Doping Copper Ions in a Metal-Organic Framework(UiO-66-NH2):Location Effect Examined by Ultrafast Spectroscopy  

金属有机框架材料UiO-66-NH2中的铜离子掺杂位置效应及相关动力学研究

作　　者：Jia Liu Shen-long Jiang Qun Zhang 刘佳;江申龙;张群(中国科学技术大学化学物理系,合肥微尺度物质科学国家研究中心,量子信息与量子科技协同创新中心,合肥230026)

机构地区：[1]Hefei National Laboratory for Physical Sciences at the Microscale,Department of Chemical Physics,and Synergetic Innovation Center of Quantum Information&Quantum Physics,University of Science and Technology of China,Hefei 230026,China

出　　处：《Chinese Journal of Chemical Physics》2020年第4期394-400,I0001,共8页化学物理学报（英文）

基　　金：the National Key Research and Development Program on Nano Science and Technology of the Ministry of Science and Technology of China(No.2016YFA0200602 and No.2018YFA0208702);the National Natural Science Foundation of China(No.21573211 and No.21633007);the Anhui Initiative in Quantum Information Technologies(No.AHY090200)。

摘　　要：We constructed two types of copper-doped metal-organic framework(MOF),i.e.,Cu@UiO-66-NH2 and Cu-UiO-66-NH2.In the former,Cu2+ions are impregnated in the pore space of the amine-functionalized,Zr-based UiO-66-NH2;while in the latter,Cu^2+ions are incorporated to form a bimetal-center MOF,with Zr^4+being partially replaced by Cu2+in the Zr-O oxo-clusters.Ultrafast spectroscopy revealed that the photoinduced relaxation kinetics associated with the ligand-to-cluster charge-transfer state is promoted for both Cudoped MOFs relative to undoped one,but in a sequence of Cu-UiO-66-NH2>Cu@UiO-66-NH2>UiO-66-NH2.Such a sequence turned to be in line with the trend observed in the visible-light photocatalytic hydrogen evolution activity tests on the three MOFs.These findings highlighted the subtle effect of copper-doping location in this Zr-based MOF system,further suggesting that rational engineering of the specific metal-doping location in alike MOF systems to promote the photoinduced charge separation and hence suppress the detrimental charge recombination therein is beneficial for achieving improved performances in MOF-based photocatalysis.

关 键 词：Metal-organic framework Copper doping Location effect Ultrafast dynamics Transient absorption spectroscopy PHOTOCATALYSIS 

分 类 号：O641.4[理学—物理化学] O643.36[理学—化学] O644.1