Why do CuAl catalysts outperform in CO2 electro-reduction to C2H4?

IF 10.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Science China Chemistry Pub Date : 2024-09-23 DOI:10.1007/s11426-024-2292-3

Dongfang Cheng, Gong Zhang, Lulu Li, Xiangcheng Shi, Wenjin Zhu, Xintong Yuan, Lyudmila Moskaleva, Peng Zhang, Zhi-Jian Zhao, Jinlong Gong

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引用次数: 0

Abstract

Highly efficient CO₂ electroreduction (CO₂RR) holds the promise of closing the carbon cycle. However, the strategies for enhancing activity and selectivity for single C₂₊ products are still limited. This paper describes the oxophilicity of doped metals on copper (Cu) as a key descriptor for predicting the selectivity in the production of ethylene and ethanol in CO₂RR. Our findings reveal a volcano-like relationship between the *O binding energy and catalytic activity, with aluminum (Al)-doped Cu alloys situated at the peak. The strong Al–O bond facilitates C–O bond cleavage, thereby promoting C₂H₄ formation. Through grand canonical density functional theory (GCDFT) calculations, we elucidate the significance of strong oxygen affinity in enhancing *CO₂ adsorption, leading to its activation into a bidentate-adsorbed form. Moreover, our results demonstrate that Al doping promotes C–C coupling by altering the adsorption mode of the key intermediate *OCCO, shifting it from a less favorable boat-type to a more stable chair-type configuration. This modification significantly contributes to the improved catalytic activity for C₂₊ products on CuAl catalysts. Our research provides a detailed mechanistic insight into the high activity and selectivity observed in CO₂RR to ethylene on CuAl catalysts, underscoring the critical role of metal oxophilicity in enhancing CO₂RR performance.

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来源期刊

Science China Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

14.40

自引率

7.30%

发文量

3787

审稿时长

2.2 months

期刊介绍： Science China Chemistry, co-sponsored by the Chinese Academy of Sciences and the National Natural Science Foundation of China and published by Science China Press, publishes high-quality original research in both basic and applied chemistry. Indexed by Science Citation Index, it is a premier academic journal in the field. Categories of articles include: Highlights. Brief summaries and scholarly comments on recent research achievements in any field of chemistry. Perspectives. Concise reports on thelatest chemistry trends of interest to scientists worldwide, including discussions of research breakthroughs and interpretations of important science and funding policies. Reviews. In-depth summaries of representative results and achievements of the past 5–10 years in selected topics based on or closely related to the research expertise of the authors, providing a thorough assessment of the significance, current status, and future research directions of the field.