Facile and reproducible electrochemical synthesis of the giant polyoxomolybdates

Tze-Kiat Ng, M., Bell, N. L. , Long, D.-L. and Cronin, L. (2021) Facile and reproducible electrochemical synthesis of the giant polyoxomolybdates. Journal of the American Chemical Society, 143(48), pp. 20059-20063. (doi: 10.1021/jacs.1c10198) (PMID:34812622)

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Abstract

Giant polyoxomolybdates are traditionally synthesized by chemical reduction of molybdate in aqueous solutions, generating complex nanostructures such as the highly symmetrical spherical {Mo102} and {Mo132}, ring-shaped {Mo154} and {Mo176}, and the gigantic protein sized {Mo368}, which combines both positive and negative curvature. These complex polyoxometalates are known to be highly sensitive to reaction conditions and are often difficult to reproduce, especially {Mo368}, which is often produced in yields far below 1%, meaning further investigation has always been limited. While the electrochemical properties of these materials have been studied, their electrochemical synthesis has not been explored. Herein, we demonstrate an alternative reliable synthetic method by means of electrochemistry. By using electrochemical synthesis, we have shown the synthesis of various reported polyoxomolybdates, along with some unreported structures with unique features that have yet to be reported by traditional synthetic methods. The six different giant polyoxomolybdates that were obtained via electrochemical synthesis range from the spherical {Mo102–xFex} and {Mo132} to the ring-shaped {Mo148} and {Mo154–x}, as well as the largest known polyoxometalate {Mo368}, with improved yield (up to 26.1% for {Mo368}), increased reproducibility, and shorter crystallization time compared to chemical reduction methods.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Ng Tze-Kiat, Marcus and Bell, Dr Nicola and Long, Dr Deliang and Cronin, Professor Lee
Authors: Tze-Kiat Ng, M., Bell, N. L., Long, D.-L., and Cronin, L.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of the American Chemical Society
Publisher:American Chemical Society
ISSN:0002-7863
ISSN (Online):1520-5126
Published Online:23 November 2021
Copyright Holders:Copyright © 2021 American Chemical Society
First Published:First published in Journal of the American Chemical Society 143(48): 20059-20063
Publisher Policy:Reproduced in accordance with the publisher copyright policy

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
166449Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J015156/1Chemistry
190796Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/L023652/1Chemistry
166779Innovative Manufacturing Research Centre for Continuous Manufacturing and Crystallisation (CMAC)Leroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/I033459/1Chemistry
167864Energy and the Physical Sciences: Hydrogen Production using a Proton Electron BufferLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/K023004/1Chemistry
172151SMARTPOM: Artificial-Intelligence Driven Discovery and Synthesis of Polyoxometalate ClustersLeroy CroninEuropean Research Council (ERC)670467Chemistry