Supportin information for the article: Lin, F.; Petrovic, P.V.; Tse, H.-Y.; Erythropel, H.; Lam, J.C.-H.; Anastas, P. Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether, Green Chem. 2023, 25, 9720-9732, DOI: https://doi.org/10.1039/D3GC01814H
Authors
Lin, FangPetrovic, Predrag V.
Tse, Ho-Yin
Erythropel, Hanno
Lam, Jason Chun-Ho
Anastas, Paul
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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 mechanist...ic 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.
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Green Chemistry, 2023, 25Publisher:
- Royal Society of Chemistry
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- Supplementary material for: https://doi.org/10.1039/d3gc01814h
- Related to published version: https://cherry.chem.bg.ac.rs/handle/123456789/6312
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https://doi.org/10.1039/d3gc01814h - Referenced by
https://cherry.chem.bg.ac.rs/handle/123456789/6312
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Inovacioni centar / Innovation CentreTY - JOUR AU - Lin, Fang AU - Petrovic, Predrag V. AU - Tse, Ho-Yin AU - Erythropel, Hanno AU - Lam, Jason Chun-Ho AU - Anastas, Paul PY - 2023 UR - http://cherry.chem.bg.ac.rs/handle/123456789/6313 AB - 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. PB - Royal Society of Chemistry T2 - Green Chemistry T1 - Supportin information for the article: Lin, F.; Petrovic, P.V.; Tse, H.-Y.; Erythropel, H.; Lam, J.C.-H.; Anastas, P. Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether, Green Chem. 2023, 25, 9720-9732, DOI: https://doi.org/10.1039/D3GC01814H VL - 25 UR - https://hdl.handle.net/21.15107/rcub_cherry_6313 ER -
@article{ author = "Lin, Fang and Petrovic, Predrag V. and Tse, Ho-Yin and Erythropel, Hanno and Lam, Jason Chun-Ho and Anastas, Paul", year = "2023", 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.", publisher = "Royal Society of Chemistry", journal = "Green Chemistry", title = "Supportin information for the article: Lin, F.; Petrovic, P.V.; Tse, H.-Y.; Erythropel, H.; Lam, J.C.-H.; Anastas, P. Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether, Green Chem. 2023, 25, 9720-9732, DOI: https://doi.org/10.1039/D3GC01814H", volume = "25", url = "https://hdl.handle.net/21.15107/rcub_cherry_6313" }
Lin, F., Petrovic, P. V., Tse, H., Erythropel, H., Lam, J. C.,& Anastas, P.. (2023). Supportin information for the article: Lin, F.; Petrovic, P.V.; Tse, H.-Y.; Erythropel, H.; Lam, J.C.-H.; Anastas, P. Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether, Green Chem. 2023, 25, 9720-9732, DOI: https://doi.org/10.1039/D3GC01814H. in Green Chemistry Royal Society of Chemistry., 25. https://hdl.handle.net/21.15107/rcub_cherry_6313
Lin F, Petrovic PV, Tse H, Erythropel H, Lam JC, Anastas P. Supportin information for the article: Lin, F.; Petrovic, P.V.; Tse, H.-Y.; Erythropel, H.; Lam, J.C.-H.; Anastas, P. Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether, Green Chem. 2023, 25, 9720-9732, DOI: https://doi.org/10.1039/D3GC01814H. in Green Chemistry. 2023;25. https://hdl.handle.net/21.15107/rcub_cherry_6313 .
Lin, Fang, Petrovic, Predrag V., Tse, Ho-Yin, Erythropel, Hanno, Lam, Jason Chun-Ho, Anastas, Paul, "Supportin information for the article: Lin, F.; Petrovic, P.V.; Tse, H.-Y.; Erythropel, H.; Lam, J.C.-H.; Anastas, P. Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether, Green Chem. 2023, 25, 9720-9732, DOI: https://doi.org/10.1039/D3GC01814H" in Green Chemistry, 25 (2023), https://hdl.handle.net/21.15107/rcub_cherry_6313 .