Operando Converting BiOCl into Bi2O2(CO3) x Cl y for Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate
Abstract Bismuth-based materials (e.g., metallic, oxides and subcarbonate) are emerged as promising electrocatalysts for converting CO2 to formate. However, Bio-based electrocatalysts possess high overpotentials, while bismuth oxides and subcarbonate encounter stability issues. This work is designat...
| Main Authors: | , , , , , , , , , , , , |
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| Format: | Article |
| Language: | English |
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SpringerOpen
2022-05-01
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| Series: | Nano-Micro Letters |
| Subjects: | |
| Online Access: | https://doi.org/10.1007/s40820-022-00862-0 |
| _version_ | 1818191865618366464 |
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| author | Huai Qin Fu Junxian Liu Nicholas M. Bedford Yun Wang Joshua Wright Peng Fei Liu Chun Fang Wen Liang Wang Huajie Yin Dongchen Qi Porun Liu Hua Gui Yang Huijun Zhao |
| author_facet | Huai Qin Fu Junxian Liu Nicholas M. Bedford Yun Wang Joshua Wright Peng Fei Liu Chun Fang Wen Liang Wang Huajie Yin Dongchen Qi Porun Liu Hua Gui Yang Huijun Zhao |
| author_sort | Huai Qin Fu |
| collection | DOAJ |
| description | Abstract Bismuth-based materials (e.g., metallic, oxides and subcarbonate) are emerged as promising electrocatalysts for converting CO2 to formate. However, Bio-based electrocatalysts possess high overpotentials, while bismuth oxides and subcarbonate encounter stability issues. This work is designated to exemplify that the operando synthesis can be an effective means to enhance the stability of electrocatalysts under operando CO2RR conditions. A synthetic approach is developed to electrochemically convert BiOCl into Cl-containing subcarbonate (Bi2O2(CO3) x Cl y ) under operando CO2RR conditions. The systematic operando spectroscopic studies depict that BiOCl is converted to Bi2O2(CO3) x Cl y via a cathodic potential-promoted anion-exchange process. The operando synthesized Bi2O2(CO3) x Cl y can tolerate − 1.0 V versus RHE, while for the wet-chemistry synthesized pure Bi2O2CO3, the formation of metallic Bio occurs at − 0.6 V versus RHE. At − 0.8 V versus RHE, Bi2O2(CO3) x Cl y can readily attain a FEHCOO- of 97.9%, much higher than that of the pure Bi2O2CO3 (81.3%). DFT calculations indicate that differing from the pure Bi2O2CO3-catalyzed CO2RR, where formate is formed via a *OCHO intermediate step that requires a high energy input energy of 2.69 eV to proceed, the formation of HCOO− over Bi2O2(CO3) x Cl y has proceeded via a *COOH intermediate step that only requires low energy input of 2.56 eV. |
| first_indexed | 2024-12-12T00:21:24Z |
| format | Article |
| id | doaj.art-1b86f49af7bc4ffb8589d105291dfd05 |
| institution | Directory Open Access Journal |
| issn | 2311-6706 2150-5551 |
| language | English |
| last_indexed | 2024-12-12T00:21:24Z |
| publishDate | 2022-05-01 |
| publisher | SpringerOpen |
| record_format | Article |
| series | Nano-Micro Letters |
| spelling | doaj.art-1b86f49af7bc4ffb8589d105291dfd052022-12-22T00:44:43ZengSpringerOpenNano-Micro Letters2311-67062150-55512022-05-0114111610.1007/s40820-022-00862-0Operando Converting BiOCl into Bi2O2(CO3) x Cl y for Efficient Electrocatalytic Reduction of Carbon Dioxide to FormateHuai Qin Fu0Junxian Liu1Nicholas M. Bedford2Yun Wang3Joshua Wright4Peng Fei Liu5Chun Fang Wen6Liang Wang7Huajie Yin8Dongchen Qi9Porun Liu10Hua Gui Yang11Huijun Zhao12Centre for Catalysis and Clean Energy, Gold Coast Campus, Griffith UniversityCentre for Catalysis and Clean Energy, Gold Coast Campus, Griffith UniversitySchool of Chemical Engineering, University of New South WalesCentre for Catalysis and Clean Energy, Gold Coast Campus, Griffith UniversityDepartment of Physics, Illinois Institute of TechnologyKey Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and TechnologyKey Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and TechnologyCentre for Catalysis and Clean Energy, Gold Coast Campus, Griffith UniversityCentre for Catalysis and Clean Energy, Gold Coast Campus, Griffith UniversityCentre for Materials Science, School of Chemistry and Physics, Queensland University of TechnologyCentre for Catalysis and Clean Energy, Gold Coast Campus, Griffith UniversityKey Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and TechnologyCentre for Catalysis and Clean Energy, Gold Coast Campus, Griffith UniversityAbstract Bismuth-based materials (e.g., metallic, oxides and subcarbonate) are emerged as promising electrocatalysts for converting CO2 to formate. However, Bio-based electrocatalysts possess high overpotentials, while bismuth oxides and subcarbonate encounter stability issues. This work is designated to exemplify that the operando synthesis can be an effective means to enhance the stability of electrocatalysts under operando CO2RR conditions. A synthetic approach is developed to electrochemically convert BiOCl into Cl-containing subcarbonate (Bi2O2(CO3) x Cl y ) under operando CO2RR conditions. The systematic operando spectroscopic studies depict that BiOCl is converted to Bi2O2(CO3) x Cl y via a cathodic potential-promoted anion-exchange process. The operando synthesized Bi2O2(CO3) x Cl y can tolerate − 1.0 V versus RHE, while for the wet-chemistry synthesized pure Bi2O2CO3, the formation of metallic Bio occurs at − 0.6 V versus RHE. At − 0.8 V versus RHE, Bi2O2(CO3) x Cl y can readily attain a FEHCOO- of 97.9%, much higher than that of the pure Bi2O2CO3 (81.3%). DFT calculations indicate that differing from the pure Bi2O2CO3-catalyzed CO2RR, where formate is formed via a *OCHO intermediate step that requires a high energy input energy of 2.69 eV to proceed, the formation of HCOO− over Bi2O2(CO3) x Cl y has proceeded via a *COOH intermediate step that only requires low energy input of 2.56 eV.https://doi.org/10.1007/s40820-022-00862-0Carbon dioxide reductionChloride-containing bismuth subcarbonateCathodic potential-promoted anion-exchangeStability |
| spellingShingle | Huai Qin Fu Junxian Liu Nicholas M. Bedford Yun Wang Joshua Wright Peng Fei Liu Chun Fang Wen Liang Wang Huajie Yin Dongchen Qi Porun Liu Hua Gui Yang Huijun Zhao Operando Converting BiOCl into Bi2O2(CO3) x Cl y for Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate Nano-Micro Letters Carbon dioxide reduction Chloride-containing bismuth subcarbonate Cathodic potential-promoted anion-exchange Stability |
| title | Operando Converting BiOCl into Bi2O2(CO3) x Cl y for Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate |
| title_full | Operando Converting BiOCl into Bi2O2(CO3) x Cl y for Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate |
| title_fullStr | Operando Converting BiOCl into Bi2O2(CO3) x Cl y for Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate |
| title_full_unstemmed | Operando Converting BiOCl into Bi2O2(CO3) x Cl y for Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate |
| title_short | Operando Converting BiOCl into Bi2O2(CO3) x Cl y for Efficient Electrocatalytic Reduction of Carbon Dioxide to Formate |
| title_sort | operando converting biocl into bi2o2 co3 x cl y for efficient electrocatalytic reduction of carbon dioxide to formate |
| topic | Carbon dioxide reduction Chloride-containing bismuth subcarbonate Cathodic potential-promoted anion-exchange Stability |
| url | https://doi.org/10.1007/s40820-022-00862-0 |
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