Homogeneous catalytic reactions involving hydrolysis have potential applications in WMD countermeasure technologies.  We are interested in enhancing metal-based homogeneous or heterogenized catalysts, and catalytic reactions, that can be directed to either chemical agents neutralization and/or bacterial/viral decontamination.  These catalysts can be finely tuned, both sterically and electronically, through a careful selection of ligands, neutral molecules, or ions bound either covalently or electrostatically to the catalytically active metal ion center.  Our goal is to enhance the catalytic rates through cooperative effects using ligand stabilized multi-metallic catalytic centers at gold nanoparticle surfaces and laser-induced plasmonic effects, an area of research using active plasmonics to drive chemical reactions at nanoparticle surfaces.  We will present examples of (i) high-charge density cobalt complexes and (ii) long-chain organic cations as examples of charged species which are designed to induce cooperative effects in the classical copper-bipyridine (Cu-bipy) catalyzed hydrolysis of phosphate esters such as methyl parathion (MP).  Further enhancement of catalytic hydrolysis of MP was achieved by irradiating 10 nm gold nanoparticles capped with thiol functionalized Cu-bipy complexes.  It was demonstrated that hydrolysis of MP increased by a factor of 2 via irradiation of the plasmon absorption band of capped gold NPs using a low power green laser.  This represents the first example of the use of plasmonics in metal catalyzed phosphate ester degradation.

Homogeneous copper catalyzed hydrolysis of phosphate esters on a gold nanoparticle platform: Modulation of activity using laser excitation and ligand cooperativity

244th National Meeting (2012)

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