Electrochemical Aminoxyl-Mediated Oxidation of Primary Alcohols in Lignin to Carboxylic Acids: Polymer Modification and Depolymerization
Abstract
An electrochemical process has been developed for chemoselective oxidation of primary alcohols in lignin to the corresponding carboxylic acids. The electrochemical oxidation reactions proceed under mildly basic conditions and employ 2,2,6,6-tetramethyl-1-piperidine Noxyl (TEMPO) and 4-acetamido-TEMPO (ACT) as catalytic mediators. Lignin model compounds and related alcohols are used to conduct structure-reactivity studies that provide insights into the origin of the reaction selectivity. Here, the method is applied to the oxidation of lignin extracted from poplar wood chips via a mild acidolysis method, and the reaction affords a novel polyelectrolyte material. Gel permeation chromatography data for the oxidized lignin shows that this material has a molecular weight and molecular weight distribution very similar to that of the extracted lignin, but notable differences are also evident. Base titration reveals a significant increase in the acid content, and the oxidized lignin has much higher water solubility relative to the extracted lignin. Lastly, treatment of the oxidized lignin under acidic conditions results in depolymerization of the material into characterized aromatic monomers in nearly 30 wt% yield.
- Authors:
-
[1];
[2];
[1]
- Univ. of Wisconsin, Madison, WI (United States)
- Univ. of Wisconsin, Madison, WI (United States). Wisconsin Energy Inst.
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1582057
- Grant/Contract Number:
- FC02-07ER64494; SC0018409
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 141; Journal Issue: 38; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Rafiee, Mohammad, Alherech, Manar, Karlen, Steven D., and Stahl, Shannon S. Electrochemical Aminoxyl-Mediated Oxidation of Primary Alcohols in Lignin to Carboxylic Acids: Polymer Modification and Depolymerization. United States: N. p., 2019.
Web. doi:10.1021/jacs.9b07243.
Rafiee, Mohammad, Alherech, Manar, Karlen, Steven D., & Stahl, Shannon S. Electrochemical Aminoxyl-Mediated Oxidation of Primary Alcohols in Lignin to Carboxylic Acids: Polymer Modification and Depolymerization. United States. https://doi.org/10.1021/jacs.9b07243
Rafiee, Mohammad, Alherech, Manar, Karlen, Steven D., and Stahl, Shannon S. Wed .
"Electrochemical Aminoxyl-Mediated Oxidation of Primary Alcohols in Lignin to Carboxylic Acids: Polymer Modification and Depolymerization". United States. https://doi.org/10.1021/jacs.9b07243. https://www.osti.gov/servlets/purl/1582057.
@article{osti_1582057,
title = {Electrochemical Aminoxyl-Mediated Oxidation of Primary Alcohols in Lignin to Carboxylic Acids: Polymer Modification and Depolymerization},
author = {Rafiee, Mohammad and Alherech, Manar and Karlen, Steven D. and Stahl, Shannon S.},
abstractNote = {An electrochemical process has been developed for chemoselective oxidation of primary alcohols in lignin to the corresponding carboxylic acids. The electrochemical oxidation reactions proceed under mildly basic conditions and employ 2,2,6,6-tetramethyl-1-piperidine Noxyl (TEMPO) and 4-acetamido-TEMPO (ACT) as catalytic mediators. Lignin model compounds and related alcohols are used to conduct structure-reactivity studies that provide insights into the origin of the reaction selectivity. Here, the method is applied to the oxidation of lignin extracted from poplar wood chips via a mild acidolysis method, and the reaction affords a novel polyelectrolyte material. Gel permeation chromatography data for the oxidized lignin shows that this material has a molecular weight and molecular weight distribution very similar to that of the extracted lignin, but notable differences are also evident. Base titration reveals a significant increase in the acid content, and the oxidized lignin has much higher water solubility relative to the extracted lignin. Lastly, treatment of the oxidized lignin under acidic conditions results in depolymerization of the material into characterized aromatic monomers in nearly 30 wt% yield.},
doi = {10.1021/jacs.9b07243},
journal = {Journal of the American Chemical Society},
number = 38,
volume = 141,
place = {United States},
year = {Wed Sep 04 00:00:00 EDT 2019},
month = {Wed Sep 04 00:00:00 EDT 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 92 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Lignin Biosynthesis
journal, June 2003
- Boerjan, Wout; Ralph, John; Baucher, Marie
- Annual Review of Plant Biology, Vol. 54, Issue 1, p. 519-546
Valorization of Biomass: Deriving More Value from Waste
journal, August 2012
- Tuck, C. O.; Perez, E.; Horvath, I. T.
- Science, Vol. 337, Issue 6095, p. 695-699
Recent Industrial Applications of Lignin: A Sustainable Alternative to Nonrenewable Materials
journal, April 2002
- Lora, Jairo H.; Glasser, Wolfgang G.
- Journal of Polymers and the Environment, Vol. 10, Issue 1/2, p. 39-48
Value-adding to cellulosic ethanol: Lignin polymers
journal, March 2011
- Doherty, William O. S.; Mousavioun, Payam; Fellows, Christopher M.
- Industrial Crops and Products, Vol. 33, Issue 2
Progress in Green Polymer Composites from Lignin for Multifunctional Applications: A Review
journal, April 2014
- Thakur, Vijay Kumar; Thakur, Manju Kumari; Raghavan, Prasanth
- ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 5
Chemical modification of lignins: Towards biobased polymers
journal, July 2014
- Laurichesse, Stéphanie; Avérous, Luc
- Progress in Polymer Science, Vol. 39, Issue 7, p. 1266-1290
Vanillin Production from Lignin and Its Use as a Renewable Chemical
journal, December 2015
- Fache, Maxence; Boutevin, Bernard; Caillol, Sylvain
- ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 1
Lignin-based hydrogels: A review of preparation, properties, and application
journal, August 2019
- Meng, Yi; Lu, Jie; Cheng, Yi
- International Journal of Biological Macromolecules, Vol. 135
The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
journal, June 2010
- Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L.
- Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599
Liquid fuels, hydrogen and chemicals from lignin A critical review
journal, May 2013
- Azadi, Pooya; Inderwildi, Oliver R.; Farnood, Ramin
- Renewable and Sustainable Energy Reviews, Vol. 21, p. 506-523
Biomass conversion: Lignin up for break-down
journal, December 2014
- Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.
- Nature Chemistry, Vol. 6, Issue 12, p. 1035-1036
Lignin transformations for high value applications: towards targeted modifications using green chemistry
journal, January 2017
- Gillet, S.; Aguedo, M.; Petitjean, L.
- Green Chemistry, Vol. 19, Issue 18
Lignin valorization through integrated biological funneling and chemical catalysis
journal, August 2014
- Linger, J. G.; Vardon, D. R.; Guarnieri, M. T.
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 33, p. 12013-12018
Transition-metal catalyzed valorization of lignin: the key to a sustainable carbon-neutral future
journal, January 2016
- Kärkäs, Markus D.; Matsuura, Bryan S.; Monos, Timothy M.
- Organic & Biomolecular Chemistry, Vol. 14, Issue 6
Chemicals from lignin: an interplay of lignocellulose fractionation, depolymerisation, and upgrading
journal, January 2018
- Schutyser, W.; Renders, T.; Van den Bosch, S.
- Chemical Society Reviews, Vol. 47, Issue 3
Bright Side of Lignin Depolymerization: Toward New Platform Chemicals
journal, January 2018
- Sun, Zhuohua; Fridrich, Bálint; de Santi, Alessandra
- Chemical Reviews, Vol. 118, Issue 2
Oxidative upgrade of lignin – Recent routes reviewed
journal, June 2013
- Lange, Heiko; Decina, Silvia; Crestini, Claudia
- European Polymer Journal, Vol. 49, Issue 6
Knocking on Wood: Base Metal Complexes as Catalysts for Selective Oxidation of Lignin Models and Extracts
journal, June 2015
- Hanson, Susan K.; Baker, R. Tom
- Accounts of Chemical Research, Vol. 48, Issue 7
Catalytic Transformation of Lignin for the Production of Chemicals and Fuels
journal, October 2015
- Li, Changzhi; Zhao, Xiaochen; Wang, Aiqin
- Chemical Reviews, Vol. 115, Issue 21, p. 11559-11624
Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis
journal, June 2016
- Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T.
- Angewandte Chemie International Edition, Vol. 55, Issue 29
Oxidative Mechanisms Involved in Lignin Degradation by White-Rot Fungi
journal, November 2001
- ten Have, Rimko; Teunissen, Pauline J. M.
- Chemical Reviews, Vol. 101, Issue 11
Pathways for degradation of lignin in bacteria and fungi
journal, January 2011
- Bugg, Timothy D. H.; Ahmad, Mark; Hardiman, Elizabeth M.
- Natural Product Reports, Vol. 28, Issue 12, p. 1883-1896
Ligninase of Phanerochaete chrysosporium. Mechanism of its degradation of the non-phenolic arylglycerol β-aryl ether substructure of lignin
journal, May 1986
- Kirk, T. K.; Tien, M.; Kersten, P. J.
- Biochemical Journal, Vol. 236, Issue 1
Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin
journal, April 2013
- Rahimi, Alireza; Azarpira, Ali; Kim, Hoon
- Journal of the American Chemical Society, Vol. 135, Issue 17, p. 6415-6418
Formic-acid-induced depolymerization of oxidized lignin to aromatics
journal, November 2014
- Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J.
- Nature, Vol. 515, Issue 7526, p. 249-252
A Photochemical Strategy for Lignin Degradation at Room Temperature
journal, January 2014
- Nguyen, John D.; Matsuura, Bryan S.; Stephenson, Corey R. J.
- Journal of the American Chemical Society, Vol. 136, Issue 4
Selective cleavage of the C α –C β linkage in lignin model compounds via Baeyer–Villiger oxidation
journal, January 2015
- Patil, Nikhil D.; Yao, Soledad G.; Meier, Mark S.
- Organic & Biomolecular Chemistry, Vol. 13, Issue 11
Copper- and Vanadium-Catalyzed Oxidative Cleavage of Lignin using Dioxygen
journal, May 2015
- Mottweiler, Jakob; Puche, Marta; Räuber, Christoph
- ChemSusChem, Vol. 8, Issue 12
Iron-catalysed oxidative cleavage of lignin and β-O-4 lignin model compounds with peroxides in DMSO
journal, January 2015
- Mottweiler, Jakob; Rinesch, Torsten; Besson, Claire
- Green Chemistry, Vol. 17, Issue 11
Two-Step, Catalytic C–C Bond Oxidative Cleavage Process Converts Lignin Models and Extracts to Aromatic Acids
journal, August 2016
- Wang, Min; Lu, Jianmin; Zhang, Xiaochen
- ACS Catalysis, Vol. 6, Issue 9
Chemoselective oxidant-free dehydrogenation of alcohols in lignin using Cp*Ir catalysts
journal, January 2016
- Zhu, Rui; Wang, Bing; Cui, Minshu
- Green Chemistry, Vol. 18, Issue 7
Promoting Lignin Depolymerization and Restraining the Condensation via an Oxidation−Hydrogenation Strategy
journal, April 2017
- Zhang, Chaofeng; Li, Hongji; Lu, Jianmin
- ACS Catalysis, Vol. 7, Issue 5
Redox Catalysis Facilitates Lignin Depolymerization
journal, June 2017
- Bosque, Irene; Magallanes, Gabriel; Rigoulet, Mathilde
- ACS Central Science, Vol. 3, Issue 6
Cobalt-Catalyzed Oxidation of the β-O-4 Bond in Lignin and Lignin Model Compounds
journal, July 2018
- Rinesch, Torsten; Bolm, Carsten
- ACS Omega, Vol. 3, Issue 7
Revisiting alkaline aerobic lignin oxidation
journal, January 2018
- Schutyser, Wouter; Kruger, Jacob S.; Robinson, Allison M.
- Green Chemistry, Vol. 20, Issue 16
Lignin Conversion to Low-Molecular-Weight Aromatics via an Aerobic Oxidation-Hydrolysis Sequence: Comparison of Different Lignin Sources
journal, January 2018
- Das, Amit; Rahimi, Alireza; Ulbrich, Arne
- ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 3
Highly Selective Oxidation and Depolymerization of α,γ‐Diol‐Protected Lignin
journal, February 2019
- Lan, Wu; de Bueren, Jean Behaghel; Luterbacher, Jeremy S.
- Angewandte Chemie International Edition, Vol. 58, Issue 9
TEMPO-mediated oxidation of softwood thermomechanical pulp
journal, September 2009
- Okita, Yusuke; Saito, Tsuguyuki; Isogai, Akira
- Holzforschung, Vol. 63, Issue 5
TEMPO-mediated oxidation of lignocellulosic fibers from date palm leaves
journal, October 2011
- Sbiai, Adil; Kaddami, Hamid; Sautereau, Henry
- Carbohydrate Polymers, Vol. 86, Issue 4
Selective TEMPO-Mediated Oxidation of Thermomechanical Pulp
journal, July 2013
- Ma, Pu; Zhai, Huamin
- BioResources, Vol. 8, Issue 3
Organocatalytic Chemoselective Primary Alcohol Oxidation and Subsequent Cleavage of Lignin Model Compounds and Lignin
journal, June 2017
- Dabral, Saumya; Hernández, José G.; Kamer, Paul C. J.
- ChemSusChem, Vol. 10, Issue 13
Oxidation of lignin and lignin β-O-4 model compounds via activated dimethyl sulfoxide
journal, January 2015
- Mobley, Justin K.; Yao, Soledad G.; Crocker, Mark
- RSC Advances, Vol. 5, Issue 127
Selective Depolymerisation of γ‐Oxidised Lignin via NHC Catalysed Redox Esterification
journal, June 2019
- Xiao, Ganyuan; Lancefield, Christopher S.; Westwood, Nicholas J.
- ChemCatChem, Vol. 11, Issue 14
Large-Scale Oxidations in the Pharmaceutical Industry †
journal, July 2006
- Caron, Stéphane; Dugger, Robert W.; Ruggeri, Sally Gut
- Chemical Reviews, Vol. 106, Issue 7
Industrial Oxidations with Organocatalyst TEMPO and Its Derivatives
journal, January 2010
- Ciriminna, Rosaria; Pagliaro, Mario
- Organic Process Research & Development, Vol. 14, Issue 1
Selective oxidation of primary alcohols mediated by nitroxyl radical in aqueous solution. Kinetics and mechanism
journal, July 1995
- de Nooy, Arjan E. J.; Besemer, Arie C.; van Bekkum, Herman
- Tetrahedron, Vol. 51, Issue 29
Mechanistic Study of the Electrocatalytic Oxidation of Alcohols by TEMPO and NHPI
journal, July 2013
- Rafiee, Mohammad; Karimi, Babak; Alizadeh, Saber
- ChemElectroChem, Vol. 1, Issue 2, p. 455-462
High-Potential Electrocatalytic O 2 Reduction with Nitroxyl/NO x Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis
journal, July 2015
- Gerken, James B.; Stahl, Shannon S.
- ACS Central Science, Vol. 1, Issue 5
Nitroxyl-mediated electrooxidation of alcohols to aldehydes and ketones
journal, June 1983
- Semmelhack, M. F.; Chou, Chuen S.; Cortes, David A.
- Journal of the American Chemical Society, Vol. 105, Issue 13
Tetramethylpiperidine N -Oxyl (TEMPO), Phthalimide N -Oxyl (PINO), and Related N -Oxyl Species: Electrochemical Properties and Their Use in Electrocatalytic Reactions
journal, April 2018
- Nutting, Jordan E.; Rafiee, Mohammad; Stahl, Shannon S.
- Chemical Reviews, Vol. 118, Issue 9
Electroorganic Synthesis 66: Selective Anodic Oxidation of Carbohydrates Mediated by TEMPO
journal, May 1999
- Schnatbaum, Karsten; Schäfer, Hans J.
- Synthesis, Vol. 1999, Issue 05
TEMPO mediated oxidation of carbohydrates using electrochemical methods
journal, April 2010
- Parpot, P.; Servat, K.; Bettencourt, A. P.
- Cellulose, Vol. 17, Issue 4
Cooxidant-free TEMPO-mediated oxidation of highly crystalline nanocellulose in water
journal, January 2014
- Carlsson, D. O.; Lindh, J.; Nyholm, L.
- RSC Adv., Vol. 4, Issue 94
Electrocatalytic upgrading of model lignin monomers with earth abundant metal electrodes
journal, January 2015
- Lam, Chun Ho; Lowe, Christy B.; Li, Zhenglong
- Green Chemistry, Vol. 17, Issue 1
Highly selective generation of vanillin by anodic degradation of lignin: a combined approach of electrochemistry and product isolation by adsorption
journal, January 2015
- Schmitt, Dominik; Regenbrecht, Carolin; Hartmer, Marius
- Beilstein Journal of Organic Chemistry, Vol. 11, p. 473-480
Anodic Degradation of Lignin at Active Transition Metal-based Alloys and Performance-enhanced Anodes
journal, September 2018
- Zirbes, Michael; Schmitt, Dominik; Beiser, Nicole
- ChemElectroChem, Vol. 6, Issue 1
Electrocatalytic Upgrading of Phenolic Compounds Observed after Lignin Pyrolysis
journal, March 2019
- Garedew, Mahlet; Young-Farhat, Daniel; Jackson, James E.
- ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 9
TEMPO-mediated electro-oxidation reactions of non-phenolic β-O-4-type lignin model compounds
journal, February 2017
- Sannami, Yumi; Kamitakahara, Hiroshi; Takano, Toshiyuki
- Holzforschung, Vol. 71, Issue 2
Electrocatalytic Alcohol Oxidation with TEMPO and Bicyclic Nitroxyl Derivatives: Driving Force Trumps Steric Effects
journal, November 2015
- Rafiee, Mohammad; Miles, Kelsey C.; Stahl, Shannon S.
- Journal of the American Chemical Society, Vol. 137, Issue 46, p. 14751-14757
Electrochemical Oxidation of Alcohols and Aldehydes to Carboxylic Acids Catalyzed by 4-Acetamido-TEMPO: An Alternative to “Anelli” and “Pinnick” Oxidations
journal, May 2018
- Rafiee, Mohammad; Konz, Zachary M.; Graaf, Matthew D.
- ACS Catalysis, Vol. 8, Issue 7
Stabilities, Regeneration Pathways, and Electrocatalytic Properties of Nitroxyl Radicals for the Electrochemical Oxidation of 5-Hydroxymethylfurfural
journal, May 2019
- Cardiel, Allison C.; Taitt, Brandon J.; Choi, Kyoung-Shin
- ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 13
Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems.
journal, April 1964
- Nicholson, R. S.; Shain, Irving
- Analytical Chemistry, Vol. 36, Issue 4, p. 706-723
Efficient Cobalt-Catalyzed Oxidative Conversion of Lignin Models to Benzoquinones
journal, May 2013
- Biannic, Berenger; Bozell, Joseph J.
- Organic Letters, Vol. 15, Issue 11
A Nuclear Magnetic Resonance Study of the Reversible Hydration of Aliphatic Aldehydes and Ketones. I. Oxygen-17 and Proton Spectra and Equilibrium Constants
journal, February 1967
- Greenzaid, P.; Luz, Z.; Samuel, David.
- Journal of the American Chemical Society, Vol. 89, Issue 4
Chemical properties of lignin from Aralia cordata
journal, January 1994
- Hibino, Takashi; Shibata, Daisuke; Ito, Takashi
- Phytochemistry, Vol. 37, Issue 2, p. 445-448
Vanillin oligomerization as a model of side reactions in lignin fragmentation
journal, July 2012
- Constant, Sandra; Robitzer, Mike; Quignard, Françoise
- Catalysis Today, Vol. 189, Issue 1, p. 123-128
Biomass conversion: attempted electrooxidation of lignin for vanillin production
journal, January 2000
- Parpot, P.; Bettencourt, A. P.; Carvalho, A. M.
- Journal of Applied Electrochemistry, Vol. 30, Issue 6, p. 727-731
Reaction pathways and mechanisms of the electrochemical degradation of phenol on different electrodes
journal, May 2005
- Li, Xiao-yan; Cui, Yu-hong; Feng, Yu-jie
- Water Research, Vol. 39, Issue 10
Electrode passivation caused by polymerization of different phenolic compounds
journal, October 2006
- Ferreira, Marystela; Varela, Hamilton; Torresi, Roberto M.
- Electrochimica Acta, Vol. 52, Issue 2
The Base-catalyzed Cleavage of β-Hydroxy Acids
journal, August 1956
- Rondestvedt, Christian S.; Rowley, M. Eugene
- Journal of the American Chemical Society, Vol. 78, Issue 15, p. 3804-3811
Studies on Lignin and Related Compounds. LXIX. Isolation of 1-(4-Hydroxy-3-methoxyphenyl)-2-propanone and 1-Ethoxy-1-(4-hydroxy-3-methoxyphenyl)-2-propanone from the Ethanolysis Products of Spruce Wood 1
journal, June 1943
- West, Einar; MacInnes, A. S.; Hibbert, Harold
- Journal of the American Chemical Society, Vol. 65, Issue 6
Studies on Lignin and Related Compounds. LXXIX. Synthesis and Properties of 3-Hydroxy-1-(3,4-dimethoxyphenyl)-2-propanone1
journal, April 1944
- Fisher, Herbert E.; Kulka, Marshall; Hibbert, Harold
- Journal of the American Chemical Society, Vol. 66, Issue 4
Aromatic Monomers by in Situ Conversion of Reactive Intermediates in the Acid-Catalyzed Depolymerization of Lignin
journal, June 2015
- Deuss, Peter J.; Scott, Martin; Tran, Fanny
- Journal of the American Chemical Society, Vol. 137, Issue 23
Production of Water-Soluble Hardwood Kraft Lignin via Sulfomethylation Using Formaldehyde and Sodium Sulfite
journal, May 2015
- Konduri, Mohan K. R.; Fatehi, Pedram
- ACS Sustainable Chemistry & Engineering, Vol. 3, Issue 6
Strategies for the Conversion of Lignin to High-Value Polymeric Materials: Review and Perspective
journal, December 2015
- Upton, Brianna M.; Kasko, Andrea M.
- Chemical Reviews, Vol. 116, Issue 4, p. 2275-2306
Production of Flocculants, Adsorbents, and Dispersants from Lignin
journal, April 2018
- Chen, Jiachuan; Eraghi Kazzaz, Armin; AlipoorMazandarani, Niloofar
- Molecules, Vol. 23, Issue 4
Works referencing / citing this record:
Guidelines for performing lignin-first biorefining
journal, January 2021
- Abu-Omar, Mahdi M.; Barta, Katalin; Beckham, Gregg T.
- Energy & Environmental Science, Vol. 14, Issue 1