氢化酶3.pptVIP

Group Meeting 2010. 01. 25 Fig. 4 CV’s in 0.1 M NaClO4, 2 mM NaOAc, 2 mM HOAc, pH 4.5. (a) Catalytic H+ reduction by 1 before (blue) and after 16h (red) electrolysis (10 mV s-1). (b) Rotating disc electrode voltammetry (1 mV s-1). Inset: Levich plot of limiting current at 1.2 V. The non-linearity of the Levich plot (current vs. w1/2, Fig. 4b) from a rotating disc electrode voltammetry experiment indicates a kinetic, rather than mass transport, limitation for the reaction under these conditions; reduction of protons must be the rate determining step since electron transfer to 1 adsorbed on GC is presumably fast. 1 we have introduced a synthetically versatile cobalt tetraimine system for electrocatalytic hydrogen evolution. 2 Investigated by CV, these systems can be modified with carboxylic acid appendages and adsorbed to ITO. 3 Similarly, the BF2-substituted glyoximato system 1 can be adsorbed to a GC electrode upon which it is active for hydrogen evolution in aqueous solutions at low overpotential. 4 We are currently investigating the mechanism of the immobilization of 1 on GC. Summary Thank you! * Aryl-substituted tetraimine complexes related to Co(dmgBF2)2- (MeCN)2 (dmg = dimethylglyoxime) were synthesized and are active for hydrogen evolution. Co(dmgBF2)2(MeCN)2 can be adsorbed to a glassy carbon electrode. The chemically modified electrode is active for hydrogen evolution in aqueous solution at pH o 4.5, with an overpotential of only 100 mV. Hydrogen evolution by cobalt tetraimine catalysts adsorbed on electrode surfaces Louise A. Berben and Jonas C. Peters* Chem. Commun., 2010, 46, 398–400 Herein, we report that these tetraimine cobalt complexes can be used to prepare chemically modified electrodes from indium tin oxide (ITO)-coated glass that are active for hydrogen evolution. We moreover establish that 1 is a substantially better hydrogen-evolving catalyst in aqueous solution once attached to a glassy carbon (GC) electrode. Fig. 1 Li