Electrochemistry for the generation of renewable chemicals: electrochemical conversion of levulinic acid

Santos, Tatiane R. dos; Nilges, Peter; Sauter, Waldemar; Harnisch, Falk; Schröder, Uwe

doi:10.1039/c4ra16303f

Cited by 83 publications

(105 citation statements)

References 75 publications

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“…The main triggers for the revival of electroorganic syntheses are their advantages for green and sustainable chemistry. [13,14] Furthermore, there are potential energetic advantages over classical routes, when using electric energy for the formation and upgrading of platform chemicals [15,16] that can be combined with the utilization of renewable electric power. [13,14] Thereby,m osto ft he recently rediscovered electroorganic syntheses can be performed at mild environmentalc onditions.…”

Section: Introductionmentioning

confidence: 99%

The Dilemma of Supporting Electrolytes for Electroorganic Synthesis: A Case Study on Kolbe Electrolysis

Stang

Harnisch

2015

ChemSusChem

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Remarkably, coulombic efficiency (CE, about 50 % at 1 Farad equivalent), and product composition resulting from aqueous Kolbe electrolysis are independent of reactor temperature and initial pH value. Although numerous studies on Kolbe electrolysis are available, the interrelations of different reaction parameters (e.g., acid concentration, pH, and especially electrolytic conductivity) are not addressed. A systematic analysis based on cyclic voltammetry reveals that solely the electrolytic conductivity impacts the current-voltage behavior. When using supporting electrolytes, not only their concentration, but also the type is decisive. We show that higher concentrations of KNO3 result in reduced CE and thus in significant increase in electric energy demand per converted molecule, whereas Na2 SO4 allows improved space-time yields. Pros and cons of adding supporting electrolytes are discussed in a final cost assessment.

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Section: Introductionmentioning

confidence: 99%

The Dilemma of Supporting Electrolytes for Electroorganic Synthesis: A Case Study on Kolbe Electrolysis

Stang

Harnisch

2015

ChemSusChem

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“…[14] Thus, for example, the presented CE of 32.7 %f or the hydroxyacetone reduction at iron electrodes in chloride solution was increased to 78.82 %b yi ncreasing the precursorc oncentration from 0.09 to 1M.Afurther concentration increasew as accompanied by side effects, such as as electivity reduction or ad rop in current density.A na ddition of the product 1,2-propanediol to the startings olution showed that it is inert for furtherr eduction and therefore inhibited the main reaction. High educt concentrations generally allow suppressing the competingH ER and thus increasing the CE of the electro-organic reaction.…”

Section: Resultsmentioning

confidence: 98%

Hydroxyacetone: A Glycerol‐Based Platform for Electrocatalytic Hydrogenation and Hydrodeoxygenation Processes

2017

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Here, we propose the use of hydroxyacetone, a dehydration product of glycerol, as a platform for the electrocatalytic synthesis of acetone, 1,2-propanediol, and 2-propanol. 11 non-noble metals were investigated as electrode materials in combination with three different electrolyte compositions toward the selectivity, Coulombic efficiency (CE), and reaction rates of the electrocatalytic hydrogenation (formation of 1,2-propanediol) and hydrodeoxygenation (formation of acetone and propanol) of hydroxyacetone. With a selectivity of 84.5 %, a reaction rate of 782 mmol h m and a CE of 32 % (for 0.09 m hydroxyacetone), iron electrodes, in a chloride electrolyte, yielded the best 1,2 propanediol formation. A further enhancement of the performance can be achieved upon increasing the educt concentration to 0.5 m, yielding a reaction rate of 2248.1 mmol h m and a CE of 64.5 %. Acetone formation was optimal at copper and lead electrodes in chloride solution, with lead showing the lowest tendency of side product formation. 2-propanol formation can be achieved using a consecutive oxidation of the formed acetone (at iron electrodes). 1-propanol formation was observed only in traces.

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“…and Dos Santos et al . previously showed that electrochemical reduction of LA using C, Cu, Fe or Ni cathodes gave low LA conversions and low selectivity towards VA compared to Pb . In our study we focused on assessing various other materials known to yield the methylene group or with a similar overpotential.…”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, new applications include the usage of VA in biofuels –. The high selectivity for the electrosynthesis of VA is attributed to the high (over)potential of lead (Pb) –. It is also known that the reduction of the carbonyl (C=O) functionality can yield a methylene (CH 2 ), olefin, pinacol, alcohol or organometallic functionality, which depends on the substrate, solvent, nature of the electrode material, potential and pH .…”

Section: Introductionmentioning

confidence: 99%

Identification of More Benign Cathode Materials for the Electrochemical Reduction of Levulinic Acid to Valeric Acid

Bisselink

Crockatt²,

Zijlstra

et al. 2019

ChemElectroChem

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The electrochemical production of valeric acid from the renewable bio‐based feedstock levulinic acid has the potential to replace the oxo‐process, which uses fossil‐based feedstock 1‐butylene. The electrochemical reduction of the ketone functionality in levulinic acid using lead or mercury cathodes has already been known for over 100 years. However, large‐scale electrochemical production of valeric acid might be limited, owing to the toxicity of these materials. In this study, we identified three additional cathode materials, cadmium, indium, and zinc, which selectively and efficiently produce valeric acid. Of these materials, indium and zinc are considered more benign. More specifically, at indium there is no formation of the side product γ‐valerolactone, thus resulting in the highest selectivity towards valeric acid. For the electrochemical reduction, a reaction mechanism involving the formation of an organometallic compound is proposed. Furthermore, a possible processing strategy is outlined to enable the continuous electrochemical production of valeric acid on a large scale.

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Electrochemistry for the generation of renewable chemicals: electrochemical conversion of levulinic acid

Abstract: Levulinic acid as a platform for electrochemical synthesis: electrochemical conversion of levulinic acid and its primary products is presented as a promising alternative for the generation of renewable chemicals and biofuels and for energy storage.

Cited by 83 publications

References 75 publications

The Dilemma of Supporting Electrolytes for Electroorganic Synthesis: A Case Study on Kolbe Electrolysis

The Dilemma of Supporting Electrolytes for Electroorganic Synthesis: A Case Study on Kolbe Electrolysis

Hydroxyacetone: A Glycerol‐Based Platform for Electrocatalytic Hydrogenation and Hydrodeoxygenation Processes

Identification of More Benign Cathode Materials for the Electrochemical Reduction of Levulinic Acid to Valeric Acid

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