The interaction of nitrogen and carbon monoxide with certain ions and neutral species

MNDO method is used to study the interaction of nitrogen and carbon monoxide molecules with a proton, hydrogen atom, hydride ion, hydrogen molecule ion and hydrogen molecule. Predicted geometries and heats of reaction of different complexes are presented. The wave functions are analyzed in terms of ground state charge distributions and overlap populations. Electronic effects accompanying complexation are also discussed.     

Chemical-assisted thermal disproportionation of porous silicon monoxide into silicon-based multicomponent systems

Under the surface: Ag nanoparticles are deposited onto the surface of commercially available SiO particles, and subsequent chemical etching results in the formation of nanoporous SiO without changing the chemical and physical properties of the original SiO. Moreover, chemical-assisted thermal annealing produces a shape-preserving Si-based multicomponent system, which exhibits high-performance electrochemical properties.     

Organothallium compounds. Mechanistic study of the disproportionation reaction of organothallium compounds with copper in acetonitrile

Disproportionation reactions of various phenyl- and thienylthallium dicarboxylates with copper in acetonitrile have been carried out. The reaction mechanism proposed involves the participation of the ArTl²⁺ dication and various cationic pairs of the dication and the intermediate formation of organothallium radicals.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1970–1973, November, 1993.     

Activity and selectivity of zeolite MCM-22 catalysts in the disproportionation of toluene

Zeolite precursor MCM-22 samples were prepared by hydrothermal synthesis. The H-zeolites, obtained from the precursors, were characterized by scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR) spectroscopy, and by their activity in the title reaction. Despite of the lower Br?nsted acid site concentration of the zeolite having smaller crystallites, showed higher activity, while the zeolite, having larger crystals were more selective for p-xylene formation.     

用密度泛函理论研究NO在H-ZSM-5分子筛不同酸性位的吸附

利用密度泛函理论(DFT),基于7T簇模型,在B3LYP/6-31G(d,p)水平上研究了NO分子在H-ZSM-5分子筛孔道中α,β,γ酸性位的吸附.在计算过程中,首先对H-ZSM-5的α,β,γ酸性位进行优化计算,然后对NO分子η1-N和η1-O两种吸附模式的红外光谱和吸附能进行计算.计算结果表明,NO分子以η1-N模式吸附于H-ZSM-5分子筛酸性位上,不同酸性位对NO分子的吸附能力排序为:α酸性位>β酸性位>γ酸性位.此外,H-ZSM-5分子筛直型孔道更有利于NO分子的吸附和扩散,因而可更有效地促进NO分子催化分解反应的进行.     

Size-dependent reactivity of cobalt cluster ions with nitrogen monoxide: Competition between chemisorption and decomposition of NO

Reactions of NO molecules on cobalt cluster ions were studied in a beam-gas geometry by using a tandem mass spectrometer. Single-particle collision reactions of Co_mNO⁺ (m = 3–10) with NO were found to proceed in such a manner that NO decomposition dominates at m = 4–6 with the maximum reaction cross section at m = 5 and chemisorption dominates in m ≥ 7. On the other hand, in two-particle collision reactions of Co_n⁺ (n = 2–10) with NO, NO decomposition at n ≥ 5 and chemisorption of two NO molecules with Co atoms loss at n ≥ 8 were found to proceed. These results indicate that the size-dependency of the multiple collision reactions originates from secondary attacking of an NO molecule to primary products of the initial single collision reactions. The DFT calculation supports the scheme that both the decomposition and chemisorption of two-particle collision reactions proceed via a common intermediate, Co_mN₂O₂⁺, in which the two NO molecules are dissociatively chemisorbed on the cobalt cluster ion, and the size-dependency of the two-particle collision reactions is explained in terms of the structure of this reaction intermediate.     

Effect of metallic cobalt particles size on occurrence of CO disproportionation. Role of fluidized metallic cobalt-carbon solution in carbon nanotube formation

The behavior of Co−MgO catalysts in the reaction of CO disproportionation was studied in the temperature range up to 800°C. Two temperature regions that differ by the morphology of graphite produced (“egg-shells” or nanotubes) were detected. The experimental data obtained were analyzed in terms of the phase equilibria “amorphous carbon”—“carbon solution in metallic Co” and “graphite”— “carbon solution in metallic Co”. Under certain assumptions, the Co° particles are considered to dissolve amorphous carbon under the reaction conditions and transform to oversaturated fluidized carbon-cobalt solution, these fluidized particles being responsible for the formation of carbon nanotubes.     

甲基噻吩在HY分子筛上的吸附、脱附及转化行为

由NH₄Y分子筛制备了HY分子筛,运用N₂吸附、NH₃-TPD和Py-FTIR等手段表征HY分子筛的物化性能;采用智能重量分析仪(IGA)方法研究了甲基噻吩(2-甲基噻吩、3-甲基噻吩)在HY分子筛上的吸附-脱附行为;采用程序升温脱附-质谱(TPD-MS)联用手段研究了甲基噻吩在HY分子筛上的转化行为。结果表明,在200 ℃下 2-甲基噻吩和3-甲基噻吩在HY分子筛中的强B酸上发生强化学吸附作用,与B酸结合后生成了甲基噻吩的碳正离子结构进而发生了歧化反应、脱烷基反应以及裂化反应;与2-甲基噻吩不同的是,3-甲基噻吩与HY通过一定的氢转移反应生成了3-甲基四氢噻吩,且200 ℃吸附条件下3-甲基噻吩比2-甲基噻吩更容易发生裂化反应。     

IR study of heterogeneity of OH groups in zeolite HY-splitting of OH and OD bands

We have been studying the problem of heterogeneity of OH groups in zeolites HY for a long time. The heterogeneity was suggested by the shift of the IR band of OH groups restoring upon ammonia desorption and also by the fact that the band of OH groups forming hydrogen bonds was relatively broad (broader than for homogeneous acidic OH). In the present study we present another important argument for heterogeneity: the splitting of the IR band of free OH and OD groups in a zeolite of Si/Al=8.3 dealuminated by (NH₄)₂SiF₆ treatment. Such a splitting is the best seen in low temperature spectra of OD groups. We found less acidic 3640 cm⁻¹ (AlO)(SiO)₂SiO₁HAl(OSi)₃ and more acidic 3625 cm⁻¹ (SiO)₃SiO₁HAl(OSi)₃ groups. The presence of these two kinds of hydroxyls corresponds to the presence of Si(2Al) and Si(1Al), respectively, detected in ²⁹Si MAS NMR spectra. We also found a small amount of strongly acidic 3599 cm⁻¹ hydroxyls interacting with extraframework Al species.     

Studies on the disproportionation of trichloromethyltin

The rate of disproportionation of trichloromethyltin in various solvents was studied by two methods, derivatization with sodium tetraethylborate and ¹³C NMR measurements, which gave similar results. The reaction followed second‐order kinetics and was more rapid in coordinating solvents than in uncoordinating ones. Moreover, it was catalyzed by nucleophiles, such as amines or alcohols, which is in favor of a nucleophile‐assisted electrophilic reaction. Copyright © 2003 John Wiley & Sons, Ltd.     

Dinitrogen and carbon monoxide hydrogen bonding in protonic zeolites: Studies from variable-temperature infrared spectroscopy

Adsorption (at a low temperature) of nitrogen on the protonic zeolite H-Y results in hydrogen bonding of the adsorbed N₂ molecules with the zeolite Si(OH)Al Brønsted-acid groups. This hydrogen-bonding interaction leads to activation, in the infrared, of the fundamental N–N stretching mode, which appears at 2334 cm⁻¹. From infrared spectra taken over a temperature range, the standard enthalpy of formation of the OH···N₂ complex was found to be ΔH⁰ = −15.7(±1) kJ mol⁻¹. Similarly, variable-temperature infrared spectroscopy was used to determine the standard enthalpy change involved in formation of H-bonded CO complexes for CO adsorbed on the zeolites H-ZSM-5 and H-FER; the corresponding values of ΔH⁰ were found to be −29.4(±1) and −28.4(±1) kJ mol⁻¹, respectively. The whole set of results was analysed in the context of other relevant data available in the literature.     

Elucidation of the CO‐Release Kinetics of CORM‐A1 by Means of Vibrational Spectroscopy

CO‐releasing molecules (CORMs) are developed for investigations of the interaction between the signaling molecule carbon monoxide (CO) and cells or tissue. Prior to their application these molecules must be fully characterized with respect to their CO‐release mechanism. One widely used CORM for biological application is sodium boranocarbonate (CORM‐A1), which shows pH‐dependent CO liberation. The complete reaction mechanism of CORM‐A1 is not fully understood yet. Therefore, in this contribution time‐resolved gas‐phase IR spectroscopy is used to monitor the headspace above decaying CORM‐A1 solutions at four different pH values (5.8 to 7.4). Borane carbonyl is found as an intermediate in the gas phase, which is formed during CORM degradation and further decays to CO. Concentration profiles of a pseudoconsecutive first‐order reaction are successfully fitted to specific band areas of the measured gas‐phase spectra, and the rate constants are obtained. The production of borane carbonyl is strongly pH dependent (half‐lives between 5 and 106 min), whereas the decay of borane carbonyl in the gas phase is nearly constant with a half‐life of about 33 min. The ratio of liberated CO molecules per CORM‐A1 is determined to be 0.91±0.09, and boric acid is identified as further end product.     

Effect of “aging” of ammonium-exchanged forms of zeolite Y by IR spectroscopic data

The changes in the structures of ammonium-exchanged forms of zeolite Y under conditions of prolonged exposure in air are studied by IR spectroscopy. It is established that the cation distribution in freshly prepared samples is nonequilibrium: the cations migrate with time to the most energetically stable sites. In addition, partial decomposition (no more than 3 to 6%) of the NH ₄ ⁺ -form is also observed, which results in a decrease in the ionic character of the framework bonds that is equivalent to an apparent increase in the framework silicate modulus.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1021–1024, June, 1995.     

IR spectroscopic signs of surface intermediates of partial oxidation of propane by nitrogen monoxide on Fe-ZSM-5

We have used IR spectroscopy to study adsorption of NO, propane, and their mixture on Fe-ZSM-5 in the temperature range 20-350 °C. We show that it is possible to form adsorbed nitrate ions, C-, N-, and O-containing intermediates leading to formation of partial oxidation products: oxygenates and nitrogen-containing compounds. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 2, pp. 121-124, March-April, 2009.     

Understanding the reactivity and basicity of zeolites: a periodic DFT study of the disproportionation of N(2)O(4) on alkali-cation-exchanged zeolite Y

The disproportionation of N(2)O(4) into NO(3)(-) and NO(+) on Y zeolites has been studied through periodic DFT calculations to unravel 1) the role of metal cations and the framework oxygen atoms and 2) the relationship between the NO(+) stretching frequency and the basicity of zeolites. We have considered three situations: adsorption on site II cations with and without a cation at site III and adsorption on a site III cation. We observed that cations at sites II and III cooperate to stabilize N(2)O(4) and that the presence of a cation at site III is necessary to allow the disproportionation reaction. The strength of the stabilization is due to the number of stabilizing interactions increasing with the size of the cation and to the Lewis acidity of the alkali cations, which increases as the size of the cations decreases. In the product, NO(3)(-) interacts mainly with the cations and NO(+) with the basic oxygen atoms of the tetrahedral aluminium through its nitrogen atom. As the cation size increases, the NO(3)(-)...cation interaction increases. As a result, the negative charge of the framework is less well screened by the larger cations and the interaction between NO(+) and the basic oxygen atoms becomes stronger. NO(+) appears to be a good probe of zeolite basicity, in agreement with experimental observations.     

含超微氧化亚钴颗粒Beta分子筛的合成及其催化乙苯氧化性能

杂原子分子筛是指在硅铝分子筛或磷铝酸盐分子筛中含有骨架内或骨架外某种原子或其化合物的分子筛.这些杂原子可以是某些主族元素(如硼、锗、镓)或有变价特性的过渡金属元素(如钛、铁、钴、镍)等.将杂原子或其化合物通过浸渍、离子交换、水热晶化等方式引入沸石分子筛骨架中形成杂原子分子筛,往往可以改变沸石分子筛的骨架结构和理化性能,并赋予沸石分子筛新的催化反应性能.自1983年钛硅分子筛TS-1被发现能够高效催化烯烃环氧化以来,许多杂原子分子筛因其在催化烷烃类及芳烃类氧化、醛酮选择氧化及烯烃类环氧化等领域表现出的优良性能得到了广泛关注.目前,合成含不同杂原子的分子筛已成为分子筛材料开发的一个重要内容.分子筛的微孔孔道结构赋予了被引入其中作为催化中心的杂原子对反应物/产物分子独特的择形选择性;同时,分子筛骨架与杂原子之间往往存在化学键或空间限域作用,使得杂原子在高温高压等反应条件下依然保持高度的分散性,避免由于团聚导致活性降低.钴离子及含钴化合物在烷烃及芳烃类催化氧化反应中表现出很好的活性,能够利用分子氧实现对高碳烷烃及烷基苯的催化氧化.将钴离子及其化合物引入具有合适孔道结构的分子筛,可以提高催化反应的选择性.目前将对含钴分子筛的合成研究主要有后处理法及直接水热法.后处理法包括负载法及离子交换法,用于制备含有钴物种的硅铝分子筛;而直接水热法主要用于制备含有骨架钴的磷酸铝分子筛.目前为止,使用水热法合成含钴的分子筛材料的合成及其催化应用至今鲜有研究报导.这主要是由于传统的分子筛合成体系的高碱性环境会导致钴盐的沉淀,导致其无法被引入分子筛.我们通过优化合成条件,利用含氟体系直接水热法将钴引入Beta分子筛,得到含超微氧化亚钴团簇的Beta沸石分子筛.通过扫描电子显微镜、X射线粉末衍射、紫外-可见漫反射光谱、X射线光电子能谱、透射电子显微镜及H2程序升温还原等表征手段对合成样品的物理化学性质进行了研究,并与使用浸渍、离子交换得到的含钴Beta沸石及水热合成得到的含钴AlPO-5分子筛的相关性质进行了对比.合成得到的含钴分子筛材料中,钴物种以亚纳米尺度的氧化亚钴颗粒形式存在.我们使用分子氧作为氧源,考察了该含超微氧化亚钴的Beta沸石作为催化剂催化乙苯氧化反应的活性.与浸渍、离子交换制得钴硅分子筛及含有骨架钴的磷酸铝分子筛材料相比,含超微氧化亚钴的Beta分子筛表现出更高的催化活性及对苯乙酮/醛的选择性.     

Peculiarities of disproportionation of toluene on acidic pentasil zeolites

Two samples of pentasil hydrogen forms were obtained: an ordinary sample and a sample lacking surface acid sites. The samples were tested in the disproportionation of toluene over short and very short periods of contact of the reaction mixture with the catalyst layer. The primary conversion products were found to be para-xylene and ethylbenzene in addition to benzene. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 2, pp. 108-111, March-April, 2009.     

Reaction kinetic behavior of different carbon monoxide adspecies on palladium-alumina during oxidation: an in-situ IR study

Carbon monoxide oxidation on Pd(10 w.t.%)-alumina was studied by in-situ infrared spectroscopy. It was found that the oxidation reactivities vary with different CO adspecies: linear COad > 2-fold bridged COad > multi-bridged COad.