In situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1-x shield
Abstract Electrochemical CO2-to-ethanol conversion is challenged by sluggish C-C coupling kinetics and wide products distribution. Although Cu+ has been demonstrated to enhance multi-carbon (C2+) formation, the stabilization of Cu+ under reduction conditions is difficult. Here, we report a hydrogen-...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-61189-z |
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| author | Fanxing Zhang Ning Cao Chentao Wang Shengxiang Wang Yi He Yao Shi Mi Yan Ying Bao Zhenglong Li Pengfei Xie |
| author_facet | Fanxing Zhang Ning Cao Chentao Wang Shengxiang Wang Yi He Yao Shi Mi Yan Ying Bao Zhenglong Li Pengfei Xie |
| author_sort | Fanxing Zhang |
| collection | DOAJ |
| description | Abstract Electrochemical CO2-to-ethanol conversion is challenged by sluggish C-C coupling kinetics and wide products distribution. Although Cu+ has been demonstrated to enhance multi-carbon (C2+) formation, the stabilization of Cu+ under reduction conditions is difficult. Here, we report a hydrogen-ethanol pretreatment strategy to obtain Cu nanoparticles covered by highly dispersed and disordered ZnO1-x clusters. Ethanol-induced ZnO1-x redispersion gives rise to abundant Cu+ on the subsurface. The optimal catalyst delivers a 73.0% ethanol Faradaic efficiency (FE) and 86.0% total C2+ FE at −0.9 V, with a 2.3 mmol cm−2 h−1 ethanol formation rate and single-pass ethanol yield of 18.0%. The catalyst also exhibits stability beyond 500 h, attributed to the stabilization of Cu+ by the ZnO1-x shield that requires a high energy barrier for lattice oxygen removal. In situ X-ray spectroscopy and calculations reveal a volcano relationship between Cu+ ratio in Cu species and ethanol FE. Optimal Cu+ density not only facilitates *OC-COH coupling but also optimizes the adsorption energy of *CH2CH2O on catalyst for ethanol electrosynthesis. |
| format | Article |
| id | doaj-art-27c7c398d9b843e5b7329df079bca116 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-27c7c398d9b843e5b7329df079bca1162025-08-20T03:37:37ZengNature PortfolioNature Communications2041-17232025-07-0116111410.1038/s41467-025-61189-zIn situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1-x shieldFanxing Zhang0Ning Cao1Chentao Wang2Shengxiang Wang3Yi He4Yao Shi5Mi Yan6Ying Bao7Zhenglong Li8Pengfei Xie9College of Chemical and Biological Engineering, Zhejiang UniversityCollege of Chemical and Biological Engineering, Zhejiang UniversityCollege of Chemical and Biological Engineering, Zhejiang UniversitySpallation Neutron Source Science CenterCollege of Chemical and Biological Engineering, Zhejiang UniversityCollege of Chemical and Biological Engineering, Zhejiang UniversitySchool of Materials Science and Engineering, Zhejiang UniversityDepartment of Chemistry, Western Washington UniversityInstitute of Zhejiang University-QuzhouCollege of Chemical and Biological Engineering, Zhejiang UniversityAbstract Electrochemical CO2-to-ethanol conversion is challenged by sluggish C-C coupling kinetics and wide products distribution. Although Cu+ has been demonstrated to enhance multi-carbon (C2+) formation, the stabilization of Cu+ under reduction conditions is difficult. Here, we report a hydrogen-ethanol pretreatment strategy to obtain Cu nanoparticles covered by highly dispersed and disordered ZnO1-x clusters. Ethanol-induced ZnO1-x redispersion gives rise to abundant Cu+ on the subsurface. The optimal catalyst delivers a 73.0% ethanol Faradaic efficiency (FE) and 86.0% total C2+ FE at −0.9 V, with a 2.3 mmol cm−2 h−1 ethanol formation rate and single-pass ethanol yield of 18.0%. The catalyst also exhibits stability beyond 500 h, attributed to the stabilization of Cu+ by the ZnO1-x shield that requires a high energy barrier for lattice oxygen removal. In situ X-ray spectroscopy and calculations reveal a volcano relationship between Cu+ ratio in Cu species and ethanol FE. Optimal Cu+ density not only facilitates *OC-COH coupling but also optimizes the adsorption energy of *CH2CH2O on catalyst for ethanol electrosynthesis.https://doi.org/10.1038/s41467-025-61189-z |
| spellingShingle | Fanxing Zhang Ning Cao Chentao Wang Shengxiang Wang Yi He Yao Shi Mi Yan Ying Bao Zhenglong Li Pengfei Xie In situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1-x shield Nature Communications |
| title | In situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1-x shield |
| title_full | In situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1-x shield |
| title_fullStr | In situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1-x shield |
| title_full_unstemmed | In situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1-x shield |
| title_short | In situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1-x shield |
| title_sort | in situ stabilization of cu for co2 electroreduction via environmental molecules induced zno1 x shield |
| url | https://doi.org/10.1038/s41467-025-61189-z |
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