A Reusable Unsupported Rhenium Nanocrystalline Catalyst for Acceptorless Dehydrogenation of Alcohols through gamma-C-H Activation

Jing Yi, Purdue University
Jeffrey T. Miller, Purdue University, Argonne National Lab
Dmitry Zemlyanov, Purdue University, Birck Nanotechnology Center
Ruihong Zhang, Purdue University
Paul J. Dietrich, Purdue University
Fabio H. Ribeiro, Purdue University
Sergey Suslov, Purdue University, Birck Nanotechnology Center
Mahdi M. Abu-Omar, Purdue University

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Rhenium nanocrystalline particles (Re NPs), of 2 nm size, were prepared from NH4ReO4 under mild conditions in neat alcohol. The unsupported Re NPs convert secondary and benzylic alcohols to ketones and aldehydes, respectively, through catalytic acceptorless dehydrogenation (AD). The oxidant-and acceptor-free neat dehydrogenation of alcohols to obtain dihydrogen gas is a green and atom-economical process for making carbonyl compounds. Secondary aliphatic alcohols give quantitative conversion and yield. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Re K-edge X-ray absorption near-edge structure (XANES), and X-ray absorption fine structure (EXAFS) data confirmed the characterization of the Re NPs as metallic rhenium with surface oxidation to rhenium(IV) oxide (ReO2). Isotope labeling experiments revealed a novel gamma-CH activation mechanism for AD of alcohols.


Nanoscience and Nanotechnology