La取代Ba对Ba1-xLaxMn3Al9O19-α催化剂结构及甲烷催化燃烧性能的影响

采用以尿素水解为基础的水热合成法制备了La和Mn取代的六铝酸盐催化剂(Ba1-xLaxMn3Al9O19-α).在Mn含量达到阈值时,研究了不同量的La取代Ba对Ba1-xLaxMn3Al9O19-α的相组成、结构、热稳定性及甲烷催化燃烧活性的影响.当x≥0.4时,水热合成过程中生成的La2(CO3)3在530-580℃分解,800-900℃时与-γAl2O3反应生成LaAlO3钙钛矿相,可抑制由BaCO3分解而生成的Ba2+的固相扩散,从而阻止了BaAl2O4尖晶石相的生成,使Ba2+在固相中保持较高的分散性,促进了六铝酸盐(-βAl2O3)相的形成.当x<0.4时,BaAl2O4尖晶石相的存在引起催化剂比表面积和催化燃烧活性的降低.La3+取代Ba2+后,六铝酸盐结构发生一定程度的扭变.这种扭变越大,所形成的六铝酸盐催化剂的热稳定性越差.Ba1-xLaxMn3Al9O19-α催化剂的甲烷催化燃烧活性随x的增大而增加,x=0.8时催化剂的活性最佳.     

La0.8Sr0.2FeMn1.5Al9.5O19-δ六铝酸盐气溶胶催化剂的催化性能

采用共沉淀-超临界干燥法制备了混合取代型La0.8Sr0.2FeMn1.5Al9.5O19-δ(LSFMAO)六铝酸盐气溶胶甲烷燃烧催化剂, 并采用XRD、BET、SEM、TPR等技术研究了超临界干燥和高温焙烧对材料结构和催化性能的影响. 超临界干燥处理的前驱物经1200 ℃焙烧后, 得到磁铅石型六铝酸盐气溶胶, 其具有较高的比表面积(16 m2·g-1)和甲烷燃烧活性; 然而高温(1300-1400 ℃)老化导致该六铝酸盐严重烧结, 比表面积和催化活性急剧下降. 研究结果表明, 对一定温度范围内(≤1200 ℃)焙烧的六铝酸盐催化剂, 超临界干燥法有助于改善其热稳定性和催化活性, 但高温(>1200 ℃)老化后, 催化剂的抗热烧结和催化性能主要由材料的组成和固有结构性质决定.     

CaxLa1-xMnAl11O19 六铝酸盐催化剂上甲烷的催化燃烧

以共沉淀法制备了CaxLa1-xMnAl11O19系列六铝酸盐催化剂,考察了Ca2 部分取代La3 对LaMnAl11O19六铝酸盐的甲烷催化燃烧活性和稳定性的影响以及活性与物理化学性能的关系,用X射线衍射、N2吸附、程序升温还原和透射电镜对其进行了表征.结果表明,当Ca2 加入量过高时,Ca2 不能进入到六铝酸盐骨架中,过量的Ca2 形成CaAl4O7杂相.当x=0.2时,催化剂活性最高,起燃温度为723 K,也提高了样品的热稳定性,1 373 K煅烧后比表面积为26.1 m2/g.Ca2 的加入使六铝酸盐晶粒变薄,这使材料的抗烧结性能增强,比表面积增大,同时Ca2 部分取代La3 使活性Mn3 的含量增加,这两方面的综合作用使得催化剂活性显著提高.对Sr2 ,Ca2 和K 部分取代La3 的六铝酸盐的比较实验结果表明,Ca2 部分取代La3 的样品具有最低的起燃温度.     

不同金属取代六铝酸盐的制备及其对甲烷燃烧的催化性能研究

采用铝溶胶作为碳酸铵共沉淀的前驱体,结合乙醇超临界干燥制备了不同金属取代六铝酸盐催化剂(Ba0.8La0.2MAl11O19-α,M=Mn,Fe,Co,Cu),并用BET,XRD,TEM,UV-Vis和O2-TPD等技术对催化剂进行了表征。结果表明,经1200℃焙烧后,生成了具有大的比表面积(42~73 m2.g-1)的棒状六铝酸盐,比表面积由大到小的顺序是Mn>Co>Fe>Cu。XRD结果表明,除Mn取代催化剂之外,其他均含有少量-αAl2O3杂质相。Fe,Mn取代六铝酸盐中的金属离子(Fe3+,Mn3+)主要为Oh配位,而Co,Cu取代六铝酸盐中的金属离子(Co3+,Cu2+)则为Oh和Td配位。O2-TPD表明,Mn,Cu取代的催化剂中具有高的晶格氧含量。催化剂活性由高到低的顺序为Mn>Cu>Fe>Co,催化活性取决于过渡金属离子的氧化还原循环的可逆性、比表面积以及晶格氧等因素。     

搀杂六铝酸盐LaMxAl12-xO19+δ上甲烷催化燃烧研究

采用共沉淀法制备了系列金属Mn搀杂的六铝酸盐LaMnxAl12-xO19+δ(x分别为0, 0.5, 1.0, 1.5, 2.0, 5.0)催化剂, 采用BET, TG-DTA, XRD进行了物性表征, 并以甲烷催化燃烧为目标反应, 研究了Mn搀杂量对催化剂活性的影响. 结果表明 LaAl12O19+δ催化活性较低, 随着Mn的引入, 催化活性逐步提高. 当x=1.5时, 催化活性达到最大值, 为理想搀杂量. 焙烧温度对晶型及催化活性有重要影响, 1200 ℃时可以形成完整的六铝酸盐晶型, 并具较高的催化性能. 所得较好催化剂起燃温度T10%为418 ℃, T90%为663 ℃.     

逆微乳液法合成六铝酸盐甲烷燃烧催化剂

采用逆微乳液为媒介合成六铝酸盐及其金属取代系列甲烷燃烧催化剂.首先研制了由表面活性剂、助剂、油相和水相四组分逆微乳液拟三元体系相图,选择十六烷基三甲基溴化铵(CTAB)为表面活性剂,脂肪醇为助剂,正辛烷为油相和水相[或Al(NO3)3溶液].研究了助剂脂肪醇链长、表面活性剂与助剂相对量和盐浓度对微乳液体系形成和稳定性影响,并以电导率随水含量变化的规律很好地印证了微乳液体系的相行为.选取相图中稳定微乳区合成了具有高温稳定性的甲烷催化燃烧催化剂六铝酸镧[La(Mnx/Fex)Al12-xO19-δ].用BET、TG-DTA和XRD表征了催化剂的物性和结构,并在微型固定床反应器中考察了对甲烷燃烧的催化活性.结果表明,利用逆微乳液作为反应介质使催化剂前驱体分散更充分,使六铝酸盐晶相形成的温度有效地降低到950℃.Fe取代的六铝酸盐具有较好高温催化活性和热稳定性,而Mn取代的同晶体则具有较好的低温催化活性,Fe和Mn离子同时对Al3 进行取代时,由于两者之间存在的协同效应明显提高了催化剂的催化活性和比表面,T10仅为475℃,T90为660℃.     

BaMn_xAl_(12-x)O_(19-δ)六铝酸盐催化剂上甲烷催化燃烧性能

采用共沉淀-超临界干燥法制备了六铝酸盐甲烷燃烧催化剂(BaMnxAl12-xO19,x≤4),利用XRD(X射线衍射),BET(BET比表面积测定),TEM(透射电子显微镜)和TPR(程序升温还原)等表征方法对催化剂进行了表征,并在微型固定床反应器中考察其对甲烷的催化活性.结果表明,经过1200℃焙烧后,六铝酸钡(BaAl12O19)中仍有铝酸钡(BaAl2O4)相存在,经Mn离子取代后可以得到单一的六铝酸盐相,过量Mn的加入(当x=4时),催化剂中又出现了杂质相,且XRD的衍射峰强度变小.TPR表征结果表明,Mn在六铝酸盐结构中以 2和 3混合价态存在,Mn3 离子的比例随x的增大而增多.实验结果表明:与普通干燥法相比较,超临界干燥法可大大提高催化剂的比表面积,它对甲烷燃烧的催化活性也有增加.未取代活性离子的六铝酸钡基质对甲烷燃烧催化活性很低,经Mn离子取代后活性大大提高,当x=3时催化活性最高.     

六铝酸盐SrNiAl11O19-δ催化二氧化碳重整甲烷制合成气反应研究

本文通过品格取代作用,制备了以Ni为活性组分的六铝酸盐复合氧化物催化剂SrNiAl11O19-δ并通过XRD,XPS,TPR等实验技术,对催化剂的结构和性质进行了表征.结果表明,六铝酸盐SrNiAl11O19-δ对二氧化碳重整甲烷制合成气反应具有良好的催化活性和稳定性,在780℃反应2小时,CH,和CO2转化率分别为95.0%和93.4%,没有发现活性组分Ni高温烧结和催化剂失活.     

La促进型六铝酸盐Ba1－xLaxFeAl11O19－δ催化甲烷燃烧性能

用碳酸铵水溶液共沉淀法制备了系列Ba_1－xLa_xFeAl₁₁O_19－δ六铝酸盐型催化剂,并以甲烷燃烧为探针反应考察催化剂的催化活性.La部分取代Ba提高了催化剂的催化甲烷燃烧活性,且随La取代量的增加,催化剂的起燃温度呈规律性变化,镧、钡之间存在最佳配比,活性最好的催化剂为Ba_0.2La_0.8FeAl₁₁O_19－δ,其催化甲烷燃烧的起燃温度仅有495 ℃（V_CH4:V_O2:V_N2=1:4:95）.XRD和SEM结果表明,不同含量镧掺杂的材料经1 200 ℃焙烧5 h后，呈现典型的六铝酸盐结构特征；不同温度的焙烧实验表明掺杂镧能够促进六铝酸盐相的形成.Diffuse UV-Vis表征表明催化剂中的铁呈＋3价,Diffuse UV-Vis, TPR和FT-IR结果表明Ba、La、Fe之间存在协同作用.     

Ba、Mn对Al2O3热稳定性和甲烷催化燃烧活性的影响

采用溶胶-凝胶法制备BaO•6Al2O3系列催化剂.考察了Ba、Mn的引入对Al2O3的热稳定性及甲烷催化燃烧性能的影响.结果表明, Ba在高温下与Al2O3首先生成BaAl2O4，然后进一步与Al2O3反应生成具有β-Al2O3结构的BaAl12O19六铝酸盐，抑制了Al2O3进一步的烧结，提高了催化剂的热稳定性. Mn的引入也能够促进六铝酸盐的生成并提高催化剂的甲烷燃烧活性.采用超临界干燥法可抑制干燥过程中因毛细收缩引起的比表面积降低.所制备的BaMnAl11O19催化剂经1200 ℃焙烧4 h后，比表面积为35.1 m2•g－1，在空速40000 h－1条件下，10％甲烷转化温度(T10％)为500 ℃，催化活性明显高于常规干燥法制备的相应催化剂.     

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.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

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.