Abstract
Magnesium vanadate (MgV2O6) and its alloys with copper vanadate were synthesized via the solution combustion technique. Phase purity and solid solution formation were confirmed by a variety of experimental techniques, supported by electronic structure simulations based on density functional theory (DFT). Powder X-ray diffraction combined with Rietveld refinement, laser Raman spectroscopy, diffuse reflectance spectroscopy, and high-resolution transmission electron microscopy showed single-phase alloy formation despite the MgV2O6and CuV2O6end members exhibiting monoclinic and triclinic crystal systems, respectively. DFT-calculated optical band gaps showed close agreement in the computed optical bandgaps with experimentally derived values. Surface photovoltage spectroscopy, ambient-pressure photoemission spectroscopy, and Kelvin probe contact potential difference (work function) measurements confirmed a systematic variation in the optical bandgap modification and band alignment as a function of stoichiometry in the alloy composition. These data indicated n-type semiconductor behavior for all the samples which was confirmed by photoelectrochemical measurements.
Original language | English (US) |
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Pages (from-to) | 8903-8913 |
Number of pages | 11 |
Journal | Inorganic chemistry |
Volume | 62 |
Issue number | 23 |
DOIs | |
State | Published - Jun 12 2023 |
Funding
This work was primarily supported by the National Science Foundation UTA/NU Partnership for Research and Education in Materials (NSF DMR-2122128) and the National Science Foundation Materials Research Science and Engineering Center at Northwestern University (NSF DMR-1720139). P.S.T. and C.J. acknowledge funding under the European Union’s Horizon Europe Research and Innovation Program from the European Research Council (ERC, Grant Agreement No. 101043617). Elemental analysis was performed at the Northwestern University Quantitative Bio-element Imaging Center. This work made use of the Keck-II facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern University’s MRSEC program (NSF DMR-1729139). This work used the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by NSF grant number ACI-1548562. Finally, the three anonymous reviewers are thanked for their constructive criticisms of an earlier manuscript version.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry