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1.
The dipping method was devised to deposit Pd onto carbon nanotube as supported catalyst(Pd/CNT) for the copolymerization of carbon monoxide(CO) and styrene(ST) towards the formation of polyketone(PK).The Pd/CNT was characterized by X-ray photoelectron spectroscopy(XPS),X-ray diffraction(XRD) and high-resolution transmission electron microscopy(HRTEM).The construction and crystallization property of PK were evaluated by Fourier transform infrared spectroscopy(FTIR),13C-nuclear magnetic resonance(NMR) and XRD,respectively.The catalyst showed excellent activity and reusability in promoting the fabrication of PK.It can be recycled 14 times with the highest total catalytic activity of 4 239.64 gPK/(gPd·h) at Pd content of 8.63wt%.The results indicate that the prepared catalyst is effective to catalyze the copolymerization of CO and styrene. 相似文献
2.
《天津大学学报(英文版)》2015,(5)
A series of 4,4'-disubstituted-[2,2']-bipyridines, featuring electron withdrawing/donating functional groups such as amino, chloro, nitro, ethoxycarbonyl, carboxy, methyl, methoxy and hydroxymethyl, have been synthesized and employed in the copolymerization of carbon monoxide(CO)and styrene. The available bipyridine and its derivatives were coordinated with palladium(Ⅱ)acetate for catalyzing the copolymerization of CO and styrene, and the concomitant polyketone was characterized by means of 13 C NMR, FTIR, differential scanning calorimetry(DSC)and element analysis techniques concerning its structure and thermal performance. The effect of different electron-donating and electron-withdrawing groups on catalyst performance and molecular weight of copolymer was studied under certain experimental condition. It has been proved that the enhancement of electron donating and conjugative effects on bipyridine ligand will not only improve the catalytic activity of the composition, but also increase the molecular weight of the as-prepared polyketone. The catalytic activity is the highest in hydroxymethyl substituted 2,2'-bipyridine ligand(1 356 g STCO/(g Pd · h)), when the molecular weight and polydispersity index of the polyketone are M n=8 502,M w=1 3440 and M w/M n=1.581, respectively. 相似文献
3.
N-valeronitrile-N’-methylimidazolium hexafluorophosphate ([C 4 CNmim]+ PF 6),as a novel ionic liquid with polar nitrile functional group,was prepared.The structure of the ionic liquid was characterized by using IR and 1 H NMR.As a medium,the ionic liquid plays an important role in copolymerization of carbon monoxide (CO) with styrene (St).Some synthetic conditions were determined,including the usage of ionic liquid,palladium composite catalyst and methanol,CO pressure,reaction time and reaction temperature.The influence of these factors on catalytic activity was analyzed.The results show that the catalytic activity has reached 1 724.1 gStCO/(gPd·h) and the catalyst could be reused 5 times under the optimal condition:composite catalyst 0.015 mmol,ionic liquid 3 mL,methanol 0.75 mL,CO pressure 2MPa,reaction time 2 h and reaction temperature 70℃.This CO/St copolymerization within [C 4 CNmim]+ PF 6 system could facilitate ionic liquids with efficient and economical applications to polymeric materials. 相似文献
4.
Hydantoinase and N-carbamoylase play important roles in the production of optically pure amino acids from racemic 5-monosubstituted hydantoins. In this report, hydantoinase and the N-carbamoylase from Burkholderia cepecia, njut01 were purified to homogeneity by chromatography (Pharmacia Explorer 100 system). The substrate specificity, enantioselectivity, pH dependence of activity and temperature stability of the activity were characterized. The results show that the hydantoinase and N-carbamoylase induced from Burkholderia cepecia, njut01 are both strict D-stereo selective enzymes. They both hydrolyze substrates with side chains containing aliphatic and aromatic residues with higher activity and affinity toward aromatic than aliphatic substituted substrates. The hydantoinase is a homotetramer with subtmit molecular weight near 52,000 and is active between pH 6.5 and 10 with an optimum near pH 9.0. The enzyme is active at temperatures up to 60~C, however, it appears instable at higher temperatures. The subunit molecular weight of N-carbamoylase is about 35KD. The N-carbamoylase is active in the pH range from 6.0 to 9.5. The optira-pH is 7.2 and the optinfizing bioconversion temperature of the N-carbamyolase is 52℃. 相似文献
5.
To lower the cost of polyketone synthesis, rare earth coordinate catalyst was introduced to the copoiymerization of carbon monoxide (CO) and styrene (ST) to synthesize aliphatic polyketone STCO. The catalytic system was composed of rare earth neodymium acetate, yttrium acetate, 2,2'-bipyridine, p-toluensulfonic acid, cupric p-toluensulfonate, and 1,4-benzoquinone. The catalyst and the copolymer were characterized by infrared spectrum and X-ray photoelectron spectrosco py respectively. The effects of each component of catalytic system and the kinds of rare earth acetates on catalytic activity of copoiymerization were investigated. The results show that the proposed rare earth has distinct catalytic activity in the copoiymerization of CO and ST and the maximum activity can reach 303.3 gSTCO/(mol·h). 相似文献
6.
A variety of barium sulfate （BaSO4） carriers with or without mesopore structure were synthesized via precipitation reaction in aqueous solution of barium hydroxide and sulfuric acid with ethylene glycol as a modifying agent, and then calcined at various temperatures. The obtained BaSO4 was used as catalyst carriers for polystyrene （PS） hydrogenation, and BaSO4 supported palladium （Pd） catalysts with Pd content of 5wt% were prepared by using impregnation method. N2 physisorption, transmission electron microscopy, X-ray diffraction and kinetics studies were used to investigate the effect of carrier structure on the dispersion and geometric location of active metal and their catalytic activities in PS hydrogenation. It was found that the pore structure of carrier played an important role in the dispersion and location of Pd grains. The activation energy values for all the Pd/BaSO4 catalysts were around 49.1 kJ/mol, while the pre-exponential factor for Pd/BSC-6H was much higher than others. The Pd/BSC-6H without mesopores had Pd grains deposited on the external surface of the carrier, and exhibited better activity than the mesoporous catalysts. It is indicated that the utilization of Pd/BSC-6H can reduce the pore diffusion of PS coils and enabled more active sites to participate in the PS hydrogenation. 相似文献
7.
《浙江大学学报(A卷英文版)》2021,(2)
Pyrolysis is a cost-effective and safe method for the disposal of radioactive spent resins. In this work, the catalytic effects of V_2O_5 on the pyrolysis of cation exchange resin are investigated for the first time. The results show that it is a better catalyst than others so far studied and achieves a lowering of final pyrolysis temperature and residual rate simultaneously when aided by physical blending. The maximum reductions of the final pyrolysis temperature and the residual rate are 173 ℃ and 11.9%(in weight), respectively. Under the action of V_2O_5, low-temperature(445℃) removal of partial sulfonic acid groups occurs and the pyrolysis of the resin copolymer matrix is promoted. This is demonstrated by the analysis of pyrolysis residues at different temperatures by X-ray photoelectron spectroscopy(XPS) and element analysis. The catalytic activity of V_2O_5 is determined by effects both at acid sites and oxidation-reduction centers via H_2-TPR(temperature programmed reduction), O_2-TPD(temperature programmed desorption), CO_2-TPD, and NH_3-TPD. The catalytic effect of oxidation-reduction centers in V_2O_5 is achieved by close contact with the sulfur bond through chemisorption under the effect of acid sites. V_2O_5 is also believed to be the reason for the removal of partial sulfonic acid groups at lower temperatures(445℃). V_2O_5 is an effective catalyst for spent resin pyrolysis and can be further applied in industry. 相似文献
8.
Acrylonitrile(AN)/1-vinyl-3-ethylimidazolium bromide(VIMB) copolymer was prepared via solution polymerization using dimethyl sulfoxide(DMSO) as a solvent and azodiisobutyronitrile as an initiator. The effects of comonomer VIMB on the polymerization, rheological properties of the polymer solution and thermal properties of the copolymer were investigated. The ionic liquid VIMB resulted in higher polymerization conversion ratio and higher average molecular weight when copolymerized with AN than itaconic acid(ITA). Rheological measurements indicated that the transition shear rate increased linearly with increasing temperature for P(AN/ITA)/DMSO solution, while an exponential growth with temperature was observed for P(AN/VIMB)/DMSO solution. The exothermic peaks of DSC curves in N_2 appeared at 276.67 and 257.34 °C for P(AN/VIMB) and P(AN/ITA), respectively. As a potential comonomer of AN for PAN carbon fibers, the VIMB resulted in about 7% higher char yield in N_2, and 23.7% less weight loss at 600 °C in air than ITA copolymer. 相似文献
9.
A new supported amorphous catalyst CoP/TiO2 was prepared by chemical reduction and characterized by ICP, XRD, TEM, BET and DSC Its application in decomposing PH3 to high purity phosphor and its catalytic activity were studied. The decomposition rate is over 95% at 450 ℃. For comparison, unsupported CoP amorphous catalyst was prepared by the same method. The result suggests that CoP/TiO2 exhibits higher thermal stability and catalytic activity than CoP, which is attributed to the high dispersion of CoP alloy particles on the support-TiO2. 相似文献
10.
In this study,Pd-Mg(Al)-LDH/γ-Al_2O_3 and Pd-Mg(Al)Zr-LDH/γ-Al_2O_3 precursors were synthesized by impregnating Na_2PdCl_4 on Mg(Al)-LDH/γ-Al_2O_3 and Mg(Al)Zr-LDH/γ-Al_2O_3,and then the precursors were calcinated and reduced to obtain Pd-Mg(Al)-MMO/γ-Al_2O_3 and Pd-Mg(Al)Zr-MMO/γ-Al_2O_3 catalysts.Compared with Pd/γ-Al_2O_3 catalyst,the hydrogenation efficiency of Pd-Mg(Al)-MMO/γ-Al_2O_3 and Pd-Mg(Al)Zr-MMO/γ-Al_2O_3 increased by 15.7%and 24.0%,respectively.Moreover,the stability of Pd-Mg(Al)Zr-MMO/γ-Al_2O_3 catalyst was also higher than that of Pd/γ-Al_2O_3.After four runs,the hydrogenation efficiency of Pd/γ-Al_2O_3 decreased from 12.1 to 10.0 g/L,while that of Pd-Mg(Al)Zr-MMO/γ-Al_2O_3 decreased from 15.0 to 14.3 g/L.The active aquinones selectivities of all catalysts were almost 99%.The structures of the catalysts were characterized by X-ray diffraction (XRD),scanning electron microscopy (SEM),N_2 adsorption-desorption,inductively coupled plasma-atomic emission spectrometry (ICP-AES),CO chemisorption analysis,transmission electron microscopy (TEM),temperature-programmed reduction with hydrogen (H_2-TPR),and X-ray photoelectron spectroscopy(XPS).The results indicate that the improved catalytic performance is attributed to the stronger interaction between Pd and Mg(Al)Zr-MMO/γ-Al_2O_3,smaller Pd particle size and higher Pd dispersion.This work develops an effective method to synthesize highly dispersed Pd nanoparticles based on the layered double hydroxides (LDHs) precursor. 相似文献
11.
Carbon encapsulated iron nanoparticles(CEINPs) with very thin shells and good core-shell structures were prepared by DC arc discharge at argon intake temperature(AIT) of 800 ℃. The results of high resolution transmission electron microscope(HRTEM), energy dispersive X-ray(EDX) spectroscope, X-ray diffraction(XRD), and X-ray photoelectron spectroscope(XPS) characterizations on the product B show that the thickness of the carbon shells of CEINPs in the product B is in the range of ca. 0.5—5.3 nm, i. e., which can be as thin as only two layers of graphite. The average diameter of the CEINPs is about 24. 7 nm. The total content of Fe element in the product B is 77.0 wt%. The saturation magnetization(Ms) and coercivity(Hc) of the product B are 107.4 emu/g and 143 Oe, respectively. The formation of the CEINPs in the product B is discussed briefly. 相似文献
12.
采用诱导法制备空心三元PdPtCu纳米材料,利用透射电镜(TEM)、扫描电镜(SEM)和X射线衍射(XRD)对其形貌、组成和结构进行表征,并在碱性条件下测试其对乙醇氧化的电催化性能。结果表明,以氧化铜为诱导剂制备的三元PdPtCu纳米材料主要呈空心结构,且其形貌和组成可控;Pd3Pt@Cu,PdPt@Cu和PdPt3@Cu三种材料的质量电流密度分别为8 510 A·g-1,9 270 A·g-1和5 490 A·g-1,无论是质量活性还是稳定性,均明显优于商业Pd/C和商业Pt/C催化剂。 相似文献
13.
The solubilities of 2-naphthalenesulfonic acid monohydrate and sodium 2-naphthalenesulfonate in sulfuric acid solutions were measured at temperatures ranging from 278.15 to 338.15 K by using a dynamic method. The concentration of sulfuric acid solution ranged from 0 to 80wt%,. The solubilities of 2-naphthalenesulfonic acid monohydrate and sodium 2-naphthalenesulfonate increased with temperature, and both of them were the lowest at 70wt %, of sulfuric acid solution(w~0_3 =0.70)while the highest in pure water. The solubility data were correlated by the modified Apelblat equation. Based on the solubility difference between 2-naphthalenesulfonic acid monohydrate and sodium 2-naphthalenesulfonate, a new technique in which sodium sulfate was used to replace sodium sulfite in the neutralization reaction was developed. The suitable mole ratio of H_2O to Na_2SO_4 in the neutralization reaction was 80∶1, and that of 2-naphthalenesulfonic acid monohydrate to Na_2SO_4 was 3.2∶1. The material balance under the suitable mole ratios was given and discussed. 相似文献
14.
The metal oxide/nitrogen-doped carbon (NC) compounds zirconium oxide/NC (ZrO2/NC) and cerium oxide/NC (CeO2/NC) were synthesized via the pyrolysis of polyaniline on the metal oxide surface. The characterization of the ZrO2/NC and CeO2/NC catalysts showed more active CO2 reduction reaction activity than that of NC catalyst without metal oxide. Gas chromatography analysis revealed that CO and H2 were the primary products, and no liquid-phase products were detected via proton nuclear magnetic resonance spectroscopy or high-performance liquid chromatography. The maximum Faraday efficiency of ZrO2/NC reached 90% at − 0.73 V (vs. RHE), with the current density of CO at 5.5 mA/cm2; this Faraday efficiency value was higher than that of NC (41%), with the current density of CO at 3.1 mA/cm2. The interaction between the metal oxide and carbon allowed the efficient formation of defect sites, especially imine-type nitrogen, strengthening the adsorption of the key reaction intermediate CO2•− and thus promoting the CO2 reduction reaction.
相似文献15.
Room temperature ionic liquids as solvents for palladium-catalyzed copolymerization of carbon monoxide and styrene were prepared by reaction of aqueous lead tetrafluoroborate with correspond-ing chloride or bromide salts. The recyclability of palladium composite catalyst in various ionic liquids was investigated.[Pd(bipy)2][BF4]2 showed a lower catalytic activity than [Pd(bipy)2][PF6]2 in similar conditions, although the catalytic activity of each composite catalyst in ionic liquids still existed after 4 successive recycles. It was shown the catalytic activity of palladium composite catalyst was higher than that of the catalyst formed in situ from palladium acetate, 2,2'-bipyridyl, and HA (A=PF6-, BF4-) in ionic liquids. The effects of volume of ionic liquids, reaction time, and the dosage of benzoquinone on the copolymerization were also studied. 相似文献
16.
Ju-qing Huang Rui-ting Qi Mei-rong Pang Cong Liu Guang-yu Li Ying Zhang 《Journal of Zhejiang University. Science. B》2017,18(2):138-151
Bamboo shavings, the outer or intermediate layer of bamboo stems, are the bulk of by-products produced in bamboo processing. In this study we investigated the isolation, chemical characterization, and immunostimulatory activity in vitro of the hemicelluloses from bamboo shavings. Shavings were first pretreated by steam explosion. The optimal pretreatment was found to be steam explosion at 2.2 MPa for 1 min. Following this pretreatment, the yield of hemicelluloses reached (2.05±0.22)% (based on the dry dewaxed raw materials), which was 5.7-fold higher than that of untreated samples. Bamboo-shavings hemicellulose (BSH) was then prepared by hot water extraction and ethanol precipitation from the steam-exploded shavings. Purification of BSH by anion-exchange chromatography of diethylaminoethanol (DEAE)-sepharose Fast Flow resulted in a neutral fraction (BSH-1, purity of 95.3%, yield of 1.06%) and an acidic fraction (BSH-2, purity of 92.5%, yield of 0.79%). The weight-average molecular weights (M w) of BSH-1 and BSH-2 were 12 800 and 11 300 g/mol, respectively. Chemical and structural analyses by Fourier transform infrared spectroscopy (FT-IR), 1D (1H and 13C) and 2D (heteronuclear single quantum correlation (HSQC)) nuclear magnetic resonance (NMR) spectra revealed that BSH-1 was O-acetylated-arabinoxylan and BSH-2 was O-acetylated-(4-Omethylglucurono)- arabinoxylan. BSH-1 had a higher content of acetyl groups than BSH-2. For the immunomodulatory activity in vitro, BSH and BSH-2 significantly stimulated mouse splenocyte proliferation while BSH-1 had no effect; BSH, BSH-1, and BSH-2 markedly enhanced the phagocytosis activity and nitric oxide production of the murine macrophage RAW264.7 in a dose-dependent manner. Our results suggest that the water-extractable hemicelluloses from steam-exploded bamboo shavings are naturally acetylated and have immunostimulatory activity. 相似文献