In Situ Generation of Active Molybdenum Octahedral Clusters for Photocatalytic Hydrogen Production from Water.

The photocatalytic hydrogen evolution reaction (HER) from water under homogeneous and heterogeneous conditions is explored for the {Mo6 Br(i) 8 }(4+) cluster core based unit starting from (TBA)2 [Mo6 Br(i) 8 F(a) 6 ] (TBA=tetra-n-butylammonium; "i" and "a" refer to the face-capping inner and terminal apical ligand, respectively). The catalytic activity of {Mo6 Br(i) 8 }(4+) is enhanced by the in situ generation of [Mo6 Br(i) 8 F(a) 5 (OH)(a) ](2-) , [Mo6 Br(i) 8 F(a) 3 (OH)(a) 3 ](2-) , and [Mo6 Br(i) 8 (OH)(a) 6 ](2-) , which are identified by ESIMS, luminescence, and NMR techniques. Full substitution of F(-) by OH(-) leads to the formation of (H3 O)2 [Mo6 Br(i) 8 (OH)(a) 6 ]⋅10 H2 O; its structure was determined by single-crystal XRD. The immobilization of the active {Mo6 Br(i) 8 }(4+) onto graphene oxide (GO) surfaces enhances its stability under catalytic conditions. The catalytic activity of the resulting (TBA)2 Mo6 Br(i) 8 @GO material is improved with respect to GO, but is reduced compared to the activity under homogeneous conditions because of changes in the GO semiconducting properties as well as lower activity and/or accessibility of the anchored cluster.