Selective oxidation of glycerol mediated by surface plasmon of gold nanoparticles deposited on titanium dioxide nanowires.

This paper describes an alternative method for the in situ synthesis of gold nanoparticles (AuNPs) with a particle size of less than 3 nm, using nanoreactors formed by reverse micelles of 1,4-bis-(2-ethylhexyl) sulfosuccinate sodium (AOT) and nanoparticle stabilization with l-cysteine, which favor the preparation of nanoparticles with size and shape control, which are homogeneously dispersed (1% by weight) on the support of titanium dioxide nanowires (TNWs). To study the activity and selectivity of the prepared catalyst (AuNPs@TNWs), an aqueous solution of 40 mM glycerol was irradiated with a green laser (λ = 530 nm, power = 100 mW) in the presence of the catalyst and O2 as an oxidant at 22 °C for 6 h, obtaining a glycerol conversion of 86% with a selectivity towards hydroxypyruvic acid (HA) of more than 90%. From the control and reactions, we concluded that the Ti-OH groups promote the glycerol adsorption on the nanowires surface and the surface plasmon of the gold nanoparticles favors the selectivity of the reaction towards the hydroxypyruvic acid.

Glycerol Electro-Oxidation in Alkaline Medium with Pt-Fe/C Electrocatalysts Synthesized by the Polyol Method: Increased Selectivity and Activity Provided by Less Expensive Catalysts.

We have investigated platinum catalysts containing iron as a modifier to obtain catalysts with superior electrocatalytic activity toward glycerol electro-oxidation in an alkaline medium. The electrocatalysts, supported on carbon Vulcan, were synthesized by the polyol method. The physicochemical characterization data showed that the metals were well distributed on the carbon support and had small particle size (2 nm). The Pt:Fe metal ratio differed from the nominal composition, indicating that reducing iron with platinum was difficult, even though some parameters of the synthesis process were changed. Electrochemical analyses revealed that PtFe/C was more active and stable than commercial Pt/C was, and analysis of the electrolysis by-products showed that iron addition to Pt/C boosted the glycerol conversion and selectivity for glyceric acid formation.

Conversion of Glycerol to Value Added Products in a Semi-Continuous Batch Reactor Using Noble Metals Supported on ZSM-11 Zeolite.

Au, Pt, and Pd supported on ZSM-11 microporous zeolite were investigated as catalysts for glycerol (GLY) oxidation towards higher value added products. ZSM-11 was synthesized by hydrothermal treatment. Subsequently, ion exchange with NH4Cl was performed to recover acidic sites and then, Au, Pt, and Pd were incorporated onto this material by wet impregnation procedure. After thermal treatment of desorption and calcination, the corresponding Au, Pt, and Pd-ZSM-11 catalysts were obtained. These materials were characterized by different techniques, such as XRD, ICP, TEM- XEDS, and XPS, and were evaluated in the glycerol oxidation reaction by using alkaline medium and molecular oxygen as oxidizing agent. The higher conversion of GLY (66.5 mol.%) was reached for the Pt-ZSM-11 catalyst with moderate selectivity towards lactic acid (LA), while the bimetallic Au-Pt-ZSM-11 catalyst offered high selectivity to LA at moderate GLY conversion. Optimization of the main reaction parameters (i.e., temperature, reaction time and NaOH/GLY ratio) was carried out to maximize the selectivity towards the LA desired product. Thus, LA selectivity values close to 55% at GLY conversion >65% can be reached by using Pt-ZSM-11 as a catalyst under mild reaction conditions.