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Title: Electrochemical Routes for the Valorization of Biomass-Derived Feedstocks: From Chemistry to Application

Journal Article · · ACS Energy Letters

The drive to reduce consumption of fossil resources, coupled with expanding capacity for renewable electricity, invites the exploration of new routes to utilize this energy for the sustainable production of fuels, chemicals, and materials. Biomass represents a possible source of platform precursors for such commodities due to its inherent ability to fix CO2 in the form of multi-carbon organic molecules. Electrochemical methods for the valorization of biomass are thus intriguing, but there is a need to objectively evaluate this field and define the opportunity space by identifying pathways suited to electrochemistry. In this contribution we offer a comprehensive, critical review of recent advances in low-temperature (liquid phase), electrochemical reduction and oxidation of biomass-derived intermediates (polyols, furans, carboxylic acids, amino acids, and lignin), with emphasis on identifying the state-of-the-art for each documented reaction. Progress in computational modeling is also reviewed. We further suggest a number of possible reactions that have not yet been explored but which are expected to proceed based on established routes to transform specific functional groups. We conclude with a critical discussion of technological challenges for scale-up, fundamental research needs, process intensification opportunities (e.g., by pairing compatible oxidations and reductions), and new benchmarking standards that will be necessary to accelerate progress toward application in this still-nascent field.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Grant/Contract Number:
AC36-08GO28308
OSTI ID:
1778698
Report Number(s):
NREL/JA-5100-78761; MainId:32678; UUID:f1ae075a-6cee-4ff5-8d49-a91321ae15e4; MainAdminID:19959
Journal Information:
ACS Energy Letters, Vol. 6, Issue 4; ISSN 2380-8195
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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110th Anniversary: Microkinetic Modeling of the Vapor Phase Upgrading of Biomass-Derived Oxygenates journal July 2019
Density Functional Theory Study of Selectivity Considerations for C–C Versus C–O Bond Scission in Glycerol Decomposition on Pt(111) journal May 2012
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Recent advances in the electrooxidation of biomass-based organic molecules for energy, chemicals and hydrogen production journal January 2020
Electrocatalytic Upgrading of Biomass‐Derived Intermediate Compounds to Value‐Added Products journal June 2018
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Formate, an Active Intermediate for Direct Oxidation of Methanol on Pt Electrode journal April 2003
Review of microwave-assisted lignin conversion for renewable fuels and chemicals journal May 2016
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Carboxylic Acids Production via Electrochemical Depolymerization of Lignin journal January 2019
Electrochemical Lignin Degradation in Ionic Liquids on Ternary Mixed Metal Electrodes journal February 2018
Calculations of the pH-Dependent Onset Potential for CO Electrooxidation on Au(111) journal November 2018
Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates journal September 2017
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Electrochemical oxidation and cleavage of peptides analyzed with on-line mass spectrometric detection journal January 2003
Polarographic Studies in Acetonitrile and Dimethylformamide journal January 1960
Suppressing Ion Transfer Enables Versatile Measurements of Electrochemical Surface Area for Intrinsic Activity Comparisons journal February 2018
One-pot electrocatalytic oxidation of glycerol to DHA journal September 2006
Controlling Selectivity in the Electrocatalytic Hydrogenation of Adiponitrile through Electrolyte Design journal June 2020
Electrochemically catalyzed conversion of cornstalk lignin to aromatic compounds: an integrated process of anodic oxidation of a Pb/PbO 2 electrode and hydrogenation of a nickel cathode in sodium hydroxide solution journal January 2020
Selective electro-conversion of glycerol to glycolate on carbon nanotube supported gold catalyst journal January 2012
Efficient electrochemical synthesis of 2-arylsuccinic acids from CO2 and aryl-substituted alkenes with nickel as the cathode journal January 2008
Electrochemical Decomposition of Wheat Straw Lignin into Guaiacyl‐, Syringyl‐, and Phenol‐Type Compounds Using Pb/PbO 2 Anode and Alloyed Steel Cathode in Alkaline Solution journal November 2018
Biomass in the manufacture of industrial products—the use of proteins and amino acids journal March 2007
Selective photoelectrochemical oxidation of glycerol to high value-added dihydroxyacetone journal April 2019
Reactivity Theory of Transition-Metal Surfaces: A Brønsted−Evans−Polanyi Linear Activation Energy−Free-Energy Analysis journal December 2009
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Cathodic reduction of glucose
  • bin Kassim, Annvar; Rice, Colin L.; Kuhn, Anselm T.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 77, Issue 3 https://doi.org/10.1039/f19817700683
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Selective Electro-Oxidation of Glycerol to Dihydroxyacetone by PtAg Skeletons journal July 2019
Study on the cleavage of alkyl-O-aryl bonds by in situ generated hydroxyl radicals on an ORR cathode journal January 2017
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Life Cycle Optimization of Biomass-to-Liquid Supply Chains with Distributed–Centralized Processing Networks journal September 2011
Rule-Based Generation of Thermochemical Routes to Biomass Conversion journal November 2010
Automatic Generation of Microkinetic Mechanisms for Heterogeneous Catalysis journal May 2017
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Catalytic hydroconversion of a wheat straw soda lignin: Characterization of the products and the lignin residue journal February 2014
Electrochemical Valorization of Furfural to Maleic Acid journal June 2018
Building Blocks for High Performance in Electrocatalytic CO 2 Reduction: Materials, Optimization Strategies, and Device Engineering journal August 2017
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Highly Selective Electro-Oxidation of Glycerol to Dihydroxyacetone on Platinum in the Presence of Bismuth journal April 2012
The importance of grand-canonical quantum mechanical methods to describe the effect of electrode potential on the stability of intermediates involved in both electrochemical CO 2 reduction and hydrogen evolution journal January 2018
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Selective Electrooxidation of Glycerol Into Value-Added Chemicals: A Short Overview journal February 2019
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Hydroxyacetone: A Glycerol-Based Platform for Electrocatalytic Hydrogenation and Hydrodeoxygenation Processes journal July 2017
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TEMPO mediated oxidation of carbohydrates using electrochemical methods journal April 2010
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Electrochemistry for the Generation of Renewable Chemicals: One‐Pot Electrochemical Deoxygenation of Xylose to δ‐Valerolactone journal April 2017
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Identification of Non-Precious Metal Alloy Catalysts for Selective Hydrogenation of Acetylene journal June 2008
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Highly Modular Flow Cell for Electroorganic Synthesis journal May 2017
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Automated identification of energetically feasible mechanisms of complex reaction networks in heterogeneous catalysis: application to glycerol conversion on transition metals journal January 2014
Anion Exchange Membrane Electrolyzers as Alternative for Upgrading of Biomass-Derived Molecules journal May 2018
Theoretical Heterogeneous Catalysis: Scaling Relationships and Computational Catalyst Design journal June 2016
The battle for biomass: A systematic review of food-feed-fuel competition journal June 2020
Selective hydrodeoxygenation of 5-hydroxy-2(5H)-furanone to γ-butyrolactone over Pt/mesoporous solid acid bifunctional catalyst journal January 2017
Unraveling Reaction Pathways and Specifying Reaction Kinetics for Complex Systems journal July 2012
Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide journal August 2017
Climate change mitigation potential of carbon capture and utilization in the chemical industry journal May 2019
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Electrochemical β‐Selective Hydrocarboxylation of Styrene Using CO 2 and Water journal December 2019
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Selective Production of Maleic Acid from Furfural via a Cascade Approach Combining Photochemistry and Electro- or Biochemistry journal July 2020
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Simultaneous Hydrogen Evolution and Lignin Depolymerization using NiSn Electrocatalysts in a Biomass-Depolarized Electrolyzer journal January 2020
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Mechanism of CO 2 Reduction at Copper Surfaces: Pathways to C 2 Products journal January 2018
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Aqueous-phase oxidation of 5-hydroxymethylfurfural over Pt/ZrO2 catalysts: exploiting the alkalinity of the reaction medium and catalyst basicity journal January 2016
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Electrochemical Oxidation of 5-Hydroxymethylfurfural with NiFe Layered Double Hydroxide (LDH) Nanosheet Catalysts journal May 2018
Mechanistic Insights Evaluating Ag, Pb, and Ni as Electrocatalysts for Furfural Reduction from First-Principles Methods journal November 2017
Double layer charging driven carbon dioxide adsorption limits the rate of electrochemical carbon dioxide reduction on Gold journal January 2020
Mediated Fuel Cells: Soluble Redox Mediators and Their Applications to Electrochemical Reduction of O 2 and Oxidation of H 2 , Alcohols, Biomass, and Complex Fuels journal March 2020
Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces journal February 2007
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The promoting effect of adsorbed carbon monoxide on the oxidation of alcohols on a gold catalyst journal December 2011
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Insight into the Mechanism of Hydrogenation of Amino Acids to Amino Alcohols Catalyzed by a Heterogeneous MoO x -Modified Rh Catalyst journal December 2014
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Integrated electrocatalytic processing of levulinic acid and formic acid to produce biofuel intermediate valeric acid journal January 2014
Liquid-Phase Catalytic Processing of Biomass-Derived Oxygenated Hydrocarbons to Fuels and Chemicals journal September 2007
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Unravelling Electrochemical Lignin Depolymerization journal May 2018
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A switchable route to valuable commodity chemicals from glycerol via electrocatalytic oxidation with an earth abundant metal oxidation catalyst journal January 2017
Electrochemical Oxidation and Cleavage of Tyrosine- and Tryptophan-Containing Tripeptides journal September 2010
Electrochemical Valorisation of Glycerol journal October 2012
Caprolactam from Renewable Resources: Catalytic Conversion of 5-Hydroxymethylfurfural into Caprolactone journal June 2011
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First-principle investigation on catalytic hydrogenation of benzaldehyde over Pt-group metals journal July 2020
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Laccases as a Potential Tool for the Efficient Conversion of Lignocellulosic Biomass: A Review journal May 2017
Transition Metal-Free CO 2 Fixation into New Carbon-Carbon Bonds journal August 2018
Wastes and biomass materials as sustainable-renewable energy resources for Jordan journal January 2017
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Light-Driven Depolymerization of Native Lignin Enabled by Proton-Coupled Electron Transfer journal November 2019
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Metal Catalysts for the Efficient Transformation of Biomass-derived HMF and Furfural to Value Added Chemicals journal March 2018
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Challenges in Modeling Electrochemical Reaction Energetics with Polarizable Continuum Models journal November 2018
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Enzymatic Carboxylation of 2-Furoic Acid Yields 2,5-Furandicarboxylic Acid (FDCA) journal February 2019
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Pitfalls and best practices in measurements of the electrochemical surface area of platinum-based nanostructured electro-catalysts journal January 2017
Structure Sensitivity of the Electrochemical Reduction of Carbon Monoxide on Copper Single Crystals journal April 2013
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