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Designing dithiolene and bis(iminothiolato)-based 1D metal-organic-frameworks for electrocatalytic hydrogen evolution reaction

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Abstract

Hydrogen is considered as one of the most important clean and renewable energy resources to get rid of carbon-based fuels and to solve the problem of environmental hazzards caused for using fossil fuels. Hence, the large-scale production of hydrogen by water splitting through hydrogen evolution reaction (HER) demands inexpensive and efficient electrocatalysts to replace the scarce and expensive noble metal-based catalysts. In this work, using the density functional theory (DFT)-based computations, we have considered a family of one dimensional (1D) metal organic frameworks (MOFs), namely TM–dithiolene (TM–BTT), and TM–bis(iminothiolato) (TM–BIT), consisting of benzene-1,2,4,5-tetrathiolate (BTT) and benzene-bis(iminothiolato) (BIT) organic ligands, respectively, and a family of first row transition metals (TM = Mn, Fe, Co, and Ni), to find their catalytic activity toward HER. Using the Gibbs free energy for the adsorption of atomic hydrogen ( \(\mathrm {\Delta {\textit{G}}_{H^{*}}}\)) as the key descriptor, we reached to the conclusion that Ni–bis(iminothiolato) MOF exhibits better catalytic activity toward HER over all other investigated 1D-MOFs.

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Acknowledgments

The authors sincerely acknowledge the Council of Scientific and Industrial Research (CSIR) [Sanction No. 01(3086)/21/EMR-II], India for financial support of this work. P.D. thanks the DST-INSPIRE, New Delhi, Govt. of India for the award of INSPIRE fellowship (No. DST/INSPIRE Fellowship/[IF200050]).

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Authors and Affiliations

  1. Department of Chemistry, Visva-Bharati University, Santiniketan, 731235, India

    Priya Das & Pranab Sarkar

  2. Department of Physics and Astronomy, The University of Maine, Orono, USA

    Biswajit Ball

  3. Department of Physics, Sreegopal Banerjee College, Bagati, Hoogly, 712148, India

    Biplab Goswami

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PD, BB, and BG did the whole work. PD, BB, and PS wrote the main manuscript. PS, PD, and BG analyses the results.

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Correspondence to Pranab Sarkar.

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This paper is dedicated to Prof. Pratim K. Chattaraj, IIT Kharagpur on the happy occasion of his \(\mathrm {65{th}}\) birth anniversary.

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Das, P., Ball, B., Goswami, B. et al. Designing dithiolene and bis(iminothiolato)-based 1D metal-organic-frameworks for electrocatalytic hydrogen evolution reaction. Theor Chem Acc 142, 41 (2023). https://doi.org/10.1007/s00214-023-02983-0

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