Based on the Warren's interface theory of liquid-solid interfacial energy for complicated compatible binary and pseudo binary systems, a physical model for the liquid-solid free interfacial energy that has been simplified at the theoretical level was obtained by taking the Pb-Al liquid-solid binary system as an example. A theoretical formula with two variables was then obtained by deducing a thermodynamic equation, and the calculational values and the experimental values by multiphase equilibrium method (MPE) were compared. Finally, research on a Pb-Al binary liquid-solid system showed that the calculated liquid-solid interfacial free energy (γSL) values from the model provided a result similar to the experimental measurement with a low average error. The calculated values only depend on the temperature and the Al concentration. A foundation to calculate γSL for other systems has therefore been established.

The thermal decomposition process of water-solublity blocked isophorone diisocyanate (IPDI) was studied using thermal gravimetric analysis (TGA). The characteristic peaks of isocyanante groups at 40 and 140 ℃ were observed by Fourier transform infrared spectroscopy (FTIR). Results from TGA and FTIR showed that the degradation stage was a deblocking reaction of the blocked adduct. The Friedman-Reich-Levi (FRL) and Flynn-Wall-Ozawa (FWO) models were employed to investigate the apparent activation energies which were 125.0 and 124.5 kJ·mol-1, respectively. Based on the double equal-double step method, the reaction was analyzed by the apparent mechanism of the process of deblocking according to the Jander equation, which indicated that the reactive mechanism was a three-dimensional diffusion. The reaction order (n) and the logarithm of pre-exponential factor (lnA) were also determined using the FWO equation.

The structure and morphology of coating carbon play an important role in improving the electronic conductivity of lithium iron phosphate. LiFePO4/C composites were synthesized using an in-situ solid state method while polypropylene and glucose were used as carbon sources. Ferrocene was used as a catalyst precursor to graphitize the pyrolytic carbon. The microstructure and morphology of lithium iron phosphate together with the amounts and structure of the coating carbon were investigated in detail. It is shown that the pyrolysis of polypropylene forms well graphitized carbon-coatings and thus improves the high-rate performance of the material. Ferrocene is effective in optimizing the carbon structure. A LiFePO4/C composite with an excellent high-rate capacity of 145 mAh·g-1 at 10C (1C=170 mA·g-1) was synthesized.

Surface analysis method, mass loss method, and electrochemical test were employed to investigate the corrosion behavior of steel A3 under the effect of Thiobacillus thiooxidans (T.t). Scanning electronic microscopy (SEM) results indicated that the presence of T.t resulted in a more compact biofilm and product film. Pitting occurred on the steel A3 coupon immersed into a sterile system while the one in the T.t system showed general corrosion. The average corrosion rate in the sterile system was greater than that in the T.t system after 3 weeks. Electrochemical impedance spectroscopy (EIS) showed that there were only two time constants for the sample immersed in the T.t system after 10 days. This demonstrates that a compact and strongly inserted product film was formed on the surface of coupon in the presence of T.t which effectively obstructed the erosion of caustic ions. Polarization curve results showed that the corrosion current density of the metal decreased after 20 days of exposure to the T.t solution.

Multi-walled carbon nanotubes were functionalized using in situ generated aryl diazonium and were then used to synthesize polypyrrole/benzenesulfonic functionalized multi-walled carbon nanotube composites (PPy/f-MWCNTs). Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) results indicated that a uniform PPy was successfully coated onto the sidewall of the f-MWCNTs, which was induced by hydrogen bonding. Cyclic voltammetry and galvanostatic charge/discharge measurements results showed that the composite possessed od electrochemical capacitive performance. The composite with m(PPy):m(MWCNTs) of 1:1 had a capacity of 266 F·g-1 at a current density of 1.0 A·g-1, and the utilization of PPy was more than one time higher than polypyrrole/un-functionalized multi-walled carbon nanotube composites (PPy/p-MWCNTs) and pure PPy.

Polytetrafluoroethylene (PTFE) emulsion used as a binder for gas diffusion electrodes was pretreated with ethanol before use in electrodes. The surface topography of the gas diffusion electrodes was characterized by scanning electron microscopy (SEM). The BET and Langmuir special surface areas and pore distribution of the gas diffusion electrode were measured using a surface area detector. A zinc-air battery was then assembled and included this pretreated gas diffusion electrode. Under different current densities, the potential changes of the gas diffusion electrodes vs a zinc anode was measured. The impact of the PTFE emulsion alcoholic pretreatment on the performance of the gas diffusion electrodes was studied. The experimental results show that the porous structure of the catalytic activity layers and the gas diffusion layers increase with pretreatment. The reaction zones also increase with an increase in the catalytic activity of the layer's porous structure. Transport of the reactant gas is easier as the porous structure of the gas diffusion layers increase. The polarization potential of the gas diffusion electrode working under a large current density thus decreased.

The structure and performance of SmSr1-xAexCo2O6 (x=0, 0.2, 0.4, 0.6, 0.8, 1; Ae=Ca, Ba) as intermediate temperature-solid oxide fuel cell (IT-SOFC) cathodes were investigated by X-ray diffraction (XRD), thermogravimetry (TG), thermal expansion, electrical conductivity, and electrochemical impedance spectroscopy (EIS). The SmSr1-xAexCo2O6 system's structure changes as x increases from 0 to 1. The SmSr0.8Ae0.2Co2O6 (SSAC; Ae=Ca, Sr, Ba) system has an orthorhombic structure with a Pnma space group. The crystal parameter of SSAC increases in the following order: Sr<Ca<Ba. The oxygen content increases in the following order: Ca<Sr<Ba while the electrocatalytic activity decreases. The thermal expansion coefficients of SSAC with different Ae elements are similar. The electrical conductivities of Sm0.5Sr0.5CoO3 (SSC) doped with Ba and Ca decrease because of a decrease in the carrier concentration and an increase in the conduction activation energy, respectively.

Two new sporopollenin-immobilized Schiff bases, S-[N-(2-aminoetil) salicylaldiimino] and S-[N-(2-aminoetil) benzaldiimino], and their cobalt (III) and nickel (II) complexes, S-[N-(2-aminoetil) benzaldiimino] aquatriacetato cobalt (III), S-[N-(2-aminoetil) salicylaldiimino] aquadiacetato cobalt (III), S-[N-(2-aminoetil) benzaldiimino] diacetato nickel (II), and S-[N-(2-aminoetil) salicylaldiimino] diacetato nickel (II), were synthesized onto a chemically modified sporopollenin with ethylenediamine. The immobilized ligands and their metal complexes were characterized by thermal analysis and spectroscopic techniques such as infrared, ultraviolet-visible, and atomic absorption spectrometry. Immobilized Schiff base metal complexes, S-[N-(2-aminoetil) benzaldiimino] aquatriacetato cobalt (III) and S-[N-(2-aminoetil) salicylaldiimino] aquadiacetato cobalt (III), were used as ligand exchanger media to investigate ligand adsorption behavior of methylene blue (MB) with column technique. The result shows that the chelation of methylene blue with S-[N-(2-aminoetil) salicylaldiimino] aquadiacetato cobalt (III) complex increases ligand adsorption capacity.

Using dimethylsulfoxide (DMSO) as solvent, an amphiphilic alternating copolymer P(St-alt-Ma-Dopa) was prepared by the ammonolysis of P(St-alt-Man) with dopamine. The influences of additives (HCl, NaOH, or NaCl) on the characteristics of P(St-alt-Ma-Dopa) colloidparticles after the self-assemblyof the copolymer in the selective solvent N,N-dimethylformamide (DMF)/H2O were studied by UV spectrophotometer, transmission electron microscopy (TEM), zeta potential measurements, and fluorescence probe. Results show that P(St-alt-Ma-Dopa) can self-assemble into spherical particles and its critical water content (CWC) is larger than that of P(St-alt-Man). The size, zeta potential, and hydrophilic-hydrophobic property of these colloid particles showed a series of regular changes after the addition of HCl, NaOH, or NaCl. The emulsification of P(St-alt-Ma-Dopa) colloid particles was improved because of the presence of dopamine.

Al2O3 nanoparticles were prepared by reverse microemulsion method that uses cyclohexane, polyethylene glycol octylphenyl ether (TritonX-100), n-butylalcohol, and water. The structure, morphology, and specific surface area of the nano-alumina particles were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electronmicroscopy (TEM), and specific surface area analysis. The specific surface area of the nano-alumina particles was about 450 m2·g-1 (changing with different reaction parameters) and the crystal structure was γ-Al2O3. The particle size was smaller than 10 nm and very uniform. The effect of molar ratio of water to surfactant (r0), volume ratio of surfactant to assistant-surfactant (φ), and calcination temperature (T) on the characteristics of the product were studied. The results indicated that the nano Al2O3 powder with a high specific surface area, high pore volume, od dispersibility, and narrow particle size distribution was obtained at r0=20, φ=0.5, and T=500 ℃.

TiO2 films on Al alloy (Al), anodic aluminumoxide (AAO/Al, formed at the surface of Al alloy), indium-tin oxide glass (ITO/glass) and glass were prepared by a dip coating method. The measurement of water drop contact angle under UV irradiation shows that TiO2 films on the conducting Al substrate have a higher activity for photoinduced hydrophilicity than that on the non-conducting AAO/Al substrate. Alternatively, TiO2 films on the conducting ITO/glass substrate have a lower activity for photoinduced hydrophilicity compared to TiO2 films on the non-conducting substrate glass. These observations are due to electron transfer between TiO2 and substrates. Al acts as an electron donor and donates electrons to TiO2, which results in an increase in the photoinduced hydrophilicity of TiO2 film. ITO accepts the photogenerated electrons, which results in a decrease in the photoinduced hydrophilicity of TiO2 films.

B-ZSM-5 zeolites with different crystal sizes were synthesized by adjusting hydrothermal synthesis temperature. Ti-ZSM-5 samples were prepared by gas-solid reaction using acid-treated B-ZSM-5 as precursors with gaseous TiCl4. The samples were characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier-transforminfrared (FT-IR) spectra, ultraviolet-visible (UV-Vis) spectroscopy, inductively coupled plasma atomic emission spectrometry (ICP-AES), Raman spectra, nitrogen adsorption-desorption, and 1,2,4-trimethylbenzene adsorption. The catalytic performance of Ti-ZSM-5 for phenol hydroxylation was investigated. Results showed that all the precursors were agglomerated by the small cuboids particles and had MFI topology structure, but there were some differences in the crystal size, the amount of framework titanium species, and pore volume. The optimized temperature range of the low-temperature crystallization stage is from 333 to 353 K for the synthesis of B-ZSM-5. Moreover, Ti-ZSM-5 sample using this B-ZSM-5 as the precursor has a better catalytic performance for phenol hydroxylation, because of the smaller cuboids particles, the larger pore volume and surface area. In phenol hydroxylation, when the molar ratio of phenol to hydrogen peroxide was 3, the conversion of phenol was 20.5%.

Polypyrrole (PPy) films were synthesized by a potentiostatic method from a para-toluenesulfonic sodium solution on stainless steel (SS). The effect on Cu(II) reduction of the PPy-modified film was investigated through potentiostatic and potentiodynamic conditions and compared with that of SS.A higher removal efficiency was achieved on PPy because of its catalytic effect. The current efficiency obtained with the PPy film is much higher than that of SS because PPy inhibits the effect of hydrogen evolution and this is the greatest advantage for using PPy to remove heavy metals. Cyclic voltammetry of PPy-modified electrodes in acidified Cu(II) solutions was conducted and the mechanism of PPy for Cu(II) reduction was discussed.

Effects of 1,5-hexadiene and benzene on the desulfurization property of NiY were investigated by Fourier transform-infrared (FT-IR), frequency-response (FR), and fixed-bed techniques. Results indicate that both 1,5-hexadiene and benzene inhibit the desulfurization of the sorbent which can be detected by a decrease in the desulfurization capacity of the NiY in the presence of 1,5-hexadiene and benzene in the model fuels. The effect of benzene on the adsorption capacity of the NiY was more conspicuous than that of 1,5-hexadiene. In the zeolite, the sulfur compounds and 1,5-hexadiene adsorbed on the protons can subsequently under an opening reaction of the heterocyclic rings, which blocks the zeolite pores and then hinders sulfide molecule access to the supercage where they could come into contact with metal cations. Distinct processes were observed in the FR spectra of thiophene and benzene on NiY zeolites, with the adsorption of thiophene in the supercage being the rate-controlling step and the diffusion process of benzene in the supercage being the rate-controlling step. The benzene molecules were replaced by thiophene molecules from the active centers and they, therefore, diffused out of the zeolite channels with difficulty. The adsorption of thiophene into the active centers will, therefore, be hindered.

Al2O3-modified Fe2O3 based ld catalysts with od thermal stability were prepared by co-precipitation and deposition-precipitation method. Characterization techniques, such as transmission electron microscope (TEM), X-ray diffraction (XRD), N2 adsorption-desorption, and thermogravimetry-differential scanning calorimetry (TG-DSC), were used to investigate the structures, and surface morphologies of the catalysts. TEM results showed that after calcination at 500 ℃ the size distribution of the ld particles in the catalyst without Al2O3 doping was wide, the average diameter of the ld particles was about 7.0 nmand the size of the support particles ranged from 50 to 100 nm. However, the size distribution of the ld particles in the Al2O3-doped catalysts was narrow and the average diameter of the ld particles was around 5.0 nm. The Al2O3-doped Fe2O3 based Au particle size remained in a range of 30-50 nm, which is smaller than that of the Fe2O3 grains that were not doped with Al2O3. N2 adsorption-desorption measurements showed that Al2O3 doping resulted in a stable mesoporous structure for the catalysts and remained a higher specific surface area, which promoted the thermal stability of the support. XRD and TG-DSC results indicated that Al2O3 doping retarded the crystallization of the support and consequently inhibited the growth of ld particles during high-temperature calcination. Low temperature CO oxidation was used as a probe reaction to evaluate the catalytic activity. Even when calcined at 500 ℃ for 12 h, the catalyst with Al2O3 doping achieved complete CO conversion at 26.7 ℃ while the lowest temperature of the complete CO conversion (T100) of the catalyst without Al2O3 doping was as high as 61.6 ℃. Apparently, thermal stability is enhanced considerably by Al2O3 doping.

Poly(ethylene glycol) (PEG)-stabilized amorphous RuB nanoparticles were prepared and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Results showed that Ru was reduced to zero valence and the average particle diameter of the RuB crystallites was about 2.4 nm. This catalytic system shows excellent activity and selectivity for the hydrogenation of pyridine and its derivates. At a reaction temperature of 100 ℃, a hydrogen pressure of 3.0 MPa, a reaction time of 60 min and using a molar ratio of 1/670 Ru to pyridine, the conversion of pyridine was found to be >99.0%and the selectivity for piperidine was 100%. The activity of the catalyst for substrates with different substituents was as follows: 2-methylpyridine>2,6-dimethylpyridine>pyridine.

ITQ-13 zeolite was successfully synthesized using three silica sources, i.e., tetraethylorthosilicate (TEOS), colloidal silica, and fumed silica, and was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), BET surface area, and acidity by the adsorption of d3-acetonitrile. Characterization results showed that the ITQ-13 samples synthesized using colloidal silica and fumed silica possessed better crystallinity and larger crystals than those synthesized by the TEOS route.

A series of Pd-containing hydrotalcite precursors (M3Al-HT) with different M2+ (M=Mg, Co, Ni, Cu, Zn) ions were synthesized by a co-precipitation method. Pd/M3AlO catalysts were derived from these hydrotalcite-like compounds by calcination. X-ray Diffraction (XRD), thermogravimetry-differential thermal gravimetry (TG-DTG), N2 adsorption and desorption, temperature programmed reduction (H2-TPR), and temperature programmed desorption (O2-TPD) techniques were used to study the influence of different M2+ ions on the composition and structures of the Pd/M3AlO catalysts and their performance during the catalytic oxidation of chlorobenzene. XRD and TG-DTG data showed that hydrotalcite precursors could be successfully prepared with different M2+ ions except Cu2+ ion. And Pd was well dispersed in different hydrotalcite precursors. The M2+ ions greatly influence the activities of the serial catalysts. Among the investigated catalysts, the activity of the Pd supported Co-containing oxide was found to be much higher than the other catalysts. The light-off and complete oxidation temperatures were 182 and 283 ℃, respectively. H2-TPR and O2-TPD results show that higher reduction abilities and higher intensities of the surface oxygen active species as well as the synergetic effect between Pd and Co contribute to excellent Pd/Co3AlO catalytic activity.

Using epichlorohydrin as bridged unit, the aromatic tertiary amine (ATA) was introduced to prepare the highly photo-crosslinkable coumarin compound C and to accelerate the photo-dimerization of coumarin unit. Ultraviolet (UV) and fluorescence (FL) spectra were used to evaluate the coumarin C. It was found that the introduced ATA could enhance the absorption between 260-400 nm. The spot UV irradiation experiments showed that, after being bridged with ATA, the coumarin C would gain a highly photo-dimerization with a high slope of 6.47 in the uniform photo-reaction, and a short time of 29 s to gain 80% photo-dimerization.

Supercritical carbon dioxide and ionic liquids(ILs) are two kinds of green solvents. Supercritical carbon dioxide can be dissolved in ionic liquids, but ionic liquids cannot be dissolved in supercritical carbon dioxide. CO2/IL binary systems, therefore, have many advantages for supercritical carbon dioxide and ILs such as decreasing the viscosity of ILs and easy phase separations. It is a new kind of coupled green solvent. Its physical chemical properties are very important for the design of reaction and separation processes. The CO2/IL binary systems (CO2/[bmim][PF6] and CO2/[bmim][NO3]) were selected as model compounds and the thermodynamic properties of these systems were simulated by molecular dynamics simulation method with available molecular force field parameters and ensembles. Results show that the ILs expanded only 15%at a CO2 molar fraction of 0.5. The diffusion coefficients of CO2/ILs are much smaller than those of CO2/methanol and CO2/ethanol systems. With the content of CO2 increasing, the diffusion coefficients of the ILs increased while their viscosities decreased significantly. These results indicate that CO2 can effectively overcome the shortcomings of ILs that have poor diffusion coefficients and high viscosities. We conclude that CO2 can improve the transport properties of ionic liquid solvent systems and enhanced the reaction and separation processes in these systems.

Photoisomerization pathways for 3,3'-azobenzene sulfonate (3,3'-AbS) in the S0 and T1 states were studied by using density functional theory (DFT) at the B3LYP/6-311++G(d,p) level. In the S0 state, there are two isomerization pathways: the inversion of one NNC angle combined with the rotation around the NC bond and the rotation of the CNNC dihedral angle. The energy barriers of the two pathways are 94.2 and 124.3 kJ·mol-1, respectively. It is worthy to notice that there exist second-order transition states on the combination pathways of inversion and rotation. In the T1 state, only the rotation pathway exists and its energy barrier is 21.1 kJ·mol-1. To investigate the photoisomerization pathway, the potential energy profiles of the vertical excitation for the excited states (T1, S1, T2, and S2) were calculated by time dependent density functional theory (TD-DFT) at the B3LYP/6-311++G(d,p) level along the two pathways. A photoexcitation at 330 nm results in the reactant molecule populating the S2 state and then under ing a rapid relaxation to the minimum of the S1 state. Two possible isomerization pathways exist through the rotation pathway as follows: (1) the isomerization can easily occur through the S0/S1 conical intersection (CI) and descend to the S0 state; (2) a relaxation to the T1 state from the S1 state may occur and the reaction can take place via the S0-T1-S0 path. Calculation results show that the primary isomerization pathways for 3,3'-AbS are a combination pathway of inversion and rotation in the S0 state and the rotation pathway when it is excited.

First-principles calculations were performed to determine the geometric structure and electronic states of Ni(110)-p2mg(2×1)-CO surface. We found that the CO molecules were adsorbed onto nearby short bridge sites. The molecular adsorption energy was calculated to be 1.753 eV. The C—O bond length was about 0.117 nm. The angle between the bond of the CO molecule and the vertical of the Ni(110) surface was 20.0°. The tilt angle of the direction linking the carbon and the center of the short bridge was 20.9°. The stretch vibration frequencies between the carbon and the oxide atoms of an adsorbed CO molecule was 1876 and 1803 cm-1. The density of states suggests that the chemical interaction between the CO molecules and Ni atoms was mainly caused by hybridization between molecular orbitals π, σ and d orbitals. Surface p2mg(2×1) reconstructionmay be attributed to the hybridization between σ molecular orbitals of CO and dxz orbitals of nickel atoms. Surface electronic states resulting from an interaction between σ molecular orbitals of CO and dxz orbitals of nickel atoms were localized below the Fermi energy (0 eV) from -10.4 to -8.8 eV and from -7.4 to -5.1 eV.

The reaction H2NCH2CN + H2O→H2NCH2C(OH)NH is an important reaction related to the formation of glycine in the interstellar medium (ISM) and the origin of amino acids in early Earth. This reaction in the gas phase proceeds slowly and this is confirmed by its energy barrier of 254.7 kJ·mol-1 as determined at the MP2/6-311+(d,p) level without considering hydrogen tunneling in the ISM. On icy grain surfaces in the ISM, however, its reactivity may be enhanced by H2Ocatalytic reactions. The reaction of H2NCH2CNwith (H2O)3 is optimal as two H2Omolecules act as a catalyst with reducing the activation energy by 77.5 kJ·mol-1 and the activation free energy by 70.9 kJ·mol-1. A proton moves in a concerted way through a hydrogen bonded bridge. Quantum hydrogen tunneling is a crucial pathway for this reaction to proceed and was investigated using the small curvature tunneling (SCT) approximation and canonical variational transition state theory (CVT). At 50 K, rate constant kSCT/CVT is 1.86×10-23 cm3·molecule-1·s-1, which demonstrates that the reaction is feasible by a hydrogen tunneling mechanism in the ISM. These results may support the theory that the origin of amino acids is fromthe materials of the Earth itself.

The two-photon absorption properties of two newly synthesized compounds containing fluorene as a π centre (denoted SK-G1 and NT-G1) were calculated using a response function method with density functional theory. Results show that both compounds have large one-photon and two-photon absorption abilities. In the low energy region, the maximum one-photon absorption strength of NT-G1 is twice as much as that of SK-G1 and its maximum absorption is red shifted compared to that for SK-G1. The maximum two-photon absorption cross section of NT-G1 is about five times as large as that of SK-G1 and those are found for the second excited states. Furthermore, NT-G1 has a wider two-photon absorption energy band. The optical properties of the molecules are closely related to their charge transfer processes when they are excited. The solvent effect on their one-photon absorption properties was calculated using the Onsager model. The numerical calculation is found to be in od agreement with experimental measurements.

A periodical model for Mg3Al-LDHs-Cl-nH2O has been proposed. A geometry optimization and elastic constant calculation for the layered double hydroxides (LDHs) were carried out using the CASTEP/LDA (local density approximation) procedure at the CA-PZ level. The influence of interlayer water content (n) on the mechanical properties of the materials was investigated by analyzing the elastic constants Cij, shear modulus, Young's modulus, and Poisson's ratio, etc. Results indicated that the interlayer water content greatly impacted the mechanical properties of the materials. Interlayer water can enhance the compression properties of the overall system. When n=1, the compression properties of the material was best. When n=2, the capacity of the material to resist shear deformation was the worst and the system was most flexible. Interlayer water molecules greatly impacted the Young's modulus of the material while the impact on Poisson's ratio was not obvious. Interlayer water molecules played a horizontal role of averaging the mechanical properties of the materials. The compression performance and the expansion of the material in the x-axis and y-axis tended to be the same.

The adsorption and diffusion properties of O atoms on the surface of Pt3Ni(111) with a Pt skin [denoted as“Pt-skin-Pt3Ni(111)”] were studied by the first-principles method based on the density functional theory (DFT). Special attention was paid to the diffusion properties of the adsorbed oxygen on the Pt-skin-Pt3Ni(111) surface as this is important in understanding the high activity of the Pt-skin-Pt3Ni(111) catalyst. We found that O atoms prefered fcc binding sites. Ni atoms in the Pt3Ni catalyst drastically influence the electronic configuration of the system and therefore the binding of oxygen atoms. Nudged elastic band (NEB) calculations were used to determine the diffusion barrier of oxygen atoms on the surface, providing a possible explanation for the distinct catalytic activity of the Pt-skin-Pt3Ni(111) catalyst.

The reaction pathways for methylamine decomposition (CH3NH2→CH3+NH2) on a clean Mo(100) surface and on a phosphorus (P) modified Mo(100) surface (P-Mo(100)) were investigated using first-principles (density functional theory based on generalized gradient approximation (DFT-GGA)) calculations with the slab model. Geometries of reactants, transition states, and products were calculated. Adsorption energies of possible species and activation energy barriers of the reaction were obtained. Calculated results show that methylamine is adsorbed in the top site while the methyl and amino groups are adsorbed in the bridge site on the clean and phosphorus modified Mo(100) surfaces. The activation energy of methylamine C—N cleavage was found to be 2.39 eV on the phosphorus modified Mo(100) surface, which is higher than that on the clean Mo(100) surface (1.99 eV). This indicates that the Mo(100) surface is passivated by phosphorus atoms. An electronic structure analysis shows that a modified phosphorus atom reduces the electron donation ability of the molybdenum which results in a downshift of the surface metal atom d-band center. Thus, the reactivity of the Mo(100) surface decreases and the activation energy for methylamine C—N cleavage increases. The decomposition of activation energy indicates that the difference in methylamine C—N cleavage activation energy for the two surfaces is caused by the structural deformation of methylamine (△EdefCH3NH2) from the initial state to the transition state, the adsorption energy of the methyl (without an amino group) in the transition state configuration (ETSCH3) and the interaction energy between methyl group and amino group in the transition state (EintCH3…NH2). Compared with Mo(100), the increase in activation energy induced by △EdefCH3NH2 and ETSCH3 is higher than the decrease in activation energy induced by EintCH3…NH2 on the phosphorus modified Mo(100) surface, which results in the methylamine C—N cleavage activation energy on the phosphorus modified Mo(100) surface being higher than the that on clean Mo(100) surface.

The structural and electronic properties of a (4, 0) zigzag single-walled carbon nanotube (SWCNT) under parallel and transverse electric fields with strengths of 0-1.4×10-2 a.u. were studied using the density functional theory (DFT) B3LYP/6-31G* method. Results show that the properties of the SWCNT are dependent on the external electric field. The applied external electric field strongly affects the molecular dipole moments. The induced dipole moments increase linearly with increase in the electrical field intensities. This study shows that the application of parallel and transverse electric fields results in changes in the occupied and virtual molecular orbitals (MOs) but the energy gap between the highest occupied MO (HOMO) and the lowest unoccupied MO (LUMO) of this SWCNT is less sensitive to the electric field strength. The electronic spatial extent (ESE) and length of the SWCNT show small changes over the entire range of the applied electric field strengths. The natural bond orbital (NBO) electric charges on the atoms of the SWCNT show that increase in the external electric field strength increases the separation of the center of the positive and negative electric charges of the carbon nanotube.

Hydrolysis processes of novel anticancer transplatin analogues, trans-[PtCl2(NH3)(Am)](Am: nonplanar heterocycle piperidine or piperazine), were explored using the B3LYP hybrid functional and isoelectric focusing polarized continuum model (IEF-PCM). Stationary points on the potential energy surfaces for the first and second hydrolysis steps that proceed via a general SN2 pathway were fully optimized and characterized. The most remarkable structural variations in the hydrolysis process were found to occur in the equatorial plane of five-coordinate tri nal-bipyramidal (TBP) like structures of the intermediates and transition states. We obtained lower activation energies for trans-[PtCl2(NH3)(piperazine)] and a slightly higher activation energy for the first step and a slightly lower activation energy for the second step during the hydrolysis of trans-[PtCl2(NH3)(piperidine)] by comparison to previous work on the hydrolysis reactions of cisplatin. Our calculations suggest that this class of non-classical transplatin analogues with one nonplanar heterocyclic amine decreases the equatorial steric effect and the hydrolysis reaction barriers.

L-ornithine is a metabolic product of L-arginine and is found in the liver and other tissues after the enzyme arginase in the urea cycle catalyses the reaction. The presence of L-ornithine has an influence on certain biochemical activities such as the proliferation of collagen production and also has an effect on airway responsiveness. Therefore, it has a role to play in the availability of nitric oxide (NO). A brief reactivity study was carried out for various substituents at the α-C atomof this amino acid. Substituents such as chlorine and fluorine affect the reactivity of the entire molecule and may alter the properties of the amino acid. To understand the properties of molecule, a detailed study was done at the density functional theory (DFT) level and compared with ab initio calculations. Fukui functions were invoked to assess reactivity and stability. The descriptive properties were correlated to logP or pKa using available software to help build a model to quantitatively assess properties and reactivity. Results showed a randomreactivity pattern upon halogen substitution and this indicates the need to exercise caution during docking and reactivity studies.

Two kinds of well-aligned CuO nanostructured arrays composed of bundles of one-dimensional (1D) nanoribbons and densely packed two-dimensional (2D) nanosheets were selectively synthesized via a convenient one-step route by adjusting the reaction temperature. Detailed time-dependent evolutions of the morphology and phase were systematically studied and the formation of both CuO nanostructured arrays was shown to be due to oxidation→growth→dehydration and oxidation→dehydration→growth processes, respectively. The kinetically controlled nucleation and growth determined the final morphology of the CuO nanostructures. The photocatalytic activity of the as-prepared CuO nanostructured arrays was evaluated by the photodegradation of Rhodamine B(RhB) dye under simulated sunlight. This work provides a simple and economical route for the preparation of novel hierarchical nanomaterials which are expected to present a number of promising applications in various fields.

Poly(phenylacetylene) (PPA) was prepared with phenylacetylene while multiwalled carbon nanotubes (MWCNTs) were purified and oxidized. The MWCNTs and PPA were then treated in toluene by ultrasonic dispersion. Results showed that the oxidized MWCNTs were coated by PPA and had a stable dispersion in toluene for more than one month. Structural changes of oxidized MWCNTs were analyzed by Fourier transform infrared (FTIR) spectrum, acid-base titration, and Raman spectrum. The dispersion of purified, oxidized, or PPA wrapped MWCNTs was investigated by using high resolution transmission electron microscopy (HRTEM).

N-doped and undoped carbon nanotubes (CNx and CNTs) were synthesized by the catalytic chemical vapor deposition of ethylenediamine and hexane on Fe/M catalysts. The Fe catalysts were obtained by calcination ofa Mg/Fe layered double hydroxide (LDH) and a mixture of Mg(NO3)2/Fe(NO3)3 precursors followed by reduction (Fe-LDH and Fe-Mg(NO3)2/Fe(NO3)3). The CNTs grown on both catalysts had tubular structures with hollow cores while some of the CNx grown on Fe-Mg(NO3)2/Fe(NO3)3 had a different morphology from the conventional bamboo-shape of those grown on Fe-LDH. This special morphology with thick walls had some space between the graphite layers. The molar content of N in the CNx grown on Fe-LDH was 6.3%, which was a little more than 5.7%found in the CNx grown on Fe-Mg(NO3)2/Fe(NO3)3. However, the latter has more defects and disorders.

The photoelectric nanocomposite poly(2-methoxy-5-butoxy)-p-phenylene vinylene/Eu2O3 (PMOBOPV/Eu2O3) was prepared by a dehydrochlorination in situ polymerization. Results from Fourier transform infrared (FT-IR) spectroscopy indicate that PMOBOPV is coated onto the surface of Eu2O3. The composite dimensions were observed by high resolution transmission electron microscopy (HRTEM). PMOBOPV/Eu2O3 nanocomposites possess core-shell structures and their diameters were about 75-145 nm with a PMOBOPV coating thickness of about 25 nm. A stronger red-shifted absorption peak was observed with an increase in Eu2O3 content for PMOBOPV/Eu2O3 in the UV-Vis spectrum. Photoluminescence spectroscopy indicates that the maximum emission wavelength of the PMOBOPV/Eu2O3 is blue-shifted and the intensity of photoluminescence increases with increasing Eu2O3 content. PMOBOPV/Eu2O3 shows increased fluorescence because of an intermolecular photo-induced charge transfer process. The optical band gap (Eg) of PMOBOPV/Eu2O3 decreased gradually with increasing Eu2O3 content. The third-order optical nonlinear susceptibility of PMOBOPV/Eu2O3 nanocomposites was measured by degenerate four wave mixing. Results show that the third-order nonlinear optical response of PMOBOPV/Eu2O3 nanocomposites increases gradually with increasing Eu2O3 content. This can be attributed to intermolecular photo-induced electron transfer and delocalized π electron coupling between PMOBOPV and Eu2O3.

The mechanical properties of Si/DLC (diamond-like carbon, around 10 nm) films on Au and Au-Cu (xAu=93%, xCu=7%) substrates were studied by nanoscratch tests. Results show that Au-Cu exhibits better adhesion to Si/DLC than Au does to Si/DLC. Ultraviolet (244 nm) Raman spectra show that DLC films on Au-Cu contain more sp3 character than those on Au using the same batch coating process. This indicates greater hardness and higher density of the films on Au-Cu. The implications of these results on the mechanisms proposed for film formation are discussed. Au-Cu is thus a better candidate for use as a lead material in Si/DLC coatings because of its better adhesion and greater hardness for magnetic recording sliders.

A novel method to synthesize single-walled carbon nanotube (SWCNT) films with large area and high purity was introduced. An arc-discharge facility was improved by adding two graphite plates to the electrodes to form a spherical cap capacitor in the vacuum cavity so that an additional electric field of appropriate intensity could be generated. Using this new facility, single-walled carbon nanotube films of different thicknesses ranging from a few microns to amillimeter (controlled by the discharge time) were synthesized on a spherical cathode graphite plate. The film structures were characterized by field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy, and thermogravimetric analysis (TGA). Results show that this is an efficient way to produce single-walled carbon nanotube films of high purity.

Amphiphilic diblock polystyrene-b-poly(N-isopropylacrylamide) (PS-b-PNIPAM) was used as a template for metal-block copolymer nanocomposite formation. Diblock copolymers were synthesized using the atom transfer radical polymerization (ATRP) method. Polyethyleneimine (PEI) acted as a crosslinking agent between Ag ions (Ag nanoparticles) and PS-b-PNIPAM colloids and was the reducing agent during the formation of Ag nanoparticles. The product was characterized by Fourier transforminfrared (FTIR) spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM). Silver crystals were monocrystalline with face-centered cubic structures, which was confirmed by electron diffraction and XRD. Results revealed that the size and size distribution of the resulting silver nanoparticles based copolymer were strongly dependent on the ratio of the initial copolymer solution to silver concentration.

By hydrothermal reaction method with the control of anionic amino acid surfactant N-lauroylsarcosine sodium (Sar-Na), single crystal hydroxyapatite (HAP) nanoplates were synthesized and different synthetic conditions were carefully studied. The products were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy. Results showed that hydroxyapatite nanocrystals with lengths of 0.5-1.0 μm, a width of 30 nm, and a high aspect ratio (20:1) were obtained. By increasing the concentration of N-lauroylsarcosine sodium, the morphology of the hydroxyapatite varied from oval to plate-like. These results show that N-lauroylsarcosine sodium can induce the formation of hydroxyapatite with different morphologies. The current work provides a new approach to tune the aspect ratio of hydroxyapatite nanoplates.