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Room-temperature liquid metal synthesis of nanoporous copper-indium heterostructures for efficient carbon dioxide reduction to syngas

室温液态金属合成纳米多孔铜铟异质结构材料应用于高性能二氧化碳转化合成气

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Abstract

Nanoporous metals show promising performances in electrochemical catalysis. In this paper, we report a self-supporting bimetallic porous heterogeneous indium/copper structure synthesized with a eutectic gallium-indium (EGaIn) material on a copper substrate. This nanoporous copper-indium heterostructure catalyst exhibits excellent performance in the reduction of carbon dioxide to syngas. The ratio of H2/CO is tunable from 0.47 to 2.0 by changing working potentials. The catalyst is highly stable, showing 96% maintenance of the current density after a 70-h continuous test. Density functional theory calculations reveal that the indium/copper interface induces charge redistribution within the copper surface, leading to the formation of two distinct active sites, namely, Cuδ and Cu0, and enabling a high-performance generation of CO and H2. This work provides a new strategy for obtaining self-supporting nanoporous metal electrode catalysts.

摘要

纳米多孔金属作为电催化剂使用时表现出了优异的性能. 我们报道了一种利用共熔镓铟合金和铜基底制备而成的自支撑铜铟双金属多孔异质结构材料. 该多孔铜铟异质结构电催化剂具有良好的二氧化碳转化为合成气的性能. 通过调整工作电压, 可以使氢气和一氧化碳的比例控制在0.47–2.0之间. 且该催化剂非常稳定, 经过70小时连续测试后还可以保持96%的电流密度. 密度泛函理论计算表明, 得益于这种铜铟异质结构的存在, 铜表面电荷发生了转变, 形成了Cuδ和Cu0等不同位点, 从而协同作用分别增**了催化剂生成一氧化碳和氢气的能力. 本工作可为多孔金属异质结构电催化剂的设计提供新思路.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51872116 and 12034002), the Project for Self-Innovation Capability Construction of Jilin Province Development and Reform Commission (2021C026), the Program for JLU Science and Technology Innovative Research Team (JLUSTIRT-2017TD-09), the Science and Technology Development Program of Jilin Province (20190201233JC), and the Fundamental Research Funds for the Central Universities. The work was carried out at LvLiang Cloud Computing Center of China, and the calculations were performed on TianHe-2.

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Authors and Affiliations

  1. State Key Laboratory of Automotive Simulation and Control, School of Materials Science and Engineering, Key Laboratory of Automobile Materials of MOE, Jilin University, Changchun, 130012, China

    **ngcheng Ma  (马星程), Dantong Zhang  (张丹彤), **ao Zhao  (赵晓), **aoqiang Cui  (崔小**) & Weitao Zheng  (郑伟涛)

  2. Key Laboratory of Photonic and Electronic Bandgap Materials, Ministry of Education, and College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin, 150025, China

    Dongxu Jiao  (焦东旭) & **gxiang Zhao  (赵景祥)

  3. Department of Physics and Astronomy and Department of Chemistry, University of Missouri, Columbia, Missouri, 65211, USA

    David J. Singh  (辛格戴维)

  4. Guangdong Provincial Key Laboratory of Functional Oxide Materials and Devices, Southern University of Science and Technology, Shenzhen, 518055, China

    Feng Wang  (王锋)

Authors
  1. **ngcheng Ma  (马星程)
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  2. Feng Wang  (王锋)
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  3. Dongxu Jiao  (焦东旭)
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  4. Dantong Zhang  (张丹彤)
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  5. **ao Zhao  (赵晓)
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  6. David J. Singh  (辛格戴维)
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  7. **gxiang Zhao  (赵景祥)
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  8. **aoqiang Cui  (崔小**)
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  9. Weitao Zheng  (郑伟涛)
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Contributions

Author contributions Ma X designed, engineered, and characterized the samples with support from Wang F and Cui X; Ma X and Cui X analyzed the data and wrote the paper with support from Singh DJ, Zhao X, Zheng W, and Zhao J; Zhang D and Jiao D conceived the models; Jiao D and Zhao J contributed to the first-principles calculations. All authors contributed to the general discussion.

Corresponding authors

Correspondence to **gxiang Zhao  (赵景祥) or **aoqiang Cui  (崔小**).

Additional information

Conflict of interest The authors declare that they have no conflict of interest.

**ngcheng Ma is currently doing his research at the School of Materials Science and Engineering, Jilin University, under the supervision of Prof. **aoqiang Cui. His research interest mainly focuses on the design of new heterogeneous electrocatalysts for carbon dioxide reduction.

**aoqiang Cui is a professor at Jilin University. He obtained his PhD degree from Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, in 2002. His research interests include the interface regulation of low-dimensional materials, and electrocatalysts and photocatalysts for energy conversion and storage.

**gxiang Zhao is a professor at Harbin Normal University. He obtained his PhD degree from Jilin University in 2009. His research interests include the theoretical study of structure, properties, and applications of low-dimensional materials.

Supplementary information Supporting data are available in the online version of the paper.

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40843_2022_2058_MOESM1_ESM.pdf

Room Temperature Liquid Metal Synthesis of Nanoporous Copper-Indium Heterostructures Yields Efficient Carbon Dioxide Reduction to Syngas

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Ma, X., Wang, F., Jiao, D. et al. Room-temperature liquid metal synthesis of nanoporous copper-indium heterostructures for efficient carbon dioxide reduction to syngas. Sci. China Mater. 65, 3504–3512 (2022). https://doi.org/10.1007/s40843-022-2058-5

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