Xixi Ren, Fei Liu, Han Wu, Qi Lu, Jun Zhao, Yuan Liu, Jinfeng Zhang, Jing Mao, Dr. Jiajun Wang, Prof. Dr. Xiaopeng Han, Prof. Dr. Yida Deng, Prof. Dr. Wenbin Hu
{"title":"通过含碳酸盐电解质原位碳化重构氧化铋,用于高活性电催化二氧化碳还原成甲酸盐。","authors":"Xixi Ren, Fei Liu, Han Wu, Qi Lu, Jun Zhao, Yuan Liu, Jinfeng Zhang, Jing Mao, Dr. Jiajun Wang, Prof. Dr. Xiaopeng Han, Prof. Dr. Yida Deng, Prof. Dr. Wenbin Hu","doi":"10.1002/anie.202316640","DOIUrl":null,"url":null,"abstract":"<p>The catalyst-reconstruction makes it challenging to clarify the practical active sites and unveil the actual reaction mechanism during the CO<sub>2</sub> electroreduction reaction (CO<sub>2</sub>RR). However, currently the impact of the electrolyte microenvironment in which the electrolyte is in contact with the catalyst is overlooked and might induce a chemical evolution, thus confusing the reconstruction process and mechanism. In this work, the carbonate adsorption properties of metal oxides were investigated, and the mechanism of how the electrolyte carbonate affect the chemical evolution of catalysts were discussed. Notably, Bi<sub>2</sub>O<sub>3</sub> with weak carbonate adsorption underwent a chemical reconstruction to form the Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>/Bi<sub>2</sub>O<sub>3</sub> heterostructure. Furthermore, in situ and ex situ characterizations unveiled the formation mechanism of the heterostructure. The in situ formed Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>/Bi<sub>2</sub>O<sub>3</sub> heterostructure with strong electron interaction served as the highly active structure for CO<sub>2</sub>RR, achieving a formate Faradaic efficiency of 98.1 % at −0.8 V<sub>vs RHE</sub>. Theoretical calculations demonstrate that the significantly tuned p-orbit electrons of the Bi sites in Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>/Bi<sub>2</sub>O<sub>3</sub> optimized the adsorption of the intermediate and lowered the energy barrier for the formation of *OCHO. This work elucidates the mechanism of electrolyte microenvironment for affecting catalyst reconstruction, which contributes to the understanding of reconstruction process and clarification of the actual catalytic structure.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"63 9","pages":""},"PeriodicalIF":16.1000,"publicationDate":"2023-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Reconstructed Bismuth Oxide through in situ Carbonation by Carbonate-containing Electrolyte for Highly Active Electrocatalytic CO2 Reduction to Formate\",\"authors\":\"Xixi Ren, Fei Liu, Han Wu, Qi Lu, Jun Zhao, Yuan Liu, Jinfeng Zhang, Jing Mao, Dr. Jiajun Wang, Prof. Dr. Xiaopeng Han, Prof. Dr. Yida Deng, Prof. Dr. Wenbin Hu\",\"doi\":\"10.1002/anie.202316640\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The catalyst-reconstruction makes it challenging to clarify the practical active sites and unveil the actual reaction mechanism during the CO<sub>2</sub> electroreduction reaction (CO<sub>2</sub>RR). However, currently the impact of the electrolyte microenvironment in which the electrolyte is in contact with the catalyst is overlooked and might induce a chemical evolution, thus confusing the reconstruction process and mechanism. In this work, the carbonate adsorption properties of metal oxides were investigated, and the mechanism of how the electrolyte carbonate affect the chemical evolution of catalysts were discussed. Notably, Bi<sub>2</sub>O<sub>3</sub> with weak carbonate adsorption underwent a chemical reconstruction to form the Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>/Bi<sub>2</sub>O<sub>3</sub> heterostructure. Furthermore, in situ and ex situ characterizations unveiled the formation mechanism of the heterostructure. The in situ formed Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>/Bi<sub>2</sub>O<sub>3</sub> heterostructure with strong electron interaction served as the highly active structure for CO<sub>2</sub>RR, achieving a formate Faradaic efficiency of 98.1 % at −0.8 V<sub>vs RHE</sub>. Theoretical calculations demonstrate that the significantly tuned p-orbit electrons of the Bi sites in Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>/Bi<sub>2</sub>O<sub>3</sub> optimized the adsorption of the intermediate and lowered the energy barrier for the formation of *OCHO. This work elucidates the mechanism of electrolyte microenvironment for affecting catalyst reconstruction, which contributes to the understanding of reconstruction process and clarification of the actual catalytic structure.</p>\",\"PeriodicalId\":125,\"journal\":{\"name\":\"Angewandte Chemie International Edition\",\"volume\":\"63 9\",\"pages\":\"\"},\"PeriodicalIF\":16.1000,\"publicationDate\":\"2023-12-26\",\"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://onlinelibrary.wiley.com/doi/10.1002/anie.202316640\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/anie.202316640","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Reconstructed Bismuth Oxide through in situ Carbonation by Carbonate-containing Electrolyte for Highly Active Electrocatalytic CO2 Reduction to Formate
The catalyst-reconstruction makes it challenging to clarify the practical active sites and unveil the actual reaction mechanism during the CO2 electroreduction reaction (CO2RR). However, currently the impact of the electrolyte microenvironment in which the electrolyte is in contact with the catalyst is overlooked and might induce a chemical evolution, thus confusing the reconstruction process and mechanism. In this work, the carbonate adsorption properties of metal oxides were investigated, and the mechanism of how the electrolyte carbonate affect the chemical evolution of catalysts were discussed. Notably, Bi2O3 with weak carbonate adsorption underwent a chemical reconstruction to form the Bi2O2CO3/Bi2O3 heterostructure. Furthermore, in situ and ex situ characterizations unveiled the formation mechanism of the heterostructure. The in situ formed Bi2O2CO3/Bi2O3 heterostructure with strong electron interaction served as the highly active structure for CO2RR, achieving a formate Faradaic efficiency of 98.1 % at −0.8 Vvs RHE. Theoretical calculations demonstrate that the significantly tuned p-orbit electrons of the Bi sites in Bi2O2CO3/Bi2O3 optimized the adsorption of the intermediate and lowered the energy barrier for the formation of *OCHO. This work elucidates the mechanism of electrolyte microenvironment for affecting catalyst reconstruction, which contributes to the understanding of reconstruction process and clarification of the actual catalytic structure.
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.