TY - JOUR
T1 - Arc Synthesis, Crystal Structure, and Photoelectrochemistry of Copper(I) Tungstate
AU - Galante, Miguel Tayar
AU - Živković, Aleksandar
AU - Alvim, Jéssica Costa
AU - Kleiner, Cinthia Cristina Calchi
AU - Sangali, Márcio
AU - Taylor, S. F. Rebecca
AU - Greer, Adam J.
AU - Hardacre, Christopher
AU - Rajeshwar, Krishnan
AU - Caram, Rubens
AU - Bertazzoli, Rodnei
AU - Macaluso, Robin T.
AU - Leeuw, Nora H. de
AU - Longo, Claudia
PY - 2021/7/21
Y1 - 2021/7/21
N2 - A little-studied p-type ternary oxide semiconductor, copper(I) tungstate (Cu2WO4), was assessed by a combined theoretical/experimental approach. A detailed computational study was performed to solve the long-standing debate on the space group of Cu2WO4, which was determined to be triclinic P1. Cu2WO4 was synthesized by a time-efficient, arc-melting method, and the crystalline reddish particulate product showed broad-band absorption in the UV–visible spectral region, thermal stability up to ∼260 °C, and cathodic photoelectrochemical activity. Controlled thermal oxidation of copper from the Cu(I) to Cu(II) oxidation state showed that the crystal lattice could accommodate Cu2+ cations up to ∼260 °C, beyond which the compound was converted to CuO and CuWO4. This process was monitored by powder X-ray diffraction and X-ray photoelectron spectroscopy. The electronic band structure of Cu2WO4 was contrasted with that of the Cu(II) counterpart, CuWO4 using spin-polarized density functional theory (DFT). Finally, the compound Cu2WO4 was determined to have a high-lying (negative potential) conduction band edge underlining its promise for driving energetic photoredox reactions.
AB - A little-studied p-type ternary oxide semiconductor, copper(I) tungstate (Cu2WO4), was assessed by a combined theoretical/experimental approach. A detailed computational study was performed to solve the long-standing debate on the space group of Cu2WO4, which was determined to be triclinic P1. Cu2WO4 was synthesized by a time-efficient, arc-melting method, and the crystalline reddish particulate product showed broad-band absorption in the UV–visible spectral region, thermal stability up to ∼260 °C, and cathodic photoelectrochemical activity. Controlled thermal oxidation of copper from the Cu(I) to Cu(II) oxidation state showed that the crystal lattice could accommodate Cu2+ cations up to ∼260 °C, beyond which the compound was converted to CuO and CuWO4. This process was monitored by powder X-ray diffraction and X-ray photoelectron spectroscopy. The electronic band structure of Cu2WO4 was contrasted with that of the Cu(II) counterpart, CuWO4 using spin-polarized density functional theory (DFT). Finally, the compound Cu2WO4 was determined to have a high-lying (negative potential) conduction band edge underlining its promise for driving energetic photoredox reactions.
UR - https://doi.org/10.1021/acsami.1c03928
U2 - 10.1021/acsami.1c03928
DO - 10.1021/acsami.1c03928
M3 - Article
SN - 1944-8244
VL - 13
SP - 32865
EP - 32875
JO - ACS Applied Materials & Interfaces
JF - ACS Applied Materials & Interfaces
ER -
