{"title":"Interfacial Diffusion-Reaction Coupling Strategy for CO2 Reduction on Copper Surface in Acidic Medium.","authors":"Xinyu Chai,Pengfei Shi,Jinyu Zhao,Senhe Huang,Kaiyue Jiang,Chenbao Lu,Liqing He,Jie Chen,Tianfu Wang,Xiaodong Zhuang","doi":"10.1002/anie.202513306","DOIUrl":null,"url":null,"abstract":"CO2 electroreduction reaction in acid medium to produce multicarbon (C2+) products has gained attention as an alternative to the traditional processes in neutral or alkaline solutions which often suffer from low single-pass conversion efficiency due to (bi)carbonate accumulation at the cathode. However, the CO2 conversion efficiency in acid remains unsatisfactory. Herein, a strong-polarized layer-covered Cu catalyst is developed as electrode for CO2 reduction reaction (CO2RR) in acid. Such a strong dipole moment layer is a sp3-hybridized nitrogen (sp3-N)-enriched azulene-based polymer, which acts as Lewis base to boost the CO2-diffusion kinetics in inner Helmholtz plane. Such unique electrode delivers nearly 84% C2 Faradaic efficiency at 200 mA cm-2, and demonstrates long-term stability over 40 h, which is the record for CO2RR in acidic media. In situ experiments manifest the moderate azulene-polarized sp3-N-enriched micro-environment can increase the local CO2/H2O ratio at electric double-layer to further stabilize the key intermediate atop-bound *CO. Theoretical calculations reveal that the strong-polarized layer decreases the reaction energy barrier for C-C coupling. This study not only uncovers the units with strong dipole moment on tuning sp3-N-enriched micro-environment, but also provides an interfacial diffusion-reaction coupling strategy to enhance the selectivity of CO2RR by decorating polycrystalline Cu with strong-polarized polymers.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"75 1","pages":"e202513306"},"PeriodicalIF":16.9000,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/anie.202513306","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
CO2 electroreduction reaction in acid medium to produce multicarbon (C2+) products has gained attention as an alternative to the traditional processes in neutral or alkaline solutions which often suffer from low single-pass conversion efficiency due to (bi)carbonate accumulation at the cathode. However, the CO2 conversion efficiency in acid remains unsatisfactory. Herein, a strong-polarized layer-covered Cu catalyst is developed as electrode for CO2 reduction reaction (CO2RR) in acid. Such a strong dipole moment layer is a sp3-hybridized nitrogen (sp3-N)-enriched azulene-based polymer, which acts as Lewis base to boost the CO2-diffusion kinetics in inner Helmholtz plane. Such unique electrode delivers nearly 84% C2 Faradaic efficiency at 200 mA cm-2, and demonstrates long-term stability over 40 h, which is the record for CO2RR in acidic media. In situ experiments manifest the moderate azulene-polarized sp3-N-enriched micro-environment can increase the local CO2/H2O ratio at electric double-layer to further stabilize the key intermediate atop-bound *CO. Theoretical calculations reveal that the strong-polarized layer decreases the reaction energy barrier for C-C coupling. This study not only uncovers the units with strong dipole moment on tuning sp3-N-enriched micro-environment, but also provides an interfacial diffusion-reaction coupling strategy to enhance the selectivity of CO2RR by decorating polycrystalline Cu with strong-polarized polymers.
在酸性介质中进行CO2电还原反应,生产多碳(C2+)产品,以替代在中性或碱性溶液中进行的传统工艺,这些工艺往往由于阴极(bi)碳酸盐堆积而导致单道转化效率低,因此受到关注。然而,CO2在酸中的转化效率仍然不理想。本文研制了一种强极化层覆盖Cu催化剂作为酸中CO2还原反应(CO2RR)的电极。这种强偶极矩层是一种sp3杂化氮(sp3-N)富氮基聚合物,它作为Lewis碱促进co2在内亥姆霍兹平面内的扩散动力学。这种独特的电极在200 mA cm-2下提供了近84%的C2法拉第效率,并表现出超过40小时的长期稳定性,这是酸性介质中CO2RR的记录。原位实验表明,适度的azulen_极化sp3- n富集微环境可以提高双电层局部CO2/H2O比,进一步稳定关键的中间顶界*CO。理论计算表明,强极化层降低了C-C耦合的反应能垒。本研究不仅揭示了调节sp3- n富集微环境中具有强偶极矩的单元,还提供了一种界面扩散-反应耦合策略,通过用强极化聚合物修饰多晶Cu来增强CO2RR的选择性。
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.