Excited-State Chemistry: Photocatalytic Methanol Oxidation by Uranyl@Zeolite through Oxygen-Centered Radicals

Li, Yong1,2,3,4; Zhang, Guoqing3; Schwarz, W. H. Eugen1,2,5; Li, Jun1,2,6

2020-05-04

10.1021/acs.inorgchem.0c00388

INORGANIC CHEMISTRY   影响因子和分区

0020-1669

1520-510X

We have elucidated the complex reaction network of partial methanol oxidation, H3COH + O-2 -> H2CO + H2O2, at a visible-light-activated actinide photocatalyst. The reaction inertness of C-H bonds and O=O diradicals at ambient conditions is overcome through catalysis by photoexcited uranyl units (*UO22+) anchored on a mesoporous silicate. The electronic ground- and excited-state energy hypersurfaces are investigated with quasirelativistic density-functional and ab initio correlated wave function approaches. Our study suggests that the molecular cluster can react on the excited energy surface due to the longevity of excited uranyl, typical for f-element compounds. The theoretically predicted energy profiles, chemical intermediates, related radicals, and product species are consistent with various experimental findings. The uranyl excitation opens various reaction pathways for the oxidation of volatile organic compounds (VOCs) by "hole-driven hydrogen transfer" (HDHT) through several exothermic steps over low activation barriers toward environmentally clean or chemically interesting products. Quantum-chemical modeling reveals the high efficiency of the uranyl photocatalysis and directs the way to further understanding and improvement of VOC degradation, chemical synthesis, and biologic photochemical interactions between uranyl and the environment.

SCI ; EI

英语

NI期刊 ; NI论文

通讯

National Natural Science Foundation of China (NSFC)[21590792][91645203][21433005] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; International Science & Technology Cooperation Program of China[2011DFB91560]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:000530668400053

AMER CHEMICAL SOC

20201808595264

CHEMISTRY

Web of Science

1.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
2.Tsinghua Univ, Key Lab Organ Optoelect & Mol Engn, Minist Educ, Beijing 100084, Peoples R China
3.Guangdong Univ Technol, Sch Mat & Energy, Guangzhou 510006, Peoples R China
4.Univ Bremen, Inst Appl & Phys Chem, Bremen 28359, Germany
5.Univ Siegen, Dept Chem, Siegen 57068, Germany
6.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China

Li, Yong,Zhang, Guoqing,Schwarz, W. H. Eugen,et al. Excited-State Chemistry: Photocatalytic Methanol Oxidation by Uranyl@Zeolite through Oxygen-Centered Radicals[J]. INORGANIC CHEMISTRY,2020,59(9):6287-6300.

Li, Yong,Zhang, Guoqing,Schwarz, W. H. Eugen,&Li, Jun.(2020).Excited-State Chemistry: Photocatalytic Methanol Oxidation by Uranyl@Zeolite through Oxygen-Centered Radicals.INORGANIC CHEMISTRY,59(9),6287-6300.

Li, Yong,et al."Excited-State Chemistry: Photocatalytic Methanol Oxidation by Uranyl@Zeolite through Oxygen-Centered Radicals".INORGANIC CHEMISTRY 59.9(2020):6287-6300.