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Concentrated water-in-salt electrolytes (WiSEs) are used in aqueous batteries and to control electrochemical reactions for fuel production. The hydrogen evolution reaction is a parasitic reaction at the negative electrode that limits cell voltage in WiSE batteries and leads to self-discharge, and affects selectivity for electrosynthesis. Mitigating and modulating these processes is hampered by a limited fundamental understanding of HER kinetics in WiSEs. Here, we quantitatively assess how thermodynamics, kinetics, and interface layers control the apparent HER activities in 20 m LiTFSI. When the LiTFSI concentration is increased from 1 to 20 m, an increase in proton activity causes a positive shift in the HER equilibrium potential of 71 mV. The exchange current density, io, derived from the HER branch for 20 m LiTFSI in 98% purity (0.56 ± 0.05 μA/cmPt2), however, is 8 times lower than for 20 m LiTFSI in 99.95% (4.7 ± 0.2 μA/cmPt2) and 32 times lower than for 1 m LiTFSI in 98% purity (18 ± 1 μA/cmPt2), demonstrating that the WiSE's impurities and concentration are both central in significantly suppressing HER kinetics. The ability and applicability of the reported methods are extended by examining additional WiSEs formulations made of acetates and nitrates.

We present a sensitive and quantitative protein detection assay that can efficiently distinguish between specific and nonspecific target binding. Our technique combines dual affinity reagents with surface-enhanced Raman spectroscopy (SERS) and chemometric analysis. We link one Raman reporter-tagged affinity reagent to gold nanoparticles and another to a gold film, such that protein-binding events create a "hot spot" with strong SERS spectra from both Raman reporter molecules. Any signal generated in this context is indicative of recognition by both affinity labels, whereas signals generated by nonspecific binding lack one or the other label, enabling us to efficiently distinguish true from false positives. We show that the number of hot spots per unit area of our substrate offers a quantitative measure of analyte concentration and demonstrate that this dual-label, SERS-linked aptasensor assay can sensitively and selectively detect human α-thrombin in 1% human serum with a limit of detection of 86 pM.

Short-chain polyphosphate (polyP) is released from platelets upon platelet activation, but it is not clear if it contributes to thrombosis. PolyP has increased propensity to clot blood with increased polymer length and when localized onto particles, but it is unknown whether spatial localization of short-chain polyP can accelerate clotting of flowing blood. Here, numerical simulations predicted the effect of localization of polyP on clotting under flow, and this was tested in vitro using microfluidics. Synthetic polyP was more effective at triggering clotting of flowing blood plasma when localized on a surface than when solubilized in solution or when localized as nanoparticles, accelerating clotting at 10-200 fold lower concentrations, particularly at low to sub-physiological shear rates typical of where thrombosis occurs in large veins or valves. Thus, sub-micromolar concentrations of short-chain polyP can accelerate clotting of flowing blood plasma under flow at low to sub-physiological shear rates. However, a physiological mechanism for the localization of polyP to platelet or vascular surfaces remains unknown.

A general, substrate-independent method for plasma deposition of nanostructured, crystalline metal oxides is presented. The technique uses a flow-through, micro-hollow cathode plasma discharge (supersonic microplasma jet) with a “remote” ring anode to deliver a highly directed flux of growth species to the substrate. A diverse range of nanostructured materials (e.g., CuO, α-Fe2O3, and NiO) can be deposited on any room temperature surface, e.g., conductors, insulators, plastics, fibers, and patterned surfaces, in a conformal fashion. The effects of deposition conditions, substrate type, and patterning on film morphology, nanostructure, and surface coverage are highlighted. The synthesis approach presented herein provides a general and tunable method to deposit a variety of functional and hierarchical metal oxide materials on many different surfaces. High surface area, conversion-type CuO electrodes for Li-ion batteries are demonstrated as a proof-of-concept example.

Developing electrode materials with high-energy densities is important for the development of lithium-ion batteries. Here, we demonstrate a mesoporous molybdenum dioxide material with abnormal lithium-storage sites, which exhibits a discharge capacity of 1,814 mAh g(-1) for the first cycle, more than twice its theoretical value, and maintains its initial capacity after 50 cycles. Contrary to previous reports, we find that a mechanism for the high and reversible lithium-storage capacity of the mesoporous molybdenum dioxide electrode is not based on a conversion reaction. Insight into the electrochemical results, obtained by in situ X-ray absorption, scanning transmission electron microscopy analysis combined with electron energy loss spectroscopy and computational modelling indicates that the nanoscale pore engineering of this transition metal oxide enables an unexpected electrochemical mass storage reaction mechanism, and may provide a strategy for the design of cation storage materials for battery systems.

Plasmonic metal/semiconductor heterostructures show promise for visible-light-driven photocatalysis. Gold nanorods (AuNRs) semi-coated with TiO2 are expected to be ideally structured systems for hydrogen evolution. Synthesizing such structures by wet-chemistry methods, however, has proved challenging. Here we report the bottom-up synthesis of AuNR/TiO2 nanodumbbells (NDs) with spatially separated Au/TiO2 regions, whose structures are governed by the NRs' diameter, and the higher curvature and lower density of CnTAB surfactant at the NRs' tips than on their lateral surfaces, as well as the morphology's dependence on concentration, and alkyl chain length of CnTAB. The NDs show plasmon-enhanced H2 evolution under visible and near-infrared light.

We propose a nanostructured Mn-doped V2O5 lithium-ion battery cathode material that facilitates cathodic charge transport. The synthesis strategy uses a layered compound, vanadium(III) jarosite, as the precursor, in which the Mn2+ ions are doped uniformly between the vanadium oxide crystal layers. Through a two-step transformation, the vanadium jarosite was converted into Mn2+-doped V2O5. The resulting aliovalent doping of the larger Mn cations in the modified V2O5 structure increases the cell volume, which facilitates diffusion of Li+ ions, and introduces oxygen vacancies that improve the electronic conductivity. Comparison of the electrochemical performance in Li-ion batteries of undoped and the Mn2+-doped V2O5 hierarchical structure made from layered vanadium jarosite confirms that the Mn-doping improves ion transport to give a high cathodic columbic capacity (253 mAhg-1 at 1C, 86% of the theoretical value, 294 mAhg-1) and excellent cycling stability.

We report a new electrochemical capacitor with an aqueous KI-KOH electrolyte that exhibits a higher specific energy and power than the state-of-the-art nonaqueous electrochemical capacitors. In addition to electrical double layer capacitance, redox reactions in this device contribute to charge storage at both positive and negative electrodes via a catholyte of IOx-/I- couple and a redox couple of H2O/Had, respectively. Here, we, for the first time, report utilizing IOx-/I- redox couple for the positive electrode, which pins the positive electrode potential to be 0.4-0.5 V vs Ag/AgCl. With the positive electrode potential pinned, we can polarize the cell to 1.6 V without breaking down the aqueous electrolyte so that the negative electrode potential could reach -1.1 V vs Ag/AgCl in the basic electrolyte, greatly enhancing energy storage. Both mass spectroscopy and Raman spectrometry confirm the formation of IO3- ions (+5) from I- (-1) after charging. Based on the total mass of electrodes and electrolyte in a practically relevant cell configuration, the device exhibits a maximum specific energy of 7.1 Wh/kg, operates between -20 and 50 °C, provides a maximum specific power of 6222 W/kg, and has a stable cycling life with 93% retention of the peak specific energy after 14,000 cycles.

Zeolites are crystalline inorganic solids with microporous structures, having widespread applications in the fields of catalysis, separation, adsorption, microelectronics, and medical diagnosis. A major drawback of zeolites is the mass transfer limitation due to the small size of the micropores (less than 1 nm). Numerous efforts have been dedicated to integrating mesopores with the microporous zeolite structures by using templating and/or destructive approaches. Here we provide a new strategy for hierarchical pore size zeolite synthesis, without using supramolecular or hard templates. The branching epitaxial growth behavior, as a result of aluminum-zoning, contributes to the formation of the hierarchical porous zeolite structures.

We have developed a facile procedure that can create asymmetrical building blocks by uniformly deforming nanospheres into C(∞v) symmetry at low cost and high quality. Concave polystyrene@carbon (PS@C) core-shell nanospheres were produced by a very simple microwave-assisted alcohol thermal treatment of spherical PS@C nanoparticles. The dimensions and ratio of the concave part can be precisely controlled by temperature and solvents. The concavity is created by varying the alcohol-thermal treatment to tune the swelling properties that lead to the mechanical deformation of the PS@C core-shell structure. The driving force is attributed to the significant volume increase that occurs upon polystyrene core swelling with the incorporation of solvent. We propose a mechanism adapted from published models for the depression of soft capsules. An extrapolation from this model predicts that the rigid shell is used to generate a cavity in the unbuckled shell, which is experimentally confirmed. This swelling and deformation route is flexible and should be applicable to other polymeric nanoparticles to produce asymmetrical nanoparticles.

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg(-1) based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30-50 Wh kg(-1) is possible with optimization.

We present a silica nanoparticle (SNP) functionalized with polyphosphate (polyP) that accelerates the natural clotting process of the body. SNPs initiate the contact pathway of the blood-clotting system; short-chain polyP accelerates the common pathway by the rapid formation of thrombin, which enhances the overall blood-clotting system, both by accelerating fibrin generation and by facilitating the regulatory anticoagulation mechanisms essential for hemostasis. Analysis of the clotting properties of bare SNPs, bare polyP, and polyP-functionalized SNPs in plasma demonstrated that the attachment of polyP to SNPs to form polyP-SNPs creates a substantially enhanced synergistic effect that lowers clotting time and increases thrombin production at low concentrations. PolyP-SNP even retains its clotting function at ambient temperature. The polyP-SNP system has the potential to significantly improve trauma-treatment protocols and outcomes in hospital and prehospital settings.

The optical resonances of plasmonic nanostructures depend critically on the geometrical details of the absorber. We show that this unique property of plasmons can potentially be used to create panchromatic absorbers covering most of the useful solar spectrum, by measuring the light-to-hydrogen conversion capabilities of a series multielectrode photocatalytic devices, based on functionalized gold nanorods of appropriately chosen aspect ratios. Judiciously combining nanorods of various aspect ratios almost doubles the H2 production of the device over what is optimally possible with a device using gold nanorods of a single aspect ratio (all other key parameters being equal). The estimated quantum efficiency (absorbed photons-to-hydrogen) averaged over the entire solar spectrum of the best performing plasmonic multielectrode array was approximately 0.1%, and the measured H2 production rate for all of the devices was found to be approximately proportional to the hot electron generation. The device was monitored continuously for over 200 hr of operation without measurable diminution in the rate.

Constructing nanoparticles into well-defined structures at mesoscale and larger to create novel functional materials remains a challenge. Inspired by atomic epitaxial growth, we propose an "epitaxial assembly" method to form two-dimensional nanoparticle arrays (2D NAs) directly onto desired materials. As an illustration, we employ a series of surfactant-capped nanoparticles as the "artificial atoms" and layered hybrid perovskite (LHP) materials as the substrates and obtain 2D NAs in a large area with few defects. This method is universal for nanoparticles with different shapes, sizes, and compositions and for LHP substrates with different metallic cores. Raman spectroscopic and X-ray diffraction data support our hypothesis of epitaxial assembly. The novel method offers new insights into the controllable assembly of complex functional materials and may push the development of materials science at the mesoscale.

In this paper, we propose a heterogeneous material for bulk thermoelectrics. By varying the quenching time of Na doped PbTe, followed by hot pressing, we synthesized heterogeneous nanocomposites, a mixture of nanodot nanocomposites and nanograined nanocomposites. It is well-known that by putting excess amounts of Na (i.e., exceeding the solubility limit) into PbTe, nanodots with sizes as small as a few nanometers can be formed. Nanograined regions with an average grain size of ca. 10 nm are observed only in materials synthesized with an extremely low quenching rate, which was achieved by using a quenching media of iced salt water and cold water. Dimensionless thermoelectric figures of merit, zT, of those heterogeneous nanocomposites exhibited a zT around 2.0 at 773 K, which is a 25% increase compared to zT of a homogeneous nanodot nanocomposite with the largest quenching time in our experiment, i.e. furnace cooled. The power factor increase is 5%, and the thermal conductivity reduction is 15%; thus, zT increase mainly comes from the thermal conductivity reduction.

We report utilization of graphitic carbon nitride (g-CN) as an electrocatalyst for dye-sensitized solar cells (DSSCs). Crystalline poly(triazine imide) based g-CN was synthesized via a modified ionothermal method, and deposited onto the counter electrodes along with a conductive additive and a sacrificial polymer binder. The resulting DSSCs exhibited a power conversion efficiency (7.8%) comparable to that of conventional Pt catalyst (7.9%), confirming the excellent catalytic activity of poly(triazine imide) g-CN as a non-precious metal electrocatalyst.

We describe a general approach for the synthesis of micro-/nanostructured metal chalcogenides from elemental precursors. The excellent solubility of sulfur, selenium, and tellurium in phosphonium ionic liquids promotes fast reactions between chalcogens and various metal powders upon microwave heating, giving crystalline products. This approach is green, universal, and scalable.

The Li-S system offers a tantalizing battery for electric vehicles and renewable energy storage due to its high theoretical capacity of 1675 mAh g(-1) and its employment of abundant and available materials. One major challenge in this system stems from the formation of soluble polysulfides during the reduction of S8, the active cathode material, during discharge. The ability to deploy this system hinges on the ability to control the behavior of these polysulfides by containing them in the cathode and allowing for further redox. Here, we exploit the high surface areas and good electrical conductivity of mesoporous carbons (MC) to achieve high sulfur utilization while functionalizing the MC with sulfur (S-MC) in order to modify the surface chemistry and attract polysulfides to the carbon material. S-MC materials show enhanced capacity and cyclability trending as a function of sulfur functionality, specifically a 50% enhancement in discharge capacity is observed at high cycles (60-100 cycles). Impedance spectroscopy suggests that the S-MC materials exhibit a lower charge-transfer resistance compared with MC materials which allows for more efficient electrochemistry with species in solution at the cathode. Isothermal titration calorimetry shows that the change in surface chemistry from unfunctionalized to S-functionalized carbons results in an increased affinity of the polysulfide intermediates for the S-MC materials, which is the likely cause for enhanced cyclability.

For the first time, we demonstrate that orthorhombic V2O5 can exhibit superior electrochemical performance in sodium ion batteries when uniformly coated inside nanoporous carbon. The encapsulated V2O5 shows a specific capacity as high as 276 mAh/g, while the whole nanocomposite exhibits a capacity of 170 mAh/g. The V2O5/C composite was fabricated by a novel ambient hydrolysis deposition that features sequential water vapor adsorption in nanoporous carbon, followed by a hydrolysis reaction, exclusively inside the nanopores. The unique structure of the nanocomposite significantly enhances the capacity as well as the rate performance of orthorhombic V2O5 where the composite retains a capacity of over 90 mAh/g at a current rate of 640 mA/g. Furthermore, by calculating, we also revealed that a large portion of the sodium-ion storage, particularly at high current rates, is due to the V2O5 pseudocapacitance.

The conversion of sunlight into electricity by photovoltaics is currently a mature science and the foundation of a lucrative industry. In conventional excitonic solar cells, electron-hole pairs are generated by light absorption in a semiconductor and separated by the "built in" potential resulting from charge transfer accompanying Fermi-level equalization either at a p-n or a Schottky junction, followed by carrier collection at appropriate electrodes. Here we report a stable, wholly plasmonic photovoltaic device in which photon absorption and carrier generation take place exclusively in the plasmonic metal. The field established at a metal-semiconductor Schottky junction separates charges. The negative carriers are high-energy (hot) electrons produced immediately following the plasmon's dephasing. Some of the carriers are energetic enough to clear the Schottky barrier or quantum mechanically tunnel through it, thereby producing the output photocurrent. Short circuit photocurrent densities in the range 70-120 μA cm(-2) were obtained for simulated one-sun AM1.5 illumination with devices based on arrays of parallel gold nanorods, conformally coated with 10 nm TiO2 films and fashioned with a Ti metal collector. For the device with short circuit currents of 120 μA cm(-2), the internal quantum efficiency is ∼2.75%, and its wavelength response tracks the absorption spectrum of the transverse plasmon of the gold nanorods indicating that the absorbed photon-to-electron conversion process resulted exclusively in the Au, with the TiO2 playing a negligible role in charge carrier production. Devices fabricated with 50 nm TiO2 layers had open-circuit voltages as high as 210 mV, short circuit current densities of 26 μA cm(-2), and a fill factor of 0.3. For these devices, the TiO2 contributed a very small but measurable fraction of the charge carriers.

An approach based on a solution-based synthesis that produces a thermally stable Ag/oxide/S₂ Te₃ -Te metal-semiconductor heterostructure is described. With this approach, a figure of merit of zT = 1.0 at 460 K is achieved, a record for a heterostructured material made using wet chemistry. Combining experiments and theory shows that the large increase in the material's Seebeck coefficient results from hot carrier filtering.

We present a rapid microwave-assisted solid-state approach to prepare complex platinum-group metal oxides with the formula La2BaMO5 (M = Pd, Pt). While conventional furnace-based preparations of these compounds take several days and often require oxidizing conditions, the microwave-assisted pathway enables the target compounds to be obtained with high phase purity in about 20 min of reaction time in air without the multiple regrindings that are required of conventional solid-state synthesis. These complex oxides are stable in various atmospheres up to 1000 °C unlike the simple noble metal oxides, which are reduced even at room temperature. Density functional theory-based calculations have been employed to establish the stability of these complex oxides and to understand the electronic structure origins of the stability, most notably the influence of electropositive cations. It is shown that the presence of electropositive ions in the oxide crystal structure "softens" the oxygen anion and results in more covalent (Pd/Pt)-O interactions.

Thermoelectric properties and phase evolution have been studied in biphasic Ti–Ni–Sn materials containing full-Heusler TiNi2Sn embedded within half-Heusler thermoelectric TiNiSn. Materials, prepared by levitation induction melting followed by annealing, were of the nominal starting composition of TiNi1+xSn, with x between 0.00 and 0.25. Phases and microstructure were determined using synchrotron X-ray diffraction and optical and electron microscopy. The full-Heusler phase is observed to be semi-coherent with the half-Heusler majority phase. Differential thermal analysis was performed to determine melting temperatures of the end-member compounds. The thermal conductivity is reduced with the introduction of a dispersed, full-Heusler phase within the half-Heusler material. This leads to an increased thermoelectric figure of merit, ZT, from 0.35 for the stoichiometric compound to 0.44 for TiNi1.15Sn. Beyond x = 0.15 ZT decreases due to a rise in thermal conductivity. Density functional theory calculations using hybrid functionals were performed to determine band alignments between the half- and full-Heusler compounds, as well as comparative energies of formation. The hybrid functional band structure of TiNiSn is presented as well.

A key challenge for the materials chemist is the development of controllable and straightforward synthetic methodologies that will integrate multiple phases/compositions with scalar designed physical properties. The intent of this Perspective is to give a brief summary of some of the current bulk-scaled approaches that might help guide researchers in the design of optimal heterostructures in large quantity for the further improvement of thermoelectric conversion efficiency. Examples of two-phase combinations on different length scales will be discussed with a focus on the hot carrier filtering effect that results from the selective scattering of carriers with different energies. On the basis of this strategy, heterostructures fabricated by both the bottom-up solution approaches at low temperature and top-down solid-state deposition routes that show promise in improving the thermoelectric figure of merit are highlighted. © 2013 American Chemical Society.

We report a method for preparing p-type silicon germanium bulk alloys directly from a boron-doped silica germania nanocomposite. This is the first successful attempt to produce and characterize the thermoelectric properties of SiGe-based thermoelectric materials prepared at temperatures below the alloy's melting point through a magnesiothermic reduction of the silica-germania nanocomposite. We observe a thermoelectric power factor that is competitive with the literature record obtained for high energy ball milled nanocomposites. The large grain size in our hot pressed samples limits the thermoelectric figure of merit to 0.5 at 800 C for an optimally doped Si80Ge20 alloy. © 2013 American Chemical Society.

The electronic and thermal properties of thermoelectric materials are highly dependent on their microstructure and therefore on the preparation conditions, including the initial synthesis and, if applicable, densification of the obtained powders. Introduction of secondary phases on the nano- and/or microscale is widely used to improve the thermoelectric figure of merit by reduction of the thermal conductivity. In order to understand the effect of the preparation technique on structure and properties, we have studied the thermoelectric properties of the well-known half-Heusler TiNiSn with addition of a small amount of nickel nanoparticles. The different parameters are the initial synthesis (levitation melting and microwave heating), the amount of nickel nanoparticles added and the exact pressing profile using spark plasma sintering. The resulting materials have been characterized by synchrotron X-ray diffraction and microprobe measurements and their thermoelectric properties are investigated. We found the lowest (lattice) thermal conductivity in samples with full-Heusler TiNi2Sn and Ni3Sn4 as secondary phases. © 2013 Elsevier Masson SAS. All rights reserved.

Simple organic cooperative assembly of triazine molecules leads to three-dimensional macroscopic assemblies of low-dimensional graphitic carbon nitrides (g-CNs), for example, nanoparticles, nanotubes, and nanosheets. The approach enables the characterization of the cooperative properties and photocatalytic activities of low-dimensional g-CN materials in hydrogen evolution reactions from water under visible light.

Nonprecious transition metal nitrides have attracted considerable attention as an alternative catalyst to noble metals for electrochemical reactions. Titanium nitride (TiN), in particular, is an interesting material that exhibits excellent thermal, chemical, and mechanical stability, electrical conductivity, and in particular electrocatalytic activity. TiN is often prepared by the nitridation of titanium oxide using gaseous ammonia or hydrazine as a nitrogen source. This high temperature synthesis, however, gives a material with low surface area, which is unfavorable for its application in heterogeneous electrocatalysis. The shape and size of the assembly, and thus the resulting g-CN materials, can be tailored simply by using different precipitation temperatures, solvents, and comonomers. Furthermore, the assembly develops unique nanostructures during the polycondensation without losing the pristine macrostructures.

Simple organic cooperative assembly of triazine molecules leads to three-dimensional macroscopic assemblies of low-dimensional graphitic carbon nitrides (g-CNs), for example, nanoparticles, nanotubes, and nanosheets. The approach enables the characterization of the cooperative properties and photocatalytic activities of low-dimensional g-CN materials in hydrogen evolution reactions from water under visible light.

Oxidative dehydrogenation is a promising way to produce olefins, diolefins and aromatics. However, the product yield is limited by the consecutive oxidation of the product to oxygenated products. The highest yield reported for propane oxidative dehydrogenation is only about 30%. Alternatively, halogens can be used as oxidants in oxidative dehydrogenations. Although the iodine process is highly selective, it requires very high reaction temperatures (≈900K) to give a good yield of C3H6+C3H7I, and iodine is too expensive for industrial deployment. Bromine is a more reactive oxidant but less selective towards C3H6 and C3H7Br. We show that the use of bromine-iodine mixtures with low iodine content (no greater than 20%) results in up to 80% of C3H6+C3H7X single-pass yield at moderate reaction temperatures (

Efficient and cost-effective conversion of solar energy to useful chemicals and fuels could lead to a significant reduction in fossil hydrocarbon use. Artificial systems that use solar energy to produce chemicals have been reported for more than a century. However the most efficient devices demonstrated, based on traditionally fabricated compound semiconductors, have extremely short working lifetimes due to photocorrosion by the electrolyte. Here we report a stable, scalable design and molecular level fabrication strategy to create photoelectrochemically active heterostructure (PAH) units consisting of an efficient semiconductor light absorber in contact with oxidation and reduction electrocatalysts and otherwise protected by alumina. The functional heterostructures are fabricated by layer-by-layer, template-directed, electrochemical synthesis in porous anodic aluminum oxide membranes to produce high density arrays of electronically autonomous, nanostructured, corrosion resistant, photoactive units (~10(9)-10(10) PAHs per cm(2)). Each PAH unit is isolated from its neighbor by the transparent electrically insulating oxide cellular enclosure that makes the overall assembly fault tolerant. When illuminated with visible light, the free floating devices have been demonstrated to produce hydrogen at a stable rate for over 24 h in corrosive hydroiodic acid electrolyte with light as the only input. The quantum efficiency (averaged over the solar spectrum) for absorbed photons-to-hydrogen conversion was 7.4% and solar-to-hydrogen energy efficiency of incident light was 0.9%. The fabrication approach is scalable for commercial manufacturing and readily adaptable to a variety of earth abundant semiconductors which might otherwise be unstable as photoelectrocatalysts.

Half-Heusler thermoelectrics offer the possibility to choose from a variety of non-toxic and earth-abundant elements. TiNiSn is of particular interest and - with its relatively high electrical conductivity and Seebeck coefficient - allows for optimization of its thermoelectric figure of merit, reaching values of up to 1 in heavily-doped and/or phase-segregated systems. In this contribution, we used an energy- and time-efficient process involving solid-state preparation in a commercial microwave oven and a fast consolidation technique, Spark Plasma Sintering, to prepare a series of Ni-rich TiNi1+xSn with small deviations from the half-Heusler composition. Spark Plasma Sintering plays an important role in the process by being a part of the synthesis of the material rather than solely a densification technique. Synchrotron powder X-ray diffraction and microprobe data confirm the presence of a secondary TiNi2Sn full-Heusler phase within the half-Heusler matrix. We observe a clear correlation between the amount of full-Heusler phase and the lattice thermal conductivity of the samples, resulting in decreasing total thermal conductivity with increasing TiNi2Sn fraction. This trend shows that phonons are scattered effectively as a result of the microstructure of the materials with full-Heusler inclusions in the size range of microns to tens of microns. The best performing samples with around 5% of TiNi2Sn phase exhibit maximum figures of merit of almost 0.6 between 750 K and 800 K which is an increase of ca. 35% compared to the zT of the parent compound TiNiSn.

Methyl bromide is used as feed in a process that converts it to gasoline. It is prepared by the gas-phase reaction of CH4 with Br2, a reaction that produces, besides the desired CH3Br, large amounts of CH2Br2. The latter cokes the catalyst used for gasoline production. The separation of CH2Br2 by distillation makes gasoline production too expensive. It is therefore important to increase the selectivity of the bromination reaction. We show that a small amount of I 2 catalyzes the reaction CH2Br2 + CH 4 → 2CH3Br, which leads to higher CH4 conversion and higher selectivity to CH3Br. These findings are promising for developing a low-cost integrated bromine-iodine based dual-halogen pathway to convert stranded natural gas into fuels and chemicals. © 2013 American Chemical Society.

Nanostructured Schottky inorganic-organic solar cells provide overall power conversion efficiencies exceeding 3%, with extremely large short-circuit photocurrents. The device EQE faithfully tracks the absorptance of the CdSe nanorods, and the IQE is approximately constant over the entire visible spectrum as opposed to a p-n junction hybrid solar cell fabricated with a highly absorbing organic polymer.

Previously reported TiO2 nanowire fabrication from Ni catalysts shows a surprising amount of phosphorous (P) contamination incorporated into the seed particle. We proposed this unintentional P-doping of Ni particles aids the mechanism for nanowire growth and occurs by an alternative pathway from the Vapor-Liquid-Solid (VLS) mechanism. To confirm this new mechanism, mixed phase NiP/Ni2P (NixPy) and Ni2P nanoparticles were fabricated and the central role of phosphorous in TiO 2 nanowire synthesis confirmed. This newly developed P-assisted fabrication method yielded crystalline rutile TiO2 nanowires. In this mechanism solid, quasi-spherical catalyst particles attached to the ends of nanowires and surrounded by a Ni/P liquid shell are responsible for the nanowire growth. The growing end of the nanowire appears to form a "tangent- plane" to the solid catalyst core with the liquid shell wetting and occupying the interstice between the catalyst and the nanowire. In Ni xPy assisted growth, nanowire diameters occurred as small as 12.3 nm, some of the thinnest yet reported TiO2 nanowires resulting from atmospheric-pressure chemical vapor deposition (APCVD) growth. © The Royal Society of Chemistry 2013.