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Spin State Differentiated [3Fe-4S] Cluster Electrocatalyzes Water Oxidation Efficiently
Rong Yan1,2,3, Qian-Cheng Luo1, Zi-Han Li1
1Frontier Institute of Science and Technology, Interdisciplinary Research Center of Frontier Science and Technology, State Key Laboratory of Electrical Insulation and Power Equipment, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter, Xi'an Key Laboratory of Electronic Devices and Material Chemistry, Xi'an Key Laboratory of Sustainable Energy and Materials Chemistry, Xi'an Jiaotong University, Xi'an, Shaanxi Province, 710054, P. R. China.
None:
Though there are many synthetic iron-sulfur clusters that have been reported to show catalytic activity mimicking the natural cofactors in metalloenzymes, the influence of the spin state on the catalytic property is seldom touched. Here, a disulfide-bridged triiron(II) complex is shown, namely [Fe3(Sip)4][CF3SO3]2 (Fe3(Sip)4, HSip = sulfanylpropyliminomethyl-pyridine), can efficiently electrocatalyze water oxidation with a turnover frequency of 932 s-1 and Faraday efficiency of 86%, better than many iron-based catalysts. More importantly, the terminal low-spin (S = 0) iron(II) sites possessing a N4S2 first coordination environment, along with the synergetic catalysis of ligands, play a crucial role in the catalytic process. This research highlights the unconventional applications of iron-sulfur clusters in electrocatalytic water oxidation and underlines a promising avenue for developing innovative catalysts.
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