Direct catalytic valorization of bioethanol to 1-butanol over different alumina supported catalysts was studied. Thirteen (13) heterogeneous catalysts were screened in search for the optimal material composition for direct one-pot conversion of ethanol to 1-butanol. For the most promising catalyst, a 25% ethanol conversion with 80% selectivity (among liquid carbon products) to 1-butanol could be reached at 250 °C. Additionally, the reaction kinetics and mechanisms were further investigated upon use of the most suitable catalyst candidate. OPEN ACCESSCatalysts 2012, 2 69

TiO 2 nanofibers decorated with Pt and Pd nanoparticles have been synthesized and studied in various photocatalytic processes. Excellent photocatalytic behavior in the decomposition of organic dyes in water, degradation of organic stains on the surface of flexible freestanding cellulose/catalyst composite films and in generation of hydrogen from ethanol using both suspended and immobilized catalysts are demonstrated. The performance of the nanofiber-based TiO 2 materials is competitive with-and in some cases outperforms-their conventional nanoparticle-based counterparts. In all cases, Pd-decorated TiO 2 nanoparticles and nanofibers proved to be more efficient than their Pt-based counterparts, which could be explained on the basis of the formation of nano-sized Schottky interfaces at the contacts between TiO 2 and metal nanoparticles. The feasibility of forming cellulose/catalyst composites provides a novel way of utilizing photocatalyst materials in large-area coatings and freestanding films.

An important reaction step in the industrial production of NaClO (electrochemical chlorate process) is the thermal decomposition of HOCl/OCl to yield ClO and Cl. It is widely accepted that this reaction is accelerated by aqueous chromium(vi) species. A detailed kinetic study was conducted under industrially relevant conditions, i.e. at high ionic strength (6.0 M) and elevated temperature (80 °C), to investigate this phenomenon. The decomposition of hypochlorous acid was followed in the presence of Cr(vi) or phosphate (PO) or without any additive. In addition to the beneficial pH buffering effect of Cr(vi), the CrO form of chromium(vi) was found to slightly catalyze the decomposition of hypochlorous acid. The overall rate of HOCl decomposition can be expressed as -dc/dt = k[HOCl][OCl] + k[HOCl][CrO]. The corresponding rate constants were determined, k = 9.4 ± 0.1 M s and k = 4.6 ± 0.8 M s, and mechanistic interpretation of the catalytic rate law is given. The contribution of the catalytic path to the overall rate of decomposition changes from ca. 30% at pH = 8 to ca. 70% at pH = 6.

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Three-dimensional carbon nanotube scaffolds created using micromachined Si/SiO2 templates are used as nanoparticulate filters and support membranes for gas-phase heterogeneous catalysis. The filtering efficiency of better than 99% is shown for the scaffolds in filtering submicrometer particles from air. In the hydrogenation of propene to propane reaction low activation energy of E(a) approximately 27.8 +/- 0.6 kJ x mol(-1), a considerably high turnover rate of approximately 1.1 molecules x Pd site(-1) x s(-1) and durable activity for the reaction are observed with Pd decorated membranes. It is demonstrated that appropriate engineering of macroscopic-ordered nanotube architectures can lead to multifunctional applications.

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The decomposition kinetics and mechanism of N-chloroglycine (MCG) was studied under very alkaline conditions ([OH(-)] = 0.01-0.10 M). The absorbance change is consistent with two consecutive first-order processes in the 220-350 nm wavelength range. The first reaction is linearly dependent on [OH(-)] and interpreted by the formation of a carbanion from MCG in an equilibrium step (KOH) and a subsequent loss of chloride ion from this intermediate: kobs1 = KOH k1 = (6.4 ± 0.1) × 10(-2) M(-1) s(-1), I = 1.0 M (NaClO4), and T = 25.0 °C. The second process is assigned to the first-order decomposition of N-oxalylglycine, which is also formed as an intermediate in this system: kobs2 = (1.2 ± 0.1) × 10(-3) s(-1). Systematic (1)H and (13)C NMR measurements were performed in order to identify and follow the concentration changes of the reactant, intermediate, and product. It is confirmed that the decomposition proceeds via the formation of glyoxylate ion and produces N-formylglycine as a final product. This compound is stable for an extended period of time but eventually hydrolyses into formate and glycinate ions. A detailed mechanism is postulated which resolves the controversies found in earlier literature results.

In this study, the formation of 17 N-chloramines from proteinogenic amino acids and HOCl was studied by direct kinetic method in the pH ¼ 3e13 range. Thus, the uncertainties associated with the indirect methods used in some of the previous studies were eliminated. Each reaction proceeds according to an overall second order kinetics: v ¼ À k [HOCl][ReNH 2 ] and the rate constants are several times 10 7 M À1 s À1. A very slight correlation was found between the lgk and the pK AA of the amino acids. The results make possible to predict the reactivity order of the amino acids toward HOCl under various conditions. A comparison of the parameters of activation indicates that the presence of a bulky substituent on the side chain close to the a-carbon atom decreases the strength of bonding between the reactants and make the structure more diffuse in the transition state. The chlorination of histidine proceeds via two pH dependent paths presumably leading to the formation of N-chloramine and a side chain chlorinated product. The latter compound may be involved in fast subsequent trans-chlorination reactions. The results presented here resolve earlier discrepancies in the literature and are relevant in chlorination water treatment technologies as well as in the interpretation of in vivo processes involving the formation of Nchloro amino acids in a wide pH range.