A New Class of Efficient Electrocatalysts for the Reduction of Protons into Hydrogen Based on the [Mo2O2S2]2+ Building Block

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• 作者：Bineta Keita ; S&eacute ; bastien Floquet ; Jean-Franç ; ois Lemonnier ; Emmanuel Cadot ; Ali Kachmar ; Marc B&eacute ; nard ; Marie-Madeleine Rohmer ; Louis Nadjo
• 刊名：Journal of Physical Chemistry C
• 出版年：2008
• 出版时间：January 31, 2008
• 年：2008
• 卷：112
• 期：4
• 页码：1109 - 1114
• 全文大小：155K
• 年卷期：v.112,no.4(January 31, 2008)
• ISSN：1932-7455

文摘

Oxothiomolybdenum wheels represent a new family of efficient electrocatalysts for the reduction of protonsinto hydrogen. The present study focuses on the complex [Mo₈S₈O₈(OH)₈(Ox)]^2- (1) as a lithium salt(Ox^2- = oxalate), which exhibits an electrocatalytic reduction wave of protons in the presence of perchloricacid at about -1.00 V versus SCE in DMF. Efficiency of this new electrocatalyst was evidenced by cyclicvoltammetry and coulometry. DFT calculations were reported and bring about data of the protonated state ofthe catalyst, the first step of the postulated mechanism in the catalytic reaction. Other weak acids such asp-toluenesulfonic acid, trifluoroacetic acid, and acetic acid in DMF were tested and found to be efficient forthe reduction of protons. The complex [Mo₁₂S₁₂O₁₂(OH)₁₂(Trim)]^3- (2) behaves also as an electrocatalyst,functioning at a very low overpotential. Finally, the biomimetic behaviors of this new class of efficientelectrocatalysts for hydrogen production mimic those of hydrogenases and compare favorably with theirperformances.