pH Dependence of Dihydroxyacetone Oxidation by Electrocatalytic Viologen Self-Assembled Monolayers on Gold Electrodes.

Carbohydrate fuel cells garner much research interest as the world's focus shifts from fossil fuels to renewable energy. Many catalyst options are available for carbohydrate fuel cell development, including enzymes and microbes, various metal-based catalysts, and natural or synthetic mediators. Research challenges include low power output, system fouling and poisoning, inefficient electron release, and complex mechanisms, with multiple pathways leading to low product selectivity. Here, we further investigate a novel approach to catalyze carbohydrate oxidation using Au electrodes with viologen self-assembled monolayers (SAMs). SAM-mediated fuel cells have the potential to address the challenges of other catalyst systems by protecting the electrode surface and controlling the local concentration and structure to increase current generation. The effects of increasing pH on dihydroxyacetone (DHA) oxidation by three viologen SAMs on Au electrodes are presented. Current and power generated during DHA oxidation at varying pH were measured and compared to those of bare Au performance. Two of the SAMs produced more current and power than bare Au at elevated pH. The SAM system produced more current and peak power per molecule than both dilute and concentrated homogeneous viologen systems in the same cell setup. These results demonstrate the benefits and limitations of electrodes modified with redox-active groups for the production of electricity from simple sugars and other carbohydrate sources. These results are encouraging for the development of new strategies for electrical power generation from renewable resources.