BiVO4 Photoanodes Enhanced with Metal Phosphide Co-Catalysts: Relevant Properties to Boost Photoanode Performance

Junyi Cui; Matyas Daboczi; Zhenyu Cui; Mengjun Gong; Joseph Flitcroft; Jonathan Skelton; Stephen C. Parker; Salvador Eslava

doi:10.1002/smll.202306757

BiVO₄ Photoanodes Enhanced with Metal Phosphide Co-Catalysts: Relevant Properties to Boost Photoanode Performance

Junyi Cui, Matyas Daboczi, Zhenyu Cui, Mengjun Gong, Joseph Flitcroft, Jonathan Skelton, Stephen C. Parker, Salvador Eslava

Research output: Contribution to journal › Article › peer-review

3 Citations (SciVal)

Abstract

Achieving highly performant photoanodes for oxygen evolution is key to developing photoelectrochemical devices for solar water splitting. In this work, BiVO₄ photoanodes are enhanced with a series of core–shell structured bimetallic nickel-cobalt phosphides (MPs), and key insights into the role of co-catalysts are provided. The best BiVO₄/Ni_1.5Co_0.5P and BiVO₄/Ni_0.5Co_1.5P photoanodes achieve a 3.5-fold increase in photocurrent compared with bare BiVO₄. It is discovered that this enhanced performance arises from a synergy between work function, catalytic activity, and capacitive ability of the MPs. Distribution of relaxation times analysis reveals that the contact between the MPs, BiVO₄, and the electrolyte gives rise to three routes for hole injection into the electrolyte, all of which are significantly improved by the presence of a second metal cation in the co-catalyst. Kinetic studies demonstrate that the significantly improved interfacial charge injection is due to a lower charge-transfer resistance, enhanced oxygen-evolution reaction kinetics, and larger surface hole concentrations, providing deeper insights into the carrier dynamics in these photoanode/co-catalyst systems for their rational design.

Original language	English
Article number	2306757
Number of pages	13
Journal	Small
Early online date	6 Oct 2023
DOIs	https://doi.org/10.1002/smll.202306757
Publication status	Published - 31 Dec 2023

Bibliographical note

Funding Information:
S.E. and M.D. thank the EPSRC grant EP/S030727/1 for financial support. J.S. and J.F. were supported by a UKRI Future Leaders Fellowship held by J.S. (MR/T043121/1), and J.S. previously held a University of Manchester Presidential Fellowship. The majority of the modeling was carried out on the UK ARCHER 2 high‐performance computing facility, J.S. and S.P.’s membership of the UK Materials Chemistry Consortium, which was funded by the EPSRC (EP/R029431).

Data Availability Statement:
The data that support the findings of this study are openly available in a research data repository at https://doi.org/10.5281/zenodo.8395647

Keywords

bimetallic co-catalysts
BiVO photoanodes
density-functional theory (DFT) calculations
IMPS-DRT analysis
nickel cobalt phosphides
synergistic effect

ASJC Scopus subject areas

Biotechnology
General Chemistry
Biomaterials
General Materials Science
Engineering (miscellaneous)

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/smll.202306757Licence: CC BY

Cite this

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title = "BiVO4 Photoanodes Enhanced with Metal Phosphide Co-Catalysts: Relevant Properties to Boost Photoanode Performance",

abstract = "Achieving highly performant photoanodes for oxygen evolution is key to developing photoelectrochemical devices for solar water splitting. In this work, BiVO4 photoanodes are enhanced with a series of core–shell structured bimetallic nickel-cobalt phosphides (MPs), and key insights into the role of co-catalysts are provided. The best BiVO4/Ni1.5Co0.5P and BiVO4/Ni0.5Co1.5P photoanodes achieve a 3.5-fold increase in photocurrent compared with bare BiVO4. It is discovered that this enhanced performance arises from a synergy between work function, catalytic activity, and capacitive ability of the MPs. Distribution of relaxation times analysis reveals that the contact between the MPs, BiVO4, and the electrolyte gives rise to three routes for hole injection into the electrolyte, all of which are significantly improved by the presence of a second metal cation in the co-catalyst. Kinetic studies demonstrate that the significantly improved interfacial charge injection is due to a lower charge-transfer resistance, enhanced oxygen-evolution reaction kinetics, and larger surface hole concentrations, providing deeper insights into the carrier dynamics in these photoanode/co-catalyst systems for their rational design.",

keywords = "bimetallic co-catalysts, BiVO photoanodes, density-functional theory (DFT) calculations, IMPS-DRT analysis, nickel cobalt phosphides, synergistic effect",

author = "Junyi Cui and Matyas Daboczi and Zhenyu Cui and Mengjun Gong and Joseph Flitcroft and Jonathan Skelton and Parker, {Stephen C.} and Salvador Eslava",

note = "Funding Information: S.E. and M.D. thank the EPSRC grant EP/S030727/1 for financial support. J.S. and J.F. were supported by a UKRI Future Leaders Fellowship held by J.S. (MR/T043121/1), and J.S. previously held a University of Manchester Presidential Fellowship. The majority of the modeling was carried out on the UK ARCHER 2 high‐performance computing facility, J.S. and S.P.{\textquoteright}s membership of the UK Materials Chemistry Consortium, which was funded by the EPSRC (EP/R029431). Data Availability Statement: The data that support the findings of this study are openly available in a research data repository at https://doi.org/10.5281/zenodo.8395647 ",

year = "2023",

month = dec,

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doi = "10.1002/smll.202306757",

language = "English",

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AU - Cui, Junyi

AU - Daboczi, Matyas

AU - Cui, Zhenyu

AU - Gong, Mengjun

AU - Flitcroft, Joseph

AU - Skelton, Jonathan

AU - Parker, Stephen C.

AU - Eslava, Salvador

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N2 - Achieving highly performant photoanodes for oxygen evolution is key to developing photoelectrochemical devices for solar water splitting. In this work, BiVO4 photoanodes are enhanced with a series of core–shell structured bimetallic nickel-cobalt phosphides (MPs), and key insights into the role of co-catalysts are provided. The best BiVO4/Ni1.5Co0.5P and BiVO4/Ni0.5Co1.5P photoanodes achieve a 3.5-fold increase in photocurrent compared with bare BiVO4. It is discovered that this enhanced performance arises from a synergy between work function, catalytic activity, and capacitive ability of the MPs. Distribution of relaxation times analysis reveals that the contact between the MPs, BiVO4, and the electrolyte gives rise to three routes for hole injection into the electrolyte, all of which are significantly improved by the presence of a second metal cation in the co-catalyst. Kinetic studies demonstrate that the significantly improved interfacial charge injection is due to a lower charge-transfer resistance, enhanced oxygen-evolution reaction kinetics, and larger surface hole concentrations, providing deeper insights into the carrier dynamics in these photoanode/co-catalyst systems for their rational design.

AB - Achieving highly performant photoanodes for oxygen evolution is key to developing photoelectrochemical devices for solar water splitting. In this work, BiVO4 photoanodes are enhanced with a series of core–shell structured bimetallic nickel-cobalt phosphides (MPs), and key insights into the role of co-catalysts are provided. The best BiVO4/Ni1.5Co0.5P and BiVO4/Ni0.5Co1.5P photoanodes achieve a 3.5-fold increase in photocurrent compared with bare BiVO4. It is discovered that this enhanced performance arises from a synergy between work function, catalytic activity, and capacitive ability of the MPs. Distribution of relaxation times analysis reveals that the contact between the MPs, BiVO4, and the electrolyte gives rise to three routes for hole injection into the electrolyte, all of which are significantly improved by the presence of a second metal cation in the co-catalyst. Kinetic studies demonstrate that the significantly improved interfacial charge injection is due to a lower charge-transfer resistance, enhanced oxygen-evolution reaction kinetics, and larger surface hole concentrations, providing deeper insights into the carrier dynamics in these photoanode/co-catalyst systems for their rational design.

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