Efficient and Stable Photo-Oxidation of Water by a Bismuth Vanadate Photoanode Coupled with an Iron Oxyhydroxide Oxygen Evolution Catalyst

Seabold, Jason A.; Choi, Kyoung‐Shin

doi:10.1021/ja209001d

Cited by 763 publications

(779 citation statements)

References 47 publications

(80 reference statements)

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“…These predicted efficiencies rival the best-performing previously reported devices for hydrogen-evolving photocathodes that involve noble-metal catalysts. 12,26 Performance of Ni-Mo nanopowder electrocatalysts…”

Section: Modelmentioning

confidence: 99%

“…1,11 Alternatively, in photoelectrode structures comprised of a single photoabsorber, a transparent back contact can be used in conjunction with ''backside'' illumination so that the catalyst layer is not in the optical path of the semiconductor. [5][6][7]12 For integrated photoelectrodes in which the interfacial reactions can be performed by photogenerated minority carriers (as well as by majority carriers, for structures that contain a buried junction [8][9][10] ), the thickness of the electrocatalyst film can be adjusted to obtain an optimum compromise between the optical density and activity of the electrocatalyst film. This type of optimization favors the use of an extremely thin (o5 nm) catalytic layer, at the expense of catalytic activity.…”

Section: Introductionmentioning

confidence: 99%

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Functional integration of Ni–Mo electrocatalysts with Si microwire array photocathodes to simultaneously achieve high fill factors and light-limited photocurrent densities for solar-driven hydrogen evolution

Shaner

McKone

Gray

et al. 2015

Energy Environ. Sci.

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An n + p-Si microwire array coupled with a two-layer catalyst film consisting of Ni-Mo nanopowder and TiO 2 light-scattering nanoparticles has been used to simultaneously achieve high fill factors and lightlimited photocurrent densities from photocathodes that produce H 2 (g) directly from sunlight and water.The TiO 2 layer scattered light back into the Si microwire array, while optically obscuring the underlying Ni-Mo catalyst film. In turn, the Ni-Mo film had a mass loading sufficient to produce high catalytic activity, on a geometric area basis, for the hydrogen-evolution reaction. The best-performing microwire array devices prepared in this work exhibited short-circuit photocurrent densities of À14.3 mA cm À2 , photovoltages of 420 mV, and a fill factor of 0.48 under 1 Sun of simulated solar illumination, whereas the equivalent planar Ni-Mo-coated Si device, without TiO 2 scatterers, exhibited negligible photocurrent due to complete light blocking by the Ni-Mo catalyst layer. Broader contextSolar-driven photoelectrochemical water splitting is a promising approach to enable the large-scale conversion and storage of solar energy. Few integrated systems have been realized that use earth-abundant semiconductor and catalyst materials for the half-reactions involved in solar-driven water-splitting, i.e. hydrogen evolution and oxygen evolution, while also achieving high energy-conversion efficiencies. We describe herein a hydrogen-evolving Si-based photoelectrode that exhibits high light-limited photocurrent densities, as well as high catalytic activities, while using a high mass loading of an earth-abundant electrocatalyst. The design is reminiscent of a membrane-electrode assembly as used for stand-alone fuel cell and electrolysis systems. The approach exploits the high aspect ratio of the absorber layer to avoid parasitic optical absorption normally associated with a thick catalyst layer on the surface of an illuminated photocathode.

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Section: Modelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Functional integration of Ni–Mo electrocatalysts with Si microwire array photocathodes to simultaneously achieve high fill factors and light-limited photocurrent densities for solar-driven hydrogen evolution

Shaner

McKone

Gray

et al. 2015

Energy Environ. Sci.

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“…Previous studies have shown that electrodeposited catalysts can be effective at improving the performance of photoanodes. 21,46 An established literature method for electrodepositing IrO x on FTO was used in this work. 38 The electrodeposition proceeded until 400 mC of charge had passed with a 1 cm 2 substrate, providing the same catalyst loading for each sample.…”

Section: àmentioning

confidence: 99%

Improving O2 production of WO3 photoanodes with IrO2 in acidic aqueous electrolyte

Spurgeon

Velázquez

McDowell

2014

Phys. Chem. Chem. Phys.

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WO 3 is a promising candidate for a photoanode material in an acidic electrolyte, in which it is more stable than most metal oxides, but kinetic limitations combined with the large driving force available in the WO 3 valence band for water oxidation make competing reactions such as the oxidation of the acid counterion a more favorable reaction. The incorporation of an oxygen evolving catalyst (OEC) on the WO 3 surface can improve the kinetics for water oxidation and increase the branching ratio for O 2 production. Ir-based OECs were attached to WO 3 photoanodes by a variety of methods including sintering from metal salts, sputtering, drop-casting of particles, and electrodeposition to analyze how attachment strategies can affect photoelectrochemical oxygen production at WO 3 photoanodes in 1 M H 2 SO 4 . High surface coverage of catalyst on the semiconductor was necessary to ensure that most minority-carrier holes contributed to water oxidation through an active catalyst site rather than a sidereaction through the WO 3 /electrolyte interface. Sputtering of IrO 2 layers on WO 3 did not detrimentally affect the energy-conversion behavior of the photoanode and improved the O 2 yield at 1.2 V vs. RHE from B0% for bare WO 3 to 50-70% for a thin, optically transparent catalyst layer to nearly 100% for thick, opaque catalyst layers. Measurements with a fast one-electron redox couple indicated ohmic behavior at the IrO 2 /WO 3 junction, which provided a shunt pathway for electrocatalytic IrO 2 behavior with the WO 3 photoanode under reverse bias. Although other OECs were tested, only IrO 2 displayed extended stability under the anodic operating conditions in acid as determined by XPS.

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“…This PEC cell relied on the consumption of sacrificial NADH (nicotinamide adenine dinucleotide),1d whereas we demonstrate overall water splitting in this work. BiVO 4 is a well‐established photoanode for water oxidation,9 which was synthesized on FTO‐coated glass according to previous reports 10. BiVO 4 was selected owing to its stability under the neutral pH conditions required for the H 2 ase, and its high photovoltage and currents are in principle suitable for bias‐free water splitting when paired with a silicon photocathode 9, 10a,10b.…”

mentioning

confidence: 99%

“…BiVO 4 is a well‐established photoanode for water oxidation,9 which was synthesized on FTO‐coated glass according to previous reports 10. BiVO 4 was selected owing to its stability under the neutral pH conditions required for the H 2 ase, and its high photovoltage and currents are in principle suitable for bias‐free water splitting when paired with a silicon photocathode 9, 10a,10b. The synthesized BiVO 4 is crystalline and exhibits a film thickness of approximately 650 nm with a nanoporous surface structure (see Figure S12 for SEM images, XRD pattern, and UV/Vis spectrum).…”

mentioning

confidence: 99%

Solar Water Splitting with a Hydrogenase Integrated in Photoelectrochemical Tandem Cells

et al. 2018

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Hydrogenases (H2ases) are benchmark electrocatalysts for H2 production, both in biology and (photo)catalysis in vitro. We report the tailoring of a p‐type Si photocathode for optimal loading and wiring of H2ase through the introduction of a hierarchical inverse opal (IO) TiO2 interlayer. This proton‐reducing Si|IO‐TiO2|H2ase photocathode is capable of driving overall water splitting in combination with a photoanode. We demonstrate unassisted (bias‐free) water splitting by wiring Si|IO‐TiO2|H2ase to a modified BiVO4 photoanode in a photoelectrochemical (PEC) cell during several hours of irradiation. Connecting the Si|IO‐TiO2|H2ase to a photosystem II (PSII) photoanode provides proof of concept for an engineered Z‐scheme that replaces the non‐complementary, natural light absorber photosystem I with a complementary abiotic silicon photocathode.

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Efficient and Stable Photo-Oxidation of Water by a Bismuth Vanadate Photoanode Coupled with an Iron Oxyhydroxide Oxygen Evolution Catalyst

Cited by 763 publications

References 47 publications

Functional integration of Ni–Mo electrocatalysts with Si microwire array photocathodes to simultaneously achieve high fill factors and light-limited photocurrent densities for solar-driven hydrogen evolution

Functional integration of Ni–Mo electrocatalysts with Si microwire array photocathodes to simultaneously achieve high fill factors and light-limited photocurrent densities for solar-driven hydrogen evolution

Improving O2 production of WO3 photoanodes with IrO2 in acidic aqueous electrolyte

Solar Water Splitting with a Hydrogenase Integrated in Photoelectrochemical Tandem Cells

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