Methanol electro-oxidation on platinum modified tungsten carbides in direct methanol fuel cells: a DFT study

In exploration of low-cost electrocatalysts for direct methanol fuel cells (DMFCs), Pt modified tungsten carbide (WC) materials are found to be great potential candidates for decreasing Pt usage whilst exhibiting satisfactory reactivity. In this work, the mechanisms, onset potentials and activity for electrooxidation of methanol were studied on a series of Pt-modified WC catalysts where the bare W-terminated WC(0001) substrate was employed. In the surface energy calculations of a series of Pt-modified WC models, we found that the feasible structures are mono- and bi-layer Pt-modified WCs. The tri-layer Pt-modified WC model is not thermodynamically stable where the top layer Pt atoms tend to accumulate and form particles or clusters rather than being dispersed as a layer. We further calculated the mechanisms of methanol oxidation on the feasible models via methanol dehydrogenation to CO involving C-H and O-H bonds dissociating subsequently, and further CO oxidation with the C-O bond association. The onset potentials for the oxidation reactions over the Pt-modified WC catalysts were determined thermodynamically by water dissociation to surface OH* species. The activities of these Pt-modified WC catalysts were estimated from the calculated kinetic data. It has been found that the bi-layer Pt-modified WC catalysts may provide a good reactivity and an onset oxidation potential comparable to pure Pt and serve as promising electrocatalysts for DMFCs with a significant decrease in Pt usage.

Alkali activated fuel ash and slag mixes:optimization study from paste to concrete building blocks

Alkali activated binders, based on ash and slag, also known as geopolymers, can play a key role in reducing the carbon footprint of the construction sector by replacing ordinary Portland cement in some concretes. Since 1970s, research effort has been ongoing in many research institutions. In this study, pulverized fuel ash (pfa) from a UK power plant, ground granulated blast furnace slag (ggbs) and combinations of the two have been investigated as geopolymer binders for concrete applications. Activators used were sodium hydroxide and sodium silicate solutions. Mortars with sand/binder ratio of 2.75 with several pfa and ggbs combinations have been mixed and tested. The optimization of alkali dosage (defined as the Na2O/binder mass ratio) and modulus (defined as the Na2O/SiO2 mass ratio) resulted in strengths in excess of 70 MPa for tested mortars. Setting time and workability have been considered for the identification of the best combination of pfa/ggbs and alkali activator dosage for different precast concrete products. Geopolymer concrete building blocks have been replicated in laboratory and a real scale factory trial has been successfully carried out. Ongoing microstructural characterization is aiming to identify reaction products arising from pfa/ggbs combinations.

Preliminary Investigation on the Electrochemical Activity of Butanol Isomers as Potential Fuel for Direct Alcohol Fuel Cell

A preliminary investigation of electrocatalytic oxidation activity ofbutanol isomers has been carried out to study their potential asfuels for direct alcohol fuel cells. The electrochemical study wascarried out on Pt and Pd electrodes using a three electrode cell setup in alkaline media. The primary alcohol isomers of butanol wereobserved to behave similarly in their electrochemical reactionswhereas 2-butanol showed completely different oxidation featureson both catalysts. For example, no poisoning effects were observedfor 2- butanol unlike for the primary butanol isomers. In contrast,tert-butanol did not show any oxidation reaction on Pt and Pdelectrodes. Furthermore, Pd was not active at all in acidic mediafor butanol oxidation. The reactivity of butanol isomers were foundto be in the order n-butanol>iso-butanol>2-butanol>tert-butanolbased on the oxidation current density values.