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

• Published in: Green chemistry : an international journal and green chemistry resource : GC 2023-11, Vol.25 (23), p.972-9732
• Main Authors: Lin, Fang, Petrovi, Predrag V, Tse, Ho-Yin, Erythropel, Hanno C, Lam, Jason Chun-Ho, Anastas, Paul T
• Format: Article
• Language: English
• Subjects: Benzyl phenyl ether; Carbon; Catalysts; Cleavage; Electrochemistry; Electrodes; Green chemistry; Hydrogenation; Hydrogenolysis; Inert atmospheres; Investigations; Lignin; Methanol; Nickel; Nickel chloride; Phenols; Protons; Reaction mechanisms; Room temperature; Toluene; X ray photoelectron spectroscopy
• ISSN: 1463-9262; 1463-9270
• DOI: 10.1039/d3gc01814h

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 NiCl 2 ·6H 2 O 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 Ni 0 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. 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.