US EPA

8783342 

Journal Article 

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

Li, Y; Zhang, G; Schwarz, W; Li, J 

2020 

Yes 

Inorganic Chemistry
ISSN: 0020-1669
EISSN: 1520-510X 

59 

9 

6287-6300 

English 

32309927 

10.1021/acs.inorgchem.0c00388 

WOS:000530668400053 

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. 

BOND COVALENT RADII; ELECTRON-TRANSFER; AQUEOUS-SOLUTION; PHOTOCHEMICAL REDUCTION; RNA-POLYMERASE; METAL-IONS; PHOTOOXIDATION; ALCOHOLS; PHOTOREDUCTION; ABSTRACTION