Preparation,characterization and catalytic activity of biomaterial-supported copper nanoparticles

Synthesis of copper nanoparticles was carried out with nanocrystalline cellulose (NCC) as a support by reducing CuSO₄·5H₂O ions using hydrazine. Ascorbic acid and aqueous NaOH were also used as an antioxidant and pH controller, respectively. The synthesized copper nanoparticles supported on NCC (CuNPs@NCC) were characterized by UV–vis, XRD, TEM, XRF, TGA, DSC, N₂ adsorption-desorption method at 77 K and FTIR. The UV–vis confirmed the formation and stability of the CuNPs, which indicated that the maximum absorbance of CuNPs@NCC was at 590 nm due to the surface plasmon absorption of CuNPs. Morphological characterization clearly showed the formation of a spherical structure of the CuNPs with the mean diameter and standard deviation of 2.71 ± 1.12 nm. Similarly, XRD showed that the synthesized CuNPs@NCC was of high purity. The thermal analysis showed that the CuNPs@NCC exhibited better thermal behaviors than NCC. BET surface area revealed that the N₂ adsorption–desorption isotherms of CuNPs@NCC featured a type IV isotherm with an H3 hysterisis loop. This chemical method is simple, cost effective, and environmentally friendly. Compared to NCC-supported CuNPs and unsupported CuNPs, the as-prepared CuNPs@NCC exhibit a superior catalytic activity and high sustainability for the reduction of methylene blue with NaBH₄ in aqueous solution at room temperature. The CuNPs@NCC achieved complete reduction of MB with completion time, rate constant and correlation coefficient (R ²) of 12 min, 0.7421 min^?1 and 0.9922, respectively.     

稀土催化材料的制备、结构及催化性能

稀土催化材料的研究和发展为La和Ce等高丰度轻稀土元素的高质、高效利用提供了有效的途径.稀土元素具有未充满电子的4f轨道和镧系收缩等特征,作为催化剂的活性组分或载体使用时表现出独特的催化性能.本文从稀土氧化物、稀土复合氧化物、稀土-贵金属催化剂、稀土改性多孔催化材料等稀土催化材料出发,重点介绍和讨论了稀土的添加对催化剂的结构、活性和稳定性等的影响,阐述了稀土与过渡金属及氧化物、稀土与贵金属之间的相互作用,及对催化剂催化性能的影响.并对稀土催化材料的研究和发展提出了思考和展望.     

Synthesis, characterization and catalytic application of SBA-15 immobilized rare earth metal sandwiched polyoxometalates

Rare earth metal sandwiched Keggin-type heteropolyoxometalates, K₁₁[RE(PW₁₁O₃₉)₂] (RE–PW₁₁, RE = La, Ce, Pr, Nd, Sm, Eu, Dy and Y), were anchored onto aminosilylated mesoporous silica SBA-15 and the resulting RE–PW₁₁/APTS/SBA-15 materials were characterized by ICP, FT-IR, XRD, N₂ adsorption, ³¹P MAS NMR and TEM. The RE–PW₁₁ clusters preserve their structure in the surface-modified mesopores. The catalytic activity of RE–PW₁₁ clusters was tested on heterogeneous oxidation of cyclohexene by H₂O₂. The interaction between RE–PW₁₁ and amino groups grafted on the channel surface of SBA-15 leads to strong immobilization of RE–PW₁₁ due to the introduction of the rare earth metal centre, which is against the leaching during the reaction.     

Spinel copper ferrite nanoparticles: Preparation,characterization and catalytic activity

The magnetic CuFe₂O₄ nanoparticles have been synthesized and characterized by various spectroscopic methods, including X‐ray diffraction (XRD), O K, Cu and Fe K ‐edge X‐ray absorption near edge structure (XANES), energy dispersive X‐ray analysis (EDX), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The azide‐alkyne cycloaddition by the reaction of various phenylacetylenes with a mixture of benzyl halides and NaN₃ and also three component (A³) coupling reaction of aldehyde, alkyne and amine catalyzed by CuFe₂O₄ nanoparticles under aerobic conditions led to the formation of the 1,4‐disubstituted‐1,2,3‐triazoles and propargylamines in excellent yields. The catalyst can be recovered by applying an external magnetic field for the subsequent cycloaddition reactions and reused without any tangible loss in catalytic efficiency.     

Generation and characterization of supported films of transition metal and rare earth metal oxide catalysts

Summary The generation of catalytically relevant metal and/or metal oxide compounds supported on silica fibres is described. The systems investigated are Ni^o, Cu^o, Cu^o/ZnO, as well as perovskite-type La/Fe, La/Ni and La/Mn oxide phases. Ultrasound-aided generated vapours containing dissolved metal salt precursors are transferred onto preheated quartz fibres and transformed into the catalytically relevant phases by subsequent calcination. Analytical SEM and X-ray diffraction reveals the presence of differently crystalline, rough surfaces. The influence of the precursor salt and the conditions of calcination on the formation of the supported catalysts is discussed.     

Preparation, characterization and investigation of catalytic activity of Li-doped LaFeO3 nanoparticles

Nanometer oxides Li-doped LaFeO₃ with a high photocatalytic activity were synthesized by the acetic acid based sol-gel route. X-ray diffraction, transmission electron microscopy, differential thermal analysis, atomic absorption spectrum, infrared absorption spectrum analyzer and UN-Vis spectrophotometer technologies were used to characterize the products. The photocatalytic activities of the samples were studied with measurement of effect of photodecomposition of Methyl blue solution and organism in arcylon effluents. The results show that LaFeO₃ doped lithium has better photocatalytic activity than pure LaFeO₃ particles, and the optimum amount doped lithium is x = 0.03.     

Synthesis, characterization, and catalytic activity of rare earth metal amides supported by a diamido ligand with a CH2SiMe2 link

A series of four coordinate rare earth metal amides with general formula ((CH2SiMe2)[(2,6- IPr2C6H3)N]2)LnN(SiMe3)2(THF) [(Ln = Yb(2), Y (3), Dy (4), Sm (5), Nd (6)] containing a diamido ligand (CH2SiMe2)[(2,6-iPr2C6H3)N]2(2-) with a CH2SiMe2 link were synthesized in good yields via reaction of [(Me3Si)2N]3Ln(III)(mu-Cl)Li(THF)3 with the corresponding diamine (CH2SiMe2)[(2,6-iPr2C6H3)NH]2 (1). All compounds were fully characterized by spectroscopic methods and elemental analyses. The structures of complexes 2, 3, 4, 5, and 6 were determined by single-crystal X-ray analyses. Investigation of the catalytic properties of the complexes indicated that all complexes exhibited a high catalytic activity on the cyclotrimerization of aromatic isocyanates, which represents the first example of cyclopentadienyl-free rare earth metal complexes exhibiting a high catalytic activity and a high selectivity on cyclotrimerization of aromatic isocyanates. The temperatures, solvents, catalyst loading, and the rare earth metal effects on the catalytic activities of the complexes were examined.     

Bis(imidazolin-2-iminato) rare earth metal complexes: synthesis, structural characterization, and catalytic application

Reaction of anhydrous rare earth metal halides MCl(3) with 2 equiv of 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH) and 2 equiv of trimethylsilylmethyl lithium (Me(3)SiCH(2)Li) in THF furnished the complexes [(Im(Dipp)N)(2)MCl(THF)(n)] (M = Sc, Y, Lu). The molecular structures of all three compounds were established by single-crystal X-ray diffraction analyses. The coordination spheres around the pentacoordinate metal atoms are best described as trigonal bipyramids. Reaction of YbI(2) with 2 equiv of LiCH(2)SiMe(3) and 2 equiv of the imino ligand Im(Dipp)NH in tetrahydrofuran did not result in a divalent complex, but instead the Yb(III) complex [(Im(Dipp)N)(2)YbI(THF)(2)] was obtained and structurally characterized. Treatment of [(Im(Dipp)N)(2)MCl(THF)(n)] with 1 equiv of LiCH(2)SiMe(3) resulted in the formation of [(Im(Dipp)N)(2)M(CH(2)SiMe(3))(THF)(n)]. The coordination arrangement of these compounds in the solid state at the metal atoms is similar to that found for the starting materials, although the introduction of the neosilyl ligand induces a significantly greater distortion from the ideal trigonal-bipyramidal geometry. [(Im(Dipp)N)(2)Y(CH(2)SiMe(3))(THF)(2)] was used as precatalyst in the intramolecular hydroamination/cyclization reaction of various terminal aminoalkenes and of one aminoalkyne. The complex showed high catalytic activity and selectivity. A comparison with the previously reported dialkyl yttrium complex [(Im(Dipp)N)Y(CH(2)SiMe(3))(2)(THF)(3)] showed no clear tendency in terms of activity.     

聚合物载体-稀土金属配合物的研究IV.含亚硫酰基聚合物载体-稀土金属配合物的合成,表征及其催化活性

Styrene-2-(methylsulfinyl)ethyl methacrylate copolymer-supported MCl3 complexes, where M = La, Pr, Nd, Eu, Ho, Er, Tm, and Yb, were prepared and characterized by IR spectroscopy. The catalytic activity of the polymer-supported NdCl3-(iso-Bu)3Al system towards stereospecific polymerisation of butadiene was 2-3 times higher than that of NdCl3-(iso-Bu)3Al-DMSO system. The cis-1,4 content of polybutadiene formed was >98%.     

石墨烯负载的金属氧化物纳米颗粒的可控制备及催化性能

采用直接浸渍法、过氧化氢均相氧化沉积法和氨水催化水解法制备了石墨烯负载的铁、钴、镍金属氧化物纳米颗粒.研究了三种沉积方法对颗粒尺寸分布的影响;采用透射电子显微镜、傅里叶变换红外光谱、X射线衍射和X射线光电子能谱表征了催化剂的形貌与结构.用过氧化氢均相氧化沉淀法可制得粒径分布最均匀的纳米颗粒.过氧化氢的氧化作用可使石墨烯表面的氧化基团含量最大化,为纳米颗粒提供了足够的吸附与成核点.氨水加速了金属离子的水解与成核,导致纳米颗粒的粒径增大与不均.以苯甲醇氧化为探针反应考察了催化剂的性能.催化剂的活性按以下顺序逐渐下降:过氧化氢辅助沉积法>直接浸渍法>氨水催化水解法,与纳米颗粒尺寸增长趋势一致.纳米催化剂颗粒尺寸与其活性的良好关联性显示,发展石墨烯负载尺寸可控的纳米催化剂的方法具有重要意义.     

稀土二氧化铈在生物领域的最新研究进展

氧化铈纳米粒子因其优异的催化活性而一直以来备受关注.它的催化性质来源于表面铈离子可以快速地进行Ce4+和Ce3+转变,能够根据环境很容易地接受或失去电子.长久以来,其应用均集中在工业催化方面.然而近年来,它被发现具有多种生物酶,如超氧化物歧化酶、过氧化氢酶、磷酸酶、过氧化物酶和氧化酶等的模拟活性,以及具有羟基自由基及氮氧化物自由基清除的能力.这些多重酶活性使其在生物方面有着众多极具前景的潜在应用价值.目前,在生物领域其已被开发用于生物检测、疾病诊断及治疗、药物载体及生物支架等方面.本文主要介绍其多种生物酶活性、活性原理,及在生物领域中的最新研究进展.     

Preparation, characterization and catalytic behavior of Pt-Cu nanoparticles in methane combustion

Fine and well dispersed Pt-Cu bimetallic nanoparticles stabilized by polyvinyl pyrrolidone (PVP) were synthesized by alkaline polyol method. The molar ratio of Pt to Cu was 1 : 1. Further, the Pt-Cu bimetallic nanoparticles were supported on alumina and their catalytic behavior in methane combustion was investigated. The as-prepared as well as the supported Pt-Cu nanoparticles were characterized by transmission elec-tron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), fractal analysis and X-ray diffraction (XRD). The dependence of methane combustion on the morphology and surface composition of Pt-Cu nanoparticles was analyzed based on the experimental results.     

Synthesis,characterization and antiviral activity of nickel-substituted rare earth molybdosilicic heteropoly blues

A series of novel heteropoly blues, Ln₂H₂[SiMo₁₁Ni(H₂O)O₃₉] · nH₂O (Ln = La, Ce, Pr, Nd, Sm, or Gd), had been prepared and characterized by elemental analysis, i.r., u.v., c.v., t.g.–d.t.a., XPS, ²⁹Si-n.m.r., electrochemistry and magnetic susceptibility. Compared with non-reduced heteropolyoxometallates, the heteropoly blue anion in Ln₂H₂[SiMo₁₁Ni(H₂O)O₃₉] · nH₂O still retains the -Keggin structure but with a slight distortion, with Ni and Mo atoms distributed statistically in the crystal. The antiviral activities of these complexes have been studied using tomato mosaic virus. Ln₂H₂[SiMo₁₁Ni(H₂O)O₃₉] · nH₂O show excellent antivirus activities, and the cure rate reaches to 80–90%.     

稀土与四甘醇醛缩苯丙氨酸Schiff碱配合物的合 成、性能与催化

合成了直链醚-氨基酸新型Schiff碱(四甘醇醛缩苯丙氨酸Schiff碱)及其与稀土新配合物,[Ln~3L~2(NO~3)~2]·(NO~3)~3·nH~2O(Ln=La,Nd,Sm,n=3;Ln=Gd,Dy,Er,Y,n=5),以元素分析、磁化率、红外光谱、^1HNMR等进行了表征,研究了的配位作用,根据预期设想,见到此类配合物在有机溶剂中的溶解性有明显改善。以EPR波谱探讨了配合物的晶体场强,并计算了晶体场参数。此外,发现在不加助催化剂条件下,此类配合物对MMA(甲基丙烯酸甲酯)聚合有一定的催化效果。     

Synthesis, characterization and reactivity of heteroleptic rare earth metal bis(phenolate) complexes

The synthesis, characterization and reactivity of heteroleptic rare earth metal complexes supported by the carbon-bridged bis(phenolate) ligand 2,2'-methylene-bis(6-tert-butyl-4-methyl-phenoxo) (MBMP(2-)) are described. Reaction of (C(5)H(5))(3)Ln(THF) with MBMPH(2) in a 1 : 1.5 molar ratio in THF at 50 degrees C produced the heteroleptic rare earth metal bis(phenolate) complexes (C(5)H(5))Ln(MBMP)(THF)(n) (Ln = La, n = 3 (); Ln = Yb (), Y (), n = 2) in nearly quantitative yields. The residual C(5)H(5)(-) groups in complexes to can be substituted by the bridged bis(phenolate) ligands at elevated temperature to give the neutral rare earth metal bis(phenolate) complexes, and the ionic radii have a profound effect on the structures of the final products. Complex reacted with MBMPH(2) in a 1 : 0.5 molar ratio in toluene at 80 degrees C to produce a dinuclear complex (MBMP)La(THF)(mu-MBMP)(2)La(THF)(2) () in good isolated yield; whereas complexes and reacted with MBMPH(2) under the same conditions to give (MBMP)Ln(MBMPH)(THF)(2) (Ln = Yb (), Y ()) as the final products, in which one hydroxyl group of the phenol is coordinated to the rare earth metal in a neutral fashion. The reactivity of complexes and with some metal alkyls was explored. Reaction of complex with 1 equiv. of AlEt(3) in toluene at room temperature afforded unexpected ligand redistributed products, and a discrete ion pair ytterbium complex [(MBMP)Yb(THF)(2)(DME)][(MBMP)(2)Yb(THF)(2)] () was isolated in moderate yield. Furthermore, reaction of complex with 1 equiv. of ZnEt(2) in toluene gave a ligand redistributed complex [(mu-MBMP)Zn(THF)](2) () in reasonable isolated yield. Similar reaction of complex with ZnEt(2) also afforded complex ; whereas the reaction of complex with 1 equiv. of n-BuLi in THF afforded the heterodimetallic complex [(THF)Yb(MBMP)(2)Li(THF)(2)] (). All of these complexes were well characterized by elemental analyses, IR spectra, and single-crystal structure determination, in the cases of complexes , and -.     

Preparation and characterization of the catalytically active forms of rare earth oxides

Catalytically active forms of the rare earth oxides Ln₂O₃(Ln = La, Sm, Eu, Dy, Ho, and Yb), Pr₆O₁₁, and CeO₂ have been prepared. The dehydration behavior of the precursors of these oxides has been studied by XRD, TG, DTA, TPD-MS, IR, and adsorption-desorption isotherms of N₂ at −196°C. Thermal analyses show that in most cases the dehydration takes place through an intermediate oxyhydroxide LnO (OH) that decomposes to the respective oxide at around 400°C. Strongly held difficult to remove carbonates were present on the surface, e.g., for Yb₂O₃ it was necessary raise the outgassing temperature to 700°C to achieve carbonate decomposition. At temperatures around 500°C these oxides are well crystallized and have moderate specific surface areas (10–40 m²g⁻¹). As a representative of the series, a detailed study of the dehydration and surface decarbonation of Yb₂O₃ was carried out by means of TPD-MS and infrared spectroscopy.     

PdAg2 nanoparticles in aqueous solution: Preparation, characterization, and catalytic properties

The reduction of a heterobimetallic complex, Pd(OOCMe)₄Ag₂(HOOCMe)₄, with hydrogen or sodium borohydride in an aqueous solution produces PdAg₂ nanoparticles of an alloy or intermetallic type. It is shown that the catalytic activity of the particles in the reduction of methyl viologen with hydrogen is lower than that of palladium nanoparticles of the same size. Therewith, ??borohydride?? nanoparticles manifest a higher catalytic activity than do ??hydrogen?? ones. Unlike silver nanoparticles, PdAg₂ nanoparticles do not catalyze the decomposition of hydrazine.     

Blue,green,red upconversion luminescence and optical characteristics of rare earth doped rare earth oxide and oxysulfide

The cold isostatic press pretreatment process was adopted to prepare fine rare earth oxysulfide up-conversion phosphors with spherical shape, narrow size distribution and high luminescence efficiency. The upconversion optical characteristics and brightness of the blue (Y2O2SYb,Tm), green (Y2O2S: Yb,Er), red (Y2O3Yb,Er) emitter were also investigated, and a novel method was successfully developed for the brightness measurement of upconversion luminescence (UPL). It is shown that a white color can be obtained by the appropriate mixture of these primary blue, green and red emissions components. The Er3 ions exhibit different upconversion mechanism in Y2O2S and Y2O3 host materials. The rare earth oxysulfide is an efficient upconversion matrix. The UPL brightness of Y2O2S: Yb,Er is 6.5 times higher than that of Y2O3: Yb,Er, and Y2O2S: Yb,Er shows UPL brightness of 1100 cd/m2 under 5.56 W/cm2 power density using a 980 nm laser diode.     

Ring opening polymerization of propylene oxide by chitosan-supported rare earth catalytic system and its kinetics

Ring opening polymerization of propylene oxide in the presence of a new type of catalytic system composed of chitosan-supported rare earth complex, triisobutyl aluminium, and acetylacetone and its kinetics have been studied for the first time. It has been found that the characteristics of this catalytic system are of high catalytic activity, of higher stereoselectivity, and of a high molecular weight polymer of 2 × 10⁶. Kinetic studies show that the polymerization rate is first order with respect to monomer concentration and catalyst concentration, respectively. The apparent activation energy of the polymerization reaction is 37.1 kJ/mol. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2177–2182, 1997     

Preparation,characterization, and antitumor activity of Chaenomeles speciosa polysaccharide-based selenium nanoparticles

Nanoparticles have been found to possess unique advantages in many fields, especially in the field of cancer treatment. Herein, based on the unique physical and chemical properties of natural polysaccharides, the polysaccharide from the edible and medicinal fruits of Chaenomeles speciosa was prepared, and the complex nanoparticles constructed by combining C. speciosa polysaccharide with selenium have been successfully developed by a chemical method. Monodisperse spherical nanoparticles with the particle size of 80.5 nm were characterized by various methods, which exhibited ideal size distribution and prominent stability under physiological conditions and alkaline conditions. Cellular studies demonstrated the nanoparticles significantly inhibited the growth of MCF-7 cells with an IC₅₀ value of 8.37 ± 0.97 μg/mL through inducing the apoptosis and arresting the cell circle at S phase. Moreover, the zebrafish assays confirmed the antitumor effects of the nanoparticles, which suppressed the proliferation and migration of tumor and blocked the angiogenesis of transgenic zebrafish. Collectively, the results suggested that the nanoparticles may be considered as a candidate agent to treat breast cancer.