Electrocatalytic alcohol oxidation by covalently immobilized ruthenium complex on carbon.

A dearth of discrete immobilized metal complexes exist that electrocatalytically oxidize methanol. Reported here is the covalent immobilization of a tris(2-pyridylmethyl)amine ruthenium complex [Ru(Cl)(DMSO)(ethynyl-TPA)] (ethynyl-TPA = (5-ethynyl-2-pyridylmethyl)bis(2-pyridylmethyl)amine) to a glassy carbon (GC) electrode through a Cu catalyzed azide-alkyne cycloaddition (click) reaction between the ethynyl-TPA ligand and an azide derivatized carbon surface forming [Ru(Cl)(DMSO)(GC-click-TPA)]. Following water substitution for DMSO and proton coupled electron transfer, [Ru(O)(Cl)(GC-click-TPA)] electrooxidizes alcohols, including methanol, efficiently relative to other immobilized metal complexes.

Gas-phase azide functionalization of carbon.

Tailoring the surface and interfacial properties of inexpensive and abundant carbon materials plays an increasingly important role for innovative applications including those in electrocatalysis, energy storage, gas separations, and composite materials. Described here is the novel preparation and subsequent use of gaseous iodine azide for the azide modification of carbon surfaces. In-line generation of gaseous iodine azide from iodine monochloride vapor and solid sodium azide is safe and convenient.