Glycerol Electrolyzer with Graphite Anode and Cathode Produces Carbonyl Compounds and Hydrogen: Background Electrocatalysis of a "Nonparticipating" Current Collector.

This study unveils a novel role of bare graphite as a catalyst in glycerol electrooxidation and hydrogen evolution reactions, challenging the prevailing notion that current collectors employed in electrolyzers are inert. Half-cell experiments elucidate the feasibility of glycerol oxidation and hydrogen production on bulk graphite electrodes at potentials exceeding 1.7 V. The investigation of varying glycerol concentrations (0.05 to 1.5 mol L-1) highlights a concentration-dependent competition between glycerol electrooxidation and oxygen evolution reactions. Employing an H-type glycerol electrolyzer, polarization curves reveal significant activation polarization attributed to the low electroactivity of the anode. Glycerol electrolysis at different concentrations yields diverse product mixtures, including formate, glycolate, glycerate, and lactate at the anode, with concurrent hydrogen generation at the cathode. The anolyte composition changes with glycerol concentration, resulting in less-oxidized compounds at higher concentrations and more oxidized compounds at lower concentrations. The cell voltage also influences the product formation selectivity, with an increased voltage favoring more oxidized compounds. The glycerol concentration also affects hydrogen production, with lower concentrations yielding higher hydrogen amounts, peaking at 3.5 V for 0.05 mol L-1. This model quantitatively illustrates graphite's contribution to current and product generation in glycerol electrolyzers, emphasizing the significance of background current and products originating from current collectors if in contact with the reactants. These results have an impact on the efficiency of the electrolyzer and raise questions regarding possible extra non-noble "nonparticipating" current collectors that could affect overall performance. This research expands our understanding of electrocatalysis on graphite surfaces with potential applications in optimizing electrolyzer configurations for enhanced efficiency and product selectivity.

Glycerol Is Converted into Energy and Carbonyl Compounds in a 3D-Printed Microfluidic Fuel Cell: In Situ and In Operando Bi-Modified Pt Anodes.

The combination of energy and chemical conversion can be achieved by designing glycerol fuel cells. However, the anode must promote the reaction at onset potentials low enough to allow a spontaneous reaction, when coupled to the cathodic reaction, and must be selective. Here, we build a three-dimensional (3D)-printed glycerol microfluidic fuel cell that produces power concomitantly to glycolate and formate at zero bias. The balance between energy and the two carbonyl compounds is tuned by decorating the Pt/C/CP anode in situ (before feeding the cell reactants) or in operando (while feeding the cell with reactants) with Bi. The Bi-modified anodes improve glycerol conversion and output power while decreasing the formation of the carbonyl compounds. The in operando method builds dendrites of rodlike Bi oxides that are inactive for the anodic reaction and cover active sites. The in situ strategy promotes homogeneous Bi decoration, decreasing activation losses, increasing the open-circuit voltage to 1.0 V, and augmenting maximum power density 6.5 times and the glycerol conversion to 72% at 25 °C while producing 0.2 mmoL L-1 of glycolate and formate (each) at 100 µL min-1. Such a performance is attributed to the low CO poisoning of the anode, which leads the glycerol electrooxidation toward a more complete reaction, harvesting more electrons at the device. Printing the microfluidic fuel cell takes 23 min and costs ∼US$1.85 and can be used for other coupled reactions since the methods of modification presented here are applied to any existing and assembled systems.