TY - JOUR
T1 - Ester Reduction with H2 on Bifunctional Metal-Acid Catalysts
T2 - Implications of Metal Identity on Rates and Selectivities
AU - Berdugo-Díaz, Claudia E.
AU - Manetsch, Melissa T.
AU - Sik Yun, Yang
AU - Lee, Jieun
AU - Luo, Jing
AU - Chen, Xue
AU - Flaherty, David W.
N1 - Publisher Copyright:
© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
PY - 2023/3/27
Y1 - 2023/3/27
N2 - 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.
AB - 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.
KW - Bifunctional Catalysis
KW - Hydrogenation
KW - Hydrogenolysis
KW - Transition Metals
KW - Zeolites
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U2 - 10.1002/anie.202216165
DO - 10.1002/anie.202216165
M3 - Article
C2 - 36755505
AN - SCOPUS:85148940604
SN - 1433-7851
VL - 62
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 14
M1 - e202216165
ER -