TY  - 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 .

TY  - 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/123456789/6312
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  - Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether
VL  - 25
SP  - 9720
EP  - 9732
DO  - 10.1039/D3GC01814H
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 = "Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether",
volume = "25",
pages = "9720-9732",
doi = "10.1039/D3GC01814H"
}

Lin, F., Petrovic, P. V., Tse, H., Erythropel, H., Lam, J. C.,& Anastas, P.. (2023). Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether. in Green Chemistry
Royal Society of Chemistry., 25, 9720-9732.
https://doi.org/10.1039/D3GC01814H

Lin F, Petrovic PV, Tse H, Erythropel H, Lam JC, 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. in Green Chemistry. 2023;25:9720-9732.
doi:10.1039/D3GC01814H .

Lin, Fang, Petrovic, Predrag V., Tse, Ho-Yin, Erythropel, Hanno, Lam, Jason Chun-Ho, Anastas, Paul, "Mechanistic investigation of a Ni-catalyzed electrochemical reductive cleavage of the α-O-4 bond in the lignin model compound benzyl phenyl ether" in Green Chemistry, 25 (2023):9720-9732,
https://doi.org/10.1039/D3GC01814H . .

TY  - JOUR
AU  - Lin, Fang
AU  - Tse, Ho-Yin
AU  - Erythropel, Hanno
AU  - Petrovic, Predrag V.
AU  - Garedew, Mahlet
AU  - Chen, Jinshan
AU  - Lam, Jason Chun-Ho
AU  - Anastas, Paul
PY  - 2022
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/6311
AB  - Current catalytichydrogenolysis of ligninC–Obonds, which is crucial for lignin valorization, often requiresanoblemetalcatalystor/andharshconditionssuchaselevatedtemperaturesandhighpressures. Herein,we report ahighlyselectiveelectrochemical protocol toreductivelycleave thebenzylicC–O bondoftheα-O-4ligninmodelcompoundbenzylphenylether(BPE)atroomtemperatureandambient pressure.NearlycompleteconversionofBPEtotolueneandphenol inmethanolwasachievedinanundividedcellusingNi foamatboththeanodeandcathode,withyieldsof97%and30%,respectively.Usinga dividedcell,yieldsof90%(toluene)and84%(phenol)couldbeachievedusinginexpensivecarbonpaper asthecathodewhenNi(II)saltswereaddedtothecathodechamber.Notably,otherdivalentmetalsalts didnotleadtoanyproductformation,suggestingauniqueroleofNi ionsinbenzylicC–Obondcleavage. Further,asubstratescopestudyrevealedthesuitabilityof themethodforavarietyofsubstitutedBPEs. Thisworkprovidesaneconomical andenvironmentally friendlymethodforselectivecleavageofC–O bondsinbenzylicethersasmodelcompoundsforlignin.
PB  - Royal Society of Chemistry
T2  - Green Chemistry
T1  - Supporting information for the article: Lin, F.; Tse, H.-Y.; Erythropel, H.; Petrovic, P.V.; Garedew, M.;Chen, J.;Lam, J.C.-H.; Anastas, P. Development of a Ni-Promoted, Selective Electrochemical Reductive Cleavage of the C-O bond in Lignin Model Compound Benzyl Phenyl Ether, Green Chem., 2022, 24, 6295-6305, DOI:10.1039/d2gc01510b
VL  - 24
UR  - https://hdl.handle.net/21.15107/rcub_cherry_6311
ER  - 

@article{
author = "Lin, Fang and Tse, Ho-Yin and Erythropel, Hanno and Petrovic, Predrag V. and Garedew, Mahlet and Chen, Jinshan and Lam, Jason Chun-Ho and Anastas, Paul",
year = "2022",
abstract = "Current catalytichydrogenolysis of ligninC–Obonds, which is crucial for lignin valorization, often requiresanoblemetalcatalystor/andharshconditionssuchaselevatedtemperaturesandhighpressures. Herein,we report ahighlyselectiveelectrochemical protocol toreductivelycleave thebenzylicC–O bondoftheα-O-4ligninmodelcompoundbenzylphenylether(BPE)atroomtemperatureandambient pressure.NearlycompleteconversionofBPEtotolueneandphenol inmethanolwasachievedinanundividedcellusingNi foamatboththeanodeandcathode,withyieldsof97%and30%,respectively.Usinga dividedcell,yieldsof90%(toluene)and84%(phenol)couldbeachievedusinginexpensivecarbonpaper asthecathodewhenNi(II)saltswereaddedtothecathodechamber.Notably,otherdivalentmetalsalts didnotleadtoanyproductformation,suggestingauniqueroleofNi ionsinbenzylicC–Obondcleavage. Further,asubstratescopestudyrevealedthesuitabilityof themethodforavarietyofsubstitutedBPEs. Thisworkprovidesaneconomical andenvironmentally friendlymethodforselectivecleavageofC–O bondsinbenzylicethersasmodelcompoundsforlignin.",
publisher = "Royal Society of Chemistry",
journal = "Green Chemistry",
title = "Supporting information for the article: Lin, F.; Tse, H.-Y.; Erythropel, H.; Petrovic, P.V.; Garedew, M.;Chen, J.;Lam, J.C.-H.; Anastas, P. Development of a Ni-Promoted, Selective Electrochemical Reductive Cleavage of the C-O bond in Lignin Model Compound Benzyl Phenyl Ether, Green Chem., 2022, 24, 6295-6305, DOI:10.1039/d2gc01510b",
volume = "24",
url = "https://hdl.handle.net/21.15107/rcub_cherry_6311"
}

Lin, F., Tse, H., Erythropel, H., Petrovic, P. V., Garedew, M., Chen, J., Lam, J. C.,& Anastas, P.. (2022). Supporting information for the article: Lin, F.; Tse, H.-Y.; Erythropel, H.; Petrovic, P.V.; Garedew, M.;Chen, J.;Lam, J.C.-H.; Anastas, P. Development of a Ni-Promoted, Selective Electrochemical Reductive Cleavage of the C-O bond in Lignin Model Compound Benzyl Phenyl Ether, Green Chem., 2022, 24, 6295-6305, DOI:10.1039/d2gc01510b. in Green Chemistry
Royal Society of Chemistry., 24.
https://hdl.handle.net/21.15107/rcub_cherry_6311

Lin F, Tse H, Erythropel H, Petrovic PV, Garedew M, Chen J, Lam JC, Anastas P. Supporting information for the article: Lin, F.; Tse, H.-Y.; Erythropel, H.; Petrovic, P.V.; Garedew, M.;Chen, J.;Lam, J.C.-H.; Anastas, P. Development of a Ni-Promoted, Selective Electrochemical Reductive Cleavage of the C-O bond in Lignin Model Compound Benzyl Phenyl Ether, Green Chem., 2022, 24, 6295-6305, DOI:10.1039/d2gc01510b. in Green Chemistry. 2022;24.
https://hdl.handle.net/21.15107/rcub_cherry_6311 .

Lin, Fang, Tse, Ho-Yin, Erythropel, Hanno, Petrovic, Predrag V., Garedew, Mahlet, Chen, Jinshan, Lam, Jason Chun-Ho, Anastas, Paul, "Supporting information for the article: Lin, F.; Tse, H.-Y.; Erythropel, H.; Petrovic, P.V.; Garedew, M.;Chen, J.;Lam, J.C.-H.; Anastas, P. Development of a Ni-Promoted, Selective Electrochemical Reductive Cleavage of the C-O bond in Lignin Model Compound Benzyl Phenyl Ether, Green Chem., 2022, 24, 6295-6305, DOI:10.1039/d2gc01510b" in Green Chemistry, 24 (2022),
https://hdl.handle.net/21.15107/rcub_cherry_6311 .

TY  - JOUR
AU  - Lin, Fang
AU  - Tse, Ho-Yin
AU  - Erythropel, Hanno
AU  - Petrovic, Predrag V.
AU  - Garedew, Mahlet
AU  - Chen, Jinshan
AU  - Lam, Jason Chun-Ho
AU  - Anastas, Paul
PY  - 2022
UR  - http://cherry.chem.bg.ac.rs/handle/123456789/6310
AB  - Current catalytic hydrogenolysis of lignin C–O bonds, which is crucial for lignin valorization, often requires a noble metal catalyst or/and harsh conditions such as elevated temperatures and high pressures. Herein, we report a highly selective electrochemical protocol to reductively cleave the benzylic C–O bond of the α-O-4 lignin model compound benzyl phenyl ether (BPE) at room temperature and ambient pressure. Nearly complete conversion of BPE to toluene and phenol in methanol was achieved in an undivided cell using Ni foam at both the anode and cathode, with yields of 97% and 30%, respectively. Using a divided cell, yields of 90% (toluene) and 84% (phenol) could be achieved using inexpensive carbon paper as the cathode when Ni(II) salts were added to the cathode chamber. Notably, other divalent metal salts did not lead to any product formation, suggesting a unique role of Ni ions in benzylic C–O bond cleavage. Further, a substrate scope study revealed the suitability of the method for a variety of substituted BPEs. This work provides an economical and environmentally friendly method for selective cleavage of C–O bonds in benzylic ethers as model compounds for lignin.
PB  - Royal Society of Chemistry
T2  - Green Chemistry
T1  - Development of a Ni-promoted, selective electrochemical reductive cleavage of the C–O bond in lignin model compound benzyl phenyl ether
VL  - 24
SP  - 6295
EP  - 6305
DO  - 10.1039/D2GC01510B
ER  - 

@article{
author = "Lin, Fang and Tse, Ho-Yin and Erythropel, Hanno and Petrovic, Predrag V. and Garedew, Mahlet and Chen, Jinshan and Lam, Jason Chun-Ho and Anastas, Paul",
year = "2022",
abstract = "Current catalytic hydrogenolysis of lignin C–O bonds, which is crucial for lignin valorization, often requires a noble metal catalyst or/and harsh conditions such as elevated temperatures and high pressures. Herein, we report a highly selective electrochemical protocol to reductively cleave the benzylic C–O bond of the α-O-4 lignin model compound benzyl phenyl ether (BPE) at room temperature and ambient pressure. Nearly complete conversion of BPE to toluene and phenol in methanol was achieved in an undivided cell using Ni foam at both the anode and cathode, with yields of 97% and 30%, respectively. Using a divided cell, yields of 90% (toluene) and 84% (phenol) could be achieved using inexpensive carbon paper as the cathode when Ni(II) salts were added to the cathode chamber. Notably, other divalent metal salts did not lead to any product formation, suggesting a unique role of Ni ions in benzylic C–O bond cleavage. Further, a substrate scope study revealed the suitability of the method for a variety of substituted BPEs. This work provides an economical and environmentally friendly method for selective cleavage of C–O bonds in benzylic ethers as model compounds for lignin.",
publisher = "Royal Society of Chemistry",
journal = "Green Chemistry",
title = "Development of a Ni-promoted, selective electrochemical reductive cleavage of the C–O bond in lignin model compound benzyl phenyl ether",
volume = "24",
pages = "6295-6305",
doi = "10.1039/D2GC01510B"
}

Lin, F., Tse, H., Erythropel, H., Petrovic, P. V., Garedew, M., Chen, J., Lam, J. C.,& Anastas, P.. (2022). Development of a Ni-promoted, selective electrochemical reductive cleavage of the C–O bond in lignin model compound benzyl phenyl ether. in Green Chemistry
Royal Society of Chemistry., 24, 6295-6305.
https://doi.org/10.1039/D2GC01510B

Lin F, Tse H, Erythropel H, Petrovic PV, Garedew M, Chen J, Lam JC, Anastas P. Development of a Ni-promoted, selective electrochemical reductive cleavage of the C–O bond in lignin model compound benzyl phenyl ether. in Green Chemistry. 2022;24:6295-6305.
doi:10.1039/D2GC01510B .

Lin, Fang, Tse, Ho-Yin, Erythropel, Hanno, Petrovic, Predrag V., Garedew, Mahlet, Chen, Jinshan, Lam, Jason Chun-Ho, Anastas, Paul, "Development of a Ni-promoted, selective electrochemical reductive cleavage of the C–O bond in lignin model compound benzyl phenyl ether" in Green Chemistry, 24 (2022):6295-6305,
https://doi.org/10.1039/D2GC01510B . .