钌多氢化合物的低温FTIR光谱研究

在氢气氛下合成了新化合物Ｒｕ２Ｈ４（ＣＯ）（ＰＰｈ３）４，建立了可至液氮温度的原位红外测试装置，在室温至液氮温度下进行了钌多氢化合物的结构研究。发现ＲｕＨ４（ＣＯ）（ＰＰｈ３）３在室温下会发生分子氢与原子氢的结构流变。

多氢键反应-纳米金共振散射光谱法测定三聚氰胺

在pH 7.0的磷酸盐缓冲溶液中,氯金酸被3,5-二羟基苯甲酸(DBA)还原生成的金纳米粒子在610nm处产生一个较强的共振散射峰;当有三聚氰胺(MA)存在时,DBA与MA形成多氢键化合物而不能还原氯金酸,导致610 nm处共振散射峰的强度降低。三聚氰胺的浓度在5.0×10-6～4.0×10-5 mol.L-1范围内与该共振散射峰强度的降低值(ΔI610nm)呈良好线性,其相关系数为0.996 8。该方法可用于牛奶样品中三聚氰胺的检测。

Ni@Pd core-shell nanoparticles supported on a metal-organic framework as highly efficient catalysts for nitroarenes reduction

Ni@Pd core-shell nanoparticles with a mean particle size of 8–9 nm were prepared by solvothermal reduction of bivalent nickel and palladium in oleylamine and trioctylphosphine.Subsequently,the first-ever deposition of Ni@Pd core-shell nanoparticles having different compositions on a metal-organic framework（MIL-101）was accomplished by wet impregnation in n-hexane.The Ni@Pd/MIL-101 materials were characterized by powder X-ray diffraction,Fourier transform infrared spectroscopy,transmission electron microscopy,and energy-dispersive X-ray spectroscopy and also investigated as catalysts for the hydrogenation of nitrobenzene under mild reaction conditions.At 30 °C and 0.1 MPa of H2 pressure,the Ni@Pd/MIL-101 gives a TOF as high as 375 h–1 for the hydrogenation of nitrobenzene and is applicable to a wide range of substituted nitroarenes.The exceptional performance of this catalyst is believed to result from the significant Ni-Pd interaction in the core-shell structure,together with promotion of the conversions of aromatics by uncoordinated Lewis acidic Cr sites on the MIL-101 support.

Preparation and characterization of MWCNTs/LDHs nanohybrids for removal of Congo red from aqueous solution

The assembly of layered double hydroxides （LDHs） and multi-walled carbon nanotubes （MWCNTs） nanohybrids was prepared as MWCNTs/LDHs by co-precipitation. The synthesized nanoparticles were characterized by using XRD, FT-IR, SEM/EDX, TGA and BET. XRD and SEM studies proved that MWCNTs phases did not enter into the interlayers of LDHs, they dispersed over the LDHs surface homogeneously. BET results showed that MWCNTs/LDHs possessed hierarchically porous nanostructure with large surface area （124.974 m^2/g） and great pore volume （0.604 cm^3/g）. Batch experiments were conducted to study the adsorption efficiency of Congo red （CR）. It was worthy to note that MWCNTs/LDHs exhibited excellent adsorption performance with the maximum CR adsorption capacity of 595.8 mg/g in weak acidic environment. The adsorption kinetics and isotherm parameters can be well described by the pseudo-second-order and the Langmuir isotherm models, respectively. The thermodynamic studies indicated that the adsorption process was spontaneous and endothermic.

A New Method for Hydrocarbon Detection Based on Multi-phase Theory

The hydrocarbon detection techniques used currently are generally based on the theory of single-phase medium, but hydrocarbon reservoir mostly is multi-phase medium, therefore, multisolutions and uncertainties are existed in the result of hydrocarbon detection. This paper presents a fast way to detect hydrocarbon in accordance with BOIT theory and laboratory data. The technique called DHAF technique has been applied to several survey area and obtained good result where the coincidence rate for hydrocarbon detection is higher than other similar techniques. The method shows a good prospect of the application in hydrocarbon detecting at exploration stage and in reservoir monitoring at production stage.

具有吸附重金属功能的聚醚砜滤芯的制备研究

目的:以聚乙二醇多氢键功能化合物为改性剂制备改性聚醚砜滤芯,增加滤芯水通量,增加滤芯去除药液中重金属的功能。方法:用改性剂改性聚醚砜,用熔融共混法制备了改性材料和改性滤芯。结果:改性聚醚砜滤芯水通量可达到96.03 L/(m^(2)·h),改性滤芯循环使用批次可达到50批,寿命大大延长。结论:改性聚醚砜滤芯水通量高,能有效截留注射液中的重金属离子,能再生循环使用,生产成本低。

Cloud Point Extraction of Polycyclic Aromatic Hydrocarbons in Aqueous Solution with Silicone Surfactants

Cloud point extraction （CPE） processes with two silicone surfactants, Dow Coming DC-190 and DC-193, were studied as preconcentration and treatment for the water polluted by three trace polycyclic aromatic hydrocarbons （PAHs）： anthracene, phenanthrene and pyrene. For all cases, the volumes of surfactant-rich phase obtained by two silicone surfactants were very small, i.e. a lower water content in the surfactant-rich phase was obtained. For example, less than 3% of the initial solution was obtained in a 1% （by mass） surfactant solution, which was much smaller than that of TX-114 in the same surfactant concentration. And TX-114 is known as a high compact surfactant-rich phase among most nonionic surfactants, thus the comparison showed that an excellent enrichment was ensured in the analysis application by the CPE process with the silicone surfactants, and the lower water content obtained in the surfactant-rich phase is also important in the large scale water treatment. The influences of additives and phase separation methodology on the recovery of PAHs were discussed. Comparing with DC-193, DC-190 has a lower cloud point and a higher recovery （near 100%） of all the three PAHs in same surfactant concentration, which was required for application as a preconcentration process prior to HPLC system. However the DC-190 solution is hard to be phase separated only by heating, whereas DC-193 has a relative higher phase separating speed by heating, but a high cloud point （around 360K） limits its application. Due to the phase separation by heating is the only method of CPE suitable to the large scale water treatment, the mixtures of two silicone surfacrants solutions were investigated in this study. A solution containing 1% of mixed DC-190 and DC-193 （in the ratio of 90 ： 10） removed anthracene, phenanthrene and pyrene near 100% with a relative low cloud point and quick phase separating speed.

Quantum Chemistry of PAHs Thermal Cracking with Different Hydrogenation Degree

In order to investigate the influence of hydrogenation degree and structural variety on reaction trend of polyaro- matic hydrocarbons (PAHs) in resins and asphaltenes portion of heavy oil, a series of PAHs with different hydrogenation degree were selected as model compounds to simulate their different hydrogenation stage, and the PAHs thermal cracking reaction was simulated based on free radical mechanism by the density functional theory (DFT) to search for reactions'transition state. By comparing the dynamic data obtained from reaction simulation, it is showed that processing difficulty could rise with increasing condensed aromatic ring number, and hydrogenation could promote ring cleavage reaction, but excessive hydrogenation would decrease the oil conversion rate to reduce light-end products. In conclusion, proper hydrogenation was quite critical in promoting light-end products conversion efficiency and saving the processing cost as well. Operational instructions were given based on both PAHs hydrogenation performance and conclusions were drawn up from reaction simulation results.

Synthesis of Bisphenols Carrying Long Hydrocarbon Side Chains

Bisphenols containing long aliphatic hydrocarbon side chains were synthesized by the condensation of phenol with aldehyde or ketone in the presence of heteropolyacid. Their structures were characterized by IR, 1H NMR, 13C NMR and element analysis. The experiment results show that when heteropolyacid was used as a catalyst, these bisphenols were obtained in high selectivity and high yields.

Synthesis of polymer/CNTs composites for the heterogeneous asymmetric hydrogenation of quinolines

The development of heterogeneous catalytic processes is crucial for the synthesis of chiral compounds for both academic and industrial applications.However,thus far,such achievements have remained elusive.Herein,we report the heterogeneous asymmetric hydrogenation of 2-methylquinoline over solid chiral catalysts,which were prepared by the one-pot polymerization of(1R,2R)-N-(4-vinyl-benzenesulfonyl)-1,2-diphenylethane-1,2-diamine(VDPEN)and divinylbenzene(DVB)in the presence or absence of activated carbon(C)or carbon nanotubes(CNTs),followed by Ru coordination and anion exchange.The solid chiral catalysts were fully characterized by N2 sorption analysis,elemental analysis,TEM,FT-IR spectroscopy,and 13C CP-MAS NMR.All the solid chiral catalysts could efficiently catalyze the asymmetric hydrogenation of 2-methylquinoline to afford 2-methyl-1,2,3,4-tetrahydroquinoline with 90%ee.Studies have shown that polymer/C and polymer/CNTs composites are more active than pure polymers.The polymer/CNTs composite exhibited the highest activity among all the solid chiral catalysts under identical conditions,owing to the unique morphology of CNTs.The recycling stabilities of the solid chiral catalysts were greatly improved when ionic liquids(ILs)were employed as solvents;this is mainly attributed to the decreased leaching amount of anions owing to the confinement effect of ILs on ionic compounds.

Tracing Changes in the Microbial Community of a Hydrocarbon-Polluted Soil by Culture-Dependent Proteomics

Hydrocarbon contamination may affect the soil microbial community, in terms of both diversity and function. A laboratory experiment was set-up, with a semi-arid control soil and the same soil but artificially contaminated with diesel oil, to follow changes in the dominant species of the microbial community in the hydrocarbon-polluted soil via proteomics. Analysis of the proteins extracted from enriched cultures growing in Luria-Bertani （LB） media showed a change in the microbial community. The majority of the proteins were related to gIycolysis pathways, structural or protein synthesis. The results showed a relative increase in the complexity of the soil microbial community with hydrocarbon contamination, especially after 15 days of incubation. Species such as Ralstonia solanacearum, Synechococcus elongatus and different Clostridium sp. were adapted to contamination, not appearing in the control soil, although Bacillus sp. dominated the growing in LB in any of the treatments. We conclude that the identification of microbial species in soil extracts by culture-dependent proteomics is able to partially explain the changes in the diversity of the soil microbial community in hydrocarbon polluted semi-arid soils, but this information is much more limited than that provided by molecular methods.

EPR and DFT Study of the Polycyclic Aromatic Radical Cations from Friedel-Crafts Alkylation Reactions

Electron paramagnetic resonance and electron-nuclear double resonance methods were used to study the polycyclic aromatic radical cations produced in a Friedel-Crafts alkylating sys- tem, with m-xylene, or p-xylene and alkyl chloride. The results indicate that the observed electron paramagnetic resonance spectra are due to polycyclic aromatic radicals formed from the parent hydrocarbons. It is suggested that benzyl halides produced in the Friedel-Crafts alkylation reactions undergo Scholl self-condensation to give polycyclic aromatic hydrocar- bons, which are converted into corresponding polycyclic aromatic radical cations in the presence of AlCl3. The identification of observed two radicals 2,6-dimethylanthracene and 1,4,5,8-tetramethylanthraeene were supported by density functional theory calculations using the B3LYP/6-31G（d,p）//B3LYP/6-31G（d） approach. The theoretical coupling constants support the experimental assignment of the observed radicals.

Correlation of Critical Loci for Water-Hydrocarbon Binary Systems by EOS Based on the Multi-Fluid Nonrandom Lattice Theory

Quantitative representation of complicated behavior of fluid mixtures in the critical region by any of equation-of-state theories re-mains as a difficult thermodynamic topics to date. In the present work, a computational efforts were made for representing various types of critical loci of binary water with hydrocarbon systems showing Type II and Type III phase behavior by an elementary equation of state [called multi-fluid nonrandom lattice fluid EOS (MF-NLF EOS)] based on the lattice statistical mechanical theory. The model EOS requires two mo-lecular parameters which representing molecular size and interaction energy for a pure component and single adjustable interaction energy pa-rameter for binary mixtures. Critical temperature and pressure data were used to obtain molecular size parameter and vapor pressure data were used to obtain interaction energy parameter. The MF-NLF EOS model adapted in the present study correlated quantitatively well the critical loci of various binary water with hydrocarbon systems.

Single-atom Fe with Fe_(1)N_(3) structure showing superior performances for both hydrogenation and transfer hydrogenation of nitrobenzene

The design of non-noble metal heterogeneous catalyst with superior performance for selective hydrogenation or transfer hydrogenation of nitroarenes to amines is significant but challenging.Herein,a single-atom Fe supported by nitrogen-doped carbon(Fe_(1)/N-C)catalyst is reported.The Fe_(1)/N-C sample shows superior performances for the selective hydrogenation and transfer hydrogenation of nitrobenzene to aniline at different temperatures.Density functional theory(DFT)calculations show that the superior catalytic activity for the selective hydrogenation at lower temperatures could be attributed to the effective activation of the reactant and intermediates by the Fe_(1)/N-C.Moreover,the excellent performance of Fe_(1)/N-C for the selective transfer hydrogenation could be attributed to that the reaction energy barrier for dehydrogenation of isopropanol can be overcome by elevated temperatures.