Catalytic dehydrogenation of natural terpenes via CuPd alloy nanoparticles generated on mesoporous graphitic carbon nitride

Abstract

A facile wet-chemical protocol for the synthesis of bimetallic CuPd alloy nanoparticles (NPs) anchored on mesoporous graphitic carbon nitride (m-gCN), serving as both stabilizer and support material, was presented herein. The presented protocol allowed to synthesize nearly monodisperse CuPd alloy NPs with an average particle size of 3.9 +/- 0.9 nm without use of any additional surfactants and to prepare CuPd/m-gCN nanocatalysts with different Cu/Pd compositions (Cu25Pd75/m-gCN, Cu35Pd65/m-gCN, Cu16Pd74/m-gCN, Cu32Pd68/m-gCN, Cu10Pd90/m-gCN, and Cu50Pd50/m-gCN). After the detailed characterization of CuPd/m-gCN nanocatalysts, they were utilized as catalysts in the dehydrogenation of terpenes. Among all tested nanocatalysts, Cu50Pd50/m-gCN showed the highest activity in terms of the product yields within the same reaction time. Various parameters influencing the catalytic activity of Cu50Pd50/m-gCN were studied using himachalene as a model substrate and the optimum conditions were determined. Under the optimized reaction conditions, the catalytic application of Cu50Pd50/m-gCN nanocatalysts was extended to nine different terpenes and the corresponding products were obtained in high conversion yields (>90%) under mild conditions. A reusability test showed that Cu50Pd50/m-gCN nanocatalysts can be re-used up to four cycles without significant loss in their initial activity.