Highly Efficient,Green Oxidation of Alcohols using Novel Heterogeneous Ruthenium Catalyst

MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions.Furthermore,this catalyst was effective towards alcohol oxidation using wate as solvent instead of toluene.     

Y沸石和多级孔Y沸石封装CuPhen配合物催化性能的比较

选用常规Y沸石和经后处理法制备的多级孔Y沸石为主体,采用自由配体法将铜菲咯啉（CuPhen）配合物封装在不同Y沸石中,制备了CuPhen/Y复合催化材料。采用X射线衍射、TEM、紫外-可见光谱、N₂吸附-脱附、ICP和TG等手段对所制备复合催化材料的物化性质进行了较为详细的表征,并对封装在不同Y沸石主体中的铜配合物在不同尺寸大小反应底物中的催化氧化性能进行了比较研究。结果表明,在以双氧水为氧化剂的反应体系中,封装于多级孔Y沸石中的铜配合物在不同环烷烃氧化反应中的催化活性均高于封装在常规Y沸石中的催化活性,体现出多级孔Y沸石更为优越的主体性能。此外,同封装于常规Y沸石中的铜配合物一样,封装在多级孔Y沸石主体中的金属配合物催化剂也具有良好的稳定性。     

Fephen/Y复合材料的制备、表征及其催化性能

近年来,采用在分子筛孔腔中组装或封装金属配合物的方法制备金属配合物/分子筛复合催化材料的研究引起了人们极大的兴趣.     

Synthesis and Characterization of an Unexpected Asymmetric Binuclear Copper（Ⅰ） Complex Containing 4-Vinyl-pyridine

The asymmetric binuclear copper(I) complex [Cu₂(dppm)₂(C₇H₇N)(μ‐HCOO)](NO₃) (dppm=Ph₂PCH₂PPh₂, C₇H₇N=4‐vinyl‐pyridine) has been prepared and characterized by physicochemical and spectroscopic methods. The complex is photoluminescent at room temperature. It crystallizes in triclinic system, space group P‐1 with a= 1.2719(3) nm, b=1.8637(4) nm, c=1.1656(2) nm, a=97.16(3)°, β= 104.94(3)″, γ=89.39(3)°, V=2.648.1(9) nm³, D_c= 1.390 g.m^?3, Z=2, μ=0.974 mm^?1, R=0.0483 for 5716 independently observed reflections with I>2δ(I). The structure consists of [Cu₂(dppm)₂(C₇H₇N)(μ‐HCOO)]⁺cations and nitrate anions. The copper atoms show different coordination modes: Cu(1) displays a distorted trigonal and Cu(2) a tetrahedred geometry.     

Silica-supported Poly-γ-aminopropylsilane Cu^2＋-Pd^2＋ Complex： A New Catalyst System for Heck Vinylation Reaction

In this paper, a new silica-supported poly-γ-aminopropylsilane Cu^2 -Pd^2 complex was studied in Heck vinylation reaction of aryl iodide with olefins. The catalyst is highly active and stereoselective at 70-100℃, and can be resused after washing without loss in activity.     

Chiral Salen Manganese Complex Immobilized on SBA-15： A New Heterogenized Enantioselective Catalyst for the Epoxidation of Alkenes

Jacobsen‘s catalyst was immobilized onto SBA-15 by multi-step grafting, and this heterogenized catalyst exhibited comparable catalytic performance with the corresponding homogeneous counterpart for the epoxidation of alkenes, and the catalyst could be recycled effectively several times.     

CuZnAl Mixed Oxide Catalyst Prepared from Hydrotalcite-like Precursor for Catalytic Wet Oxidation of Phenol

Theefficiencyofseveralnoblemetalsforcatalyt icwetoxidation (CWO )ofvarious pollutantshasbeendemonstrated[1,2 ] .However ,thenoblemetalsareexpensive ,affectinggreatlytheeconomicsofthecorrespondingprocess .Asanalternative ,theuseoftransition metaloxideshasbeenconsidered[3～ 5] ,buttheyhaveamainproblemofleachinginthecorrosivereactionmixtures .Alejandreetal[6,7] reportedthattheleachingcanbemuchreducedwhenCuAlorCu NiAlmixedoxide preparedfromhydrotalcite likecompound (HTLC) precursorsisusedasth…     

Studies on the Recycling Efficiency of Thermoregulated Phase-separable Rh/PETPP Complex Catalyst

Effects on the recycling efficiency of thermoregulated phase-separable Rh/PETPP(P-[p-C6H4O(CH2CH2O)nH]3,N=3n) complex catalyst involved in hydroformylation of 1-decene are for the first time presented.It was found that the loss of Rh is dependent greatly on the composition of phosphine ligand PETPP and the organic solvent employed in the reaction.     

Effect of Different Dopant in the Mo-V-Te-O Catalyst on the Performance of Selective Oxidation Propane to Acrolein

Several Mo-V-Te-O mixed metal oxides catalysts with different dopant were prepared and used for catalytic oxidation propane to acrolein. It was revealed that the addition of P could greatly improve the performance of the Mo-V-Te-O catalyst. The catalysts were examined by XRD and H2-TPR. The XRD characteristic of the Mo-V-Te-P-O showed that the addition of P could aggrandize the (V0.07Mo0.93)5O14 phase. H2-TPR illuminated that the MoV0.3Te0.23P0.15On catalyst took on the best redox ability.     

铁络合物/八面沸石催化剂中沸石主体的纳米效应

 采用自由配体法制备了Fephen／nano－X和Fephen／nano－Y两种\r\n不同粒度的Fephen／八面沸石纳米复合材料（简称为Fephen／FAU），\r\n并采用X射线衍射、傅里叶变换红外光谱、漫反射紫外－可见光谱、热\r\n重－差热分析和催化反应等手段对其进行了表征．研究结果发现，采用\r\n纳米沸石作主体是自由配体法制备金属络合物／分子筛复合材料中提高\r\n络合物负载量的有效方法．催化反应结果表明，与普通粒度的Fephen／\r\nY复合材料相比，两种不同粒度的Fephen／nano－X和Fephen／nano－Y\r\n纳米复合材料对环己烷氧化反应的催化活性有很大的提高．由于两种纳\r\n米沸石主体的差异，两种纳米复合材料的催化性能也明显不同，不仅对\r\n环己烷的转化能力不同，对氧化产物的选择性也不同．     

The Influence of the Synthesis Temperature on Cobalt Phthalocyanine Encapsulation in Zeolite Y

Several characterization techniques were applied to study the effect of the synthesis temperature on the physicochemical properties of cobalt phthalocyanine incoporated into zeolite Y. The cobalt phthalocyanine was synthesized in the supercages of zeolite Y by the template synthesis method at two different temperatures of 200 and300 °C and characterized by diffuse reflectance spectroscopy, Fourier transform infraredspectroscopy, pore volume analysis, unit cell dimension calculation, UV-vis spectroscopy,thermogravimetric analysis and X-ray diffraction. The results show that the catalyst synthesizedat 200 °C contains 11 wt.% cobalt phthalocyanine and almost all of thiscomplex is encapsulated in the supercages as monomeric species. At higher temperature aconsiderable amount of the cobalt phthalocyanine is hosted in the mesopores and/or on theexternal surface of the zeolite as aggregates. The migration of one part of the cobalt cationsfrom the supercages to the small cages at 300 °C decreases the formation of thenon-aggregated encapsulated phthalocyanine molecules in the zeolite supercages. Theaggregated cobalt phthalocyanine formed at the surface corresponds to the -polymorph stateof the phthalocyanine.     

Y型分子筛超笼内酞菁锰的合成及对烯烃形状选择性催化环氧化反应研究

酞菁锰(MnPc)具有与四苯基卟啉锰(Mn TPP)相似的大环结构,因此金属酞菁用于烯烃催化环氧化的研究,被认为是对细胞色素P-450体系的模拟。催化剂的活性中心是MnPc与单氧源作用生成单氧锰络合物O=MnPc(O×O络合物),在反应中它除了能催化烯烃环氧化外,还会氧化催化剂本身,或发生二聚作用,使催化剂失活。生物酶具有高的选择性和催化活性,除了与酶活性中心有关外,还与酶中蛋白质的三级结构有关,因此活性中心周围的空间结构对反应的选择性和催化活性是非常重要的。人们用具有特殊结构及性能的Y型分子筛,试图来代替细胞色素P-450酶的蛋白质,希望获得特殊的选择性和高的催化活性。有     

M（phen）3／Y分子筛复合催化材料的制备与表征

采用沸石合成法,制备了封装Ｍ（ｐｈｅｎ）３（Ｍ＝Ｆｅ,Ｃｏ,Ｃｒ）配合物于Ｙ型分子筛超笼中的复合催化材料,并利用ＸＲＤ,ＦＴＩＲ,ＵＶ－ｖｉｓ,ＩＣＰ的环己烷氧化反应等手段对其进行了表征。ＦＴ ＩＲ和ＵＶ－ｖｉｓ测试,有力地证明了合成产物中封装有Ｍ（ｐｈｅｎ）３配合物;ＸＲＤ和ＩＣＰ测试结果表明,在合成体系中引入不同的Ｍ（ｐｈｅｎ）３配合物,对Ｙ型分子筛的晶化有不同的影响     

Direct Hydroxylation of Benzene with Hydrogen Peroxide Using Fe Complexes Encapsulated into Mesoporous Y-Type Zeolite

Mesoporous Y-type zeolite (MYZ) was prepared by an acid and base treatment of commercial Y-type zeolite (YZ). The mesopore volume of MYZ was six times higher than that of YZ. [Fe(terpy)₂]²⁺ complexes encapsulated into MYZ and YZ with different Fe contents (Fe(X)L-MYZ and Fe(X)L-YZ; X is the amount of Fe) were prepared and characterized. The oxidation of benzene with H₂O₂ using Fe(X)L-MYZ and Fe(X)L-YZ catalysts was carried out; phenol was selectively produced with all Fe-containing zeolite catalysts. As a result, the oxidation activity of benzene increased with increasing iron complex content in the Fe(X)L-MYZ and Fe(X)L-YZ catalysts. The oxidation activity of benzene using Fe(X)L-MYZ catalyst was higher than that using Fe(X)L-YZ. Furthermore, adding mesopores increased the catalytic activity of the iron complex as the iron complex content increased.     

以催化裂化废催化剂粉合成超细 Y 型分子筛

 针对催化裂化 (FCC) 废催化剂细粉带来的环境污染和未开发利用的现状, 以此为原料合成了小晶粒 Y 型分子筛, 并采用 X 射线衍射、扫描电镜、29Si和27Al 固体核磁共振和激光粒度分析等技术对样品进行了表征. 结果表明, 以 FCC 废催化剂细粉为原料可以合成粒径为 200 nm 左右的 Y 型分子筛, 且制备过程中原料的活化方法和导向剂对所得样品结构影响很大. 对原料采用碱熔活化, 并在合成体系中加入导向剂, 所得 Y 型分子筛的相对结晶度提高, 比表面积增大, 粒度减小.     

HZSM-5分子筛催化剂在催化苯氧化合成苯酚反应中的积炭和失活行为

 在固定床反应器中进行了HZSM-5分子筛催化剂催化苯氧化生成苯酚时的积炭和失活实验,催化剂经高温水蒸气处理,反应条件为: 9.7%N2O-90.3%N2混合气流速115 ml/min,苯流速6 g/h,反应温度400 ℃. 采用TG,吸附吡啶的IR谱,13C NMR和低温N2吸附法对催化剂进行了表征,并用连续流动吸附法测定催化剂上正己烷和环己烷的吸附量. 结果表明,苯氧化生成苯酚的反应过程中,催化剂表面积炭导致分子筛微孔孔口堵塞是造成催化剂失活的主要原因. 与其他有机物在ZSM-5上的积炭相似,B酸中心是积炭的活性中心. 积炭物种主要为带有烷基的芳烃和多环芳烃,同时含有少量带有羟基的多环芳烃,这可能是由在L酸中心上生成的苯酚进一步氧化、脱氢和聚合形成的.     

A Lamellar MWW Zeolite With Silicon and Niobium Oxide Pillars: A Catalyst for the Oxidation of Volatile Organic Compounds

In this work, an MWW-type zeolite with pillars containing silicon and niobium oxide was synthesized to obtain a hierarchical zeolite. The effect of niobium insertion in the pillaring process was determined by combining a controllable acidity and accessibility in the final material. All pillared materials had niobium occupying framework positions in pillars and extra-framework positions. The pillared material, Pil-Nb-4.5 with 4.5 wt % niobium, did not compromise the mesoporosity formed by pillaring, while the increase of niobium in the structure gradually decreased the mesoporosity and ordering of lamellar stacking. The morphology of the pillared zeolites and the niobium content were found to directly affect the catalytic activity. Specifically, we report on the activity of the MWW-type zeolites with niobium catalyzing the gas-phase oxidation of volatile organic compounds (VOCs), which is an important reaction for clean environmental. All produced MWW-type zeolites with niobium were catalytically active, even at low temperatures and low niobium loading, and provided excellent conversion efficiencies.     

沸石负载的钒络合物催化剂对烷烃氧化反应的催化性能

 将钒氧吡啶甲基络合物VO（pic）2负载于Y及ZSM－5沸石分子筛\r\n中，制备出沸石负载的钒络合物催化剂．用X射线衍射、电子自旋共振\r\n、红外光谱和元素分析等方法对催化剂进行了表征．结果表明，VO（p\r\nic）2络合物确实负载于分子筛孔道内，负载后的络合物仍保持着原来\r\n的结构．考察了催化剂对正己烷和环己烷氧化反应的催化性能，发现沸\r\n石分子筛负载的VO（pic）2络合物催化剂保留有络合物原有的催化性能\r\n，虽然催化活性有所下降，但显示出较好的形状选择性．与未负载的络\r\n合物相比，NaY和ZSM－5沸石负载的VO（pic）2络合物催化剂对正己烷\r\n氧化反应的伯醇选择性分别提高了2～3倍和5～6倍．