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A Trimetallic Cu(II) Derivative as an Efficient and Stable Electrocatalyst for Reduction of Proton to Molecular Hydrogen

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Abstract

A trinuclear copper(II) complex, namely [Cu3(L)2(CF3COO)2] (1) is afforded integrating a ‘compartmental’ Schiff base, H2L [where H2L = N,N′-bis(salicylidene)-1,3-propanediamine] and fully characterized. Complex 1 is implemented for electrocatalytic proton reduction to originate molecular hydrogen in a homogenous system. The electrochemical study involving CV (cyclic voltammetry), CPE (controlled potential electrolysis) and GC (gas chromatography) reveals that in homogeneous system, 1 is highly active towards proton reduction in presence of trifluoro acetic acid as a proton source. Following CPE at − 1.8 V vs Ag/AgCl, the headspace gas is sampled and gas chromatography is carried out to quantify the amount of hydrogen discharged. The ratio of theoretical H2 production from charge aggregation during electrolysis to the practical amount of H2 resolved on GC is yielded a Faradaic efficiency value of 87%. Moreover, an extended bulk electrolysis experiment carried out for 35 h illustrates the presence of a stable catalytic system in which 230 C of charge is accumulated. As a consequence, this efficient and stable H2 evolution obtained using a Cu(II) derivative (CuII is cheap and earth abundant) has shown that the synthesis of judiciously designed copper complex is a promising strategy towards potential catalysts from proton reduction.

Graphic Abstract

Electrochemical and catalytic study of a trimetallic Cu(II) derivative in DMSO with the presence of trifluoroacetic acid as weak proton source shows the hydrogen evolution Faradaic efficiency as 87%. A continuous increment of the charge accumulation through time is observed, indicating the high stability of our catalyst under electrochemical H2 generation.

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Acknowledgements

KD expresses her appreciation to the SERB (Science and Engineering Research Board, India) Grant (PDF/2016/002832) for financial assistance. AD and CHH would like to express their appreciation to the Ministry of Science and Technology, Taiwan for financial assistance.

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Authors and Affiliations

  1. Department of Chemistry, University of Calcutta, 92 A.P.C. Road, Kolkata, 700009, India

    Kuheli Das & Sanchita Goswami

  2. Institute of Chemistry, Academia Sinica, Nankang, Taipei, 115, Taiwan

    Kuheli Das, Belete B. Beyene, Amogne W. Yibeltal, Amitabha Datta & Chen-Hsiung Hung

  3. Department of Chemistry, Bahir Dar University, P.O. Box 79, Bahir Dar, Ethiopia

    Belete B. Beyene

  4. Dipartimento di Scienze Chimiche, della Vita e della Sostenibilità Ambientale, Università degli Studi di Parma, Viale delle Scienze 17/A, Parma, 43124, Italy

    Chiara Massera

  5. Dipartimento di Chimica e Farmacia, Università di Sassari, Via Vienna 2, Sassari, 07100, Italy

    Eugenio Garribba

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  1. Kuheli Das
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Das, K., Beyene, B.B., Yibeltal, A.W. et al. A Trimetallic Cu(II) Derivative as an Efficient and Stable Electrocatalyst for Reduction of Proton to Molecular Hydrogen. Catal Lett 150, 2200–2207 (2020). https://doi.org/10.1007/s10562-020-03150-x

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