Rong Shang , Yulong Li , Junjing Guo , Bang Gu , Feng Qiu , Qinghu Tang , Qiue Cao , Wenhao Fang
{"title":"揭示掺杂铈催化剂在木质素基苯胺和苯甲醇氧化偶联过程中的缺陷化学性质","authors":"Rong Shang , Yulong Li , Junjing Guo , Bang Gu , Feng Qiu , Qinghu Tang , Qiue Cao , Wenhao Fang","doi":"10.1016/j.jcat.2024.115537","DOIUrl":null,"url":null,"abstract":"<div><p>The defect chemistry of doped-ceria is vital but tangled for sustainable conversion of biomass resources. In this work, a group of Zr-doped CeO<sub>2</sub> solid solutions were prepared and the defect chemistry in CeZr<em><sub>x</sub></em>O<em><sub>y</sub></em> (0.02 ≤ <em>x</em> ≤ 5) catalyst was elucidated over the oxidative coupling of lignin-based aniline and benzyl alcohol. Varying the Zr molar fraction enabled to successfully adjust the defect sites of catalysts and further influence their catalytic performances. In addition, the optimal CeZr<sub>1</sub>O<em><sub>y</sub></em> catalyst exhibited a flexible temperature adaptability, wide substrate scope and superior reusability. Various characterizations, kinetic investigations, controlled experiments, DFT calculations and <em>in situ</em> DRIFT-IR technique were used to unravel the roles of Ce<sup>3+</sup> and oxygen defects and the reaction mechanism. It was disclosed that Zr-doped defects can obviously increase surface Ce<sup>3+</sup> cations, oxygen species (peroxide and superoxide anions) and oxygen vacancies. These coordinatively unsaturated sites were shown to play critical roles in absorbing and activating substrates hence can accelerate the formation rate of bio-based imines.</p></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":null,"pages":null},"PeriodicalIF":6.5000,"publicationDate":"2024-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Unraveling defect chemistry in doped-ceria catalyst for oxidative coupling of lignin-based aniline and benzyl alcohol\",\"authors\":\"Rong Shang , Yulong Li , Junjing Guo , Bang Gu , Feng Qiu , Qinghu Tang , Qiue Cao , Wenhao Fang\",\"doi\":\"10.1016/j.jcat.2024.115537\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The defect chemistry of doped-ceria is vital but tangled for sustainable conversion of biomass resources. In this work, a group of Zr-doped CeO<sub>2</sub> solid solutions were prepared and the defect chemistry in CeZr<em><sub>x</sub></em>O<em><sub>y</sub></em> (0.02 ≤ <em>x</em> ≤ 5) catalyst was elucidated over the oxidative coupling of lignin-based aniline and benzyl alcohol. Varying the Zr molar fraction enabled to successfully adjust the defect sites of catalysts and further influence their catalytic performances. In addition, the optimal CeZr<sub>1</sub>O<em><sub>y</sub></em> catalyst exhibited a flexible temperature adaptability, wide substrate scope and superior reusability. Various characterizations, kinetic investigations, controlled experiments, DFT calculations and <em>in situ</em> DRIFT-IR technique were used to unravel the roles of Ce<sup>3+</sup> and oxygen defects and the reaction mechanism. It was disclosed that Zr-doped defects can obviously increase surface Ce<sup>3+</sup> cations, oxygen species (peroxide and superoxide anions) and oxygen vacancies. These coordinatively unsaturated sites were shown to play critical roles in absorbing and activating substrates hence can accelerate the formation rate of bio-based imines.</p></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2024-05-06\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0021951724002501\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0021951724002501","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Unraveling defect chemistry in doped-ceria catalyst for oxidative coupling of lignin-based aniline and benzyl alcohol
The defect chemistry of doped-ceria is vital but tangled for sustainable conversion of biomass resources. In this work, a group of Zr-doped CeO2 solid solutions were prepared and the defect chemistry in CeZrxOy (0.02 ≤ x ≤ 5) catalyst was elucidated over the oxidative coupling of lignin-based aniline and benzyl alcohol. Varying the Zr molar fraction enabled to successfully adjust the defect sites of catalysts and further influence their catalytic performances. In addition, the optimal CeZr1Oy catalyst exhibited a flexible temperature adaptability, wide substrate scope and superior reusability. Various characterizations, kinetic investigations, controlled experiments, DFT calculations and in situ DRIFT-IR technique were used to unravel the roles of Ce3+ and oxygen defects and the reaction mechanism. It was disclosed that Zr-doped defects can obviously increase surface Ce3+ cations, oxygen species (peroxide and superoxide anions) and oxygen vacancies. These coordinatively unsaturated sites were shown to play critical roles in absorbing and activating substrates hence can accelerate the formation rate of bio-based imines.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.