{"title":"Shielding effect in the synthesis of Gd-doped copper oxide catalysts with enhanced CO2 electroreduction to ethylene","authors":"Zenan Cao, Zhichao Chen, Hanlei Sun, Shuo Yao, Ziyong Liu, Fu-Li Li, Xiaobo Yang, Wei Zhou, Jingxin Fan, Wang Hongzhi, Licheng Liu","doi":"10.1039/d4ta05284f","DOIUrl":null,"url":null,"abstract":"Electrocatalytic reduction reaction of carbon dioxide (CO<small><sub>2</sub></small>RR) into ethylene can achieve efficient conversion and utilization of CO<small><sub>2</sub></small>, which also provides a new and sustainable way to mitigate climate change. Copper based catalysts exhibit special activity for CO<small><sub>2</sub></small>RR to C<small><sub>2</sub></small>H<small><sub>4</sub></small>, but limited by the low selectivity and high overpotential. The controlled doping of rare-earth metal ions into copper catalyst is supposed to modulate the electron density of Cu active sites and thus to promote C-C coupling reaction and enhance the selectivity of C<small><sub>2</sub></small>H<small><sub>4</sub></small>. Herein, we report a Gd-doped copper oxide catalyst (Gd-CuO) synthesized by a typical solvothermal method, in which the content of Gd doping and chemical state of Cu can be regulated precisely through the shielding effect of solvents used. The shielding effect is assigned to the modification of cation-anion and cation-solvent interactions, which affects the crystallization of CuO and incorporation of Gd in the solvothermal process. Under optimal conditions, the Faraday efficiency of ethylene product can reach up to 58.6% at −1.2 V <em>vs.</em> RHE in an H-cell. When applied in a flow cell, the Faraday efficiency of ethylene can reach 52.4% with a current density of 397.8 mA cm<small><sup>−</sup></small><small><sup>2 </sup></small>at the same applied voltage. In situ FTIR and DFT calculations demonstrated that the controlled doping Gd by means of shielding effect in synthesis facilitates the improvement of electron density of Cu active sites and promotes the C-C coupling and adsorption of *COCOH intermediates, thus enhancing the selectivity of ethylene. This work provides insights for design and development of rare earth doping Cu-based catalysts in the future.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":null,"pages":null},"PeriodicalIF":10.7000,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Materials Chemistry A","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1039/d4ta05284f","RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Electrocatalytic reduction reaction of carbon dioxide (CO2RR) into ethylene can achieve efficient conversion and utilization of CO2, which also provides a new and sustainable way to mitigate climate change. Copper based catalysts exhibit special activity for CO2RR to C2H4, but limited by the low selectivity and high overpotential. The controlled doping of rare-earth metal ions into copper catalyst is supposed to modulate the electron density of Cu active sites and thus to promote C-C coupling reaction and enhance the selectivity of C2H4. Herein, we report a Gd-doped copper oxide catalyst (Gd-CuO) synthesized by a typical solvothermal method, in which the content of Gd doping and chemical state of Cu can be regulated precisely through the shielding effect of solvents used. The shielding effect is assigned to the modification of cation-anion and cation-solvent interactions, which affects the crystallization of CuO and incorporation of Gd in the solvothermal process. Under optimal conditions, the Faraday efficiency of ethylene product can reach up to 58.6% at −1.2 V vs. RHE in an H-cell. When applied in a flow cell, the Faraday efficiency of ethylene can reach 52.4% with a current density of 397.8 mA cm−2 at the same applied voltage. In situ FTIR and DFT calculations demonstrated that the controlled doping Gd by means of shielding effect in synthesis facilitates the improvement of electron density of Cu active sites and promotes the C-C coupling and adsorption of *COCOH intermediates, thus enhancing the selectivity of ethylene. This work provides insights for design and development of rare earth doping Cu-based catalysts in the future.
期刊介绍:
The Journal of Materials Chemistry A, B & C covers a wide range of high-quality studies in the field of materials chemistry, with each section focusing on specific applications of the materials studied. Journal of Materials Chemistry A emphasizes applications in energy and sustainability, including topics such as artificial photosynthesis, batteries, and fuel cells. Journal of Materials Chemistry B focuses on applications in biology and medicine, while Journal of Materials Chemistry C covers applications in optical, magnetic, and electronic devices. Example topic areas within the scope of Journal of Materials Chemistry A include catalysis, green/sustainable materials, sensors, and water treatment, among others.