Jiajun Du, Jun Deng, ChangAn Zhou, Hairong Yue, Chong Liu, Patrik Schmuki, Štěpán Kment and Xuemei Zhou
{"title":"Regulating protonation paths for enhanced photocatalytic CO2 methanation by coupling Pt sites on WO2.9/TiO2†","authors":"Jiajun Du, Jun Deng, ChangAn Zhou, Hairong Yue, Chong Liu, Patrik Schmuki, Štěpán Kment and Xuemei Zhou","doi":"10.1039/D5CY00167F","DOIUrl":null,"url":null,"abstract":"<p >CO<small><sub>2</sub></small> methanation <em>via</em> photocatalysis with water vapor is a sustainable technique for reducing CO<small><sub>2</sub></small> emission but is challenged by the high energy barrier associated with the initial adsorption, activation and protonation of CO<small><sub>2</sub></small> molecules. In this work, a substoichiometric WO<small><sub>2.9</sub></small> thin film with strong Lewis acidity was coated on TiO<small><sub>2</sub></small> microspheres, followed by the deposition of Pt cocatalysts on WO<small><sub>2.9</sub></small> with controlled Pt single atoms and clusters (Pt–WO<small><sub>2.9</sub></small>/TiO<small><sub>2</sub></small>). The methane production rate reached 10.74 μmol h<small><sup>−1</sup></small> g<small><sup>−1</sup></small> with a selectivity of 99.8%, which was ∼40 times higher than that of bare TiO<small><sub>2</sub></small> (0.27 μmol h<small><sup>−1</sup></small> g<small><sup>−1</sup></small>). The high methane production rate was attributed to the synergy of Pt sites on the WO<small><sub>2.9</sub></small>/TiO<small><sub>2</sub></small> heterojunction, where the Pt clusters facilitated water dissociation, thereby providing H* through hydrogen spillover on the surface, and the presence of a substoichiometric WO<small><sub>2.9</sub></small> surface further enhanced the spillover process. The high density of active H* promoted the protonation pathway for CO<small><sub>2</sub></small> activation (CO<small><sub>2</sub></small> → COOH<small><sup>+</sup></small> → *COOH), which improved the adsorption of the essential intermediate *CO on Pt single atoms and displayed a significantly reduced energy barrier for the protonation reaction of C1 intermediates, resulting in a mixed reaction pathway. This work provides new insights into a mechanism to regulate the reaction path to facilitate efficient photocatalytic CO<small><sub>2</sub></small> methanation.</p>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":" 13","pages":" 4002-4011"},"PeriodicalIF":4.4000,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Catalysis Science & Technology","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/cy/d5cy00167f","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
CO2 methanation via photocatalysis with water vapor is a sustainable technique for reducing CO2 emission but is challenged by the high energy barrier associated with the initial adsorption, activation and protonation of CO2 molecules. In this work, a substoichiometric WO2.9 thin film with strong Lewis acidity was coated on TiO2 microspheres, followed by the deposition of Pt cocatalysts on WO2.9 with controlled Pt single atoms and clusters (Pt–WO2.9/TiO2). The methane production rate reached 10.74 μmol h−1 g−1 with a selectivity of 99.8%, which was ∼40 times higher than that of bare TiO2 (0.27 μmol h−1 g−1). The high methane production rate was attributed to the synergy of Pt sites on the WO2.9/TiO2 heterojunction, where the Pt clusters facilitated water dissociation, thereby providing H* through hydrogen spillover on the surface, and the presence of a substoichiometric WO2.9 surface further enhanced the spillover process. The high density of active H* promoted the protonation pathway for CO2 activation (CO2 → COOH+ → *COOH), which improved the adsorption of the essential intermediate *CO on Pt single atoms and displayed a significantly reduced energy barrier for the protonation reaction of C1 intermediates, resulting in a mixed reaction pathway. This work provides new insights into a mechanism to regulate the reaction path to facilitate efficient photocatalytic CO2 methanation.
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