Alcohol oxidation as alternative anode reactions paired with (photo)electrochemical fuel production reactions

Bender, Michael; Yuan, Xin; Choi, Kyoung‐Shin

doi:10.1038/s41467-020-18461-1

Cited by 88 publications

(95 citation statements)

References 19 publications

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“…[ 1–3 ] It allows the production of precious chemicals via a more benign, facile, and less expensive route than the traditional routes. [ 4–10 ] Furthermore, water oxidation is often associated with a large overpotential and with catalyst decomposition. [ 11–14 ] In contrast, the oxidation of oxidizable organic molecules usually requires a lower potential, reducing the total hydrogen production cost.…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Mechanisms of Electrocatalytic Oxygenation and Dehydrogenation of Organic Molecules to Value‐Added Chemicals Over a Ni–Fe Oxide Catalyst

Mondal

Karjule

Singh

et al. 2021

Advanced Energy Materials

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Electrocatalytic oxidative upgrading of organic molecules is a promising alternative process to water oxidation for clean hydrogen production. Yet, its underlying mechanism is still not fully understood, and suitable low‐cost electrocatalysts with good product selectivity and activity are still sought after. Here, an active NiFeOx‐based catalyst is reported on as a general platform for the electro‐oxidative upgrading of organic molecules through oxygenation and dehydrogenation, with hydrogen coproduction. Detailed mechanistic studies unveil that C–H bond oxidation (with a bond dissociation energy BDEC–H of ≈88–96 kcal mol−1) is involved in the rate‐limiting step, which differs significantly from the oxygen evolution reaction mechanism. These findings show that the oxidation efficacy is linearly correlated with the BDEC–H of the molecule. Thus, the catalyst can be used as a general platform for large‐scale electro‐oxidation of various substrates through oxygenation and dehydrogenation at high current density (25 mA cm−2), with a good Faradaic yield. The platform's generality is further demonstrated by the selective oxidation of 5‐(hydroxymethyl)furfural into 2,5‐furandicarboxylic acid with good efficiency.

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Section: Introductionmentioning

confidence: 99%

Unraveling the Mechanisms of Electrocatalytic Oxygenation and Dehydrogenation of Organic Molecules to Value‐Added Chemicals Over a Ni–Fe Oxide Catalyst

Mondal

Karjule

Singh

et al. 2021

Advanced Energy Materials

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“…For Ni and Co two reaction mechanisms were proposed, as illustrated in Figure 8D: i) direct electron transfer in which alcohol molecules adsorb on the M(OH) 2 and get oxidized by the OH − ions trapped on the surface; ii) indirect electron transfer from the reactant to MOOH, restoring the M(OH) 2 . [128][129][130] The works reported by Fleischmann et al in 1970s point toward the indirect reaction pathway. [131,132] At lower glycerol concentration though, Houache et al observed direct electron transfer pathway for Ni.…”

Section: H O H O Oxidation Products H E Anode Reactionmentioning

confidence: 97%

“…[134] Under these conditions, oxidation rate becomes dependent of potential. [128] With the above knowledge at hand, in the following sections we will review in detail for different organic molecules, how the choice of electrocatalysts will affect the reaction activity and selectivity.…”

Section: Intrinsic Metal Properties For Different Chemical Bond Activationmentioning

confidence: 99%

Progress and Perspectives in Photo‐ and Electrochemical‐Oxidation of Biomass for Sustainable Chemicals and Hydrogen Production

Luo

Barrio

Sunny

et al. 2021

Advanced Energy Materials

254

197

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Elevated concentrations of atmospheric greenhouse gases (GHGs), particularly carbon dioxide (CO 2 ), have affected the global environment, causing climate deviations and threatening the biodiversity. [1,2] Deep-cutting solutions and new technologies are thus imperative to repay the carbon debt. [3] Hydrogen (H 2 ) is an ideal fuel to enable a successful transition to a global zero emission economy: With a gravimetric energy density more than double that of conventional fuels like diesel, gasoline, and natural gas it is a lightweight energy carrier which can be converted to electricity and water via fuel cells and thus holds great promise to cut emissions of the transport and energy sectors to zero. Furthermore, it is an energy dense chemical which is already used in the chemical industry (i.e., ammonia via the Haber-Bosch process) and steel manufacturing. However, these industries currently use brown (made from coal via gasification and subsequent water gas shift reaction) and gray (made by steam methane reforming) hydrogen which both have significant CO 2 footprints. Thus, synthesizing green (meaning renewable) hydrogen cost-effectively is a solution which could green such industries and the transport sector and simultaneously meet our growing demands for viable energy storage solutions. However, switching from fossilfuels to a hydrogen economy requires efficient technologies that permit clean, sustainable and cost-effective production, storage, and utilization of H 2 . [4][5][6] Water electrolysis is a clean technology for green H 2 production, where water is split into H 2 at the cathode while O 2 is generated at the anode. Thermodynamically, the energy input required for this reaction equals an applied voltage of 1.23 V but in practice >1.8 V is commonly applied due to the sluggish kinetics of the oxygen evolution reaction (OER). The kinetics of the OER are complex. In addition to the thermodynamic potential of 1.23 V, even the best OER catalysts to date show significant overpotentials (0.35-0.4 V) which is due to suboptimal scaling relation between OOH and OH adsorption energies. [7,8] As a consequence, a significant amount of energy is spent on Biomass is recognized as an ideal CO 2 neutral, abundant, and renewable resource substitute to fossil fuels. The rich proton content in most biomass derived materials, such as ethanol, 5-hydroxymethylfurfural (HMF) and glycerol allows it to be an effective hydrogen carrier. The oxidation derivatives, such as 2,5-difurandicarboxylic acid from HMF, glyceric acid from glycerol are valuable products to be used in biodegradable polymers and pharmaceuticals. Therefore, combining biomass-derived compound oxidation at the anode and hydrogen evolution reaction at the cathode in a biomass electrolysis or photo-reforming reactor would present a promising strategy for coproducing high value chemicals and hydrogen with low energy consumption and CO 2 emissions. This review aims to combine fundamental knowledge on photo and electro-assisted catalysis to provide a comprehensive und...

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“…[36] Alternatively, a different anodic process could generate a second product in a paired electrochemical process, as in chlor-alkali technology that produces Cl2 and NaOH from brine. [50] Multiple oxidation candidates are available, including biomass, [40,51] various amines, [52] or the production of high value oxidants e.g. HClO and S2O8 2-.…”

Section: Latest Developments For H 2 O 2 Electrosynthesismentioning

confidence: 99%

Future perspectives for the advancement of electrochemical hydrogen peroxide production

Perry

Mavrikis

Wang

et al. 2021

Current Opinion in Electrochemistry

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H2O2 is an important chemical with multiple uses across domestic and industrial settings. A global need for wider adoption of green synthetic methods, there has been a growing interest in the electrochemical synthesis of H2O2 from oxygen reduction or water oxidation. State of the art catalyst and reactor developments are beginning to advance to a stage where electrochemical synthesis is discussed as a viable alternative to current industrial methods. In this review, we highlight some of the most promising candidates for H2O2 electrosynthesis technologies, and what further advancements are needed before the electrochemical route could challenge the ubiquitous anthraquinone process.

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Alcohol oxidation as alternative anode reactions paired with (photo)electrochemical fuel production reactions

Abstract: (Photo)electrochemical cells that produce fuels have often relied on water oxidation to complete the redox cycle. Here, the authors discuss alcohol oxidation as an alternative reaction and consider general mechanistic features of oxidation electrocatalysts.

Cited by 88 publications

References 19 publications

Unraveling the Mechanisms of Electrocatalytic Oxygenation and Dehydrogenation of Organic Molecules to Value‐Added Chemicals Over a Ni–Fe Oxide Catalyst

Unraveling the Mechanisms of Electrocatalytic Oxygenation and Dehydrogenation of Organic Molecules to Value‐Added Chemicals Over a Ni–Fe Oxide Catalyst

Progress and Perspectives in Photo‐ and Electrochemical‐Oxidation of Biomass for Sustainable Chemicals and Hydrogen Production

Future perspectives for the advancement of electrochemical hydrogen peroxide production

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