/adfm.202306340.
[9]

Zhang, H.; Xi, B. J.; Gu, Y.; Chen, W. H.; Xiong, S. L. Interface engineering and heterometal doping Mo-NiS/Ni(OH)2 for overall water splitting. Nano Res. 2021, 14, 3466–3473
DOI Google Scholar
[10]

Franco, F.; Rettenmaier, C.; Jeon, H. S.; Cuenya, B. R. Transition metal-based catalysts for the electrochemical CO2 reduction: From atoms and molecules to nanostructured materials. Chem. Soc. Rev. 2020, 49, 6884–6946.
DOI Google Scholar
[11]

Jin, S.; Hao, Z. M.; Zhang, K.; Yan, Z. H.; Chen, J. Advances and challenges for the electrochemical reduction of CO2 to CO: From fundamentals to industrialization. Angew. Chem. 2021, 133, 20795–20816.
DOI Google Scholar
[12]

Lv, X. M.; Zhao, H. Y.; Wang, Y. G. Continuous constant potential model for describing the potential-dependent energetics of CO2RR on single atom catalysts. J. Chem. Phys. 2023, 159, 094109.
DOI Google Scholar
[13]

Wang, L. G.; Wang, D. S.; Li, Y. D. Single-atom catalysis for carbon neutrality. Carbon Energy 2022, 4, 1021–1079.
DOI Google Scholar
[14]

Wang, J. L.; Tan, H. Y.; Zhu, Y. P.; Chu, H.; Chen, H. M. Linking the dynamic chemical state of catalysts with the product profile of electrocatalytic CO2 reduction. Angew. Chem. 2021, 133, 17394–17407.
DOI Google Scholar
[15]

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.
DOI Google Scholar
[16]

Hao, J. C.; Zhuang, Z. C.; Hao, J. C.; Cao, K. C.; Hu, Y. X.; Wu, W. B.; Lu, S. L.; Wang, C.; Zhang, N.; Wang, D. S. et al. Strain relaxation in metal alloy catalysts steers the product selectivity of electrocatalytic CO2 reduction. ACS Nano 2022, 16, 3251–3263.
DOI Google Scholar
[17]

Zhang, J. C.; Cai, W. Z.; Hu, F. X.; Yang, H. B.; Liu, B. Recent advances in single atom catalysts for the electrochemical carbon dioxide reduction reaction. Chem. Sci. 2021, 12, 6800–6819.
DOI Google Scholar
[18]

Zhu, H. J.; Lu, M.; Wang, Y. R.; Yao, S. J.; Zhang, M.; Kan, Y. H.; Liu, J.; Chen, Y. F.; Li, S. L.; Lan, Y. Q. Efficient electron transmission in covalent organic framework nanosheets for highly active electrocatalytic carbon dioxide reduction. Nat. Commun. 2020, 11, 497.
DOI Google Scholar
[19]

Hao, J. C.; Zhuang, Z. C.; Hao, J. C.; Wang, C.; Lu, S. L.; Duan, F.; Xu, F. P.; Du, M. L.; Zhu, H. Interatomic electronegativity offset dictates selectivity when catalyzing the CO2 reduction reaction. Adv. Energy Mater. 2022, 12, 2200579.
DOI Google Scholar
[20]

Ye, K.; Zhou, Z.; Shao, J.; Lin, L.; Gao, D.; Ta, N.; Si, R.; Wang, G.; Bao, X. In situ reconstruction of a hierarchical Sn-Cu/SnO x core/shell catalyst for high-performance CO2 electroreduction. Angew. Chem., Int. Ed. 2020, 59, 4814–4821.
DOI Google Scholar
[21]

Shen, J.; Wang, D. S. How to select heterogeneous CO2 reduction electrocatalyst. Nano Res. Energy 2024, 3, e9120096.
DOI Google Scholar
[22]
Li, J. J.; Sun, Y. J.; Zhang, Z. C. Revealing active Cu nanograins for electrocatalytic CO2 reduction through operando studies. SmartMat, in press, DOI: 10.1002/smm2.1209.
[23]

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.
DOI Google Scholar
[24]

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.
DOI Google Scholar
[25]

Zhu, H.; Hu, J. W.; Zhang, Z. L.; Zhuang, Z. C.; Hao, J. C.; Duan, F.; Lu, S. L.; Wang, X. F.; Du, M. L. Lewis acid sites incorporation promotes CO2 electroreduction to multicarbon oxygenates over B-CuO nanotubes. Appl. Catal. B: Environ. 2023, 339, 123082.
DOI Google Scholar
[26]

Shang, H. S.; Liu, D. Atomic design of carbon-based dual-metal site catalysts for energy applications. Nano Res. 2023, 16, 6477–6506.
DOI Google Scholar
[27]

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.
DOI Google Scholar
[28]

Da, Y. M.; Jiang, R.; Tian, Z. L.; Han, X. P.; Chen, W.; Hu, W. B. The applications of single-atom alloys in electrocatalysis: Progress and challenges. SmartMat 2023, 4, e1136.
DOI Google Scholar
[29]

Sun, Z. Y.; Hu, Y. N.; Zhou, D. N.; Sun, M. R.; Wang, S.; Chen, W. X. Factors influencing the performance of copper-bearing catalysts in the CO2 reduction system. ACS Energy Lett. 2021, 6, 3992–4022.
DOI Google Scholar
[30]

Zhang, M.; Hu, Z.; Gu, L.; Zhang, Q. H.; Zhang, L. H.; Song, Q.; Zhou, W.; Hu, S. Electrochemical conversion of CO2 to syngas with a wide range of CO/H2 ratio over Ni/Fe binary single-atom catalysts. Nano Res. 2020, 13, 3206–3211.
DOI Google Scholar
[31]

Li, L. L.; Hasan, I. M. U.; Farwa; He, R. N.; Peng, L. W.; Xu, N. N.; Niazi, N. K.; Zhang, J. N.; Qiao, J. L. Copper as a single metal atom based photo-, electro-, and photoelectrochemical catalyst decorated on carbon nitride surface for efficient CO2 reduction: A review. Nano Res. Energy 2022, 1, 9120015.
DOI Google Scholar
[32]

Cheng, Y. J.; Wang, H.; Song, H. Q.; Zhang, K.; Waterhouse, G. I. N.; Chang, J. W.; Tang, Z. Y.; Lu, S. Y. Design strategies towards transition metal single atom catalysts for the oxygen reduction reaction—A review. Nano Res. Energy 2023, 2, e9120082.
DOI Google Scholar
[33]

Hao, J. C.; Zhu, H.; Zhuang, Z. C.; Zhao, Q.; Yu, R. H.; Hao, J. C.; Kang, Q.; Lu, S. L.; Wang, X. F.; Wu, J. S. et al. Competitive trapping of single atoms onto a metal carbide surface. ACS Nano 2023, 17, 6955–6965.
DOI Google Scholar
[34]

Chen, K.; Zhang, Y.; Xiang, J. Q.; Zhao, X. L.; Li, X. G.; Chu, K. p-Block antimony single-atom catalysts for nitric oxide electroreduction to ammonia. ACS Energy Lett. 2023, 8, 1281–1288
DOI Google Scholar
[35]

Chen, K.; Ma, Z. Y.; Li, X. C.; Kang, J. L.; Ma, D. W.; Chu, K. Single-atom Bi alloyed Pd metallene for nitrate electroreduction to ammonia. Adv. Funct. Mater. 2023, 33, 2209890.
DOI Google Scholar
[36]

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/FeO x . Nat. Chem. 2011, 3, 634–641.
DOI Google Scholar
[37]

Hu, Y. N.; Ying, D.; Sun, Z. Y.; Li, B.; Zhou, H. X.; Wang, S.; Hu, X. M.; He, K.; Qu, M.; Chen, W. X. et al. Rational design, application and dynamic evolution of Cu-N-C single-atom catalysts. J. Mater. Chem. A 2022, 10, 21769–21796.
DOI Google Scholar
[38]

Li, X. G.; Tang, S. S.; Dou, S.; Fan, H. J.; Choksi, T. S.; Wang, X. Molecule confined isolated metal sites enable the electrocatalytic synthesis of hydrogen peroxide. Adv. Mater. 2022, 34, 2104891.
DOI Google Scholar
[39]

Du, W. Y.; Zhang, Y.; Chen, K.; Zhang, G. K.; Chu, K. Mo single-atom catalyst boosts nitrite electroreduction for ammonia synthesis. J. Clean. Prod. 2023, 424, 138875.
DOI Google Scholar
[40]

Wan, Y. Y.; Du, W. Y.; Chen, K.; Zhang, N. N.; Chu, K. Electrocatalytic nitrite-to-ammonia reduction on isolated Cu sites. J. Colloid Interf. Sci. 2023, 652, 2180–2185.
DOI Google Scholar
[41]

Chen, K.; Wang, J. X.; Zhang, H.; Ma, D. W.; Chu, K. Self-tandem electrocatalytic NO reduction to NH3 on a W single atom catalyst. Nano Lett. 2023, 23, 1735–1742.
DOI Google Scholar
[42]

Gao, W. Q.; Xu, Y. F.; Fu, L. K.; Chang, X. X.; Xu, B. J. Experimental evidence of distinct sites for CO2-to-CO and CO conversion on Cu in the electrochemical CO2 reduction reaction. Nat. Catal. 2023, 6, 885–894.
DOI Google Scholar
[43]

Wang, X. L.; Klingan, K.; Klingenhof, M.; Möller, T.; Ferreira de Araújo, J.; Martens, I.; Bagger, A.; Jiang, S.; Rossmeisl, J.; Dau, H. et al. Morphology and mechanism of highly selective Cu(II) oxide nanosheet catalysts for carbon dioxide electroreduction. Nat. Commun. 2021, 12, 794.
DOI Google Scholar
[44]

Yang, B. P.; Liu, K.; Li, H. J. W.; Liu, C. X.; Fu, J. W.; Li, H. M.; Huang, J. E.; Ou, P. F.; Alkayyali, T.; Cai, C. et al. Accelerating CO2 electroreduction to multicarbon products via synergistic electric-thermal field on copper nanoneedles. J. Am. Chem. Soc. 2022, 144, 3039–3049.
DOI Google Scholar
[45]

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.
DOI Google Scholar
[46]

Sun, Z. Y.; Yang, Y. Q.; Fang, C. H.; Yao, Y. C.; Qin, F. J.; Gu, H. F.; Liu, Q. Q.; Xu, W. J.; Tang, H.; Jiang, Z. et al. Atomic-level Pt electrocatalyst synthesized via iced photochemical method for hydrogen evolution reaction with high efficiency. Small 2022, 18, 2203422.
DOI Google Scholar
[47]

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.
DOI Google Scholar
[48]
Liu, W. J.; Zhou, X.; Min, Y.; Huang, J. W.; Chen, J. J.; Wu, Y. E.; Yu, H. Q. Engineering of local coordination microenvironment in single-atom catalysts enabling sustainable conversion of biomass into a broad range of amines. Adv. Mater., in press, DOI: 10.1002/adma.202305924.
[49]

Guo, X.; Wang, C. D.; Wang, W. J.; Zhou, Q.; Xu, W. J.; Zhang, P. J.; Wei, S. Q.; Cao, Y. Y.; Zhu, K. F.; Liu, Z. F. et al. Vacancy manipulating of molybdenum carbide MXenes to enhance Faraday reaction for high performance lithium-ion batteries. Nano Res. Energy 2022, 1, e9120026.
DOI Google Scholar
[50]

Wang, Y. T.; Wang, Y. H. Recent progress in MXene layers materials for supercapacitors: High-performance electrodes. SmartMat 2023, 4, e1130.
DOI Google Scholar
[51]

Liu, Y.; Zou, W. Z.; Zhao, N.; Xu, J. Electrically insulating PBO/MXene film with superior thermal conductivity, mechanical properties, thermal stability, and flame retardancy. Nat. Commun. 2023, 14, 5342.
DOI Google Scholar
[52]

Wei, C. L.; Xi, B. J.; Wang, P.; Wang, Z. R.; An, X. G.; Tian, K. D.; Feng, J. K.; Xiong, S. L. In situ growth engineering on 2D MXenes for next-generation rechargeable batteries. Adv. Energy Sustain. Res. 2023, 4, 2300103.
DOI Google Scholar
[53]

Diao, J. Y.; Hu, M. M.; Lian, Z.; Li, Z. J.; Zhang, H.; Huang, F.; Li, B.; Wang, X. H.; Su, D. S.; Liu, H. Y. Ti3C2T x MXene catalyzed ethylbenzene dehydrogenation: Active sites and mechanism exploration from both experimental and theoretical aspects. ACS Catal. 2018, 8, 10051–10057.
DOI Google Scholar
[54]

Wang, Y. X.; Yue, Y.; Cheng, F.; Cheng, Y. F.; Ge, B. H.; Liu, N. S.; Gao, Y. H. Ti3C2T x MXene-based flexible piezoresistive physical sensors. ACS Nano 2022, 16, 1734–1758.
DOI Google Scholar
[55]

Naguib, M.; Mochalin, V. N.; Barsoum, M. W.; Gogotsi, Y. 25th anniversary article: MXenes: A new family of two-dimensional materials. Adv. Mater. 2014, 26, 992–1005
DOI Google Scholar
[56]

Hao, J. C.; Zhu, H.; Zhao, Q.; Hao, J. C.; Lu, S. L.; Wang, X. F.; Duan, F.; Du, M. L. Interatomic electron transfer promotes electroreduction CO2-to-CO efficiency over a CuZn diatomic site. Nano Res. 2023, 16, 8863–8870.
DOI Google Scholar
File
12274_2023_6386_MOESM1_ESM.pdf (3 MB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 02 October 2023
Revised: 19 November 2023
Accepted: 30 November 2023
Published: 12 January 2024
Issue date: May 2024

Copyright

© Tsinghua University Press 2023

Acknowledgements

Acknowledgements

This work was supported by the Open Research Fund of State Environmental Protection Key Laboratory of Eco-industry, Chinese Research Academy of Environmental Sciences (No. 2022KFF-07), the National Natural Science Foundation of China (Nos. 22201262, 52302092, and 22375019), Natural Science Foundation of Henan Province (No. 222300420290), Fundamental Research Funds for the Central Universities (No. 2023MS057), and Beijing Institute of Technology Research Fund Program for Young Scholars (No. 2022CX01011). The authors also thank the BL14W1 in the Shanghai Synchrotron Radiation Facility (SSRF) for help with characterizations.

Return