Search

Motivated by the prominent catalytic performance and durability of nanoalloy catalysts, the Pd-based bimetallic nanoalloy catalysts were prepared using an aqueous reduction method. The Fe-Pd bimetallic nanoalloy catalyst (nano-Fe/Pd) demonstrated 98.4% yield and 99.7% selectivity for the unsaturated 1,4-dicarboxylic acid diesters. Moreover, the inductively coupled plasma (ICP) analysis shows that the Pd leaching of the catalyst can be effectively suppressed by alloying Fe atoms into the Pd crystal lattice for acetylene dicarbonylation. The detailed catalyst structure and morphology characterization demonstrate that introducing Fe into the Pd nanoparticles tunes the electronic–geometrical properties of the catalyst. Theoretical calculations indicate that the electrons of Fe transfer to Pd in the nano-Fe/Pd catalyst, enhancing activation of the C≡C bond in acetylene and weakening CO absorption capacity on catalyst surfaces. Alloying Fe into the Pd nanocatalyst effectively inhibits active metal leaching and improves catalyst activity and stability under high-pressure CO reactions. [ABSTRACT FROM AUTHOR]

The integrated synergistic effect of the ligand and the strong metal-support interaction (SMSI) effectively improves the selectivity and stability of heterogeneous Pd-based catalysts for acetylene dicarbonylation under high-pressure CO conditions. [Display omitted] • Stabilizing the catalytic active site Pdδ+ for acetylene dialkoxycarbonylation. • Oxygen-containing functional groups of AC provide anchoring sites for stabilize active Pd2+ ions. • The coordination of I- not only accelerates the reaction but also stabilizes the catalyst. The support and ligand play a crucial role in regulating the catalytic performance, selectivity, and stability of heterogeneous catalysis. Herein, activated carbon (AC) supported palladium (Pd) catalysts (2.0 wt%) were prepared by impregnation for acetylene dicarbonylation. The oxygen-containing groups on the surface of the AC support were modulated by nitric acid (HNO 3) to investigate metal–support interactions on the catalytic performance and stability of the Pd/AC. The characterization of the chemical composition and structure of the supports and catalysts demonstrates that high concentrations of oxygen-containing groups on the surface of the carbon support lead to the fine dispersion of Pd nanoparticles. Notably, the finely dispersed Pd/AC 70 catalyst exhibited good activity and stability for acetylene dicarbonylation under high-pressure CO conditions after several rounds of regeneration. Furthermore, operational parameters including the type of support, co-catalyst (KI), and reaction time and temperature were identified for their impact on the reaction. It was found that I- anions serve as a co-catalyst and can ligate with Pd species, thereby preventing the leaching of Pd and improving reaction selectivity. This study presents a straightforward and sustainable modulation strategy to improve the dispersion of active metals, as well as to prevent the leaching and sintering of these metals during high-pressure CO reactions. [ABSTRACT FROM AUTHOR]