Porous Li-Si thin films (LSFs) were prepared by a multi-step constant current electrodeposition onto Cu foil. The structure and morphology of the electrodeposited films were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). As anodes for Li-ion batteries, Li-Si films give high cycling stability, adjustable Li-storage capacity and initial coulombic efficiency under different electrodeposition conditions. For instance, LSF^-3 was electrodeposited in an electrolyte of 0.5 mol·L^-1 SiCl₄+0.7 mol·L^-1 LiClO₄+propylene caronate (PC) under certain conditions (i₁=-3.82 mA·cm^-2, t₁=600 s; i₂=-1.27 mA·cm^-2, t₂=7200 s). LSF^-3 showed the first coulombic efficiency of 97.1% at a current density of 12.7 μA·cm^-2. After the two initial pre-cycles, it delivered gravimetric and geometric charge capacities of 1410 mAh·g^-1 and 240.6 μAh·cm^-2 at 25.5 μA·cm^-2. After 50 cycles, its charge capacity was 179.0 μAh·cm^-2 (1049 mAh·g^-1), retaining 74.4% of its initial capacity. The porous structure in LSFs can accommodate a part of the volume change during Li insertion/extraction and this favors the structural stability.

A porous nickel film was prepared by the selective anodic dissolution of copper from an electrodeposited Ni-Cu alloy film. A porous nanostructured nickel-based complex film electrode was further fabricated by oxidizing the obtained porous nickel film using cyclic voltammetry in 1 mol·L^-1 KOH solution. The physical properties and pseudocapacitive performance of the as-prepared film electrodes were investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and electrochemical techniques. The results of SEM, XRD, and XPS indicate that the obtained complex film electrode consists of Ni, Ni(OH)₂, and NiOOH, and it has a porous nanostructure. The electrochemical experiments revealed that the as-prepared porous nanostructured nickel-based complex film electrode had a specific capacitance of 578 F·g^-1 at a current density of 20 A·g^-1 at the initial cycle and it gave a specific capacitance of 544 F·g^-1 after 1000 cycles with a capacitance retention of 94%. The nanoporous structure enhances the accessibility of the KOH electrolyte and promotes reactive species transport within the electrode. The nanoporous Ni substrate may improve the electronic conductivity of the thin Ni(OH)₂ film at its surfaces. The nanosized Ni(OH)₂ grains can shorten the proton diffusion pathways in the bulk of the solid nickel hydroxide. These factors are responsible for the superior pseudocapacitive performance of the porous nanostructured nickel-based complex film electrode.

In this paper we attempt to establish a theoretical model to deal with the laser focusing problem during confocal Raman measurements within a spherical droplet. A depth penetration formula was deduced and the actual penetrating depth of the laser focus in a spherical droplet was related to the vertical moving distance of a Raman spectrograph′s platform. The results indicate that a nonlinear correlation exists between the platform′s moving distance and the moving distance of the laser focus. The moving distance of the laser spot is equal to the moving distance of the platform when the laser focus is located at the surface or at the center of the droplet. However, the moving distance of the laser spot is found to be longer than the moving distance of the platform when the laser is focused at the zone between the surface and the center. Therefore, spatial distribution information for the MgSO₄ droplet gel structure can be obtained according to the above-mentioned conclusion. We found that the gelation of an MgSO₄ droplet under low relative humidity (RH) was a shell structure with a certain thickness and this thickness was closely related to the relative humidity of the local environment.

The weak interactions of 5-imidazolylmethylphenyl-10,15,20-tri-tert-butylphenylporphyrin (1) and 5-imidazolylmethylphenyl-10,15,20-triphenylporphyrin (2) were investigated in chloroform by ¹H NMR, UV-Vis and fluorescence spectroscopies, and molecular modeling simulation. The ¹H NMR chemical shifts of imidazole in compounds 1 and 2 move upfield compared with that of free imidazole and this shows that intramolecular or intermolecular weak interactions exist in both compounds. Compared with the UV-Vis spectra of compounds 1 and 2 in acetone, their spectra in chloroform show a split Soret band for compound 1, which indicates a weak intramolecular interaction and a red shift of 27 nm for compound 2, which also suggests a weak intermolecular interaction. The fluorescence data supports these results and the data obtained from the molecular simulation are consistent with those of the spectral analyses.

Density functional theory calculations at the B3LYP/6-311+G^**/LANL2DZ(metal) level were used to predict the infrared (IR) and Raman spectra for pyridine and α-pyridyl upon interaction with platinum (Pt), palladium (Pd), rhodium (Rh), and nickel (Ni) clusters. After carefully comparing the simulated IR and Raman spectra with the corresponding experimental spectra from literature, the characteristic frequencies for the metal surface adsorbed pyridine and α-pyridyl were determined. Our results show that on these metal surfaces α-pyridyl has a far lower Raman activity compared with pyridine, but their characteristic frequencies have comparable IR intensities. This is the reason why different adsorption configurations are proposed for the IR and the surface-enhanced Raman spectra (SERS). Our results indicate that IR spectroscopy is an effective tool to detect α-pyridyl adsorbed on metal surface.

The mechanism of acetylene hydrogenation catalyzed by Pd₈ cluster was investigated by density functional theory (DFT) method at B3PW91/GEN level. The calculation results showed that H₂ dissociated into H atoms wherever it adsorbed and the H atoms then adsorbed onto the surface of the Pd₈ cluster. The dissociation of H₂ is necessary for the hydrogenation of acetylene to ethane catalyzed by the Pd₈ cluster. The mechanism of acetylene hydrogenation is dependent on two isomers: acetylene and vinylidene on the Pd₈ cluster (Pd₈(2H)－CH＝CH and Pd₈(2H)－C＝CH₂). The two pathways follow a multistep and successive process to complete the hydrogenation of acetylene. However, a difference exists between Pd₈(2H)－CH＝CH and Pd₈(2H)－C＝CH₂. For the Pd₈(2H)－CH＝CH pathway, dissociated H atoms add to the C atom of acetylene on the Pd₈ cluster in different steps until they produce ethane. The Pd₈(2H)－CH＝CH₂ pathway is complex and proceeds by two different transition states to create ethylidyne, and then H atoms add to the C atom until hydrogenation ceases. Many valuable C₂ organic intermediate compounds are produced during the process and some of them transform by proton translocation, which connects the Pd₈(2H)－CH＝CH and Pd₈(2H)－C＝CH₂ pathways.

The anionic production pathways involved in the reaction between hydroxide anion (OH^-) and chlorofluoromethane (CH₂ClF) were theoretically investigated. The optimized geometries of all the important species on the reaction potential energy surface were obtained at the B3LYP/6-31+G(d,p) and B3LYP/6-311++G(2d,p) levels. Consequently, harmonic vibrational frequencies and zero point energies (ZPEs) were calculated. Based on the relative energies of all the species that were calculated at the CCSD(T)/6-311+G(3df,3dp) level, the anionic production channels for the H⁺-abstraction and the bimolecular nucleophilic substitution (S_N2) reaction processes are elaborated upon. According to the calculated barrier heights for the production pathways, the H⁺-abstraction channel is dominant, which agrees very well with previous experimental conclusions. In addition, non-typical anionic products are suggested to form during the S_N2 reaction processes where the serious dynamic effect probably causes the S_N2 reaction process to produce F^-.

The adsorption property of a single ethanol molecule on Au_n(n=2-9) clusters was investigated using density functional theory. The results show that the most stable structure of the Au_n(n=2-9) clusters is a two-dimensional plane structure. Among all the Au_n(n=2-9) clusters, the Au6 cluster is the most stable. The adsorption is achieved by an interaction between a specific Au atom in the Au_n(n=2-9) clusters and an oxygen atom in ethanol resulting in the formation of 20 stable structures. The adsorption is strongly influenced by the coordination number of the Au atoms. The structures of Au_n clusters as the main adsorbing body and ethanol molecule change slightly in the process, which reveals that the interaction between the Au_n clusters and the ethanol molecules is a weak interaction.

The diffusion behaviors of water molecules in oil-cellulose composite media were studied at different temperatures using a molecular dynamics simulation. By analyzing the formation of hydrogen bonds between the water molecules and cellulose we found that the water molecules that were initially present in the oil gradually spread to the cellulose, and hydrogen bonds were formed between them. The water molecules that were present in the cellulose initially also formed hydrogen bonds and were bound to cellulose molecules. By analyzing the diffusion coefficients of the water molecules at different temperatures we found that the diffusion behaviors of the water molecules in the two single-media, namely oil and cellulose, were very different because of their different polarities. The diffusion coefficients of the water molecules in the composite media were influenced greatly by the ratio of water molecules present in the oil and cellulose and a strong correlation was apparent between them. The water molecule-oil interaction energy and the water molecule-cellulose interaction energy were also strongly related to the polarities of the oil and the cellulose. The interaction energies also exhibited a strong correlation to the distribution of water molecules at different temperatures. This was the reason for the weakened influence of temperature on the diffusion coefficient of the water molecules, which was due to the different distributions of water molecules at different temperatures.

A semiclassical dynamics simulation study was undertaken to investigate the deactivation of the lowest excited state of π-stacked adenines, as induced by a laser pulse. Only one of the adenines was subjected to a laser pulse in this simulation. The simulation results show that the interaction between the excited adenines (A) and their unexcited neighbors (A′) increases significantly, followed by a shortening of the intermolecular distance. The interbases interaction leads to a new deactivated pathway in which atom C₂ in molecule A and atom C₂′ in molecule A′ are link to each other and form a “bonded excimer” intermediate. The lifetime of the “bonded excimer” intermediate is about 390 fs. The deformation of the pyrimidine ring at the C₂ atom and the displacement of the H₂′ atom away from the pyrimidine ring play a significant role in the deactivation process of the “bonded excimer” intermediate. After deactivation, the C₂－C₂′ dissociates and the released bond energy converts to molecular kinetic energy. Both adenine molecules return to the planar geometries of their ground states.

The geometries, stability and chemical bonding of XB₆⁺(X=C, Si, Ge, Sn, Pb) clusters were investigated using ab initio (MP2) and density functional theory (DFT: B3LYP and B3PW91) methods. Analytical gradients with polarized split-valence basis sets (6-311+G(d)) were used for B, C, Si, and Ge. The relativistic effective core potential with the LANL2DZ basis sets were chosen for Sn and Pb. The results show that the C_s symmetric pseudo-planar XB₆⁺(X=C, Si, Ge, Sn, Pb) structures are the global minima on the potential energy surfaces, which are more stable than the C_6v symmetric pyramidal and C₂ symmetric quasi-pyramidal structures. We carried out a natural bond orbital (NBO) analysis of all these minima at the B3LYP level, and calculated and discussed the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO) energy gaps, the molecular orbitals (MO), and the nucleus-independent chemical shifts (NICS) of the most stable structure. The nature of the X―B and B＝B bonds in these minimum structures and the aromatic characteristics (σ and π) of the most stable configuration were analyzed at the B3LYP level.

We investigated eight divalent metal cations M(II) (M=Ca, Mg, Mn, Zn, Cu, Ni, Fe, Co) for the formation of singly H₂S-bonded metalated porphyrin-imidazole complexes (L-MP) and H₂S bi-bonding of these metalated porphyrin complexes (L-MP^*-L, L=H₂S, P=porphyrin-imidazole, P^*=porphyrin). We investigated their structures, spectroscopic and reactivity properties using density functional theory (DFT), time dependent (TD) DFT, and conceptual DFT approaches using global and local descriptors. Their bonding properties were also analyzed by natural bond orbital (NBO) analysis and by the frontier-electron theory of chemical reactivities. The calculated results reveal that the structures, spectra and reactivities of the L-MP and L-MP^*-L complexes are very different from those of their precursor MP. Mg²⁺ can form stable complexes with porphyrin-imidazole while Ca²⁺ can not. The ligand L has little influence on the structure of the porphyrin-imidazole. L-MP is more reactive during electrophilic and nucleophilic reactions. UV-Vis spectra showed shifted peaks because of metalation. The iron complex differs from the other metal ion complexes in bonding and reactivity properties such as charge distribution, stability, and nucleophilicity. The transition from the high-spin (S=3) five-coordinate FeP to the lower-spin (S=1) six-coordinate L-FeP leads to a change in the Fukui index (f_Fe⁺) of the iron porphyrin. A few quantitative linear relationships were found for the bonding interactions, the charge distributions, and the DFT chemical reactivity indices. In addition, we note that the spin polarization Fukin function plays an important role in metal specificity and reactivity. These results provide in-depth insights into the vascular disorder from endogenous H₂S bonded with metal porphyrin complexes.

The electronic structures and optical properties of ZnO_0.875 were calculated by the ultra-soft pseudo-potential plane wave (pp-pw) method based on density functional theory. The crystal structure of ZnO with oxygen vacancies was optimized using first-principles. The electronic-state densities in pure ZnO and ZnO_0.875 were then calculated. The dielectric functions, absorption spectrum, refractive index, extinction coefficient, and reflectivity of ZnO_0.875 dominated by electron inter-band transitions were analyzed in terms of the precisely calculated density of state and the polarization dependencies of the optical properties were discussed in detail. Results indicate that the ZnO_0.875 crystal is a uniaxial crystal and exhibits some features in the low energy region, which are caused by the O vacancy. Our results provide new insights into the study of the luminescent behavior of ZnO and offer theoretical data for the design and application of ZnO optoelectronic materials.

We investigated the adhesion behavior of Cu clusters (Cu_x, x=1-4) on a CeO₂(111) surface using first-principles density functional theory (DFT). We found that small Cu_x clusters (x=2, 3) tended to adhere as two dimensional (2D) planar structures on the CeO₂(111) surface. For the Cu4 cluster, a three dimensional (3D) tetrahedral structure is preferred and the 3D Cu4 particle is positively charged because of charge transfer from Cu 3d to Ce 4f. The transition from a 2D planar structure to 3D particles occurs with a transition barrier of 1.05 eV and the favorable route consists of one Cu atom hopping directly from the interface site to the hollow site above the Cu triangle. Because the Cu-O interactions are comparable with the Cu-Cu intra-cluster interactions, their competition determines the morphologies of the eventual Cu clusters on CeO₂. The 3D positively charged Cu4 particle obtained on CeO₂ is expected to result in distinct catalytic performance compared to the unsupported Cu4 cluster for water dissociation, and thus the water gas shift reactions.

Graphene (Gr) is synthesized by the direct reduction of tetrachloroethylene with sodium in paraffin oil rather than by the intermediate steps of oxidized graphite ( ) and oxidized graphene (GrO). Gr is used as support for the subsequent deposition of Pt nanoparticles and the catalytic behavior during oxygen reduction (OR) on the as-prepared Pt/Gr is studied. The structure, morphology, composition, and surface properties of the as-prepared Pt/Gr catalysts were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and electrochemical measurements. We found that the Pt nanoparticles with a mean particle size of 3.1 nm were well-dispersed on the Gr. The onset potential of the oxygen reduction on the Pt/Gr electrode shifted to the positive direction by 24 mV compared with the electrode made from commercial Pt/C catalysts (Johnson-Matthey Co. JM-Pt/C). The exchange current density of the OR on the Pt/Gr electrode was found to be 1×10^-3 mA·cm^-2, which is 2.5 times as that of the electrode made from the JM-Pt/C catalysts.

A series of ceramic samples La₂(Mo_1-xV_x)₂O_9-α (x = 0.02, 0.04, 0.06, 0.08) were synthesized by a solid-state reaction method. X-ray powder diffraction (XRD) patterns show that all the ceramic samples have a single cubic structure. The conductive properties of the ceramic samples were investigated using gas concentration cells and electrochemical impedance spectroscopy at 823-1123 K. All the samples have completely suppressed the phase transition, which occurs in La₂Mo₂O₉ at around 853 K. The ceramic samples are almost pure oxide-ionic conductors and do not possess the protonic conduction in dry and wet oxygen atmospheres. The oxide-ionic conductivity (σ) is affected by the doping level, and increases as follows: σ(x=0.02)<σ(x=0.08)<σ(x = 0.06)<σ(x=0.04). This order is consistent with that of the free volume of the crystal lattice. La₂(Mo_0.96V_0.04)₂O_9-α has the highest oxide-ionic conductivity of 0.051 S·cm^-1. The dependence of conductivity on oxygen partial pressure reveals that the samples are almost pure oxide-ionic conductors in the high oxygen partial pressure range whereas they exhibit mixed ionic and electronic conduction in the low oxygen partial pressure range.

A Li₃V₂(PO₄)₃/C composite cathode material was obtained by a sol-gel method using deionized water and organic solvents as mixed solvents. Ethanol, ethylene glycol, and 1,2-propylene glycol were used as the organic solvents and polyacrylic acid (PAA) was used as the chelating agent and carbon source. The structure, morphology, and electrochemical performance of the synthesized materials were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), charge-discharge tests, and cyclic voltammetry. XRD analysis showed that all the materials were well crystallized and that the addition of organic solvents did not affect the crystal structure of Li₃V₂(PO₄)₃. The results of galvanostatic cycling showed that the electrochemical performance of the products was improved by the addition of organic solvents. The material synthesized using 1,2-propylene glycol had the best electrochemical performance. It exhibited an initial discharge capacity of 132.89 mAh·g^-1 at 0.1C (1C=150 mA·g^-1) in the voltage range of 3.0-4.5 V. The initial discharge capacity was as high as 125.42 mAh·g^-1 upon discharging at 10C, and it had a capacity retention of 95.79% after 700 cycles. These results indicate a od rate and cycling performance in the voltage range of 3.0-4.5 V; while in the voltage range of 3.0-4.8 V, it exhibits a bad rate performance. SEM images indicated that the sample prepared using the mixed solvents had a flake-like and needle-like shape, which facilitates the interface ion-transfer process and thus improves the overall electrochemical properties.

Several polymer solar cells consisting of ITO/PEDOT:PSS/P3HT:PCBM/Al (indium tin oxide/ poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester/aluminum cathode) were fabricated by spin coating. The influence of annealing temperature on the performance of the polymer solar cells was studied using absorption spectra, photoluminescence spectra, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and atomic force microscopy (AFM). These devices were treated at 120 °C for 10 min in an ambient atmosphere and the best power conversion efficiency (PCE) of 2.00% was obtained at an open circuit voltage (V_oc) of 0.64 V, a short circuit current density (J_sc) of 10.25 mA·cm^-2, and a fill factor (FF) of 38.1%. The intensities of the absorption peaks at 560 and 610 nm increased because of the increased absorption π→π^* transition of P3HT after annealing treatment. XRD spectra showed that the intensity of the diffraction peaks at (100) for P3HT increased 1.8 times by comparison with that of the cells that did not under annealing treatment. The P3HT:PCBM phase separation increased markedly after annealing treatment, which is valuable for exciton dissociation. FTIR results also showed that the polymer materials did not deteriorate during the annealing treatment process.

A co-adsorbents modified nanocrystalline TiO₂ thin-film electrode was studied for application in dye-sensitized solar cells. The effects of di(3,3-dimethylbutyl) phosphoric acid and chenodeoxycholic acid modification on the flat band potential and the passivation of the TiO₂ thin-film electrode were investigated by determining the flat-band potential and undertaking electrochemical impedance spectroscopy (EIS). The results suggest that di(3,3-dimethylbutyl) phosphoric acid is more effective in passivating the TiO₂ film surface and in shifting the flat-band potential negatively. For the dye-sensitized solar cells, EIS measurements indicate that the use of di(3,3-dimethylbutyl) phosphoric acid as a co-adsorbent may be more effective in increasing the electronic lifetime and the open-circuit voltage of the device than chenodeoxycholic acid.

A graphite electrode (GE) was electrochemically modified by recurrent galvanic pulses. The pseudo-capacitive behavior in acidic and neutral solutions and the electrocatalytic property in HCl and HNO₃ solutions of the modified graphite electrode (MGE) were evaluated by cyclic voltammetry (CV). We found that the MGE exhibited a considerable pseudo-capacitance (the specific capacitance was high up to 1.730 F·cm^-2) in H₂SO₄ solution and excellent pseudo-capacitive behavior was obtained in HCl solution as well except for a narrow potential window. This was due to the excellent electrocatalytic activity of the MGE toward the chlorine evolution reaction (the onset potential of chlorine evolution was negatively shifted 238 mV). However, the MGE showed no pseudo-capacitive behavior in HNO₃ solution but did show electrocatalytic activity toward the reduction of nitric acid. Compared with the pseudo-capacitive behavior in acidic solutions, the potential window of the MGE in neutral solution was substantially broadened and its energy density improved greatly eventually even though the corresponding peak current density decreased.

Manganese dioxide (MnO₂) was synthesized using a fluid phase method with potassium permanganate and manganous acetate as precursors. The obtained MnO₂ was treated thermally at different temperatures. The structural transformation of MnO₂, its electrochemical behavior as an electrode material for use in a supercapacitor were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 physical adsorption, thermogravimetry (TG), cyclic voltammetry, and galvanostastic charge-discharge. The results indicate that the synthesized MnO₂ can be assigned to its α phase and that it possesses a mesoporous feature with a high surface area of up to 253 m²·g^-1. After a low temperature thermal treatment (<350 °C), the manganese oxide retained its α-MnO₂ crystal structure and its specific surface area was found to be approximately 170 m²·g^-1. The specific capacitance of the single electrode increased from 267 F·g^-1 for untreated MnO₂ to 286 F·g^-1 for the sample treated at 250 °C. However, high temperature thermal treatment (>450 °C) results in a transformation of the manganese oxide structure to α-Mn₂O₃ and then to α-Mn₃O₄. Additionally, the surface area reduced to ca 30 m²·g^-1 and this lead to a dramatic decrease in the specific capacitance of manganese oxide. The electrochemical cycling stability of manganese oxide improved noticeably after low temperature thermal treatment and the electrode retained a od rate performance at a scan rate of 50 mV·s^-1.

A Ni-W-P alloy nanowire array was fabricated in the nanochannels of an aluminum anodic oxide (AAO) membrane by electrodeposition. Scanning electron microscopy (SEM) was used to characterize the morphology of the Ni-W-P nanowire arrays. These nanowires had uniform diameters of about 100 nm and this accorded with the diameters of the holes. The length of these nanowires was about 20 μm. Cathodic polarization curves and electrochemical impedance spectroscopy (EIS) were used to study the electrocatalytic activity of the electrodeposited Ni-W-P alloy for the hydrogen evolution reaction (HER). The results clearly showed that the Ni-W-P alloy nanowire array electrodes had the highest electrocatalytic activity for the HER and the overpotential was lowered by 250 mV at 10 mA·cm^-2 compared with the as-electroplated Ni-W-P alloy.

Tetraethylenepentamine (TEPA) was surveyed to show strong inhibition on pitting corrosion of Q345B carbon steel in a carbonated synthetic pore solution (SPS) by electrochemical noise (ECN), electrochemical impedance spectroscopy (EIS), and polarization curves. The pitting corrosion potential shifts positively with an increase in the TEPA concentration. ECN data show that the low content of TEPA can increase the nucleation rate of the metastable pits slightly and can effectively reduce their lifespan. The high content (0.10 mol·L^-1) of TEPA accelerates the repassivation of metastable pitting and this is accompanied by an increase in noise resistance and a decrease in the nucleation rate and average pitting charge until the noise current transients disappear completely. Both the baseline current and the amplitude of the current transients decrease with an increase in the TEPA concentration, indicating that TEPA retards not only the pitting corrosion but also the general dissolution of the passive film. Micrographs show that the metastable pits mainly initiate and develop around the stable pits because of the induction of corrosion products, which causes the pitting cavity on carbon steel to grow generally in a planar rather than in a perpendicular direction.

The effect of sodium salicylate (NaSal) on the formation and properties of wormlike micelles in aqueous solutions of 2-hydroxyl-propanediyl-α,ω-bis(dimethyldodecylammonium bromide) (12-3(OH)-12) and propanediyl-α,ω-bis(dimethyldodecylammonium bromide) (12-3-12) at a surfactant concentration of 50 mmol·L^-1 was investigated using steady-state and frequency sweep rheological measurements. In the absence of a salt, 12-3(OH)-12 or 12-3-12 only produced spherical or small rod-like micelles at 50 mmol·L^-1. The addition of NaSal promoted micellar growth yielding wormlike micelles in both systems. 12-3(OH)-12 showed a more sensitive response to the added NaSal compared with 12-3-12 and formed wormlike micelles at relatively lower salt concentrations. Moreover, the wormlike micelles formed by 12-3(OH)-12 were longer than those formed by 12-3-12, resulting in higher viscosity for the former solution. These were attributed to the hydrogen bonding interactions between the hydroxyl substituted spacers in the 12-3(OH)-12 system, which increased hydration on the aggregate surface and stimulated the dissociation of counterions. The higher charge on the 12-3(OH)-12 micellar surface was strongly associated with Sal^-, which led to a tighter packing of the surfactant molecules in the micelles and thus strengthened the intermolecular hydrogen bonding interactions and effectively reinforced the growth of the 12-3(OH)-12 micelles.

An oli aramide duplex containing multiple hydrogen bonds was found to under self-assembly in the absence of its corresponding complementary strand. The self-assembly behavior of the molecular oli aramide was examined using multiple techniques including ultraviolet-visible (UV-Vis) spectrum, dynamic light scattering (DLS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The result from the UV-Vis experiment indicated a hypsochromic shift within the ultraviolet region in 1,2-dichloroethane with increasing temperature, suggesting partial disintegration of supramolecular aggregates. The oli aramide was found to self-assemble in solvents of different polarity presenting different types of morphologies. For example, reticulation-like morphology was observed when using toluene as a solvent; an irregular honeycomb appeared in the mixed, relatively less polar dichloromethane and cyclohexane. In addition, stable solid balls formed instead of vesicles upon self-assembling in a mixed polar solvent of chloroform and methanol. The diameters of these spherical aggregates increased with concentration. Furthermore, the transformation of assemblies from tubular fibers in hot acetonitrile to solid spherical aggregates was observed upon cooling.

Ce_0.5+x Zr_0.4-x La_0.1O₂-Al₂O₃ catalysts were prepared by co-precipitation, where 0≤x≤0.4 and the mass ratio of Ce_0.5+xZr_0.4-xLa_0.1O₂:Al₂O₃ was 1:1. The catalytic activities of these catalysts for the catalytic combustion of diesel soot were investigated. The catalysts were further characterized by low temperature nitrogen adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H₂- temperature-programmed reduction (H₂-TPR), and O₂-temperature-programmed desorption (O₂-TPD). The results showed that all the catalysts formed solid solutions with a fluorite-like structure. When x=0.2, the Ce³⁺ ions were partly rich on the surface of the catalyst. The catalyst was easily reduced by H₂ and the desorption peak area of the β oxygen species was the largest. The light-off temperature was 360 °C for the catalytic combustion of diesel soot over the catalyst suggesting od catalytic activity and potential application in diesel soot catalytic combustion.

CN-REC/Cu₂O nanocomposites were synthesized with Cu(CH3COO)2·H₂O as a copper source and cross-linked sodium rectorite (CN-REC) as a carrier and template. The obtained samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and ultraviolet visible diffuse reflectance spectrum (UV-Vis DRS). The results indicate that the regulatory effects of CN-REC on Cu₂O are significant. Cu₂O is dispersed in the interlayer and on the surface of?the lamellar structure of CN-REC. A Si―O―Cu bond was formed between the cuprous oxide crystal and the CN-REC crystal, which established a bridge for the transfer of photogenerated charge. The energy band gap of the nanocomposites became wider and the photoresponse properties of the nanocomposites became stronger. To study the visible light photocatalytic activity of the nanocomposites, reactive brilliant red (X-3B) was selected as a target contaminant. The photocatalytic degradation rate of X-3B with the nanocomposites is more than 80%, which is better than that with Cu₂O. The degradation progress accorded with the L-H kinetics equations.

Improving the photocatalytic activity and the utilization of visible light of TiO₂ is the most important research topics in the photocatalytic field. To improve the photocatalytic activity of TiO₂, we used chemical vapor deposition (CVD) to dope TiO₂ nanotubes with fluorine. Scanning electron microscopy (SEM) images showed that the annealing temperature significantly affected the morphological integrity of TiO₂ nanotubes. Upon annealing at 550 and 700 °C, the structure of F-doped TiO₂ nanotubes suffered from an observable disintegration of morphological integrity. X-ray diffraction (XRD) results indicated that the F impurity retarded the anatase-rutile phase transition. Fluorine was successfully doped into TiO₂ by CVD, as indicated by the X-ray photoelectron spectroscopy (XPS) results. F-doped TiO₂ nanotubes showed higher photocatalytic activity. First-principles calculations suggested that the F 2p states were located in the lower-energy range of valence band (VB) and less mixed with O 2p states. It thus contributed little to the reduction of the optical band gap. This is consistent with the finding that the band gap of F-doped TiO₂ is very close to that of undoped TiO₂. Therefore, the higher catalytic activity of F-doped TiO₂ should be attributed to the creation of surface oxygen vacancies upon F-doping, which enhances surface acidity and increases the amount of Ti³⁺ ions.

Three kinds of aminosilane (APTS: 3-aminopropyltrimethoxysilane, TPED: N-[3-(trimethoxysilyl)-propylethylene]diamine, TPDT: trimethoxysilyl propyl diethylenetriamine) functionalized mesoporous SBA- 15 molecular sieves (denoted APTS-SBA-15, TPED-SBA-15 and TPDT-SBA-15) were synthesized by post-grafting. Using the static interaction between the amino group and chloroauric acid followed by chemical reduction, the ld nanoparticles were immobilized into the channels of SBA-15. The Au/aminosilane-SBA-15 catalysts were systematically characterized by N₂ physisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The liquid phase hydrogenation of crotonaldehyde to crotyl alcohol (CROL) was used to investigate the effect of aminosilanes on the catalytic performance of the Au/amine-SBA-15 catalysts. The results revealed that the electron-donating ability of the aminosilane determines the selectivity towards the hydrogenation of the C＝O bond on the ld catalyst. A stronger aminosilane electron-donating ability results in higher electron density on the ld active sites, which leads to the higher selectivity and yield of CROL.

NiB amorphous alloy catalyst (NiB-CS) was prepared by direct reduction using the chemical- reduction method with chitosan as a stabilizer. The amorphous structure, atomic composition, and particle size of the as-prepared catalysts were characterized by X-ray diffraction (XRD), inductively coupled plasma spectrometry (ICP), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and selected area electron diffraction (SAED). The catalytic behavior during the hydrogenation of furfuryl alcohol (FA) to tetrafurfural alcohol (THFA) was studied and compared with the NiB catalyst prepared without chitosan. The amorphous NiB-CS catalyst was found to be more reactive than the NiB catalyst. The superior catalytic activity of the NiB-CS catalyst is attributed to the small NiB particles and the high surface content of Ni active species.

We hydrothermally synthesized sheet-like crystals of zeolite Y at high temperature (140 °C) using methyltriethoxysilane (MTS) as an additivity. Compared with the zeolite Y synthesized at 100 °C, the zeolite Y synthesized at high temperature has a high Si/Al ratio, a large crystalline width/thickness ratio and has od adsorption for organic volatile compounds. Characterization by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), ²⁹Si nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectroscopy, elemental analysis and water contact angle measurements suggests that the zeolite Y synthesized at high temperature contains methyl groups, which can be responsible for the improvement in sample hydrophobicity and adsorption capacity.

Ultrafast dynamics of the first excited state (S₁) of chlorobenzene was studied using a combination of femtosecond time-resolved photoelectron imaging and time-resolved mass spectroscopy. One-photon absorption at 266.7 nm was used to populate the S₁ state of chlorobenzene. The time evolution of the parent ion signals consists of different biexponential decays. One is a fast component on a timescale of (152±3) fs and the other is a slow component with a timescale of (749±21) ps. Time- resolved electron kinetic energies (eKE) and time-resolved photoelectron angular distributions (PADs) were extracted from time-resolved photoelectron imaging and are discussed in detail. The ultrafast process with a time constant of (152±3) fs is a population transfer within the S₁ state, and only a vibrational energy transfer process with strong coupling is a reasonable explanation. This is attributed to an ultrafast process of dissipative intramolecular vibrational energy redistribution (IVR). The lifetime of the S₁ state was determined to be (749±21) ps, and its deactivation was due to slow internal conversion to the ground state. Additionally, nonadiabatic alignment and rotational dephasing of the S₁ state of chlorobenzene, as a typical asymmetric top molecule, were observed. The first C-type and J-type recurrences are expected at delay time of 205.8 and 359.3 ps, respectively.

Using benzil (BZ) as a probe molecule, the photochemical properties of the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]) and its binary mixed solutions with acetonitrile (MeCN) were investigated by nanosecond laser photolysis. We found that the decay of the triplet excited state of benzil (³BZ^*) in a N₂-saturated solution followed mono-exponential kinetics. Along with the increase in the volume fraction (V_IL) of [bmim][BF₄] in the mixed solvents, the absorption peak of ³BZ^* did not change. However, the effect of different V_IL values on the photoinduced electron transfer process in the mixture of [bmim][BF₄]/MeCN was obvious. Moreover, the apparent rate constant (k_gr) of the formed radical decreased obviously with an increase in V_IL. When the ratio of [bmim][BF₄] was sufficiently high, the electron transfer reaction between ³BZ^* and triethylamine or N,N,N′,N′-tetramethyl-p-phenylenediamine was retarded.

Poly(9,9-diallylfluorene) (PAF) with single green emission was synthesized through polymerization of allyl substituted 2,7-dibromofluorene in the presence of NiCl₂ as the catalyst. PAF shows deep blue fluorescence at 403 nm in solution and 456 nm in solid film state. The organic electroluminescence device (OLED) gives a green emission with the peak at 532 nm by using PAF as the emitter with a structure of ITO/PEDOT:PSS/PAF/LiF/Al (ITO: indium tin oxides; PEDOT: poly(3,4- ethylenedioxythiophene); PSS: poly(styrenesulfonate)). The photoluminescence (PL) of the PAF film red- shifted after thermal anealing, the original peak of blue emission decreased and a new peak of green emissioin increased. However, there is no change in the chemical structure based on the Fourier transform infrared (FT-IR) spectra of PAF after thermal annealing under vacuum. Moreover, there is no change on the PL spectra of PAF before and after the evaporation of metal cathode. It can be deduced that the single green emisson of PAF based OLED is original from the inter-chain aggregation which can be confirmed from their atomic force microscopy (AFM) images.

Cesium-12CaO·7Al₂O₃ (Cs-C12A7) was fabricated by adding CsI to the C12A7 surface using incipient wetness impregnation. The X-ray diffraction (XRD) structure determined for the Cs-C12A7 material is the same as that of the 12CaO·7Al₂O₃ (C12A7) crystal, which belongs to the I43d] space group. The concentrations of O^- and O₂^- in Cs-C12A7 were about (1.3±0.3)×10²⁰ cm^-3 and (1.2±0.2)×10²⁰ cm^-3, respectively, according to a simulation of the measured electron paramagnetic resonance (EPR) spectrum. This is similar to the data obtained for fresh C12A7 ([O^-]=(1.4±0.3)×10²⁰ cm^-3 and [O₂^-]=(1.4±0.3)×10²⁰ cm^-3). The CsI particles from the C12A7 surface were observed using field emission scanning electron microscope (FESEM) and conventional transmission electron microscopy (TEM). The emission features of Cs-C12A7, including the emission distribution, field effect and apparent activation energy were investigated in detail and compared with those of C12A7. The advanced emission behavior was attributed to a reduction in the apparent activation energy.

Solid solutions of Pb_1-xTb_xTi_1-xMn_xO₃ (0≤x≤0.10) were synthesized by a traditional solid state reaction and characterized by powder X-ray diffraction. The solutions crystallize in the P4mm space group at room temperature. Differential scanning calorimetry (DSC) measurements were performed to obtain phase transition temperatures (T_c) for the samples, and these were found to decrease with an increase in the amount of doped Tb and Mn. The temperature dependent dielectric constant shows a peak close to the T_c, indicating that the corresponding phase transition is a ferroelectric phase transition. Magnetic measurements indicate that a paramagnetic to antiferromagnetic phase transition occurs at 25 and 29 K for Pb_1-xTb_xTi_1-xMn_xO₃ with x=0.08 and x=0.10, respectively.