Water oxidation catalysed by quantum-sized BiVO<sub>4</sub>

Olmo, L. del; Dommett, Michael; Oevreeide, Ingrid H.; Walsh, Aron; Tommaso, Devis Di; Crespo‐Otero, Rachel

doi:10.1039/c8ta08015a

Cited by 11 publications

(5 citation statements)

References 39 publications

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“…The band gap of ∼2.4 eV agrees well with the published band gap and reflects the energy separation between the occupied lone pair orbital state and unoccupied V 3d derived conduction band [102]. Although BiVO 4 has a direct band gap, it suffers from recombination and poor transport of charge carriers which led to the investigation of quantum dots for improved photocatalytic performance [108]. Quantum confinement effects are believed to result in a negative shift of the conduction band and/or oxygen vacancies, which decreases the activation energy for water splitting reactions.…”

Section: Natural Lone Pair Metal Oxide Photoanode: Bivosupporting

confidence: 77%

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Designing catalysts for water splitting based on electronic structure considerations

et al. 2020

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The disproportionation of H2O into solar fuels H2 and O2, or water splitting, is a promising strategy for clean energy harvesting and storage but requires the concerted action of absorption of photons, separation of excitons, charge diffusion to catalytic sites and catalysis of redox processes. It is increasingly evident that the rational design of photocatalysts for efficient water splitting must employ hybrid systems, where the different components perform light harvesting, charge separation and catalysis in tandem. In this topical review, we report on the recent development of a new class of hybrid photocatalysts that employs M x V2O5 (M = p-block cation) nanowires in order to engineer efficient charge transfer from the photoactive chalcogenide quantum dots (QDs) to the water-splitting and hydrogen evolving catalysts. Herein, we summarize the oxygen-mediated lone pair mechanism used to modulate the energy level and orbital character of mid-gap states in the M x V2O5 nanowires. The electronic structure of M x V2O5 is discussed in terms of density functional theory and hard x-ray photoelectron spectroscopy (HAXPES) measurements. The principles of HAXPES are explained within the context of its unique sensitivity to metal 5(6)s orbitals and ability to non-destructively study buried interface alignments of quantum dot decorated nanowires i.e., M x V2O5/CdX (X = S, Se, Te). We illustrate with examples how the M x V2O5/CdX band alignments can be rationally engineered for ultra-fast charge-transfer of photogenerated holes from the quantum dot to the nanowires; thereby suppressing anodic photo-corrosion in the CdX QDs and enabling efficacious hydrogen evolution.

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Section: Natural Lone Pair Metal Oxide Photoanode: Bivosupporting

confidence: 77%

“…Computational studies have investigated the effects of interactions between quantum-sized BiVO 4 clusters and water molecules. Radial distribution calculations showed that water molecules only interact with the bismuth atoms [108].…”

Section: Natural Lone Pair Metal Oxide Photoanode: Bivomentioning

confidence: 99%

Designing catalysts for water splitting based on electronic structure considerations

et al. 2020

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“…experimentally observed that quantum‐sized BiVO 4 can decompose water into H 2 and O 2 at the same time, which is quite different from the bulk material only having the ability of water oxidation . A recent theoretical work got insight into the experimental phenomenon by using the (BiVO 4 ) 4 cluster model through a combination of TDDFT, ab initio MD (AIMD) and transition state theory . They pointed out that the enhanced efficiency of photocatalytic water oxidation for quantum‐sized BiVO 4 is related to the local distribution of the spin density on the terminal oxygen of cluster and the dramatic decrease of Gibbs activation energy associated with the hydrogen transfer process between water and BiVO 4 cluster compared with the crystalline phase.…”

Section: Controlling Crystal Morphologymentioning

confidence: 99%

A Theoretical Perspective on Charge Separation and Transfer in Metal Oxide Photocatalysts for Water Splitting

Zhou

Dong

2019

ChemCatChem

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Semiconductor‐based photocatalytic decomposition of water is one of the most promising techniques to produce clean and renewable energy in the future. Photogenerated charge separation and transfer is considered as one of the crucial steps controlling the conversion efficiency of solar energy in heterogeneous photocatalysis. Many experimental methods have been developed to enhance the efficiency of this process, such as fabricating junction structures, manipulating exposed facets, and loading suitable cocatalysts. Besides a variety of time and spatial resolved spectroscopic techniques, density functional theory calculations have been widely used to explore the photoinduced charge dynamics due to the advances of relevant theory and methodologies along with the improved computer performance. This article reviews recent theoretical researches mainly by means of density functional theory calculations in the charge separation and transportation in metal oxide photocatalytic systems. We introduce some common theoretical and computational methods for investigating physicochemical properties of photocatalytic materials, discuss the charge mobility in bulk and surface of semiconductors, the interfacial charge transfer in junction structures, and the role of cocatalysts in complex photocatalysts, and then evaluate potential research directions for superior photocatalytic systems on the basis of computational investigation and theoretical comprehension of intrinsic properties.

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“…BiVO 4 , a visible light-responsive photocatalyst, has been extensively applied in photocatalytic H 2 O 2 production owing to its suitable energy-band structure (Figure A) and good stability. − However, pure BiVO 4 lacks active sites of oxygen reduction reaction, which limits its H 2 O 2 production. To solve the above problems, nano-cocatalyst modification is deemed to be a valid method to boost the photocatalytic performance. − Among various electron cocatalysts, nano-Au has been proven to be an excellent cocatalyst owing to its special d-band electrons, which can result in weak “side-on” adsorption configuration to O 2 and thus promote the selective two-electron O 2 reduction to H 2 O 2 . − Benefiting from the above specific catalytic property and its excellent stability, nano-Au has been considered as an efficient electron cocatalyst to improve the photocatalytic H 2 O 2 production performance of BiVO 4 .…”

Section: Introductionmentioning

confidence: 99%

BiVO₄ Microparticles Decorated with Cu@Au Core-Shell Nanostructures for Photocatalytic H₂O₂ Production

Wang

et al. 2021

ACS Appl. Nano Mater.

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The nanostructured Au cocatalyst modification of BiVO4 photocatalyst, as a prospective method, can significantly promote its photocatalytic H2O2 production performance. However, the contact between Au and BiVO4 causes a strong built-in field, which impedes the photogenerated-electron transfer and the accumulation of negative charge density for Au, which reduces its catalytic activity of two-electron O2 reduction, thus limiting the enhanced H2O2 production performance of the Au/BiVO4 photocatalyst. To solve the above problems, here, a Cu@Au core-shell nanostructured cocatalyst is designed to selectively modify on the electron-enriched (010) facet of a single-crystal BiVO4 microparticle by facile photodeposition and subsequently galvanic displacement. In this case, ohmic contact between the Cu nanoparticle and (010) facet of BiVO4 can effectively transfer the photogenerated electrons to the Au cocatalyst and simultaneously facilitate the catalytic activity improvement of two-electron O2 reduction for the Au cocatalyst due to its low negative charge accumulation. As a result, the optimized BiVO4 photocatalyst with Cu@Au core-shell nanostructured modification exhibits obviously improved photocatalytic performance of H2O2 formation (91.1 μmol L–1) compared with Au/BiVO4 (62.5 μmol L–1). The present strategy of a bimetal cocatalyst with a core-shell nanostructure opens up an insight to explore effective photocatalytic materials for the application of H2O2 production.

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Water oxidation catalysed by quantum-sized BiVO₄

Abstract: First principle calculations show the effect of the reduction of dimensions on the mechanism of water oxidation catalysed by BiVO4.

Cited by 11 publications

References 39 publications

Designing catalysts for water splitting based on electronic structure considerations

Designing catalysts for water splitting based on electronic structure considerations

A Theoretical Perspective on Charge Separation and Transfer in Metal Oxide Photocatalysts for Water Splitting

BiVO₄ Microparticles Decorated with Cu@Au Core-Shell Nanostructures for Photocatalytic H₂O₂ Production

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Water oxidation catalysed by quantum-sized BiVO4

Abstract: First principle calculations show the effect of the reduction of dimensions on the mechanism of water oxidation catalysed by BiVO4.

Cited by 11 publications

References 39 publications

Designing catalysts for water splitting based on electronic structure considerations

Designing catalysts for water splitting based on electronic structure considerations

A Theoretical Perspective on Charge Separation and Transfer in Metal Oxide Photocatalysts for Water Splitting

BiVO4 Microparticles Decorated with Cu@Au Core-Shell Nanostructures for Photocatalytic H2O2 Production

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Product

Resources

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Water oxidation catalysed by quantum-sized BiVO₄

BiVO₄ Microparticles Decorated with Cu@Au Core-Shell Nanostructures for Photocatalytic H₂O₂ Production