Reactive and inhibiting species in the electrocatalytic oxidation of glycerol on gold. A study combining in-situ visible reflectance and ATR-SEIRAS

Pérez-Martínez, Laura; Balke, Lisa; Cuesta, Ángel

doi:10.1016/j.jcat.2020.12.010

Cited by 11 publications

(7 citation statements)

References 48 publications

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“…Glucose at the interface proved to be difficult to detect due to its low normal Raman scattering (NRS) cross section 37 , however, it was noticed that the oxidation state of the gold surface can be tracked, similar to what Pérez-Martinéz et al have reported for glycerol oxidation on gold using visible reflectance and ATR-SEIRAS 38 . Raman spectra were continuously recorded in the range of 200 cm -1 to 1300 cm -1 while cycling a gold bead electrode between 0.57 and 1.67 V at 7 mV s -1 .…”

Section: Resultssupporting

confidence: 60%

On the electrooxidation of glucose on gold: towards an electrochemical glucaric acid production as value-added chemical

Schlegel

Wiberg

Arenz

2021

Preprint

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The electrocatalytic oxidation of glucose to value-added chemicals, such as glucaric acid, has gathered increased interest in recent years. Glucose oxidation is a promising process which has the potential to contribute to establishing renewable resources as alternatives to fossil carbon sources. Herein, we present rotating disk electrode (RDE) studies on polycrystalline gold surfaces and subsequent Koutecký-Levich analysis as a benchmark to expand the understanding of reaction kinetics and competition between glucose, reaction intermediates and OH- at the catalyst surface. Combining electrochemical studies and Raman spectroscopy, it is shown that increasing glucose concentrations lead to a delayed oxidation of the gold catalyst surface, presumably by increased consumption rates of Au-hydroxide species.

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Section: Resultssupporting

confidence: 60%

On the electrooxidation of glucose on gold: towards an electrochemical glucaric acid production as value-added chemical

Schlegel

Wiberg

Arenz

2021

Preprint

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“…Under high [NaOH] and at high potentials, like the −1.4 V used here, Au(OH) ads can easily be passivated through oxidation to Au(OH) 3 , Au 2 O 3 , and AuOOH, none of which are active for GEOR. 62,63 However, prior work has been shown that increased [GLY] can delay the onset of Au surface oxidation. 62 None of the evaluated catalysts herein show any surface-bound oxygen atoms (Table S5, Figs.…”

Section: Resultsmentioning

confidence: 99%

Optimizing the Flow Electrooxidation of Glycerol Using Statistical Design of Experiments

Gaines,

Kleimenhagen,

Griebler

et al. 2024

J. Electrochem. Soc.

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Many studies have investigated the conversion of biomass derivatives to value-added products. However, the influence of different factors on the reaction outcomes of these often-complex systems is not well understood. Herein, a statistical design of experiments – specifically, response surface methodology – is applied to the glycerol electrooxidation reaction in a flow electrolyzer. Four operational variables (glycerol concentration, NaOH concentration, flow rate, and catalyst loading) were investigated for their effects on measurable responses of the electrochemical reaction: current density and Faradaic efficiency to a given product. Independent optimizations of current density and Faradaic efficiency, as well as simultaneous optimization of both, were investigated. Each optimization was evaluated using response surface coefficients to analyze sensitivity and simulated runs to visualize the parameter space. These evaluations revealed contradictions in operating conditions required to simultaneously maximize current density and Faradaic efficiency to C3 products glycerate and lactate, leading to low current densities and Faradaic efficiencies. However, simultaneously maximizing current density and Faradaic efficiency to C1 product formate led to high current densities and Faradaic efficiencies. These insights guide tuning GEOR production to maximize overall reactor performance. Furthermore, this study outlines a framework for experimental evaluation and optimization of other electrolysis chemistries.

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“…51 Similar conclusions have recently been drawn from studies of glycerol oxidation on Au(111), where glycerol or other intermediates also react with adsorbed OH. 52 In contrast, we will show that the experimental observations can be described without taking into account the participation of OH or O species in the FAOR.…”

mentioning

confidence: 85%

Au(111) Surface Oxidation Kinetics Probed by Electrocatalytic Oxidation of Formic Acid

Matzik¹,

Hermann²,

Kibler³

et al. 2022

J. Electrochem. Soc.

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The kinetics of surface oxidation for Au(111) in 0.1 M HCOOH + 0.1 M HClO4 was studied at 20°C utilizing the electrocatalytic formic acid oxidation reaction (FAOR). In the surface oxidation region, cyclic voltammetry shows a distinct dependence of FAOR on scan rate revealing simultaneous deactivation of active surface sites. The surface oxide is essentially inactive for the FAOR. A series of current-time curves was recorded after potential steps into the potential range between 0.65 and 1.00 V vs. saturated mercury-mercurous sulfate electrode and analyzed within a three-step surface oxidation model, which successively involves (i) adsorption at surface defects, (ii) adsorption on well-defined Au(111) terraces, and (iii) two-dimensional nucleation-and-growth on terraces. Although Au surface oxidation is by far more complex, the system can be described in terms of the intrinsic activity of the Au(111) surface and the oxide coverage. The chronoamperometric measurements can be modeled without considering the interaction of the oxide species with the FAOR and the co-adsorption of anions. The potential dependence of the kinetic parameters is used to obtain theoretical current-time curves for FAOR on Au(111). This study sheds light on the "fast FAOR" and contributes to the understanding of degradation phenomena in electrocatalysis

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Reactive and inhibiting species in the electrocatalytic oxidation of glycerol on gold. A study combining in-situ visible reflectance and ATR-SEIRAS

Cited by 11 publications

References 48 publications

On the electrooxidation of glucose on gold: towards an electrochemical glucaric acid production as value-added chemical

On the electrooxidation of glucose on gold: towards an electrochemical glucaric acid production as value-added chemical

Optimizing the Flow Electrooxidation of Glycerol Using Statistical Design of Experiments

Au(111) Surface Oxidation Kinetics Probed by Electrocatalytic Oxidation of Formic Acid

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