Direct Anchoring of Molybdenum Sulfide Molecular Catalysts on Antimony Selenide Photocathodes for Solar Hydrogen Production.

Molybdenum sulfide serves as an effective nonprecious metal catalyst for hydrogen evolution, primarily active at edge sites with unsaturated molybdenum sites or terminal disulfides. To improve the activity at a low loading density, two molybdenum sulfide clusters, [Mo3S4]4+ and [Mo3S13]2-, were investigated. The Mo3S x molecular catalysts were heterogenized on Sb2Se3 with a simple soaking treatment, resulting in a thin catalyst layer of only a few nanometers that gave up to 20 mA cm-2 under one sun illumination. Both [Mo3S4]4+ and [Mo3S13]2- exhibit catalytic activities on Sb2Se3, with [Mo3S13]2- emerging as the superior catalyst, demonstrating enhanced photovoltage and an average faradaic efficiency of 100% for hydrogen evolution. This superiority is attributed to the effective loading and higher catalytic activity of [Mo3S13]2- on the Sb2Se3 surface, validated by X-ray photoelectron and Raman spectroscopy.

Optimizing Photocatalytic H2 Production by Introduction of Pyrazinyls to WRCs and a New tris-Rhenium Photosensitizer.

The replacement of pyridyl by pyrazinyl in ligands of polypyridyl-based cobalt water reducing catalysts (WRC) shifts reduction potentials anodically. Together with a new, trinuclear ReI photosensitizer, these WRCs show strongly improved photocatalytic performances in turnover numbers (TONs) and maximal H2 evolution rate. Depending on the catalyst structure, up to 65 kTONs at 1 µM WRC concentration were reached. Under electrocatalytic conditions in both DMF and H2O, one of the reported WRCs displays remarkable stability, producing H2 steadily over 21 and 14 d, respectively.

Induced fac-mer rearrangements in {M(CO)3}+ complexes (M = Re, 99(m)Tc) by a PNP ligand.

The fac-mer rearrangements in [MX3(CO)3]2- (M = Re, 99Tc) induced by a pincer-type ligand (PNP) and a "halide scavenger" are reported. The reactions of fac-[99mTc(CO)3(OH2)3]+ or [99mTcO4]- in saline both yield mer-[99mTc(PNP)(CO)3]+, the first example of a mer-{99mTc(CO)3}+ type complex. In contrast, reactions with terpyridine (terpy) only gave the facial κ2-terpy complexes with Re and 99Tc.

Light-Driven Ring Slippage in [Re(η7-C7H7)(η5-C7H9)]+ and the Inertness of Its Technetium Homologue.

Here, we present the light-driven reactions of [Re(η7-C7H7)(η5-C7H9)]+ (1+) with nitriles, phosphines, and isocyanides, which are added to 1+ via a ring slippage of the tropylium cation from η7 to η3, forming [Re(η3-C7H7)(η5-C7H9)(L)2]+ (L= acetonitrile 2+; 2-phenylacetonitrile 3+; 1,3,5-triaza-5-phosphoadamantane (PTA) 4+; tert-butyl isocyanide 6+; benzyl isocyanide 7+) and [Re(η3-C7H7)(η5-C7H9)(L)]+ with L = (ethane-1,2-diyl)bis(diphenylphosphane) (dppe) 5+. To compare the reactivities of rhenium and technetium, we also investigated the synthesis of [99Tc(η6-C10H8)2]+, its substitution of naphthalene with cyclohepta-1,3,5-triene to obtain [99Tc(η7-C7H7)(η5-C7H9)]+, and its reactivity (or lack thereof) with light.