Bidentate carboxylate linked TiO2 with NH2-MIL-101(Fe)photocatalyst:a conjugation effect platform for high photocatalytic activity under visible light irradiation  

羧基双齿结构连接二氧化钛与NH2-MIL-101(Fe):一种共轭效应引发的高效可见光光催化平台

作　　者：Yuwei Ma Yunfeng Lu Guangtong Hai Wenjun Dong Rongjie Li Jinghai Liu Ge Wang 马雨威;卢云峰;海广通;董文钧;李荣洁;刘景海;王戈(Beijing Advanced Innovation Center for Materials Genome Engineering,Beijing Key Laboratory of Function Materials for Molecule&Structure Construction,School of Materials Science and Engineering,University of Science and Technology Beijing,Beijing 100083,China;Department of Chemical and Biomolecular Engineering,University of California,Los Angeles,CA 90095,USA;Inner Mongolia Key Laboratory of Carbon Nanomaterials,Nano Innovation Institute(NII),College of Chemistry and Chemical Engineering,Inner Mongolia University for Nationalities,Tongliao 028000,China)

机构地区：[1]Beijing Advanced Innovation Center for Materials Genome Engineering,Beijing Key Laboratory of Function Materials for Molecule&Structure Construction,School of Materials Science and Engineering,University of Science and Technology Beijing,Beijing 100083,China [2]Department of Chemical and Biomolecular Engineering,University of California,Los Angeles,CA 90095,USA [3]Inner Mongolia Key Laboratory of Carbon Nanomaterials,Nano Innovation Institute(Nil),College of Chemistry and Chemical Engineering,Inner Mongolia University for Nationalities,Tongliao 028000,China

出　　处：《Science Bulletin》2020年第8期658-669,M0004,共13页科学通报（英文版）

基　　金：supported by the National Natural Science Foundation of China(51572022 and 51872025);the National Key Research and Development Program of China(2016 YFB0701100);the National Key Research and Development H863 Program of China(18H86303ZT0032702)。

摘　　要：Interfacial conjugation was employed to engineering preparation of TiO2@NH2-MIL-101(Fe)heterojunction photocataysts through carboxylate bidentate linkage with TiO2 and NH2-MIL-101(Fe),which can enhance the electron transfer capability from metal-organic frameworks(MOFs)to TiO2 and photocatalytic activity.The carbon nanospheres derived from glucose act as reducing agent and template to synthesize oxygen vacancies TiO2 hollow nanospheres.Then,the oxygen vacancies were employed as antennas to connect 2-aminoterephtalic acid as bidentate carboxylate chelating linkage on TiO2,which have been proved by the density functional theory(DFT)calculations.Subsequently,NH2-MIL-101(Fe)was coordinatingly formed on the surface of TiO2.The conjugation effects between TiO2 and NH2-MIL-101(Fe)enhanced the electron transfer capability and could also induce the band tail states to narrow bandgap of the composites.Thus,the photodegradability of methylene blue was remarkably enhanced under visible light irradiation.The degradation rate of TiO2@17%NH2-MIL-101(Fe)was 0.131 min-1,which was about 3.5 and 65 times higher than that of NH2-MIL-101(Fe)and TiO2,respectively.经过数十年的深入研究,半导体光催化技术已经发展成为一种处理废水的高效技术.TiO2由于其低成本、无毒、可循环性和高稳定性成为光催化降解污染物的最有前途的半导体光催化材料之一.金属有机骨架具有较大的比表面积,可调节的孔径,较多的活性位点和稳定化学性质.将铁基金属有机骨架材料通过羧基双齿结构锚定在TiO2表面是一种增强异质结结构稳定的方法.此外,靠近锚定部分的羧基双齿结构具有较强的吸电子效应,会从Fe-MOFs中拉出电子密度并注入TiO2中.羧基双齿螯合结构可以连接供体和受体,使分子内的电荷从供体向TiO2的迁移能力增强并产生共轭效应.本文使用羧基双齿结构可控的将NH2-MIL-101(Fe)锚定到TiO2空心纳米球表面,TiO2和NH2-MIL-101(Fe)之间的共轭效应有效地提升了光生电子从NH2-MIL-101(Fe)向TiO2的转移能力.同时,引入的带尾结构缩短了复合物的带隙并提升了复合物(TiO2@NH2-MIL-101(Fe))的光催化性能.

关 键 词：Photocatalysis CONJUGATION EFFECT Electron transfer capability Bandgap METAL-ORGANIC frameworks 

分 类 号：X703[环境科学与工程—环境工程] O643.36[理学—物理化学] O644.1[理学—化学]