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Enhancing electrocatalytic reduction of CO2 to C2+ products with high efficiency at Cu0/Cuδ+ interfaces via iodine modification strategy

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Abstract

Electrocatalytic CO2 reduction reaction (CO2RR) to produce multicarbon (C2+) products over Cu-based catalysts represents an ideal approach for renewable energy storage and carbon emissions reduction. The Cu0/Cuδ+ interfaces are widely recognized as crucial sites that promote C–C coupling and enhance the generation of C2+ products. However, a major challenge arises from the tendency of Cuδ+ active sites within Cu0/Cuδ+ interfaces to undergo reduction to Cu0 during the CO2RR process, leading to a decline in catalytic performance. Hence, it is crucial to establish durable Cu0/Cuδ+ interfaces to enhance the conversion of CO2 to C2+ products. In this work, an iodine modification strategy is proposed to prepare a stable Cu@CuI composite catalyst with well-maintained Cu0/Cuδ+ interfaces through a one-step redox reaction between iodine and copper. The optimized Cu@CuI-3 composite catalyst demonstrates an excellent performance in CO2RR, achieving a Faradaic efficiency of 75.7% for C2+ products and a partial current density of 288 mA·cm−2 at − 1.57 VRHE in a flow cell. Operando techniques reveal that a numerous persistent Cuδ+ species exist on the surface of the Cu@CuI-X composite catalyst even after CO2RR due to the presence of adsorbed iodine ions, which prevent complete reduction of Cuδ+ species to Cu0 owing to their high electronegativity. Density functional theory calculations further verify that adsorbed iodine ions on the surface of Cu@CuI-X serve as charge regulators by adjusting local charge density, thereby facilitating the formation of *CHO intermediates from CO2 and lowering the energy barriers associated with coupling the *CHO and *CO intermediates during CO2RR. Consequently, this phenomenon enhances the selectivity toward C2+ products during electrocatalytic CO2 reduction.

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摘要

在铜基催化剂上进行电催化二氧化碳还原反应（CO2RR）生成多碳（C2+）产物，是一种理想的可再生能源储存和碳减排方法。Cu0/Cuδ+界面被广泛认为是促进 C-C 偶联和促进C2+产物生成的关键位置。然而，Cu0/Cuδ+界面中的Cuδ+活性位点在CO2RR过程中容易被还原成 Cu0，从而导致催化性能衰减，这是目前面临的一个重大挑战。因此，建立持久的 Cu0/Cuδ+界面对于促进 CO2 还原成C2+产物至关重要。在这项工作中，我们介绍了一种碘改性策略，通过碘和铜之间的一步氧化还原反应制备具有稳定 Cu0/Cuδ+界面的 Cu@CuI 复合催化剂。优化后的Cu@CuI-3复合催化剂具有优异的 CO2RR 性能，在流动池中的C2+法拉第效率达到75.7%，−1.57 VRHE 时的部分电流密度达到 288 mA·cm‒2。通过原位技术，我们发现即使在 CO2RR 之后，Cu@CuI-X 复合催化剂上仍然存在大量的Cuδ+物种，这是因为吸附了碘离子，而碘离子的高电负性阻止了Cuδ+物种完全还原为Cu0。密度泛函理论计算进一步验证了Cu@CuI-X上吸附的碘离子可作为电荷调节器，调整局部电荷密度，加速 CO2 转化为 *CHO 中间体，并降低*CHO和*CO中间产物耦合的能垒。因此，这种现象提高了 CO2RR 过程中 C2+ 产物的选择性。

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 52073009, 52272182, 51872013 and 52011530190), the Program of the Ministry of Education of China for Introducing Talents of Discipline to Universities (No. B14009).

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  1. Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology School of Chemistry, Beihang University, Bei**g, 100191, China

    Shao-Song Ding, **ng-Pu Wang, Ming-Wei Fang, Rong Zhang, Zi-Hao Huang, Ze-Wen Wang, Mei-Ling Wang, Ying Zhu, Wen-**u Jiang, **ao-Chen Feng & Ying Zhu

  2. Bei**g Advanced Innovation Center for Biomedical Engineering, Beihang University, Bei**g, 100191, China

    Ying Zhu

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Ding, SS., Wang, XP., Fang, MW. et al. Enhancing electrocatalytic reduction of CO2 to C2+ products with high efficiency at Cu0/Cuδ+ interfaces via iodine modification strategy. Rare Met. (2024). https://doi.org/10.1007/s12598-024-02840-4

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