Tuning the electrocatalytic hydrogen evolution reaction promoted by [Mo2O2S2]-based molybdenum cycles in aqueous medium.
We report the syntheses and characterizations, in the solid state and in solution, of three new cyclic polyoxothiomolybdates self-assembled around 2,5-dimethylterephthalate (DMT) and 2,5-bis(trifluoromethyl)terephthalate (DFMT) ligands, namely [Mo12DMT](2-), [Mo12DFMT](2-) and [Mo16DFMT](2-). A series of these two Mo12-compounds completed by the two Mo12-compounds obtained with 2,3,5,6-tetramethylterephthalate and trimesate ligands offer the opportunity to compare their electro-catalytic properties for reduction of protons into hydrogen. The ability of these compounds to promote the reduction of protons into hydrogen in aqueous medium is evidenced and the influence of the embedded ligand is highlighted, thus allowing proposal of a mechanism for the hydrogen evolution reaction catalyzed by these clusters.
Institut Lavoisier de Versailles, UMR 8180, Université de Versailles Saint-Quentin en Yvelines, 45 avenue des Etats-Unis, 78035 Versailles Cedex, France.
Akram
A
Hijazi
Justin Claude
JC
Kemmegne-Mbouguen
Sébastien
S
Floquet
Jérôme
J
Marrot
Jennifer
J
Fize
Vincent
V
Artero
Olivier
O
David
Emmanuel
E
Magnier
Bruce
B
Pégot
Emmanuel
E
Cadot
D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D006859:Hydrogen / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D010795:Phthalic Acids / Q000737:chemistry; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
D056831:Coordination Complexes; D010795:Phthalic Acids; D014867:Water; C011363:terephthalic acid; D006859:Hydrogen; D008982:Molybdenum