There is great significance to produce C₂-oxygenates such as ethanol via syngas fromcoal, natural gas or biomass frompractical and academy of view; and supported Rh-based catalysts are the most effective for this conversion. The choice of promoter is critical for obtaining high-performance catalysts, of which Fe, Mn, and Li are most widely used. The effects of promoters have been studied extensively and comprehensively, but their roles remain the subject of much debate. We review the progress on the promotion nature of Fe, Mn, and Li. The roles of these promoters depend on the catalyst systemand preparation procedures empolyed, which affect directly the interaction between Rh and promoter(s). This interaction determines the displayed structures and properties of the promoters, which behaves different effects on the elemental steps of CO hydrogenation reaction. This review is expected to deeply aid our understanding of the effects of these promoters.

The density and surface tension of aqueous 1-pentyl-3-methylimidazoliumpropionate ([C₅mim][Pro]) of various molarities were determined at 288.15 to 318.15 K, and the coefficient of thermal expansion, the apparent molar volume, and the parachor for these solutions were calculated. The values of the apparent molar expansibility of solute obtained fromdata of the apparent molar volume are in good agreement with the values calculated by Harned-Owen equation.The empirical equation of the parachor was used to estimate the parachor and surface tensions of the solutions. Estimated values were within the experimental error of experimental values.

An iridium(Ⅲ) complex of (MDPPF)₂Ir(acac) (MDPPF=4,4'-difluoro-5-methyl-2,3-diphenylpyrazine, acac=acetylacetone) has been prepared and characterized by X-ray single crystal diffraction. The photophysical properties of (MDPPF)₂Ir(acac) were investigated using UV-Vis spectroscopy and photoluminescence (PL) techniques. X-ray diffraction (XRD) studies revealed that the complex belongs to a triclinic systemof the P1 space group with cell dimensions a=1.13984(3) nm, b=1.26718(3) nm, c=1.29541(3) nm, α=93.7181(19)°, β= 101.638(2)°, γ=110.853(3)° and V=1.69336(7) nm³.Asolution of the (MDPPF)₂Ir(acac) complex in dichloromethane was found to emit yellowlight with amaximumpeak at 555 nmat roomtemperature. Furthermore, (MDPPF)₂Ir(acac) was used as a phosphorescence dopant in organic light-emitting diodes (OLEDs) with the structures of ITO/NPB (40 nm)/CBP:(MDPPF)₂Ir(acac) (20 nm)/TPBi (10 nm)/Alq₃ (30 nm)/LiF (1 nm)/Al (100 nm). These devices showed yellowemission at 558 nm, a maximumbrightness of 32700 cd·m^-2, current efficiency of 44.7 cd·A^-1 and power efficiency of 20.7 lm·W^-1.

(Fluorocarbonyl) sulfenyl isocyanate (FC(O)SNCO) contains ―C(O)S― and ―NCO groups, so has an interesting electronic and molecular structure. FC(O)SNCO was prepared by the metathesis of FC(O)SCl and AgNCO. HeI photoelectron spectroscopy (PES), photoionization mass spectrometry (PIMS), and theoretical calculations were used to study the molecular and electronic structure of FC(O)SNCO. The experimental, theoretical calculations, and NBO results indicated the most stable conformer of FC(O)SNCO. In addition to the outer-valence Green's function calculation, the PES spectrumwas assigned fromanalogous studies of similar molecules. The syn-syn non-planar conformer (δ_FCSN=180°) with C₁ symmetry was favored by the neutral molecule, and changed to the syn-syn planar structure with C_s symmetry after ionization. The experimental first vertical ionization potential mainly fromthe S lone pair orbital was 10.33 eV. The second to sixth ionization potentials of FC(O)SNCO were 12.44, 13.23, 13.77, 14.78, and 15.99 eV, respectively, and were also assigned. The FC(O)⁺, SN⁺, FC(O)SN⁺, SNCO⁺, C(O)SNCO⁺, and FC(O)SNCO^+· peaks were observed in the PIMS spectrum, the highest intensity of which was FC(O)SNCO^+·. The PIMS data were analyzed based on the PES and theoretical results. Possible ionization and dissociation processes are discussed.

Partially premixed laminar flames were formed using our purpose-built burner. The soot reduction mechanism of blends of diesel and oxygenated fuel was explored. The mixture of toluene and n-heptane (volume ratio, 20:80) (T20) was used as a diesel surrogate. Methanol, ethanol, n-butanol, methyl butyrate, and 2,5-dimethylfuran (DMF) were blended with T20, whilst retaining a 4% oxygen content. Laser-induced fluorescence (LIF) was used to obtain spatial fluorescence spectra of polycyclic aromatic hydrocarbons (PAHs) in partially premixed co-flowflames. Laser-induced incandescence (LII) was used to measure soot concentration (volume fraction). The formation and growth of PAHs in flames varied with the fuel blend. Four-ring aromatics (A4) exhibited similar formation and oxidation to soot, so A4 was suitable for estimating soot formation and oxidation. With oxygenated additives, the content of toluene is reduced in T20 fuel, which is the major reason for the reduction of PAH fluorescence spectral intensity and soot concentration. The contribution of different oxygenated additives to PAH formation also affected soot reduction. The PAH-LIF spectral intensity and soot concentration of n-butanol /T20 blends were lower than those of fuels containing methanol, ethanol, methyl butyrate, and DMF. Therefore, n-butanol more effectively reduced PAHs and soot emission during the combustion of the diesel surrogate (T20).

Natural gas is a highly efficient energy source subject to growing demand. Natural gas contains H₂S, which can harmhuman health and cause equipment corrosion and environmental pollution. Effective H₂S adsorbents are necessary to overcome these problems. Grand canonical Monte Carlo (GCMS) simulations were performed to study the selectivity and working capacity (pressure swing adsorption (PSA) and vacuumpressure swing adsorption (VSA) processes) of H₂S in 33 kinds of stable metal-organic frameworks (MOFs), with the aim of separating H₂S from H₂S/CH₄ gas mixture. ZIF-80, Zn₂-bpydtc, CAU-1-(OH)₂, and CH₃O-MOFa were suitable materials for the VSAprocess. CAU-1-(OH)₂ and CH₃O-MOFa were suitable for the PSA process. The structures of materials exhibiting high selectivity and working capacity suggested that appropriate functionality and small pore sizes were important for high selectivity. MOFs with ―Cl, ―OH, and ―OCH₃ functionality exhibited the strongest adsorption. Materials exhibiting high selectivity, strong interaction with H₂S, and large numbers of adsorption sites may have high working capacities. High selectivity and high working capacity stable MOFs were screened and analyzed, to enhance the selectivity and working capacity toward H₂S. This provides a theoretical basis for separating H₂S fromnatural gas using MOFs.

^#271C₅₀Cl₁₀ is widely postulated to be a direct chlorination product of cage ^#271C₅₀. We suggest an alternative formation mechanism of ^#271C₅₀Cl₁₀, based on the topological relationship of these C₅₀ fullerenes. Density functional theory (DFT) calculations of the proposed cage transformation pathway in the chlorination of C₅₀ were performed. The proposed pathway is stimulated by chlorination-promoted fullerene cage transformation, with a lowactivation barrier. DFTcalculations of the Stone-Wales (SW) transformation pathways revealed that the thermodynamically favored rearrangement of other C₅₀ chlorofullerene into ^#271C₅₀Cl₁₀ requires a lower activation energy than that of the pristine carbon cage. This suggested that it is a more effective pathway of chlorinating C₅₀ to ^#271C₅₀Cl₁₀.

Themethylation of 4-methylbiphenyl (4-MBP) can yield 4,4'-dimethylbiphenyl (4,4'-DMBP), an important precursor for advanced polymers. The reaction mechanismof the shape-selective methylation of 4-MBP with methanol within the pores of H-ZSM-5 zeolite was studied, using“our own-N-layered integrated molecular orbital+molecular mechanics”(ONIOM) and density functional theory (DFT) methods. Stepwise and concerted mechanisms were considered, with the former having a lower activation energy. 4,4'-DMBPis kinetically favored by both mechanisms. Transition state selectivity accounts for the preferential methylation to 4,4'-DMBP. The isomerization of 4-MBPto 3-methylbiphenyl (3-MBP) is restricted within the zeolite. The isomerization of 4-MBP to 3-MBPis kinetically favored over methylation on the external zeolite surface, which causes a decrease in 4, 4'-DMBP selectivity. Passivating the external surface will suppress 4-MBP isomerization, therefore increasing 4,4'-DMBP selectivity by restricting reaction within the zeolite. The computational results of shape-selective and non-selective reactions over H-ZSM-5 zeolite well account for the experimental observations.

Time-dependent density functional theory has been used to investigate the plasmon excitation processes in silicene quantumdots. Two main plasmon resonance bands were observed running parallel to the direction to the silicene quantumdot plane around 2.0 and 7.0 eV. Given that delocalized π electrons can participate in the excitation of the two plasmon resonance bands, an increase in the side length of the rectangular silicene quantumdots in the direction of the excitation led to the red-shifting of the two main plasmon resonance bands. Plasmon excitation in silicene quantumdots is also dependent on the edge configuration. Furthermore, because of the relatively high symmetry of the hexagonal silicene quantum dot, the plasmon resonance modes of the quantumdots were found to be identical along the different excitation directions running parallel to the quantumdot plane.

Quantitative structure-property relationship (QSPR) studies on retention and separation factors of chiral compounds play a key role in predicting the retention and separation factors even the elution order of enantiomers. Chiral diarylmethane derivates were selected for computing molecular structural descriptors using VolSurf program. Models were built between the descriptors and retention as well as separation factors. The robustness of the model with respect to separation factors was assessed by external validation through the test set, leave-many-out cross-validation and Y-randomization test. The results were satisfactory. Analysis on the variables shows that the molecular globularity, hydrophilic regions at median energy levels, hydrophilic-lipophilic balance, amphiphilic moment, suitable hydrogen bond donors and acceptors are beneficial to the retention of enantiomers on the chiral stationary phase. Large differences of the hydrophilic regions at high energy levels, hydrophobic regions at lowenergy levels, amphiphilic moment, suitable hydrogen bond donors and acceptors, and anion regions between enantiomers are advantageous to the separation of enantiomers on the chiral stationary phase. These models allowthe prediction of retention and separation factors, especially the elution order of enantiomers.

Molecular dynamics (MD) simulations have been carried out to study the micro-interfaces between counterions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺) and dodecyl sulfate surfactant at the air/liquid interface. The morphology of the monolayer was analyzed by the density profile of the surfactant components, and the interactions between the polar head groups of the surfactants and the counterions were analyzed using the radial distribution function (RDF). The results showed that the interfacial thickness and thicknesses of the Stern and diffusion layers increased as the radius of counterion increased, whereas the surface tension and the degree of counterion association at the adsorbed layer decreased as the radius increased. These results indicated that the different counterions had a significant effect on the adsorption behavior of the dodecyl sulfate surfactants at the interface.

Three-dimensional reduced graphene oxide (RGO)/polyaniline (PANI) composite has been prepared in a single step by the ultrasonic irradiation of a suspension of graphite oxide gels and PANI nanowire using a hydrothermal method. Scanning electronic microscopy (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectra (FT-IR), X-ray photoelectron spectra (XPS), and electrochemical measurements were performed to investigate the morphology, structure, and supercapacitive performance of the composite. The result showed that the composite maintained the basic morphology of RGO, and that the PANI was inlayed inside the RGO network. An outstanding supercapacitive performance was obtained when the mass ratio of graphite oxide and PANI was 1:1. Furthermore, the capacities reached 758 and 400 F·g^-1 at 0.5 and 30A·g^-1, respectively. The retention rate was found to be 86% after 1000 cycles at 1 A·g^-1. These results therefore indicate that this new composite possesses good rate capability and cycle stability, and that its supercapacitive performance is better than that of pure RGO or PANI. The excellent supercapacitive performance of this composite can be attributed to the mutual synergy of RGO and PANI.

Anickel-based composite filmwas fabricated on Ni foil, by two-electrode anodization and galvanostatic charge-discharge (GCD) treatment. The surface morphology, states of chemical species, and crystal structure of the filmwere characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). The electrochemical performance was tested using an electrochemical workstation and battery program-control test system. The test results indicated that the filmpossessed a nanoflower-like morphology, and consisted of NiO, α-Ni(OH)₂ and β-Ni(OH)₂. The NiO-α-Ni(OH)₂-β-Ni(OH)₂ compounds exhibiting a high specific capacitance, superior rate capability, and good cyclability (1509 F·g^-1 at 6.7A·g^-1, 1120 F·g^-1 at 66.7 A·g^-1, after 2000 cycles, the capacitance of the filmremained unchanged).

The single-molecule junction conductance of terephthalic acid binding to Cu andAg electrodes was measured by an electrochemical jump-to-contact scanning tunneling microscopy break junction (ECSTM-BJ) approach. The Cu andAg electrodes were formed in-situ, via electrodeposition froma solution. The conductance histograms of the single-molecule junctions formed via the binding of terephthalic acid to the Cu and Ag electrodes showed a well-defined shape, in the absence of any data selection. The single-molecule junction conductance values for the terephthalic acid binding to the Cu electrode were 11.5 nS (high conductance) and 4 nS (lowconductance), while the high and lowconductance values for theAg electrode were 10.3 and 3.8 nS, respectively. The high conductance values were typically approximately three times larger than the low conductance values, for both the Cu and the Ag electrodes. The conductance (G) value for the terephthalic acid followed the order of G_Cu>G_Ag, which indicated the different electronic coupling efficiencies between the molecule and electrodes. In contrast with the single set conductance value measured for alkanedicarboxylic acid using the same approach, two set conductance values were found for the terephthalic acid junctions with the Cu and Ag electrodes. These results illustrated the important role of the backbone of the chain in conductance measurements. The present work demonstrated the influence of the electrode and the molecular structure on the single-molecule junction conductance.

The effects of different cathode current collectors (stainless steel, nickel, copper, and titanium) on the electrochemical performance of rechargeable magnesiumbatteries were investigated. Chevrel phase Mo₆S₈ acted as the cathode, (PhMgCl)₂- AlCl₃/tetrahydrofuran (THF) (the second generation electrolyte) as the electrolyte, and magnesium as the anode. Constant current discharge-charge results indicated that the electrochemical polarization of the electrode on stainless steel was the smallest and its cycling stability was the best, followed by nickel, copper, and titanium. Microstructure analyses for the electrodes and current collectors before and after discharge-charge were analyzed to investigate the differing electrochemical performance. The electrolyte corroded the current collectors to differing degrees. The surfaces of the electrodes differed after coating the active material on different current collectors. The corrosion potentials of the current collectors decreased after loading the active material. This resulted in the current collectors being more susceptible to corrosion by the electrolyte.

Dye-sensitized solar cells (DSCs) have aroused much interest because of their low cost and comparatively high power conversion efficiency. Stability is paramount for any photovoltaic technology. Traditional liquid electrolytes tend to leak and evaporate, which limits the long-termperformance of the DSC. N,N'-1,5-Pentanediylbis-dodecanamide was synthesized and used as a low molecular mass organogelator (LMOG), to gelate an ionic liquid electrolyte (ILE) and fabricate a quasi-solid-state DSC(QS-DSC). Differential scanning calorimetry indicated that the gel-to-solution transition temperature of the ionic gel electrolyte (IGE) was 104.7℃, which indicated good intrinsic stability. Electron transport and recombination were investigated by cyclic voltammetric (CV) and electrochemical impedance measurements, and intensity-modulated photocurrent and photovoltage spectroscopy (IMPS and IMVS) measurements. Electron recombination at the TiO₂ photoanode/ electrolyte interface was accelerated by the cross-linked gel network. The shorter electron recombination lifetime decreased the photoelectric conversion efficiency of the QS-DSC, compared with the ILE-based DSC. The photoelectric conversion efficiency of the QS-DSC exhibited no change during accelerated aging test for 1000 h, while that of the ILE-based DSC decreased to 86% of its initial value.

The effect of acetylation on the microstructure of alkali lignin (AL) in tetrahydrofuran (THF) was studied. The physicochemical properties of AL and acetylated alkali lignin (ACAL) were compared. Dynamic light scattering, gel penetration chromatography (GPC), transmission electron microscopy (TEM), intrinsic viscosity, fluorescence spectrophotometry, quartz crystal microbalance with dissipation (QCM-D) measurements, and layer-by-layer (LbL) self-assembly were used to investigate the aggregation and adsorption of AL and ACAL. Intermolecular and intramolecular associations in AL decreased following acetylation. AL in THF existed mainly as mono-molecules and intermolecular associations and had a more compact conformation. ACAL existed mainly as mono-molecules with a more stretched conformation. ACAL had a larger hydrodynamic radius than AL(of the same absolute molecular mass), because of its stretched conformation. QCM-D and LbLself-assembly measurements suggested that AL aggregates have a strong tendency to adsorb at the liquid-solid interface, but ACAL hardly adsorb at this interface because of its stronger interaction with THF. The compact conformation and strong adsorption property of AL resulted in inaccurate molecular weights of non-acetylated AL, as measured by GPC with a THF mobile phase. In order to get more reliable molecular weights from GPC measurements, acetylation for AL should be used in the sample pretreatment.

The metal-organic frameworks (MOFs), MIL-53(Al), MIL-96(Al), and MIL-120(Al) (MIL: Material Institute of Lavorisier) were synthesized and used as supports, to incorporate low-cost Ni nanoparticles (NPs) by wet impregnation. The samples were used as catalysts in the hydrogenation of nitrobenzene to aniline. The catalyst prepared with MIL- 53(Al) as a support exhibited excellent catalytic performance. Ni/MIL- 53(Al) heterogeneous catalysts were prepared using nickel nitrate, nickel acetate, and nickel ethanediamine as precursors. Characterization by powder X-ray diffraction, Fourier-transforminfrared spectroscopy, inductively coupled plasma spectroscopy, N₂ sorption measurements, H₂-temperature programmed reduction, and transmission electron microscopy showed that the Ni precursor affected the metal-support interaction, Ni particle size and particle distribution. The catalyst prepared using nickel ethanediamine possessed moderate metalsupport interactions, smaller Ni nanoparticles (4-5 nm), and a high Ni distribution. This resulted in its superior catalytic activity, with 100% conversion of nitrobenzene in the hydrogenation. The Ni/MIL-53(Al) catalyst retained its catalytic activity after five cycles, and exhibited a nitrobenzene conversion of ~92%.

Reported here is a facile route for the synthesis of polyvinyl pyrrolidone (PVP)-stabilized Pd/Co bimetallic nanoparticles via a chemical co-reduction process. The effects of molar ratio of PVP and reducing reagent (NaBH₄) to the total metal ions, and metal ion concentration and composition on the catalytic activity for hydrogen generation from NaBH₄ over Pd/Co bimetallic nanoparticles (BNPs) were studied. The transmission electron microscopy (TEM) results indicated that the prepared Pd/Co bimetallic nanoparticles, which had an average size of 1.5-2.8 nm, showed much higher catalytic activity than Pd and Co monometallic nanoparticles (MNPs). The highest catalytic activity of all the prepared bimetallic nanoparticles was 15570 mol·mol^-1·h^-1 (the activity was normalized by the content of Pd in the BNPs), which was achieved with Pd/Co theoretical atomratio of 1/9. The higher catalytic activity of the Pd/Co BNPs compared with the corresponding MNPs was ascribed to electronic charge transfer effects; this hypothesis was validated using density functional theory (DFT) calculations, which showed that the Pd atoms were indeed negatively charged, while the Co atoms were positively charged because of electron donation fromthe Co atoms to the Pd atoms. The positively charged Co atoms and negatively charged Pd atoms acted as catalytic active sites for the hydrolysis reaction of the alkaline NaBH₄ solution. Good catalytic stability was observed with the existing high catalytic activity, even after five runs of evaluating the catalytic activity. Moreover, no clear agglomeration was observed in the nanoparticle catalyst used. The corresponding apparent activation energy was determined as 54 kJ·mol^-1, based on the kinetic study of the hydrogen generation achieved via the NaBH₄ hydrolysis over the PVP-protected Pd₁₀Co₉₀ bimetallic nanoparticles.

NiS-modified Cd_1-xZn_xS has been prepared using a simple hydrothermal method. Notably, the H₂ evolution rate of 0.5% (y, molar fraction) NiS/Cd_0.3Zn_0.7S(1840 μmol·h^-1) was found to be 2.1- and 1.3-fold greater than those of Cd_0.3Zn_0.7S(884 μmol·h^-1) and 0.5% (w, mass fraction) Pt (1390 μmol·h^-1), respectively, when 0.35 mol·L^-1 Na₂SO₃ and 0.25 mol·L^-1 Na₂Swere used as sacrificial agents. The apparent quantumefficiency of 0.5% (y) NiS/Cd_0.3Zn_0.7S at 420 nm was 36.8%. The characterization of this material by X-ray diffraction (XRD), ultraviolet-visible diffuse reflection spectroscopy (UV-Vis DRS), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) showed that the NiS particles provided the active sites required for H₂ evolution and transferring the photo generated electrons, and therefore enhanced the photocatalytic activity of the catalyst towards H₂ production.

Aseries of band gap-tunable K⁺ doped graphitic carbon nitride (g-C₃N₄) photocatalysts have been prepared using potassiumhydrate and melamine as precursors, and fully characterized by X-ray diffraction (XRD), UV-Vis spectroscopy, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), Fourier transform infrared (FTIR) spectroscopy, N₂ adsorption, photoluminescence (PL), and X-ray photoelectron spectroscopy (XPS). The results of these analyses indicated that the positions of the valence and conduction bands were obviously changed as the concentration of K⁺ increased. The K⁺ ions were found to be embedded in the structural units of the g-C₃N₄, which inhibited the growth of the graphitic carbon nitride crystals, enhanced the surface area, and increased the separation rate of the photogenerated electrons and holes. The activity of K⁺ doped g-C₃N₄ catalysts was tested towards the photocatalytic degradation of rhodamine B (RhB) under visible light irradiation. The result indicated that the activity improved significantly after K⁺ doping. Furthermore, the K⁺ doped g-C₃N₄ catalysts exhibited outstanding structural and catalytic stability.

The K-LaZrO₂ and K-CuLaZrO₂ catalysts used for the synthesis of isobutanol fromsyngas have been characterized by X-ray diffraction (XRD), temperature programmed desorption (TPD), X-ray photoelectron spectrometry (XPS), Fourier transforminfrared (FTIR) spectroscopy, and chemical enrichment methods. The results of these analyses indicated that a solid solution of Cu-Zr was formed after the addition of Cu, and that the CuO was well dispersed. Furthermore, the addition of Cu inhibited the formation of t-ZrO₂. CO-TPD showed that the addition of Cu led to an increase in the amount of COadsorbed by the catalyst. Furthermore, H₂-TPD showed that the addition of Cu led to an increase in the amount of H₂ adsorbed at lowtemperatures, which was related to the activity of catalyst. The results of FTIR and chemical enrichment analyses also revealed that the level of CO adsorption increased following the addition of Cu, as well as amount of C₁ intermediates. Taken together, these results indicated that the activity of catalyst was significantly enhanced by the addition of Cu and that the selectivity towards isobutanol increased up to 48.5% when the reaction was conducted at p=10.0 MPa, gas hourly space velocity (GHSV) = 3000 h^-1, T=360℃, and V(H₂)/V(CO)=1:1.

Pt/γ-Al₂O₃ catalyst nanoparticles were prepared by self-assembly (AS) and wetness impregnation (WI) methods, and evaluated for the oxidation of volatile organic compounds including toluene, isopropanol, acetone, and ethyl acetate. The morphology, structure, and surface properties of the catalyst particles were correlated to their oxidation activity. Toluene, isopropanol, acetone, and ethyl acetate (1000×10^-6, volume fraction) in the feed stream (gas hourly space velocity of 18000 mL·g^-1·h^-1) were completely oxidized and removed by Pt/γ-Al₂O₃-AS at below 130, 135, 145, and 215℃, respectively. Pt/γ-Al₂O₃-AS exhibited outstanding activity and stability at high concentrations and space velocities. The high catalytic activity of Pt/γ-Al₂O₃-AS was attributed to its high surface area, small size, finely dispersed Pt nanoparticles, better reproducible activity at lowtemperature, and a higher number of hydroxyl groups.

Diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) were used as single templates to synthesize mesoporous zeolite ZSM-5 microspheres. The obtained 10-15 μm hierarchical aggregates had a uniformspherical morphology, which was spontaneously assembled by primary zeolite nanocrystals of 50 nmin size during the hydrothermal synthesis. The ZSM-5 aggregates had a tunable textual porosity, large mesopore volume, and high catalytic activity in the Friedel-Crafts alkylation. Diamine templates only acted as structure directing agents in our previous work. The current alkyl-polyamine templates acted as structure directing agents and space fillers in the synthesis of the hierarchical zeolites.

Heteroepitaxial growth of single-crystalline witherite (BaCO₃) microcone arrays on the (104) face of calcite (CaCO₃) was realized, by the interface-coupled dissolution-precipitation reaction in water/ethanol at roomtemperature. The witherite microcone long axis was parallel to the [001] direction of witherite and [001] direction of the calcite substrate. The top of the microcones appeared as uniformtri-symmetrical hexagons while the long axis of the witherite microcones was parallel to the electron beam. The witherite microcones increased in size and decreased in length:diameter ratio with extending crystallization time. The size and morphology of the epitaxially grown witherite could be tuned by changing the water:ethanol volume ratio, or the Ba(NO₃)₂ concentration of the precursor solution. Increasing the water:ethanol volume ratio or Ba(NO₃)₂ concentration yielded smaller, denser witherite single-crystalline microstructures. The witherite microcone arrays were thought to form by the synergetic epitaxial growth of witherite and dissolution of calcite. Carbonate crystals of witherite and calcite contained middle-high misfits on calcite (104) and (001) faces. Witherite microcones may have grown epitaxially on these two calcite faces, according to the Volmer-Weber model.

White organic light-emitting diodes (WOLEDs) are now approaching mainstream display markets, and they are also being aggressively investigated for next-generation lighting applications because of their extraordinary characteristics, such as high efficiency, high luminance, lower power consumption, wide viewing angle, fast switching, ultralight weight, and flexibility. In this paper, we first introduce the various approaches to realize WOLEDs, and then summarize the properties and differences of the four types of WOLEDs from the perspective of the emitting materials. The recent development of fluorescent, phosphorescent, fluorescent/ phosphorescent hybrid, and delayed fluorescence WOLEDs is comprehensively illustrated. By combining with our published works, we systematically review the device structures, design strategies, working mechanisms, physical theories, and electroluminescent processes of the reported WOLEDs. Then, the development of flexible WOLED is presented. Finally, the existing problems and trends of WOLEDs are discussed.

The MgO-P₂O₅ and CaO-P₂O₅ systems have been thermodynamically assessed based on the available phase diagram and thermodynamic data using the Calculation of Phase Diagram (CALPHAD) method. The liquid phase is described by the modified quasichemical model with the pair approximation, which takes short-range ordering in liquid solution into account. The PO₄^3- is considered as the basic building unit of P₂O₅ in the liquid solution since the maximum short-range ordering occurs at the M₃(PO₄)₂ (M = Mg, Ca) composition. All intermetallic phases are treated as stoichiometric compounds and the phase transformations are considered. A set of self-consistent model parameters is obtained to describe the thermodynamic property of every phase in these two binary systems, by which the published phase diagram, enthalpy, entropy, and activity data are reproduced well within experimental error limits. The present study can be used as a basis for the development of a thermodynamic database of molten slag system for the steelmaking dephosphorus process.

Transition metal-catalyzed carbon-carbon bond formation utilizing CO₂ is of great importance. The heteroatom functionality and CO₂ are simultaneously and catalytically incorporated into unsaturated substrates to form highly functionalized carboxylic acid derivatives. Here, density functional theory (DFT) is used to study the reaction mechanisms of the Cu-catalyzed silacarboxylation of internal alkynes. Two possible paths were proposed depending on the relative positions of the substituents (path I: methyl and path II: phenyl). The calculations reveal that the initial alkyne insertion into the Cu―Si bond determined both the rate and the selectivity. In path I, the calculated free energy barrier for alkyne insertion is 112.8 kJ·mol^-1, while that in path II is 127.6 kJ·mol^-1. Thus, path I is more kinetically favorable than path II, which is consistent with the experimentally observed product ratio of 97 : 3. Our analysis revealed that the electronic effects of the alkyne substituents dominated the observed regioselectivity.

Dicyandiamide is a dimer of cyanamide that generally isomerizes into imino and amino forms. The behaviors of tautomeric dicyandiamide adsorbed on gold surface were studied by the density functional theory method combined with surface enhanced Raman spectroscopy (SERS). By using DFT method the energies, molecular orbital, vibration spectral information of imino and amino forms of dicyandiamide and the SERS spectra of tautomeric dicyandiamide adsorbed on Au clusters were given. The results show that both tautomeric dicyandiamides form stable complexes with Au₃ clusters, and the N(2) atom preferentially adsorbs on Au clusters. The experimental results are consistent with the calculated results, which show that the tautomeric dicyandiamides coexist on the Au substrate, are adsorbed vertically on the gold surface through the N(2) atom, and the SERS enhancement factors conform to electromagnetic-field enhancement mechanism.

This study investigated the deformation behavior of < 111> twin Ag nanowires with differing parallel twin boundary (TB) densities under tensile loading via molecular dynamics (MD) simulations. The effect of TB density on the ultimate stress of nanowires is discussed, and the plastic deformation mechanisms of nanowires are illustrated. The results show that, in contrast to a single crystalline nanowire with the same size, the introduction of the TB can strengthen or soften nanowires through individual deformation modes, which indicates that there exists a critical twin boundary space (TBS) (where the value of the critical 1/TBS is 0.2 nm^-1). Below 0.2 nm^-1, softening occurs, whereby TBs become the source of dislocations. Above 0.2 nm^-1, TBs impede dislocation movement, which results in a strengthening effect. The strengthening mechanisms are divided into two types. When 1/TBS ranges from 0.2 to 0.5 nm^-1, the TB-dislocation interaction is the controlling factor. Fracture opening appears within the nanowires, and voids form, with dislocation multiplication, and then spread to the surrounding regions. When 1/TBS is greater than 0.5 nm^-1, TBs migrate to accommodate dislocation activity. Dislocations increase and transfer across the TBs. Shear banding is activated during the process, which contributes to the necking of nanowires. The strengthening and weakening effects caused by differences in TB density decrease with increasing temperature.

A novel dendritic carbazole derivative (BTCPh) was designed and synthesized by simple chemical route. Its homopolymer and copolymer of BTCPh with (3, 4-ethoxylene dioxythiophene) (EDOT) were electrochemically synthesized and characterized. Cyclic voltammetry and UV-Vis spectroscopy were used to investigate the spectroelectrochemical and electrochromic properties of the two polymers. The copolymer P(BTCPh-EDOT) film revealed richer electrochromic color than that of the homopolymer PBTCPh film (yellow, green, blue, and grey) and showed five different colors (orange, green, brown-green, blue, and grey) under various potentials, which may be attributed to the introduction of the EDOT unit generating more doped states of the polymer, resulting in richer colors. Electrochromic switching tests indicated that both polymers possess good optical contrast and fast switching times. These properties show promise for potential applications on smart windows and displays.

Surface modification of semiconductor materials is an effective way to improve their photocatalysis and photo-conversion activities. Bare and V-modified α-Fe₂O₃ photoelectrode materials were prepared using hydrothermal, chemical bath deposition and heat treatment approaches. Their physicochemical and photoelectrochemical (PEC) properties were then investigated with X-ray diffractometry (XRD), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), voltammetry, and electrochemical AC impedance spectroscopy (EIS) techniques. The existence of FeVO₄ was indicated by its characteristic X-ray diffractometry patterns, while no significant red shifts in the photoabsorption edge were detected in UV-Vis diffuse reflectance spectroscopy spectra. With V-modified and bare Fe₂O₃ serving as a photoanode, photoelectrochemical measurements were carried out for water splitting in 1 molmol·L^-1 NaOH (pH 13.6). The enhancement of α-Fe₂O₃ photoelectrochemical activities through V-modification was indicated by significantly increased photocurrents and decreased photocharge-recombination probability. By measuring electrochemical AC impedance spectroscopy spectra, pseudo-first-order rate constants for the charge transfer at the illuminated electrode/solution interface were estimated. The rate constant for V-modification of the Fe₂O₃ electrode was higher than that of the bare Fe₂O₃ electrode. Improved interfacial charge transfer kinetics through V-modification is responsible for the enhanced photoelectrochemical activities of α-Fe₂O₃. The interfacial photocharge transfer and recombination processes and their properties are discussed with a semiconductor energy band model constructed for the electrode system.

Poly(vinylidene fluoride)-graft-poly(sulfobetaine methacrylate) (PVDF-g-PSBMA) proton exchange membranes were synthesized via single-step grafting sulfobetaine methacrylate (SBMA) onto PVDF. Benzoyl peroxide (BPO) was the initiator, and the PVDF was initially modified by tetramethylammonium hydroxide (TMAH) in the liquid phase. Microstructure morphologies and sulfur distributions in the membrane were characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM-EDX), respectively. The PVDF formed C=C double bonds following dehydrofluorination by TMAH. SBMA was grafted onto the modified PVDF backbones, forming a homogeneous sulfur distribution in the interior and exterior of the membrane. Proton conductivities and methanol permeabilities of PVDF-g-PSBMA membranes increased with the increasing of the TMAH mass fraction in methanol. When the mass fraction was 20%, the proton conductivity of the membrane was 0.0892 S·cm^-1 at 20 ℃, and the methanol permeability was 4.04 × 10^-7 cm²·s^-1 at ambient temperature, respectively. The membrane exhibited good thermal stability up to 270 ℃, as verified by thermogravimetric analysis (TGA). With this membrane, the peak power density of a direct methanol fuel cell (DMFC) was 17.06 mW·cm^-2.

Random copolymers of 2-(2-methoxyethoxy)ethyl methacrylate (MEO₂MA) and oligo(ethylene glycol) methacrylate (OEGMA, M_n = 500 g·mol^-1) were synthesized by atom transfer radical polymerization (ATRP). Thermally induced aggregation of the co-polymers P(MEO₂MA-co-OEGMA) in aqueous solutions was investigated with dynamic light scattering (DLS), UV-Vis absorption, and transmission electron microscopy (TEM). In addition, the lower critical solution temperature (LCST) in aqueous solutions of P(MEO₂MA-co-OEGMA), and its change with respect to the composition of the copolymer, were obtained. The results indicate that the copolymers have an appreciably reversible thermal responsivity that can be attributed to a delicate balance between hydrogen bonds between the copolymers and water molecules and hydrophobic interactions of polymer segments. If the balance is broken, the polymers attain a new thermodynamic equilibrium by spontaneously changing the extent of aggregation. The LCST correlates linearly with the mole fraction of OEGMA units in the copolymer, and can be adjusted by changing the mole ratio of the two monomers.

The wetting properties of aqueous solutions of zwitterionic surfactants, benzyl-substituted alkyl carboxylbetaine (BCB), and benzyl-substituted alkyl sulfobetaine (BSB) on a poly(tetrafluoroethylene) (PTFE) surface were investigated using sessile drop analysis. The influences of surfactant concentration on surface tension, contact angle, adhesional tension, PTFE-solution interfacial tension (γ_SL) and adhesion work were examined. The results indicate that at low bulk concentration, surfactant molecules adsorb onto PTFE through hydrophobic interactions. Moreover, the adsorption of branched surfactants on the air-solution interface is higher than that on the PTFE-liquid interface and the values of contact angle for BCB and BSB remain almost constant over a wide range of surfactant concentrations. The adsorption of BCB and BSB molecules on PTFE are greatly enhanced again when the bulk concentration exceeds the critical micelle concentration. The molecules straighten, with hydrophilic group oriented towards the bulk phase, resulting in a decrease in γ_SL and a decrease in contact angle. The introduction of larger polar group in BSB makes it difficult to change the contact angle to the same extent as BCB at high surfactant concentrations because of steric effects.

Graphene oxide (GO) was fabricated from graphite powder by Hummers oxidation method and then, under ultrasonic irradiation, a series of GO/Ag₃PO₄ composite photocatalysts (4% (w, mass fraction) GO/Ag₃PO₄, 8% GO/Ag₃PO₄, 16% GO/Ag₃PO₄, 32% GO/Ag₃PO₄) were synthesized by a facile liquid deposition process. The products were characterized by N₂-physical adsorption, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, Fourier transform infrared (FT-IR) spectroscopg, and UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS). The effect of GO content on the photocatalytic activity of Ag₃PO₄ was evaluated by photocatalytic degradation of methyl orange (MO) under visible light irradiation. The results show that GO can be easily dispersed into Ag₃PO₄, producing a well-connected GO/Ag₃PO₄ composite. Coupling of GO largely enhanced the surface area of the catalyst and the adsorption of MO. At the optimal GO content (16%), the degradation rate of MO over GO/Ag₃PO₄ was 83% after 120 min of light irradiation, exhibiting 7.5 times higher activity than that of pure Ag₃PO₄. The increase in photocatalytic activity and stability can be mainly attributed to the coupling of GO, which increased the surface area and suppressed the recombination rate of electron-hole (e^-/h⁺) pairs and generated greater numbers of active free radicals.

Ag₃PO₄ polyhedrons were synthesized by a facile hydrothermal route using polyethylene glycol-6000 (PEG-6000). The effects of hydrothermal temperature, reaction time, and PEG-6000 dosage on the morphologies and structures of the products were systematically investigated. The photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible diffuse reflectance spectra (UV-Vis DRS), and photoluminescence (PL) spectra. The hydrothermal temperature and the PEG dosage are key factors in the production of Ag₃PO₄ polyhedrons with oriented {110} facets. The Ag₃PO₄ polyhedrons evolve via Ostwald ripening, and exhibit superior visible-light photocatalytic degradation of Rhodamine B (RhB) relative to Ag₃PO₄ samples without oriented {110} facets and Ag₃PO₄ nanoparticles prepared by anion-exchange. The reaction rate constant of the Ag₃PO₄ polyhedrons was 8.3 times that of the Ag₃PO₄ nanoparticles. Total organic carbon (TOC) analysis and cycling experiments revealed that the polyhedrons have better mineralization efficiency and exhibit good circulation runs. Holes (h+) and hydroxyl radicals (·OH) are confirmed to be the dominant active species in the presence of radical scavengers and in N₂-saturated solution. Given the redox potential of the active species and the band structure of Ag₃PO₄ polyhedron, the separation and migration mechanism of photogenerated electron-hole (e^--h⁺) pairs at the photocatalytic interface was proposed.

Three types of hierarchical, flower-like CuS particles were prepared by a hydrothermal method and samples were formulated as thin nanosheets. The aggregation density of the sheets could be readily controlled with the aid of polyvinylpyrrolidone (PVP) or 1, 3, 5-benzenetricarboxylic acid (BTC) organic molecules. The three substrates were then used for the growth of nickel nanocatalysts and the structures of the composites characterized by environment scanning electron microscopy (SEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). Ultraviolet-visible absorption spectrometry was applied to study the catalytic reduction of 4-nitrophenol. Results show that a sample of Ni nanoparticles (Ni NPs, ~5 nm in diameter) grown on CuS micro-flowers, composed of the sparsest nanosheets (Ni@SUB2) with an ultralow loading of 0.469% (w), showed the best catalytic properties amongst the three Ni@SUB composites. During reduction of 4-nitrophenol with initial 4-nitrophenol concentrations of 0.2 mmol·L^-1, the Ni@SUB2 showed almost 100% transformation within 4 min, while the same quantity of pure Ni NPs showed a transformation of only ~43%. The enhanced catalytic properties for 4-nitrophenol degradation could be ascribed to well-dispersed Ni NPs supported on the CuS substrate providing greater numbers of catalytic active sites. Furthermore, because of CuS is insoluble, it can be easily collected by centrifugation, which can be environmentally beneficial.