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

Sheng-Nan Sun ¹Qian Niu ²Jiao-Min Lin ¹Li-Ling He ¹Jing-Wen Shi ¹Qing Huang ³Jiang Liu ¹Ya-Qian Lan¹

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作者信息

1. School of Chemistry,South China Normal University,Guangzhou 510006,China
2. School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China
3. College of Materials Science and Engineering,Nanjing Forestry University,Nanjing 210037,China
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Abstract

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.

Key words

Zirconium/hafnium-oxo clusters/Amine oxidation reaction/Photocatalytic reaction/Synergistic catalysis

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基金项目

National Natural Science Foundation of China(22225109)

National Natural Science Foundation of China(92061101)

National Natural Science Foundation of China(22071109)

National Natural Science Foundation of China(22101089)

Top Youth Project of Guangdong Province Pearl River Talents Program(2021QN02L617)

Excellent Youth Foundation of Jiangsu Provincial Natural Science Foundation(BK20211593)

Open Fund of Energy and Materials Chemistry Joint Laboratory of South China Normal University and Guangzhou Tinci Materials (SCNU-TINCI-202204)

Guangdong Provincial Basic and Applied Basic Research Foundation(2023A1515030097)

Guangdong Provincial Basic and Applied Basic Research Foundation(2020A1515110836)

出版年

2024

科学通报(英文版)

中国科学院

科学通报(英文版)

CSTPCD

ISSN：1001-6538

参考文献量53

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