High capacity and od cycling stability of the electrode materials are the key points to develop high-performance lithium ion battery. Based on the latest research over the world, especilly from our group, in this paper we summarized the progress in chemical lithiation and electroactivity of nanomaterials. Firstly, we introduced the preparation of high capacity nanomaterials (molybdenum oxide, vanadium oxides, selenium hydrates, etc) and the chemical problems in lithiation process. Then we summed up the progress in assembly, chemical lithiation and electroactivity of single nanowire devices and nanowire lithium ion battery. Finally, we pointed out that assembly of single nanowire (nanobelts, nanotubes, etc.) device, in situ probe of lithium ion transport, design and construction of ordered array and complex structure, investigation of lithiation mechanism, electrostatic coupling, interface interaction, etc. are effective methods to deeper exploration of the relationship between chemical lithiation and electroactivity of nanomaterials and main directions of nanoscale lithium ion battery research field.

A numerical study was performed to determine the effects of methanol addition on the two stage oxidation of a dimethyl ether/air mixture and on the production of formaldehyde and formic acid in a micro-flow reactor with a fixed temperature profile. The results indicate that methanol addition influences the reaction pathway for dimethyl ether oxidation at low velocity and this results in the low temperature reactions of dimethyl ether being suppressed. The low temperature reactions of dimethyl ether nearly vanish when methanol is added in the same mass fraction as dimethyl ether. The major cause of this is a decrease in the OH radical concentration. With increasing the amount of methanol the emission index of formic acid decreases sharply but the emission index of formaldehyde increases slightly at first, and then it decreases gradually. Therefore, appropriate methanol addition can result in the reduction of the emission indexes of formic acid and formaldehyde.

An energetics analysis of the possible elementary steps involved in the partial oxidation of methane (POM) over different chemical states of Ni was carried out using the unity bond index-quadratic exponential potential (UBI-QEP) method. The results show that the rate determining step for the partial oxidation mechanism of methane is related to the chemical state of the Ni. Over reduced Ni the rate determining step for CO formation is the association of surface CH₃ species with surface O species. Over a partial positive charged Ni surface the rate determining step is that methane dissociates into the CH_xO species with the assistance of oxygen. Over the reduced and partial positive charged Ni sites in coexistence, however, the rate determining step depends on the competition between the formation of surface CH₃ species and the recombination of surface CH₃ species with surface O species. This competition is related to the chemical states of the Ni sites. If the partial positive charged Ni sites are predominant on the surface, the recombination of surface C species with surface O species and the recombination of surface H atom species favor CO and H₂ formation because of decreasing barriers. The surface CHx species does not dissociate easily and surface carbon deposition is significantly inhibited.

A series of electrodes were used to form a new accelerated electric field for ion focusing optics of a threshold photoelectron-photoion coincidence (TPEPICO) mass spectrometer. Ion groups with higher kinetic energy gradually expanded along the direction of flight while they were restricted along the direction perpendicular to the flight tube. Consequently, contractible velocity imaging was achieved on the surface of the detector for all the ions where a magnification factor (N) of less than 1 was obtained for the images. Therefore, od kinetic energy resolution and mass resolving power were obtained simultaneously. Using this novel focusing lens the dissociation of vibrational state-selected O₂ ions in the B²Σ_g^- state was reinvestigated and three-dimentional time-sliced velocity images of the O fragment were recorded. By comparing the kinetic energy released distributions of the O that dissociated from the two dissociation channels, satisfied velocity imaging was obtained for the ions with a wide kinetic energy range.

The formation of a 1:1 supramolecular complex between β-cyclodextrin (β-CD) and 18- crown-6 (18C6) by simply mixing them was confirmed by elemental analysis, ¹H nuclear magnetic resonance (¹H NMR) and electrospray ionization mass spectrometry. The probable interaction sites between these species were determined by two-dimensional rotating frame nuclear Overhauser effect spectroscopy (ROESY), which showed that 18C6 tended to be located on the narrow end of the cavity of β-CD. Also, the degradation process including the degree of degradation and the degradation products of the complex was carefully compared with those of β-CD and 18C6 through thermogravimetric analysis and gas chromatography coupled to time-of-flight mass spectrometry. The experimental data indicated that the presence of 18C6 resulted in an earlier degradation of β-CD. Furthermore, the relative abundance of larger fragments from the degradation process of the two components was reduced drastically because of an intermolecular interaction. These results strongly indicate that a supramolecular complex can be constructed using the flexible macrocyclic molecule 18C6 as a guest and the rigid macrocyclic molecule β-CD as the host via molecular assembly between them.

Three Mn(II) complexes [Mn(SO₄)(H₂O)₃]_n (1), [Mn2.5(HPO₄)(PO₄)(H₂O)₂]_n (2), [Mn(phen)₂(H₂O)₂]?(C₄H₄O₄)?4H₂O (3) (phen=1,10-phenanthroline) were synthesized by a hydrothermal method and characterized by infrared spectrum (IR), ultraviolet-visible spectrum (UV-Vis), electron paramagnetic resonance spectrum (EPR), single crystal X-ray diffraction and surface photovoltage spectrum (SPS). The structural analyses indicate that complex 1 is a 2D coordination polymer and hydrogen bonds link the polymer to a 3D infinite structure. Complex 2 is a 3D coordination polymer. Complex 3 is a mononuclear complex and diverse hydrogen bonds connect the complex to the 3D supramolecule. SPS results indicate that the three complexes exhibit obvious surface photovoltage responses between 300-800 nm, which reveals that they possess a definite photoelectric conversion property. The structure of the complex, its dimensions and the coordination environment of the central metal affect obviously SPS: the intensity of the surface photovoltage (SPV) response bands become larger with increasing of dimensions and regularity of structure; differences in the species of direct coordination atoms and the strength of the crystal field around the central metal ions lead to the change of number and position of the response bands. Additionally, the association between SPS and UV-Vis were discussed.

We prepared and obtained a novel dinuclear copper(II) coordination complex [Cu₂(mMP)₂(H₂O)₂]₂·2H₂O (1) using mono-methyl phthalate as a ligand (mMP is a mono-methyl phthalate or 1,2- benzenedicarboxylate monomethyl ester). The crystal structure of complex 1 was characterized by elemental analysis, IR spectroscopy, and X-ray analysis. This tetra-carboxylato-bridged dinuclear complex adopts a dimeric paddle-wheel cage structure and the coordination configuration around each copper(II) cation is square-pyramidal with four oxygen atoms of the carboxylate groups from four different mono- methyl phthalate ligands and one oxygen atom of water at the apical position. Intermolecular hydrogen bonds are found between the hydrogen atoms of the coordinated or uncoordinated water and the oxygen atoms of the carboxyl from the adjacent molecules and it forms a three-dimensional (3D) network structure. The magnetic data for complex 1 indicate a strong intramolecular antiferromagnetic interaction between the two paramagnetic metal ions with a magnetic coupling constant of 2J=-324 cm^-1. In this paper, we analyzed the magnetostructural correlation of complex 1 in detail and discuss the main factor that determines the strong antiferromagnetic interaction in dimeric copper(II) carboxylates. Compared with the structure and the magnetic property of other related complexes, the main factor that determines the strong antiferromagnetic interaction in the dimeric copper(II) carboxylate is an electronic structure of the bridging O－C－O moiety.

Molecular assembly was used to prepare a 4,4′-dithiodipyridine (PySSPy) self-assembled monolayers (SAMs) modified ld electrode. The prepared PySSPy SAMs modified on ld electrode were then used as linkage monolayers to fabricate ld nanoparticle assembled films. In our research, surface- enhanced Raman scattering (SERS) technique was used to investigate the structural characteristics of the linkage monolayers. Moreover, electrochemical in situ SERS spectroscopy was used to characterize the effect of electrode potential on the molecular structure of this linkage monolayer. An analysis of the regular variations in intensities and shifts of the characteristic Raman peak pairs related to the adsorbed molecules in this linkage monolayer, such as at 1011 and 1093 cm^-1, 1575 and 1610 cm^-1, 1206 and 1215 cm^-1, revealed that the aromaticity of the pyridyl ring groups in the linkage monolayer changed with the applied electrode potential. The results show that the adsorbed molecule exists mainly in the form of a thiol tautomer in the negative potential range while it exists mainly in the form of a thione tautomer in the positive potential range.

The structural stability and electronic properties of MgF₂(010), MgF₂(001), MgF₂(011), and MgF₂(110) surfaces were investigated using density functional theory (DFT). We found that the atoms located in the top layers near the surface are obviously relaxed and that the fluorine-terminated surface structure is much more stable than the other two structures. According to the surface energy values of the four different fluorine-terminated surfaces we conclude that the structural stability of the MgF₂ surfaces decreases in the following order: MgF₂(110), MgF₂(011), MgF₂(010), and MgF₂(001). The density of states of the MgF₂(110) surface shows that more bonding electrons are in low level areas and, furthermore, because of the influence of the surface the fluorine atom charges gather at the surface, which makes the surface electronegative and results in an increase in its activity.

We calculated the formation energies, band structure, density of states, and magnetic properties of Au-doped hydrogen-passivated silicon nanowires (SiNWs) along the [100] direction at different positions by first-principles method based on density functional theory. We considered the substitutional positions, the interstitial positions with tetrahedral symmetry, and the interstitial positions with hexa nal symmetry. The results show that Au preferentially occupies the center substitutional position of the silicon nanowire. The doping of Au into silicon nanowires introduces an impurity level near the Fermi level. The bandgap values were less than those of pure silicon nanowires. For the substitutionally doping of silicon nanowires the density of states near the Fermi level were mainly contributed to by the Au d and p orbitals and the Si p orbital. Ferromagnetic behavior of the substitutionally doped nanowire was observed upon coupling the Au d and Si p states. For the interstitial doping of silicon nanowires nonmagnetic behavior was predicted. In addition, we also interpret the electronic and magnetic properties in terms of a simple analysis based on the atomic orbitals and electron filling.

First-principles calculations were carried out to investigate the crystal structures, band structure, density of states, partial densities of states, Mulliken population and elastic properties of two BeP₂N₄ polymorphs namely phenakite and spinel. The generalized gradient approximation (GGA) and local density approximation (LDA) were used. The calculated results agree well with the experimental data and other theoretical calculations. The electronic structures of BeP₂N₄ indicate that they are insulators with wide bandgaps. The mechanical moduli of the spinel structure are larger than that of phenakite. The hardness of the two polymorphs was evaluated based on the methods proposed by Sung and Gao et al. Although the bulk modulus of phenakite is small the results indicate that it is a relatively hard material. On the other hand, the spinel structure is a super hard phase. When the pressure increases the phenakite structure gradually becomes malleable. The calculated GGA transition pressure from phenakite to spinel is 14 GPa, which is smaller than the predicted value of 24 GPa.

The geometries of the cobalt complexes [Co(MeO-salen)(Im)₂]⁺, [Co(MeO-salen)(2-MeIm)₂]⁺,and [Co(MeO-salen)(MeIm)₂]⁺ (Im=imidazole; MeIm=1-methylimidazole, 2-MeIm=2-methylimidazole, MeO- salenH₂=salen type Schiff base: (R,R)-N,N′-bis(5-methoxy-salicylidene)-1,2-diiminocyclohexane) in dichloromethane solution were optimized using density functional theory (DFT) at the B3LYP level of theory with the mixed basis set: 6-31G^* for C and H, and 6-311+G(2d,p) for Co, N, and O atoms. Based on the optimized geometries the excitation energies, oscillator and rotational strengths, and the electronic circular dichroism (ECD) spectra of the complexes were calculated using time-dependent density functional theory (TDDFT) with the same functional and basis sets. In these calculations solvent effects were included using the polarized continuum model (PCM). The calculated ECD spectra are in od agreement with the observed ones. Detailed analyses of the dominant transitions reveal that the first circular dichroism (CD) band in the long wavelength region is dominated by the ligand-to-metal charge transfer transition π→d, which was wrongly assigned to a d→d transition in the literature. The introduction of imidazole ligands to the axial positions has no influence on the sign of the first two CD bands, but it does have a significant influence on the shape and intensity of the CD spectra. For complexes with the λ(RR) chiral configuration the first CD absorption band is positive and the second is negative. These findings provide a deep insight into the electronic structures and chiroptical properties of the chelates.

The absorption and fluorescence spectra of 3-(dicyanomethylene)-5,5-dimethyl-1-(4-[9- carbazol]-styryl)cyclohexene (DCDCC), an organic light emitting material with pull-push structure, were investigated using a time-dependent density functional theory (TD-DFT) approach and bulk solvent effects were taken into account. The performance of eight exchange-correlation functionals including both local and long-range hybrids was assessed by comparing the calculated electron transition energies to experimental observations. It turns out that the appropriate choice of functionals is crucial to obtain an accurate value and BMK hybrids, which contain 44% Hartree Fock exchange, in the frame of DFT and TD-DFT with the polarizable continuum model and a medium sized basis set, emerges as an effective strategy for DCDCC. Moreover, the planar and twisted intramolecular charge transfer (PICT and TICT) models were used to interpret the excited state structure of DCDCC although the charge transfer character of the excited-state was not as intense as to emit obvious double fluorescence. The accurate structures were optimized by BMK and supported the PICT model.

Hydrogen adsorption on zeolite Na-MAZ and Li-MAZ clusters was investigated using density functional theory (DFT) with the generalized gradient approximation (GGA) of the Perdew-Burke- Ernzerhof (PBE) exchange-correction functional and the double numerical plus polarization (DNP) basis set. Equilibrium structural parameters, vibration frequencies, and adsorption energies were obtained and compared. The calculated results show that four stable adsorption sites are present on zeolite MAZ. They are designated SI′, SI″, SII′, and SII″, respectively. The most stable adsorption structure was hydrogen on the SII″ site of zeolite Na-MAZ and the hydrogen on the SI″ and SII″ sites of zeolite Li-MAZ were the most stable. We also found that larger adsorption energies indicate longer H―H bond distances and a lower vibration frequency shift. The adsorption ability of zeolite Li-MAZ toward hydrogen is stronger than that of zeolite Na-MAZ. Zeolite Li-MAZ has a higher theoretical hydrogen storage capacity and it may be a potential hydrogen storage material.

Each amino acid residue of one peptide was characterized directly by 531 physicochemical property parameters. Based on support vector regression (SVR) we developed a new nonlinear rapid feature selection method for high dimensional data, which was applied to a quantitative sequence- activity relationship (QSAR) study of two peptide systems (bitter tasting thresholds and angiotensin converting enzyme inhibitors). In both systems, 10 descriptors with clear meaning were reserved. We established a SVR model for both peptide systems using the reserved descriptors of the peptides. For both models the accuracies of fitting, the leave-one-out cross validation, and the external prediction improved significantly compared with the results reported in literature. To enhance the interpretability of the models, significance tests of the nonlinear regression model, single-factor relative importance, and a single-factor effect analysis were carried out. The new method has broad application prospects for regression forecasting of high dimensional data such as QSAR modeling of peptide or proteins.

The electronic structures and second-order nonlinear optical (NLO) properties of a series of Pt―Pt bond-containing metal complexes were calculated using density factional theory (DFT) combined with the finite field (FF) method. The results show that the replacement of a conjugated ligand does not substantially affect the Pt―Pt bond. Additionally, the strength of charge transfer (CT) from the ligand to the metal group increases as the length of the conjugated ligand becomes longer. The first-order hyperpolarizabilities of these metal complexes increase as the length of the conjugated ligand becomes longer but this is not sensitive to the change in charge of these metal complexes. Complex IId containing a relevant long π-conjugated ligand possesses the largest first-order hyperpolarizability according to our DFT-FF calculations. Time-dependent (TD)-DFT calculations show that the π→π^* intraligand mixing metal to ligand charge transfer transitions directly contribute to the second-order NLO response of the Pt―Pt bond-containing metal complex IId.

The Cr₂O₃/TiO₂ composite material was prepared by a high-temperature solid-state reaction and its structure, morphology, and electrochemical performance were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), charge-discharge test, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). We found that TiO₂ doping significantly improved the cyclic performance of Cr₂O₃ and the reversible capacity of the Cr₂O₃/TiO₂ composite material was 454 mAh·g^-1 after 22 charge-discharge cycles, therefore, it has a capacity retention of 73.6% and this is mainly due to TiO₂ doping that significantly increases the conductivity of Cr₂O₃. Our results revealed that the initial large irreversible capacity and the capacity fading could be attributed to an increase in the thickness of the solid electrolyte interface (SEI) film and a reduction in the conductivity of the materials. This was caused by a volume expansion of the Cr₂O₃/TiO₂ electrode during the first discharge process.

Mn₃O₄ and Ce doped Mn₃O₄ were synthesized via a sol-gel route using metal nitrates as raw materials and citric acid as the chelating agent. The gel precursors were calcined at 300 ℃ for 12 h in a muffle furnace. Their morphology and structure were characterized using powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). Their electrochemical performance as a supercapacitor electrode material was investigated comparatively by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge. The experimental results indicated that Ce- doping did not change the structure of Mn₃O₄ but greatly affected the morphology and considerably enhanced the electrochemical performance of Mn₃O₄. A specific capacitance of 477 F·g^-1 was obtained when the mole ratio of Ce ion to total metal ions was 3%, which was 43.7% higher than that of the undoped material. Moreover, Ce-doping significantly improved the capacitance retention ability.

Activated carbons for electrochemical double-layer capacitor electrodes were prepared from peasecod-based carbons using ZnCl₂ or KOH as activating agents. The pore structures of the prepared activated carbon materials were characterized using N2 adsorption. The specific surface area of the peasecod-based carbon materials increased obviously from 1.69 m²·g^-1 to 2237 m²·g^-1 by KOH activation and to 621 m²·g^-1 by ZnCl₂ treatment. The electrochemical properties of the prepared peasecod-based activated carbon materials were evaluated by cyclic voltammetry and galvanostatic charge-discharge, and a specific capacitance as high as 297.5 F·g^-1 in 6 mol·L^-1 KOH aqueous electrolyte was obtained for the KOH-treated carbon material. Additionally, the KOH-activated peasecod-based carbon material showed excellent long-term charge-discharge cycle stability and a 8.6% decrease in the specific capacitance was observed at a high current density of 5 A·g^-1 after 500 cycles.

Platinum nanowire arrays (Pt NWs) catalyst was fabricated by electrodepositing with anodic aluminum oxide (AAO) as a template. The morphology and oxygen reduction reaction (ORR) electrocatalytic properties of the as-prepared platinum nanowire array catalysts were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical measurements. The cyclic voltammetry (CV) showed that the specific electrochemical surface area (ECSA) of the Pt NWs was much higher than the geometric area. The half wave potential in the oxygen reduction reaction curves of the Pt NWs was more positive than that of Pt/C from the rotating disk electrode (RDE) measurements. Moreover, Pt NWs catalysts give higher limiting diffusion current by comparison with that of conventional Pt/C catalyst.

Poly(acrylonitrile-methyl methacrylate-styrene) (PAMS) was synthesized by emulsion polymerization and a polyethylene (PE)-supported membrane was prepared using urea as foaming agent (PE-PAMS-U). The structure and performance of the PAMS copolymer, PE-PAMS-U membrane and corresponding gel polymer electrolyte (GPE) were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetry (TG), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and by a charge/discharge test. We found that the performance of the PE-PAMS-U based GPE could be improved when using urea as a foaming agent. With the use of urea the pore size of the membrane becomes uniform, the ionic conductivity of the GPE improves from 1.1×10^-3 to 2.15×10^-3 S·cm^-1 at room temperature and the interfacial resistance between the GPE and lithium is reduced from 480 to 250 Ω·cm². The GPE is stable up to 5.0 V (vs Li/Li⁺) at room temperature and the battery made using the Li/PE-supported GPE/LiCoO₂ shows a od rate and od cycle performance.

To get rid of impurities on a Li surface and avoid hydrogen gas generation during the preparation of a lithium pyrrolide film, tetrahydrofuran (THF) was used to pretreat the surface of a Li electrode. We found that THF pretreatment can obviously refresh the Li surface as well as improve the uniformity and density of the lithium pyrrolide film. The interface resistance effectively decreases and the interfacial stability improves. Additionally, the reversibility of the lithium deposition/dissolution process increases. All the ‘sponge-shaped’ lithium deposits are homogeneously distributed on the electrode surface and the lithium cycling efficiency is enhanced by THF pretreatment.

TiO₂ anatase nanorods (ANR) were synthesized by a two-step hydrothermal method. The materials were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). To increase the light harvesting efficiency and electron transfer rate, N719 dye-sensitized solar cells (DSSCs) were constructed and compared by adjusting the doping ratio of the anatase nanoparticles (ANP) and ANR in the TiO₂ nanocrystalline film that was used as a photoanode in the DSSCs. The best light-to-electricity conversion efficiency (7.3%) was obtained for a double-layered photoanode (ANP/(ANR+ANP)) cell, which is 20% higher than the traditional single-layered ANP cell (6.1%) when tested under the same conditions and at AM 1.5, 100 mW·cm^-2.

Ultrafine Mg nanoparticles of around 40 nm in size were prepared by an acetylene plasma metal reaction, which is a revised approach of the traditional hydrogen plasma metal reaction. The morphology and the cyclic hydrogenation properties were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), specific surface area (BET) tests, and the kinetics of hydrogenation and dehydrogenation. Because of the short diffusion distance and the large specific surface area, the kinetics of hydrogenation and dehydrogenation of the small Mg nanoparticles improved. The nanostructured carbon cover on the Mg nanoparticles decreased the amount of Mg nanoparticle oxidation and also prevented the growth of Mg nanoparticles during the hydrogenation and dehydrogenation process. Therefore, the Mg ultrafine nanoparticles exhibited excellent cycling stability. Cycling tests showed little loss in hydrogen storage capacity after 30 cycles.

A low-molecular-weight partially hydrolyzed polyacrylamide (HPAM) was synthesized because of its similar segment distribution to that of the random copolymer of acrylamide and acrylic acid P(AM- co-AA) to investigate the self-assembly of random copolymers in aqueous phase. The pH responsive self-assembly of HPAM with hydroxyethyl cellulose (HEC) in aqueous solution was investigated by transmission electron microscopy (TEM) and various polymeric micelle morphologies were observed in different pH ranges such as 100 nm cube-like micelles, 200 nm×100 nm pseudo ellipsoidal micelles, 100 nm string beads-like micelles, and 500 nm×300 nm×50 nm half-moon micelles. A method to couple the in situ reduction of ld at the polymeric micelle surface and TEM characterization was established and used to detect the nanoscale details of the low contrast polymer micelles. We confirmed by the above method and with the assistance of electron probe X-ray microanalysis (EPMA) and scanning electron microscopy (SEM) that the delicate conformation of the half-moon polymeric micelle was a multivesicular vesicle (MVV) which possessed the following hierarchical structure: hydrophilic inner vesicle @ hydrophobic continuous cystwall @ hydrophilic shell. This structure collapsed at pH 0.9 and it disintegrated into 10 nm pseudo spherical polymeric micelles with the following structure: hydrophobic core @ hydrophilic shell. The respective compositions of the core and the shell of the micelles were interpreted based on an understanding of the pH responsive degree of protonation of the various chain units and the experimentally obtained zeta potential and light absorbance. Therefore, we obtained new information about the driving force and morphology of HPAM self-assembly in the aqueous phase.

A series of discotic molecules containing triphenylbenzene group and three monochains were synthesized and their self-assembly properties were studied. These derivatives formed stable gels in many low polarity organic solvents. The lamellar and fibrous aggregate morphologies of the xerogels and the layered structure of the gel aggregates were studied by scanning electron microscopy (SEM) and small angle X-ray diffraction (SA-XRD), respectively. Fourier transform infrared (FT-IR) spectroscopy and UV-Vis absorption spectroscopy revealed that the hydrogen bonding and π-π interactions were the main driving force for the formation of a self-assembled gel. During gel formation, the gelator molecules self-assemble into ordered lamellar aggregates in organic solvents through a π-π conjugation stacking effect and hydrogen bonding. The ordered lamellar aggregates are juxtaposed and interlocked by van der Waals interactions to form sheet-like structure or fiber superstructure and finally immobilize into the organic liquids.

The 1-ethyl-3-methyl imidazolium hexafluorophosphate ionic liquid ([EMIM][PF₆]) was absorbed onto the surfaces of several kinds of nano-SiO_x particles by mechanical grinding using an agate mortar. The samples were investigated by differential scanning calorimetry (DSC), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and X-ray diffraction (XRD). We found that the melting point of the [EMIM][PF₆] adsorbed on the surface of nano-SiO_x was significantly less than that of the bulk ionic liquid. For the pure ionic liquid [EMIM][PF₆], the melting point was 62 ℃. After absorption onto SiO_x nanoparticles the melting point decreased to 52 ℃ and ΔT was -10 ℃. For the other two types of nano-SiO_x particles the ΔT was -20 and -17 ℃, respectively. These results indicate that the melting point depression was dependent on the surface properties of the nano-SiO_x particles. Furthermore, the characteristics of the surface-adsorbed ionic liquid were also found to be quite different from that of the bulk ionic liquid by Raman and XRD analyses. The difference in the density of the surface hydroxyl groups and the specific surface area of the nano-SiO_x particles may induce different interfacial interactions between [EMIM][PF₆] and the nano-SiO_x particles. Our results suggest that the density of the surface hydroxyl groups and specific surface area are the major factors responsible for the behavior of the adsorbed ionic liquid [EMIM][PF₆].

A series of Au-Cu/Co₃O₄ catalysts with different mass fractions of Cu were synthesized by a two-step method that consists of depositing ld and copper onto a Co₃O₄ support, which was synthesized by coprecipitation. The effect of copper on the catalytic activity of Au-Cu/Co₃O₄ was evaluated for the complete oxidation of ethylene at different temperatures and the prepared catalysts were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), H₂ temperature- programmed reduction (H₂-TPR), and O₂ temperature-programmed desorption (O₂-TPD). The results show that Au-Cu/Co₃O₄ bimetal catalysts exhibit higher catalytic activities than the Au/Co₃O₄ catalyst. At a ld loading amount of 4% (w, mass fraction) the AuCu₃/Co₃O₄ catalyst gives higher catalytic activity compared to catalysts AuCu/Co₃O₄ and Au₃Cu/Co₃O₄. Ethylene conversion was 15.3% for AuCu₃/Co₃O₄ even at 0 ℃ whereas at 120 ℃ the full conversion of ethylene was obtained. The results of XRD and HRTEM indicate the formation of an Au-Cu alloy in AuCu₃/Co₃O₄. However, we have found that the majority of Cu is present in the form of Cu2O in Au₃Cu/Co₃O₄. The interaction between Au and Cu on the surface of the catalysts decreases the particle size of the ld and, therefore, it is much easier to activate ethylene. H₂-TPR and O₂-TPD results show that the high reduction ability and the high intensity of surface oxygen active species contribute to the excellent catalytic activity of the AuCu₃/Co₃O₄ catalyst.

The catalyst precursors of B-Ni₂P/SBA-15 were synthesized by co-impregnation using (NH₄)₂HPO₄ as the source of phosphorus, Ni(NO)₃ as the source of nickel and H₃BO₃ as the source of boron. The B-Ni₂P/SBA-15 catalysts with an initial P/Ni molar ratio of 0.8 and a boron content from 0.35% to 2.10%(w) were prepared by temperature-programmed reduction in a H₂ flow. The structure of the catalysts was characterized by X-ray diffraction (XRD), N₂ adsorption-desorption, transmission electron microscopy (TEM) and NH₃ temperature-programmed desorption (NH₃-TPD). The catalytic performances of hydrodesulfurization (HDS) were evaluated in a fixed-bed microreactor using dibenzothiophene (DBT) as a model compound. The results showed that the B-Ni₂P/SBA-15 catalysts still retained mesoporous structure. The Ni₂P phase was mainly active phases in all the catalysts. The proper addition of boron reduced the Ni₂P active phases but increased the specific surface area of the catalysts. The amount of acid in B-Ni₂P/SBA-15 also increased with addition of boron. When the reaction temperature was increased from 300 to 360 ℃, the HDS conversion of DBT over the catalyst clearly improved with an increase in the content of boron. The B-Ni₂P/SBA-15 catalyst with a boron content of 1.40%(w) had the best catalytic activity. The mechanism of the HDS of DBT consisted of main direct desulfurization (DDS) over the B-Ni₂P/SBA-15 catalysts.

Mesoporous single-crystalline NiAl₂O₄ nanorods were successfully synthesized by a one-step hydrothermal method using a pore-forming agent (NH₄HCO₃). A series of controlled experiments were also carried out to better understand the formation mechanism of NiAl₂O₄ nanorods. The experimental results indicate that the reaction time, reactant concentration and the amount of NH₄HCO₃ play an important role in determining the morphology. The morphology, structure and composition of the nanorods were investigated using transmission electron microscopy, high resolution transmission electron microscopy, scanning electron microscopy and X-ray diffraction. The specific surface area and pore-size distribution of the obtained product was determined by nitrogen adsorption-desorption measurements. NiAl₂O₄ nanorods have a high Brunauer-Emmett-Teller surface area and od porosity properties. The catalytic performance of the NiAl₂O₄ nanorods during toluene hydrocracking was investigated using a fixed bed reactor. After the toluene catalytic reactions over 400 min at a water stream/carbon molar ratio (H₂O/C) of 1.0 with a reaction temperature of 700 ℃ the average conversion efficiency of toluene was about 86.5%. Compared to the NiAl₂O₄ nanoparticles prepared by alkaline precipitation, the mesoporous NiAl₂O₄ nanorods exhibited higher catalytic activity and stability during toluene hydrocracking. A possible formation mechanism for the mesoporous NiAl₂O₄ nanorods is proposed and discussed.

TiO₂-coated/activated carbon composites (TCS) were prepared by supercritical pretreatment and sol-gel processing. The prepared TCS were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption analysis. The photocatalytic performances of the composites were evaluated by the decolorization of an acid red 27 solution. The results show that the TCS have higher photocatalytic activity than bare TiO₂ because of the smaller crystalline size of TiO₂ and the higher amount of adsorbed acid red 27 as well as hydroxyl radicals. The photocatalytic activity of TCS increased and then decreased with an increase in surface area. The kinetic behavior of the photocatalytic degradation of acid red 27 over various composites is described in terms of a modified Langmuir-Hinshelwood model. The kinetic results clearly indicate differences in the photocatalytic activity of TCS, which is mainly attributed to interactions between the surface areas and the adsorption strength. TCS3 gave the highest photocatalytic activity with an optimal adsorption strength resulting from its moderate surface areas.

Time-resolved polarized optical waveguide spectroscopy is a powerful technique for the kinetic study of the adsorption of metal nanoparticles and chromophore molecules. We monitored the self- assembling processes of ld nanoparticles and cytochrome c in situ and in real time using this technique. A localized surface plasmon resonance (LSPR) absorption peak for the adsorbed ld nanoparticles gradually red shifted with an increase in the number of adlayers. Moreover, the red shift of the LSPR peak detected with the transverse magnetic (TM) modes is faster than that with the transverse electric (TE) modes. We found that with the TM modes the adsorption of cytochrome c on the ld-nanoparticle adlayer results in a significant red shift of the LSPR peak and a large increase in the peak intensity. In contrast, no obvious changes in the LSPR peak were detected with the TE modes. An analysis of the experimental data verified that the adsorption kinetic behavior of the ld nanoparticles follows a diffusion- control model and cytochrome c adsorption kinetics follows a Langmuir isotherm model. The kinetic parameters for cytochrome c adsorption including the adsorption and desorption rate constants as well as the adsorption free energy were estimated by best fitting the experimental data to the Langmuir model.

Cetyltrimethyl ammonium bromid (CTMAB)-ZrP complexes that contained different amounts of CTMAB that intercalate into α-zirconium phosphate were successfully prepared while methylamine weakened the interlayer forces in α-zirconium phosphate. The CTMAB-ZrP samples were characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and N₂ sorption isotherm analysis. We discuss the arrangement of CTMAB in the interlayers of zirconium phosphate according to the characterization results. The results of the adsorption of phenol by CTMAB-ZrP showed that the amount of phenol adsorption depended on the content of CTMAB in the complex, the interlayer steric hindrance, and the pH value of the solution. The adsorption of phenol, 2-chlorophenol, 2,4-dichlorophenol, p-methylphenol, and 3,5- dimethylphenol onto CTMAB-ZrP showed that the amount of adsorption correlated positively with the hydrophobicity of the phenols and it was not related to the acidity of the phenolic compounds. The sorption isotherms of phenol, 2-chlorophenol, and 2,4-dichlorophenol fit the Henry and Freundlich equations well. Therefore, the adsorption mechanism is mainly associated with the partition of different phenols in the organic phase of the intercalated CTMAB-ZrP.

We report a one-step method for the synthesis of M(Fe, Co, Ni) nanocrystals supported by ordered mesoporous carbon (OMC) materials. M/OMC composites were obtained by the soft templating route under acidic conditions using resorcinol and formaldehyde as carbon precursors, triblock copolymer Pluronic F127 as a template and Fe, Co, Ni nitrates as metal precursors. The as-synthesized materials were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and N₂ adsorption. Characterization revealed that the as-synthesized materials possessed an ordered hexa nal mesoporous structure similar to SBA-15. The specific surface areas of the Fe/OMC, Co/OMC, and Ni/OMC composites were found to be 586, 626, and 698 m²·g^-1, respectively. The fact that the metal species were present as highly dispersed nanocrystals in the OMC matrix was confirmed by XRD and high-resolution TEM.

A polymeric nanofilm with a low surface free energy and high dielectric constant on the surface of a Mg-Mn-Ce magnesium alloy was prepared by a self-developed technique which was designed as polymer plating. The reaction mechanism during polymer plating was analyzed by X-ray photoelectron spectroscopy (XPS). The film formed on the magnesium alloy surface as determined by Fourier transform infrared (FT-IR) spectroscopy. The contact angle of distilled water and the surface free energy of the polymeric film were determined using a contact angle meter. The film thickness was characterized by spectroscopic ellipsometry. The dielectric property of the film was evaluated using a precision impedance analyzer. The experimental results show that the nanoscale polymeric film was successfully formed on the magnesium alloy surface after polymer plating. The contact angle of distilled water for the polymer-plated magnesium alloy increased to 150.5° compared with 70.8° for the substrate and the surface free energy of the polymer-plated magnesium alloy decreased to 1.57 mJ·m^-2 from 37.96 mJ·m^-2 for the substrate. Therefore, the functional performance changed from hydrophilic to hydrophobic. The film mass and thickness increased with the polymer-plating time before 20 min and then decreased slightly. The film mass and thickness after polymer-plating for 20 min increased to 23.5 μg·cm^-2 and 147.48 nm, respectively. The polymer-plated nanofilm at 20 min possesses a high relative dielectric constant of 24.922 at a frequency of 1 kHz.