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There exists a strong demand to replace expensive noble metal catalysts with cheap metal sulfides or phosphides for hydrogen evolution reaction (HER). Recently metal phosphides such as NixP, FeP and CoP have been considered as promising candidates to replace Pt cathodes. Here we report that the nanocrystalline CoP nanosheet assembly on carbon cloth can be formed by a two-step process: electrochemical deposition of Co species followed by gas phase phosphidation. The CoP catalyst in this report exhibits a Tafel slope of 30.1 mV/dec in 0.5 M H2SO4 and 42.6 mV/dec in 1 M KOH. The high HER performance of our CoP catalysts is attributed to the rugae-like morphology which results in a high double-layer capacitance and high density of active sites, estimated as 7.77×1017 sites/cm2.

Efficient photocatalytic hydrogen generation in a suspension system requires a sophisticated nano-device that combines a photon absorber with effective redox catalysts. This study demonstrates an innovative molecular linking strategy for fabricating photocatalytic materials that allow effective charge separation of excited carriers, followed by efficient hydrogen evolution. The method for the sequential replacement of ligands with appropriate molecules developed in this study tethers both quantum dots (QDs), as photosensitizers, and metal nanoparticles, as hydrogen evolution catalysts, to TiO2 surfaces in a controlled manner at the nano-level. Combining hydrophobic and hydrophilic interactions on the surface, CdSe-ZnS core-shell QDs and an Au-Pt alloy were attached to TiO2 without overlapping during the synthesis. The resultant nano-photocatalysts achieved substantially high-performance visible-light-driven photocatalysis for hydrogen evolution. All syntheses were conducted at room temperature and in ambient air, providing a promising route for fabricating visible-light-responsive photocatalysts.

There is a strong demand to replace expensive Pt catalysts with cheap metal sulfides or phosphides for hydrogen generation in water electrolysis. Earth-abundant Fe can be electroplated on carbon cloth (CC) to form high surface area rugae-like FeOOH assembly. Subsequent gas phase phosphidation converts the FeOOH to FeP or FeP2 and the morphology of the crystal assembly is controlled by the phosphidation temperature. FeP prepared at 250 °C presents lower crystallinity and that prepared at higher temperatures of 400 °C and 500 °C possesses higher crystallinity, but lower surface area. The phosphidation at 300 °C produces nanocrystalline FeP and preserves the high-surface area morphology; thus, it exhibits the highest HER efficiency in 0.5 M H2SO4, i.e., the required overpotential to reach 10 and 20 mA cm(-2) is 34 and 43 mV, respectively. These values are lowest among the reported non-precious metal phosphides on CC. The Tafel slope for FeP prepared at 300 °C is around 29.2 mV dec(-1), which is comparable to that of Pt/CC; this indicates that the hydrogen evolution for our best FeP is limited by the Tafel reaction (same as Pt). Importantly, the FeP/CC catalyst exhibits much better stability in a wide-range working current density (up to 1 V cm(-2)), suggesting that it is a promising replacement of Pt for HER.

75 Mo–V–Nb mixed oxide catalysts with a broad range of compositions were prepared by a simple evaporation method, and were screened for the ethane oxidative dehydrogenation (ODH) reaction. The compositions of these 75 catalysts were systematically changed by varying the Nb loading, and the Mo/V molar ratio. Characterization by XRD, XPS, H2-TPR and SEM revealed that an intimate structure is formed among the 3 components. The strong interaction among different components leads to the formation of a new phase or an “intimate structure”. The dependency of conversion and selectivity on the catalyst composition was clearly demonstrated from the results of high-throughput testing. The optimized Mo–V–Nb molar composition was confirmed to be composed of a Nb content of 4–8%, a Mo content of 70–83%, and a V content of 12–25%. The enhanced catalytic performance of the mixed oxides is obviously due to the synergistic effects of the different components. The optimized compositions for ethane ODH revealed in our high-throughput tests and the structural information provided by our characterization studies can serve as the starting point for future efforts to improve the catalytic performance of Mo–V–Nb oxides.

The growth of TiO2 films by plasma enhanced atomic layer deposition using Star-Ti as a precursor has been systematically studied. The conversion from amorphous to crystalline TiO2 was observed either during high temperature growth or annealing process of the films. The refractive index and bandgap of TiO2 films changed with the growth and annealing temperatures. The optimization of the annealing conditions for TiO2 films was also done by morphology and density studies.

Correlation of charge state of Mn with the increase in resistivity with Mn concentration is demonstrated in Mn-doped indium tin oxide films. Bonding analysis shows that Mn 2p3/2 core level can be deconvoluted into three components corresponding to Mn2+ and Mn4+ with binding energies 640.8 eV and 642.7 eV, respectively, and a Mn2+ satellite at ?5.4 eV away from the Mn2+ peak. The presence of the satellite peak unambiguously proves that Mn exists in the +2 charge state. The ratio of concentration of Mn2+ to Mn4+ of ?4:1 suggests that charge compensation occurs in the n-type films causing the resistivity increase. � 2010 American Institute of Physics.

Arsenic trisulfide (As 2 S 3 ) glass is an interesting material for photonic integrated circuits (PICs) as infrared (IR) or nonlinear optical components. In this paper, direct laser writing was applied to engineer the refractive index of As 2 S 3 thin film. Film samples were exposed to focused above bandgap light with wavelength at 405nm using different fluence adjusted by laser power and exposure time. The index of refraction before and after laser irradiation was calculated by fitting the experimental data obtained from Spectroscopic Ellipsometer (SE) measurement to Tauc-Lorenz dispersion formula. A positive change in refractive index (Δn=0.19 at 1.55μm) as well as an enhancement in anisotropy was achieved in As 2 S 3 film by using 10mW, 0.3μs laser irradiation. With further increasing the fluence, refractive index increased while anisotropic property weakened. Due to the rapid and large photo-induced modification of refractive index obtainable with high spatial resolution, this process is promising for integrated optic device fabrication.

Porous activated nanocarbons with well-controlled dimensionality and morphology (i.e. 0D activated carbon nanoparticles, 1D activated carbon nanotubes, and 2D activated carbon nanosheets) were derived successfully from different template-induced polyaniline nanostructures by facile carbonization and activation processes. The obtained nanocarbons show large specific surface areas (1332–2005 m2 g−1), good conductivities, and highly porous nanoscale architectures. The supercapacitors fabricated using the shape-controlled nanocarbons exhibit high specific capacitance, excellent rate capability, and superior long-term cycling stability in both aqueous and ionic liquid electrolytes. More importantly, a very high energy density of 50.5 W h kg−1 with a power density of 17.4 kW kg−1 can be obtained from the activated carbon nanotube based supercapacitors in an ionic liquid electrolyte (with a charge time of ∼10 s), making the shape-controlled nanocarbons promising candidates for high-performance energy storage devices.

A detailed study of the role of oxygen vacancies in determining the effective mass and high temperature (300–1000 K) thermoelectric properties of La-doped epitaxial SrTiO3 thin films is presented. It is observed that at intermediate temperatures, a transition from degenerate to non-degenerate behavior is observed in the Seebeck coefficient, but not electrical conductivity, which is attributed to heterogeneous oxygen non-stoichiometry. Heikes formula is found to be invalid for the films with oxygen vacancies. By fitting the spectroscopic ellipsometry (SE) data, obtained in the range 300–2100 nm, using a Drude-Lorentz dispersion relation with two Lorentz oscillators, the electrical and optical properties of the films are extracted. Using the excellent agreement between the transport properties extracted from SE modeling and direct electrical measurements, we demonstrate that an increase in concentration of oxygen vacancies results in a simultaneous increase of both carrier concentration and electron effecti...

The influence of oxygen vacancies on the transport properties of epitaxial thermoelectric (Sr,La)TiO3 thin films is determined using electrical and spectroscopic ellipsometry (SE) measurements. Oxygen vacancy concentration was varied by ex-situ annealing in Ar and Ar/H2. All films exhibited degenerate semiconducting behavior, and electrical conductivity decreased (258–133 S cm−1) with increasing oxygen content. Similar decrease in the Seebeck coefficient is observed and attributed to a decrease in effective mass (7.8–3.2 me), as determined by SE. Excellent agreement between transport properties deduced from SE and direct electrical measurements suggests that SE is an effective tool for studying oxide thin film thermoelectrics.