{"title":"通过碘改性策略提高 Cu0/Cuδ+ 界面上 CO2 高效还原为 C2+ 产物的电催化性能","authors":"Shao-Song Ding, Xing-Pu Wang, Ming-Wei Fang, Rong Zhang, Zi-Hao Huang, Ze-Wen Wang, Mei-Ling Wang, Ying Zhu, Wen-Xiu Jiang, Xiao-Chen Feng, Ying Zhu","doi":"10.1007/s12598-024-02840-4","DOIUrl":null,"url":null,"abstract":"<p>Electrocatalytic CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) to produce multicarbon (C<sub>2+</sub>) products over Cu-based catalysts represents an ideal approach for renewable energy storage and carbon emissions reduction. The Cu<sup>0</sup>/Cu<sup><i>δ</i>+</sup> interfaces are widely recognized as crucial sites that promote C–C coupling and enhance the generation of C<sub>2+</sub> products. However, a major challenge arises from the tendency of Cu<sup><i>δ</i>+</sup> active sites within Cu<sup>0</sup>/Cu<sup><i>δ</i>+</sup> interfaces to undergo reduction to Cu<sup>0</sup> during the CO<sub>2</sub>RR process, leading to a decline in catalytic performance. Hence, it is crucial to establish durable Cu<sup>0</sup>/Cu<sup><i>δ</i>+</sup> interfaces to enhance the conversion of CO<sub>2</sub> to C<sub>2+</sub> products. In this work, an iodine modification strategy is proposed to prepare a stable Cu@CuI composite catalyst with well-maintained Cu<sup>0</sup>/Cu<sup><i>δ</i>+</sup> interfaces through a one-step redox reaction between iodine and copper. The optimized Cu@CuI-3 composite catalyst demonstrates an excellent performance in CO<sub>2</sub>RR, achieving a Faradaic efficiency of 75.7% for C<sub>2+</sub> products and a partial current density of 288 mA·cm<sup>−2</sup> at − 1.57 V<sub>RHE</sub> in a flow cell. Operando techniques reveal that a numerous persistent Cu<sup><i>δ</i>+</sup> species exist on the surface of the Cu@CuI-<i>X</i> composite catalyst even after CO<sub>2</sub>RR due to the presence of adsorbed iodine ions, which prevent complete reduction of Cu<sup><i>δ</i>+</sup> species to Cu<sup>0</sup> owing to their high electronegativity. Density functional theory calculations further verify that adsorbed iodine ions on the surface of Cu@CuI-<i>X</i> serve as charge regulators by adjusting local charge density, thereby facilitating the formation of *CHO intermediates from CO<sub>2</sub> and lowering the energy barriers associated with coupling the *CHO and *CO intermediates during CO<sub>2</sub>RR. Consequently, this phenomenon enhances the selectivity toward C<sub>2+</sub> products during electrocatalytic CO<sub>2</sub> reduction.</p><h3 data-test=\"abstract-sub-heading\">Graphical abstract</h3>\n","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":null,"pages":null},"PeriodicalIF":9.6000,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Enhancing electrocatalytic reduction of CO2 to C2+ products with high efficiency at Cu0/Cuδ+ interfaces via iodine modification strategy\",\"authors\":\"Shao-Song Ding, Xing-Pu Wang, Ming-Wei Fang, Rong Zhang, Zi-Hao Huang, Ze-Wen Wang, Mei-Ling Wang, Ying Zhu, Wen-Xiu Jiang, Xiao-Chen Feng, Ying Zhu\",\"doi\":\"10.1007/s12598-024-02840-4\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Electrocatalytic CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) to produce multicarbon (C<sub>2+</sub>) products over Cu-based catalysts represents an ideal approach for renewable energy storage and carbon emissions reduction. The Cu<sup>0</sup>/Cu<sup><i>δ</i>+</sup> interfaces are widely recognized as crucial sites that promote C–C coupling and enhance the generation of C<sub>2+</sub> products. However, a major challenge arises from the tendency of Cu<sup><i>δ</i>+</sup> active sites within Cu<sup>0</sup>/Cu<sup><i>δ</i>+</sup> interfaces to undergo reduction to Cu<sup>0</sup> during the CO<sub>2</sub>RR process, leading to a decline in catalytic performance. Hence, it is crucial to establish durable Cu<sup>0</sup>/Cu<sup><i>δ</i>+</sup> interfaces to enhance the conversion of CO<sub>2</sub> to C<sub>2+</sub> products. In this work, an iodine modification strategy is proposed to prepare a stable Cu@CuI composite catalyst with well-maintained Cu<sup>0</sup>/Cu<sup><i>δ</i>+</sup> interfaces through a one-step redox reaction between iodine and copper. The optimized Cu@CuI-3 composite catalyst demonstrates an excellent performance in CO<sub>2</sub>RR, achieving a Faradaic efficiency of 75.7% for C<sub>2+</sub> products and a partial current density of 288 mA·cm<sup>−2</sup> at − 1.57 V<sub>RHE</sub> in a flow cell. Operando techniques reveal that a numerous persistent Cu<sup><i>δ</i>+</sup> species exist on the surface of the Cu@CuI-<i>X</i> composite catalyst even after CO<sub>2</sub>RR due to the presence of adsorbed iodine ions, which prevent complete reduction of Cu<sup><i>δ</i>+</sup> species to Cu<sup>0</sup> owing to their high electronegativity. Density functional theory calculations further verify that adsorbed iodine ions on the surface of Cu@CuI-<i>X</i> serve as charge regulators by adjusting local charge density, thereby facilitating the formation of *CHO intermediates from CO<sub>2</sub> and lowering the energy barriers associated with coupling the *CHO and *CO intermediates during CO<sub>2</sub>RR. Consequently, this phenomenon enhances the selectivity toward C<sub>2+</sub> products during electrocatalytic CO<sub>2</sub> reduction.</p><h3 data-test=\\\"abstract-sub-heading\\\">Graphical abstract</h3>\\n\",\"PeriodicalId\":749,\"journal\":{\"name\":\"Rare Metals\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":9.6000,\"publicationDate\":\"2024-06-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Rare Metals\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://doi.org/10.1007/s12598-024-02840-4\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"MATERIALS SCIENCE, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Rare Metals","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1007/s12598-024-02840-4","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
Enhancing electrocatalytic reduction of CO2 to C2+ products with high efficiency at Cu0/Cuδ+ interfaces via iodine modification strategy
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.
期刊介绍:
Rare Metals is a monthly peer-reviewed journal published by the Nonferrous Metals Society of China. It serves as a platform for engineers and scientists to communicate and disseminate original research articles in the field of rare metals. The journal focuses on a wide range of topics including metallurgy, processing, and determination of rare metals. Additionally, it showcases the application of rare metals in advanced materials such as superconductors, semiconductors, composites, and ceramics.