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Cobalt Oxide-Coated Single Crystalline Bismuth Vanadate Photoanodes for Efficient Photoelectrochemical Chlorine Generation

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [2];  [2];  [2];  [3];  [2];  [2]
  1. Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Stony Brook University, NY (United States)
  2. Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  3. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States

Bismuth vanadate (BiVO4) is an outstanding photoanode material for photoelectrochemical water splitting. Here in this work, a series of single crystalline BiVO4 photoanodes are synthesized by pulsed laser deposition (PLD). Once coated with a thin layer of cobalt oxide (CoOx) cocatalyst, also by PLD, the photoanodes support efficient photoelectrochemical generation of chlorine (Cl2) from brine under simulated solar light. The activity of the chlorine generation reaction (ClER) is optimized when the thickness of CoOx is about 3 nm, with the faradic efficiency of ClER exceeding 60%. Detailed studies show that the CoOx cocatalyst layer is amorphous, uniform in thickness, and chemically robust. As such, the cocatalyst also effectively protects the underlying BiVO4 photoanodes against chlorine corrosion. This work provides insights into using artificial photosynthesis for byproducts that carry significant economic value while avoiding the energetically expensive oxygen evolution reactions.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
2222385
Report Number(s):
BNL--225029-2023-JAAM
Journal Information:
ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 42 Vol. 15; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (47)

Highly Efficient Sunlight‐Driven Seawater Splitting in a Photoelectrochemical Cell with Chlorine Evolved at Nanostructured WO3 Photoanode and Hydrogen Stored as Hydride within Metallic Cathode journal December 2019
A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water journal January 2016
Towards Long‐Term Photostability of Nickel Hydroxide/BiVO 4 Photoanodes for Oxygen Evolution Catalysts via In Situ Catalyst Tuning journal February 2020
Stable Cocatalyst‐Free BiVO 4 Photoanodes with Passivated Surface States for Photocorrosion Inhibition journal October 2020
Electrolyte Engineering for Oxygen Evolution Reaction Over Non‐Noble Metal Electrodes Achieving High Current Density in the Presence of Chloride Ion journal September 2022
Application of ultrathin TiO 2 layers in solar energy conversion devices journal March 2022
Interpretation of the x-ray photoemission spectra of cobalt oxides and cobalt oxide surfaces journal October 1976
Electrocatalysis of chlorine evolution on different materials and its influence on the performance of an electrochemical reactor for indirect oxidation of pollutants journal February 2005
Toward solar fuels: Water splitting with sunlight and “rust”? journal November 2012
Co3O4 nanosheet arrays treated by defect engineering for enhanced electrocatalytic water oxidation journal January 2018
Cobalt oxide as photocatalyst for water splitting: Temperature-dependent phase structures journal October 2019
Facile loading of cobalt oxide on bismuth vanadate: Proved construction of p-n junction for efficient photoelectrochemical water oxidation journal June 2020
Activation of chloride by oxygen vacancies-enriched TiO2 photoanode for efficient photoelectrochemical treatment of persistent organic pollutants and simultaneous H2 generation journal February 2023
Recent advances in BiVO4 semiconductor materials for hydrogen production using photoelectrochemical water splitting journal September 2019
Photoelectrocatalytic sea water splitting using Kirkendall diffusion grown functional Co3O4 film journal November 2017
Interstitial Lithium Doping in BiVO 4 Thin Film Photoanode for Enhanced Solar Water Splitting Activity journal July 2020
Anomalous Conductivity Tailored by Domain-Boundary Transport in Crystalline Bismuth Vanadate Photoanodes journal February 2018
Mechanistic Insights into Defect-Assisted Carrier Transport in Bismuth Vanadate Photoanodes journal July 2019
Temperature Effect on Photoelectrochemical Water Splitting: A Model Study Based on BiVO4 Photoanodes journal December 2021
Solar Water Splitting Cells journal November 2010
Inner-orbital binding-energy shifts of antimony and bismuth compounds journal April 1973
One-Dimensional Arrays of Co 3 O 4 Nanoparticles:  Synthesis, Characterization, and Optical and Electrochemical Properties journal October 2004
Single-Ion Solvation Free Energies and the Normal Hydrogen Electrode Potential in Methanol, Acetonitrile, and Dimethyl Sulfoxide journal January 2007
Novel Carbon-Doped TiO 2 Nanotube Arrays with High Aspect Ratios for Efficient Solar Water Splitting journal January 2006
Electrochemical Photolysis of Water at a Semiconductor Electrode journal July 1972
Photoelectrochemical cells journal November 2001
Artificial photosynthesis for solar water-splitting journal July 2012
Single-atomic-site platinum steers photogenerated charge carrier lifetime of hematite nanoflakes for photoelectrochemical water splitting journal May 2023
The impact of surface composition on the interfacial energetics and photoelectrochemical properties of BiVO4 journal February 2021
Nanostructured bismuth vanadate/tungsten oxide photoanode for chlorine production with hydrogen generation at the dark cathode journal May 2019
Photosynthesis-to-fuels: from sunlight to hydrogen, isoprene, and botryococcene production journal January 2012
Engineering heterogeneous semiconductors for solar water splitting journal January 2015
Photoelectrochemical devices for solar water splitting – materials and challenges journal January 2017
Electrocatalysis for the oxygen evolution reaction: recent development and future perspectives journal January 2017
A high-activity bimetallic OER cocatalyst for efficient photoelectrochemical water splitting of BiVO4 journal January 2020
Stable complete seawater electrolysis by using interfacial chloride ion blocking layer on catalyst surface journal January 2020
NiMoOx as a highly protective layer against photocorrosion for solar seawater splitting journal January 2022
Facile synthesis of carbon-coated hematite nanostructures for solar water splitting journal January 2013
Generation and reactions of the chlorine atom in aqueous solution
  • Gilbert, Bruce C.; Stell, Jonathan K.; Peet, Wendy J.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 84, Issue 10 https://doi.org/10.1039/f19888403319
journal January 1988
Solar-driven, highly sustained splitting of seawater into hydrogen and oxygen fuels journal March 2019
Ru-P pair sites boost charge transport in hematite photoanodes for exceeding 1% efficient solar water splitting journal June 2023
The chlor-alkali process: A review of history and pollution journal June 2016
Artificial Photosynthesis: From Molecular Catalysts for Light-driven Water Splitting to Photoelectrochemical Cells journal August 2011
Dynamic semiconductor-electrolyte interface for sustainable solar water splitting over 600 hours under neutral conditions journal January 2023
Photoelectrochemistry: Applications to Solar Energy Conversion journal October 1978
The Concentration of Chloride, Sodium, Potassium, Calcium, and Sulfate in rain Water over the United States journal October 1958
The Chlorine Industry journal September 1996

Figures / Tables (6)