Microscopic structures and mechanism of Zn(II) adsorbed onto anatase at different temperatures were studied using extended X-ray absorption fine structure (EXAFS) spectroscopy. Macroscopic adsorption-desorption experiments indicated that adsorption isotherms and adsorption reversibility increased substantially with increasing temperature. When temperature increased from 5 ℃ to 40 ℃, the adsorption capacity increased from 0.125 mmol·g-1 to 0.446 mmol·g-1, while the desorption hysteresis angle (θ) decreased from 32.85°to 8.64°. The thermodynamic parameters ⊿H and ⊿S of the reaction were evaluated as 24.55 kJ·mol-1 and 159.13 J·mol-1·K-1, respectively. EXAFS spectra results showed that Zn(II) was adsorbed onto the solid surface in the form of octahedral hydrous Zn(II) ions, which were linked to TiO2 surface by sharing O atoms, with an average bond length RZn-O=(0.199±0.001) nm. EXAFS analysis of the second Zn-Ti coordination sphere resulted in two Zn-Ti atomic distances of (0.325±0.001) nmand (0.369±0.001) nm, corresponding to edge-sharing linkage (stronger adsorption site) and corner-sharing linkage (weaker adsorption site), respectively. The number of stronger adsorption sites (CN1) remained relatively stable while the number of weaker adsorption sites (CN2) increased remarkably as the temperature increased, making the proportion of two adsorption modes (CN1/CN2) drop from0.690 to 0.543. These results revealed that the increased adsorption capacity and reversibility at higher temperature were due to the increase in CN2 and the decrease in CN1/CN2. This result implies that, in a given environment (soils or rivers), the bioavailability of zinc is higher at high temperature than that at low temperature.

Polyaniline(PANI) microtubes were prepared at low temperature with camphorsulfonic acid (CSA) as dopant. The structure and morphology of the microtubes were examined by Fourier-transforminfrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The length of the microtubes was 2-3 μm and the outer diameter was 300-400 nm. The results indicated that the higher concentration of dopant was liable to the PANI-CSA microtube formation. Electrochemical capacitance properties of the doped polyaniline electrode were investigated by means of cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge measurements. When the molar ratio of aniline/CSA was 1:1, polyaniline had a od stability and cyclic performance, and the specific capacitance reached up to 522 F·g-1.

The adsorption of creatinine (CR, a kind of metabolin in the human body) on the rice husk-based carbons (RHCs) with high specific area was studied. Comparison was made between the CR adsorption on four samples of porous carbon prepared by NaOH activation from rice husk at different activation conditions and two samples of commercial carbon. Meanwhile, the adsorption of CR on the modified carbon surfaces treated with HCl, H2O2, and HNO3, respectively, and calcined at 800 ℃ was investigated. Compared with commercial carbons, it was shown that the RHCs had larger capacity for the adsorption of CR. Generally, the CR adsorption capacity increased after the modification of the carbon surfaces. With regard to the adsorbability towards CR, the porous carbons treated by HCl was the best, the porous carbons treated by HNO3 was the worst, and the one treated by H2O2 was in the middle. The adsorbability of porous carbons after being calcined at high temperature (800 ℃) was obviously worse. The experiment testified that the adsorption of CR by porous carbons followed the Freundlich equation.

Well-crystallized and regular lithium iron phosphate (LiFePO4) particles were synthesized via solvothermal reaction in H2O-isopropanol mixture solvents. FESEM micrographs indicated that the morphology of as-prepared LiFePO4 was strongly dependent on the conductive additives, i.e. when the additive changed from sucrose, carbon black to graphite, the LiFePO4 morphology changed from rod to square block. TEMand SAED results showed that rod-like LiFePO4 crystal grows along [201] direction preferentially. A rationalmechanismbased on the crystal growth prohibiting effect of additive was proposed. LiFePO4 sample with additive sucrose showed the best charge/discharge performance. It was able to deliver a high reversible capacity of 145.2 mAh·g-1 at 0.1C as well as a favorable capacity retention. Furthermore, it exhibited excellent rate performance and temperature performance. It could deliver 98.1 mAh·g-1 at 4C, about 67.6%of that at 0.1C, and the discharge voltage plateau still remained to be 3.12 V(vs Li/Li+).

Non-faradic phenomena were found during the glow discharge plasma electrolysis of methanol solution, and the main products of the reactions induced by the glow discharge plasmas were hydrogen, formaldehyde, monoxide, methane, ethane, propane, sym-trioxane, and water. The chemical yields were affected by the polarity of the glow discharge plasma and supporting electrolytes of the solutions. The gas yield of the anodic glow discharge electrolysis of methanol was 55.90 mol/(mol electrons) when the discharge voltage across the circuit was 700 V and the conductivity of the solution was 11.40 mS·cm-1. The gas yield of the cathodic glow discharge was 707.90 mol/(mol electrons), 12.66 times of the anodic glow discharge gas yield, under the same conditions. The hydrogen concentration in the emission gas of the glow discharge electrolysis was higher than 86% (molar fraction). The decomposition of methanol molecules induced by the glow discharge plasmas around discharge electrode was similar to those induced by corona plasmas and dielectric discharge plasmas. Non-faradic phenomena of the glow discharge electrolysis of the methanol solutions were stirred up by the accelerated electrons within the gas sheath around the discharge electrode. Neutral species and electrons excited the methanol molecules on the plasma-electrolyte interface during cathodic glow discharge, while positive ions and neutral species played a more important role to excite the methanol molecules on the plasma-electrolyte interface during anodic glow discharge. The reactions in the liquid phase near the plasma-solution interface were affected by the supporting electrolytes of the solutions.

High density of Ge quantumdots (QDs) with size of less than 10 nmwere obtained on Si(001) surface by optimizing the growth parameters. The results of extended X-ray absorption fine structure (EXAFS) showed that the contents of GeSi alloy in these QDs fabricated at 500 ℃ and 550 ℃ were 75% and 80%, respectively. According to thermodynamics analysis, it was believed that during the annealing process after the QDs’ growth, Si atoms might diffuse fromthe substrate surface to the QDs surface, then intermix with Ge atoms by surface segregation. On the other hand, the higher height/diameter ratio might also induce high content of GeSi alloy in small size of Ge QDs.

A series of MoBiTeO/SiO2 catalysts with different Te contents was prepared by impregnation method. Effect of Te on the catalysts’ structure, acidity and catalytic performance for selective oxidation of propane to acrolein was investigated by XRD, Raman, XPS, NH3-TPD, FT-IR, and performance evaluation techniques. The results indicated that by forming Mo—O—Te bond with the Mo species, tellurium component in the catalyst improved the dispersion of Mo oxide species that would be favorable to the formation of isolate active sites on the catalysts. Besides, Te could be the centers for α-H abstraction of propene and O-insertion to allyl species. So, the addition of Te to MoBiO/SiO2 catalyst promoted the acrolein selectivity greatly. However, the addition of telluriumalso could contribute the formation of B acid sites in MoBiTeO/SiO2 catalysts that had been proved to be harmful to the generation of acrolein. Therefore, there existed an optimal scale for the amount of Te-content in the MoBiTeO/SiO2 catalysts. When the nTe/nMo ratio was 0.05-0.1, the catalyst showed the best catalytic performance.

Oleic acid was used in low-temperature hydrothermal reaction of tetrabutyl titanate (TBOT) to control the growth direction of TiO2 particles. TiO2 nano-crystallines in the shapes of needle and spindle were synthesized. The morphology and structure of these TiO2 particles were confirmed by means of TEM and XRD. The FT-IR spectrum analysis proved that oleic acid molecule was absorbed onto the surface of TiO2 particles through electrostatic interaction. The band-gap energies of TiO2 nano-crystallines were calculated according to their UV-Vis spectra. In the photocatalytic reaction, the spindle TiO2 particles showed higher activity, and 90% rhodanmine B was degraded in 60 min.

The influence of hydrogen contamination on the atomic geometry of Ru(0001) surface was studied by using the density-functional theory and the projector-augmented wave (PAW) method. Based on the optimized structural parameters of hcp Ru from the PAWtotal energy calculation, the surface relaxation, surface energy, and work function of clean Ru(0001) surface were calculated in the same way. The adsorption geometries and total energies of several coverages of hydrogen on Ru(0001) surface including p(1×1), p(1×2), (3^(1/2)×3^(1/2))R30°, and p(2×2), were studied for the hcp and fcc site absorptions combined with the both sites occupation in p(1×1) structure. These results suggested that the Ru(0001) p(1×1)-H geometry had the largest energy gain among all these conformations, so under the condition of low coverage and low H2 pressure, the most possible conformation was p(1×1)-H adsorption. The shrink of Ru(0001) surface with H contamination was -3.7%fromavailable experiments and this work yields -1.11%for hcp and -1.55% for fcc adsorption geometries. It was deduced that the most possible adsorption configuration for a hydrogen contaminated Ru(0001) surface was a mixture of hcp and fcc adsorptions. For a clean Ru(0001) surface the surface contraction was calculated to be near -3.9%, while the experimental measurement predicted -1.9%. This observation implied that even for a“clean”Ru (0001) surface there was still about 13.6%of surface area covered with hydrogen adsorption. These results reflected that the hydrogen contamination could affect the Ru(0001) surface structure dramatically. Furthermore the present study could yield a conclusion naturally that the shrink of the Ru(0001) surface would be reduced with the increase of H atomadsorption below 1.0 ML (monolayer).

The density functional theory (DFT) method was used to investigate the geometries, electronic structures, and frequencies of CnAl (n=2-11) clusters. At the B3LYP/6-311++G** level, the ground state of C2Al was a planar structure while other CnAl (n =3-11) were linear structures with terminal aluminum atom. The energetic analysis showed that CnAl clusters with even n were more stable than those with odd n.

To obtain polypyrrole (PPy) films with high area specific capacitance as electrode material for supercapacitors, the multi-step polymerization method was proposed for preparing PPy thick films with polymerization charge of 8, 10, and 12 mAh·cm-2, doped with Cl- and p-toluenesulfonate (TOS-), respectively. The capacitance properties of the PPy films were investigated by galvanostatic charge/discharge, cyclic voltammetry (CV), and electrochemical impedance spectrum (EIS) technologies. The section morphology of the PPy films was observed by using field emission electron scanning microscope (SEM). The results showed that two kinds of even porous PPy films with area specific capacitance up to 5 F·cm-2 could be obtained by multi-step method. Moreover, the mass specific capacitance (referring to the masses of polymer and doping ions) of PPy-Cl could reach 330 F·g-1, and the value of PPy-TOS could reach 191 F·g-1, which were similar with that of PPy thin films. However, the discharge rate of the PPy-TOS film was more rapid than that of the PPy-Cl film. In addition, the growth processes of PPy films from one-step
polymerization method and multi-step polymerization method were discussed.

Polyaniline-titanium dioxide (PANI/TiO2) composite thin film and polyaniline (PANI) thin film were prepared by combined techniques of electrostatic self-assembly and in situ chemical oxidation polymerization at room temperature, which were characterized by XPS and SEM. The PANI/TiO2 and PANI thin film gas sensors with planar interdigitated electrodes were fabricated, and the sensitive properties of sensors to toxic gases NH3 and CO were studied at room temperature. The results showed that the sensitivity, response and recovery characteristics of PANI/TiO2 thin filmwere superior to those of PANI thin film.

The molecular dynamics method was used to investigate the elastic properties of armchair and zigzag single-walled carbon nanotubes grafted by carboxyls on their ports. The results showed that the Young’s moduli of ungrafted armchair (5, 5), (10, 10) and zigzag (9, 0) , (18, 0) single-walled carbon nanotubes were 948, 901 GPa and 804, 860 GPa, respectively. When the single-walled carbon nanotubes were grafted by 2 to 8 carboxylic functional groups, the Young’s modulus of the armchair single-walled carbon nanotubes had few varieties, while the zigzag single-walled carbon nanotubes were different, namely, the Young’s modulus of the nanotubes decreased significantly due to the grafting and the Young’s modulus increased appreciably with increasing of the grafts. The reasons were analyzed in terms of the isoline structure of deformation electron density, the bond-length and the system potential energy varieties of the carbon nanotubes with different graft numbers.

After properly heat-activating the polymers poly(furancarbinol-co-phenol) (PFP-0) and polyparaphenylene (PPP-0), two new functional polymer nanomaterials, PFP and PPP were obtained. Their properties as catalysts in water pollution treatment were studied. The samples were determined by means of DTA-TG, TEM, FT-IR, and UV-Vis. The results showed that under natural light and air conditions, dye methylene blue (MB) could be almost fully degraded and largely mineralized on them within a few minutes; the variation of the conjugation structure had great influence on their stabilities; compared with each other, the existence of polar groups was found to be decisive factor to the catalytic properties.

Grand Canonical Monte Carlo(GCMC) and molecular dynamics (MD) techniques were employed to simulate the adsorption and diffusion properties in mordenite (MOR) zeolites. By the GCMC, the adsorption of methane, ethane, propane, and butane in MOR zeolites at 300 K、330 K was studied. The results indicated that the adsorbed amounts decreased with increasing temperature and the order of saturated adsorption amounts was methane>ethane>propane>butane. Adsorption diagrams of binary alkanes mixtures were simulated by MD and calculated by ideal adsorption solution theory (IAST). The calculated results were in agreement with the simulated results. Finally, the diffusion properties of ethane and propane in MOR zeolites were studied by molecular dynamics. The results showed that the diffusion coefficients were different in different directions and the biggest diffusion coefficients in z direction.

The reaction mechanism of the activation of ethane via cobalt atom catalysis was investigated by DFT method at two different basis sets at the temperature of 500 K. The geometries and vibration frequencies of reactants, intermediates, transition states, and products were calculated. In addition, the bonding circumstances and orbital interactions were analyzed by natural bond orbital (NBO). The results of two different levels indicated that themechanism and the corresponding energy changing trend were consistent. The activation process could be divided into C—C bond activation and C—H bond activation, and the C—H bond activation was easier than the C—C bond activation.

The coexistence curves of (T-n) (T and n are temperature and refractive index, respectively) for the system of DMA+AOT+n-octane have been determined within about 7 K from the critical temperature (Tc) by measurements of refractive index at a constantmolar ratio of DMAto AOT (3.46). The coexistence curves of (T-n) have been converted to the coexistence curves of (T-φ) and (T-ψ) (φand ψare volume fraction and effective volume fraction, respectively) through the standard curves determined by measurements of refractive indexes at various volume fractions and temperatures. The critical exponent β was deduced from the coexistence curves, which was found to be inconsistent with the 3D-Ising value and approach the Fisher-normalization value 0.365 in a rather wide temperature range. The experimental results were also analyzed to obtain the critical amplitude B and the Wegner correction terms B1 to examine the diameters of coexistence curves, and to discuss the odness of the order parameter.

The adsorption of polyethylene glycol (PEG) on SiC surface was measured by thermal gravimetric (TG) and differential thermal analysis (DTA). The result showed that PEG completely decomposed at 411.5 ℃ in Ar atmosphere. The adsorption amount decreased with the increase of pH and most free dispersant remained in liquid phase at higher pH. The adsorption amount was calculated by the formula (1). This method is adapted to measure the adsorption of organic polymer on oxide or non-oxide which can’t be analyzed by ultraviolet-visible spectrometry.

A new calculation method was developed in this paper. With the natural collision coordinate, the core translational equation along the reactive coordinate was solved by the numerical propagation method on the partial potential energy surface. Then the resonance lifetime matrix of reactive system was constructed by the eigen-phase shift of the wave function of transient collision complex. So it was a direct calculation method on the lifetime of scattering resonance states. The lifetime of first scattering resonance state of the I+HI(υ)→IH(υ’)+I reaction has been calculated by our method, which is in od agreement with Neumark’s experimental results of the high-resolved-threshold-photodetachment spectroscopy of this reaction.

A simplified W/O/W (water/oil/water) multiple emulsion model-statistic mean radius model was established in order to keep the stability of multiple emulsions by controlling their water transport. Salt concentrations in the internal and external phases were predicted by this model so that water transport equilibrium among droplets in oil phase and between the internal and external phases was attained by tailoring the solvent chemical potential of the multiple emulsion. Differential scanning calorimetry (DSC) was used to test the extent of water transport for multiple emulsions experienced a circle of freezing and thawing process. The testing results agreed well with our theoretic prediction for the stability of multiple emulsions. Therefore, it was feasible to maintain W/O/W multiple emulsions’ stability by controlling their water transport process.

The films with Ag nanoparticles embedded in amorphous titanium oxide were successfully prepared by radio frequency magnetron sputtering method. The changes in size, shape, absorption, and binding energy of Ag nanoparticles irradiated with picosecond laser of 800 nm were studied. TEM images showed that Ag nanoparticles became smaller in size and more roundish in shape after irradiation. The optical absorption spectra indicated that the absorption was reduced in the wavelength range from 586 nm to 1200 nm, and increased at the wavelength range from 350 nmto 586 nm. The photoluminescence intensity was greatly enhanced after the samples had been irradiated, which was attributed to the Ag2Oformed by photo oxidation.

Nanoparticles were synthesized under pulsed laser ablation of Pt, Ru, and Ag in water with or without PVP(poly(vinylpyrrolidone). Scanning electron microscopy, high resolution transmission electron microscopy, selected area electron diffraction and UV-Vis absorption spectroscopy were used to characterize the nanoparticles. Nano-sized particles were found to be in the range from several to tens nanometers. The plasma absorption bands of generated Pt, Ru, and Ag nanoparticles at around 254, 300, and 420 nm were observed. The water solution containing PVP with appropriate concentration was found to be in favor of the formation of noble metal nanoparticles and to be capable of stabilizing nanoparticle suspensions. Meanwhile, the mechanism of the formation of nanoparticles by laser ablation in liquid media was discussed. Results suggested that the colloidal solution of noble metal nanoparticles could be obtained simply by pulsed laser ablation of their bulk as targets in liquid, indicating the advantage over other methods especially for the synthesis of noble metals with high melting points.

Lithium ion sieve IE-H was obtained by acid-modifying Li4Ti5Ol2 precursor, which was prepared by sol-gel method. Its properties of ion-exchange for Li+ and Na+, such as the saturation capacity of exchange and pH titration curves, were determined. The Li4Ti5Ol2 precursor and lithium ion sieve IE-H were characterized by XRD. The ion exchange mechanism was judged by broken phase contact method. The kinetics of the ion sieve with Li+ was depicted by the shrinking-core model. It was shown that both the Li4Ti5Ol2 and lithium ion sieve IE-H are spinel structure. After acid treatment, the extraction ratio of Li+ from Li4Ti5Ol2 was 19.6%- 81.5%, while the extraction ratio of Ti4+ was less than 4.2%; Further, the obtained ion sieve IE-H showed superior saturated ion exchange capacity for Li+, with a value of 5.95 mmol·g -1. In addition, the reaction of the ion sieve with Li + was determined to be controlled by particle diffusion. Finally, different kinetics equations and diffusion coefficients of the ion sieve IE-H for Li+ at 25 ℃ were obtained with the Li+ concentrations of 20.0 mmol·L-1 and 5.0 mmol·L-1.

Correlation equation between the enthalpy of formation and the ionization potential was deduced for alkanes, based on the relationship between the heat of formation and the valence electronic energy change in the formation of a compound from its component atoms, and the relationship between the first ionization potential and the average valence electronic energy. The proposed correlation model was confirmed by taking 21 alkanes as model compounds and correlating their experimental ionization potentials to their standard enthalpies of formation, in which the expression with od correlation (correlation coefficient R is 0.9999) and lower error (standard derivation is 0.03 eV) was obtained. Using the obtained correlation expression, the ionization potentials of a set of alkanes were predicted with their experimental enthalpies of formation.

In 0.050 mol·L-1 phosphate buffer solution (pH=6.4), methylene blue (MB) exhibited a pair of small peaks at about -0.2 V on a platinum electrode. In the presence of m-4-m structured Gemini surfactants, such as Br-C16H33N+-(CH3)2-C4H8-N+(CH3)2C16H33Br-, Br -C12H25N+(CH3)2-C4H8-N+(CH3)2C12H25Br-, and Br -C8H17N+(CH3)2-C4H8-N+-(CH3)2C8H17Br-, the anodic peak of MB grewrapidly but the cathodic peak decreased, and the peak potentials moved in positive direction due to the associated adsorption of Gemini surfactants and MB on the electrode surface. The influence of Gemini surfactants increased with their length of alkyl chain growing. When their concentrations were enhanced, the anodic peak increased firstly and then lowered. For Br-C16H33N+(CH3)2-C4H8-N+(CH3)2C16H33Br- the anodic peak of 5 μmol·L-1 MB achieved the maximum when its concentration was 15 μmol·L-1. In addition, solution pH and accumulation potential also showed effect on their adsorption behavior.