SAPO-5分子筛的晶化过程研究

采用X射线衍射、 X射线荧光光谱、 扫描电子显微镜和固体核磁共振波谱等方法对SAPO-5分子筛的晶化过程进行了研究. 结果表明, SAPO-5分子筛的生成遵循液相晶化机理. 在晶化前期首先生成一种具有较为规整形貌的无定形磷酸铝(记为Am), 晶化温度大于200 ℃后开始出现SAPO-5, 同时无定形物质Am的量也明显增加, 随后Am逐渐溶解并贡献于SAPO-5的生长; 硅原子在晶化初期直接参与晶化进入SAPO-5分子筛骨架, 随着晶化时间延长, 分子筛晶体中硅含量逐渐增加; SAPO-5骨架仅能容纳少量的Si(4Al)物种, 在样品含有较低硅含量时骨架中即出现硅岛. XPS分析进一步揭示SAPO-5分子筛存在表面富硅现象, 硅在晶体中从核到壳含量递增. 研究结果也表明, 分子筛的拓扑结构和硅源选择影响晶体表面富硅程度.     

Y沸石中不同状态铁离子的还原和催化性质

制备了Fe(Ⅲ)处于骨架四面体内、阳离子位及以氧化物形式分散在沸石表面的含铁Y沸石.用TPR方法测定样品的可还原性,发现不同形态的Fe(Ⅲ)其还原情况不同,在800℃以下均不能被还原成金属Fe.以异丙醇脱水和脱氢为探针,考察了样品的酸碱性,证实在沸石结构内引入不同形态的Fe(Ⅲ)可调变沸石的酸碱性.用乙苯脱氢和裂解反应考察了样品的脱氢活性.当样品表面金属离子和强酸位同时存在时,由于二者的协同作用,裂解反应有可能占主导地位.消除强酸位,增加碱性位,可显著提高脱氢的选择性.     

含骨架铁ZSM-5的合成及其负载Pt催化剂在正十二烷脱氢反应中的催化性能

采用水热合成法使铁进入分子筛MFI骨架结构,成功合成出含骨架铁的分子筛Na-[Fe]-ZSM-5,并通过离子交换法负载Pt制备脱氢催化剂Pt/Na-[Fe]-ZSM-5。通过正十二烷脱氢反应,研究了该催化剂对长链烷烃脱氢制单烯烃反应的催化性能。采用N2吸附-脱附测试、X射线衍射(XRD)、傅立叶变换红外光谱(FT-IR)、氨气程序升温脱附(NH3-TPD)、吡啶吸附的红外光谱(Py-IR)、CO化学吸附、透射电子显微镜(TEM)等不同方法对催化剂进行了表征。结果表明,通过控制骨架铁含量可调控催化剂表面酸性;含骨架铁的ZSM-5分子筛载体具有抑制负载金属晶粒长大,保持金属高分散度的作用;其负载铂催化剂Pt/Na-[Fe]ZSM-5-50具有表面弱酸中心(0.69 mmol·g^-1)和高分散Pt中心,因而具有良好的长链烷烃脱氢活性、稳定性和单烯烃选择;在转化率稳定在~20%时,TOF为4.56 s^-1,单烯烃选择性为92.7%;在实验范围内,Pt/Na-[Fe]ZSM-5催化剂表面弱酸量和脱氢反应的本征活性(TOF)均随催化剂铁含量的增加而增加。     

SAPO-5分子筛中硅的取代及其性能研究

本文采用三乙胺为模板剂,用水热法合成不同含硅量的SAPO-5分子筛,并用X射线衍射、扫描电镜、电子探针分析、真空重量吸附等方法对其进行了表征,结果表明硅已进入了骨架,硅同晶非等比取代磷和铝,并且分子筛的孔道是畅通的。 用微型反应器测定了AlPO₄-5及不同量硅取代的SAPO-5分子筛上的异丙苯裂解和邻二甲苯异构化催化反应,结果表明Si引入了催化活性很低的磷酸铝骨架后使其催化活性明显增加,进一步证实了硅是同晶非等比取代磷和铝,因而使分子筛骨架带负电性。 硅进入磷酸铝分子筛骨架的SAPO-5分子筛经红外光谱实验发现不仅具有表面羟基,而且都是酸性羟基。吸附吡啶后的红外光谱结果表明SAPO-5上同时存在B酸和L酸中心,B酸中心数目随着硅含量的增加而增加。     

通过SAPO-34分子筛笼中引入金属物种提升甲醇制烯烃反应中乙烯选择性

低碳烯烃(乙烯、丙烯)是化学工业极其重要的基本原料.甲醇制烯烃(MTO)反应是重要的烯烃生产石油替代路线.其中,磷酸硅铝类SAPO-34分子筛在MTO反应中表现出优异的低碳烯烃选择性.与丙烯相比,乙烯具有更高的经济附加值,因此提升MTO反应中乙烯的选择性有着重要的意义.本文采用传统离子交换法(CIE)、模板辅助离子引入法(TII)和醇相离子交换法(AIE)对SAPO-34分子筛进行金属Zn、Cu改性,利用多种表征手段对金属Zn、Cu改性SAPO-34分子筛的物理结构、化学组成、金属物种状态与分布、酸性及扩散性质等进行表征.首先,对金属Zn、Cu改性SAPO-34分子筛的物理结构和化学组成进行分析.X射线衍射表明,相比AIE法,CIE法和TII法改性基本保持SAPO-34分子筛的结晶度.X射线荧光分析表明,相比Co、Ni,金属Zn、Cu更易引入SAPO-34分子筛.N2物理吸附-脱附表明,CIE法改性能够保持SAPO-34分子筛的BET比表面积和微孔孔容.其次,考察了金属Zn、Cu改性SAPO-34分子筛中金属物种的状态.氢气-程序升温还原(H2-TPR)和X射线光电子能谱(XPS)结果表明,Zn物种主要以孤立态的Zn2+阳离子形式存在.H2-TPR、XPS、紫外-可见光谱和电子顺磁共振谱结果表明,Cu物种主要以孤立态的Cu2+阳离子以及部分CuO形式存在.继而对金属Zn、Cu改性SAPO-34分子筛中金属物种的分布进行表征.XPS表明,Zn阳离子改性的SAPO-34表层富硅、富Zn,呈类核壳结构;XPS和扫描式电镜-能量色散X射线光谱结果表明,Cu物种在Cu改性SAPO-34分子筛中均匀分布.进一步研究了金属Zn、Cu改性SAPO-34分子筛中酸性的变化.氨气-程序升温脱附和核磁共振氢谱结果表明,Zn、Cu改性SAPO-34酸性位点的酸量降低.最后,对金属Zn、Cu改性SAPO-34分子筛的扩散性质进行分析.智能重量分析表明,Zn、Cu阳离子的引入降低探针分子(乙烷、丙烷)的扩散系数,推断Zn、Cu阳离子的引入增加对MTO反应产物的扩散限制.热重表明,Zn阳离子改性SAPO-34分子筛反应初期积炭量略微增加.综上所述,Zn阳离子改性SAPO-34催化剂表层富硅、富Zn,呈现类核壳结构.Zn阳离子的引入增加对MTO反应产物的扩散限制,而且Zn阳离子的引入促进MTO反应初始阶段的碳沉积.因此,Zn阳离子改性SAPO-34分子筛显著增加MTO反应产物的扩散限制,对分子尺寸较大的反应产物的扩散限制更为明显,从而提高MTO反应初始阶段的乙烯选择性,增大乙烯/丙烯比.     

Cr-AlPO4-5的合成及其对苯直接氧化制苯酚反应的催化性能

 以Cr(NO3)3为Cr源用水热法合成了Cr-AlPO4-5分子筛,并用XRD,FT-IR和XPS对分子筛进行了表征. 结果表明,Cr已进入到Cr-AlPO4-5分子筛骨架结构中; 焙烧后分子筛样品的L酸中心和B酸中心数量均大幅度增加,Cr主要以Cr(Ⅴ)形式存在. 将分子筛样品用于催化H2O2氧化苯制苯酚反应,苯酚收率最高可达4.7%,选择性可达99.5%以上. 非骨架Cr物种是导致H2O2无效分解和选择性下降的主要因素,而骨架Cr物种是反应的活性中心. 提出了以骨架Cr过氧化物为中间物种的可能的反应机理,并用原位红外光谱初步验证了中间物种的存在.     

通过SAPO-34分子筛笼中引入金属物种提升甲醇制烯烃反应中乙烯选择性（英文）

低碳烯烃(乙烯、丙烯)是化学工业极其重要的基本原料.甲醇制烯烃(MTO)反应是重要的烯烃生产石油替代路线.其中,磷酸硅铝类SAPO-34分子筛在MTO反应中表现出优异的低碳烯烃选择性.与丙烯相比,乙烯具有更高的经济附加值,因此提升MTO反应中乙烯的选择性有着重要的意义.本文采用传统离子交换法(CIE)、模板辅助离子引入法(TII)和醇相离子交换法(AIE)对SAPO-34分子筛进行金属Zn、Cu改性,利用多种表征手段对金属Zn、Cu改性SAPO-34分子筛的物理结构、化学组成、金属物种状态与分布、酸性及扩散性质等进行表征.首先,对金属Zn、Cu改性SAPO-34分子筛的物理结构和化学组成进行分析.X射线衍射表明,相比AIE法,CIE法和TII法改性基本保持SAPO-34分子筛的结晶度.X射线荧光分析表明,相比Co、Ni,金属Zn、Cu更易引入SAPO-34分子筛.N_2物理吸附-脱附表明,CIE法改性能够保持SAPO-34分子筛的BET比表面积和微孔孔容.其次,考察了金属Zn、Cu改性SAPO-34分子筛中金属物种的状态.氢气-程序升温还原(H2-TPR)和X射线光电子能谱(XPS)结果表明,Zn物种主要以孤立态的Zn2+阳离子形式存在.H_2-TPR、XPS、紫外-可见光谱和电子顺磁共振谱结果表明,Cu物种主要以孤立态的Cu~(2+)阳离子以及部分CuO形式存在.继而对金属Zn、Cu改性SAPO-34分子筛中金属物种的分布进行表征.XPS表明,Zn阳离子改性的SAPO-34表层富硅、富Zn,呈类核壳结构;XPS和扫描式电镜-能量色散X射线光谱结果表明,Cu物种在Cu改性SAPO-34分子筛中均匀分布.进一步研究了金属Zn、Cu改性SAPO-34分子筛中酸性的变化.氨气-程序升温脱附和核磁共振氢谱结果表明,Zn、Cu改性SAPO-34酸性位点的酸量降低.最后,对金属Zn、Cu改性SAPO-34分子筛的扩散性质进行分析.智能重量分析表明,Zn、Cu阳离子的引入降低探针分子(乙烷、丙烷)的扩散系数,推断Zn、Cu阳离子的引入增加对MTO反应产物的扩散限制.热重表明,Zn阳离子改性SAPO-34分子筛反应初期积炭量略微增加.综上所述,Zn阳离子改性SAPO-34催化剂表层富硅、富Zn,呈现类核壳结构.Zn阳离子的引入增加对MTO反应产物的扩散限制,而且Zn阳离子的引入促进MTO反应初始阶段的碳沉积.因此,Zn阳离子改性SAPO-34分子筛显著增加MTO反应产物的扩散限制,对分子尺寸较大的反应产物的扩散限制更为明显,从而提高MTO反应初始阶段的乙烯选择性,增大乙烯/丙烯比     

不同类型含铁分子筛上N2O催化分解反应

采用固态离子交换法制备了一系列Fe/Al摩尔比为0.33的Fe/分子筛(ZSM-35,ZSM-5,beta和mordenite (丝光沸石))样品,并利用紫外-可见漫反射光谱、原位红外光谱和可见拉曼光谱以及瞬态应答实验考察了分子筛种类对N₂O分解反应性能的影响.研究表明,经高温处理(HT)后分子筛的催化活性顺序为 Fe/ZSM-35 > Fe/beta > Fe/ZSM-5 > Fe/mordenite,与骨架外铝稳定的双核铁物种含量一致.这说明双核铁物种是高温处理后Fe/分子筛样品中N₂O分解的活性位,而它的形成与分子筛种类密切相关.Fe/ZSM-35分子筛十元环孔道中相邻两个α位和八元环孔道中相邻两个β位都能稳定两个Fe(II)离子而形成能高效分解N₂O的双核铁活性中心.Fe/beta和Fe/ZSM-5分子筛中只有落在相邻两个β位上的两个Fe(II)离子才能形成参与N₂O分解的高活性的双铁活性中心.Fe/mordenite-HT分子筛上的铁物种绝大部分以孤立Fe离子的形式存在,因此其催化N₂O分解反应活性很低.     

(Fe)ZSM-5的水热稳定性及转化甲醇为低碳烯烃的反应性能

用XRD,ESR,Mossbauer谱,TPD,IR及连续反应等技术,考察了水热处理对杂原子(Fe)ZSM-5的结构稳定性、表面酸性和对甲醇转化为低碳烯烃反应性能的影响。在水蒸汽的影响下,骨架铁易向分子筛表面迁移而使分子筛骨架向silicalite-1转化。(Fe)ZSM-5的表面酸性明显弱于(Al)ZSM-5,而且酸中心以L酸为主,随着水热处理温度的提高,B酸下降程度大于L酸。另外,随着水热处理温度的提高,甲醇转化的活性降低。     

SAPO-5分子筛中硅的取代及其性能研究

本文采用三乙胺为模板剂,用水热法合成不同含硅量的SAPO-5分子筛,并用X射线衍射、扫描电镜、电子探针分析、真空重量吸附等方法对其进行了表征,结果表明硅已进入了骨架,硅同晶非等比取代磷和铝,并且分子筛的孔道是畅通的。 用微型反应器测定了AlPO_4-5及不同量硅取代的SAPO-5分子筛上的异丙苯裂解和邻二甲苯异构化催化反应,结果表明Si引入了催化活性很低的磷酸铝骨架后使其催化活性明显增加,进一步证实了硅是同晶非等比取代磷和铝,因而使分子筛骨架带负电性。 硅进入磷酸铝分子筛骨架的SAPO-5分子筛经红外光谱实验发现不仅具有表面羟基,而且都是酸性羟基。吸附吡啶后的红外光谱结果表明SAPO-5上同时存在B酸和L酸中心,B酸中心数目随着硅含量的增加而增加。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

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.