Insight into the Electrooxidation Mechanism of Ethylene Glycol on Palladium‐Based Nanocatalysts: In Situ FTIRS and LC‐MS Analysis

Abstract

The ethylene glycol oxidation reaction on nickel and ruthenium modified palladium nanocatalysts was investigated with electrochemical, spectroelectrochemical, and chromatographic methods. These carbon-supported materials, prepared by a revisited polyol approach, exhibited high activity towards the ethylene glycol electrooxidation in alkaline medium. Electrolysis coupled with high performance liquid chromatography/mass spectrometry (HPLC-MS) and in situ Fourier transform infrared spectroscopy (FTIRS) measurements allowed us to determine the different compounds electrogenerated in the oxidative conversion of this two-carbon molecule. High value-added products such as oxalate, glyoxylate, and glycolate were identified in all electrolytic solutions, whereas glyoxylate was selectively formed at the Ru 45 @Pd 55 /C electrode surface. In situ FTIRS results also showed a decrease in the pH value in the thin layer near the electrode as a consequence of OH À consumption during the spectroelectrochemical experiments.

Highly Active Hollow RhCu Nanoboxes toward Ethylene Glycol Electrooxidation

“…[ 30 ] Generally, it is well accepted that the effective adsorption of EG molecule and OH on electrocatalyst surface in alkaline media and the poisoning effect of CO largely determine the electrocatalytic activity. [ 31 ] According to d‐band center theory, [ 32 ] the d‐band center moving toward the Fermi level is commonly an important indication of the high activity of electrocatalyst. [ 33 ] Compared to Rh, the d‐band center of RhCu alloy down‐shifts and is away from the Fermi level (Figure S11, Supporting Information), indicating the weak electron interaction between RhCu and the adsorbent.…”

Carbon Nanotube PtSn Nanoparticles for Enhanced Complete Biocatalytic Oxidation of Ethylene Glycol in Biofuel Cells

“…Most of the time, investigations of EG oxidation at Pt-based catalyst have been conducted under drastic conditions such as extremely acidic or basic medium . Studies based on spectral electrochemical techniques have provided evidence of carbon–carbon bond cleavage . However, the main products were carbon acids (oxalic, glyoxylic, and glycolic acids), resulting from partial oxidation of the C2 products at the Pt-based catalysts. , The use of Pt-based catalysts coupled with the enzymatic pathway extends the possibility of applying this technology to a large number of systems …”

“…41 However, the main products were carbon acids (oxalic, glyoxylic, and glycolic acids), resulting from partial oxidation of the C2 products at the Pt-based catalysts. 40,41 The use of Pt-based catalysts coupled with the enzymatic pathway extends the possibility of applying this technology to a large number of systems. 42 Because bioelectrochemical systems generate small currents, comparing the results obtained with electrochemical techniques and analytical experiments is difficult.…”

Preparação e caracterização de sistemas híbridos para biocélulas enzimáticas operando com etilenoglicol/O>sub<2>/sub<

“…Na maioria das vezes, os trabalhos e oxidação do EG em catalisadores metálicos baseados em platina foram realizados em condições extremas, em meios muito ácidos ou muito básicos [153,154]. Estudos baseados em técnicas de espectroscopia eletroquímica forneceram evidências de clivagem da ligação carbonocarbono no EG [177]. No entanto, os principais produtos foram os ácidos carboxílicos (ácidos oxálico, glioxílico e glicólico), resultantes da oxidação parcial do EG pelos catalisadores à base de Pt [177,178].…”

“…Estudos baseados em técnicas de espectroscopia eletroquímica forneceram evidências de clivagem da ligação carbonocarbono no EG [177]. No entanto, os principais produtos foram os ácidos carboxílicos (ácidos oxálico, glioxílico e glicólico), resultantes da oxidação parcial do EG pelos catalisadores à base de Pt [177,178]. Até o momento, apenas um único trabalho de EBFC utilizou EG como combustível [161].…”