A new class of efficient electrocatalysts for the reduction of protons into hydrogen based on the [Mo2O2S2](2+) building block

作者：Keita Bineta; Floquet Sabastien; Lemonnier Jean Francois; Cadot Emmanuel; Kachmar Ali; Benard Marc; Rohmer Marie Madeleine; Nadjo Louis^*

来源：Journal of Physical Chemistry C, 2008, 112(4): 1109-1114.

DOI：10.1021/jp0774138

Oxothiomolybdenum wheels represent a new family of efficient electrocatalysts for the reduction of protons into 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 perchloric acid at about - 1.00 V versus SCE in DMF. Efficiency of this new electrocatalyst was evidenced by cyclic voltammetry and coulometry. DFT calculations were reported and bring about data of the protonated state of the catalyst, the first step of the postulated mechanism in the catalytic reaction. Other weak acids such as p-toluenesulfonic acid, trifluoroacetic acid, and acetic acid in DMF were tested and found to be efficient for the 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 efficient electrocatalysts for hydrogen production mimic those of hydrogenases and compare favorably with their performances.

• 出版日期2008-1-31