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[MoO(S2)2L]1– (L = picolinate or pyrimidine-2-carboxylate) Complexes as MoSx‑Inspired Electrocatalysts for Hydrogen Production in Aqueous Solution

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posted on 03.10.2016, 00:00 by Benjamin R. Garrett, Kevin A. Click, Christopher B. Durr, Christopher M. Hadad, Yiying Wu
Crystalline and amorphous molybdenum sulfide (Mo–S) catalysts are leaders as earth-abundant materials for electrocatalytic hydrogen production. The development of a molecular motif inspired by the Mo–S catalytic materials and their active sites is of interest, as molecular species possess a great degree of tunable electronic properties. Furthermore, these molecular mimics may be important for providing mechanistic insights toward the hydrogen evolution reaction (HER) with Mo–S electrocatalysts. Herein is presented two water-soluble Mo–S complexes based around the [MoO­(S2)2L2]1– motif. We present 1H NMR spectra that reveal (NEt4)­[MoO­(S2)2picolinate] (Mo-pic) is stable in a d6-DMSO solution after heating at 100 °C, in air, revealing unprecedented thermal and aerobic stability of the homogeneous electrocatalyst. Both Mo-pic and (NEt4)­[MoO­(S2)2pyrimidine-2-carboxylate] (Mo-pym) are shown to be homogeneous electrocatalysts for the HER. The TOF of 27–34 s–1 and 42–48 s–1 for Mo-pic and Mo-pym and onset potentials of 240 mV and 175 mV for Mo-pic and Mo-pym, respectively, reveal these complexes as promising electrocatalysts for the HER.

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