三(羟甲基)氨基甲烷改性SiO_2固载钯纳米粒子:合成、表征及其催化Heck偶联反应活性（英文）

The preparation of supported Pd nanoparticles on Tris(tris(hydroxymethyl)aminomethane)‐ modi‐fied Si O2 gel and their catalytic application in Heck coupling are investigated. The catalyst was char‐acterized using a combination of X‐ray diffraction, transmission electron microscopy, field‐emission scanning electron microscopy, and scanning electron microscopy/energy‐dispersive X‐ray spec‐troscopy. The supported Pd nanoparticles were found to be a highly active and reusable catalyst for the Heck reaction at a low Pd loading(0.02 mol%) because of stabilization by the Tris moieties. Several reaction parameters, including the type and amount of solvent, base, and temperature, were evaluated. The heterogeneity of the catalytic system was investigated using different approaches, and showed that slight Pd leaching into the reaction solution occurred under the reaction condi‐tions. Despite this metal leaching, the catalyst can be reused seven times without significant loss of its activity.     

可磁性回收纳米级负载型杂多酸催化剂用于水中生物活性化合物的绿色合成(英文)

12‐Tungstophosphoric acid supported on aerosil silica and silica‐coated γ‐Fe2O3 nanoparticles was prepared and characterized using transmission electron microscopy,scanning electron microscopy,and inductively coupled plasma atomic emission spectroscopy.The catalytic activity of the two prepared catalysts was compared in the synthesis of 1,8‐dioxo‐9,10‐diaryldecahydroacridines in water.12‐Tungstophosphoric acid was highly dispersed on the silica‐coated γ‐Fe2O3 nanoparticles and showed higher activity and a higher reuse number compared with the acid supported on aerosil silica.The catalyst could be recovered simply by using an external magnetic field and could be reused several times without appreciable loss of its catalytic activity.     

磷酸铜锆催化剂上醇选择性氧化（英文）

The catalytic activity of copper zirconium phosphate(ZPCu) in the selective oxidation of alcohols to their corresponding ketones or aldehydes, using H2O2 as an oxidizing agent, was studied. The oxida‐tion reaction was performed without any organic solvent, phase‐transfer catalyst, or additive. Steric factors associated with the substrates influenced the reaction. The catalyst was characterized using X‐ray diffraction, inductively coupled plasma atomic emission spectroscopy, energy‐dispersive X‐ray spectroscopy, and scanning electron microscopy. It was shown that the interlayer distance increased from 0.74 to 0.80 nm and the crystallinity was reduced after Cu2+ intercalation into the layers. This catalyst can be recovered and reused three times without significant loss of activity and selectivity.     

Fe_3O_4纳米粒子作为高效、可重复使用催化剂用于无溶剂条件下合成9,9-二甲基-9,10-二氢-8H-苯并[α]占吨11(12H)-酮（英文）

A simple and efficient method for the synthesis of 9,9‐dimethyl‐9,10‐dihydro‐8H‐benzo‐[α]xanthen‐11(12)‐one derivatives (DDBXs) was developed by the condensation reaction of various substituted aryl aldehydes with 2‐naphthol and dimedone using Fe3O4 magnetic nanoparticles (MNPs) as a heterogeneous catalyst under solvent‐free conditions at 90–110 °C.The experimental procedure is very simple,the products are formed in high yields and the catalyst is easily separated by applying an external magnetic field.     

新的金属氧化物纳米催化剂CuO-ZnO高效催化醇化学选择性乙酰化（英文）

A new method has been developed for the chemoselective acetylation of alcohols with acetic anhy‐dride in the presence of phenols using a novel,recyclable Cu O‐Zn O nanocatalyst.The catalyst was synthesized using the co‐precipitation method and characterized by N2 adsorption‐desorption,X‐ray diffraction,scanning electron microscopy,transmission electron microscopy and energy dis‐persion scanning analyses.Furthermore,this catalyst could be recycled up to six times without significant loss in its activity.     

磺化碳催化Biginelli反应一锅法合成3,4-二氢-2(1H)-酮和硫酮(英文)

A sulfonated carbon material was shown to be a highly efficient,eco-friendly,and recyclable solid acid catalyst for the Biginelli reaction of β-ketoester,aldehyde,and urea or thiourea under solvent-free conditions.It gave 3,4-dihydropyrimidin-2(1H)-ones and-thiones in good to excellent yields.This method has the advantages of a simple procedure with easy work-up,short reaction time,and high yields.The catalyst can be recycled after a simple work-up and was reused four times without substantial reduction in activity.     

Pt/十六烷基三甲基溴化铵纳米聚集体修饰玻碳电极促进析氢(英文)

A novel, cost‐effective, and simple electrocatalyst based on a Pt‐modified glassy carbon electrode (GCE), using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, is reported. Am‐phiphilic CTAB molecules were adsorbed on GCE by immersion in a CTAB solution. The positively charged hydrophilic layer, which consisted of small aggregates of average size less than 100 nm, was used for accumulation and complexation of [PtCl6]2? anions by immersing the electrode in K2PtCl6 solution. The modified electrode was characterized using scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, impedance spectroscopy, and electrochemical methods. The electrocatalytic activity of the Pt particles in the hydrogen evolution reaction (HER) was investigat‐ed. The results show that the CTAB surfactant enhances the electrocatalytic activity of the Pt parti‐cles in the HER in acidic solution.     

原位生成的Ph_3C~+均相有机催化剂催化4,4'-芳亚甲基-二(3-甲基-1-苯基-1H-吡唑-5-醇)高效合成（英文）

Trityl chloride(Ph3CCl) efficiently catalyzes the condensation of 3‐methyl‐1‐phenyl‐1H‐pyrazol‐ 5(4H)‐one and aromatic aldehydes under mild and solvent‐free conditions, affording 4,4'‐(arylmethylene)‐ bis(3‐methyl‐1‐phenyl‐1H‐ pyrazol‐5‐ol)s in high to excellent yields and in short reaction time. The presence of the requisite organocatalytic trityl carbocation(Ph3C+) species was confirmed by analysis of infrared, 1H NMR, and ultra violet spectral data. A plausible mechanism was proposed for the reaction based on the observations and literature precedent.     

非对称N-(亚水杨基)二亚乙基三胺铜(Ⅱ)配合物的合成、结构分析和催化活性评价(英文)

A new copper(Ⅱ) complex of a non‐symmetric Schiff base, [CuII(saldien)(H2O)]+(1), has been synthesized and characterized by elemental analysis and several other spectroscopic methods (Hsaldien = N‐(salicylidene)diethylenetriamine). The crystal structure of 1 has also been determined by X‐ray crystallography. The geometry of the complex cation in 1 was found to be distorted square pyramidal with the mononegative Schiff base coordinating to the copper in a tetradentate mode via the O,N,N’, and N’’‐donor atoms. The remaining coordination site was occupied by the O atom of a H2O molecule in the axial position. The catalytic potential of 1 was tested in the oxidation reactions of cyclooctene and cyclohexene with aqueous 30% H2O2/NaHCO3 in acetonitrile. These reactions proceeded smoothly to give the corresponding epoxides with selectivity levels greater than 99%. This catalytic system also showed high levels of activity and selectivity towards the oxidation of cyclohexane (i.e., cyclohexanol 37% and cyclohexanone 54%) in comparison with most of the other Cu‐based systems reported in the literature.     

以聚(4-乙烯基吡啶)硫酸氢盐为催化剂三组分一锅法合成苯并[f]茚并喹啉(英文)

7‐Aryl‐8H‐benzo[f]indeno[2,1‐b]quinoline‐8‐one derivatives were synthesized by means of a one‐pot condensation of 2‐naphthylamine, aromatic aldehydes, and indane‐1,3‐dione in ethanol under refluxing conditions in the presence of poly(4‐vinylpyridinium) hydrogen sulfate, a solid acid catalyst. This method has the advantages of high yield, clean reaction, simple methodology, and short reaction time. The catalyst could be recycled and reused four times without significant loss of activity. The structure of the novel compounds was confirmed by IR, 1H NMR, and 13C NMR spec-troscopy and elemental analysis.     

二氧化硅负载磷钨酸催化合成3,4-二氢嘧啶-2(1H)-酮衍生物

以取代苯甲醛、乙酰乙酸乙酯和尿素为原料,以溶胶凝胶法制备二氧化硅负载的磷钨酸（H3PW12O40/SiO2）为催化剂,催化合成3,4-二氢嘧啶-2(1H)-酮,考察了三组分摩尔比、反应温度、催化剂用量及反应时间对反应收率的影响。 研究表明,H3PW12O40/SiO2是合成3,4-二氢嘧啶-2(1H)-酮的良性催化剂,在取代苯甲醛的用量为0.04 mol,反应温度为90 ℃的条件下,收率可达73.1%~88.4%。 催化剂和产品结构分别经IR、XRD、SEM和1H NMR、IR、MS等技术手段表征。     

Waste to wealth: conversion of nano‐magnetic eggshell (Fe3O4@Eggshell) to Fe3O4@Ca(HSO4)2: cheap,green and environment‐friendly solid acid catalyst

Eggshell is a hazardous waste by European Union regulations, so that discarded thousands of tons per year. To convert waste (eggshell) to wealth (catalyst), nano‐magnetic eggshell was prepared based on the nano‐Fe₃O₄, and then the eggshell was converted to Ca(HSO₄)₂ with organic acid, namely, chlorosulfonic acid. Based on the back titration, 5.18 mmol SO₄H group was loaded per gram of the nano‐structure. Using this method eggshell was converted to cheap, green and environment‐friendly solid acid catalyst. The prepared catalyst (nano‐ Fe₃O₄@Ca(HSO₄)₂) was characterized by Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), energy dispersive X‐ray spectroscopy (EDX), field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), and thermal gravimetric analysis (TGA). The activity of eggshell waste‐derived catalysts was successfully evaluated in the synthesis of value‐added products, namely indazolo[1,2‐b]‐phthalazinetrione derivatives as a benchmark multicomponent reaction. In addition, design of experiments shows that increase in amount of catalyst (and temperature), boost the reaction yield, especially with steeper slope at higher temperature.     

A simple synthesis route and characterisation of Co(3)Mo(3)C

A simple, one-step thermal decomposition method for the preparation of Co(3)Mo(3)C is reported in this paper. In this novel synthesis route, a mixed-salt precursor, containing Co(CH(3)COO)(2) x 4H(2)O, (HMT)(2)(NH(4))(4)Mo(7)O(24) x 2H(2)O (HMT = hexamethylenetetramine), and excess HMT is directly decomposed to the bimetallic carbide under flowing argon at 1023 K. The role of HMT in the preparation process has been investigated and a detailed reaction mechanism is proposed based on the experimental results. The bimetallic carbide is characterised by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, BET surface area measurement and X-ray photoelectron spectroscopy. Furthermore, the activity of the as-prepared Co(3)Mo(3)C is evaluated by a 3-methylpyridine hydrodenitrogenation (HDN) reaction. The catalyst produced from this method provides better reactivity compared to the Co(3)Mo(3)C catalyst prepared by the conventional temperature-programmed reduction method.     

Copper(I) oxide nanoparticles supported on magnetic casein as a bio‐supported and magnetically recoverable catalyst for aqueous click chemistry synthesis of 1,4‐disubstituted 1,2,3‐triazoles

Copper(I) oxide nanoparticles supported on magnetic casein (Cu₂O/Casein@Fe₃O₄NPs) has been synthesized as a bio‐supported catalyst and was characterized using powder X‐ray diffraction, transmission electron microscopy, energy dispersive X‐ray and Fourier transform infrared spectroscopies, thermogravimetric analysis and inductively coupled plasma optical emission spectrometry. The catalytic activity of the synthesized catalyst was investigated in one‐pot three‐component reactions of alkyl halides, sodium azide and alkynes to prepare 1,4‐disubstituted 1,2,3‐triazoles with high yields in water. The reaction work‐up is simple and the catalyst can be magnetically separated from the reaction medium and reused in subsequent reactions.     

氯化亚锡催化“一锅法”合成N1-取代的3,4-二氢嘧啶-2(1H)-酮

以芳香醛、乙酰乙酸乙酯(甲酯)、单取代脲为原料,氯化亚锡为催化剂,在无溶剂、80℃条件下,通过三组分"一锅法"合成了一系列N1-取代的3,4-二氢嘧啶-2(1H)-酮衍生物。考察了催化剂用量和反应温度对产品收率的影响。通过IR、~1H NMR、~(13)C NMR和元素分析对目标产物结构进行确证,提出了可能的催化作用机理。本文的合成方法具有催化剂活性高、廉价易得和反应时间短、条件温和、产率高、绿色环保等优点。     

A Novel Inorganic-Organic Composite Constructed from Cobalt（Ⅱ）-Monosubstituted Polyoxometalates and Poly（amidoamine）-NH2 DendrimersA Novel Inorganic-Organic Composite Constructed from Cobalt（Ⅱ）-Monosubstituted Polyoxometalates and Poly（amidoamine）-NH2 Dendrimers

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.     

Synthesis and characterization of copper(II) Schiff base complex supported on Fe3O4 magnetic nanoparticles: a recyclable catalyst for the one‐pot synthesis of 2,3‐dihydroquinazolin‐4(1H)‐ones

Fe₃O₄–Schiff base of Cu(II) is found to be a recyclable and heterogeneous catalyst for the rapid and efficient synthesis of various 2,3‐dihydroquinazolin‐4(1H)‐one derivatives from the two‐component condensation of 2‐aminobenzamide and an aldehyde. This reaction is simple, green and cost‐effective. Separation and recycling can also be easily done by magnetic decantation of the Fe₃O₄ nanoparticles with an external magnet. The prepared catalyst was characterized using thermogravimetry, Fourier transform infrared spectroscopy, vibrating sample magnetometry, inductively coupled plasma analysis, X‐ray diffraction and scanning electron microscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

H2O和SO2对Ce(1)Mn(3)Ti催化剂催化氧化NO性能的影响

为了提高MNO_x/TiO₂催化剂催化氧化NO的活性,在载体TiO₂上负载醋酸锰的同时掺杂了一定量的硝酸铈,构成了Ce(1)Mn(3)Ti催化剂,并对催化剂进行XRD、BET和XPS等表征。重点考察了H₂O和SO₂对催化剂活性的影响,通过FT-IR、SEM和BET等表征手段对毒化前后的催化剂组成及结构进行了分析。结果表明,Ce(1)Mn(3)Ti催化剂具有较好的活性,在空速41 000 h^-1、NO体积分数为300×10^-6及O₂含量10%的条件下,反应温度200℃时NO转化率可达58%,250℃时NO转化率达到最高值85%。单独加入4%H₂O使得催化剂活性降低,升高反应温度,H₂O对催化剂的影响减弱;同时通入4%H₂O和100×10^-6SO₂,在反应温度250℃时,NO转化率下降并维持在48%左右,停止通入后恢复到61%。H₂O和SO₂使催化剂活性物种硫酸盐化失活。     

Selective oxidation of ethylbenzene to acetophenone over Cr(III) Schiff base complex intercalated into layered double hydroxide

A new heterogeneous catalyst, Cr(III) Schiff base‐containing layered double hydroxide, was synthesized using the intercalation method. The Cr(III) Schiff base complex derived from 2‐hydroxy‐1‐naphthaldehyde and 4‐aminobenzoic acid was intercalated into the layered double hydroxide. The synthesized materials were characterized using inductively coupled plasma atomic emission spectrometry, energy‐dispersive X‐ray analysis, scanning electron microscopy, X‐ray diffraction, Brunauer–Emmett–Teller surface area measurement, Fourier transform infrared spectroscopy, thermogravimetric analysis, diffuse reflectance UV–visible spectroscopy and electron paramagnetic resonance spectroscopy. The catalytic activity was investigated for the oxidation of ethylbenzene with tert‐butylhydroperoxide as an oxidant under solvent‐free conditions as well as with lower chromium concentrations. In the oxidation reaction, ethylbenzene was oxidized to acetophenone and benzaldehyde. The catalyst was recycled ten times without significant loss of catalytic activity. Leaching studies performed with hot filtration experiments showed that the chromium catalyst was heterogeneous in nature and stable under the reaction conditions.     

Magnetic Fe3O4 nanoparticles supported imine/Thiophene‐nickel (II) complex: A new and highly active heterogeneous catalyst for the synthesis of polyhydroquinolines and 2, 3‐dihydroquinazoline‐4(1H)‐ones

A new magnetically separable nickel catalyst (Ni(NO₃)_2?Imine/Thiophene‐Fe₃O₄@SiO₂) was readily prepared and structurally characterized by Fourier transform infrared spectroscopy (FT‐IR), Scanning electron microscopy (SEM), Energy‐dispersive X‐ray spectroscopy (EDX), Vibrating sample magnetometer (VSM), X‐Ray diffraction (XRD) and Atomic absorption spectroscopy (AAS). The Ni(NO₃)_2?Imine/Thiophene‐Fe₃O₄@SiO₂ exhibited efficient catalytic activity in the synthesis of 2,3‐dihydroquinazoline‐4(1H)‐ones and polyhydroquinolines. Catalysis research under water and solvent‐free conditions makes also this synthetic protocol ideal and fascinating from the environmental point of view. The catalyst can be magnetically recovered after the reaction and can be reused for many times without appreciable decrease in activity.