Dimeric [Mo₂S₁₂]²⁻ Cluster: A Molecular Analogue of MoS₂ Edges for Superior Hydrogen‐Evolution Electrocatalysis

Abstract

Proton reduction is one of the most fundamental and important reactions in nature. MoS2 edges have been identified as the active sites for hydrogen evolution reaction (HER) electrocatalysis. Designing molecular mimics of MoS2 edge sites is an attractive strategy to understand the underlying catalytic mechanism of different edge sites and improve their activities. Herein we report a dimeric molecular analogue [Mo2 S12 ](2-) , as the smallest unit possessing both the terminal and bridging disulfide ligands. Our electrochemical tests show that [Mo2 S12 ](2-) is a superior heterogeneous HER catalyst under acidic conditions. Computations suggest that the bridging disulfide ligand of [Mo2 S12 ](2-) exhibits a hydrogen adsorption free energy near zero (-0.05 eV). This work helps shed light on the rational design of HER catalysts and biomimetics of hydrogen-evolving enzymes.

Redox and Acid–Base Properties of Binuclear 4‐Terphenyldithiophenolate Complexes of Nickel

“…Numeration scheme used for ligands [Mes 2 tBu 2 S 2 ] 2À and [tBu 4 S 2 ] 2À in coordination compounds: Chem. Eur.J.2016, 22,14640 -14647 www.chemeurj.org…”

“…HNMR(500 MHz,[D8]THF,2 99 K): d = 7.69 (d, (HH) = 2.1 Hz, 1H, 7.52 (d,4 J(HH) = 2.1 Hz, 1H, 7.47 (d, (HH) = 2.3 Hz, 1H, 7.29 (d,4 J(HH) = 2.3 Hz, 1H, 6.06 (m, 2H,, 4.06 (m, 2H,H -9,-11), 2.01 (s, 9H,H -24), 1.67 (s, 9H,H -23), 1.59 (br m, 1H,H -10), 1.41 (s, 9H,H -25), 1.34 (s, 9H,H -26), 1.24 ppm (AA'X 9 X 9 ', J(PP) @ J(HP), Dn (N-lines) = 9.5 Hz, 18 H, P(CH 3 ) 3 ); 13 C{ 1 H} NMR (126 MHz, CDCl 3 ,2 98 K): d = 152.74 (C-1), 151.72 (C-13), 150.44 (C-15), 150.16 (C-6), 149,47 (C-4), 148.06 (C17), 147.11( br m, C-7), 142.94 (C-2), 127.87 (C-14), 126.53 (C18), 124.08 (C-16), 123.67 (C-5), 120.28 (quartet, 1 J(CF) = 322 Hz, NTF 2 -anion), 118.09 (C-3), 88.05 (C-8,-12), 70.42 (C-9,-11), 48.83 (C(sp 3 )-10), 37.71 (C-20), 36.8 (C-19), 34.77 (C-21), 34.46 (C-22), 30.89 (C-24), 30.62 (C-25), 30.56 (C-26), 30.1 (C-23), 15.71 ppm (ABX, J(PP) @ J(CP), Dn (Nlines) = 28.4 Hz, P(CH 3 ) 3 ); 19 FNMR (376 MHz, [D8]THF,2 99 K): dÀ81.6 ppm (s, NTf 2 -anion); 31 P{ 1 H} NMR (202 MHz, [D8]THF,2 99 K): d = À20.53 ppm;U V/Vis (THF): l max (e): 240…”

Ligand‐Exchange‐Induced Amorphization of Pd Nanomaterials for Highly Efficient Electrocatalytic Hydrogen Evolution Reaction

“…The majority of surface S atoms in Pd NPs‐Bis‐24h are located at 163.8 and 165.0 eV (Figure d), which have the same binding energy as the bridging S 2 2− and apical S 2− in amorphous MoS x . These S atoms have been reported to be active sites of amorphous MoS x in electrocatalytic HER, as their hydrogen adsorption energy is near zero …”

Gas-Phase Reactivity Studies of Small Molybdenum Cluster Ions with Dimethyl Disulfide

“…The most efficient catalyst for the hydrogen evolution reaction (HER) is platinum, but the available supplies of this element are not sufficient to meet the expected demand for large-scale hydrogen production. Molybdenum sulfide (MoS 2 ) based catalysts have the potential to replace platinum as a HER catalyst in electrochemical water splitting [1][2][3][4][5][6][7]. The material is also discussed as a catalyst for methanol synthesis from carbon dioxide and molecular hydrogen [8,9].…”

“…Fielicke and co-workers studied the effect of molybdenum doping on the reactivity of metal and metal oxide clusters [26,27]. Bohme and coworkers established that a gas-phase Mo(C 60 ) 4 + complex can be formed in a flow reactor [28]. The same group studied the reactions of Mo + with heavy water [29], carbon disulfide [30], O 2 [31] and N 2 O [32] as part of a large-scale investigations of periodic trends.…”