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Published on: June 12, 2019
Selective CH4 Partial Photooxidation by Positively Charged Metal Clusters Anchored on Carbon Aerogel under Mild
Kai Zheng1, Yang Wu1, Zexun Hu1
1Hefei National Laboratory for Physical Sciences at Microscale, National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230026, People's Republic of China.
Abstract:
Selective partial photooxidation of CH4 into value-added chemicals under mild conditions still remains a huge bottleneck. Herein, we design positively charged metal clusters anchored on a three-dimensional porous carbon aerogel. With 0.75FeCA800-4 as an example, X-ray photoelectron spectra and Raman spectra disclose that the iron sites are positively charged. In situ electron paramagnetic resonance spectra show that the Feδ+ sites could donate electrons to activate CH4 into CH4- by virtue of the excited-state carbon atoms; meanwhile, they could convert H2O2 into •OH radicals under irradiation. In addition, in situ diffuse Fourier-transform infrared spectra suggest the CH3OOH obtained is derived from CH4 oxidation by the hydroxylation of *CH3 and *CH3O intermediates. Consequently, 0.75FeCA800-4 displays a CH3OOH selectivity of near 100% and a CH3OOH evolution rate of 13.2 mmol gFe-1 h-1, higher than those of most previously reported supported catalysts under similar conditions.
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