Photogeneration of Hydrogen from Water by Hybrid Molybdenum Sulfide Clusters Immobilized on Titania

Abstract

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Binuclear Sulfide Niobium Clusters Coordinated by Diimine Ligands: Synthesis, Structure, Photocatalytic Activity and Optical Limiting Properties

“…The rate of the hydrogen evolution was 10 nmol/min or 12 μmol/g(cat) per hour. No H 2 evolution was evolved under the same conditions on bare TiO 2 and no photocatalytic activity was observed upon substitution of the [Nb 2 S 4 (NCS) 6 [12] This might indicate a similar mechanism of TiO 2 activation. We have previously shown that the Mo 3 S 7 diimine cluster was a precatalyst and its reduction electrochemically or by photogenerated electrons produced electrocatalytic Mo x S y species.…”

“…[27] In our previous work, we have found that nanoparticles of TiO 2 modified with Mo 3 S 7 diimine clusters show a high photocatalytic activity for H 2 production in the presence of Na 2 S/Na 2 SO 3 as sacrificial electron-donor system. [12] The question then arises: What will happen if we substitute trinuclear Mo 3 S 7 diimine clusters by binuclear Nb 2 S 4 diimine clusters? We have studied the photocatalytic activity of (Et 4 N) 2 [Nb 2 S 4 (NCS) 6 -(bipy)] (2) deposited on TiO 2 (Degussa P25) nanoparticles in HER in the presence of 0.1 m Na 2 S + 0.02 m Na 2 SO 3 in a setup that was described previously.…”

“…[5] Examples of group 6 complexes featuring N-donor ligands such as [M(Mebipy) 3 ] and [M(tpy) 2 ] (M = Cr, Mo and W; Mebipy = 4,4Ј-dimethyl-2,2Ј-bipyridine and tpy = 2,2Ј,6Ј,2ЈЈ-terpyridine) have been provided by Wieghardt's group. [6,7] However, coordination chemistry of such noninnocent ligands with chalcogenide clusters is rather limited, with reported examples including coordination of bipyridine or phenanthroline to V 3 S 7 , [8] Mo 3 S 4 , [9,10] Mo 3 Q 7 (Q = S, Se), [11][12][13] M(μ 3 -S) 3 Cu 3 (M = Mo, W), [14] and Mo 2 S 2 O 2 cluster units. [15] It is expected that "electron sink" properties of the chalcogenide cluster cores coupled with their structural and electronic diversity may lead to novel and potentially important properties.…”

Heteroleptic Phenanthroline Complexes of Trinuclear Molybdenum Clusters with Luminescent Properties

“…[3][4][5][6] Interestingly, the reaction of [Mo 3 (μ 3 -S)(μ-S 2 ) 3 Br 6 ] 2with an excess of a diimine ligand selectively replaces two bromido ligands on one metal atom to afford neutral Mo 3 S 7 Br 4 (diimine) complexes in high yields. [11,12] To extend the scope of this synthetic route, we employed other metal precursors, that is, [Mo 3 (μ 3 -S)(μ-S 2 ) 3 Cl 6 ] 2-, and other 1,10-phenanthroline derivatives. The synthetic approaches used for the synthesis of the target molecules are shown in Scheme 1.…”

“…[8][9][10] In the recent past, our group developed a straightforward approach to synthesize heteroleptic Mo 3 S 7 Br 4 (diimine) complexes containing bipyridine or phenanthroline based ligands. [12] The resulting Mo x S y @TiO 2 system shows a high photocatalytic activity for hydrogen evolution in the presence of a sacrificial donor system. [12] The resulting Mo x S y @TiO 2 system shows a high photocatalytic activity for hydrogen evolution in the presence of a sacrificial donor system.…”