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Published on: April 10, 2018
Electrocatalytic properties of two nickel(II) complexes for use in the hydrogen evolution reaction: theoretical
Suparna Roy1, Manjula Pal2, Pritam Ghosh3
1Department of Chemistry, Jadavpur University, Jadavpur, Kolkata 700032, India. partha.roy@jadavpuruniversity.in.
Abstract:
Ni(II) complexes have been used as electrocatalysts in the hydrogen evolution reaction (HER) to produce clean, environmentally friendly fuel. Geometry around the metal centre may play a crucial role in its electrocatalytic activities. For this purpose, two nickel complexes, [Ni(L1)2] (complex 1) and [Ni(L2)NO3] (complex 2), where HL1 = 1-((2-(pyrrolidin-1-yl)ethylimino)methyl)naphthalen-2-ol and HL2 = 1-((3-((3-aminopropyl)(methyl)amino)propylimino)methyl)naphthalen-2-ol, were synthesized and characterized by different standard methods, including single crystal X-ray diffraction analysis. The Ni in complex 1 is characterized by a square planar geometry, and the metal center in complex 2 is hexacoordinated. Various experiments reveal that (i) the diffusion coefficient of complex 1 (18.01 × 10-2 cm2 s-1) is higher than that of complex 2 (3.45 × 10-2 cm2 s-1), (ii) the overpotential values are 0.47 V and 0.56 V for complex 1 and complex 2, respectively, (iii) the TOF values are 389.5 and 182.5 for complex 1 and complex 2, respectively, and (iv) the faradaic efficiency is 90% for complex 1 and 86% for complex 2. On the basis of the electrochemical results and the DFT-optimized local-minimum structures, an ECEC-type HER pathway is proposed, although other proton-/electron-transfer sequences cannot be ruled out from the present data. These results suggest more robust catalytic activity of complex 1 than complex 2 in the HER.
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