STUDY OF CATALYTIC BEHAVIOR OF PEROVSKITE-TYPE MIXED OXIDES La_(1-x)Sr_xFeO_(3-λ)(Ⅰ)——RELATIONS OF SOLID STRUCTURE AND DEFECT CHARACTER WITH CATALYTIC BEHAVIOR

According to X-ray structure analysis, it was found that there exist oxygen disordered defects in the crystal lattice of the samples without exception as x was changed from 0 to 1 in La_(1-x)Sr_xFeO_(3-x). With the doping of Sr~(2+), the crystal lattice was distorted extremely, even the crystal type varied. The results of TG showed a large amount of lattice oxygen released under high temperatures as x>0.5 in the samples. After comparison between the experiment results of the three systems La_(1-x)(Ca, Sr)_xMO_(3+x) (M=Mn, Fe and Co), it was concluded that the occurrence of solid defects is affected by the geometric factor and the catalytic activity is related to the concentration and the ordering extent of oxygen defects.     

Evolution of the composition and structure of PAN carbon fiber during preoxidation

Using scanning electronic microscope, X-ray diffraction analysis, PYR-GCMS and IR etc., we studied the evolving process of the composition and structure of PAN carbon fiber during preoxidation. In the initial stage of preoxidation, PAN filament tows disappear and become semi-thaw. At first, reactions happen between the copolymers and esters disappear. The molecules annularly crosslink and the index of cyclation slowly increases. It is easy to fix the structure and form defects during the initial and the medium stages, which are most reactive. More traction is advised in these stages to minimize the structural deficiencies. In the medium stage of preoxidation, the fiber was reshaped into new sheet stacks and gradually changed to sheet sectors, and this structure tends to be stable in the final stage. Induced by acid and ester copolymer, PAN fiber forms a very stable cycle structure in the final stage. Besides, monomer, dimmer and trimer obviously decrease. In the final stage of the preoxidation, there exi     

Water／Oil Biphasic Hydroformylation of Higher Olefins over a TPPTS-Rh／SiO2 Catalyst

A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of masstransfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performancefor hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of thetraditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersedRh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation ofhigher olefins such as 1-dodecene.     

Analytical Bond-order Potential for hcp-Y

The lattice parameters, elastic constants, cohesive energy, structural energy differences, as well as the properties of point defects and planar defects of hexagonal closepacked yttrium （hcpY） have been studied with ab initio density functional theory for constructing an ex tensive database. Based on an analytical bondorder poial scheme, empirical manybody interatomic potential for hcpY has been developed. The model is fitted to some properties of Y, e.g., the lattice parameters, elastic constants, bulk modulus, cohesive energy, vacancy formation energy, and the structural energy differences. The present potential has ability to reproduce defect properties including the selfinterstitial atoms formation energies, vacancy formation energy, divacancy binding energy, as well as the bulk properties and the thermal dynamic properties.     

Structural Properties of Nitromethane Molecular Crystal under High Pressure： An ab initio Investigation

The pressure-dependent structural properties under hydrostatic pressure up to 120 GPa and the decomposition under uniaxial compression along the b lattice vector up to 40 GPa of nitromethane molecular crystal using ab initio method are presented. The internal molecular bond lengths and bond angles were calculated for different pressures. All bond lengths decrease as the pressures are increased under hydrostatic compression. The obvious rotation of methyl group is 33.89° under hydrostatic pressure at 120 GPa. In addition, we observe the change of C-H bonds, which have been stretched under uniaxial compression along b lattice vector in the range of 0-40 GPa of nitromethane.     

Quantum Chemical Studies on the Mechanism of Producing Oxygenates in Fischer-Tropsch Synthesis on M/SiO2(M = Ni,Ru,Rh,Pd)

EHMO calculations and orbital analyses of fragment;;have been performed for the formation of oxygenates in Fischer-Tropsch synthesis on the butterfly model for four different metal (Ni,Ru,Rh,Pd) catalysts supported on SiO2.Calculations were made for the four processes,i.e.,CO-dissociation;Coupling of CO and H to produce CHO;Insertion of CO to M-CH3;insertion of CH2 to M-CH3 On the basis of comparing the degree of CO bonds activation and the energy barriers of the foregoing processes for these four catalysts,it is concluded that Ni/SiO2 can be used as the methanation catalyst.On Ru/SiO2 and Rh/SiO2 C2-oxygenated compound can be produced (acetaldehyde),especially Rh/SiO2 is the even better catalyst,and Pd/SiO2 is a methanol synthesis catalyst.     

Promotional Effect of Bismuth as Dopant in Bi-Doped Vanadyl Pyrophosphate Catalysts for Selective Oxidation of n-Butane to Maleic Anhydride

Bismuth-promoted (1% and 3%) vanadyl pyrophosphate catalysts were prepared by refluxing Bi(NO3)3·5H2O and VOPO4·2H2O in isobutanol. The incorporation of Bi into the catalysts lattice increased the surface area and lowered the overall V oxidation state. Profiles of temperature programmed reduction (TPR) in H2 show a significant shift of the maxima of major reduction peaks to lower temperatures for the Bi-promoted catalysts. A new peak was also observed at the low temperature region for the catalyst with 3% of Bi dopant. The addition of Bi also increased the total amount of oxygen removed from the catalysts. The reduction pattern and reactivity information provide fundamental insight into the catalytic properties of the catalysts. Bi-promoted catalysts were found to be highly active (71% and 81% conversion for 1% and 3% Bi promoted catalysts, respectively, at 703 K), as compared to the unpromoted material (47% conversion). The higher activity of the Bi-promoted catalysts is due to that these catalysts possess highly active and labile lattice oxygen. The better catalytic performance can also be attributed to the larger surface area.     

Effects of the Different Supports on the Activity and Selectivity of Iron-Cobalt Bimetallic Catalyst for Fischer-Tropsch Synthesis

Silica, alumina, and activated carbon supported iron-cobalt catalysts were prepared by incipient wetness impregnation. These catalysts have been characterized by BET, X-ray diffraction (XRD), and temperature-programmed reduction (TPR). Activity and selectivity of iron-cobalt supported on different carriers for CO hydrogenation were studied under the conditions of 1.5 MPa, 493 K, 630 h-1, and H2/CO ratio of 1.6. The results indicate that the activity, C4 olefin/(C4 olefin C4 paraffin) ratio, and C5 olefin/(C5 olefin C5 paraffin) decrease in the order of Fe-Co/SiO2, Fe-Co/AC1, Fe-Co/Al2O3 and Fe-Co/AC2. The activity of Fe-Co/SiO2 reached a maximum. The results of TPR show that the Fe-Co/SiO2 catalyst is to some extent different. XRD patterns show that the Fe-Co/SiO2 catalyst differs significantly from the others; it has two diffraction peaks. The active spinel phase is correlated with the supports.     

Biopolymer passivation for high-performance perovskite solar cells by blade coating

Thin films of perovskite deposited from solution inevitably introduce large number of defects,which serve as recombination centers and are detrimental for solar cell performance.Although many small molecules and polymers have been delicately designed to migrate defects of perovskite films,exploiting credible passivation agents based on natural materials would offer an alternative approach.Here,an ecofriendly and cost-effective biomaterial,ploy-L-lysine(PLL),is identified to effectively passivate the defects of perovskite films prepared by blade-coating.It is found that incorporation of a small amount(2.5 mg mL^-1)of PLL significantly boosts the performance of printed devices,yielding a high efficiency of 19.45% with an increase in open-circuit voltage by up to 100 mV.Density functional theory calculations combined with X-ray photoelectron spectroscopy reveal that the functional groups(-NH2,-COOH)of PLL effectively migrate the Pb-I antisite defects via Pb-N coordination and suppress the formation of metallic Pb in the blade-coated perovskite film.This work suggests a viable avenue to exploit passivation agents from natural materials for preparation of high-quality perovskite layers for optoelectronic applications.     

Selective Oxidation of Propane by Lattice Oxygen of Vanadium-Phosphorous Oxide in a Pulse Reactor

Selective oxidation of propane by lattice oxygen of vanadium-phosphorus oxide (VPO) catalysts was investigated with a pulse reactor in which the oxidation of propane and the re-oxidation of catalyst were implemented alternately in the presence of water vapor. The principal products are acrylic acid (AA),acetic acid (HAc), and carbon oxides. In addition, small amounts of C1 and C2 hydrocarbons were also found, molar ratio of AA to HAc is 1.4-2.2. The active oxygen species are those adsorbed on catalyst surface firmly and/or bound to catalyst lattice, i.e. lattice oxygen; the selective oxidation of propane on VPO catalysts can be carried out in a circulating fluidized bed (CFB) riser reactor. For propane oxidation over VPO catalysts, the effects of reaction temperature in a pulse reactor were found almost the same as in a steady-state flow reactor. That is, as the reaction temperature increases, propane conversion and the amount of C1 C2 hydrocarbons in the product increase steadily, while selectivity to acrylic acid and to acetic acid increase prior to 350℃ then begin to drop at temperatures higher than 350℃, and yields of acrylic acid and of acetic acid attained maximum at about 400℃. The maximum yields of acrylic acid and of acetic acid for a single-pass are 7.50% and 4.59% respectively, with 38.2% propane conversion. When theamount of propane pulsed decreases or the amount of catalyst loaded increases, the conversion increases but the selectivity decreases. Increasing the flow rate of carrier gases causes the conversion pass through a minimum but selectivity and yields pass through a maximum. In a fixed bed reactor, it is hard to obtainhigh selectivity at a high reaction conversion due to the further degradation of acrylic acid and acetic acid even though propane was oxidized by the lattice oxygen. The catalytic performance can be improved inthe presence of excess propane. Propylene can be oxidized by lattice oxygen of VPO catalyst at 250℃, nevertheless, selectivity to AA and to HAc are even lower, much more acetic acid was produced (molar ratio of AA to HAc is 0.19:1-0.83:1) though the oxidation products are the same as from propane.     

Boosting the electrochromic performance of TiO_2 nanowire film via successively evolving surface structure

Electrochromic transition metal oxides(ETMOs) are useful in energy saving devices and smart indicators. Among these ETMO candidates, titanium dioxide(TiO_2) is intriguing for its abundance and environmental safety, but the low color efficiency and slow coloring rate are still barricades to promote its electrochromic application. Herein, we demonstrate an amorphization strategy to comprehensively enhance the performance of TiO_2 nanowire film(TNF) via atomic layer deposition(ALD) of an additional TiO_2 conformal layer onto TNF surface, of which the layer structure evolves successively from ordered to disordered,achieving tunable electrochromism by controlling ALD cycles. Besides the remarkable increment of charging efficiency by～35% and color efficiency by ～40%, bleached transmittance rectified optical density(BTR density) and ion diffusion coefficient are boosted by ～90% and over 15 times, respectively for TNF deposited with 150 cycles. A large number of self-doped Ti~(3+) defects and hydroxyl units together with order-disorder interconnections in the ALD TiO_2 layer are responsible for the performance enhancement. The concept for successively evolving surface structure shares the feasibility of upgrading conventional ETMOs as well as designing new electrochromic materials.     

Molecular dynamics simulations of La2O3 thin films on SiO2

Classical molecular dynamics is used to investigate the equilibrium state of the surface region and interface of heteroepitaxial La2O3 thin films.Due to the lattice mismatch,heteroepitaxial thin films are subject to very large stress.For this reason the behavior of La2O3 thin films at SiO2interface becomes an important concern.Our result indicates that La2O3 can uniformly wet SiO2 surface.The properties of the simulated films are analyzed and the lack of any discernible crystalline phase in epitaxial La2O3 on SiO2 indicates that the lattice mismatch between SiO2 and La2O3 is sufficiently large to prevent the formation of even short-range orders in La2O3 film.     

Effects of ammonium exchange and Si/Al ratio on the conversion of methanol to propylene over a novel and large partical size ZSM-5

One type of ZSM-5 zeolite with large partical size was prepared and characterized by XRD, SEM, N2 adsorption-desorption, XRF, Py-IR and NH3-TPD techniques. Effects of ammonium exchange and SiO2/Al2O3 molar ratios on the reaction of methanol to propylene (MTP) over Na-ZSM-5 and H-ZSM-5 zeolites have been studied in a fixed-bed flow reactor under the operating conditions of T = 500 °C, P = 1 atm, and WHSV = 6 h-1. Ammonium exchange led to a rapid decrease in Na content for Na-ZSM-5 zeolite. The reaction results indicated that Na-ZSM-5 and H-ZSM-5 with different SiO2/Al2O3 molar ratios all exhibited high activity for methanol conversion. Ammonium exchange and the decreased SiO2/Al2O3 molar ratio of ZSM-5 zeolite led to an increase both in strong acid sites and weak acid sites. Na-ZSM-5 with high SiO2/Al2O3 molar ratio was favorable for the formation of propylene. The highest propylene selectivity (45.9%) was obtained over Na-ZSM-5 zeolite catalyst with SiO2/Al2O3 molar ratio of 220.     

Water/Oil Diphasic Hydroformylation of Higher Olefins over a TPPTS-Rh/SiO_2 Catalyst

A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.     

X-ray Multiple Diffraction Topographic Imaging Technique For Growth History Study of Habit Modifying Impurity Doped Crystals

A novel crystal characterization instrument has been built up in which a combination of X-ray multiple diffraction and X-ray topography is applied to enabling the cross-correlation between micro-crystallographic symmetry and its spatial dependence in relation to lattice defects. This facility is used to examine, in a self-consistent manner, growth sector-dependant changes to both the crystallographic structure and the lattice de-fects associated with the action of habit-modifying additives in a number of representative crystal growth sys-tems. In addition, the new instrument can be used to probe micro-crystallographic aspects(such as distortion to crystal symmetry) and relate these in a spatially resolved manner to the crystal defect structure in crystals doped with known habit modifiers.     

甲烷在Rh/SiO2催化剂表面解离的红外光谱研究

 FT-IR spectroscopy is employed to investigate the methane dissociation and methane partial oxidation over the Rh/SiO2 catalyst. When CH4 is adsorbed onto the catalyst surface, it dissociates into adsorbed CHx (x=1～3) and atomic hydrogen on Rh surface. Atomic hydrogen can diffuse from Rh surface to SiO2 surface where a proton exchange reaction of H with the surface Si-OH occurs, or it reacts with the lattice oxygen of SiO2 to form new Si-OH.     

Effect of Fumed SiO<Subscript>2</Subscript> on Pore Formation Mechanism and Various Performances of <Emphasis Type="Italic">β</Emphasis>-<Emphasis Type="Italic">i</Emphasis>PP Microporous Membrane Used for Lithium-ion Battery Separator

In this work,four samples containing different contents of fumed SiO2 were prepared to improve the pore size distribution and various properties of βnucleated isotatic polypropylene (β-iPP) biaxial membrane used for lithium-ion battery separator.The wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC) results show that the fumed SiO2 promotes the formation of r-crystal slightly and narrows down the thickness distribution of β-lamellae;meanwhile,evenly distributed SiO2 within β-iPP can be inspected by scanning electron microscopy (SEM).Moreover,further detailed characterization of morphological evolutions during biaxial stretching by tensile testing and SEM manifests that SiO2 can strengthen β-iPP and make the samples deform more homogeneously,resulting in a gradually elaborate and finer oriented microfibril structure after longitudinal stretching,in which more uniform defects distribute between fibrils and restrain the formation of coarse fibrils effectively.Therefore,more superior microporous structure emerges with the addition of SiO2,accompanied by narrower pore size distribution and better connectivity between microvoids,which is confirmed by mercury porosimeter and diminished Gurley value.Moreover,the lower thermal shrinkage,decreased shrinkage rate and suppressed porosity reduction indicate that fumed SiO2 improves thermal and dimensional stability of membrane dramatically.Furthermore,due to the excellent wettability of SiO2 with electrolyte,the microporous membranes doped with SiO2 have higher electrolyte uptake,even after heat treatment at elevated temperature.     

In situ Deposition of ‘Naked’ Gold Nanoparticles Supported on Silica Spheres as Recyclable Catalysts in Styrene Epoxidation

Tlie rational designs of particle size, morphology and surface states of the Au nanoparticles(AuNPs) are crucial for Au nanocatalyst. We herein report a method to synthesize the silica microspheres supported AuNPs(ca.1 nm) and their application in controlling the reaction conversion and selectivity in styrene epoxidation. Surfactant-ftee AuNPs deposited on silica microspheres were in situ fabricated with aid of the Ag nanoparticles (AgNPs) as sacrificial template by galvanic replacement reaction, leading to AuNPs/SiO2 catalyst directly without any post-treatment to expose crystal facets.A high conversion of 46.7% and selectivity of 91.7% to styrene oxide was achieved with H2O2 as oxidant in ethanol. The solid catalyst could be reused at least 10 reaction cycles without significant decrease in activity and selectivity. This study not only supplies an active, recoverable catalyst for styrene oxidation with green oxidant and solvent, but also demonstrates that the silica microspheres functionalized with thiol groups have a superior ability in stabilizing noble metal nanoparticles even without any surfactant.     

STUDIES OF MULTICOMPONENT COMPLEX OXIDE CATALYSTS FOR OXIDATIVE COUPLING OF METHANE VII.EFFECT OF CALCINATION TEMPERATURE ON Ti-La-Li PEROVSKITE-TYPE OXIDE CATALYSTS

The correlations of the calcination temperature.structure and catalvtic activity of the LiLa_（0.5）Ti_（0.5）O_(2-(?)) catalvsts with main phase and major active phase of perovskite-type trmary complex oxide LaTi_(l-y)Li_yO_(3-λ）m the Oxidative coupling of methane(OCM)have been studied The surface and bulk structures of the catalysts were characterized by means of XRD,XPS. IR.BFT and so on. The results clearly indicated that the effect of calcination temperature on the activity for the oxidative coupling of methaneis twofold On one hand.high calcination temperature is favoragble for Lisubstitution for Ti~(3 )into the lattice of LaTiO_3 and the production of moreoxygen vacancies at which active oxygen species are formed However,excessivelv high calcmation temperature makes Li~ substitution for Ti~(3 )less due to a httle change of structure or phases of the catalvst On the otherhand,the conversion of CH_4 drops because of the decrease of surface area,when the calcination temperature is raised.     

Synthesis, structural characterization and magnetic property of nanocomposite materials: Intercalation compounds of FePS_3 with 1,10-phenanthroline or 2,2''''-bipyridine

Two new intercalation compounds Fe0.90PS3(phen)0.41 (1) (phen stands for 1,10-phenanthroline including a part of 1, 10-phenanthroline H ) and Fe0.83PS3(bipy)0.34 (2) (bipy stands for 2,2'-bipyridine H ) were synthesized by the reaction of the layered FePS, with 1,10-phenanthroline or 2,2'-bipyridine in the presence of anilinium chloride. They were characterized by elemental analyses, powder X-ray diffraction (XRD), infrared spectroscopy. The lattice spacing of the intercalate was expanded by 0.90 nm for Fe0.90PS3(phen)0.41 and 0.57 nm for Fe0.83PS3(bipy)0.34 withrespect to the pristine FePS3, indicating that the ring plane of the guests is perpendicular to the layer of the host. The UV-vis absorption spectra of the filtrate in preparation of the intercalates indicate that 1, 10-phenanthroline or 2,2'-bipyridine also acts as a complexing agent to remove intralamellar Fe2 ions into the solution during intercalation. The magnetic properties of 1 and 2 were studied.