Tuning redox active polyoxometalates for efficient electron‐coupled proton buffer mediated water splitting

Lie, J., Yang, J.-J., Liu, T., Yuan, R.-M., Deng, D.-R., Zheng, M.-S., Chen, J.-J., Cronin, L. and Dong, Q.-F. (2019) Tuning redox active polyoxometalates for efficient electron‐coupled proton buffer mediated water splitting. Chemistry: A European Journal, 25(49), pp. 11432-11436. (doi:10.1002/chem.201903142) (PMID:31309625)

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Abstract

We present strategies to tune the redox properties of polyoxometalate clusters to enhance the electron‐coupled proton‐buffer‐mediated water splitting process, in which the evolution of hydrogen and oxygen can occur in different forms and is separated in time and space. By substituting the heteroatom template in the Keggin‐type polyoxometalate cluster, H6ZnW12O40, it is possible to double the number of electrons and protonation in the redox reactions (from two to four). This increase can be achieved with better matching of the energy levels as indicated by the redox potentials, compared to the ones of well‐studied H3PW12O40 and H4SiW12O40. This means that H6ZnW12O40 can act as a high‐performance redox mediator in an electrolytic cell for the on‐demand generation of hydrogen with a high decoupling efficiency of 95.5 % and an electrochemical energy efficiency of 83.3 %. Furthermore, the H6ZnW12O40 cluster also exhibits an excellent cycling behaviour and redox reversibility with almost 100 % H2‐mediated capacity retention during 200 cycles and a high coulombic efficiency >92 % each cycle at 30 mA cm−2.

Item Type:Articles
Additional Information:The authors gratefully acknowledge the financial support from the National 973 Program (2015CB251102), the Key Project of NSFC (U1805254, 21673196,21621091,21703186), and the Fundamental Research Funds for the Central Universities (20720150042,20720170101, 20720190035). Dr .Jia Jia Chen also thanks the support from Nanqiang Young Top-notch Talent Fellowship in Xiamen University.
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Cronin, Professor Lee and Chen, Dr Jiajia
Authors: Lie, J., Yang, J.-J., Liu, T., Yuan, R.-M., Deng, D.-R., Zheng, M.-S., Chen, J.-J., Cronin, L., and Dong, Q.-F.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Chemistry: A European Journal
Publisher:Wiley
ISSN:0947-6539
ISSN (Online):1521-3765
Published Online:16 July 2019
Copyright Holders:Copyright © 2019 The Authors
First Published:First published in Chemistry: A European Journal 25(49): 11432-11436
Publisher Policy:Reproduced under a Creative Commons License

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
190217Molecular-Metal-Oxide-nanoelectronicS (M-MOS): Achieving the Molecular LimitLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/H024107/1Chemistry
165511International Collaboration in Chemistry - Modular microtubular architectures for photo-driven water splittingLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J00135X/1Chemistry
166449Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/J015156/1Chemistry
190623The Multi-Corder: Poly-Sensor TechnologyDavid CummingEngineering and Physical Sciences Research Council (EPSRC)EP/K021966/1ENG - Electronics & Nanoscale Engineering
167864Energy and the Physical Sciences: Hydrogen Production using a Proton Electron BufferLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/K023004/1Chemistry
190796Programmable 'Digital' Synthesis for Discovery and Scale-up of Molecules, Clusters and NanomaterialsLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/L023652/1Chemistry
172151SMARTPOM: Artificial-Intelligence Driven Discovery and Synthesis of Polyoxometalate ClustersLeroy CroninEuropean Research Council (ERC)Cronin, Professor LeroyChemistry