Sulfur atom-directed metal-ligand synergistic catalysis in zirconium/hafnium-oxo clusters for highly efficient amine oxidation

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外文摘要：The performance applications(e.g.,photocatalysis)of zirconium(Zr)and hafnium(Hf)based complexes are greatly hindered by the limited development of their structures and the relatively inert metal reac-tivity.In this work,we constructed two ultrastable Zr/Hf-based clusters(Zr9-TC4A and Hf9-TC4A)using hydrophobic 4-tert-butylthiacalix[4]arene(H4TC4A)ligands,in which unsaturated coordinated sulfur(S)atoms on the TC4A4-ligand can generate strong metal-ligand synergy with nearby active metal Zr/Hf sites.As a result,these two functionalized H4TC4A ligands modified Zr/Hf-oxo clusters,as catalysts for the amine oxidation reaction,exhibited excellent catalytic activity,achieving very high substrate conver-sion(＞99％)and product selectivity(＞90％).Combining comparative experiments and theoretical calcula-tions,we found that these Zr/Hf-based cluster catalysts accomplish efficient amine oxidation reactions through synergistic effect between metals and ligands:(ⅰ)The photocatalytic benzylamine(BA)oxidation reaction was achieved by the synergistic effect of the dual active sites,in which,the naked S sites on the TC4A4-ligand oxidize the BA by photogenerated hole and oxygen molecules are reduced by photogener-ated electrons on the metal active sites;(ⅱ)in the aniline oxidation reaction,aniline was adsorbed by the bare S sites on ligands to be closer to metal active sites and then oxidized by the oxygen-containing rad-icals activated by the metal sites,thus completing the catalytic reaction under the synergistic catalytic effect of the proximity metal-ligand.In this work,the Zr/Hf-based complexes applied in the oxidation of organic amines have been realized using active S atom-directed metal-ligand synergistic catalysis and have demonstrated very high reactivity.

外文关键词：

Zirconium/hafnium-oxo clustersAmine oxidation reactionPhotocatalytic reactionSynergistic catalysis

作者：

Sheng-Nan Sun、Qian Niu、Jiao-Min Lin、Li-Ling He、Jing-Wen Shi、Qing Huang、Jiang Liu、Ya-Qian Lan

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作者单位：

School of Chemistry,South China Normal University,Guangzhou 510006,China

School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China

College of Materials Science and Engineering,Nanjing Forestry University,Nanjing 210037,China

基金：

National Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaTop Youth Project of Guangdong Province Pearl River Talents ProgramExcellent Youth Foundation of Jiangsu Provincial Natural Science FoundationOpen Fund of Energy and Materials Chemistry Joint Laboratory of South China Normal University and Guangzhou Tinci Materials Guangdong Provincial Basic and Applied Basic Research FoundationGuangdong Provincial Basic and Applied Basic Research Foundation

项目编号：

222251099206110122071109221010892021QN02L617BK20211593SCNU-TINCI-2022042023A15150300972020A1515110836

出版年：

2024

DOI：

10.1016/j.scib.2023.11.047

科学通报(英文版)

中国科学院

科学通报(英文版)

CSTPCD

ISSN：1001-6538

年,卷(期)：2024.69(4)

参考文献量53