Herein we investigate the effect of irreversibly adsorbed bismuth on polycrystalline platinum (Pt p) on the electrooxidation of glycerol in alkaline media by combining electrochemical, spectroscopic (in situ FTIR) and analytical (HPLC on line) techniques. We found that the activity of Pt p increases by about fivefold when the optimal quantity of Bi ions is added to the solution. Besides, the adatom strongly impacts the reaction products by suppressing the pathways with CC bond breaking, hindering the formation of CO (and other unknown intermediates) and enhancing the production of Glycerate. Different to the results in acid media for Pt p-Bi systems where Bi block the oxidation pathway through the primary carbon, glycerate is the main product in alkaline media and dihydroxyacetone is either produced in extremely low quantities or not produced. Besides, comparing our results with those in acid media, the peak current recorded at 1 mV.s-1 in this work was one order of magnitude higher. These results show the strong impact of the pH in the reaction rate and selectivity.

Herein we investigated the effect of the adsorption of Bi and Pb on polycrystalline platinum (Pt p ) on the electrooxidation of glycerol (EOG) in alkaline media by combining electrochemical, spectroscopic (in situ FTIR), and analytical (online HPLC) techniques. Besides, we used single crystal Pt electrodes to understand the effect of the modification of Pt p in terms of the atomic arrangements on its surface. We found that the activity of Pt p increases in the presence of Pb (Pt p −Pb), which acts by suppressing the pathways with complete CC bond breaking (to produce carbonate) and enhancing the production of glycerate, formate, tartronate, and glycolate. We also found that Pt(100) and Pt(111) are affected by the adsorption of both adatoms. However, the modification of Pt(110) explains the results obtained with Pt p . This basal plane is highly activated by Bi and Pb and its behavior is similar to those of Pt p −Bi and Pt p −Pb, respectively. These results permit the conclusion that the adatoms acts mainly by activating Pt atoms with low coordination, which generally binds the adsorbates more strongly and, in consequence, suffers more from poisoning. The adatoms act by preventing the formation of multiple bonded intermediates, likely through a combination of a third body effect and also to a change in the electronic configuration at the surface of the catalyst. We propose in this work that the higher promotion of the EOG by the adatoms in alkaline media is due to a stabilization of the negatively charged intermediates by the Coulombic interaction with the positively charged adatoms.

This study describes a systematic investigation of the electrocatalytic activity of poly [Ni(salen)] films, as catalysts for the electrooxidation of Cn alcohols (Cn = methanol, ethanol, and glycerol) in alkaline medium. The [Ni(salen)] complex was electropolymerized on a glassy carbon surface and electrochemically activated in NaOH solution by cyclic voltammetry. X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy results indicate that during the activation step the polymeric film hydrolyzes, leading to the formation of β-Ni(OH) 2 spherical nanoparticles, with an average size of 2.4 ± 0.5 nm, encapsulated with the poly[Ni(salen)] film. Electrochemical results obtained together with the in situ Fourier transform infrared spectroscopy confirm that the electrooxidation of methanol, ethanol, and glycerol occurs by involving a cycling oxidation of β-Ni(OH) 2 with the formation of β-NiOOH species, followed by the charge transfer to the alcohols, which regenerates β-Ni(OH) 2 . Analyses of the oxidation products at low potentials indicate that the major product obtained during the oxidation of methanol and glycerol is the formate, while the oxidation of ethanol leads to the formation of acetate. On the other hand, at high potentials (E = 0.6 V), there is evidence that the oxidation of Cn alcohols leads to carbonate ions as an important product.

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Many polyols are abundant and cheap molecules highly spread in the biomass. These molecules have an enormous potential to be used in electrochemical devices to generate energy and/or value-added molecules. The electrooxidation of polyols can produce different substances of interest in the chemical industry concomitantly to high purity hydrogen in electrolyzers. The cost in the production of all these chemicals depends, among other factors, on the develop of more active and selective catalysts. However, in order to search for these materials using computational experiments, it is mandatory to have a better understanding of the fundamental aspect of the reactions, which permit to base the search on the adsorption energies of one or more key reaction intermediates. To contribute to this task, we performed (spectro)electrochemical and computational experiments to study the electrooxidation of C 4 polyols. We show that the electrooxidation of polyols does not depend on the relative orientation of their OH groups. Besides, using Pt single crystals, we demonstrate that the trend for the oxidation of the primary carbon (relative to the secondary) increases in the order Pt(111) < Pt(100) < Pt(110) and that this result can be extended to polyols with longer carbon chains. Finally, computational experiments permit us to rationalize these trends looking at the relative stability of double dehydrogenated intermediates on the Pt basal planes.

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In the last few years, transition metal carbides have emerged as novel materials with promising catalytic properties toward important practical reactions. In this work, cubic and hexagonal molybdenum carbides are synthesized and evaluated as carbon‐supported catalysts and as support materials for Pt nanoparticles for the electrochemical oxygen reduction reaction (ORR). The catalysts are characterized by XRD, energy‐dispersive X‐ray spectroscopy, TEM, XPS, and cyclic voltammetry on stationary and rotating ring‐disk electrodes. The results suggest different reactivity of the molybdenum carbide phases as both catalysts and supports for the ORR. Enhanced mass and specific ORR activities at 0.9 V are calculated for Pt–molybdenum carbide‐derived composites compared to commercial Pt and Pt/C catalysts prepared by depositing Pt by the same method. The origin of the improved ORR activity is discussed in terms of the synergistic effect between Pt and the carbide‐derived support and a decrease in the adsorption strength of oxygen‐containing species on the Pt surface, similar to that proposed for Pt–metal alloys. Additionally, the possible formation of a Pt–Mo alloy on the catalyst surface is proposed.