Optimizing the nickel boride layer thickness in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in glycerol oxidation

Cychy, Steffen; Lechler, Sebastian; Huang, Zijian; Braun, Michael; Brix, Ann Cathrin; Blümler, Peter; Andronescu, Corina; Schmid, Friederike; Schuhmann, Wolfgang

doi:10.1016/s1872-2067(20)63766-4

Cited by 10 publications

(13 citation statements)

References 35 publications

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“…However, the lower catalyst loading due to detachment led to an again higher selectivity to less strongly oxidized products such as 74 % for glyceric acid, which is in agreement with our recent findings for the GOR. [13] The selectivity to formate, which was formed in second highest selectivity from 23 to 19 %, behaves conversely for the individual potentials. This is reasonable, because Ni x B exhibits high selectivity towards CÀ C cleavage in GOR.…”

Section: Resultsmentioning

confidence: 95%

“…Obviously, solketal does not suppress the OER as strongly as ethanol, ethylene glycol, and glycerol. [12][13][14] Presumably, the bulky 5-membered ring moiety renders the orientation of the molecule during adsorption more important, and the SOR to solketalate only provides 4 e À per molecule. In the reverse scan, minor hysteresis is observed and a current crossing at 1.5 V vs. RHE occurs either due to a larger amount of active Ni species or residual adsorbed species being oxidized.…”

Section: Resultsmentioning

confidence: 99%

“…This is reasonable, because Ni x B exhibits high selectivity towards CÀ C cleavage in GOR. [13] Thus, if the acetal moiety is split off, protection is lost and rapid conversion to formate proceeds as shown below the red box in Scheme 3. The same trends are valid for C 2 species such as glyoxylic acid, glycolic acid, and oxalic acid.…”

Section: Resultsmentioning

confidence: 99%

“…More details are provided elsewhere. [11][12][13] Inks were prepared as 5, and 10 mg mL À 1 suspensions using a 49 : 49 : 2 water:ethanol:Nafion mixture for rotating disk electrodes (RDEs) and borehole electrodes (BHEs), Scheme 1. Synthesis of solketal via acetalization of vicinal hydroxyl groups of glycerol and acetone.…”

Section: Methodsmentioning

confidence: 99%

“…The material was used after annealing in N 2 atmosphere at 500 °C for 2 h with a heating ramp of 10 K min −1 . More details are provided elsewhere [11–13] . Inks were prepared as 5, and 10 mg mL −1 suspensions using a 49 : 49 : 2 water:ethanol:Nafion mixture for rotating disk electrodes (RDEs) and borehole electrodes (BHEs), respectively.…”

Section: Methodsmentioning

confidence: 99%

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Selective Anodic Oxidation of Solketal as Acetal‐Protected Glycerol over Nickel Boride in Alkaline Media to Glyceric Acid**

Cychy

Lechler

2021

ChemElectroChem

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Alkaline anodic oxidation of glycerol suffers from facile C−C bond cleavage, especially when using non‐precious metal electrocatalysts, which limits the yield of more valuable C3 oxygenates. Usually, a high C3 selectivity is a tradeoff with conversion for most catalysts. Thus, we used solketal as the reactant, which is acetal‐protected glycerol with acetone. CV experiments showed that solketal is oxidized over nickel boride (NixB) at potentials where NiOOH is formed. Electrolysis over NixB in a thin‐film spectroelectrochemical flow cell at 1.58 V vs. RHE to avoid pronounced oxygen evolution showed a stable current density of ca. 6 mA cm−2. Simultaneously recorded ATR‐FTIR spectra revealed solketal conversion to solketalate and formate. Indeed, 59 % conversion and 77 % selectivity to glyceric acid were determined by HPLC after acidic cleavage of the acetal, resulting in a yield of 45 %. Therefore, solketal is a promising reactant for the selective electrosynthesis of glyceric acid.

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Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Selective Anodic Oxidation of Solketal as Acetal‐Protected Glycerol over Nickel Boride in Alkaline Media to Glyceric Acid**

Cychy

Lechler

2021

ChemElectroChem

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Spectroelectrochemical Exploration of Biogenic Substrates for Electrosynthesis

Kurig,

Palkovits

2024

Chemie Ingenieur Technik

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Spectroelectrochemistry, especially ATR‐SEIRAS, is an emerging method to identify key descriptors for optimizing reaction systems in organic electrosynthesis. Here, the upgrading of biogenic acids via Kolbe electrolysis and reductive transformations was studied. The findings affirm acid group adsorption on electrodes, consistent with existing literature. The effectiveness of Kolbe reaction in suppressing the parasitic ethanol oxidation reaction was observed, whereas it faces stiff competition from the methanol oxidation reaction. Parallel reduction and reductive amination of levulinic acid were uncovered, both relying on adsorbed organic species rather than molecular H2. Intriguingly, the electrode's polarization influences the bond strength, enabling discrimination between acid and ketone species within levulinic acid.

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Anodic Reactions in Alkaline Hybrid Water Electrolyzers: Activity versus Selectivity

van Lieshout,

Morales

2024

ChemPlusChem

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Affordable and abundant sources of green hydrogen can give a large impetus to the Energy Transition. While conventional water electrolysis has positioned itself as a prospective candidate for this purpose, it lacks cost competitiveness. Hybrid water electrolysis (HWE) has been praised for its ability to address the issues of conventional water electrolysis due to its decreased energy requirements and its ability to generate value‐added products, among other advantages. In this perspective, we discuss the challenges related to the applicability of HWE, using the glycerol oxidation reaction as an example, and we identify pitfalls often found in the literature. Reported catalysts, especially those based on abundant materials, suffer from a severe selectivity‐activity tradeoff, hampering their industrial applicability due to large costs associated with product separation and purification. Additionally, testing electrocatalysts under conditions that are relevant for their applications is encouraged, yet these conditions are largely unknown, as in‐depth knowledge of the catalytic mechanisms is largely missing. Lastly, an opportunity to increase the amount of interdisciplinary research concerning both the engineering requirements and financial performance of HWE is discussed. Increased focus on these objectives may boost the development of HWE on an industrial scale.

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Optimizing the nickel boride layer thickness in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in glycerol oxidation

Cited by 10 publications

References 35 publications

Selective Anodic Oxidation of Solketal as Acetal‐Protected Glycerol over Nickel Boride in Alkaline Media to Glyceric Acid**

Selective Anodic Oxidation of Solketal as Acetal‐Protected Glycerol over Nickel Boride in Alkaline Media to Glyceric Acid**

Spectroelectrochemical Exploration of Biogenic Substrates for Electrosynthesis

Anodic Reactions in Alkaline Hybrid Water Electrolyzers: Activity versus Selectivity

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