Influence of the preparation procedure on the catalytic activity of gold supported on diamond nanoparticles for phenol peroxidation

Abstract

The catalytic activity of diamond-supported gold nanoparticle (Au/D) samples prepared by the deposition/precipitation method have been correlated as a function of the pH and the reduction treatment. It was found that the most active material is the one prepared at pH 5 followed by subsequent thermal treatment at 300°C under hydrogen. TEM images show that Au/D prepared under optimal conditions contain very small gold nanoparticles with sizes below 2 nm that are proposed to be responsible for the catalytic activity. Tests of productivity using large phenol (50 g L-1) and H2O2 excesses (100 gL-1) and reuse gives a minimum TON of 458,759 moles of phenol degraded per gold atom. Analysis of the organic compounds extracted from the deactivated solid catalyst indicates that the poisons are mostly hydroxylated dicarboxylic acids arising from the degradative oxidation of the phenyl ring. By determining the efficiency for phenol degradation and the amount of O2 evolved two different reactions of H2O2 decomposition (the Fenton reaction at acidic pH values and spurious O2 evolution at basic pH values) are proposed for Au/D catalysis. The activation energy of the two processes is very similar (ranging between 30 and 35 kJ mol-1). By using dimethylsulfoxide as a radical scavenger and N-tert-butyl-a-phenylnitrone as a spin trap under aerated conditions, the EPR spectrum of the expected PBN OCH3 adduct was detected, supporting the generation of HO., characteristic of Fenton chemistry in the process. Phenol degradation, on the other hand, exhibits the same activation energy as H2O2 decomposition at pH 4 (due to the barrierless attack of HO. to phenol), but increases the activation energy gradually up to about 90 kJ mol-1 at pH 7 and then undergoes a subsequent reduction as the pH increases reaching another minimum at pH 8.5 (49 kJ mol-1).