期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 12, 页码 4902-4907出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201916131
关键词
electrocatalysis; electrosynthesis; oxygen reduction reaction; porphyrins; supramolecular chemistry
资金
- Office of Science, Office of Basic Energy Sciences, and the Division of Chemical Sciences, Geosciences, and Bioscience of the U.S. Department of Energy at Lawrence Berkeley National Laboratory [DE-AC02-05CH11231]
- Institute for Basic Science [IBS-R007-D1]
- NSF
We report a supramolecular strategy for promoting the selective reduction of O-2 for direct electrosynthesis of H2O2. We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90-100 % H2O2 from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H2O2 and H2O. Bimolecular pathways have been implicated in facilitating H2O formation, therefore, we attribute this high H2O2 selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host-guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.
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