Electrochemical Reduction Selectivity of Crotonaldehyde on Copper

Barton, Zachary J.; Garrett, Grey H.; Kurtyka, Nicholas; Spivey, Taylor D.; Schaidle, Joshua A.; Holewinski, Adam

doi:10.1007/s10800-020-01415-2

Electrochemical Reduction Selectivity of Crotonaldehyde on Copper

Journal Article · Thu Apr 02 00:00:00 EDT 2020 · Journal of Applied Electrochemistry

DOI:https://doi.org/10.1007/s10800-020-01415-2· OSTI ID:1660110

Barton, Zachary J.; Garrett, Grey H.; Kurtyka, Nicholas; Spivey, Taylor D.; ; Holewinski, Adam

Lignocellulosic waste is a potential feedstock for the generation of fuels and commodity chemicals, but existing conversion methods are too cost-intensive to be viable long-term solutions. Electrochemical reductions are promising for decentralized biomass valorization due to their modular scaling and capacity to run intermittently and without high temperatures or pressures. Using crotonaldehyde as a multi-functional model compound for the many partially unsaturated oxygenates found in processed biomass, we here demonstrate the production of butanal, butanol, butene, and butane (variously useful as commodity chemicals and major components of liquified petroleum gas) under ambient conditions by reductive bulk electrolysis with a copper mesh working electrode. We identify an optimum potential for reduced organic production under the reaction conditions and compare product distributions from reductions of intermediate species to further propose branching reaction pathways. Though butanal is typically the most abundant product from crotonaldehyde reduction, most of the butene and butane appear to result from a pathway involving initial reduction of the aldehyde group. We discuss evidence that selectivity is driven by interplay between crotonaldehyde reduction, local pH shifts due to the hydrogen evolution reaction, and changes in site reactivity and availability due to electrode fouling. This demonstration of model electrochemical biomass valorization also serves to inform further exploration into reduction of multi-functional molecules and electrochemical biomass processing in general.

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE National Renewable Energy Laboratory (NREL), Laboratory Directed Research and Development (LDRD) Program

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 1660110

Report Number(s):: NREL/JA-5100-75748; MainId:6536; UUID:869f95e5-812d-ea11-9c2f-ac162d87dfe5; MainAdminID:14119

Journal Information:: Journal of Applied Electrochemistry, Journal Name: Journal of Applied Electrochemistry Vol. 51

Country of Publication:: United States

Language:: English

References (59)

Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis Rinaldi, Roberto; Jastrzebski, Robin; Clough, Matthew T. Angewandte Chemie International Edition, Vol. 55, Issue 29 https://doi.org/10.1002/anie.201510351	journal	June 2016
The Importance of Cannizzaro-Type Reactions during Electrocatalytic Reduction of Carbon Dioxide Birdja, Yuvraj Y.; Koper, Marc T. M. Journal of the American Chemical Society, Vol. 139, Issue 5 https://doi.org/10.1021/jacs.6b12008	journal	January 2017
Hydrogenation of the α,β-Unsaturated Aldehydes Acrolein, Crotonaldehyde, and Prenal over Pt Single Crystals: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study Kliewer, Christopher J.; Bieri, Marco; Somorjai, Gabor A. Journal of the American Chemical Society, Vol. 131, Issue 29 https://doi.org/10.1021/ja8092532	journal	July 2009
Electrodimerization of crotonic aldehyde in aqueous media on a mercury electrode González-Arjona, D.; Rueda, M.; Ruiz, J. J. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 239, Issue 1-2 https://doi.org/10.1016/0022-0728(88)80283-3	journal	January 1988
Reforming Biomass Derived Pyrolysis Bio-oil Aqueous Phase to Fuels Mukarakate, Calvin; Evans, Robert J.; Deutch, Steve Energy & Fuels, Vol. 31, Issue 2 https://doi.org/10.1021/acs.energyfuels.6b02463	journal	January 2017
High-Octane Gasoline from Biomass: Experimental, Economic, and Environmental Assessment Dupuis, Daniel P.; Grim, R. Gary; Nelson, Eric Applied Energy, Vol. 241 https://doi.org/10.1016/j.apenergy.2019.02.064	journal	May 2019
The Base-catalyzed Self-condensation of 2-Ethyl-2-hexenal. I. Formation of a Cyclic Aldol, C ₁₆ H ₂₈ O ₂ ¹ Nielsen, Arnold T. Journal of the American Chemical Society, Vol. 79, Issue 10 https://doi.org/10.1021/ja01567a044	journal	May 1957
Selective hydrogenation of ά,β-unsaturated aldehydes and other C=O and C=C bonds containing compounds Claus, Peter Topics In Catalysis, Vol. 5, Issue 1/4, p. 51-62 https://doi.org/10.1023/A:1019177330810	journal	January 1998
Aqueous metal recovery techniques from e-scrap: Hydrometallurgy in recycling Tuncuk, A.; Stazi, V.; Akcil, A. Minerals Engineering, Vol. 25, Issue 1 https://doi.org/10.1016/j.mineng.2011.09.019	journal	January 2012
Identifying “Optimal” Electrocatalysts: Impact of Operating Potential and Charge Transfer Model Román, Alex M.; Dudoff, Jessica; Baz, Adam ACS Catalysis, Vol. 7, Issue 12 https://doi.org/10.1021/acscatal.7b03235	journal	November 2017
Electrochemical reduction of geranial, farnesal, and crotonaldehyde Johnston, Judy C.; Faulkner, James D.; Mandell, Leon. The Journal of Organic Chemistry, Vol. 41, Issue 15 https://doi.org/10.1021/jo00877a021	journal	July 1976
Valorization of aqueous waste streams from thermochemical biorefineries Wilson, A. Nolan; Dutta, Abhijit; Black, Brenna A. Green Chemistry, Vol. 21, Issue 15 https://doi.org/10.1039/C9GC00902G	journal	January 2019
Electrocatalytic hydrogenation of alkyl-substituted phenols in aqueous solutions at a Raney nickel electrode in the presence of a non-micelle-forming cationic surfactant Ilikti, H.; Rekik, N.; Thomalla, M. Journal of Applied Electrochemistry, Vol. 34, Issue 2, p. 127-136 https://doi.org/10.1023/B:JACH.0000009932.06652.a0	journal	February 2004
Co-electrolysis of CO2 and glycerol as a pathway to carbon chemicals with improved technoeconomics due to low electricity consumption Verma, Sumit; Lu, Shawn; Kenis, Paul J. A. Nature Energy, Vol. 4, Issue 6 https://doi.org/10.1038/s41560-019-0374-6	journal	April 2019
Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates Chadderdon, Xiaotong H.; Chadderdon, David J.; Matthiesen, John E. Journal of the American Chemical Society, Vol. 139, Issue 40 https://doi.org/10.1021/jacs.7b06331	journal	September 2017
Liquid-Phase Catalytic Processing of Biomass-Derived Oxygenated Hydrocarbons to Fuels and Chemicals Chheda, Juben N.; Huber, George W.; Dumesic, James A. Angewandte Chemie International Edition, Vol. 46, Issue 38, p. 7164-7183 https://doi.org/10.1002/anie.200604274	journal	September 2007
Characterization of Various Fast-Pyrolysis Bio-Oils by NMR Spectroscopy ^† Mullen, Charles A.; Strahan, Gary D.; Boateng, Akwasi A. Energy & Fuels, Vol. 23, Issue 5 https://doi.org/10.1021/ef801048b	journal	May 2009
A rotating disc study of crotyl alcohol reduction Chien, Chen-Yie; Schade, Georg Electrochimica Acta, Vol. 33, Issue 1 https://doi.org/10.1016/0013-4686(88)80032-X	journal	January 1988
Mild electrocatalytic hydrogenation of lactic acid to lactaldehyde and propylene glycol Dalavoy, T.; Jackson, J.; Swain, G. Journal of Catalysis, Vol. 246, Issue 1 https://doi.org/10.1016/j.jcat.2006.11.009	journal	February 2007
Elucidating Acidic Electro-Oxidation Pathways of Furfural on Platinum Román, Alex M.; Hasse, Joseph C.; Medlin, J. Will ACS Catalysis, Vol. 9, Issue 11 https://doi.org/10.1021/acscatal.9b02656	journal	September 2019
CVI.—Electrolytic reduction. Part VI. Unsaturated aldehydes and ketones Law, Herbert Drake J. Chem. Soc., Trans., Vol. 101, Issue 0 https://doi.org/10.1039/CT9120101016	journal	January 1912
Catalysis for the Valorization of Exhaust Carbon: from CO ₂ to Chemicals, Materials, and Fuels. Technological Use of CO ₂ Aresta, Michele; Dibenedetto, Angela; Angelini, Antonella Chemical Reviews, Vol. 114, Issue 3 https://doi.org/10.1021/cr4002758	journal	November 2013
Progress in Accurate Chemical Kinetic Modeling, Simulations, and Parameter Estimation for Heterogeneous Catalysis Matera, Sebastian; Schneider, William F.; Heyden, Andreas ACS Catalysis, Vol. 9, Issue 8 https://doi.org/10.1021/acscatal.9b01234	journal	June 2019
Polarographic reduction of aldehydes and ketones Barnes, D.; Zuman, P. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 46, Issue 2 https://doi.org/10.1016/S0022-0728(73)80140-8	journal	September 1973
Progress and Perspectives of Electrochemical CO ₂ Reduction on Copper in Aqueous Electrolyte Nitopi, Stephanie; Bertheussen, Erlend; Scott, Soren B. Chemical Reviews, Vol. 119, Issue 12 https://doi.org/10.1021/acs.chemrev.8b00705	journal	April 2019
The electrochemistry of α-β unsaturated aldehydes Vadaszy, Richard; Cover, Richard E. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 49, Issue 3 https://doi.org/10.1016/S0022-0728(74)80175-0	journal	January 1974
The behaviour of a platinized-platinum electrode in solutions of alcohols containing more than one carbon atom, aldehydes and formic acid Podlovchenko, B. I.; Petry, O. A.; Frumkin, A. N. Journal of Electroanalytical Chemistry (1959), Vol. 11, Issue 1 https://doi.org/10.1016/0022-0728(66)80053-0	journal	January 1966
Electrocatalytic Upgrading of Biomass‐Derived Intermediate Compounds to Value‐Added Products Li, Kui; Sun, Yujie Chemistry – A European Journal, Vol. 24, Issue 69 https://doi.org/10.1002/chem.201803319	journal	June 2018
A mechanistic investigation on the electrocatalytic reduction of aliphatic ketones at platinum Bondue, C. J.; Koper, M. T. M. Journal of Catalysis, Vol. 369 https://doi.org/10.1016/j.jcat.2018.11.019	journal	January 2019
Electrochemistry for the generation of renewable chemicals: electrochemical conversion of levulinic acid dos Santos, Tatiane R.; Nilges, Peter; Sauter, Waldemar RSC Advances, Vol. 5, Issue 34 https://doi.org/10.1039/C4RA16303F	journal	January 2015
Production of Fuels and Chemicals from Biomass: Condensation Reactions and Beyond Wu, Lipeng; Moteki, Takahiko; Gokhale, Amit A. Chem, Vol. 1, Issue 1 https://doi.org/10.1016/j.chempr.2016.05.002	journal	July 2016
Modulating Electrocatalysis on Graphene Heterostructures: Physically Impermeable Yet Electronically Transparent Electrodes Hui, Jingshu; Pakhira, Srimanta; Bhargava, Richa ACS Nano, Vol. 12, Issue 3 https://doi.org/10.1021/acsnano.8b00702	journal	February 2018
Electrocatalytic reduction of simple α,β unsaturated aliphatic carbonyl compounds on a platinized platinum electrode in acid media Horanyi, G.; Torkos, K. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 136, Issue 2 https://doi.org/10.1016/0022-0728(82)85051-1	journal	June 1982
Reductive cleavage of C-OH bonds in allyl position-formation of gaseous products in the course of the cathodic reduction of some simple unsaturated alcohols Horányi, G.; Inzelt, G.; Torkos, K. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 101, Issue 1 https://doi.org/10.1016/S0022-0728(79)80082-0	journal	July 1979
Advancing the Frontiers in Nanocatalysis, Biointerfaces, and Renewable Energy Conversion by Innovations of Surface Techniques Somorjai, Gabor A.; Frei, Heinz; Park, Jeong Y. Journal of the American Chemical Society, Vol. 131, Issue 46, p. 16589-16605 https://doi.org/10.1021/ja9061954	journal	November 2009
Fundamentals and Challenges of Electrochemical CO2 Reduction Using Two-Dimensional Materials Sun, Zhenyu; Ma, Tao; Tao, Hengcong Chem, Vol. 3, Issue 4 https://doi.org/10.1016/j.chempr.2017.09.009	journal	October 2017
Implementation of concepts derived from model compound studies in the separation and conversion of bio-oil to fuel Resasco, Daniel E.; Crossley, Steven P. Catalysis Today, Vol. 257 https://doi.org/10.1016/j.cattod.2014.06.037	journal	November 2015
The Mechanism of the Kolbe Electrosynthesis and Allied Reactions Glasstone, S.; Hickling, A. Transactions of The Electrochemical Society, Vol. 75, Issue 1 https://doi.org/10.1149/1.3498383	journal	January 1939
Revealing Structural Effects: Electrochemical Reactions of Butanols on Platinum Rodríguez, José L.; Souto, Ricardo M.; Fernández-Mérida, Luis Chemistry - A European Journal, Vol. 8, Issue 9 https://doi.org/10.1002/1521-3765(20020503)8:9<2134::AID-CHEM2134>3.0.CO;2-C	journal	May 2002
Techno-economic analysis of biobased chemicals production via integrated catalytic processing Brown, Tristan R.; Zhang, Yanan; Hu, Guiping Biofuels, Bioproducts and Biorefining, Vol. 6, Issue 1 https://doi.org/10.1002/bbb.344	journal	January 2012
The Acid-Catalyzed Isomerization of α- and cis- and trans-γ-Methylallyl Alcohols Young, W. G.; Franklin, J. S. Journal of the American Chemical Society, Vol. 88, Issue 4 https://doi.org/10.1021/ja00956a034	journal	February 1966
Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide Kortlever, Ruud; Shen, Jing; Schouten, Klaas Jan P. The Journal of Physical Chemistry Letters, Vol. 6, Issue 20 https://doi.org/10.1021/acs.jpclett.5b01559	journal	September 2015
Production of drop-in fuels from biomass at high selectivity by combined microbial and electrochemical conversion Urban, Carolin; Xu, Jiajie; Sträuber, Heike Energy & Environmental Science, Vol. 10, Issue 10 https://doi.org/10.1039/c7ee01303e	journal	January 2017
A perspective on the modeling of biomass processing Guo, Na; Caratzoulas, Stavros; Doren, Douglas J. Energy & Environmental Science, Vol. 5, Issue 5 https://doi.org/10.1039/c2ee02663e	journal	January 2012
Growing the Bioeconomy through Catalysis: A Review of Recent Advancements in the Production of Fuels and Chemicals from Syngas-Derived Oxygenates Grim, R. Gary; To, Anh T.; Farberow, Carrie A. ACS Catalysis, Vol. 9, Issue 5 https://doi.org/10.1021/acscatal.8b03945	journal	April 2019
The Interconversion of Crotyl Alcohol and Methylvinylcarbinol in Aqueous Sulfuric acid Young, William G.; Nozaki, Kenzie.; Warner, Ruth. Journal of the American Chemical Society, Vol. 61, Issue 9 https://doi.org/10.1021/ja01878a521	journal	September 1939
Electrochemical oxidation and indirect electrochemical reduction of simple secondary alcohols Horanyi, G.; Vertes, G.; K�nig, P. Die Naturwissenschaften, Vol. 60, Issue 11 https://doi.org/10.1007/BF00603259	journal	November 1973
Towards sustainable hydrocarbon fuels with biomass fast pyrolysis oil and electrocatalytic upgrading Lam, Chun Ho; Das, Sabyasachi; Erickson, Nichole C. Sustainable Energy & Fuels, Vol. 1, Issue 2 https://doi.org/10.1039/C6SE00080K	journal	January 2017
Electrocatalytic upgrading of model lignin monomers with earth abundant metal electrodes Lam, Chun Ho; Lowe, Christy B.; Li, Zhenglong Green Chemistry, Vol. 17, Issue 1 https://doi.org/10.1039/C4GC01632G	journal	January 2015
Combined biomass valorization and hydrogen production in a photoelectrochemical cell Cha, Hyun Gil; Choi, Kyoung-Shin Nature Chemistry, Vol. 7, Issue 4, p. 328-333 https://doi.org/10.1038/nchem.2194	journal	March 2015
The Role of Electrochemistry in Future Dynamic Bio‐Refineries: A Focus on (Non‐)Kolbe Electrolysis Palkovits, Stefan; Palkovits, Regina Chemie Ingenieur Technik, Vol. 91, Issue 6 https://doi.org/10.1002/cite.201800205	journal	March 2019
Effect of hydration on polarographic reduction of some carbonyl compounds Zuman, Petr Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 75, Issue 2 https://doi.org/10.1016/S0022-0728(77)80194-0	journal	January 1977
A mild approach for bio-oil stabilization and upgrading: electrocatalytic hydrogenation using ruthenium supported on activated carbon cloth Li, Zhenglong; Kelkar, Shantanu; Raycraft, Lauren Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/C3GC42303D	journal	January 2014
Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance Yan, Ming; Kawamata, Yu; Baran, Phil S. Chemical Reviews, Vol. 117, Issue 21 https://doi.org/10.1021/acs.chemrev.7b00397	journal	October 2017
A Combined Experimental and Theoretical Study on the Activity and Selectivity of the Electrocatalytic Hydrogenation of Aldehydes Cantu, David C.; Padmaperuma, Asanga B.; Nguyen, Manh-Thuong ACS Catalysis, Vol. 8, Issue 8 https://doi.org/10.1021/acscatal.8b00858	journal	June 2018
Polarographic reduction of aldehydes and ketones. Part 6.—Behaviour of cinnamaldehyde at lower pH-values Barnes, D.; Zuman, P. Trans. Faraday Soc., Vol. 65, Issue 0 https://doi.org/10.1039/TF9696501668	journal	January 1969
Characterization and Catalytic Upgrading of Aqueous Stream Carbon from Catalytic Fast Pyrolysis of Biomass Starace, Anne K.; Black, Brenna A.; Lee, David D. ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 12 https://doi.org/10.1021/acssuschemeng.7b03344	journal	November 2017
Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2 – The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates Luca, Oana R.; Fenwick, Aidan Q. Journal of Photochemistry and Photobiology B: Biology, Vol. 152 https://doi.org/10.1016/j.jphotobiol.2015.04.015	journal	November 2015
Modulating the Electrode–Electrolyte Interface with Cationic Surfactants in Carbon Dioxide Reduction Banerjee, Soumyodip; Han, Xu; Thoi, V. Sara ACS Catalysis, Vol. 9, Issue 6 https://doi.org/10.1021/acscatal.9b00449	journal	May 2019

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INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Electrochemical Reduction Selectivity of Crotonaldehyde on Copper

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