常温常湿CO氧化催化剂Au/Fe2O3的制备与稳定性研究

研究了不同方法制备的Ａｕ／Ｆｅ２Ｏ３催人上常温常湿条件下ＣＯ的氧化性能。结果表明,加料顺序、焙烧温度、沉淀剂种类、金含量等因素对催化剂的稳定性均有较大影响,其中以Ｋ２ＣＯ３或Ｎａ２ＣＯ３为沉淀剂,金含量３％,焙烧温度２５０～３５０℃制得的催化剂具有较好的稳定性和抗水性,于２５℃连续加篱水蒸气反应４３０ｈ可保持ＣＯ完全转化,ＸＲＤ结果表明,催化剂的稳定性与单质金及α－Ｆｅ２Ｏ３的粒径成反比,并与反应     

常温常湿CO氧化催化剂An/Fe_2O_3 的制备与稳定性研究

研究了不同方法制备的 Ａｎ／Ｆｅ２Ｏ３催化剂上常温常湿条件下 ＣＯ的氧化性能．结果表明,加料顺序、焙烧温度、沉淀剂种类、金含量等因素对催化剂的稳定性均有较大影响,其中以Ｋ２ＣＯ３或Ｎａ２ＣＯ３为沉淀剂,金含量３％,焙烧温度２５０～３５０℃ 制得的催化剂具有较好的稳定性和抗水性,于２５℃连续加入水蒸气反应４３０ ｈ可保持ＣＯ完全转化． ＸＲＤ结果表明,催化剂的稳定性与单质金及α－Ｆｅ２Ｏ３的粒径成反比,并与金和铁的化学状态有关．     

Au／Fe2O3催化剂在CO低温氧化中的催化活性

制备了过渡金属氧化物分散的金催化剂,考察了该催化剂在ＣＯ低温氧化中的催化活性及其制备条件,如过渡金属氧化物的选择、沉淀剂、催化剂的预处理温度及处理时间、金含量、Ｃｌ－ 、催化剂制备方法及催化剂前体等因素对催化活性的影响。最佳结果显示： 以Ｋ２ＣＯ３ 为沉淀剂、采用共沉淀法制备的１ ％ Ａｕ／Ｆｅ２Ｏ３ 催化剂,可使空气中含１％ 的ＣＯ在２５７Ｋ的低温下完全转化成ＣＯ２ 。     

CuO／CeO2和CuO／Al2O3催化剂的催化性能

本文以ＣＯ氧化为模式反应考察了ＣｅＯ２和Ａｌ２Ｏ３负载氧化铜催化剂的氧化活性，运用ＸＲＤ和ＴＰＲ技术研究了催化剂的还原性能和物相结构，结果表明：载体性质对负载ＣｕＯ催化剂的ＣＯ氧化活性有很大影响，ＣｕＯ／ＣｅＯ２催化剂活性明显高于ＣｕＯ／Ａｌ２Ｏ３催化剂．催化剂的还原特性随载体不同而不同．同时发现，热处理对催化剂铜物种的存在形式，晶粒大小、还原特性及其催化活性有明显影响，ＣｕＯ／Ａｌ２Ｏ３催化剂活性下降的主要因素是生成了活性较低的ＣｕＡｌ２Ｏ４相，而ＣｕＯ／ＣｅＯ２催化剂活性下降是由于ＣｕＯ和ＣｅＯ２发生烧结，晶粒变大     

异丁烷催化脱氢制异丁烯Cr2O3／Al2O3体系催化剂

对异丁烷催化脱氢催化剂进行了研究。助催化剂Ｋ２Ｏ,ＣｕＯ的引入改进了Ｃｒ２Ｏ３／Ａｌ２Ｏ３催化剂的活性和抗积炭性能。同时考察了原料气空速、反应温度以及催化剂制备的焙烧温度对Ｋ２Ｏ－ＣｕＯ－Ｃｒ２Ｏ３／Ａｌ２Ｏ３催化剂反应性能的影响。ＸＲＤ谱图表明,Ｃｒ２Ｏ３在催化剂中高分散,７００℃焙烧的催化剂中出现的ＫＣｕＯ晶相对催化剂活性不利。用ＮＨ３－ＴＰＤ和ＣＯ２－ＴＰＤ检测了催化剂表面的酸碱中心,表明助     

甲醇催化氧化重整反应制氢的研究

研究了Ｃｕ／Ｚｎ／Ａｌ系列催化剂催化甲醇氧化重整反应制氢,得到活性,选择性及稳定性较好的催化剂Ｃｕ６０Ｚｎ３０Ａｌ５Ｃｅ５;并且考察了Ｃｕ６０Ｚｎ３０Ａｌ５Ｃｅ５为催化剂时,该反应的工艺条件如温度,物料配比等,当压力为０．１ＭＰａ,温度为２４０℃,ＣＨ３ＯＨ：Ｈ２Ｏ＝１：０．８,ＣＨ３ＯＨ：Ｏ２＝４：１时,甲醇的转化率达９７．７５％,在此反应条件下,反应１００ｈ后,甲醇的转化率仍在９６％以上。     

临氢还原处理对Al2O3负载的CuO-MOx催化剂的影响

研究了Ｈ２预处理对Ａｌ２Ｏ３负载ＣｕＯ和ＣｕＯ－ＭＯｘ催化剂的作用。考察了Ｈ２处理时间、Ｈ２处理浓度以及多次还原氧化循环对ＣｕＯ系催化剂ＣＯ氧化活性的影响规律,并用原位还原氧化反应技术、ＸＰＳ对Ｈ２预处理的作用进行了研究。结果表明,ＣｕＯ－ＣｏＯ／Ａｌ２Ｏ３和ＣｕＯ－Ｃｅ２Ｏ３／Ａｌ２Ｏ３催化剂受Ｈ２还原处理后ＣＯ氧化活性明显增加,并随Ｈ２处理时间、处理浓度的增加而增强。而且催化剂的ＣＯ氧化活性还     

以Au(PPh3)(NO3)为前体的Au/NiO催化剂的制备及其对CO的催化氧化

采用有机金属配合物固载法,将金的有机配合物Ａｕ（ＰＰｈ３）（ＮＯ３）沉积于刚制备出的Ｎｉ（ＯＨ）２沉淀上,与其表面的－ＯＨ基反应,再于注动空气中程序升温焙烧,制和轩出了颗粒度小,分散度高的金催化剂,改变制备条件,研究其对催化剂活性的影响。结果表明,以Ｋ２ＣＯ３作为制备Ｎｉ（ＯＨ）２的沉淀剂,金担载量为３％（质量分数）,在焙烧温度为３００℃的条件下,制备出的负载型金催化剂Ａｕ／ＮｉＯ对ＣＯ的低温氧化     

稀土氧化物对Ni／α—Al2O3催化甲烷部分氧化制合成气反应的影响

研究了稀土金属氧化物（Ｌａ２Ｏ３，ＣｅＯ２，Ｐｒ６Ｏ１１和Ｎｄ２Ｏ３）对Ｎｉ／α－Ａｌ２Ｏ３催化剂上甲烷部分氧化制合成气反应的影响．Ｘ光粉末衍射和活性考察结果表明，稀土氧化物使Ｎｉ／α－Ａｌ２Ｏ３催化剂的稳定性有显著提高．稀土氧化物与活性组份Ｎｉ之间的相互作用抑制了催化剂表面Ｎｉ晶粒的生长和迁移，由于这种作用也抑制了催化剂表面积炭的生成．在实验中还发现ＣｅＯ２容易进行Ｃｅ３＋Ｃｅ４＋氧化还原反应而对反应具有催化活性．     

制备条件对Ａｕ／ＬａＣｏＯ３催化氧化ＣＯ性能的影响

采用溶胶凝胶法制备了钙钛矿型复合氧化物ＬａＣｏＯ３,并用沉积沉淀法（ＤＰ法）制备了Ａｕ／ＬａＣｏＯ３催化剂．考察了制备条件对催化剂催化氧化ＣＯ活性的影响．结果表明,制备过程中,溶液ｐＨ、ｐＨ调节顺序及催化剂焙烧温度对催化剂活性均有一定影响．Ａｕ／ＬａＣｏＯ３催化剂的最佳制备条件为：沉积过程中在ＨＡｕＣｌ４溶液中先加入载体后,再调节溶液ｐＨ＝８,得到的催化剂经２５０℃焙烧后可提高催化剂稳定性．     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.     

Copper-catalyzed multicomponent reactions of 2-iodoanilines,benzylamines, and elemental sulfur toward 2-arylbenzothiazoles

A relatively cheap copper salt-catalyzed, three-component approach providing 2-arylbenzothiazoles in good to excellent yields from readily available 2-iodoanilines, benzylamines, and sulfur powder is reported. This methodology allows preparation of various classes of 2-arylbenzothiazoles and provides a general, reliable approach.