Catalytic synthesis of diethyl carbonate with supported Pd-Cu bimetallic nanoparticle catalysts: Cu(I) as the active species

doi:10.1016/S1872-2067(15)60973-1

Abstract

Abstract:

Cupric oxide (CuO) and copper-cuprous oxide (Cu-Cu₂O) nanoparticles were prepared by a simple hydrothermal method for the synthesis of diethyl carbonate (DEC) from ethanol. During these syntheses, varying NaOH and glucose concentrations were applied to explore and pinpoint the active species. It was found that PdCl₂/CuO and PdCl₂/Cu-Cu₂O both catalysts exhibited good thermal stability and morphology. The results of catalytic tests showed that the catalysts prepared with 5 mol/L NaOH show superior catalytic performances because of their lower extent of agglomeration. It is noteworthy that the PdCl₂/Cu-Cu₂O catalysts were the most active, especially the PdCl₂/Cu-Cu₂O catalyst prepared with 10 mmol glucose and having a higher Cu₂O concentration. In Pd(II)-Cu(II) (PdCl₂/CuO) catalysts, there is an induction period, during which Pd(II) is reduced to Pd(0), that must occur prior to electron transfer between Pd and Cu, and this can slow the catalytic reaction. To further pinpoint the active species, PdCl₂/Cu-Cu₂O catalysts with different Cu₂O contents were prepared by controlling the dosages of glucose. The maximum DEC yield obtained with these catalysts was 151.9 mg·g^-1·h^-1, corresponding to an ethanol conversion of 7.2% and 97.9% DEC selectivity on an ethanol basis. Therefore, it was concluded that Cu⁺ was the active species in this catalytic system, possibly because a higher proportion of Cu⁺ reduces the Pd²⁺ concentration and limits the CO oxidation side reaction, thus increasing DEC selectivity. In addition, Cu⁺ promotes electron transfer between Pd and Cu without an induction period, which could also promote the catalytic activity.

Key words: Cupric oxide, Copper-cuprous oxide, Diethyl carbonate, Sodium hydroxide concentration, Dosages of glucose, Active species

Pingbo Zhang, Yan Zhou, Mingming Fan, Pingping Jiang. Catalytic synthesis of diethyl carbonate with supported Pd-Cu bimetallic nanoparticle catalysts: Cu(I) as the active species[J]. Chinese Journal of Catalysis, 2015, 36(11): 2036-2043.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(15)60973-1

https://www.cjcatal.com/EN/Y2015/V36/I11/2036

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