Campus Units

Chemistry, Biochemistry, Biophysics and Molecular Biology, Roy J. Carver Department of, Ames Laboratory

Document Type

Article

Publication Version

Submitted Manuscript

Publication Date

8-20-2021

Journal or Book Title

ACS Catalysis

Volume

11

Issue

16

First Page

10553

Last Page

10564

DOI

10.1021/acscatal.1c02716

Abstract

The hydrodehalogenation (HDH) of halophenols is efficiently catalyzed by palladium supported on high-surface ceria (Pd/CeO2) under mild conditions (35 °C, 1 atm H2). A combination of NMR, diffuse reflectance infrared Fourier transform spectroscopy, Raman spectroscopy, and XPS studies and HDH kinetics of substituted halobenzenes suggests that the reaction proceeds mainly via a sequence of dissociative adsorption of phenolic hydroxyl onto the support, oxidative addition of the C–halogen bond to Pd, and reductive elimination to give phenol and hydrogen halide. The dissociative adsorption of the −OH group onto oxygen vacancies of the ceria support results in an electron-rich intermediate that facilitates the turnover-limiting reductive elimination step. In contrast, the direct pathway catalyzed by Pd without dissociative adsorption of the reactants on the support takes place at a slower rate. The mechanistic insights gained in this study were used to modify the reaction conditions for enabling HDH of recalcitrant halides such as fluorides and iodides.

Comments

This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in ACS Catalysis, copyright © American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/acscatal.1c02716 Posted with permission.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Published Version

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