Increased Water Reduction Efficiency of Polyelectrolyte-Bound Trimetallic [Ru,Rh,Ru] Photocatalysts in Air-Saturated Aqueous Solutions.
The groundbreaking use of polyelectrolytes to increase the efficiency of supramolecular photocatalysts in solar H2 production schemes under aqueous aerobic conditions is reported. Supramolecular photocatalysts of the architecture [{(TL)2 Ru(BL)}2 RhX2 ](5+) (BL=bridging ligand, TL=terminal ligand, X=halide) demonstrate high efficiencies in deoxygenated organic solvents but do not function in air-saturated aqueous solution because of the quenching of the metal-to-ligand charge-transfer (MLCT) excited state under these conditions. The new photocatalytic system incorporates poly(4-styrenesulfonate) (PSS) into aqueous solutions containing [{(bpy)2 Ru(dpp)}2 RhCl2 ](5+) (bpy=2,2'-bipyridine, dpp=2,3-bis(2-pyridyl)pyrazine). PSS has a profound impact on the photocatalyst efficiency, increasing H2 production over three times that of deoxygenated aqueous solutions alone. H2 photocatalysis proceeds even under aerobic conditions for PSS-containing solutions, an exciting consequence for solar hydrogen-production research.
Department of Chemistry, Virginia Tech, Blacksburg, VA 24061-0212 (USA).
Theodore R
TR
Canterbury
Department of Chemistry, Virginia Tech, Blacksburg, VA 24061-0212 (USA).
Shamindri M
SM
Arachchige
Department of Chemistry, Virginia Tech, Blacksburg, VA 24061-0212 (USA). rbmoore3@vt.edu.
Robert B
RB
Moore
Department of Chemistry, Virginia Tech, Blacksburg, VA 24061-0212 (USA).
Karen J
KJ
Brewer
hydrogen; photocatalysis; polyelectrolytes; rhodium; ruthenium