Hydrogen energy future with formic acid: a renewable chemical hydrogen storage system

Formic acid, the simplest carboxylic acid, is found in nature or can be easily synthesized in the laboratory (major by-product of some second generation biorefinery processes); it is also an important chemical due to its myriad applications in pharmaceuticals and industry. In recent years, formic acid has been used as an important fuel either without reformation (in direct formic acid fuel cells, DFAFCs) or with reformation (as a potential chemical hydrogen storage material). Owing to the better efficiency of DFAFCs compared to several other PEMFCs and reversible hydrogen storage systems, formic acid could serve as one of the better fuels for portable devices, vehicles and other energy-related applications in the future. This perspective is focused on recent developments in the use of formic acid as a reversible source for hydrogen storage. Recent developments in this direction will likely give access to a variety of low-cost and highly efficient rechargeable hydrogen fuel cells within the next few years by the use of suitable homogeneous metal complex/heterogeneous metal nanoparticle-based catalysts under ambient reaction conditions. The production of formic acid from atmospheric CO2 (a greenhouse gas) will decrease the CO2 content and may be helpful in reducing global warming.

Role of Si modification on the compressive flow behavior of Al-Si based alloy

The flow characteristics of a near-eutectic heat-treated Al-Si based cast alloy have been examined in compression at strain rates varying from 3 x 10(-4) to 10(2) s(-1) and at three different temperatures, i.e., room temperature (RT), 100 degrees C and 200 degrees C. The dependence of flow behavior on modification is examined by testing the alloy in both the unmodified and modified conditions. Modification has strong influence on strain rate sensitivity (SRS), strength and work hardening behavior of the alloy. The strength of the alloy is found to increase with increase in strain rate for both the conditions. The increase is more rapid above the strain rate of 10(-1) s(-1) for the unmodified alloy at all the temperatures. This rapid increase is observed at 1 s(-1) at RT and 100 degrees C, and at 10(-2) s(-1) at 200 degrees C for the modified alloy. The thermally dependent process of the Al matrix is rate controlling in the unmodified alloy. On the other hand, the thermally dependent process of both Al matrix and Si particles are rate controlling, which is responsible for the higher strain rate sensitivity (SRS) in the modified alloy. The unmodified alloy exhibits a larger work hardening rate than the modified alloy during the initial stages of straining due to fiber loading of unmodified Si particles. However, the hardening rate decreases sharply at higher strains for the unmodified alloy due to a higher rate of Si particle fracture. Thermal softening is observed for both alloys at 200 degrees C due to precipitate coarsening, which leads to a decrease in SRS at higher temperatures. Stress simulations by microstructure based finite element method support the experimentally observed particle and matrix fracture behavior. Negative SRS and serrated flow are observed at lower strain rate regime (3 x 10(-4) to 10(-2) s(-1)) at RT and 100 degrees C, in both alloys. The critical onset strain is found to be lower and the magnitude of serration is found to be higher for the modified alloy, which suggests that, in addition to dynamic strain aging, Si particle size and morphology also play a role in serrated flow. (C) 2015 Elsevier Inc All rights reserved.

Surface modification of mild steel by a self-assembled cetyl-trimethyl ammonium bromide (CTAB) monolayer: Evaluation of its corrosion protection property

The surface of mild steel was modified by generating cetyl-trimethyl ammonium bromide (CTAB) self-assembled monolayer (SAM) to enhance the corrosion resistance property. The experimental parameters (pH and time) for SAM generation were optimized. The modified surface was characterized by infrared reflection absorption spectroscopy (IRRAS) and contact angle measurements. The SAM generated in 1 mM solution of CTAB at pH 2.5 for 2 h showed a regimented monolayer. Polarization and electrochemical impedance spectroscopic (EIS) studies demonstrated a significant enhancement in the corrosion resistance property of the SAM protected steel in both 1 M HCl and 3.5% NaCl solution. The CTAB SAM surface substantially reduced the corrosion rate by approximately 4 times in 1 M HCl and 1.5 times in 3.5% NaCl media as compared to bare steel. Scanning electron microscopy images confirmed the formation of lesser amounts of corrosion products on the SAM protected surface. (C) 2015 Elsevier B.V. All rights reserved.

Tailoring of Electronic Structure and Thermoelectric Properties of a Topological Crystalline Insulator by Chemical Doping

Topological crystalline insulators (TCIs) are a new quantum state of matter in which linearly dispersed metallic surface states are protected by crystal mirror symmetry. Owing to its vanishingly small bulk band gap, a TCI like Pb0.6Sn0.4Te has poor thermoelectric properties. Breaking of crystal symmetry can widen the band gap of TCI. While breaking of mirror symmetry in a TCI has been mostly explored by various physical perturbation techniques, chemical doping, which may also alter the electronic structure of TCI by perturbing the local mirror symmetry, has not yet been explored. Herein, we demonstrate that Na doping in Pb0.6Sn0.4Te locally breaks the crystal symmetry and opens up a bulk electronic band gap, which is confirmed by direct electronic absorption spectroscopy and electronic structure calculations. Na doping in Pb0.6Sn0.4Te increases p-type carrier concentration and suppresses the bipolar conduction (by widening the band gap), which collectively gives rise to a promising zT of 1 at 856 K for Pb0.58Sn0.40Na0.02Te. Breaking of crystal symmetry by chemical doping widens the bulk band gap in TCI, which uncovers a route to improve TCI for thermoelectric applications.

Measuring the magnetic-field-dependent chemical potential of a low-density three-dimensional electron gas in n-GaAs and extracting its magnetic susceptibility

We report the magnetic-field-dependent shift of the electron chemical potential in bulk, n-type GaAs at room temperature. A transient voltage of similar to 100 mu V was measured across a Au-Al2O3-GaAs metal-oxide-semiconductor capacitor in a pulsed magnetic field of similar to 6 T. Several spurious voltages larger than the signal that had plagued earlier researchers performing similar experiments were carefully eliminated. The itinerant magnetic susceptibility of GaAs is extracted from the experimentally measured data for four different doping densities, including one as low as 5 x 10(15) cm(-3). Though the susceptibility in GaAs is dominated by Landau-Peierls diamagnetism, the experimental technique demonstrated can be a powerful tool for extracting the total free carrier magnetization of any electron system. The method is also virtually independent of the carrier concentration and is expected to work better in the nondegenerate limit. Such experiments had been successfully performed in two-dimensional electron gases at cryogenic temperatures. However, an unambiguous report on having observed this effect in any three-dimensional electron gas has been lacking. We highlight the 50 year old literature of various trials and discuss the key details of our experiment that were essential for its success. The technique can be used to unambiguously yield only the itinerant part of the magnetic susceptibility of complex materials such as magnetic semiconductors and hexaborides, and thus shed light on the origin of ferromagnetism in such systems.

How to be a dioecious fig: Chemical mimicry between sexes matters only when both sexes flower synchronously

In nursery pollination mutualisms, which are usually obligate interactions, olfactory attraction of pollinators by floral volatile organic compounds (VOCs) is the main step in guaranteeing partner encounter. However, mechanisms ensuring the evolutionary stability of dioecious fig-pollinator mutualisms, in which female fig trees engage in pollination by deceit resulting in zero reproductive success of pollinators that visit them, are poorly understood. In dioecious figs, individuals of each sex should be selected to produce odours that their pollinating wasps cannot distinguish, especially since pollinators have usually only one choice of a nursery during their lifetime. To test the hypothesis of intersexual chemical mimicry, VOCs emitted by pollen-receptive figs of seven dioecious species were compared using headspace collection and gas chromatography-mass spectrometry analysis. First, fig-flower scents varied significantly among species, allowing host-species recognition. Second, in species in which male and female figs are synchronous, intersexual VOC variation was not significant. However, in species where figs of both sexes flower asynchronously, intersexual variation of VOCs was detectable. Finally, with one exception, there was no sexual dimorphism in scent quantity. We show that there are two ways to use scent to be a dioecious fig based on differences in flowering synchrony between the sexes.

Electrochemical, gravimetric and quantum chemical analysis of mild steel corrosion inhibition by colchicine in 1 M HCl medium

The inhibition effect of colchicine (CC) on mild steel (MS) corrosion in 1 M HCl solution has been investigated by electrochemical techniques such as electrochemical impedance spectroscopy, potentiodynamic polarization, chronoamperometry and also by the gravimetric method. Polarization studies showed that CC acts as mixed type corrosion inhibitor. The inhibitor adsorption process in the MS/CC/HCl system was studied at different temperatures (303-333 K). The adsorption of CC on MS surface is an exothermic process and obeys the Langmuir adsorption isotherm. Based on potential of zero charge values and quantum chemical parameters, the mechanism of adsorption has been proposed.

Comments on ``Influence of chemical reaction and viscous dissipation on MHD mixed convection flow'' by K. Das JMST 28 (5) (2014) 1881 similar to 1885] and ``Cu-water nanofluid flow and heat transfer over a shrinking sheet'' by K. Das JMST 28 (12) 5089 similar to 5094]

In this letter, we submit our comment on the following recently published papers by Kalidas Das: (1) ``Influence of chemical reaction and viscous dissipation on MHD mixed convection flow,'' Journal of Mechanical Science and Technology 28 (5) (2014) 1881-1885; and (2) ``Cu-water nanofluid flow and heat transfer over a shrinking sheet,'' Journal of Mechanical Science and Technology 28 (12) (2014) 5089-5094. The authors attempt to present the similarity solutions in both papers. We comment that the similarity transformations considered in Refs. 1, 2] are incorrect. Thus, the results presented by Kalidas Das lead to invalid conclusions.

Reconciling results of MOCVD of a CNT composite with equilibrium thermodynamics

Composition and microstructure of the composite films can be tailored by controlling the CVD process parameters if an appropriate model can be suggested for quantitative prediction of growth. This is possible by applying equilibrium thermodynamics. A modification of such standard modeling procedure was required to account for the deposition of a hybrid film comprised of carbon nanotubes (CNTs), metallic iron (Fe), and magnetite (Fe3O4), a composite useful for energy storage. In contrast with such composite nature of the deposits obtained by inert-ambient CVD using Fe(acac)3 as precursor, equilibrium thermodynamic modeling with standard procedure predicts the deposition of only Fe3C and carbon, without any co-deposition of Fe and Fe3O4. A modification of the procedure comprising chemical reasoning is therefore proposed herein, which predicts simultaneous deposition of FeO1-x, Fe3C, Fe3O4 and C. At high temperatures and in a carbon-rich atmosphere, these convert to Fe3O4, Fe and C, in agreement with experimental CVD. Close quantitative agreement between the modified thermodynamic modeling and experiment validates the reliability of the modified procedure. Understanding of the chemical process through thermodynamic modeling provides potential for control of CVD process parameters to achieve desired hybrid growth. (C) 2016 Elsevier B.V. All rights reserved.

Isotopes in cosmochemistry: recipe for a Solar System

Extreme isotopic variations among extraterrestrial materials provide great insights into the origin and evolution of the Solar System. In this tutorial review, we summarize how the measurement of isotope ratios can expand our knowledge of the processes that took place before and during the formation of our Solar System and its subsequent early evolution. The continuous improvement of mass spectrometers with high precision and increased spatial resolution, including secondary ion mass spectrometry (SIMS), thermal ionization mass spectrometry (TIMS) and multi collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS), along with the ever growing amounts of available extraterrestrial samples have significantly increased the temporal and spatial constraints on the sequence of events that took place since and before the formation of the first Solar System condensates (i.e., Ca-Al-rich inclusions). Grains sampling distinct stellar environments with a wide range of isotopic compositions were admixed to, but possibly not fully homogenized in, the Sun's parent molecular cloud or the nascent Solar System. Before, during and after accretion of the nebula, as well as the formation and subsequent evolution of planetesimals and planets, chemical and physical fractionation processes irrevocably changed the chemical and isotopic compositions of all Solar System bodies. Since the formation of the first Solar System minerals and rocks 4.568 Gyr ago, short-and long-lived radioactive decay and cosmic ray interaction also contributed to the modification of the isotopic framework of the Solar System, and permit to trace the formation and evolution of directly accessible and inferred planetary and stellar isotopic reservoirs.

Temperature measurement of reflected shock wave by using chemical indicator

This report describes a new method for measuring the temperature of the gas behind the reflected shock wave in shock tube, corresponding to the reservoir temperature of a shock tunnel, based on the chemical reaction of small amount of CF4 premixed in the test gas. The final product C2F4 is used as the temperature indicator, which is sampled and detected by a gas chromatography in the experiment. The detected concentration of C2F4 is correlated to the temperature of the reflected shock wave with the initial pressure P-1 and test time tau as parameters in the temperature range 3 300 K < T < 5 600 K, pressure range 5 kPa < P1 <12 kPa and tau similar or equal to 0.4 ms.

Mechano-Chemical Coupling at Molecular Level: Forced Dissociation of Selectin/Ligand Binding

Mechano-chemical coupling is a common phenomenon that exists in various biological processes at different physiological levels. Bone tissue remodeling strongly depends on the local mechanical load. Leukocytes are sheared to form the transient aggregates with platelets or other leukocytes in the circulation. Flow pattern affects the signal transduction pathways in endothelial cells. Receptor/ligand interactions are important to cell adhesion since they supply the physical linkages...

Modified Simplified Rate Equation Model of Flowing Chemical Oxygen-Iodine Laser and its Application

A modified simplified rate equation (RE) model of flowing chemical oxygen-iodine laser (COIL), which is adapted to both the condition of homogeneous broadening and inhomogeneous broadening being of importance and the condition of inhomogeneous broadening being predominant, is presented for performance analyses of a COIL. By using the Voigt profile function and the gain-equal-loss approximation, a gain expression has been deduced from the rate equations of upper and lower level laser species. This gain expression is adapted to the conditions of very low gas pressure up to quite high pressure and can deal with the condition of lasing frequency being not equal to the central one of spectral profile. The expressions of output power and extraction efficiency in a flowing COIL can be obtained by solving the coupling equations of the deduced gain expression and the energy equation which expresses the complete transformation of the energy stored in singlet delta state oxygen into laser energy. By using these expressions, the RotoCOIL experiment is simulated, and obtained results agree well with experiment data. Effects of various adjustable parameters on the performances of COIL are also presented.