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

Claudia E. Berdugo-Díaz, Melissa T. Manetsch, Yang Sik Yun, Jieun Lee, Jing Luo, Xue Chen, David W. Flaherty

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish (US)
Article numbere202216165
JournalAngewandte Chemie - International Edition
Volume62
Issue number14
DOIs
StatePublished - Mar 27 2023

Keywords

  • Bifunctional Catalysis
  • Hydrogenation
  • Hydrogenolysis
  • Transition Metals
  • Zeolites

ASJC Scopus subject areas

  • General Chemistry
  • Catalysis

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