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Synergistically electronic tuning of metalloid CdSe nanorods for enhanced electrochemical CO2 reduction

协同电子调控增强类金属特性CdSe纳米棒的电催化CO2还原性能

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Abstract

Engineering the electronic properties of catalysts to target intermediate adsorption energy as well as harvest high selectivity represents a promising strategy to design advanced electrocatalysts for efficient CO2 electroreduction. Herein, a synergistically tuning on the electronic structure of the CdSe nanorods is proposed for boosting electrochemical reduction of CO2. The synergy of Ag doping coupled with Se vacancies tuned the electronic structure of the CdSe nanorods, which shows the metalloid characterization and thereby the accelerated electron transfer of CO2 electroreduction. Operando synchrotron radiation Fourier transform infrared spectroscopy and theoretical simulation revealed that the Ag doping and Se vacancies accelerated the CO2 activation process and lowered the energy barrier for the conversion from CO2 to *COOH; as a result, the performance of CO2 electroreduction was enhanced. The as-obtained metalloid Ag-doped CdSe nanorods exhibited a 2.7-fold increment in current density and 1.9-fold Faradaic efficiency of CO than pristine CdSe nanorod.

摘要

通过定制催化剂的电子特性以达到合适的中间体吸附能, 从而获得高选择性, 是一种可用于设计先进的CO2电还原催化剂的有前景的策略, 在本文中, 我们报道了一种通过协同调控CdSe纳米棒的电子结构以促进电化学CO2还原的方法. 银掺杂与硒空位协同调控了CdSe纳米棒的电子结构, 导致该结构显示出类金属特性, 从而加速了CO2电还原过程中的电子传递. 此外, 原位同步辐射傅里叶变换红外光谱和理论计算表明, 银掺杂和硒空位的耦合加速了CO2活化过程, 同时降低了将CO2转化为*COOH中间体的能垒, 从而有效增强了电催化CO2还原性能. 与原始的CdSe纳米棒相比, 银掺杂的CdSe纳米棒表现出2.7倍的电流密度和1.9倍的法拉第效率.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (12025505 and 21873050), China Ministry of Science and Technology (2017YFA0208300), the Open Fund Project of State Key Laboratory of Environmentally Friendly Energy Materials (20KFHG08), and the Youth Innovation Promotion Association CAS (CX2310007007 and CX2310000091). We thank National Synchrotron Radiation Laboratory (NSRL), Beijing Synchrotron Radiation Facility (BSRF), Shanghai Synchrotron Radiation Facility (SSRF) for the synchrotron beam time.

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Authors and Affiliations

  1. National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, China

    Tao Chen  (陈涛), Xinyi Shen  (沈心怡), Wei Zhang  (张伟), Tao Ding  (丁韬), Lan Wang  (王兰), Xiaokang Liu  (刘潇康), Linlin Cao  (曹林林) & Tao Yao  (姚涛)

  2. State Key Laboratory of Environmentally Friendly Energy Materials, School of National Defense Science and Technology, Southwest University of Science and Technology, Mianyang, 621010, China

    Tao Chen  (陈涛), Lan Wang  (王兰) & Wenkun Zhu  (竹文坤)

  3. Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing, 210023, China

    Tianyang Liu  (刘天阳) & Yafei Li  (李亚飞)

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  1. Tao Chen  (陈涛)
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  2. Tianyang Liu  (刘天阳)
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  11. Tao Yao  (姚涛)
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Contributions

Yao T, Chen T and Zhu W developed the idea and designed the experiments. Chen T, Shen X, Zhang W, Wang L and Ding T performed the catalyst synthesis and characterizations, FT-IR measurements and electrochemical experiments. Cao L and Ding T performed the TEM characterization. Zhang W and Liu X carried out the XAFS calculation and analysis on Cd, Se, and Ag K-edge. Chen T and Yao T co-wrote the paper. Liu T and Li Y performed the DFT calculations. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Wenkun Zhu  (竹文坤), Yafei Li  (李亚飞) or Tao Yao  (姚涛).

Additional information

Tao Chen received his BSc (2016) and MSc (2019) degrees at the School of National Defense Science and Technology, Southwest University of Science and Technology, China. He is currently a PhD student at the National Synchrotron Radiation Laboratory, University of Science and Technology of China. His present research interest focuses on the design of 2D catalysts and their application in photoelectrocatalysis.

Tao Yao received his PhD degree from the National Synchrotron Radiation Laboratory, University of Science and Technology of China in 2011. He is currently a professor of the University of Science and Technology of China and principle investigator (PI) of the group of “Synchrotron Radiation and Energy Material”. His scientific interest foucses on operando/time-resolved spectroscopy and the development of new catalysts for energy conversion.

Conflict of interest

The authors declare that they have no conflict of interest.

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Chen, T., Liu, T., Shen, X. et al. Synergistically electronic tuning of metalloid CdSe nanorods for enhanced electrochemical CO2 reduction. Sci. China Mater. 64, 2997–3006 (2021). https://doi.org/10.1007/s40843-021-1696-x

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