Selective glucose electro-oxidation catalyzed by TEMPO on graphite felt

Long-term electrolyses of glucose in a potassium carbonate (K2CO3) aqueous electrolyte have been performed on graphite felt electrodes with TEMPO as a homogeneous catalyst. The influences of the operating conditions (initial concentrations of glucose, TEMPO, and K2CO3 along with applied anode potential) on the conversion, selectivity toward gluconate/glucarate, and faradaic efficiency were assessed first. Then, optimizations of the conversion, selectivity, and faradaic efficiency were performed using design of experiments based on the L9 (34) Taguchi table, which resulted in 84% selectivity toward gluconate with 71% faradaic efficiency for up to 79% glucose conversion. Side products such as glucaric acid were also obtained when the applied potential exceeded 1.5 V vs. reversible hydrogen electrode

Preliminary study of electrochemical conversion of glucose on novel modified nickel electrodes

International audienceGluconic acid and sorbitol are among the value-added chemicals that can be derived from biomass. Nowadays, these compounds are typically produced through biotechnological processes, but electrochemical methods offer numerous advantages over alternative approaches. While studies have extensively explored metals like copper, palladium, gold, and platinum, nickel has received relatively limited attention in this context. Notably, nickel exhibits electrochemical activity suitable for organic electrosynthesis. This work has been achieved with 5-h long-term electrolysis, glucose as a reactant, utilizing modified nickel electrodes in a KOH solution. While these studies achieved substantial conversion rates, the selectivities and Faraday efficiencies toward gluconic acid and sorbitol remained comparatively low. The long-term electrolysis of glucose using modified nickel electrodes resulted in the identification of various side products. These include formic acid, oxalic acid, glycolic acid, tartronic acid, glyceric acid, and arabinose

Electrochemical oxidation of glucose in alkaline environment — A comparative study of Ni and Au electrodes

International audienceThe glucose oxidation reaction (GOR) was studied on Au and Ni electrodes by cyclic voltammetry (CV), rotating disk electrode (RDE) measurements coupled with Koutecky-Levich analysis, Differential Electrochemical Mass Spectrometry (DEMS), In situ Fourier Transform Infrared spectroscopy (FTIRS) and High Per-formance Liquid Chromatography (HPLC) analysis of the reaction products after electrolysis in potentiostatic mode under continuous flow conditions. This study allowed to identify the reaction products and propose tentative reaction mechanisms. On gold, glucose is adsorbed on metallic sites through its anomeric function (C1) resulting in the formation of gluconate as the main GOR product at potentials close to 0.6 V vs. RHE, with a selectivity towards gluconate close to 100% and a projected faradaic efficiency of ca. 70%. The conversion rate is rather low,close to 20%, due to poisoning of the surface, leading to a strong deactivation. At potentials above 0.8 V vs. RHE, the selectivity towards gluconate decreases and non-selective GOR oxidation proceeds through C-C bond cleavage. On nickel, the GOR occurs at high potentials (close to 1.2 V vs. RHE) on Ni(OH)2 and NiOOH sites, and proceeds through C1-C2 bond breaking, resulting in arabinose and formate. At higher potentials, the electivity towards arabinose decreases, formate being the main reaction product