Small volume laboratory on a chip measurements incorporating the quartz crystal microbalance to measure the viscosity-density product of room temperature ionic liquids

A microfluidic glass chip system incorporating a quartz crystal microbalance (QCM) to measure the square root of the viscosity-density product of room temperature ionic liquids (RTILs) is presented. The QCM covers a central recess on a glass chip, with a seal formed by tightly clamping from above outside the sensing region. The change in resonant frequency of the QCM allows for the determination of the square root viscosity-density product of RTILs to a limit of ∼ 10 kg m−2 s−0.5. This method has reduced the sample size needed for characterization from 1.5 ml to only 30 μl and allows the measurement to be made in an enclosed system

Insights into the mechanism of electrochemical ozone production via water splitting on the Ni and Sb Doped SnO2 catalyst

The H2O splitting mechanism is a very attractive alternative used in electrochemistry for the formation of O3. The most efficient catalysts employed for this reaction at room temperature are SnO2-based, in particular the Ni/Sb-SnO2 catalyst. In order to investigate the H2O splitting mechanism Density Functional Theory (DFT) was performed on a Ni/Sb-SnO2 surface with oxygen vacancies. By calculating different SnO2 facets, the (110) facet was deemed most stable, and further doped with Sb and Ni. On this surface, the H2O splitting mechanism was modelled paying particular attention to the final two steps, the formation of O2 and O3. Previous studies on β-PbO2 have shown that the final step in the reaction (the formation of O3) occurs via an Eley-Rideal style interaction where surface O2 desorbs before attacking surface O to form O3. It is revealed that for Ni/Sb-SnO2, although the overall reaction is the same the surface mechanism is different. The formation of O3 is found to occur through a Langmuir-Hinshelwood mechanism as opposed to Eley-Rideal. In addition to this the relevant adsorption energies (Eads), Gibb’s free energy (ΔGrxn) and activation barriers (Eact) for the final two steps modelled in the gas phase have been shown; providing the basis for a tool to develop new materials with higher current efficiencies

Combined Superbase Ionic Liquid Approach to Separate CO2 from Flue Gas

[Image: see text] Superbase ionic liquids (ILs) with a trihexyltetradecylphosphonium cation and a benzimidazolide ([P(66614)][Benzim]) or tetrazolide ([P(66614)][Tetz]) anion were investigated in a dual-IL system allowing the selective capture and separation of CO(2) and SO(2), respectively, under realistic gas concentrations. The results show that [P(66614)][Tetz] is capable of efficiently capturing SO(2) in preference to CO(2) and thus, in a stepwise separation process, protects [P(66614)][Benzim] from the negative effects of the highly acidic contaminant. This results in [P(66614)][Benzim] maintaining >53% of its original CO(2) uptake capacity after 30 absorption/desorption cycles in comparison to the 89% decrease observed after 11 cycles when [P(66614)][Tetz] was not present. Characterization of the ILs post exposure revealed that small amounts of SO(2) were irreversibly absorbed to the [Benzim](−) anion responsible for the decrease in CO(2) capacity. While optimization of this dual-IL system is required, this feasibility study demonstrates that [P(66614)][Tetz] is a suitable sorbent for reversibly capturing SO(2) and significantly extending the lifetime of [P(66614)][Benzim] for CO(2) uptake

Structured ZSM-5/SiC foam catalysts for bio-oils upgrading

ZSM-5 zeolite coating supported on SiC foams was prepared by a precursor dispersion-secondary growth method and the resulting structured ZSM-5/SiC foam catalyst was used for the proof-of-concept study of catalytic bio-oils upgrading (i.e. deoxygenation of the model compounds of methanol and anisole) in reference to ZSM-5 catalyst pellets. A layer of ZSM-5 coating with inter-crystal porosity on SiC foams was produced by curing the zeolite precursor thermally at 80 °C. The use of SiC foam as the zeolite support significantly improved transport phenomena compared to the packed-bed using ZSM-5 pellets, explaining the comparatively good catalytic performance achieved by the structured ZSM-5/SiC foam catalyst. In comparison with the ZSM-5 pellets, the ZSM-5/SiC foam catalyst showed 100.0% methanol conversion (at the weight hourly space velocity, WHSV, of 8 h–1) and 100.0% anisole conversion (at WHSV =5 h−1) at the initial stage of the processes, while only about 3% were obtained for the ZSM-5 pellets, under the same conditions. Based on the comparative analysis of the characterisation data on the fresh and spent catalysts, the deactivation mechanisms of the ZSM-5/SiC and the ZSM-5 pellet catalysts were explained. The process intensification using SiC foam to support ZSM-5 improved the global gas-to-solid mass transfer notably, and hence mitigating the pore blocking due to the carbon deposition on the external surface of supported ZSM-5

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

Physical and Electrochemical Investigations into Blended Electrolytes Containing a Glyme Solvent and Two Bis{(trifluoromethyl)sulfonyl}imide-Based Ionic Liquids

International audienceIn this paper, we report on thermophysical and electrochemical investigations of a series of molecular solvent/ionic liquid (IL) binary mixture electrolytes. Tetraethylene glycol dimethyl ether (TEGDME) is utilized as the molecular solvent component in separate mixtures with two bis{(trifluoromethyl)sulfonyl}imide anion based ILs paired with similarly sized cyclic and acyclic alkylammonium cations; 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide, [Pyrr14][TFSI], or N-butyl-N,N-dimethyl-N-ethylammonium bis{(trifluoromethyl)sulfonyl}imide, [N1124][TFSI]. The blending of ILs with select molecular solvents is an important strategy for the improvement of the typically sluggish transport capabilities of these interesting electrolytic solvents. Bulk volumetric and transport properties are reported as a function of temperature and binary mixture formulation; demonstrating the capacity for enhancing desired properties of the IL. Micro-disk electrode voltammetry and chronoamperometry in O2-saturated binary mixture electrolytes was used to assess the effect of formulation on the solubility and diffusivity of the dissolved gas. In addition, further investigations of the behavior of the O2 redox couple at a GC macro-disk electrode are discussed

Reversible Reaction of CO2 with Superbasic Ionic Liquid [P66614][benzim] Studied with in Situ Photoelectron Spectroscopy

Ionic liquids (ILs) are of significant interest as CO2 capture agents, and one subgroup of ILs that has shown particular promise is that of superbasic ILs. They can absorb large quantities of CO2 in the dry state, but some will have a diminished CO2 capacity when prewetted. In the work presented here, the superbasic IL trihexyl-tetradecylphosphonium benzimidazolide, or [P66614][benzim], was exposed to 3 mbar of CO2, 2 mbar of H2O vapor, and a CO2 + H2O gas mixture and was investigated using near-ambient pressure X-ray photoelectron spectroscopy. The results show that the IL reacts with CO2 to form carbamate and that the reaction is reversible through reduction of the surrounding gas pressure. Regardless of whether the IL was exposed to CO2 or H2O vapor first, the presence of H2O under these experimental conditions does not significantly hinder the IL’s ability to absorb and react with CO2. Furthermore, the IL appears to preferentially react with CO2 over H2O vapor

Amrita Bazar Patrika, March 13 (1898)

Amrita Bazar Patrika was one of the oldest newspapers in India and started on 20th February, 1868 in the village of Amrita Bazar as a Bengali weekly newspaper. In 1871 the offices of the Patrika moved to Calcutta and published news in English and Bengali as a bilingual weekly till 1878, when it turned into an English newspaper due to the Vernacular Press Act of 1878. From 1891 onwards Amrita Bazar Patrika was published as a daily newspaper. In some years the newspaper was also published bi-weekly on Thursday and Sunday