A pdc-pinched copper complex for sustainable hydrogen production through ligand supported-metal centric proton-coupled electron transfer†

IF 5 3区材料科学 Q2 CHEMISTRY, PHYSICAL Sustainable Energy & Fuels Pub Date : 2024-10-11 DOI:10.1039/D4SE00953C

Meena Chettri, Subhajit Saha, Nilankar Diyali, Rakesh Debnath, Harshita Bagdwal, Monika Singh and Bhaskar Biswas

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Abstract

A water-stable [Cu(pdc)(H₂O)₂] complex, promising functional mimics of hydrogenase active sites and promoting sustainable hydrogen production in acidic water, was designed and synthesised using an ONO-type pincer ligand, 2,6-pyridine dicarboxylic acid (pdc), and copper(II) nitrate. X-ray crystallographic analysis reveals that [Cu(pdc)(H₂O)₂] crystallizes in a triclinic crystal system with square pyramidal geometry. The complex shows an excellent faradaic efficiency of 91% with remarkable stability up to 60 equivalents of acetic acid (AcOH), relative to [Cu(pdc)(H₂O)₂]. Moreover, comprehensive spectroscopic, analytical, electrochemical, and computational analyses were performed to validate the proton-coupled electron transfer reaction. pdc coordinated with the Cu centre offers a delicate balance in shuttling syn-conformational proton coupling (H_pdc^δ+⋯H_Cu^δ−, 2.1 Å), promoting sustainable hydrogen production in water. Further, the scope of the electrocatalytic fate of [Cu(pdc)(H₂O)₂] towards industrial prospects was ensured by examining the electrocatalytic capacity of [Cu(pdc)(H₂O)₂] in 0.5 M H₂SO₄. The complex exhibits a significant elevation in cathodic current with H₂SO₄ in water collected from the Relli river (27.066668° N, 88.466667° E), Kalimpong, West Bengal, envisioning its true-catalytic capacity in pilot-scale application and real prospect for industrial use.

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通过配体支持-金属中心质子耦合电子转移†实现可持续制氢的 pdc 针状铜配合物

利用 ONO 型钳形配体、2,6-吡啶二羧酸（pdc）和硝酸铜设计并合成了一种水稳定性[Cu(pdc)(H2O)2]复合物，该复合物有望在功能上模拟氢化酶的活性位点，并促进酸性水中的可持续制氢。X 射线晶体学分析表明，[Cu(pdc)(H2O)2] 结晶为具有正方金字塔几何形状的三棱晶系。相对于 [Cu(pdc)(H2O)2]，该复合物显示出 91% 的出色远红外效率和高达 60 等效乙酸（AcOH）的显著稳定性。此外，还进行了全面的光谱、分析、电化学和计算分析，以验证质子耦合电子转移反应。与铜中心配位的 pdc 在穿梭同步构型质子耦合（Hpdcδ+⋯HCuδ-，2.1 Å）中实现了微妙的平衡，促进了水中可持续的氢气生产。此外，通过研究[Cu(pdc)(H2O)2]在 0.5 M H2SO4 中的电催化能力，确保了[Cu(pdc)(H2O)2]的电催化命运具有工业前景。在西孟加拉邦卡林邦 Relli 河（北纬 27.066668°，东经 88.466667°）采集的水中，该复合物在 H2SO4 的作用下显示出明显的阴极电流升高，这预示着它在中试规模应用中的真正催化能力和真正的工业应用前景。

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来源期刊

Sustainable Energy & Fuels Energy-Energy Engineering and Power Technology

CiteScore

10.00

自引率

3.60%

发文量

394

期刊介绍： Sustainable Energy & Fuels will publish research that contributes to the development of sustainable energy technologies with a particular emphasis on new and next-generation technologies.

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