Molecular adsorption and growth of naphthalene films on Ag(1 0 0)

The adsorption of naphthalene, vacuum deposited on a Ag(1 0 0) surface, was comprehensively investigated by means of low-energy electron diffraction (LEED), temperature-programmed thermal desorption (TPD) spectroscopy, X-ray photoelectron spectroscopy (XPS), and polarization-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in the mono- and multilayer regime. A growth of long-range ordered monolayer at 140 K is observed with LEED. The polarization-dependent C 1s NEXAFS shows that the naphthalene molecules in the monolayer lie almost parallel to the Ag(1 0 0) surface. With increasing film thickness, the molecular orientation turns to upright position. Furthermore, NEXAFS measurements show that in the multilayer regime the molecular orientation depends on the substrate temperature during deposition.     

Investigation of monolayer dispersion of MoO3 supported on titanate nanotubes

The monolayer dispersion of MoO₃ supported on the surface of titanate nanotubes (TNT) were prepared by heating mechanical mixture of molybdate (HMA) and TNT. The result shows that MoO₃ can disperse spontaneously onto the surface of TNT, and the dispersion capacity is ca. 27 mg MoO₃/g TNT by X-ray diffraction (XRD). On the basis of thermogravimetric (TG) and X-ray photoelectron spectroscopy (XPS) analysis, it was found that the HMA as precursor could not decompose completely into MoO₃ crystal on the surface of TNT around the threshold above decomposed temperature due to the strong interaction between HMA and the surface of TNT.     

A green synthetic approach to graphene nanosheets for hydrogen adsorption

A green and facile strategy of preparing graphene by reducing exfoliated graphite oxide (GO) with glucose was developed in this study. The as-prepared samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Atomic force microscopy (AFM). The characterization results indicated that the graphene sheets (GS) were of high quality with smooth surface, rich pore structure and few layer graphene. The samples have a BET specific surface area of 1205.8 m² g⁻¹ measured by N₂ adsorption at 77 K. The hydrogen storage capacity of 2.7 wt.% at 298 K and 25 bar demonstrated that the as-prepared graphene employing glucose as reductant is supposed to be a promising material with outstanding property for hydrogen storage.     

Characterization of gallium-doped CdS thin films grown by chemical bath deposition

Ga-doped CdS thin films, with different [Ga]/[Cd] ratios, were grown using chemical bath deposition. The effect of Ga-doping on optical properties and bandgap of CdS films is investigated. Resistivity, carrier density, and mobility of doped films were acquired using Hall effect measurements. Crystal structure as well as crystal quality and phase transition were determined using X-ray diffraction (XRD) and Micro-Raman spectroscopy. Film morphology was studied using scanning electron microscopy, while film chemistry and binding states were studied using X-ray photoelectron spectroscopy (XPS). A minimum bandgap of 2.26 eV was obtained at [Ga]/[Cd] ratio of 1.7 × 10⁻². XRD studies showed Ga³⁺ ions entering the lattice substitutionally at low concentration, and interstitially at high concentration. Phase transition, due to annealing, as well as induced lattice defects, due to doping, were detected by Micro-Raman spectroscopy. The highest carrier density and lowest resistivity were obtained at [Ga]/[Cd] ratio of 3.4 × 10⁻². XPS measurements detect an increase in sulfur deficiency in doped films.     

Facile synthesis of α-MnO2 nanorods for high-performance alkaline batteries

Single-crystalline α-MnO₂ nanorods have been successfully synthesized by a novel hydrothermal method based on the redox reactions between the permanganate anion MnO₄^- and H₂O in mixture containing KMnO₄ and HNO₃. The products have been characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), Fourier transform infrared spectrum (FT-IR) and Brunauer-Emmett-Teller (BET). The results prove that the grain size of α-MnO₂ nanorods with the surface area ∼95.2 m² g⁻¹ is homogeneous with diameters ranging from 10 to 20 nm. The electrochemical property of the material shows that compared with the commercial electrolytic manganese dioxide (EMD), the discharge capacity of the as-prepared α-MnO₂ nanorods is increased by 70.4%, 104.1% and 135.7% at different constant currents of 50, 250 and 500 mA g⁻¹, respectively.     

CuO-PAA hybrid films: Chemical synthesis and supercapacitor behavior

We report the synthesis of CuO-Poly (acrylic) acid (PAA) hybrid thin films by a cost-effective spin coating technique for supercapacitor application. Coated films were annealed at 300, 400 and 500 °C, to study the annealing effect on the supercapacitor behavior. Further films were characterized by X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform-Raman spectroscopy (FT-Raman) and Fourier transform-Infrared spectroscopy (FT-IR) techniques. Energy dispersive spectroscopy (EDS) shows the formation of amorphous blend of CuO and Cu₂O phases at 300 °C. Further, films annealed at 400 and 500 °C exhibit polycrystalline phase pure CuO with monoclinic structure. The scanning electron microscopy (SEM) micrographs show the transition of island-like structure to CuO crystals surrounded by PAA grafted composite ring with increase in annealing temperature. The possible growth mechanism of PAA and CuO bonding is discussed. Cyclic voltammetry (CV) is employed to calculate the specific capacitance (C_sp) in 1 M H₂SO₄ electrolyte. It is observed that the C_sp increases from 41 to136 F g⁻¹ with increase in annealing temperature.     

Study on the electrochemical behavior of vanadium nitride as a promising supercapacitor material

Vanadium nitride (VN) powder was synthesized by calcining V₂O₅ xerogel in a furnace under an anhydrous NH₃ atmosphere at 400 °C. The structure and surface morphology of the obtained VN powder were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The supercapacitive behavior of VN in 1 M KOH electrolyte was studied by means of cyclic voltammetry (CV), constant current charge-discharge cycling (CD) and electrochemical impedance spectroscopy (EIS). The XRD result indicates that the obtained VN belongs to the cubic crystal system (Fm3m [2 2 5]) with unit-cell parameter 4.15 Å. SEM images show the homogeneous surface of the obtained VN. The CV diagrams illustrate the existence of fast and reversible redox reactions on the surface of VN electrode. The specific capacitance of VN is 161 F g⁻¹ at 30 mV s⁻¹. Furthermore, the specific capacitance remains 70% of the original value when the scan rate increases from 30 to 300 mV s⁻¹. CD experiments show that VN is suitable for CD at high current density, and the slow and irreversible faradic reactions exist during the charge-discharge process of the VN electrode. The experimental results indicate that VN is a promising electrode material for electrochemical supercapacitors.     

A novel method to synthesize LiVPO4F/C composite materials and its electrochemical Li-intercalation performances

Triclinic LiVPO₄F/C composite materials were prepared from a sucrose-containing precursor by one-step heat treatment. As-prepared composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical measurements. XRD studies showed that Li₃PO₄ impurity phase appeared in the sample synthesized at 600 °C and pure LiVPO₄F samples could be obtained when the sintered temperature was higher than 650 °C. The sample synthesized at 650 °C presents the highest initial discharge capacity of 132 mAh g⁻¹ at 0.2 C rate, and exhibited better cycling stability (124 mAh g⁻¹ at 50th cycle at 0.2 C rate) and better rate capability (100 mAh g⁻¹ at 50th cycle under 1 C rate) in the voltage range 3.0-4.4 V.     

Surface chemical study on the covalent attachment of hydroxypropyltrimethyl ammonium chloride chitosan to titanium surfaces

An anti-microbial and bioactive coating could not only reduce the probability of infection related to titanium implants but also support the growth of surrounding osteogenic cells. Our previous study has showed that hydroxypropyltrimethyl ammonium chloride chitosan (HACC) with a DS (degrees of substitution) of 18% had improved solubility and significantly higher antibacterial activities against three bacteria which were usually associated with infections in orthopaedics. In the current study, HACC with a DS of 18% coating was bonded to titanium surface by a three-step process. The titanium surface after each individual reaction step was analyzed by X-ray photoelectron spectroscopy (XPS) and attenuated total reflection (ATR) of Fourier-transformed infrared (FT-IR) spectroscopy. The XPS results demonstrated that there were great changes in the atomic ratios of C/Ti, O/Ti, and N/Ti after each reaction step. The XPS high resolution and corresponding devolution spectra of carbon, oxygen, nitrogen, and titanium were also in good coordination with the anticipated reaction steps. Additionally, the absorption bands around 3365 cm⁻¹ (-OH vibration), 1664 cm⁻¹ (Amide I), 1165 cm⁻¹ (ν_as, C-O-C bridge), and the broad absorption bands between 958 cm⁻¹ and 1155 cm⁻¹ (skeletal vibrations involving the C-O stretching of saccharide structure of HACC) verified that HACC was successfully attached to titanium surface.     

Formation and hydrogenation of p(2 × 2)-N on Pt(1 1 1)

The formation of a well-ordered p(2 × 2) overlayer of atomic nitrogen on the Pt(1 1 1) surface and its reaction with hydrogen were characterized with reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The p(2 × 2)-N overlayer is formed by exposure of ammonia to a surface at 85 K that is covered with 0.44 monolayer (ML) of molecular oxygen and then heating to 400 K. The reaction between ammonia and oxygen produces water, which desorbs below 400 K. The only desorption product observed above 400 K is molecular nitrogen, which has a peak desorption temperature of 453 K. The absence of oxygen after the 400 K anneal is confirmed with AES. Although atomic nitrogen can also be produced on the surface through the reaction of ammonia with an atomic, rather than molecular, oxygen overlayer at a saturation coverage of 0.25 ML, the yield of surface nitrogen is significantly less, as indicated by the N₂ TPD peak area. Atomic nitrogen readily reacts with hydrogen to produce the NH species, which is characterized with RAIRS by an intense and narrow (FWHM ∼ 4 cm⁻¹) peak at 3322 cm⁻¹. The areas of the H₂ TPD peak associated with NH dissociation and the XPS N 1s peak associated with the NH species indicate that not all of the surface N atoms can be converted to NH by the methods used here.     

Optical properties of cadmium sulfide nanocrystal film prepared by electrochemical synthesis at liquid-liquid interface

Dendritic nanocrystalline CdS film was deposited at liquid-liquid interface of surfactants and an electrolyte containing 4 mmol L⁻¹ cadmium chloride (CdCl₂) and 16 mmol L⁻¹ thioacetamide (CH₃CSNH₂) with an initial pH value of 5 at 15 °C by electrochemical synthesis. The nanofilm was characterized by transmission electron microscopy (TEM), field emission scanning electron microscope (FE-SEM), atomic force microscopy (AFM), ultraviolet visible (UV-vis) absorption spectroscopy and fluorescence spectroscopy. The surface morphology and particle size of the nanofilm were investigated by AFM, SEM and TEM, and the crystalline size was 30-50 nm. The thickness of the nanofilm calculated by optical absorption spectrum was 80 nm. The microstructure and composition of the nanofilm was investigated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), showing its polycrystalline structure consisting of CdS and Cd. Optical properties of the nanofilm were investigated systematically by UV-vis absorption and fluorescence spectroscopy. A λ_onset blue shift compared with bulk CdS was observed in the absorption spectra. Fluorescence spectra of the nanofilm indicated that the CdS nanofilm emitted blue and green light. The nanocomposites film electrode will bring about anodic photocurrent during illumination, showing that the transfer of cavities produces photocurrent.     

Attenuated total reflectance spectroscopy of coumarin organosilane molecules adsorbed on a fused silica surface

Attenuated total reflectance (ATR) spectroscopy was used to investigate the adsorption of coumarin organosilane molecules onto a fused silica surface. The difference between the absorption spectra of the molecules on the surface and in solution was explained by the interaction of the adsorbed coumarin organosilane molecules with the hydroxyl groups on the fused silica surface. This interaction produces a perturbation of the π electron distribution and the electronic transitions of the coumarin chromophore of the organosilane molecules adsorbed on the surface. From the kinetics adsorption curves, the calculated enthalpy values of 74.8 ± 5.2 kJ mol⁻¹ and free energy of −38.22 ± 0.70 kJ mol⁻¹ at 23 °C indicates a chemisorption process. The high sensitivity of ATR spectroscopy allows the detection of a monolayer formed by a 10 nM concentration of coumarin organosilane molecules, which covers more than half of the maximum surface coverage at 60 °C.     

Cleaning of SiC surfaces by low temperature ECR microwave hydrogen plasma

N-type 4H-SiC (0 0 0 1) surfaces were cleaned by low temperature hydrogen plasma in electronic cyclotron resonance (ECR) microware plasma system. The effects of the hydrogen plasma treatment (HPT) on the structure, chemical and electronic properties of surfaces were characterized by in situ reflection high energy electron diffraction (RHEED) and X-ray photoelectron spectroscopy (XPS). The RHEED results indicate that the structures of the films are strongly dependent on the treatment temperature and time. Significant improvements in quality of 4H-SiC films can be obtained with the temperature ranging from 200 °C to 700 °C for an appropriate treatment period. The XPS results show that the surface oxygen is greatly reduced and the carbon contamination is completely removed from the 4H-SiC surfaces. The hydrogenated SiC surfaces exhibit an unprecedented stability against oxidation in the air. The surface Fermi level moves toward the conduction band in 4H-SiC after the treatment indicating an unpinning Fermi level with the density of surfaces states as low as 8.09 × 10¹⁰ cm⁻² eV⁻¹.     

Protein imprinting and recognition via forming nanofilms on microbeads surfaces in aqueous media

In this paler, we present a technique of forming nanofilms of poly-3-aminophenylboronic acid (pAPBA) on the surfaces of polystyrene (PS) microbeads for proteins (papain and trypsin) in aqueous. Papain was chosen as a model to study the feasibility of the technique and trypsin as an extension. Obtained core-shell microbeads were characterized using scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and BET methods. The results show that pAPBA formed nanofilms (60-100 nm in thickness) on the surfaces of PS microbeads. The specific surface area of the papain-imprinted beads was about 180 m² g⁻¹ and its pore size was 31 nm. These imprinted microbeads exhibit high recognition specificity and fast mass transfer kinetics. The specificity of these imprinted beads mainly originates from the spatial effect of imprinted sites. Because the protein-imprinted sites were located at, or close to, the surface, the imprinted beads have good site accessibility toward the template molecules. The facility of the imprinting protocol and the high recognition properties of imprinted microbeads make the approach an attractive solution to problems in the field of biotechnology.     

Structure and electrical properties of CdIn2O4 thin films prepared by DC reactive magnetron sputtering

CdIn₂O₄ thin films were prepared by direct-current (DC) reactive magnetron sputtering. The structure, surface morphology and the chemical composition of the thin films were analyzed by X-ray diffraction (XRD), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS), respectively. The electrical properties of the films prepared in different oxygen concentration and annealing treatment were determined, and the effects of the preparing conditions on the structure and electrical properties were also explored. It indicates that the CdIn₂O₄ thin films with uniform and dense surface morphology contain mainly CdIn₂O₄, In₂O₃ phases, and CdO phase is also observed. The XPS analysis confirms the films are in oxygen-deficient state. The electrical properties of these films significantly depend on the preparing conditions, the resistivity of the films with the oxygen concentration of 4.29% is 2.95 × 10⁻⁴ Ω cm and the Hall mobility is as high as 60.32 cm²/V s. Annealing treatment can improve the electrical performance of the films.     

Porous LiNi0.75Co0.25O2 microspheres prepared via a hydrothermal process as cathode material for lithium ion batteries

Porous LiNi_0.75Co_0.25O₂ microspheres are successfully prepared by a simple hydrothermal process by using H[Ni_0.75Co_0.25OOH]₃ and LiOH as starting materials in the presence of urea for the first time. The synthesized samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), specific surface area (S_BET), and electrochemical performance. The synthesized LiNi_0.75Co_0.25O₂ has a good electrochemical performance with an initial discharge capacity of 169.3 mA g⁻¹ and good capacity retention of 96.7% after 50 cycles at 0.2 C (25 mA g⁻¹). The electrochemical lithium ion insertion/extraction process is quite reversible even at 5 C. Furthermore, the structure in the charge-discharge process is stable and the impedance increased slowly during cycling.     

Probing the properties of the (1 1 1) and (1 0 0) surfaces of LaB6 through infrared spectroscopy of adsorbed CO

The adsorption of carbon monoxide on the LaB₆(1 0 0) and LaB₆(1 1 1) surfaces was studied experimentally with the techniques of reflection absorption infrared spectroscopy and X-ray photoelectron spectroscopy. The interaction of CO with the two surfaces was also studied with density functional theory. Both surfaces adsorb CO molecularly at low temperatures but in markedly different forms. On the LaB₆(1 1 1) surface CO initially adsorbs at 90 K in a form that yields a CO stretching mode at 1502-1512 cm⁻¹. With gentle annealing to 120 K, the CO switches to a bonding environment characterized by multiple CO stretch values from 1980 to 2080 cm⁻¹, assigned to one, two, or three CO molecules terminally bonded to the B atoms of a triangular B₃ unit at the (1 1 1) surface. In contrast, on the LaB₆(1 0 0) surface only a single CO stretch is observed at 2094 cm⁻¹, which is assigned to an atop CO molecule bonded to a La atom. The maximum intensity of the CO stretch vibration on the (1 0 0) surface is higher than on the (1 1 1) surface by a factor of 5. This difference is related to the different orientations of the CO molecules on the two surfaces and to reduced screening of the CO dynamic dipole moment on the (1 0 0) surface, where the bonding occurs further from the surface plane. On LaB₆(1 0 0), XPS measurements indicate that CO dissociates on the surface at temperatures above 400 K.     

MAO-synthesized Al2O3-supported V2O5 nano-porous catalysts: Growth, characterization, and photoactivity

V₂O₅-loaded Al₂O₃ layers were successfully grown via micro-arc oxidation (MAO) process for the first time. Surface morphology and topography of the layers were investigated by scanning electron microscope (SEM) and atomic force microscope (AFM). It was found that the composite layers had a porous structure with a rough surface which is suitable for catalytic applications. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectroscopy (EDS) techniques were also employed to study phase structure and chemical composition of the composite layers. The layers consisted of γ-alumina, α-alumina, and vanadium pentoxide phases in which their relative contents varied with the applied voltage. Meanwhile, optical properties of the composite layers were investigated using UV-vis spectrophotometry technique, and the band gap energy was calculated as 3.15 eV. Furthermore, photocatalytic performance of the synthesized composite layers was determined by measuring the decomposition rate of methylene blue solution, as a model compound, on the surface of the layers under ultra violet photo-irradiation. It was found that more than 91% of the methylene blue was degraded after 120 min with a rate constant of k = 0.0192 min⁻¹.     

α-Sexithiophene on Cu(1 1 0) and Cu(1 1 0)-(2 × 1)O: An STM and NEXAFS study

The adsorption of α-sexithiophene (6T) on Cu(1 1 0), Cu(1 1 0)-(2 × 1)O and the mesoscopically patterned Cu-O striped surface have been studied by STM (scanning tunnelling microscopy), XPS (X-ray photoelectron spectroscopy) and NEXAFS (near edge X-ray absorption fine structure). The molecular resolution of the STM allowed to determine the orientation and local order of the molecules in the submonolayer and monolayer regime. It is shown that the 6T molecules align with their long molecular axis along the densely packed copper rows on Cu(1 1 0) and along the Cu-O rows on the Cu(1 1 0)-(2 × 1)O surface. On the striped phase with alternating copper and Cu-O regions the molecules adsorb first on the Cu regions and after complete filling of these regions, on the Cu-O. The orientation is the same on both areas as on the respective pristine surfaces with the only exception that the molecules reorient by 90° if the width of the copper regions is smaller than the molecular length. The NEXAFS measurements allowed for a determination of the adsorption geometry of the molecules: while 6T lies flat on the surface on clean copper, the molecular planes are inclined with an angle as high as 39° with respect to the substrate on (2 × 1)O. For the latter, this inclination angle is 4° higher than in the bulk crystal structure of 6T observed for thicker films to release stress and allow commensurability with the substrate lattice, while for the former it is a result of the aromatic system bonding to the Cu(1 1 0) surface, as confirmed by XPS.     

Generation of oxygen vacancies in the surface of ferroelectric Pb(Nb,Zr,Ti)O3

Controlled generation of oxygen vacancies in the surface of ferroelectric thin films is crucial to study how surface reduction affects molecular adsorption and catalysis of gas-surface phenomena. We demonstrate the effective reduction in the surface of 4% niobium doped 20/80 PZT (PNZT) thin films. The sample was characterized by X-ray diffraction (XRD), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), and heated at 200, 250 and 300 °C in a high vacuum system at 10⁻⁵ T of H₂. Auger peak-to-peak intensities was used to study the elemental concentrations during the reduction experiment. High-resolution XPS spectra were acquired before and after reduction process for detecting the changes of the oxygen signal. Vacancies production rates as slow as 0.21% per minute were achieved and the temperature was not a key parameter in the process. Experiments at higher hydrogen pressures and lower temperatures might improve the control of the vacancies production.