Biobutanol as Fuel for Direct Alcohol Fuel Cells-Investigation of Sn-Modified Pt Catalyst for Butanol Electro-oxidation

Direct alcohol fuel cells (DAFCs) mostly use low molecular weight alcohols such as methanol and ethanol as fuels. However, short-chain alcohol molecules have a relative high membrane crossover rate in DAFCs and a low energy density. Long chain alcohols such as butanol have a higher energy density, as well as a lower membrane crossover rate compared to methanol and ethanol. Although a significant number of studies have been dedicated to low molecular weight alcohols in DAFCs, very few studies are available for longer chain alcohols such as butanol. A significant development in the production of biobutanol and its proposed application as an alternative fuel to gasoline in the past decade makes butanol an interesting candidate fuel for fuel cells. Different butanol isomers were compared in this study on various Pt and PtSn bimetallic catalysts for their electro-oxidation activities in acidic media. Clear distinctive behaviors were observed for each of the different butanol isomers using cyclic voltammetry (CV), indicating a difference in activity and the mechanism of oxidation. The voltammograms of both n-butanol and iso-butanol showed similar characteristic features, indicating a similar reaction mechanism, whereas 2-butanol showed completely different features; for example, it did not show any indication of poisoning. Ter-butanol was found to be inactive for oxidation on Pt. In situ FTIR and CV analysis showed that OHads was essential for the oxidation of primary butanol isomers which only forms at high potentials on Pt. In order to enhance the water oxidation and produce OHads at lower potentials, Pt was modified by the oxophilic metal Sn and the bimetallic PtSn was studied for the oxidation of butanol isomers. A significant enhancement in the oxidation of the 1° butanol isomers was observed on addition of Sn to the Pt, resulting in an oxidation peak at a potential ∼520 mV lower than that found on pure Pt. The higher activity of PtSn was attributed to the bifunctional mechanism on PtSn catalyst. The positive influence of Sn was also confirmed in the PtSn nanoparticle catalyst prepared by the modification of commercial Pt/C nanoparticle and a higher activity was observed for PtSn (3:1) composition. The temperature-dependent data showed that the activation energy for butanol oxidation reaction over PtSn/C is lower than that over Pt/C.

Essential scientific mapping of the value chain of thermochemical converted second-generation bio-fuels

As the largest contributor to renewable energy, biomass (especially lignocellulosic biomass) has significant potential to address atmospheric emission and energy shortage issues. The bio-fuels derived from lignocellulosic biomass are popularly referred to as second-generation bio-fuels. To date, several thermochemical conversion pathways for the production of second-generation bio-fuels have shown commercial promise; however, most of these remain at various pre-commercial stages. In view of their imminent commercialization, it is important to conduct a profound and comprehensive comparison of these production techniques. Accordingly, the scope of this review is to fill this essential knowledge gap by mapping the entire value chain of second-generation bio-fuels, from technical, economic, and environmental perspectives. This value chain covers i) the thermochemical technologies used to convert solid biomass feedstock into easier-to-handle intermediates, such as bio-oil, syngas, methanol, and Fischer-Tropsch fuel; and ii) the upgrading technologies used to convert intermediates into end products, including diesel, gasoline, renewable jet fuels, hydrogen, char, olefins, and oxygenated compounds. This review also provides an economic and commercial assessment of these technologies, with the aim of identifying the most adaptable technology for the production of bio-fuels, fuel additives, and bio-chemicals. A detailed mapping of the carbon footprints of the various thermochemical routes to second-generation bio-fuels is also carried out. The review concludes by identifying key challenges and future trends for second-generation petroleum substitute bio-fuels.