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Polyoxometalate based hybrid compound as a pre-catalyst for electrocatalytic water reduction at neutral pH

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Abstract

Polyoxometalate (POM) supported metal complex has proved to be a suitable catalyst for water reduction/oxidation in recent studies. To catalyze hydrogen evolution reaction (HER), we have employed a POM-based inorganic-organic hybrid compound [CuII(2,2′-bpy)(H2O)2Cl][CuII(2,2′-bpy)(H2O)2Al(OH)6Mo6O18]·4H2O (1) with a spiral-chain-like structure consisting of Anderson type polyoxometalate, [Al(OH)6Mo6O18]3− onto which Cu-complex, [Cu(H2O)2(bpy)]2+ fragments are supported. This compound acts as a pre-catalyst towards forming the active catalyst for catalyzing hydrogen evolution reaction (HER) by water reduction in a neutral medium. The active catalyst derived from this compound 1 achieves a current density of 1 mA/cm2 at an overpotential of 348 mV. The turnover frequency calculated for the active catalyst is found to be 1.780 [mol H2 (mol Cu)−1s−1] with the Faradaic efficiency of 85%.

Graphic abstract

A unique electrochemical structural rearrangement under the electrochemical condition observed for a chain-like structured Cu-complex supported on Anderson type polyoxometalate, [CuII(2,2′-bpy)(H2O)2Cl][CuII(2,2′-bpy)(H2O)2Al(OH)6Mo6O18]·4H2O (1) resulting in the formation of the active catalyst for the electrochemical HER activity. The active catalyst achieves the current density of 1 mA/cm2 with an overpotential of 348 mV with faradic efficiency of 85% at neutral pH.

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Acknowledgements

We thank the Department of Science and Technology (DST), Government of India, for financial support (DST-SERB project, Grant Number: EMR/2017/002971). The National X-ray Diffractometer facility at the University of Hyderabad by the Department of Science and Technology, Government of India, is gratefully acknowledged. We acknowledge UGS-CAS, DST-PURSE and DST-FIST. C.S. thanks UGC-BSR, for her fellowship. We thank IoE, University of Hyderabad (project # UoH/IoE/RC1/RC1-20-007) for support.

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  1. School of Chemistry, University of Hyderabad, Hyderabad, 500 046, India

    CHANDANI SINGH & SAMAR K DAS

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  1. CHANDANI SINGH
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Correspondence to SAMAR K DAS.

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In the memory of late Prof. Bhaskar G Maiya.

Special Issue on Beyond Classical Chemistry

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12039_2021_1928_MOESM1_ESM.pdf

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SINGH, C., DAS, S.K. Polyoxometalate based hybrid compound as a pre-catalyst for electrocatalytic water reduction at neutral pH. J Chem Sci 133, 81 (2021). https://doi.org/10.1007/s12039-021-01928-z

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