Qinhui Guan, Chengzhe Ni, Tingjiang Yan, Na Li, Lu Wang, Zhe Lu, Weiguang Ran, Yipin Zhang, Wenjuan Li, Lulu Zhang, Dapeng Zhang, Baibiao Huang and Geoffrey A. Ozin
{"title":"Amine functionalized surface frustrated Lewis pairs boost CO2 photocatalysis†‡","authors":"Qinhui Guan, Chengzhe Ni, Tingjiang Yan, Na Li, Lu Wang, Zhe Lu, Weiguang Ran, Yipin Zhang, Wenjuan Li, Lulu Zhang, Dapeng Zhang, Baibiao Huang and Geoffrey A. Ozin","doi":"10.1039/D3EY00261F","DOIUrl":null,"url":null,"abstract":"<p >The archetype surface frustrated Lewis pair (SFLP) that facilitates CO<small><sub>2</sub></small> photocatalytic hydrogenation to methanol and carbon monoxide, is an InOH⋯In site positioned in the surface of a nanoscale indium oxide hydroxide, denoted In<small><sub>2</sub></small>O<small><sub>3−<em>x</em></sub></small>(OH)<small><sub><em>y</em></sub></small>. Proximal Lewis acid In(<small>III</small>) and Lewis base InOH of this genre serve as surface active sites that enable the photochemical heterolytic H<small><sub>2</sub></small> dissociation and reduction of CO<small><sub>2</sub></small> to the mentioned products. The conversion rate enabled by light has been found to far exceed that enabled by heat. Efforts to enhance the CO<small><sub>2</sub></small> photocatalytic performance of the SFLP have involved modifications of the Lewis acidity and basicity through isomorphic substitution of In(<small>III</small>) with Bi(<small>III</small>) and changes in the population of oxygen vacancies through control of oxide non-stoichiometry. Replacement of the Lewis base hydroxide InOH by the stronger Lewis base amine InNH<small><sub>2</sub></small> heretofore remains unexplored. The strategy described herein to explore this opportunity begins with the synthesis of In<small><sub>2</sub></small>O<small><sub>3−<em>x</em></sub></small>(EDA)<small><sub><em>y</em></sub></small>. This new material is proven to contain an InNH<small><sub>2</sub></small>⋯In SFLP and its CO<small><sub>2</sub></small> photocatalytic performance is demonstrated to outperform that of its In<small><sub>2</sub></small>O<small><sub>3−<em>x</em></sub></small>(OH)<small><sub><em>y</em></sub></small> progenitor. Tailored Lewis acidity and basicity surfaces bring CO<small><sub>2</sub></small> photocatalysis another step closer to the vision of solar CO<small><sub>2</sub></small> refineries.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2024-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d3ey00261f?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"EES catalysis","FirstCategoryId":"1085","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/ey/d3ey00261f","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
Abstract
The archetype surface frustrated Lewis pair (SFLP) that facilitates CO2 photocatalytic hydrogenation to methanol and carbon monoxide, is an InOH⋯In site positioned in the surface of a nanoscale indium oxide hydroxide, denoted In2O3−x(OH)y. Proximal Lewis acid In(III) and Lewis base InOH of this genre serve as surface active sites that enable the photochemical heterolytic H2 dissociation and reduction of CO2 to the mentioned products. The conversion rate enabled by light has been found to far exceed that enabled by heat. Efforts to enhance the CO2 photocatalytic performance of the SFLP have involved modifications of the Lewis acidity and basicity through isomorphic substitution of In(III) with Bi(III) and changes in the population of oxygen vacancies through control of oxide non-stoichiometry. Replacement of the Lewis base hydroxide InOH by the stronger Lewis base amine InNH2 heretofore remains unexplored. The strategy described herein to explore this opportunity begins with the synthesis of In2O3−x(EDA)y. This new material is proven to contain an InNH2⋯In SFLP and its CO2 photocatalytic performance is demonstrated to outperform that of its In2O3−x(OH)y progenitor. Tailored Lewis acidity and basicity surfaces bring CO2 photocatalysis another step closer to the vision of solar CO2 refineries.