M/BiOCl‐(M = Pt, Pd, and Au) Boosted Selective Photocatalytic CO2 Reduction to C2 Hydrocarbons via *CHO Intermediate Manipulation
Abstract Selective CO2 photoreduction to C2 hydrocarbons is significant but limited by the inadequate adsorption strength of the reaction intermediates and low efficiency of proton transfer. Herein, an ameliorative *CO adsorption and H2O activation strategy is realized via decorating bismuth oxychlo...
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Wiley
2024-09-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202400934 |
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| author | Qiong Liu Chengbo Bai Chengxin Zhu Wenjin Guo Guangfang Li Sheng Guo Devesh Kripalani Kun Zhou Rong Chen |
| author_facet | Qiong Liu Chengbo Bai Chengxin Zhu Wenjin Guo Guangfang Li Sheng Guo Devesh Kripalani Kun Zhou Rong Chen |
| author_sort | Qiong Liu |
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| description | Abstract Selective CO2 photoreduction to C2 hydrocarbons is significant but limited by the inadequate adsorption strength of the reaction intermediates and low efficiency of proton transfer. Herein, an ameliorative *CO adsorption and H2O activation strategy is realized via decorating bismuth oxychloride (BiOCl) nanostructures with different metal (Pt, Pd, and Au) species. Experimental and theoretical calculation results reveal that distinct *CO binding energies and *H acquisition abilities of the metal cocatalysts mediate the CO2 reduction activity and hydrocarbon selectivity. The relatively moderate *CO adsorption and *H supply over Pd/BiOCl endows it with the lowest free energy to generate *CHO, leading to its highest activity of hydrocarbon production. Specifically, the Pt cocatalyst can efficiently participate in H2O dissociation to deliver more *H for facilitating the protonation of the *CHO and *CHOH, thereby favoring CH4 production with 76.51% selectivity. A lower *H supply over Pd/BiOCl and Au/BiOCl results in a large energy barrier for *CHO or *CHOH protonation and thus a more thermodynamically favored OC─CHO coupling pathway, which endows them with vastly increased C2 hydrocarbon selectivity of 81.21% and 92.81%, respectively. The understanding of efficient C2 hydrocarbon production in this study sheds light on how materials can be engineered for photocatalytic CO2 reduction. |
| format | Article |
| id | doaj-art-e463107c20f740e49d23b8ccda6f68b8 |
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| issn | 2198-3844 |
| language | English |
| publishDate | 2024-09-01 |
| publisher | Wiley |
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| series | Advanced Science |
| spelling | doaj-art-e463107c20f740e49d23b8ccda6f68b82025-08-20T01:55:16ZengWileyAdvanced Science2198-38442024-09-011135n/an/a10.1002/advs.202400934M/BiOCl‐(M = Pt, Pd, and Au) Boosted Selective Photocatalytic CO2 Reduction to C2 Hydrocarbons via *CHO Intermediate ManipulationQiong Liu0Chengbo Bai1Chengxin Zhu2Wenjin Guo3Guangfang Li4Sheng Guo5Devesh Kripalani6Kun Zhou7Rong Chen8State Key Laboratory of New Textile Materials and Advanced Processing Technologies Wuhan Textile University Wuhan 430200 P. R. ChinaState Key Laboratory of New Textile Materials and Advanced Processing Technologies Wuhan Textile University Wuhan 430200 P. R. ChinaState Key Laboratory of New Textile Materials and Advanced Processing Technologies Wuhan Textile University Wuhan 430200 P. R. ChinaState Key Laboratory of New Textile Materials and Advanced Processing Technologies Wuhan Textile University Wuhan 430200 P. R. ChinaKey Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education) Hubei Key Laboratory of Material Chemistry and Service Failure Huazhong University of Science and Technology Wuhan 430074 P. R. ChinaState Key Laboratory of New Textile Materials and Advanced Processing Technologies Wuhan Textile University Wuhan 430200 P. R. ChinaSchool of Mechanical and Aerospace Engineering Nanyang Technological University 50 Nanyang Avenue Singapore 639798 SingaporeSchool of Mechanical and Aerospace Engineering Nanyang Technological University 50 Nanyang Avenue Singapore 639798 SingaporeState Key Laboratory of New Textile Materials and Advanced Processing Technologies Wuhan Textile University Wuhan 430200 P. R. ChinaAbstract Selective CO2 photoreduction to C2 hydrocarbons is significant but limited by the inadequate adsorption strength of the reaction intermediates and low efficiency of proton transfer. Herein, an ameliorative *CO adsorption and H2O activation strategy is realized via decorating bismuth oxychloride (BiOCl) nanostructures with different metal (Pt, Pd, and Au) species. Experimental and theoretical calculation results reveal that distinct *CO binding energies and *H acquisition abilities of the metal cocatalysts mediate the CO2 reduction activity and hydrocarbon selectivity. The relatively moderate *CO adsorption and *H supply over Pd/BiOCl endows it with the lowest free energy to generate *CHO, leading to its highest activity of hydrocarbon production. Specifically, the Pt cocatalyst can efficiently participate in H2O dissociation to deliver more *H for facilitating the protonation of the *CHO and *CHOH, thereby favoring CH4 production with 76.51% selectivity. A lower *H supply over Pd/BiOCl and Au/BiOCl results in a large energy barrier for *CHO or *CHOH protonation and thus a more thermodynamically favored OC─CHO coupling pathway, which endows them with vastly increased C2 hydrocarbon selectivity of 81.21% and 92.81%, respectively. The understanding of efficient C2 hydrocarbon production in this study sheds light on how materials can be engineered for photocatalytic CO2 reduction.https://doi.org/10.1002/advs.202400934*CHO intermediate*CO adsorptionH2O activationOC─CHO couplingphotocatalytic CO2 reduction |
| spellingShingle | Qiong Liu Chengbo Bai Chengxin Zhu Wenjin Guo Guangfang Li Sheng Guo Devesh Kripalani Kun Zhou Rong Chen M/BiOCl‐(M = Pt, Pd, and Au) Boosted Selective Photocatalytic CO2 Reduction to C2 Hydrocarbons via *CHO Intermediate Manipulation Advanced Science *CHO intermediate *CO adsorption H2O activation OC─CHO coupling photocatalytic CO2 reduction |
| title | M/BiOCl‐(M = Pt, Pd, and Au) Boosted Selective Photocatalytic CO2 Reduction to C2 Hydrocarbons via *CHO Intermediate Manipulation |
| title_full | M/BiOCl‐(M = Pt, Pd, and Au) Boosted Selective Photocatalytic CO2 Reduction to C2 Hydrocarbons via *CHO Intermediate Manipulation |
| title_fullStr | M/BiOCl‐(M = Pt, Pd, and Au) Boosted Selective Photocatalytic CO2 Reduction to C2 Hydrocarbons via *CHO Intermediate Manipulation |
| title_full_unstemmed | M/BiOCl‐(M = Pt, Pd, and Au) Boosted Selective Photocatalytic CO2 Reduction to C2 Hydrocarbons via *CHO Intermediate Manipulation |
| title_short | M/BiOCl‐(M = Pt, Pd, and Au) Boosted Selective Photocatalytic CO2 Reduction to C2 Hydrocarbons via *CHO Intermediate Manipulation |
| title_sort | m biocl m pt pd and au boosted selective photocatalytic co2 reduction to c2 hydrocarbons via cho intermediate manipulation |
| topic | *CHO intermediate *CO adsorption H2O activation OC─CHO coupling photocatalytic CO2 reduction |
| url | https://doi.org/10.1002/advs.202400934 |
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