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Ester Reduction with H2 on Bifunctional Metal‐Acid Catalysts: Implications of Metal Identity on Rates and Selectivities

Enabling sustainable and continuous processes for ether production from bioderived esters on bifunctional solid catalysts: esters hydrogenate to hemiacetals on Pd, Rh, and Pt nanoparticles and diffuse to nearby Brønsted acids sites to form ethers or alcohols. Ester reduction rates are determined by H* addition to the C=O bond on metal sites and cleavage of C−O bonds on acid sites.


Abstract

Esters reduce to form ethers and alcohols on contact with metal nanoparticles supported on Brønsted acidic faujasite (M-FAU) that cleave C−O bonds by hydrogenation and hydrogenolysis pathways. Rates and selectivities for each pathway depend on the metal identity (M=Co, Ni, Cu, Ru, Rh, Pd, and Pt). Pt-FAU gives propyl acetate consumption rates up to 100 times greater than other M-FAU catalysts and provides an ethyl propyl ether selectivity of 34 %. Measured formation rates, kinetic isotope effects, and site titrations suggest that ester reduction involves a bifunctional mechanism that implicates the stepwise addition of H* atoms to the carbonyl to form hemiacetals on the metal sites, followed by hemiacetal diffusion to a nearby Brønsted acid site to dehydrate to ethers or decompose to alcohol and aldehyde. The rates of reduction of propyl acetate appear to be determined by the H* addition to the carbonyl and by the C−O cleavage of hemiacetal.

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