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1.
We have synthesized ultra‐small and uniform FexCo1‐x/graphitic carbon shell (FexCo1‐x/GC) nanocrystals (x=0.13, 0.36, 0.42, 0.50, 0.56, and 0.62, respectively) with average diameters of <4 nm by thermal decomposition of metal precursors in approximately 60 nm MCM‐41 and methane CVD. The composition of the FexCo1‐x/GC nanocrystals can be tuned by changing the Fe:Co ratios of the metal precursors. The FexCo1‐x/GC nanocrystals show superparamagnetic properties at room temperature. The Fe0.50Co0.50/GC, Fe0.56Co0.44/GC, and Fe0.62Co0.38/GC nanocrystals have a single bcc FeCo structure, whereas the Fe0.13Co0.87/GC, Fe0.36Co0.64/GC, and Fe0.42Co0.58/GC nanocrystals have a mixed structure of bcc FeCo and fcc Co. The single bcc‐phased FexCo1‐x/GC nanocrystals functionalized with phospholipid–poly(ethylene glycol) (PL–PEG) in phosphate buffered saline (PBS) are demonstrated to be excellent T1 MRI contrast agents.  相似文献   

2.
The catalytic efficiency of ammonium dihydrogenphosphate was evaluated in the two heterogeneous forms of NH4H2PO4/MCM‐48 and NH4H2PO4/MCM‐41, as mesoporous catalysts, in the solvent free synthesis of 3,4‐dihydropyrimidin‐2(1H)‐ones through one‐pot three‐component condensation of ethyl acetoacetate, an aryl aldehyde and urea. Different reaction parameters including catalytic efficacy, solvent effect, and urea concentration are considered.  相似文献   

3.
In acetate buffer media (pH 4.5–5.4) thiosulfate ion (S2O32?) reduces the bridged superoxo complex, [(NH3)4CoIII(μ‐NH2,μ‐O2)CoIII(NH3)4]4+ ( 1 ) to its corresponding μ‐peroxo product, [(NH3)4CoIII(μ‐NH2,μ‐O2)CoIII(NH3)4]3+ ( 2 ) and along a parallel reaction path, simultaneously S2O32? reacts with 1 to produce the substituted μ‐thiosulfato‐μ‐superoxo complex, [(NH3)4CoIII(μ‐S2O3,μ‐O2)CoIII(NH3)4]3+ ( 3 ). The formation of μ‐thiosulfato‐μ‐superoxo complex ( 3 ) appears as a precipitate which on being subjected to FTIR shows absorption peaks that support the presence of Co(III)‐bound S‐coordinated S2O32? group. In reaction media, 3 readily dissolves to further react with S2O32? to produce μ‐thiosulfato‐μ‐peroxo product, [(NH3)4CoIII(μ‐S2O3,μ‐O2)CoIII(NH3)4]2+ ( 4 ). The observed rate (k0) increases with an increase in [TThio] ([TThio] is the analytical concentration of S2O32?) and temperature (T), but it decreases with an increase in [H+] and the ionic strength (I). Analysis of the log At versus time data (A is the absorbance of 1 at time t) reveals that overall the reaction follows a biphasic consecutive reaction path with rate constants k1 and k2 and the change of absorbance is equal to {a1 exp(–k1t) + a2 exp(–k2t)}, where k1 > k2.  相似文献   

4.
Two well‐ordered 2D ‐ hexagonal cerium (IV) and erbium (III) embedded functionalized mesoporous MCM ‐ 41(MCM‐41@Serine/Ce and MCM ‐ 41@Serine/Er) have been developed via functionalization of mesoporous MCM ‐ 41. The surface modification method has been used in the preparation of serine‐grafted MCM ‐ 41 and led to the development of MCM‐41@Serine. The reaction of MCM‐41@Serine with Ce (NH4)2(NO3)6·2H2O or ErCl3·6H2O in ethanol under reflux led to the organization of MCM‐41@Serine/Ce and MCM‐41@Serine/Er catalysts. The structures of these catalysts were determined using scanning electron microscopy, mapping, energy‐dispersive X‐ray spectroscopy, Fourier transform‐infrared, thermogravimetric analysis, X‐ray diffraction, inductively coupled plasma, and Brunauer–Emmett–Teller analysis. These MCM‐41@Serine/Ce and MCM‐41@Serine/Er catalysts show outstanding catalytic performance in sulfides oxidation and synthesis of 5‐substituted tetrazoles. These catalysts can be recycled for seven repeated reaction runs without showing a considerable decrease in catalytic performance.  相似文献   

5.
DABCO (1,4‐diazabicyclo[2.2.2]octane)‐modified magnetite with silica‐MCM‐41 shell (Fe3O4@silica‐MCM‐41@DABCO) as an effective, magnetic and novel heterogeneous reusable nanocatalyst was synthesized and analysed using various techniques. Evaluation of the catalytic activity of this nanocatalyst was performed in the clean synthesis of substituted 2‐aminodihydropyrano[3,2‐b]pyran‐3‐cyano in high yields via in situ reaction of azido kojic acid, malononitrile and various aldehydes.  相似文献   

6.
《Electroanalysis》2017,29(10):2323-2331
In this study, the perovskite‐type oxides Ba0.5Sr0.5Ni0.2Co0.6Fe0.2O3‐δ (BSNCF) with different B‐site transition metal elements were investigated as a new catalyst for methanol oxidation. They were prepared by the partial substitution of cobalt by nickel in Ba0.5Sr0.5Co0.8Fe0.2O3‐δ (BSCF) sample. Both materials prepared using a combined citrate/EDTA complexing method and their catalytic activitiesfor methanol oxidation were comparativelystudied using cyclic‐voltammetry (CV) and chronoamperometry (CA) in alkaline media at room temperature. Structural, textural, morphological and redox properties of the synthesized solids were investigated by several physicochemical methods such as XRD, FTIR, LRS, SEM‐EDX, BET and H2‐TPR. The as‐prepared materials were obtained with high purity and high crystallinity. The partial substitution of cobalt by nickel in BSCF perovskite changes the structure of the solid which pass from cubic structure to a mixture of cubic and hexagonal forms. This change is accompanied by an increase in BET surface area and a decrease in crystalline size. For the electro‐catalysis measurements, results demonstrated that partially substituting of Co by Ni in BSCF structure enhance the electro‐catalytical activity towards the oxidation of methanol under alkaline conditions, making it an electro‐catalyst candidate for practical utilization in DMFCs.  相似文献   

7.
A novel two‐dimensional CoII coordination framework, namely poly[(μ2‐biphenyl‐4,4′‐diyldicarboxylato‐κ2O4:O4′){μ2‐bis[4‐(2‐methyl‐1H‐imidazol‐1‐yl)phenyl] ether‐κ2N3:N3′}cobalt(II)], [Co(C14H8O4)(C20H18N4O)]n, has been prepared and characterized by IR, elemental analysis, thermal analysis and single‐crystal X‐ray diffraction. The crystal structure reveals that the compound has an achiral two‐dimensional layered structure based on opposite‐handed helical chains. In addition, it exhibits significant photocatalytic degradation activity for the degradation of methylene blue.  相似文献   

8.
The study reports the synthesis of complexes Co(HL)Cl2 ( 1 ), Ni(HL)Cl2 ( 2 ), Cu(HL)Cl2 ( 3 ), and Zn(HL)3Cl2 ( 4 ) with the title ligand, 5‐(pyrazin‐2‐yl)‐1,2,4‐triazole‐5‐thione (HL), and their characterization by elemental analyses, ESI‐MS (m/z), FT‐IR and UV/Vis spectroscopy, as well as EPR in the case of the CuII complex. The comparative analysis of IR spectra of the metal ion complexes with HL and HL alone indicated that the metal ions in 1 , 2 , and 3 are chelated by two nitrogen atoms, N(4) of pyrazine and N(5) of triazole in the thiol tautomeric form, whereas the ZnII ion in 4 is coordinated by the non‐protonated N(2) nitrogen atom of triazole in the thione form. pH potentiometry and UV/Vis spectroscopy were used to examine CoII, NiII, and ZnII complexes in 10/90 (v/v) DMSO/water solution, whereas the CuII complex was examined in 40/60 (v/v) DMSO/water solution. Monodeprotonation of the thione triazole in solution enables the formation of the L:M = 1:1 species with CoII, NiII and ZnII, the 2:1 species with CoII and ZnII, and the 3:1 species with ZnII. A distorted tetrahedral arrangement of the CuII complex was suggested on the basis of EPR and Vis/NIR spectra.  相似文献   

9.
A polyoxometalate‐based inorganic–organic hybrid compound [CoII(2, 2′‐bpy)2]2[Mo8O26] ( 1 ) was synthesized by hydrothermal methods and structurally characterized by IR spectrum, TG analysis and X‐ray diffraction. The compound crystallizes in the monoclinic system, space group P21/n, a = 10.0681(2), b = 16.4467(2), c = 15.7838(3) Å, β = 100.046(1)°, V = 2573.52(8) Å3, Z = 2. The structure of 1 is built up from β‐[Mo8O26]4? subunits covalently linked via [CoII(2, 2′‐bpy)2]2+ fragments into a infinite 1D {[CoII(2, 2′‐bpy)2]2[Mo8O26]} polymer.  相似文献   

10.
Chitosan ( 1 ) was prepared by basic hydrolysis of chitin of an average molecular weight of 70000 Da, 1H‐NMR spectra indicating almost complete deacetylation. N‐Phthaloylation of 1 yielded the known N‐phthaloylchitosan ( 2 ), which was tritylated to provide 3a and methoxytritylated to 3b . Dephthaloylation of 3a with NH2NH2?H2O gave the 6‐O‐tritylated chitosan 4a . Similarly, 3b gave the 6‐O‐methoxytritylated 4b . CuSO4‐Catalyzed diazo transfer to 4a yielded 95% of the azide 5a , and uncatalyzed diazo transfer to 4b gave 82% of azide 5b . Further treatment of 5a with CuSO4 produced 2‐azido‐2‐deoxycellulose ( 7 ). Demethoxytritylation of 5b in HCOOH gave 2‐azido‐2‐deoxy‐3,6‐di‐O‐formylcellulose ( 6 ), which was deformylated to 7 . The 1,3‐dipolar cycloaddition of 7 to a range of phenyl‐, (phenyl)alkyl‐, and alkyl‐monosubstituted alkynes in DMSO in the presence of CuI gave the 1,2,3‐triazoles 8 – 15 in high yields.  相似文献   

11.
The nonlinear optical property of new polyester has been studied via second harmonic generation (SHG). The values of electro‐optic coefficients, d33 and d31, of the poled polymer film were 3.15 × 10 ?7 and 1.5 × 10?7 esu, respectively. Thermal behavior of this polyester was studied through thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). 4‐di‐(2′‐hydroxyethoxy)‐4‐diphenyl‐hydrazonomethyl was synthesized from the reaction of 3,4‐dihydroxy‐4‐diphenyl‐hydrazonomethyl with 2–chloro–1‐ethanol in a 1:2 mole ratio and subsequently reacted with terephthaloyl chloride (TPC) in the presence of pyridine, as catalyst, to produce the new nonlinear polyester. The chemical structures of the resulting monomers and polymer were characterized by CHN analysis, 1H‐NMR, FT‐IR, and UV–Vis spectroscopy. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

12.
Some novel 4‐amino‐6‐aryl‐2‐methylthio pyrimidine‐5‐carbonitrile derivatives were synthesized through a one‐pot three‐component reaction of an aldehyde, malononitrile, and S‐methylisothiouronium iodide, using MCM‐41‐NH2 as nanoreactor and nanocatalyst. This protocol has some advantages including application of readily available and nonhazardous materials, benign reaction conditions (ambient temperature, solvent‐free, and one‐pot approach), easy work‐up, and high overall yields of the products.  相似文献   

13.
Transition metal oxides are regarded as promising anode materials for lithium‐ion batteries because of their high theoretical capacities compared with commercial graphite. Unfortunately, the implementation of such novel anodes is hampered by their large volume changes during the Li+ insertion and extraction process and their low electric conductivities. Herein, we report a specifically designed anode architecture to overcome such problems, that is, mesoporous peapod‐like Co3O4@carbon nanotube arrays, which are constructed through a controllable nanocasting process. Co3O4 nanoparticles are confined exclusively in the intratubular pores of the nanotube arrays. The pores between the nanotubes are open, and thus render the Co3O4 nanoparticles accessible for effective electrolyte diffusion. Moreover, the carbon nanotubes act as a conductive network. As a result, the peapod‐like Co3O4@carbon nanotube electrode shows a high specific capacity, excellent rate capacity, and very good cycling performance.  相似文献   

14.
Ligand N2,N6‐bis(2‐hydroxyethyl)pyridine‐2,6‐dicarboxamide (L=BHPC) was synthesized and used to construct lanthanide‐based mesoporous material Eu‐L‐MCM‐41. In the structure of resulting Eu‐L‐MCM‐41, Eu3+ was chelated by BHPC, and the Eu‐L complexes were anchored into the forming MCM‐41 host by the reaction between the hydroxyl group and active Si‐OH. The mesoporous material Eu‐L‐MCM‐41 was characterized by UV, IR, small‐angle X‐ray diffraction (SAXRD) patterns, nitrogen adsorption/desorption isotherms, TGA and fluorescence spectra. The results indicate that ligand and Eu3+ have been introduced into the MCM‐41 host, and Eu‐L‐MCM‐41 exhibits characteristic luminescence of Eu3+.  相似文献   

15.
A mononuclear‐cobalt(II)‐substituted silicotungstate, K10[Co(H2O)2(γ‐SiW10O35)2] ? 23 H2O (POM‐ 1 ), has been evaluated as a light‐driven water‐oxidation catalyst. With in situ photogenerated [Ru(bpy)3]3+ (bpy=2,2′‐bipyridine) as the oxidant, quite high catalytic turnover number (TON; 313), turnover frequency (TOF; 3.2 s?1), and quantum yield (ΦQY; 27 %) for oxygen evolution at pH 9.0 were acquired. Comparison experiments with its structural analogues, namely [Ni(H2O)2(γ‐SiW10O35)2]10? (POM‐ 2 ) and [Mn(H2O)2(γ‐SiW10O35)2]10? (POM‐ 3 ), gave the conclusion that the cobalt center in POM‐ 1 is the active site. The hydrolytic stability of the title polyoxometalate (POM) was confirmed by extensive experiments, including UV/Vis spectroscopy, linear sweep voltammetry (LSV), and cathodic adsorption stripping analysis (CASA). As the [Ru(bpy)3]2+/visible light/sodium persulfate system was introduced, a POM–photosensitizer complex formed within minutes before visible‐light irradiation. It was demonstrated that this complex functioned as the active species, which remained intact after the oxygen‐evolution reaction. Multiple experimental parameters were investigated and the catalytic activity was also compared with the well‐studied POM‐based water‐oxidation catalysts (i.e., [Co4(H2O)2(α‐PW9O34)2]10? (Co4‐POM) and [CoIIICoII(H2O)W11O39]7? (Co2‐POM)) under optimum conditions.  相似文献   

16.
Ni‐loaded pure siliceous and aluminosilicate MCM‐41 (Ni/MCM‐41) and nickel‐loaded silica (15Ni/SiO2) were synthesized via wet impregnation and were characterized by various techniques. The H2 consumption in the TPR analysis was found to be proportional to the Ni amount in the calcined samples. After reduction the average Ni particle sizes of 15Ni/MCM‐41 and 15Ni/SiO2 were 9–12 and 16 nm, respectively, by means of XRD and TEM measurements. All catalysts owned weak and intermediate Lewis acid sites that increased slightly with increasing the Ni amount and the Al content. In the liquid phase hydrogenation of t,t,c‐1,5,9‐cyclododecatriene over Ni/MCM‐41, the catalytic activity was parallel to the Ni content and enhanced slightly with the acid amount of the catalysts. Consequently, it was proposed that the Ni metallic sites contributed the major effect to the catalytic activity while the Lewis acid sites promoted a small but significant influence on the catalytic performance. It is noteworthy that all 15Ni/MCM‐41 catalysts exhibited remarkably higher activity than that of the conventional 15Ni/SiO2 catalyst.  相似文献   

17.
A new magnetic metal–organic framework nanocomposite (CoFe2O4/TMU‐17‐NH2) was prepared via an embedding approach by synthesis of the metal–organic framework crystals in the presence of magnetic cobalt ferrite nanoparticles. We demonstrated that the resulting magnetic nanocomposite can serve as a recyclable nanocatalyst for one‐pot synthesis of bis‐3,4‐dihydropyrimidin‐2(1H)‐one and 3,4‐dihydropyrimidin‐2(1H)‐one derivatives via three‐component reaction of 1,3‐diketone, urea or thiourea and aromatic aldehyde under solvent‐free conditions. CoFe2O4/TMU‐17‐NH2 was characterized using various techniques. The recovery of the nanocomposite was achieved by a simple magnetic decantation and it was reused at least seven times without significant degradation in catalytic activity.  相似文献   

18.
An inorganic-organic composite was prepared by poly(amidoamine) (PAMAM) dendrimer reacting with cobalt(Ⅱ)-monosubstituted polyoxometalates Na5Co^Ⅱ(H2O)PW11O39 (PW11CO) in an aqueous solution. The hybrid composite PW11Co/PAMAM was characterized by FT-IR, UV-Vis diffuse reflectance spectra (DR-UV-Vis), XPS, XRD and TG/DTA, indicating that the PWI iCo was chemically anchored to PAMAM. The morphologies of the title composite were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The catalytic activity was evaluated by oxidation of isobutyraldehyde (IBA) to isobutyric acid (IBAc) in MeCN under mild conditions (20 ℃, ambient pressure), showing that the title compound is a more effective and recoverable catalyst than corresponding PW11Co.  相似文献   

19.
Ruthenium(III)‐substituted α‐Keggin‐type silicotungstates with pyridine‐based ligands, [SiW11O39RuIII(Py)]5?, (Py: pyridine ( 1 ), 4‐pyridine‐carboxylic acid ( 2 ), 4,4′‐bipyridine ( 3 ), 4‐pyridine‐acetamide ( 4 ), and 4‐pyridine‐methanol ( 5 )) were prepared by reacting [SiW11O39RuIII(H2O)]5? with the pyridine derivatives in water at 80 °C and then isolated as their hydrated cesium salts. These compounds were characterized using cyclic voltammetry (CV), UV/Vis, IR, and 1H NMR spectroscopy, elemental analysis, titration, and X‐ray absorption near‐edge structure (XANES) analysis (Ru K‐edge and L3‐edge). Single‐crystal X‐ray analysis of compounds 2 , 3 , and 4 revealed that RuIII was incorporated in the α‐Keggin framework and was coordinated by pyridine derivatives through a Ru? N bond. In the solid state, compounds 2 and 3 formed a dimer through π? π interaction of the pyridine moieties, whereas they existed as monomers in solution. CV indicated that the incorporated RuIII–Py was reversibly oxidized into the RuIV–Py derivative and reduced into the RuII–Py derivative.  相似文献   

20.
Convergent syntheses of the 9‐(3‐X‐2,3‐dideoxy‐2‐fluoro‐β‐D ‐ribofuranosyl)adenines 5 (X=N3) and 7 (X=NH2), as well as of their respective α‐anomers 6 and 8 , are described, using methyl 2‐azido‐5‐O‐benzoyl‐2,3‐dideoxy‐2‐fluoro‐β‐D ‐ribofuranoside ( 4 ) as glycosylating agent. Methyl 5‐O‐benzoyl‐2,3‐dideoxy‐2,3‐difluoro‐β‐D ‐ribofuranoside ( 12 ) was prepared starting from two precursors, and coupled with silylated N6‐benzoyladenine to afford, after deprotection, 2′,3′‐dideoxy‐2′,3′‐difluoroadenosine ( 13 ). Condensation of 1‐O‐acetyl‐3,5‐di‐O‐benzoyl‐2‐deoxy‐2‐fluoro‐β‐D ‐ribofuranose ( 14 ) with silylated N2‐palmitoylguanine gave, after chromatographic separation and deacylation, the N7β‐anomer 17 as the main product, along with 2′‐deoxy‐2′‐fluoroguanosine ( 15 ) and its N9α‐anomer 16 in a ratio of ca. 42 : 24 : 10. An in‐depth conformational analysis of a number of 2,3‐dideoxy‐2‐fluoro‐3‐X‐D ‐ribofuranosides (X=F, N3, NH2, H) as well as of purine and pyrimidine 2‐deoxy‐2‐fluoro‐D ‐ribofuranosyl nucleosides was performed using the PSEUROT (version 6.3) software in combination with NMR studies.  相似文献   

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