A platinum porphyrin modified TiO<sub>2</sub> electrode for photoelectrochemical hydrogen production from neutral water driven by the conduction band edge potential of TiO<sub>2</sub>

Morita, Kenichi; Takijiri, Kohei; Sakai, Ken; Ozawa, Hiroki

doi:10.1039/c7dt03710d

Cited by 29 publications

(43 citation statements)

References 35 publications

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“…NHE in aqueous solution (pH=7) according to our literature [31] and obtained as −0.80 V vs . NHE in aqueous solution (pH=12) since the CBE potential showed a linear pH dependence with the slope of 59 mV per pH unit [35] …”

Section: Resultsmentioning

confidence: 99%

A Robust Photocatalytic Hybrid Material Composed of Metal‐Organic Cages and TiO₂ for Efficient Visible‐Light‐Driven Hydrogen Evolution

Yang

Huang

et al. 2021

Chemistry An Asian Journal

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The design of photochemical molecular devices (PMDs) for photocatalytic H2 production from water is a meaningful but challenging subject currently. Herein, a Pd2L4 type metal‐organic cage (denoted as MOC‐Q2) is designed as a PMD, which consists of two catalytic centers (Pd2+) and four photosensitive ligands (L‐2) with four pyridine anchoring groups. Subsequently, the MOC‐Q2 is combined with TiO2 to form TiO2‐MOC‐Q2 hybrid materials with different MOC‐Q2 contents by a facile sol‐gel method, which have micro/mesoporous structures and large surface areas. The optimized TiO2‐MOC‐Q2 (6.5 wt%) exhibits high H2 production activity (7.9 mmol g−1 h−1 within 5 h) and excellent durability, giving a TON value of 23477 or 11739 (based on MOC‐Q2 or Pd moles) after recycling for 7 rounds. By contrast, the pure MOC‐Q2 only shows an ordinary photocatalytic H2 production rate (0.84 mmol g−1 h−1 within 5 h) in the homogeneous system. It can be deduced that TiO2 drives the photocatalysis and simultaneously acts as the structure promoter. This study presents a meaningful and distinctive attempt of a new approach for the design and development of MOC‐based heterogeneous photocatalysts.

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Section: Resultsmentioning

confidence: 99%

A Robust Photocatalytic Hybrid Material Composed of Metal‐Organic Cages and TiO₂ for Efficient Visible‐Light‐Driven Hydrogen Evolution

Yang

Huang

et al. 2021

Chemistry An Asian Journal

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“…Comparison with analogous phosphonate-derivatized [Ru(bpy) 3 ] 2+ complexes demonstrates improved surface stability in aqueous solution at pH 5. Another example was also reported by the same group, where a pyridine-derivatized platinum(II) porphyrin was used as an electrocatalyst for water reduction 21 .…”

Section: Introductionmentioning

confidence: 89%

Stabilization of a molecular water oxidation catalyst on a dye−sensitized photoanode by a pyridyl anchor

et al. 2020

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Understanding and controlling the properties of water-splitting assemblies in dye-sensitized photoelectrosynthesis cells is a key to the exploitation of their properties. We demonstrate here that, following surface loading of a [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) chromophore on nanoparticle electrodes, addition of the molecular catalysts, Ru(bda)(L)2 (bda = 2,2′-bipyridine-6,6′-dicarboxylate) with phosphonate or pyridyl sites for water oxidation, gives surfaces with a 5:1 chromophore to catalyst ratio. Addition of the surface-bound phosphonate derivatives with L = 4-pyridyl phosphonic acid or diethyl 3-(pyridin-4-yloxy)decyl-phosphonic acid, leads to well-defined surfaces but, following oxidation to Ru(III), they undergo facile, on-surface dimerization to give surface-bound, oxo-bridged dimers. The dimers have a diminished reactivity toward water oxidation compared to related monomers in solution. By contrast, immobilization of the Ru-bda catalyst on TiO2 with the 4,4′-dipyridyl anchoring ligand can maintain the monomeric structure of catalyst and gives relatively stable photoanodes with photocurrents that reach to 1.7 mA cm−2 with an optimized, applied bias photon-to-current efficiency of 1.5%.

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“…Thus, PdTCP (H‐type) is the electron donor (photosensitizer) and PtTCP (J ‐ type) the electron acceptor (catalyst) in the mixed component catalytic system (PdTCP‐PtTCP/TiO 2 ). Sakai, Ozawa and co‐workers have reported that the H 2 evolution mechanism of a Pt porphyrin onto TiO 2 is based on two electron transfer processes [30] . It is very reasonable to consider that the H 2 production in our work also proceeds via two consecutive one‐electron processes.…”

Section: Resultsmentioning

confidence: 76%

Controlling Solar Hydrogen Production by Organizing Porphyrins

et al. 2020

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In this study, a highly efficient photocatalytic H2 production system is developed by employing porphyrins as photocatalysts. Palladium and platinum tetracarboxyporphyrins (PdTCP and PtTCP) are adsorbed or coadsorbed onto TiO2 nanoparticles (NPs), which act as the electron transport medium and as a scaffold that promotes the self‐organization of the porphyrinoids. The self‐organization of PdTCP and PtTCP, forming H‐ and J‐aggregates, respectively, is the key element for H2 evolution, as in the absence of TiO2 NPs no catalytic activity is detected. Notably, J‐aggregated PtTCPs are more efficient for H2 production than H‐aggregated PdTCPs. In this approach, a single porphyrin, which self‐organizes onto TiO2 NPs, acts as the light harvester and simultaneously as the catalyst, whereas TiO2 serves as the electron transport medium. Importantly, the concurrent adsorption of PdTCP and PtTCP onto TiO2 NPs results in the most efficient catalytic system, giving a turnover number of 22,733 and 30.2 mmol(H2) g(cat)−1.

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A platinum porphyrin modified TiO₂ electrode for photoelectrochemical hydrogen production from neutral water driven by the conduction band edge potential of TiO₂

Cited by 29 publications

References 35 publications

A Robust Photocatalytic Hybrid Material Composed of Metal‐Organic Cages and TiO₂ for Efficient Visible‐Light‐Driven Hydrogen Evolution

A Robust Photocatalytic Hybrid Material Composed of Metal‐Organic Cages and TiO₂ for Efficient Visible‐Light‐Driven Hydrogen Evolution

Stabilization of a molecular water oxidation catalyst on a dye−sensitized photoanode by a pyridyl anchor

Controlling Solar Hydrogen Production by Organizing Porphyrins

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A platinum porphyrin modified TiO2 electrode for photoelectrochemical hydrogen production from neutral water driven by the conduction band edge potential of TiO2

Cited by 29 publications

References 35 publications

A Robust Photocatalytic Hybrid Material Composed of Metal‐Organic Cages and TiO2 for Efficient Visible‐Light‐Driven Hydrogen Evolution

A Robust Photocatalytic Hybrid Material Composed of Metal‐Organic Cages and TiO2 for Efficient Visible‐Light‐Driven Hydrogen Evolution

Stabilization of a molecular water oxidation catalyst on a dye−sensitized photoanode by a pyridyl anchor

Controlling Solar Hydrogen Production by Organizing Porphyrins

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A platinum porphyrin modified TiO₂ electrode for photoelectrochemical hydrogen production from neutral water driven by the conduction band edge potential of TiO₂

A Robust Photocatalytic Hybrid Material Composed of Metal‐Organic Cages and TiO₂ for Efficient Visible‐Light‐Driven Hydrogen Evolution

A Robust Photocatalytic Hybrid Material Composed of Metal‐Organic Cages and TiO₂ for Efficient Visible‐Light‐Driven Hydrogen Evolution