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Glycerol electro‐oxidation reaction was performed in an alkaline environment with an anion exchange membrane fuel cell (AEMFC) operating in bath mode at low Pt‐loadings. BAE‐synthesized Pt/C and PtCe/C nanostructured catalysts were used as anode materials during 4‐hour operation to selectively obtain 65 % and 41 % of glycerate as main product, respectively. The modification of Pt with Ce improved the catalytic activity of the Pt/C catalyst generating 30 % more energy density after 4‐hour operation by achieving a higher degree of glycerol oxidation in cogeneration with added‐value products confirmed by spectroelectrochemical (in situ FTIR) and liquid chromatography coupled with mass spectrometry (LC–MS) analyses. The bifunctional mechanism generated by the presence of Ce is used to explain the improvement in the catalytic activity of Pt/C, due to the properties of this rare earth element to adsorb oxygenated species (OH−) and promote oxidation. The cathode material was a polyol‐synthesized PdFe/C electro‐catalyst for ORR that presented impressive stability and tolerance to glycerol. [ABSTRACT FROM AUTHOR]

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 Ru45@Pd55/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− consumption during the spectroelectrochemical experiments. [ABSTRACT FROM AUTHOR]

The selective electrochemical conversion of highly functionalized organic molecules into electricity, heat, and added-value chemicals for fine chemistry requires the development of highly selective, durable, and low-cost catalysts. Here, we propose an approach to make catalysts that can convert carbohydrates into chemicals selectively and produce electrical power and recoverable heat. A 100 % Faradaic yield was achieved for the selective oxidation of the anomeric carbon of glucose and its related carbohydrates (C1-position) without any function protection. Furthermore, the direct glucose fuel cell (DGFC) enables an open-circuit voltage of 1.1 V in 0.5 m NaOH to be reached, a record. The optimized DGFC delivers an outstanding output power Pmax=2 mW cm−2 with the selective conversion of 0.3 m glucose, which is of great interest for cogeneration. The purified reaction product will serve as a raw material in various industries, which thereby reduces the cost of the whole sustainable process. [ABSTRACT FROM AUTHOR]

Experimental evidence for Pd-based structure modification of electrocatalysts with hydrogen during their chemical synthesis is still missing. Therefore, in situ X-ray diffraction (XRD) techniques were as used to investigate hydrogen insertion into the lattice of Pd nanomaterials during their preparation. It was shown that the use of NaBH4 as reducing agent led to PdH x whereas L-ascorbic acid gave Pd nanoparticles. The subsequent influence of hydrogen insertion on the catalytic properties of Pd nanostructures was demonstrated by using carbon monoxide and glucose as probing molecules. High active surface areas and catalytic activities were found for the unmodified Pd nanostructures through electrochemical studies. Notably, the reducing agent has a significant effect on the size distribution of the nanoparticles. Its use can precisely and effectively tune their catalytic properties. Consequently, the remarkable behavior uncovered herein provides new strategic routes that can be used for the preparation of Pd-based nanomaterials. [ABSTRACT FROM AUTHOR]

The oxygen reduction reaction (ORR) is the oldest studied and most challenging of the electrochemical reactions. Due to its sluggish kinetics, ORR became the major contemporary technological hurdle for electrochemists, as it hampers the commercialization of fuel cell (FC) technologies. Downsizing the metal particles to nanoscale introduces unexpected fundamental modifications compared to the corresponding bulk state. To address these fundamental issues, various synthetic routes have been developed in order to provide more versatile carbon-supported low platinum catalysts. Consequently, the approach of using nanocatalysts may overcome the drawbacks encountered in massive materials for energy conversion. This review paper aims at summarizing the recent important advances in carbon-supported metal nanoparticles preparation from colloidal methods (microemulsion, polyol, impregnation, Bromide Anion Exchange...) as cathode material in low temperature FCs. Special attention is devoted to the correlation of the structure of the nanoparticles and their catalytic properties. The influence of the synthesis method on the electrochemical properties of the resulting catalysts is also discussed. Emphasis on analyzing data from theoretical models to address the intrinsic and specific electrocatalytic properties, depending on the synthetic method, is incorporated throughout. The synthesis process-nanomaterials structure-catalytic activity relationships highlighted herein, provide ample new rational, convenient and straightforward strategies and guidelines toward more effective nanomaterials design for energy conversion. [ABSTRACT FROM AUTHOR]

Cover Feature: Insight into the Electrooxidation Mechanism of Ethylene Glycol on Palladium-Based Nanocatalysts: In Situ FTIRS and LC-MS Analysis (ChemElectroChem 21/2020) Keywords: ethylene glycol; electrooxidation; energy conversion; fuel cells; heterogeneous catalysis EN ethylene glycol electrooxidation energy conversion fuel cells heterogeneous catalysis 4285 4285 1 11/16/20 20201102 NES 201102 B The Cover Feature b illustrates the mechanism of ethylene glycol electrooxidation at the surface of Pd-based catalysts. Ethylene glycol, electrooxidation, energy conversion, fuel cells, heterogeneous catalysis. [Extracted from the article]

[Display omitted] • Cellulosic biomass-based glucose is selectively oxidized in a co-generation direct fuel cell. • Real-time evidence of glucose oxidation in fuel cell by C1-position to gluconate (90% selectivity). • Glucuronate production (10% selectivity) via the glucose oxidation at the C6-position. • Products distribution in direct alkaline glucose fuel cell is the same as in half-cell setup. Cellulosic biomass, which is basically a polymer of glucose, is the most abundant organic polymer on earth and there is significant interest in the development of advanced materials for its valorization through the waste-to-energy and water-to-chemical scenarios. Hence, a precise investigation of the monomer (glucose) electrooxidation in electrochemical reactors is a key starting point to tackle the whole cellulose and ultimately the entire biomass. To this end, we report herein new insights about the operation of a cogeneration direct alkaline glucose fuel cell (which includes an anion exchange membrane) that simultaneously produces electricity and mainly gluconate as the reaction product. The AuPt nanocatalysts of 3–5 nm particle size finely dispersed onto reduced graphene oxide (rGO) at a 20 wt% metal loading are obtained from an organic surfactant-free method, so-called the bromide anion exchange (BAE). Specifically, the electroanalytical investigation carried out with high-performance liquid ionic chromatography (HPLIC) and liquid chromatography coupled to mass spectrometry (LC-MS) demonstrate no carbon–carbon bond cleavage occurs, which represents an advance towards a CO 2 -free biomass valorization process. The comparison of the results commonly obtained in a three-electrode half-cell with those in an anion exchange membrane fuel cell shows that the trends in selectivity are the same. The fuel cell operation produces gluconate via a two-electron transfer process at 90% selectivity and 65% Faradaic efficiency. In addition to gluconate, glucuronate is also observed; both compounds are high value-added chemicals. This work contributes towards the engineering of novel electrocatalytic interfaces for the valorization of the surplus biomass into energy and chemicals. [ABSTRACT FROM AUTHOR]