Mechanism of the formation of dihydrogen from the photoinduced reactions of poly(pyridine)ruthenium(II) and poly(pyridine)rhodium(III) complexes

CHAN, S.-F.; Chou, Mei H.; Creutz, Carol; Matsubara, Tadashi; Sutin, Norman

doi:10.1021/ja00392a022

Cited by 211 publications

(116 citation statements)

References 12 publications

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“…Materials: Tetramethylammonium bromide (TMABr, > 97 %) and ethylene glycol (> 99.5 %) were obtained from Tokyo Chemical Industry Co., Ltd. Iron pentacarbonyl (Fe(CO) 5 ) was purchased from Kanto Chemicals. Oleylamine (OA, 70 %), 1-octadecene (ODE, 90 %), ammonium tetrachloroplatinate(II) ((NH 4 ) 2 Pt II Cl 4 , 99 %), and poly(vinylpyrrolidone) (PVP, M w = 29 000) were purchased from Sigma-Aldrich.…”

Section: Methodsmentioning

confidence: 99%

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Size‐ and Shape‐Dependent Activity of Metal Nanoparticles as Hydrogen‐Evolution Catalysts: Mechanistic Insights into Photocatalytic Hydrogen Evolution

Kotani

Hanazaki

Ohkubo

et al. 2011

Chemistry A European J

103

126

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The catalytic activity of Pt nanoparticles (PtNPs) with different sizes and shapes was investigated in a photocatalytic hydrogen-evolution system composed of the 9-mesityl-10-methylacridinium ion (Acr(+)-Mes: photocatalyst) and dihydronicotinamide adenine dinucleotide (NADH: electron donor), based on rates of hydrogen evolution and electron transfer from one-electron-reduced species of Acr(+)-Mes (Acr·-Mes) to PtNPs. Cubic PtNPs with a diameter of (6.3±0.6) nm exhibited the maximum catalytic activity. The observed hydrogen-evolution rate was virtually the same as the rate of electron transfer from Acr·-Mes to PtNPs. The rate constant of electron transfer (k(et)) increased linearly with increasing proton concentration. When H(+) was replaced by D(+), the inverse kinetic isotope effect was observed for the electron-transfer rate constant (k(et)(H)/k(et)(D)=0.47). The linear dependence of k(et) on proton concentration together with the observed inverse kinetic isotope effect suggests that proton-coupled electron transfer from Acr·-Mes to PtNPs to form the Pt-H bond is the rate-determining step for catalytic hydrogen evolution. When FeNPs were used instead of PtNPs, hydrogen evolution was also observed, although the hydrogen-evolution efficiency was significantly lower than that of PtNPs because of the much slower electron transfer from Acr·-Mes to FeNPs.

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Section: Methodsmentioning

confidence: 99%

“…Synthesis of water-soluble FeNPs: Oleylamine-stabilized FeNPs (Fe-OA) were synthesized by thermal decomposition of Fe(CO) 5 in the presence of OA as a surfactant. [52] The synthesized Fe-OA was dried in a vacuum and stored under N 2 atmosphere.…”

Section: Methodsmentioning

confidence: 99%

Size‐ and Shape‐Dependent Activity of Metal Nanoparticles as Hydrogen‐Evolution Catalysts: Mechanistic Insights into Photocatalytic Hydrogen Evolution

Kotani

Hanazaki

Ohkubo

et al. 2011

Chemistry A European J

103

126

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“…The choice of an electron relay is generally crucial to the success of a system; a good relay oxidatively quenches the excited photosensitizer, thereby creating charge separation at the cost of reducing the systems free energy. Numerous relays have been used in place of methyl viologen, including a variety of quaternary bipyridines [24,25] as well as several cobalt [26][27][28] and rhodium [8,[29][30][31] complexes. Other alternatives include bridged systems where a photosensitizer is covalently linked to a hydrogen evolving metal complex.…”

Section: -A C H T U N G T R E N N U N G (N^n)]mentioning

confidence: 99%

Visible Light Induced Catalytic Water Reduction without an Electron Relay

Tinker

McDaniel

Curtin

et al. 2007

Chemistry A European J

211

238

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Protons from water are reduced by a catalytic system composed of a heteroleptic iridium(III) photosensitizer [Ir(ppy)2(bpy)]+, platinum catalyst, and sacrificial reductant. The hydrogen quantum yield reaches 0.26 in this study, which proceeds via reductive quenching of the excited photosensitizer by triethanolamine. This simplified approach allows the characterization of degradation products that are otherwise obscured in more complex systems. A novel 16-well setup for parallel kinetic analysis of H2 evolution enables high-throughput screening of reaction conditions and quantization of the decaying reaction rate. DFT calculations rationalize the differences between this and previous studies on tris-diimine ruthenium(II) photosensitizers.

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“…Abstraction of a proton at this TEOA radical by a further TEOA molecule yields the carbon-centered radicals (Scheme 4) [12,[99][100][101][102]. Unlike the aminyl radical TEOA·, these carbon-centered radicals are strong reducing agents that prevent back electron transfer from the OER and are capable of donating a second electron [12,[99][100][101][102][103][104]. [107].…”

Section: Oxidation Sitementioning

confidence: 99%

Conversion of CO2 via Visible Light Promoted Homogeneous Redox Catalysis

2012

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Abstract:This review gives an overview on the principles of light-promoted homogeneous redox catalysis in terms of applications in CO 2 conversion. Various chromophores and the advantages of different structures and metal centers as well as optimization strategies are discussed. All aspects of the reduction catalyst site are restricted to CO 2 conversion. An important focus of this review is the question of a replacement of the sacrificial donor which is found in most of the current publications. Furthermore, electronic parameters of supramolecular systems are reviewed with reference to the requisite of chromophores, oxidation and reduction sites.

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Mechanism of the formation of dihydrogen from the photoinduced reactions of poly(pyridine)ruthenium(II) and poly(pyridine)rhodium(III) complexes

Cited by 211 publications

References 12 publications

Size‐ and Shape‐Dependent Activity of Metal Nanoparticles as Hydrogen‐Evolution Catalysts: Mechanistic Insights into Photocatalytic Hydrogen Evolution

Size‐ and Shape‐Dependent Activity of Metal Nanoparticles as Hydrogen‐Evolution Catalysts: Mechanistic Insights into Photocatalytic Hydrogen Evolution

Visible Light Induced Catalytic Water Reduction without an Electron Relay

Conversion of CO2 via Visible Light Promoted Homogeneous Redox Catalysis

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