Reactions of radicals with hydrolyzed Bi(III) ions: a pulse radiolysis study.

Radiolytic reduction of BiOClO4 in aqueous solutions leads to the formation of bismuth clusters and larger nanoparticles. The mechanisms of redox reactions of the polycationic Bi(III) species that exist in the solution were investigated with pulse radiolysis. The kinetic and spectral properties of the transients formed by the reaction of these species with the primary radicals from water radiolysis are reported. The single-electron reduction product, Bi9(OH)224+, absorbs at lambdamax = 273 nm, while the OH adduct, Bi9(OH)235+, has a broad absorption spectrum with a maximum at 280 nm and a shoulder at 420 nm. Several rate constants were measured: k (e-aq + Bi9(OH)225+) = 1.2 x 1010 M-1 s-1 and k (OH + Bi9(OH)225+) = 1.5 x 109 M-1 s-1. The reduced species, Bi9(OH)224+ further reacts with (CH3)2COH radicals, but not with CH2C(CH3)2OH radicals from t-butanol, to produce a doubly reduced polynuclear species. A few reactions of the reduction of the Bi salt in the presence of poly(acrylic acid) are also described. In the presence of the polymer, a metal-polymer complex is formed prior to the irradiation, and the reduction reactions are significantly slowed down.

Radiolytic hydrogen yields in aqueous suspensions of gold particles.

The effect of high concentrations of large gold particles, in the hundreds of nanometer size regime, on the yields of molecular hydrogen, G(H(2)), produced in the radiolysis of several aqueous solutions was determined. In particular we look for direct effect of radiation absorbed by the solid particles on the yield of water products. These particles, however, are catalytically active in the conversion of reducing radicals to molecular hydrogen as well. A very small increase in G(H(2)) observed in bromide solutions upon addition of 50 wt % of gold particles indicates that the radiolysis of the solid particles does not affect the yields in the aqueous phase. Very little exchange of charge carriers or energy between the two phases occurs in these large particle suspensions. On the other hand, efficient catalytic conversion of (CH(3))(2)C(*)OH radicals to H(2) is shown to occur. The efficiency of the presently studied suspensions in the redox-catalytic process is similar to that of suspensions of small particles of similar total surface area. In the presence of radicals from hydrogen atom abstraction from tert-butyl alcohol the yield decreases significantly, again similar to the behavior in suspensions of small particles. We conclude that the redox catalysis does not depend on the size of the particles when their size exceeds a few nanometers.

The photophysics of 1-hydroxypyrene, the acidity of its singlet excited state, and the nature of its photoionization process in polar media.

The photophysics of 1-hydroxypyrene, Py-OH, in various media has been examined by pulsed laser and steady state methods. In alkaline polar media the photophysics of the ionized form, Py-O(-), the pyrenolate ion, is reported. From the data the pK(a) is calculated to be 8.93 for the ground state and 4.5 for the excited state. However, the excited singlet state lifetime of Py-OH is too short to lead to significant dissociation into excited Py-O(-*) and H+, and no equilibrium between the species exists. Excitation of Py-OH leads to the excited singlet, the triplet, electrons (trapped), and a short-lived radical cation. The radical cation rapidly dissociates to give the pyrenyloxyl radical. Excitation of Py-O(-) gives the excited singlet state, the triplet state, solvated electrons and the pyrenyloxyl radical. No evidence of a radical cation of Py-O(-), i.e.,(+.)Py-O(-) is forthcoming, and only the neutral pyrenyloxyl radical is observed. Low temperature experiments in glasses are used to identify the various species produced.