Acid-Induced, Oxygen-Atom Defect Formation in Reduced Polyoxovanadate-Alkoxide Clusters
- 20 May 2020
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 142 (22), 9915-9919
- https://doi.org/10.1021/jacs.0c03864
Abstract
Here, we present the first example of acid-induced, oxygen-atom abstraction from the surface of a polyoxo-metalate cluster. Generation of the oxygen-deficient vanadium oxide, [V6O6(OC2H5)12]1-, was confirmed via in-dependent synthesis. Spectroscopic analysis using infrared and electronic absorption spectroscopies affords resolution of the electronic structure of the oxygen-deficient cluster (oxidation state distribution = [VIIIVIV5]). This work has direct implications toward the elucidation of possible mechanisms of acid-assisted vacancy for-mation in bulk transition metal oxides, in particular electron-proton co-doping that has recently been de-scribed for vanadium oxide (VO2). Ultimately, these molecular models deepen our understanding of proton-dependent redox chemistry of transition metal oxide surfaces.Funding Information
- Division of Chemistry (CHE-1653195)
- Research Corporation for Science Advancement
- University of Rochester
This publication has 54 references indexed in Scilit:
- Metal oxides based electrochemical pH sensors: Current progress and future perspectivesProgress in Materials Science, 2019
- Electron–Proton Co‐doping‐Induced Metal–Insulator Transition in VO2 Film via Surface Self‐Assembled l‐Ascorbic Acid MoleculesAngewandte Chemie-International Edition, 2019
- Enhancement effect of acid treatment on Mn2O3 catalyst for toluene oxidationCatalysis Today, 2018
- Non-catalytic hydrogenation of VO2 in acid solutionNature Communications, 2018
- Tartaric acid assisted hydrothermal synthesis of different flower-like ZnO hierarchical architectures with tunable optical and oxygen vacancy-induced photocatalytic propertiesApplied Surface Science, 2015
- Effect of Protons on the Redox Chemistry of Colloidal Zinc Oxide NanocrystalsJournal of the American Chemical Society, 2013
- Titanium and Zinc Oxide Nanoparticles Are Proton-Coupled Electron Transfer AgentsScience, 2012
- Controllable growth of SnO2 nanoparticles by citric acid assisted hydrothermal processColloids and Surfaces A: Physicochemical and Engineering Aspects, 2008
- Oxygen Vacancy Promoting Catalytic Dehydration of Formic Acid on TiO2(110) by in Situ Scanning Tunneling Microscopic ObservationThe Journal of Physical Chemistry B, 2005
- Energetics of the Nanocrystalline Titanium Dioxide/Aqueous Solution Interface: Approximate Conduction Band Edge Variations between H0 = −10 and H- = +26The Journal of Physical Chemistry B, 1999