首页|π-conjugated chromophore functionalized high-nuclearity titanium-oxo clusters containing structural unit of anatase for photocatalytic selective oxidation of sulfides

π-conjugated chromophore functionalized high-nuclearity titanium-oxo clusters containing structural unit of anatase for photocatalytic selective oxidation of sulfides

扫码查看
原文链接
  • NETL
  • NSTL
  • 万方数据
N-doping has significant influence in manipu-lating the properties of TiO2,and this has stimulated the development of N-donor-functionalized titanium-oxo clusters(TOCs)as molecular models to study the struc-ture-property relationship.However,the structural type and photoresponsive application are still limited for such TOCs,especially regarding the high-nuclearity TOCs that contain structure unit of TiO2 for photocatalysis.Herein,we showed the synthesis of a series of high-nuclearity TOCs 1-3 compounds using π-conjugated 1,10-phenan-throline(phen)as chromophore and N-donor functional ligand.Compound 1 features cocrystal structure composed of one[Ti26]2+and half[Ti22]2+,which renders it as the first cocrystallized TOC containing two positively charged species and phen-functionalized TOC showing the highest nuclearity up to 37 Ti centers.By adjusting the synthetic conditions,the individual {Ti22} and(Ti26} clusters can also be isolated as Compounds 2 and 3,respectively.The core structure of {Ti22} is mainly constructed from four lacunary {Ti4} derived from pentagonal {Ti(Ti)5} unit,while {Ti26} is built from four complete {Ti(Ti)5} unit.Notably,a {Ti8O14} structure unit of anatase TiO2 can be identified in {Ti26}.Based on the unique structural features and proper photophysical and photochemical properties of Compounds 1-3,they are applied for photocatalytic sul-foxidation.Owing to the presence of anatase structure unit in {Ti26} and the synergistic effect from {Ti22} and {Ti26},the catalytic performance presents in the order of Com-pound 1＞Compound 3＞Compound 2.This work pro-vides excellent models to understand the structure-property relationship from the perspective of cocrystal-lization and Ti-O binding model and will further promote the application of TOCs as functional catalysts for organic transformation.

Titanium-oxo clusterMolecular model of anatase TiO2High nuclearityπ-conjugated chromophorePhotocatalytic sulfoxidation

Ling-Rong Liao、Dong-Chun Zheng、Pin-Xi Ou、Qi-Xin Zhao、Wei-Min Xuan、Qi Zheng

展开 >

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials & College of Materials Science and Engineering,Donghua University,Shanghai 201620,China

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials and College of Chemistry and Chemical Engineering,Donghua University,Shanghai 201620,China

National Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaProgram for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher LearningFundamental Research Funds for the Central UniversitiesInternational Cooperation Fund of Science and Technology Commission of Shanghai Municipality

2190103721901038921611112232019G-0721130750100

2024

10.1007/s12598-023-02545-0

稀有金属(英文版)
中国有色金属学会

稀有金属(英文版)

CSTPCDEI
影响因子：0.801
ISSN：1001-0521
年,卷(期)：2024.43(4)
  • 71