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Title: A small bandgap semiconductor, p-type MnV 2 O 6 , active for photocatalytic hydrogen and oxygen production

Abstract

Extensive research has been conducted with the goal to find a single bandgap material that can absorb visible light and efficiently drive the catalysis of water to both hydrogen and oxygen. The p-type MnV 2O 6 (C2/m, Z = 2, a = 9.289 Å, b = 3.535 Å, and c = 6.763 Å, β = 112.64°), synthesized via solid-state techniques, was investigated for its potential use in the visible-light photocatalysis of water. Mott–Schottky analysis was used to experimentally determine the energetic positions of the valence and conduction bands as +0.985 V and -0.464 V, respectively, at pH 5.68 vs. RHE. These are found to be suitable potentials to drive the reduction and oxidation of water under irradiation. The bandgap transitions, probed using spin-polarized density functional calculations, consist of the excitation of electrons from the half-filled Mn 3d 5 orbitals to the empty V 3d 0 orbitals. Both hydrogen and oxygen gas were observed as products during suspended-particle photocatalysis experiments under visible-light irradiation. The rate and total moles of gas produced were found to increase with the reaction temperature. As the temperature was raised from 30 °C to 37 °C and 44 °C, the moles of hydrogen produced over 6 hoursmore » inreased b ~1.5 and ~2.5 times. Only oxygen is produced in pure water, showing that methanol is needed to drive hydrogen production.« less

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Department of Chemistry; North Carolina State University; Raleigh; USA
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE
OSTI Identifier:
1492852
Resource Type:
Journal Article
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 46; Journal Issue: 32; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Zoellner, Brandon, Gordon, Elijah, and Maggard, Paul A. A small bandgap semiconductor, p-type MnV 2 O 6 , active for photocatalytic hydrogen and oxygen production. United States: N. p., 2017. Web. doi:10.1039/c7dt00780a.
Zoellner, Brandon, Gordon, Elijah, & Maggard, Paul A. A small bandgap semiconductor, p-type MnV 2 O 6 , active for photocatalytic hydrogen and oxygen production. United States. doi:10.1039/c7dt00780a.
Zoellner, Brandon, Gordon, Elijah, and Maggard, Paul A. Sun . "A small bandgap semiconductor, p-type MnV 2 O 6 , active for photocatalytic hydrogen and oxygen production". United States. doi:10.1039/c7dt00780a.
@article{osti_1492852,
title = {A small bandgap semiconductor, p-type MnV 2 O 6 , active for photocatalytic hydrogen and oxygen production},
author = {Zoellner, Brandon and Gordon, Elijah and Maggard, Paul A.},
abstractNote = {Extensive research has been conducted with the goal to find a single bandgap material that can absorb visible light and efficiently drive the catalysis of water to both hydrogen and oxygen. The p-type MnV2O6 (C2/m, Z = 2, a = 9.289 Å, b = 3.535 Å, and c = 6.763 Å, β = 112.64°), synthesized via solid-state techniques, was investigated for its potential use in the visible-light photocatalysis of water. Mott–Schottky analysis was used to experimentally determine the energetic positions of the valence and conduction bands as +0.985 V and -0.464 V, respectively, at pH 5.68 vs. RHE. These are found to be suitable potentials to drive the reduction and oxidation of water under irradiation. The bandgap transitions, probed using spin-polarized density functional calculations, consist of the excitation of electrons from the half-filled Mn 3d5 orbitals to the empty V 3d0 orbitals. Both hydrogen and oxygen gas were observed as products during suspended-particle photocatalysis experiments under visible-light irradiation. The rate and total moles of gas produced were found to increase with the reaction temperature. As the temperature was raised from 30 °C to 37 °C and 44 °C, the moles of hydrogen produced over 6 hours inreased b ~1.5 and ~2.5 times. Only oxygen is produced in pure water, showing that methanol is needed to drive hydrogen production.},
doi = {10.1039/c7dt00780a},
journal = {Dalton Transactions},
issn = {1477-9226},
number = 32,
volume = 46,
place = {United States},
year = {2017},
month = {1}
}

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