Journal
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY
Volume 12, Issue 1, Pages 585-590Publisher
AMER SCIENTIFIC PUBLISHERS
DOI: 10.1166/jnn.2012.5411
Keywords
Coordination Polymer; Hydrogen Production; Photocatalyst; Decomposition of Water; Porphyrin; Dinuclear Ruthenium Complex
Categories
Funding
- Ministry of Education, Culture, Sports, Science and Technology of Japan [19350077]
- Grants-in-Aid for Scientific Research [19350077] Funding Source: KAKEN
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In this study, we investigated the photochemical production of hydrogen from water using bioinspired heterogeneous microporous porphyrin coordination lattices (PCLs), [Ru-2(MTCPP)BF4] (M = H-2 (PCL-1), Zn (PCL-2); TCPP = Tetrakis(4-carboxyphenyl)porphyrin), under visible (380 nm <) and UV (320 nm <) light irradiations. In the presence of Na(2)EDTA (as a sacrificial donor) and MV2+ (methyl-vilologen; as a electron relay), PCLs exhibits photocatalytic activity for hydrogen evolution; the maximum amounts of turnover numbers (TONs) of PCL-1 and PCL-2 at 24 h irradiation were 20.8 and 29.9, respectively. In the catalytic reactions, the relation between PCLs and MV2+ was similar to the relation between a [cytochrome c(3) hydrogenase] pair and lysine residues in enzymatic reactions. By using the hydrogen production rate and the MV+ (methyl-vilologen radicalcation) concentration, kinetic parameters such as affinities between MV+ and PCLs, maximum reaction rate, and total efficiency of the reaction are introduced using the Michaelis-Menten equation. These parameters indicated that PCLs are good artificial enzyme model catalysts. The stability of the PCLs after the catalytic reactions was confirmed by X-ray photoelectron spectroscopy and Fourier transform-infrared spectra. These results indicated that the frameworks of PCLs are stable for this catalytic reaction.
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