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.
Highlights
We present strategies to tune the redox properties of polyoxometalate clusters to enhance the electroncoupled 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
Hydrogen could be spontaneously evolved from the reduced-ECPB on a conventional hydrogen evolution reaction (HER)-catalyst if its redox potential is more negative than the HER onset potential of the catalyst.[12,13]
By exploiting the overpotentials related to hydrogen evolution on carbon, an ECPB can be reduced past the point of the normal hydrogen electrode (NHE) without any H2 evolution
Summary
We present strategies to tune the redox properties of polyoxometalate clusters to enhance the electroncoupled 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. The desired redox potentials of H6ZnW12O40 enhance its ECPB performance for on-demand storage and generation of H2 with a high decoupling efficiency of 95.5 % and an electrochemical energy efficiency of 83.3 %.
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