No abstract

The silver-nanoparticle-catalyzed decomposition of hydrogen peroxide (H2O2) in pH 9.5 bicarbonate buffer is investigated here with attention given to (i) the mechanism of decomposition, (ii) the role of superoxide in mediating silver nanoparticle re-formation, and (iii) the effect of nanoparticle size on decomposition rate. Silver nanoparticles (AgNPs) of average size between 25.0 and 69.4 nm were synthesized via the reduction of Ag+ [the dominant Ag(I) species present] by photochemically produced superoxide at pH 9.5 and characterized by UV−visible spectroscopy and dynamic light scattering. The ability of these particles to catalytically decompose H2O2 was examined by measuring the decay of H2O2 and the approach to steady state in AgNP and Ag+ concentrations. Additionally, the generation of superoxide on reaction of AgNPs with H2O2 was monitored using a chemiluminescence-based method. The second-order rate constants for reaction between AgNPs and H2O2 correlated linearly with their average particle size ranging from 35.0 to 3.0 × 102 M−1 s−1 for average sizes between 69.4 and 25.0 nm. A sensitive trap-and-trigger chemiluminescence-based method for hydroxyl radical detection showed no evidence for the presence of hydroxyl radicals, though an inhibitory effect of tert-butyl alcohol suggested the presence of a strongly oxidizing species. A process involving the superoxide-mediated charging of silver nanoparticles with subsequent discharge by reaction with oxygen and Ag+ leading to regeneration of Ag0 and superoxide is proposed to account for the results obtained.

No abstract

The oxidation kinetics of nanomolar concentrations of Cu(I) in NaCl solutions have been investigated over the pH range 6.5-8.0. The overall apparent oxidation rate constant was strongly affected by chloride, moderately by bicarbonate, and to a lesser extent by pH. In the absence of bicarbonate, an equilibrium-based speciation model indicated that Cu(+) and CuClOH(-) were the most kinetically reactive species, while the contribution of other Cu(I) species to the overall oxidation rate was minor. A kinetic model based on recognized key redox reactions for these two species further indicated that oxidation of Cu(I) by oxygen and superoxide were important reactions at all pH values and chloride concentrations considered, but back reduction of Cu(II) by superoxide only became important at relatively low chloride concentrations. Bicarbonate concentrations from 2 to 5 mM substantially accelerated Cu(I) oxidation. Kinetic analysis over a range of bicarbonate concentrations revealed that this was due to formation of CuCO(3)(-), which reacts relatively rapidly with oxygen, and not due to inhibition of the back reduction of Cu(II) by formation of Cu(II)-carbonate complexes. We conclude that the simultaneous oxygenation of Cu(+), CuClOH(-), and CuCO(3)(-) is the rate-limiting step in the overall oxidation of Cu(I) under these conditions.

Contemporary studies indicate that reactive oxygen species (ROS) such as superoxide play a key role in the toxicity and behavior of silver nanoparticles (AgNPs). While there have been suggestions that superoxide is able to reduce silver(I) ions with resultant production of AgNPs, no experimental evidence that this process actually occurs has been produced. Here we present definitive experimental evidence for the reduction of silver(I) by superoxide. A second-order rate constant of 64.5 ± 16.3 M(-1)·s(-1) is determined for this reaction in the absence of AgNPs. The overall rate constant, however, increases by at least 4 orders of magnitude in the presence of AgNPs. A model based on electron charging and discharging of AgNPs satisfactorily describes the kinetics of this process. The ability for AgNPs to undergo catalytic cycling provides a pathway for the continual generation of ROS and the regeneration of AgNPs following oxidation.