{"title":"Enhancement of Selective Catalytic Oxidation of Lignin β-O-4 Bond via Orbital Modulation and Surface Lattice Reconstruction.","authors":"Haonan Chen, Baolong Qin, Qi Zhang, Xiaohong Hu, Longlong Ma, Xinghua Zhang, Zhiyuan Tang, Lungang Chen","doi":"10.1002/cssc.202402194","DOIUrl":null,"url":null,"abstract":"<p><p>The orbital modulation and surface lattice reconstruction represent an effective strategy to regulate the interaction between catalyst interface sites and intermediates, thereby enhancing catalytic activity and selectivity. In this study, the crystal surface of Au-K/CeO<sub>2</sub> catalyst can undergo reversible transformation by tuning the coordination environment of Ce, which enables the activation of the C<sub>β</sub>-H bond and the oxidative cleavage of the C<sub>β-O</sub> and C<sub>α</sub>-C<sub>β</sub> bonds, leading to the cleavage of 2-phenoxy-1-phenylethanol. The t<sub>2g</sub> orbitals of Au 5d hybridize with the 2p orbitals of lattice oxygen in CeO<sub>2</sub> via π-coordination, modulating the coordination environment of Ce 4 f and reconstructing the lattice oxygen in the CeO<sub>2</sub> framework, as well as increasing the oxygen vacancies. The interface sites formed by the synergy between Au clusters in the reconstructed Ce-O<sub>L1</sub>-Au structure and doped K play dual roles. On the one hand, it activates the C<sub>β</sub>-H bond, facilitating the enolization of the pre-oxidized 2-phenoxy-1-phenylethanone. On the other hand, through single-electron transfer involving Ce<sup>3+</sup> 4f<sup>1</sup> and the adsorption by oxygen vacancies, it enhances the oxidative cleavage of the C<sub>β-O</sub> and C<sub>α</sub>-C<sub>β</sub> bonds. This study elucidates the complex mechanistic roles of the structure and properties of Au-K/CeO<sub>2</sub> catalyst in the selective catalytic oxidation of lignin β-O-4 bond.</p>","PeriodicalId":149,"journal":{"name":"ChemSusChem","volume":" ","pages":"e202402194"},"PeriodicalIF":7.5000,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemSusChem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cssc.202402194","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The orbital modulation and surface lattice reconstruction represent an effective strategy to regulate the interaction between catalyst interface sites and intermediates, thereby enhancing catalytic activity and selectivity. In this study, the crystal surface of Au-K/CeO2 catalyst can undergo reversible transformation by tuning the coordination environment of Ce, which enables the activation of the Cβ-H bond and the oxidative cleavage of the Cβ-O and Cα-Cβ bonds, leading to the cleavage of 2-phenoxy-1-phenylethanol. The t2g orbitals of Au 5d hybridize with the 2p orbitals of lattice oxygen in CeO2 via π-coordination, modulating the coordination environment of Ce 4 f and reconstructing the lattice oxygen in the CeO2 framework, as well as increasing the oxygen vacancies. The interface sites formed by the synergy between Au clusters in the reconstructed Ce-OL1-Au structure and doped K play dual roles. On the one hand, it activates the Cβ-H bond, facilitating the enolization of the pre-oxidized 2-phenoxy-1-phenylethanone. On the other hand, through single-electron transfer involving Ce3+ 4f1 and the adsorption by oxygen vacancies, it enhances the oxidative cleavage of the Cβ-O and Cα-Cβ bonds. This study elucidates the complex mechanistic roles of the structure and properties of Au-K/CeO2 catalyst in the selective catalytic oxidation of lignin β-O-4 bond.
期刊介绍:
ChemSusChem
Impact Factor (2016): 7.226
Scope:
Interdisciplinary journal
Focuses on research at the interface of chemistry and sustainability
Features the best research on sustainability and energy
Areas Covered:
Chemistry
Materials Science
Chemical Engineering
Biotechnology