Effective Prevention of Palladium Metal Particles Sintering by Histidine Stabilization on Silica Catalyst Support

Abstract

AbstractA robust method for enhancing the dispersion and stabilization of small metal nanoparticles in heterogeneous catalysts is developed. It involves in situ complexation of palladium(II) by histidine, in water, prior to impregnation in fumed silica. TEM images show that the histidine facilitates dispersion of the Pd(II) into finer nanoscale particles (≈2 nm) uniformly distributed on the support, rather than the large clusters (≈5 nm) seen in the absence of histidine. After hydrogen reduction, assessments using CO chemisorption and propylene hydrogenation indicate that the coordinated histidine might obscure the active sites on the Pd particles. However, as histidine decomposes between 220 and 300 °C in air, these materials are treated at 225 °C in air for 48 h. Afterwards the Pd(II) particles remain the same size, but after hydrogen reduction, there is a 2.4‐fold increase in CO gas adsorption, indicative of an expanded Pd surface area. Furthermore, superior catalyst stability (activity >200 h) is observed during propylene hydrogenation at 250 °C. This is consistent with histidine use having generated widely spaced, uniformly small, Pd nanoparticles on the silica support which is expected to help prevent agglomeration (sintering) during catalysis. This is a convenient low‐cost strategy for reducing metal content, preventing sintering and optimizing catalyst performance.