Atomically dispersed calcium as solid strong base catalyst with high activity and stability

Solid strong base catalysts are highly attractive for diverse reactions owing to their advantages of neglectable corrosion,facile separation,and environmental friendliness.However,their widespread applications are impeded by basic components aggregation and low stability.In this work,we fabricate single calcium atoms on graphene(denoted as Ca1/G)by use of a redox strategy for the first time,producing solid strong base catalyst with high activity and stability.The precursor Ca(NO_(3))_(2)is first reduced to CaO at 400℃ by the support graphene,forming CaO/G with conventional basic sites,and the subsequent reduction at 850℃results in the generation of Ca1/G with atomically dispersed Ca.Various characterizations reveal that Ca single atoms are anchored on graphene in tetra-coordination(Ca-C_(2)-N_(2))where N is in situ doped from Ca(NO_(3))_(2).The atomically dispersed Ca,along with their anchoring on the support,endow Ca1/G with high activity and stability toward the transesterification reaction of ethylene carbonate with methanol.The turnover frequency value reaches 128.0 h^(-1)on Ca1/G,which is much higher than the traditional counterpart CaO/G and various reported solid strong bases(2.9-46.2 h^(-1)).Moreover,the activity of Ca1/G is well maintained during 5 cycles,while 60%of activity is lost for the conventional analogue CaO/G due to the leaching of Ca.

Influence of the preparation method on the catalytic activity of Mg-Al hydrotalcites as solid base catalysts

Mg-Al hydrotalcites were synthesized using different preparation methods(a co-precipitation method, a urea method, and a simple one) to analyze their effect on the catalytic activity of these solid base catalysts. The method strongly affected the structure of their layers(e.g., the growth and stacking of the layers, and the type of intercalated anions) and, accordingly, their catalytic activity. The Mg-Al hydrotalcite prepared by co-precipitation showed the best catalytic performance in the isomerization of glucose into fructose, due to the small crystallite size and sand rose morphology enhancing the exposure of surface active sites to reactants.

Acetalization of carbonyl compounds with 2,2,4-trimethyl-1,3-pentanedio catalyzed by novel carbon based solid acid catalyst

The synthesis of 2, 4-diisopropyl-5,5-dimethy1- 1.3-dioxane through the acetalization of isobutyraldehyde with 2, 2, 4-trimethy1-1,3-pentanediol （TMPD） catalyzed by the novel carbon based acid was first carried out. High conversion （≥98%） and specific selectivity were obtained using the novel carbon based acid, which kept high activity after it was reused 5 times. Moreover. the catalyst could be used to catalyze the acetalization and ketalization of different aldehydes and ketones with superior yield. The yield of several products was over 90%. The novel heterogeneous catalyst has the distinct advantages of high activity, strikingly simple workup procedure, non-pollution, and reusability, which will contribute to the success of the green process greatly.

Wet carbon-based solid acid/NaNO_3 as a mild and efficient reagent for nitration of aromatic compound under solvent free conditions

Nitro aromatic compound can be obtained in high yields via nitration of aromatic compound with wet carbon-based solid acid and NaNO_3 under solvent free oxidation at room temperature.

Effect of solid-solution temperature on the microstructure of Fe-Ni based high strength low thermal expansion (HSLTE) alloy

The influence of solid-solution temperature on the dissolution of carbide precipitates, the average grain size and the microhardness of the austenite matrix in an Fe-Ni based high strength low thermal expansion （HSLTE） alloy was investigated to obtain the proper temperature range of the solid-solution process. The XRD analysis, microstructure observations, and the theoretical calculations showed that the Mo-rich M2C-type precipitates in the Fe-Ni based HSLTE alloy dissolve completely at about 1100℃. The average grain size of the studied alloys increases from 14 to 46 μm in the temperature range of 1050 to 1200℃. The microhardness of the matrix decreases gust for the sake of solid-solution treatment, but then increases later with increasing solution temperature because of the solution strengthening effect.

Wet carbon-based solid acid/potassium permanganate as an efficient heterogeneous reagents for oxidation of alcohols under mild conditions

Wet carbon-based solid acid and potassium permanganate were used as new reagents for oxidation of alcohols to their corresponding aldehydes and ketones in heterogeneous mixtures. The experiments were done moderately at mild condition and high yields in suitable times were obtained.

Formability of Rare Earth-Containing Solid Solution Based on Compounds with Scheelite-Type Structure

The regularities of the solid solutions between the scheelite-type compounds and rare earth molybdates or tungstates were investigated by the atomic parameter-support vector machine method and the intelligent database of phase diagrams of molten salt systems. The crystal structure of scheelite-type compounds having M^1M^′Ⅲ （XO4）2（X = Mo, W） as common formula and the formability of the continuous solid solution between these compounds and rare earth molybdates or tungstates were also investigated. Besides, the cell constants of these compounds can be calculated by some semi-empirical equations. Based on the obtained relationships, the results of computerized prediction of the solid solubility of T1Pr （MoO4）2-Pr2 （MoO4）3 system have good agreement with experimental results.

The Development of Gear Pump CAD/CAPP Based on Solid Works

Nowadays, many kinds of software, which have succes sf ully created the integration of CAD, CAPP and CAM, find their disadvantages in p ractical manufacturing. As a result, it is welcomed to develop small CAD/CAPP sy stems on a proper CAD platform, which aim at requirements of factories. Based on the one of the most popular three-dimensional design software SolidWorks, we successfully developed a set of gear pump CAD /CAPP software for Huaiyin Gene ral Factory of Mechanics. 1 The architecture and function of the software According to the need of the enterprises, the general structure of the software contain two subsystems, which are detailed as follows: · The gear pump CAD subsystem contains four main modules, including the optiona l design module of gear pump, module of part design, the module of entity modeli ng and the module of drawing which creates 2 D drawings of parts and assembly c orresponding 3 D modals. · The gear pump CAPP subsystem, which is a combination of creative mode and der ivate mode, also includes four modules, they are the module of access to feature s, the module of planning process route, the module of designing process sheets and the module of generating process documents. 2 The developing environment of the system Basing on Windows 98 and SolidWorks2001 platform, this system creates all functi ons by using Visual C++ 6.0 as developing tools. 3 The keys to the CAD/CAPP integration 3.1 The establishment of product information modal The information of parts is the basis of process planning. In this system, we us e feature modeling to describe the information of parts and assembly of gear pum p, and set up a fundamental basis for the whole system. The information module o f gear pump includes the information of both the assembly and the parts; the par t-describing module uses four-layer structure that is subassembly layer, part layer, feature layer and geometric layer. 3.2 The operation of the information on feature modeling After establishment of information mode of gear pump, the next key problem is ho w to transmit information of product to CAPP subsystem. In order to integrate pe rfectly, connecting CAD with CAPP directly can be a good method. In this system, all information of parts is store in the part drawing files, and the CAPP syste m can load these files to get information. The gear pumps, which are produced by Huaiyin General Factory of Mechanics, are usually belong to several similar typ es, and this means that most products possess large number of similar feature. T herefore, we can easily establish a specific feature for gear pump CAD/CAPP syst em. All parts are created by selecting these features and/or adding few special features. In the module of access to feature of CAPP subsystem, the main task is to find the features and the information will be easily got. 4 Conclusion This system successfully creates gear pump CAD/CAPP integration based on SolidWo rks. 3D CAD software provide more convenient platform for integration and will i nevitably become the mainstream of product design. By developing this system, we clearly realize the promising future of SolidWorks.

High-Efficiency Generation of 0.12 mJ, 8.6 Fs Pulses at 400 nm Based on Spectral Broadening in Solid Thin Plates

We demonstrate eftlcient generation of continuous spectrum centered at 40Ohm from solid thin plates. By frequency doubling of 0.8m J, 3Ors Ti：sapphire laser pulses with a BBO crystal, 0.2m J, 33fs laser pulses at 400nm are generated. Focusing the 400-nm pulses into 7 thin fused silica plates, we obtain 0.15mJ continuous spectrum covering 350-450 nm. After compressing by 3 pairs of chirped mirrors, 0. 12 m J, 8.6 fs pulses are achieved. To the best of our knowledge, this is the first time that sub-10-fs pulses centered at 400nm are generated by solid thin plates, which shows that spectral broadening in solid-state materials works not only at 800nm but also at different wavelengths.

Magnetic Field Measurement with Heisenberg Limit Based on Solid Spin NOON State

The maximum entangled number state （NOON state） can improve the sensitivity of physical quantity measure- ment to the Heisenberg limit 1/N. In this work, the magnetic field measurement based on the individual solid spin NOON state is investigated. Based on the tunable effective coupling coefficient, we propose a generation scheme of the three-spin NOON state, i.e, the Creenberger-Horne-Zeilinger （CHZ） state, and discussed the mea- surement resolution reduction due to decoherence. It is unnecessary to entangle spins as many as possible when decoherence exists. In practice, defect spins in diamond and alp donors with long coherence time can be applied with current techniques in the nano-scaled high resolution magnetic measurement.

Solid Solution Characteristics of Pb(B_(1/3)Nb_(2/3))O_(3)-based Composite Ceramics

The solid solution characteristics of Pb（B1/3Nb2/3）O3-based （B=Zn^2＋, Mg^2＋, Ni^2＋） composite ceramics prepared by two-phase mixed-sintering method were developed based on dielectric measurements. Results show that there are double dielectric peaks for PZN-based composite ceramic, implying two phases coexist. However single dielectric peak was presented in PMN- and PNN-based composite ceramics, respectively. It is indicated that obvious solid solution reaction exists during the sintering process of these two systems. The effects of B-site ion difference on the solid solution characteristics were discussed by crystal chemistry. SEM was employed to investigated the microstructures of composite ceramics. The influences of solid solution reaction on grain growth were discussed.

Study of Bi_2O_3-based Rare Earth Solid Electrolyte Used in Fuel Cell

Solid ceramic electrolyte materials (Bi_2O_3)_(0.75)(Y_2O_3)_(0.25) and(Bi_2O_3)_(0.65)(Gd_2O_3 )_(0.35)were synthesized.Their crystal structure, XPS spectra and the change of ionic conductivity versus temperature were measured.A Bi_2O_3-based rare earth solid electrolyte fuel cell with ZrO_2-Y_2O_3 protection film was made.

Amine-grafted on lanthanide metal-organic frameworks:Three solid base catalysts for Knoevenagel condensation reaction

A post-synthetic modification strategy has been used to prepare three solid base catalysts, including Er（btc）（ED）075（H2O）0.25 （2, btc = 1,3,5-benzenetricarboxylates, ED = 1,2-ethanediamine）, Er（btc）（PP）0.55（H20）0.45 （3, PP = piperazine）, and Er（btc）（DABCO）0.15（H2O）0.85 （4, DABCO = 1,4- diazabicyclo[2.2.2]octane）, by grafting three different diamines onto the coordinatively unsaturated Er（III） ions into the channels of the desolvated lanthanide metal-organic framework （Er（otc））. The resulting metal-organic frameworks were characterized by elemental analysis, thermogravimetric analysis, powder X-ray diffraction, and N2 adsorption. Based on its higher loading ratio of the diamine, as well as its greater stability and porosity, catalyst 2 exhibited higher catalytic activity and reusability than catalysts 3 and 4- for the Knoevenagel condensation reaction. The catalytic mechanism of 2 has also been investigated using size-selective catalysis tests.

Simulation of biodiesel industrial production via solid base catalyst in a fixed-bed reactor

Biodiesel industrial production based on a solid base catalyst in a fixed-bed was simulated. The lab and bench scale experiments were carded out effectively, in which the kinetic model is established and it can describe the transesterification reaction well. The Antoine equation of biodiesel is regressed with the vapor-liquid data cited of literature. The non-random two liquid （NRTL） model is applied to describe the system of fatty acid methyl ester （FAME）, methanol and glycerol and parameters are obtained. The Ternary phase map is obtained from Aspen Plus via the liquid-liquid equilibrium （LLE） data. In order to describe the production in a fixed-bed performs in industrial scale after being magnified 1 000 times, the Aspen Plus simulation is employed, where two flowsheets are simulated to predict material and energy consumption. The simulation results prove that at least 350. 42 kW energy consumption can be reduced per hour to produce per ton biodiesel compared with data reported in previous references.

Virtual population pharmacokinetic using physiologically based pharmacokinetic model for evaluating bioequivalence of oral lacidipine formulations in dogs

The aim of the present study was to investigate virtual population pharmacokinetic using physiologically based pharmacokinetic(PBPK) model for evaluating bioequivalence of oral lacidipine formulations in dogs. The dissolution behaviors of three lacidipine formulations including one commercial product and two self-made amorphous solid dispersions(ASDs)capsules were determined in 0.07% Tween 80 media. A randomized 3-period crossover design in 6 healthy beagle dogs after oral administration of the three formulations at a single dose of 4 mg was conducted. The PBPK modeling was utilized for the virtual bioequivalence study.In vitro dissolution experiment showed that the dissolution behaviors of lacidipine amorphous solid dispersions(ASDs) capsules, which was respectively prepared by HPMC-E5 or Soluplus, as polymer displayed similar curves compared with the reference formulation in 0.07% Tween 80 media. In vivo pharmacokinetics experiments showed that three formulations had comparable maximum plasma drug concentration(Cmax), and the time(Tmax) to reach Cmax of lacidipine tablet, which was prepared by Soluplus, as polymer was slower than other two formulations in consistency with the in vitro dissolution rate. The 90% confidence interval(CI) for the Cmax, AUC0–24 h and AUC0–∞ of the ratio of the test drug to the reference drug exceeded the acceptable bioequivalence(BE) limits(0.80–1.25). However, the 90% CI of the AUC0–24 h, AUC0–∞ and Cmax of the ratio of test to reference drug were within the BE limit,calculated using PBPK modeling when the virtual subjects reached 24 dogs. The results all demonstrated that virtual bioequivalence study can overcome the inequivalence caused by inter-subject variability of the 6 beagle dogs involved in in vivo experiments.

Solid base catalysts derived from Ca-M-Al(M = Mg, La, Ce, Y) layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol with propylene carbonate

Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffraction analyses of the catalysts show that all of the catalysts were in the form of composite oxides.Compared with the Ca‐Al LDH catalyst,the specific surface areas and pore volumes of the catalysts were increased with the introduction of Mg,La or Ce.The catalytic performance of these catalysts increases in the order of Ca‐Y‐Al<Ca‐Al<Ca‐Ce‐Al<Ca‐La‐Al<Ca‐Mg‐Al,which is consistent with the total surface basic amounts of these materials and the formation of especially strong basic sites following modification with Mg and La.The Ca‐Mg‐Al catalyst shows the highest(Ca+Mg):Al atomic ratio,indicating that it likely contains more unsaturated O2?ions,providing it with the highest concentration of very strong basic sites.The recyclability of these catalysts is improved following the addition of Mg,La,Ce or Y,with the Ca‐Mg‐Al maintaining a high level of activity after ten recycling trials.X‐ray diffraction analyses of fresh and used Ca‐Mg‐Al demonstrate that this catalyst is exceptionally stable,which could be of value in practical applications related to heterogeneous catalysis.

INVESTIGATION OF SURFACE MORPHOLOGY, STRUCTURE AND ELECTROCATALYTIC PROPERTIES FOR O_2 EVOLUTION OF TITANIUM BASED IrO_2+Ta_2O_5 COATINGS

Titanium based IrO2 +Ta2O5 oxide anodes with different compositions and pyrolysis temperatures were prepared by termodecompoisition method. By using X-ray diffraction (XRD), the structure and texture coefficient of the coatings, TC(hkl), of IrO2 rutile crystal have been tested. It showed that, the crystallization processes of IrO2 and Ta2O5 in xIrO2 +(100-x) Ta2 O5 (x is in mol%) films affected and confined each other.In the mixed system, IrO2 rutile phase existed as a solid solution with Ta, and attained the maximum solubility when x=70mol%, i.e. for the coating of 70% IrO2 +Ta2O5.For the coatings of low iridium content or at low preparing tem pemture, (110) and (101) pwtered orientations were dominant. However, preferred growth of IrO2 weakened with increasing either iridium content or temperature. Three typical surface morphologies were observed by using scanning electron tnicroscopy(SEM). The crystallite size of the mixed oxide coatings were finest for the the film of 70%IrO2 +30%Ta2O5,and decreased with the pyrolysis tempemture. As the results of the finest crystallite segregating on sudece and the maxitnum solid solubility of Ir and Ta component in deposits, the coatings with the composition of 70%IrO2 +Ta2O5 prepared at 450℃ presented the mdrimutn electrocatalgtic activitg for O2 evolution in 0. 5M H2SO4 solution.UP to 550℃, Ti base suffered to oxidation resulting in decreasing anode conductivity,therefore, coatings performed a low activity.

Laser cladding of Ni-based alloy on copper substrate

The laser cladding of Ni1015 alloy on Cu substrate was prepared by a high power continuous wave CO2 laser. Its microstructure was analyzed by optical microscope （OM）, scanning electron microscope （SEM）, and X-Ray diffraction （XRD）. The average microhardness of the cladding coating was Hv 280, which was almost three times of that of the Cu substrate （Hv 85）. OM and SEM observations showed that the obtained coating had a smooth and uniform surface, as well as a metallurgical combination with the Cu substrate without cracks and pores at the interface. With the addition of copper into the nickel-based alloy, the differences of thermal expansion coefficient and melting point between the interlayer and cladding were reduced, which resulted in low stresses during rapid cooling. Moreover, large amount of （Cu, Ni） solid solution formed a metallurgical bonding between the cladding coating and the substrate, which also relaxed the stresses, leading to the reduction of interfacial cracks and pores after laser cladding.

Electrochemical properties of TiV-based hydrogen storage alloys

The electrochemical properties of the super-stoichiometric TiV-based hydrogen storage electrode alloys(Ti 0.8Zr 0.2)(V 0.533Mn 0.107Cr 0.16Ni 0.2) x(x=2, 3, 4, 5, 6) were studied. It is found by XRD analysis that all the alloys mainly consist of a C14 Laves phase with hexagonal structure and a V-based solid solution phase with BCC structure. The lattice parameters and the unit cell volumes of the two phases decrease with increasing x. The cycle life, the linear polarization, the anode polarization and the electrochemical impedance spectra of the alloy electrodes were investigated systematically. The overall electrochemical properties of the alloy electrode are found improved greatly as the result of super-stoichiometry and get to the best when x=5.