Issue 23, 2023

Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether

Abstract

The electrochemical reductive cleavage of the C–O bond in the lignin α-O-4 model compound benzyl phenyl ether (BPE) at room temperature was investigated using earth-abundant nickel as a catalyst in methanol. Experiments using a divided cell setup using either NiCl2·6H2O salt or pre-deposited Ni on a carbon paper cathode (Ni/CP) under an inert atmosphere revealed the essential role of freshly and uniformly deposited Ni0 on the electrode surface for the reductive, catalytic cleavage to yield phenol and toluene. To better understand the reaction mechanism, the surface morphology and composition of the Ni/CP electrode were investigated by SEM, XRD, and XPS. Additionally, the role of methanol as a proton donor was established, and electrochemical hydrogenation/hydrogenolysis (ECH) experiments of BPE with sterically hindered substituents revealed that the reaction mechanism shares similarities with Pd/C hydrogenation/hydrogenolysis chemistry. DFT calculations further supported this mechanistic route and were consistent with the experimental observations. Based on both experimental and calculation results, a mechanism including (1) the interaction of the benzylic side of BPE with the catalyst surface, (2) adsorbed hydrogen interacting with the benzylic carbon to induce C–O bond scission, and (3) proton transfer to the phenoxy anion from the methanol was proposed.

Graphical abstract: Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether

Supplementary files

Article information

Article type
Paper
Submitted
30 May 2023
Accepted
09 Oct 2023
First published
13 Oct 2023

Green Chem., 2023,25, 9720-9732

Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether

F. Lin, P. V. Petrović, H. Tse, H. C. Erythropel, J. C. Lam and P. T. Anastas, Green Chem., 2023, 25, 9720 DOI: 10.1039/D3GC01814H

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