流动-差热吸附量热系统Ⅱ. 氢型丝光沸石吸附热的研究

用自行装置的流动-差热吸附量热系统测定了氨、吡啶及芳烃在氢型丝光沸石(HM)上的吸附热。发现氨的吸附热-吸附量曲线上存在拐点, 证实HM表面上存在能量差异较大的两类氨吸附中心。氨中毒的HM对芳烃的吸附热测定结果表明, 不同的吸附区域对氨和芳烃的吸附强度各有不同。     

FFA—1离子交换纤维的物理与化学性能的研究

利用IR谱，热分析及SEM技术对FFA-1离子交换纤维的物理与化学性能进行了表征，测定了它的pH滴定曲线，吸水率，机械强度，对SO2的动态吸附以及气体阻力性能，为这种功能纤维在吸附净化有害气体等方面的实际应用提供了必要的性能参数。     

高灵敏宽温区吸附热测定装置的建立

 描述了一个适于气／固体系的宽温区、高灵敏的微分吸附热测定装置．在该装置中，吸附放热由Setaram公司热流式微量热量计测定，吸附量由MKS公司电容式压力传感器测定．此外，设计、制作了可在高真空和宽温区内进行吸附热测定的试样池以及对高活泼金属催化剂进行预处理的试样处理池．用标准物质对热量计进行了标定．为验证该装置对吸附热测定的可靠性，测定了H2在Pt／SiO2和γ－Mo2N上的吸附热，所得结果与文献值一致．数据的误差分析结果表明，吸附热测定的相对误差在4％以内．     

热重分析技术测定二苯并呋喃在活性炭上的吸附相平衡

以吸附动力学为基础,建立了热重分析技术测定难挥发性有机物吸附等温线的方法.通过热重分析实验测定了不同升温速率下二苯并呋喃从Norit RB1和Chemviton BPL活性炭上脱附速率曲线,及对应的脱附峰温度.运用所提出的方法,对二苯并呋喃在Norit RB1和ChemvironBPL活性炭上的Langmuir吸附等温线方程进行了估算.估算结果与静态吸附实验测定结果相比,误差不超过10%.     

ZSM-5沸石分子筛的吸附性能

对ZSM-5沸石分子筛的吸附性能进行了研究。测定了环己烷、正己烷、苯和水分子在ZSM-5沸石上的吸附等温线;发现室温下环己烷分子的吸附受到阳离子的空间障碍作用。计算了ZSM-5佛石单胞中的吸附分子数、等量吸附热、微分吸附功和微分吸附熵等值。吸附热曲线表明ZSM-5沸石分子筛的表面是不均匀的。     

用于气/固吸附的微分吸附热测定装置

本文介绍了一套吸附热测定装置, 它是对法国SETARAM高温量热计进行了适当变动后而建成的。用它可以测定在室温～800 K范围内气/固吸附的微分吸附热。在实验过程中, 吸附量是用光标微压计进行测量。用电标定法代替标准物质法来测定该装置的热定量因子, 这更适合于在恒温条件下的吸附热测定。用这套装置测定了吡啶在HY分子筛上于不同温度下的吸附热。     

氧在Co3O4催化剂上的化学吸附

测定了氧在氨氧化催化剂Co_3O_4上于100—400℃下的吸附动力学和室温-600℃的热脱附谱,并与离子探针质谱测定的结果进行了比较。动力学曲线指出氧具有快速和慢速不同类型的吸附,热脱附谱显示有相应的脱附曲线。快速吸附对应于两个脱附峰,峰的极大值温度各为165℃,380—420℃;相应的吸附氧粒子可指定为O_2~-,O~-;脱附活化能分别为13.3千卡/克分子,26.7千卡/克分子。慢速吸附服从Elovich吸附规律,吸附过程可能是快速吸附的氧粒子在催化剂表面上迁移生成O~(2-)并入氧化物表面晶格,脱附温度高于500℃时可由表面晶格中逸出。吸附中心可能是表面Co~(2+)离子。讨论了氧吸附与氨催化氧化反应之间的关系。     

DFC-1氢型丝光沸石的吸附热与甲苯歧化催化活性的研究

在工业生产条件下对催化剂和催化作用的动态研究已经引起重视。吸附热能反映催化剂表面能量状况和吸附分子间的相互作用,是表征催化剂表面性质的重要参量。对于国产甲苯歧化催化剂DFC-1氢型丝光沸石(简称HMDFC-1)的吸附热和催化活性之间关系的报道还不多。在用吸附差热方法考察HMDFC-1的表面酸性时发现,在动态条件下HMDFC-1存在着对NH_3可逆和不可逆两种吸附,而对吡啶则只有不可逆吸附。本文利用脉冲色谱法分别测定了苯、甲苯、二甲苯在HMDFC-1上以及在被NH_3中毒的HM吸附热,和甲苯在被吡啶中毒的HMDFC-1上的吸附热,并以吸附热的差别区别了两类DFC-1上的酸中心,找出了催化活性随甲苯吸附热的变化曲线。     

适于脉冲法和连续法两用的气／固吸附量热装置

适于脉冲法和连续法两用的气／固吸附量热装置周立幸（中国科学院大连化学物理研究所，１１６０１２）吸附热是表面热力学研究中的一个重要数据，在催化、吸附现象的基础研究和有关工业的应用等都很有意义。获得吸附热数据的方法很多，但最准确可靠的还是用量热法直接测定...     

铈对氧化铁吸附性能的影响

利用脉冲气相色谱保留体积法测定了不同铈含量的氧化铁对水蒸汽吸附的影响。实验结果表明，随着铈含量的增加，样品对水蒸汽的可逆吸附过程的吸附热降低，铈含量超过一定值后吸附热又略有升高。而铈含量对吸附中心数的多少影响不大。不同铈含量的氧化铁样品催化变换反应的活性测定结果表明，吸附热最小的样品的催化活性最高，说明铈在无铬铁系中温变换催化剂中起助催化剂的作用。     

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.     

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.     

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.