Journal
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
Volume 20, Issue 8-11, Pages 935-949Publisher
WORLD SCI PUBL CO INC
DOI: 10.1142/S1088424616300111
Keywords
oxygen reduction; proton reduction; carbon dioxide reduction; proton-coupled electron-transfer catalysis; cobalt complexes; photocatalytic reaction
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Funding
- Japan Science and Technology Agency (JST), Japan
- Grants-in-Aid for Scientific Research [16K13964, 26288037, 16H02268] Funding Source: KAKEN
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The conversion of solar energy into chemical energy by the reduction of small molecules provides a promising solution for the effective energy storage and transport. In this manuscript, we have highlighted our recent researches on the catalysis of cobalt-macrocycle complexes for the reduction of O-2, proton and CO2. We have successfully clarified the reaction mechanisms of catalytic O-2 reduction with cobalt phthalocyanine (Co-II(Pc)) and cobalt chlorin (Co-II(Ch)) based on detailed kinetic study under homogeneous conditions. The presence of proton-accepting moieties on these macrocyclic ligands enhances the electron-accepting ability, leading to the efficient catalytic two-electron reduction of O-2 to produce hydrogen peroxide (H2O2) with high stability and less overpotential in acidic solutions. When Co-II(Ch) is adsorbed on multi-walled carbon nanotubes (MWCNTs) and employed as an electrocatalyst, CO2 was successfully reduced to form CO with a Faradaic efficiency of 89% at an applied potential of -1.1 V vs. NHE in an aqueous solution. Finally, photocatalytic H-2 evolution was attained from ascorbic acid with Co-II(Ch) as a catalyst and [Ru(bpy)(3)](2+) (bpy = 2,2'-bipyridine) as a photocatalyst via a one-photon two-electron process.
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