NDLI: Electronic structure, photovoltage, and photocatalytic hydrogen evolution with p-CuBi<sub>2</sub>O<sub>4</sub> nanocrystals

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Journal of Materials Chemistry A Vol - 4 Issue - 7

Journal of Materials Chemistry A Vol - 4 Issue - 6

Journal of Materials Chemistry A Vol - 4 Issue - 5

Journal of Materials Chemistry A Vol -3

Journal of Materials Chemistry A Vol -2

Journal of Materials Chemistry A Vol -1

Electronic structure, photovoltage, and photocatalytic hydrogen evolution with p-CuBi₂O₄ nanocrystals

Content Provider	Royal Society of Chemistry (RSC)
Author	Huda, Muhammad N. Osterloh, Frank E. Sharma, Geetu Nail, Benjamin A. Zhao, Zeqiong Sarker, Pranab Wang, Jiarui
Copyright Year	2016
Abstract	As a visible light active p-type semiconductor, CuBi2O4 is of interest as a photocatalyst for the generation of hydrogen fuel from water. Here we present the first photovoltage and photocatalytic measurements on this material and DFT results on its band structure. Single crystalline CuBi2O4 nanoparticles (25.7 ± 4.7 nm) were synthesized from bismuth and cupric nitrate in water under hydrothermal conditions. Powder X-ray diffraction (XRD) confirms the CuBi2O4 structure type and UV-Vis spectroscopy shows a 1.75 eV optical band gap. Surface photovoltage (SPV) measurements on CuBi2O4 nanoparticle films on fluorine doped tin oxide yield 0.225 V positive photovoltage at >1.75 eV photon energy confirming holes as majority carriers. The photovoltage is reversible and limited by light absorption. When dispersed in 0.075 M aqueous potassium iodide solution, the CuBi2O4 particles support photochemical hydrogen evolution of up to 16 μmol h−1 under ultraviolet but not under visible light. Based on electrochemical scans, CuBi2O4 is unstable toward reduction at −0.2 V, but a pH-dependent photocurrent of 6.45 μA cm−2 with an onset potential of +0.75 V vs. NHE can be obtained with 0.01 M Na2S2O8 as a sacrificial electron acceptor. The photoelectrochemical properties of CuBi2O4 can be explained on the basis of the band structure of the material. DFT calculations show that the valence and conduction band edges arise primarily from the combination of O 2p and Cu 3d orbitals, respectively, with additional contributions from Cu 3d and Bi 6s orbitals just below the Fermi level. Trapping of photoelectrons in the Cu 3d band is the cause for reductive photocorrosion of the material, while the p-type conductivity arises from copper vacancy states near the VB edge. These findings provide an improved understanding of the photophysical properties of p-CuBi2O4 and its limitations as a proton reduction photocatalyst.
Starting Page	2936
Ending Page	2942
Page Count	7
File Format	HTM / HTML PDF
ISSN	20507488
Volume Number	4
Issue Number	8
Journal	Journal of Materials Chemistry A
DOI	10.1039/c5ta07040f
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Extrinsic semiconductor Photocatalysis Hydrogen Electronic band structure Bismuth Copper(II) nitrate Hydrothermal synthesis X-ray crystallography Ultraviolet\u2013visible spectroscopy Electronvolt Band gap Surface photovoltage Special purpose entity Nanoparticle Fluorine Tin Photon Potassium iodide Photochemistry Ultraviolet Electrochemistry Photocurrent Oxidizing agent Photoelectrochemical process Valence and conduction bands Fermi level Copper
Content Type	Text
Resource Type	Article
Subject	Chemistry Renewable Energy, Sustainability and the Environment Materials Science

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Electronic structure, photovoltage, and photocatalytic hydrogen evolution with p-CuBi₂O₄ nanocrystals

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