Ni基催化剂催化燃油重整耦合选择性催化还原NOx反应

分别以La₂O₂CO₃, CeO₂, ZrO₂和Al₂O₃为载体, 采用浸渍法制备了Ni基重整催化剂, 并以正十二烷模拟车载燃油进行催化重整反应以同时制备小分子碳氢化合物(HCs)和H₂, 考察了其在4wt%Ag/Al₂O₃上选择性催化还原(HC-SCR)氮氧化物(NO_x)的性能. 采用N₂吸附-脱附、X射线粉末衍射、H₂程序升温还原和热重等手段对Ni基催化剂进行了表征. 结果表明, 随着重整催化剂氧化还原性能增强, 产物中H₂浓度增加, 可参与SCR反应的HCs含量减少, 从而导致重整-SCR耦合体系上NO_x净化活性温度窗口向低温移动, NO_x最高转化率降低. Ni/ZrO₂+Ag/Al₂O₃耦合体系中H₂/HCs符合SCR反应所需的最优比例, 在柴油车典型排气温度范围内表现出良好的NO_x净化能力. 同时, 在Ni/ZrO₂+Ag/Al₂O₃耦合体系上考察了其燃油重整-SCR的活性稳定性. 结果显示, 重整催化剂的耐久性有待进一步提高.     

Synthesis and Crystal Structure of a B-H Activated Compound Containing a Furan Ring and an ortho-Carborane Cage

A new compound [CpCo（Se2C2BIoH9）CH2C（O）C4H30] has been synthesized and characterized by elemental analysis, IR spectroscopy, NMR, MS and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group P21/c with a = 10.9481（10）, b = 24.6600（12）, c = 25.7430（14） A, β = 100.863（3）°, C42H57B30Co306Se6＂CH2C12＂0.25H20, Mr = 1722.16, V = 6825.6（8） A3, Dc= 1.676 g/cm3, Z = 1 and F（000） = 3346. The molecular structure shows a 1：1 ratio product of the two reactants of 16e half-sandwich complex CpCo（Se2C2B10H10） and alkyne 1-（2-furyl）-2-propyn-l-one. The hydrogen atom in the B（3） position of CpCo（Se2C2B10HIo） has been activated and migrated to the terminal carbon of 1-（2-furyl）- 2-propyn-l-one to form the B-CH2 unit. The title compound molecules are linked and extended further into a one-dimensional chain through atypical hydrogen bonds.     

Synthesis, Structure and Properties of a Novel Cobalt(Ⅱ) Bromide Complex Supported by Phosphine Ligands

<正>The C-Br bond of 2-bromothiophene was successfully cleavaged by tetrakis(trimethylphosphine)cobalt(0). Penta-coordinate cobalt(II) bromide complex 1 (α-C_4H_3S)CoBr(PMe_3)_3 as C-Br bond activation product was obtained. The molecular and crystal structures of complex 1 were determined by single-crystal X-ray diffraction. Complex 1 belongs to the orthorhombic crystal system, space group Pnma with a = 20.428(4) , b =11.036(2) , c = 9.201(2), V = 2074.3(7)~3, Z = 4, D_c = 1.442 g/cm~3, μ = 0.401 mm~(-1), F(000) = 924 and T = 273 K. Complex 1 was also characterized by elemental analysis, IR, UV-Vis, photoluminescence (PL) spectroscopy and TGA.     

Crowding effect induced phase transition of amphiphilic diblock copolymer in solution

The crowding agent induced phase transition of amphiphilic block copolymers in solution was explicitly considered. The influence of the size and the volume fraction of the crowding agent on the phase separation of amphiphilic diblock copolymers is investigated by using self-consistent field theory (SCFT) method. The concentration of the disorder to order transition of the block copolymer decreases when the size of the crowding agent is larger than that of the solvent. The higher volume fraction of the crowding agent will induce the transition of the block copolymer from disorder to order state at a lower concentration. The relation between the size and the volume fraction of the crowding agent is elucidated. When the size of the crowding agent is larger, its volume fraction of the disorder to order transition of the block copolymer will be lower. The conformation of the crowding agent considered as a polymer chain is also studied and compared.     

Thin-film polymerization and characterization of Sumitomo's Sumikasuper®-type liquid crystalline polymers

Using the thin film polymerization approach, we have studied the texture evolution when synthesizing a novel liquid crystalline polymer (LCP) system based on Sumikasuper^® LCPs. The main monomers used were p-acetoxybenzoic acid (ABA), 4,4′-biphenol (BP), isophthalic acid (IA), phthalic acid (PA) and terephthalic acid (TA). Polarizing optical microscopy (POM), FTIR, X-ray diffraction (XRD) and atomic force microscopy (AFM) were employed to study the thin film polymerization process and characterize the products. The generation and evolution of liquid crystal phases were monitored; the results revealed that there exists a composition range for the monomers to react and form liquid crystal materials. The critical temperature for LC formation in ABA/BP/IA system decreased with increasing ABA content. FTIR results confirmed the formation of polymers. AFM investigation suggested a similar process of morphological change to that observed using POM. An increasing surface roughness of the thin films with the progress of polymerization was also obtained from AFM analysis. A nematic LC texture of the polymer system was suggested by XRD examination. Results obtained by replacing BP with acetylated BP, and by conducting polymerization using two-monomer systems, suggest that BP units are included in polymers obtained by the thin film polymerization method.     

Analysis of cell gap-dependent driving voltage in a fringe field-driven homogeneously aligned nematic liquid crystal display

We have studied cell gap-dependent driving voltage characteristics in a homogeneously aligned nematic liquid crystal (LC) cell driven by a fringe electric field, termed the fringe field switching (FFS) mode. The results show that for the FFS mode using a LC with positive dielectric anisotropy, the operating voltage decreases as the cell gap decreases, whereas it increases with a decreasing cell gap when using a LC with negative dielectric anisotropy. The difference between LCs is explained by simulation and experiment.     

Flow-induced ordering of particles and flow velocity profile transition in a tube flow of graphene oxide dispersions

We measured the S- and P-order parameters of flow-induced ordered graphene oxide (GO) particles and the flow velocity profiles for a flowing aqueous GO dispersion in a tube, by using an optical method. The order parameters clearly exhibit increasing concentric biaxial ordering as the flow velocity increases, with the exception of a disordered centre. Newtonian to non-Newtonian transition in the flow velocity profile is found, changing from a parabolic shape to a fuller shape at very low Reynolds numbers less than 10. This is attributed to the shear thinning effect (i.e., an ordering-induced reduction in viscosity). In the Newtonian flow, a uniaxial ordering was dominant; whereas a biaxial ordering sharply increased in the non-Newtonian flow, indicating that both the ordering of GO particles and the interparticle interactions influence the flow profile transition.     

Orientational ordering in the nematic phase of 4-alkyl-4'-cyanobicyclohexanes

The orientational ordering of three liquid crystals (trans,trans-4-n-alkyl-4'-cyanobicyclohexanes) has been investigated using ¹³C NMR. 2D proton-encoded local field spectroscopy was used to determine the ¹³C-¹H dipolar coupling constants, from which the order parameters were calculated. Semi-empirical linear relations between the obtained order parameters and anisotropic ¹³C chemical shifts were established. It was found that the order parameters of the major axis of the cyclohexane rings are smaller than those of liquid crystals with phenyl rings, and the order parameters of the C-H bonds in the aliphatic chains also behave differently.     

Effect of electron donor-acceptor interaction on the thermal stability of supramolecular side chain liquid crystalline polymers based on poly(3-carboxypropylmethylsiloxane)

Supramolecular side chain liquid crystalline polymers were prepared from poly(3-carboxypropylmethylsiloxane) (PSI100) and azobenzene-based derivatives through intermolecular hydrogen bonding between the carboxylic acid groups of PSI100 and the imidazole rings in the azobenzene-based derivatives. The presence of H-bonding was confirmed using FTIR spectroscopy. The polymeric complexes behave as liquid crystalline polymers and exhibit nematic mesophases identified on the basis of the observation of Schlieren textures. The mesogenic behaviour of these complexes was studied by polarizing optical microscopy and X-ray diffraction. The thermal behaviour of the complexes was investigated by differential scanning calorimetry. On increasing the spacer length, the transition temperatures initially increase. A further increase in spacer length, however, leads to a decrease in the transition temperatures. The electron donor-acceptor interaction between unlike mesogenic units in supramolecular copolymeric complexes helps to stabilize the mesophase.     

Preparation of macroporous polyHIPE foams via radiation-induced polymerization at room temperature

PolyHIPEs are highly porous, crosslinked polymer foams typically synthesized within high internal-phase emulsions (HIPEs). Two kinds of polyHIPEs including poly(styrene-divinylbenzene) [P(St-DVB)] and poly(methyl methacrylate-divinylbenzene) [P(MMA-DVB)] foams are synthesized in this work, which are fabricated from HIPEs template via radiation-induced polymerization at room temperature. Traditional free radical polymerization initiated by potassium peroxydisulfate (KPS) at 60 °C for producing polyHIPE P(St-DVB) foams is also conducted for comparison. It is found that the amount of emulsifier can be reduced greatly in the radiation-induced polymerization of HIPEs at room temperature, compared with the traditional polymerization approach. Besides, P(MMA-DVB) PolyHIPE foams with a fine microstructure of highly interconnected pores have been successfully fabricated via radiation-induced polymerization in this work, which is usually difficult to be prepared by thermal-initiation method because of the intermediate hydrophobicity of methyl methacrylate monomer. The influences of the fraction of internal aqueous phase and the concentration of emulsifier on the structure and performance of foams are carefully explored. The structure and compression strength of the foams are characterized by scanning electron microscopy and a mechanical testing machine, respectively.