Utilisation and valorisation of distillery whisky waste streams via biomass electrolysis: electrosynthesis of hydrogen.

Fuel-flexible hydrogen generation methods, such as electrochemical conversion of biomass, offer a route for sustainable production of hydrogen whilst valorising feedstocks that are often overlooked as waste products. This work explores the potential of a novel, two-stage electrolysis process to convert biomass-containing solid (draff/spent barley) and liquid (pot ale and spent lees) whisky co-products, from the Isle of Raasay Distillery, into hydrogen, using a phosphomolybdic acid (H3[PMo12O40] or PMA) catalyst. Characterisation results for whisky distillery co-products will be presented, including thermogravimetric, differential scanning calorimetric, CHN elemental, total organic carbon and chemical oxygen demand analysis data. The results indicated that the characteristics of these co-products align well with those reported across the Scotch whisky distillation sector. Subsequently, the concept of thermal digestion of each co-product type, using the Keggin-type polyoxometalate PMA catalyst to abstract protons and electrons from biomass, will be outlined. UV-visible spectrophotometry was employed to assess the extent of reduction of the catalyst, after digestion of each co-product, and indicated that draff and pot ale offer the largest scope for hydrogen production, whilst digestion and electrolysis of spent lees is not viable due to the low biomass content of this distillation co-product. Finally, details of electrolysis of the PMA-biomass solutions using a proton-exchange membrane electrolysis cell (PEMEC) will be provided, including electrochemical data that help to elucidate the performance-limiting processes of the PEMEC operating on digested biomass-PMA anolytes.

The Role of Tungsten Oxide in Enhancing the Carbon Monoxide Tolerance of Platinum-Based Hydrogen Oxidation Catalysts.

Significant reductions in total cost of ownership can be realized by engineering PEM fuel cells to run on low-purity hydrogen. One of the main drawbacks of low-purity hydrogen fuels is the carbon monoxide fraction, which poisons platinum electrocatalysts and reduces the power output below useful levels. Platinum-tungsten oxide catalyst systems have previously shown high levels of CO tolerance during both ex situ and in situ investigations. In this work, we explore the mechanism of enhanced tolerance using in situ electrochemical attenuated total reflection-infrared (ATR-IR) and Raman spectroscopy methods and investigate, using a mixture of Pt/C and WO3 powders, the role of the WV/WVI redox couple in the oxidation of adsorbed CO.

Degradation Study by Start-Up/Shut-Down Cycling of Superhydrophobic Electrosprayed Catalyst Layers Using a Localized Reference Electrode Technique.

Degradation of a polymer electrolyte membrane fuel cell (PEMFC) with electrosprayed cathode catalyst layers is investigated during cyclic start-up and shut-down events. The study is carried out within a single cell incorporating an array of reference electrodes that enables measurement of cell current as a function of local cathode potential (localized polarization curves). Accelerated degradation of the cell by start-up/shut-down cycling gives rise to inhomogeneous performance loss, which is more severe close to the gas outlet and occurs predominantly during start-up. The degradation consists primarily of loss of cathode catalyst activity and increase in cell internal resistance, which is attributed to carbon corrosion and Pt aggregation in both anode and cathode. Cells with an electrosprayed cathode catalyst layer show lower degradation rates during the first 100 cycles, compared with those of a conventional gas diffusion electrode. This difference in behavior is attributed to the high hydrophobicity of the electrosprayed catalyst layer microstructure, which retards the kinetics of corrosion of the carbon support. In the long term, however, the degradation rate is dominated by the Pt/C ratio in the cathode catalyst layer.

Reduction Dynamics of Doped Ceria, Nickel Oxide, and Cermet Composites Probed Using In Situ Raman Spectroscopy.

The redox properties of gadolinium doped ceria (CGO) and nickel oxide (NiO) composite cermets underpin the operation of solid oxide electrochemical cells. Although these systems have been widely studied, a full comprehension of the reaction dynamics at the interface of these materials is lacking. Here, in situ Raman spectroscopic monitoring of the redox cycle is used to investigate the interplay between the dynamic and competing processes of hydrogen spillover and water dissociation on the doped ceria surface. In order to elucidate these mechanisms, the redox process in pure CGO and NiO is studied when exposed to wet and dry hydrogen and is compared to the cermet behavior. In dry hydrogen, CGO reduces relatively rapidly via a series of intermediate phases, while NiO reduces via a single-step process. In wet reducing atmospheres, however, the oxidation state of pure CGO is initially stabilized due to the dissociation of water by reduced Ce(III) and subsequent incorporation of oxygen into the structure. In the reduction process involving the composite cermet, the close proximity of the NiO improves the efficiency and speed of the composite reduction process. Although NiO is already incorporated into working cells, these observations suggest direct routes to further improve cell performance.