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Nanocavity enriched CuPd alloy with high selectivity for CO2 electroreduction toward C2H4

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Abstract

Electrocatalysis of CO2 reduction reaction is an effective way to convert CO2 into high value-added products, but the selectivity of Cu-based catalysts for C2+ products needs to be improved due to the high energy barrier of C–C coupling. Therefore, a viable catalyst design strategy to decrease energy barrier of C–C coupling should be put forward. Here, a nanocavity-enriched CuPd single atom alloy (CuPd SAA) catalyst is designed to promote C–C coupling process. The faradaic efficiency of CuPd SAA for ethylene and C2+ reaches 75.6% and 85.7% at − 0.7 V versus reversible hydrogen electrode (RHE), respectively. Based on the results given by in situ characterization, the porous hollow structure dramatically increases the ratio of the linear-bond *CO, thus enhancing the faradaic efficiency for ethylene. Density functional theory (DFT) calculation reveals that the Pd doping can regulate the electronic structure of neighboring Cu atoms to decrease the energy barrier of C–C coupling, further improving the faradaic efficiency. This work provides a new idea for designing catalyst with high selectivity for ethylene.

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摘要

电催化CO2还原反应是将CO2转化为高附加值产物的有效途径，但由于C–C偶联具有较高能势，Cu基催化剂对C2+产物的选择性有待提高。因此，我们应提出一种可行的降低C-C偶联能垒的催化剂设计策略。本文设计了一种富含纳米空腔的CuPd单原子合金(CuPd-SAA)催化剂，以促进C–C偶联过程。在− 0.7 V versus RHE的电位下，CuPd-SAA对乙烯和C2+的法拉第效率分别达到75.6%和85.7%。根据原位表征的结果，多孔中空结构显著提高了线性键*CO的比例，从而提高了乙烯的法拉第效率。密度泛函理论计算表明，Pd掺杂可以调节邻近Cu原子的电子结构，降低C–C偶联的能垒，进一步提高产物的法拉第效率。本研究为设计高选择性生成乙烯的催化剂提供了新的思路。

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Nos. 50835002 and 51105102).

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Authors and Affiliations

  1. Institute of New-Energy Materials, School of Materials Science and Engineering, Tianjin University, Tianjin, 300350, China

    Ze-Yu Zhang, Hai-Bin Wang, Fei-Fei Zhang, Jing-Wei Li, Xin-Zhuo Hu, Si-Wei Yan, Yi-Ming Bai, Xun Zhang, Gu-Rong Shen, Peng-Fei Yin, Jing Yang, Cun-Ku Dong, Jing Mao, Hui Liu & Xi-Wen Du

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  1. Ze-Yu Zhang
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Correspondence to Jing Mao, Hui Liu or Xi-Wen Du.

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Zhang, ZY., Wang, HB., Zhang, FF. et al. Nanocavity enriched CuPd alloy with high selectivity for CO2 electroreduction toward C2H4. Rare Met. 43, 1513–1523 (2024). https://doi.org/10.1007/s12598-023-02527-2

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