Boosting the valorization of biomass and green electrons to chemical building blocks: A study on the kinetics and mass transfer during the electrochemical conversion of HMF to FDCA in a microreactor

Delparish, Amin; Uslu, Alperen; Cao, Yiran; Groot, Thijs de; Schaaf, J. van der; Noël, Timothy; d’Angelo, M.F. Neira

doi:10.1016/j.cej.2022.135393

Cited by 24 publications

(23 citation statements)

References 47 publications

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“…[23] Comparison to prior literature We note that most prior studies, which were performed without knowledge of the presence of two different oxidation pathways on NiOOH, have reported that HMF oxidation on NiOOH proceeds though the HMFCA route. [14,21,[25][26][27][28][29][30][31] While it is difficult to be certain without performing the rate deconvolution experiments, these studies were often conducted under conditions we would expect to favor PD oxidation as much as or more than those used in this study (0.55 V vs. Ag/AgCl in a pH 13 solution containing 5 mm HMF) where the PD pathway (and thus DFF formation) dominates. Therefore, we believe it is unlikely that the reason they all observed HMFCA instead of DFF is because they all were using conditions that heavily favored the indirect pathway.…”

Section: Chemsuschemmentioning

confidence: 99%

“…Most works have assumed this reaction proceeds though the long-established indirect mechanism proposed by Fleischmann et al for oxidation of alcohols and amines on NiOOH (and later extended to include aldehydes as they are oxidized after undergoing an initial hydration to form a 1,1-geminal diol) (Scheme 1). [6,9,[18][19][20][21] In this mechanism, Scheme 1. Literature mechanism proposed by Fleischmann et al for the indirect oxidation of alcohols at NiOOH electrodes in alkaline aqueous media.…”

Section: Introductionmentioning

confidence: 99%

“…for oxidation of alcohols and amines on NiOOH (and later extended to include aldehydes as they are oxidized after undergoing an initial hydration to form a 1,1‐geminal diol) (Scheme 1). [6,9,18–21] In this mechanism, Ni(OH) 2 is first oxidized to NiOOH by the applied bias. This NiOOH then acts as a chemical oxidizing agent, reacting with alcohols through a non‐electrochemical and rate‐limiting hydrogen atom transfer (HAT) from the carbon at the α‐position of the alcohol (or geminal diol in the case of aldehyde oxidation) to a Ni 3+ site in the NiOOH, thereby reducing the NiOOH back to Ni(OH) 2 [18,19] .…”

Section: Introductionmentioning

confidence: 99%

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Electrochemical Oxidation of HMF via Hydrogen Atom Transfer and Hydride Transfer on NiOOH and the Impact of NiOOH Composition

Bender

Choi

2022

ChemSusChem

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A great deal of attention has been directed toward studying the electrochemical oxidation of 5-hydroxymethylfurfural (HMF), a molecule that can be obtained from biomass-derived cellulose and hemicellulose, to 2,5-furandicarboxylic acid (FDCA), a molecule that can replace the petroleum-derived terephthalic acid in the production of widely used polymers such as polyethylene terephthalate. NiOOH is one of the best and most well studied electrocatalysts for achieving this transformation; however, the mechanism by which it does so is still poorly understood. This study quantitatively examines how two different dehydrogenation mechanisms on NiOOH impact the oxidation of HMF and its oxidation intermediates on the way to FDCA. The first mechanism is a well-established indirect oxidation mechanism featuring chemical hydrogen atom transfer to Ni 3 + sites while the second mechanism is a newly discovered potential-dependent (PD) oxidation mechanism involving electrochemically induced hydride transfer to Ni 4 + sites. The composition of NiOOH was also tuned to shift the potential of the Ni(OH) 2 /NiOOH redox couple and to investigate how this affects the rates of indirect and PD oxidation as well as intermediate accumulation during a constant potential electrolysis. The new insights gained by this study will allow for the rational design of more efficient electrochemical dehydrogenation catalysts.

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Section: Chemsuschemmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Electrochemical Oxidation of HMF via Hydrogen Atom Transfer and Hydride Transfer on NiOOH and the Impact of NiOOH Composition

Bender

Choi

2022

ChemSusChem

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“…15 This electrochemical strategy has recently been applied to the conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid. 22 Notably, it has also been applied on an industrial scale: anodic oxidation of diacetone-L-sorbose to diacetone-2-keto-L-gulonic acid, an intermediate in the synthesis of ascorbic acid, was carried out by F. Hoffmann-LaRoche in a 2 ton per day scale in the 1980s. 23 We questioned whether this methodology is also suitable for the oxidation of alcohols bearing heteroaromatics relevant to active pharmaceutical ingredients and their intermediates to the corresponding carboxylic acids.…”

Section: ■ Introductionmentioning

confidence: 99%

Electrochemical Oxidation of Alcohols Using Nickel Oxide Hydroxide as Heterogeneous Electrocatalyst in Batch and Continuous Flow

Jud

Salazar

Imbrogno

et al. 2022

Org. Process Res. Dev.

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An electrochemical method has been developed for a mediated oxidation of primary alcohols to carboxylic acids. The method is compatible with a variety of alcohols bearing nitrogen-containing heterocycles in undivided batch and flow modes. The use of a heterogeneous NiOOH electron−proton transfer mediator avoids the need for homogeneous catalysts that contribute to more unit operations during downstream purging and increased process mass intensity. To demonstrate the applicability of this method for continuous processing, a single-pass flow electrochemical oxidation of nicotinyl alcohol to nicotinic acid is demonstrated with a 77% isolated yield. The NiOOH-coated anodes show no reduction in catalysis efficiency over 12 h, and minimal Ni metal leaching (22.3 μg per liter) is observed.

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“…We note that the majority of papers studying HMF oxidation using MOOH deposited on high surface area 3D electrodes argue that oxidation occurs almost exclusively through the HMFCA route. ,,,,− As these papers were published before we elucidated the differences between PD and indirect oxidation, they do not discuss which mechanism dominates; however, the potentials used in these studies appear to be sufficient to make the PD pathway dominant for HMF oxidation. Their argument that FDCA is formed through the HMFCA route is based primarily on the fact that these studies detect HMFCA as an intermediate but no DFF.…”

Section: Electrochemical Oxidative Valorization Via Dehydrogenationmentioning

confidence: 99%

Electrochemical Hydrogenation, Hydrogenolysis, and Dehydrogenation for Reductive and Oxidative Biomass Upgrading Using 5-Hydroxymethylfurfural as a Model System

et al. 2022

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Ever increasing energy demands and concerns about the environment necessitate the discovery of methods for producing fuels and chemicals from renewable resources in an environmentally benign manner. Electrochemical biomass conversion is particularly promising due to the abundance of renewable biomass and the advantages of electrochemistry, including the use of renewable electricity to drive chemical reactions without consumption of additional reductants and oxidants. Biomass intermediates are chemically complex and contain multiple functional groups, requiring selective reduction or oxidation for effective biomass conversion. Reductively, controlling the selectivity between hydrogenation and hydrogenolysis is necessary for efficient reduction of oxygenated functional groups to produce desired fuels and chemicals. Oxidatively, selective dehydrogenation of a particular functional group (e.g., alcohol or aldehyde oxidation to carboxylic acid) while preventing complete oxidation to CO2 is required for conversion of biomass to value-added products. In this Perspective, we use biomass-derived 5-hydroxymethylfurfural (HMF) as an especially useful model molecule for discussing recent developments in electrochemical hydrogenation, hydrogenolysis, and dehydrogenation reactions for biomass conversion, as HMF, which contains multiple functional groups, can be transformed into various valuable chemicals by both reductive and oxidative processes. For each reaction, the electrocatalysts, reaction conditions, and mechanisms will be discussed. Through this discussion, this Perspective aims to provide researchers with a foundational understanding of electrochemical hydrogenation, hydrogenolysis, and dehydrogenation reactions that can be applied to a wide variety of organic transformations, including biomass conversion.

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Boosting the valorization of biomass and green electrons to chemical building blocks: A study on the kinetics and mass transfer during the electrochemical conversion of HMF to FDCA in a microreactor

Cited by 24 publications

References 47 publications

Electrochemical Oxidation of HMF via Hydrogen Atom Transfer and Hydride Transfer on NiOOH and the Impact of NiOOH Composition

Electrochemical Oxidation of HMF via Hydrogen Atom Transfer and Hydride Transfer on NiOOH and the Impact of NiOOH Composition

Electrochemical Oxidation of Alcohols Using Nickel Oxide Hydroxide as Heterogeneous Electrocatalyst in Batch and Continuous Flow

Electrochemical Hydrogenation, Hydrogenolysis, and Dehydrogenation for Reductive and Oxidative Biomass Upgrading Using 5-Hydroxymethylfurfural as a Model System

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