Adaptation of the porosity of zeolites for shape selective reactions

The selectivity of zeolite catalysts can be adjusted by modifying the characteristics of the active sites, and by modifying the diffusion path of the reactants and products, as well as the space available around the active sites. In this context shape selectivity, in its multiple aspects, and the most important parameters that influence it, will be discussed. Some examples of selectivity improvement by modification of the zeolite porosity in particular grafting or deposition of various compounds on the outer surface of the crystallite are given.     

USY型分子筛晶胞对其酸性及焦炭选择性的影响

采用NH3-TPD、FTIR、XRD、快速精密定炭仪研究了不同晶胞USY分子筛的水热稳定性、酸性以及其焦炭选择性。结果表明,用高温水蒸气法改性分子筛时,提高水热处理温度有利于其晶胞的收缩,使其稳定性增加。分子筛强酸量、总酸量、B酸都随着分子筛晶胞常数的减小而减小,而分子筛L酸的酸量、酸强随着分子筛晶胞的减小而增加。不同晶胞USY分子筛的晶胞越小其活性越强,而其积碳越小,分子筛的焦炭选择性也随着其晶胞的减小而减小。     

Preparation of poly(butylene succinate) vitrimer with thermal shape stability via transesterification reaction

Poly(butylene succinate) (PBS) refers to a high-performance biodegradable polymer employed to substitute petroleum polymers that cause environmental issues. However, PBS exhibits the defect of flowing above the melting point and rapid dripping for its poor melt strength. Accordingly, this study proposed a novel method to fabricate PBS vitrimer by exploiting reactive extrusion technology to mix diepoxide with PBS and then by employing zinc acetate as a catalyst to crosslink the PBS. Therefore, after the reaction extrusion blending, the blend still has a lower viscosity and high processing performance; in the subsequent curing process, the polymer undergoes a transesterification reaction and the viscosity increases. Via transesterification to form a cross-linked network, the storage modulus, and loss modulus of PBS vitrimer at 140°C reach 55,800% and 3500% of pure PBS, respectively. At this time, the crystallinity of PBS vitrimer is still as high as 56.9% (The crystallinity of pure PBS is 47.4%). And the shape stability of PBS at high temperatures was significantly improved. Moreover, PBS vitrimer could still be reshaped after the cross-linking process. This study proposed a facile method to produce PBS materials exhibiting high thermal shape stability.     

Synthesis and characterization of ferrisilicate analogs of ferrierite (Fe-FER) zeolites

Ferrisilicate analogs of ferrierite (FER) type zeolite having SiO₂/Fe₂O₃ ratios ranging between 30 and 200 have been synthesized using pyrrolidine as the templating agent. On calcination, the samples develop a typical buff color indicating conversion of some tetrahedral Fe³⁺ into octahedral Fe³⁺. Correspondingly, a doublet in the Mössbauer spectrum with isomer shift at 0.15 and 0.68 mm s^-1 was observed. The Fe-FER samples were further characterized by UV-vis, IR and TG/DTA. Fe-FER samples were found to exhibit catalytic activity for n-hexane oxidation reactions with hydrogen peroxide as oxidizing agent.     

Synthesis of dodecylbenzene via the alkylation of benzene and 1-dodecene over mesopore Beta zeolites

The alkylation of benzene with long chain α-olefins is a crucial process in the production of fine chemicals, which requires the upgrading from traditional homogeneous catalysis to heterogeneous catalysis involving zeolites. However, the application of zeolite catalysts has been limited by their fast deactivation due to constrained diffusion resulting from the sole micropores. To address this challenge, a desilication and secondary-crystallization strategy has been employed to fabricate hierarchically structured mesoporous Beta zeolites. The resultant mesoporous Beta zeolites demonstrate excellent catalytic activity and stability in the alkylation of benzene with 1-dodecene, arising from the exposed acid sites and enhanced internal diffusion. Importantly, the internal diffusion limitations for these mesopore Beta zeolites are negligible, which significantly extends their lifetime and improves their regeneration performance. To achieve these benefits, the degree of mesopores must be deliberately controlled. Overall, this approach provides a promising solution for achieving efficient and environmentally friendly alkylation processes.     

Deep desulfurization of gasoline using ion-exchange zeolites: Cu(I)- and Ag(I)-beta

Solid adsorbents Cu(I) and Ag(I) metal exchanged beta zeolites were prepared by solid-state ion-exchange (SSIE) method. Crystallographic structure of the prepared adsorbents has been characterized by XRD analysis. The texture of the prepared adsorbents was investigated using N₂ sorption. Pyridine IR measurements have been carried out to investigate the nature of the acid sites of the adsorbents. The deep-desulfurization performance of such adsorbents has been evaluated through fixed-bed adsorption technique with model gasoline containing thiophene and benzothiophene at ambient temperature and pressure. The obtained results revealed that the breakthrough capacities of Cu(I)- and Ag(I)-beta zeolite with the optimized Cu⁺ or Ag⁺ content are 0.239 mmol S/g and 0.237 mmol S/g, respectively. The remaining sulfur in the desulfurized gasoline is less than 1 ppmw. Their desulfurization capacity for actual FCC gasoline blend is reduced about 30% due to the competitive adsorption from olefins and aromatics. However, The capacity regeneration of Cu(I)- and Ag(I)-beta zeolite sorbents was carried out for 9 times. It is more than 95% recovery of desulfurization after the first regeneration, and it keeps little reduction after subsequent 8 times of regeneration. Such studies included the effect factors on desulfurization performance, such as metal exchange content, SiO₂/Al₂O₃ ratio, acidity, and other texture properties of the zeolite etc.     

The relation between morphology of (Co)MoS2 phases and selective hydrodesulfurization for CoMo catalysts

A series of CoMo catalysts were prepared by various methods with three different supports (Al₂O₃-1 of γ phase, Al₂O₃-2 containing γ and δ mixed phases, SiO₂). And the effect of morphology of (Co)MoS₂ phases on selective hydrodesulfurization was studied systematically. The TEM images showed, in general, the average slab length, the stacking number and the ratio of edge/corner of the sulfided catalysts increase remarkably in the order: SiO₂ > Al₂O₃-2 > Al₂O₃-1, with the extent of metal–support interaction decreasing in the order: SiO₂ < Al₂O₃-2 < Al₂O₃-1. And the hydrodesulfurization selectivity correlates linearly with the slab length (or the ratio of edge/corner) of (Co)MoS₂ phases, the longer average slab length, the higher ratio of edge/corner, and then the better hydrodesulfurization selectivity. Among all the catalysts, sulfided CoMo/SiO₂ of the longest average slab length and the highest edge/corner ratio exhibits the best hydrodesulfurization selectivity.     

Craze shape and fracture in poly(methyl methacrylate)

The shape of the primary craze at the tip of a crack has been studied by optical microscopy for two grades of poly(methyl methacrylate). The craze shapes are compared with the predictions of the Dugdale model for the plastic zone at a crack tip, and used to obtain a quantitative estimate of the craze stress and the effective stress intensity factor. The values of the stress intensity factor are then compared with those obtained directly from fracture toughness measurements.     

Stability of protonic zeolites in the catalytic oxidation of chlorinated VOCs (1,2-dichloroethane)

The deactivation of protonic zeolites in the catalytic oxidation of 1,2-dichloroethane (DCA) was evaluated. DCA oxidation reactions were carried out in a conventional fixed-bed reactor at atmospheric pressure under conditions of lean DCA concentration in air (1000 ppm). The outlet composition was analysed by a gas chromatograph, an IR spectroscopy-based analyser and another UV analyser. The effect of the zeolite crystalline structure was examined in order to track the catalytic stability of H-ZSM-5, H-MOR and H-BEA under typical reaction environment and conditions (1000 ppm DCA, 300 °C, 13,500 h⁻¹). With the aim of a better understanding of the deactivation pathway, the influence of the space velocity and temperature on the durability of protonic zeolites was analysed. Since some products formed during reaction could also cause deactivation, H₂O and HCl were introduced in the feed stream along with the DCA itself, so as to evaluate their effect. In general terms, coke formation was concluded to be the main reason for zeolite catalyst deactivation. Coke was formed from the intermediate vinyl chloride (VC), which resulted from a first dehydrochlorination step of DCA.     

Adsorptive removal of tetrahydrothiophene (THT) and tert-butylmercaptan (TBM) using Na-Y and AgNa-Y zeolites for fuel cell applications

Adsorptive removal of tetrahydrothiophene (THT) and tert-butylmercaptan (TBM) that are widely used sulfur odorants in pipeline natural gas was studied using AgNa-Y zeolites at ambient temperature and atmospheric pressure. The AgNa-Y were obtained via Ag⁺-exchange with Na⁺ of Na-Y at various exchange levels, and the contributions of formed adsorption sites (Ag⁺, Na⁺, Ag⁰, H⁺, and Ag₂O) in the THT and TBM adsorption uptake and selectivity were characterized. THT adsorption strength on these sites followed an order of Ag⁺ > Na⁺ ∼ Ag⁰ > H⁺ > Ag₂O. The adsorption strength of THT on Na⁺ sites was sufficiently high, thus an increase in the Ag⁺-exchange level did not lead to a notable increase in the breakthrough THT uptake. Differently, adsorption of TBM on Na⁺ sites was weak, whereas that on Ag⁺ sites was strong. This resulted in a marked increase in the breakthrough TBM uptake with an increase in the Ag⁺-exchange level, showing an order of magnitude higher uptake on AgNa-Y compared with that on Na-Y. Noticeably, the adsorption strength of THT on these adsorption sites was higher than that of TBM. This resulted in an almost 100% adsorption selectivity for THT over TBM, when these two sulfur species coexisted in the feed stream.     

Adsorption of thiophene and toluene on NaY zeolites exchanged with Ag(I), Ni(II) and Zn(II)

The present study evaluates the adsorption capacity of thiophene and toluene and their competitive behaviour on zeolite NaY exchanged with transition metals (5 wt% Ni, Zn and Ag). The headspace chromatography technique was used to obtain monocomponent apparent adsorption isotherms of thiophene and toluene with NaY, NiY, ZnY and AgY using isooctane as an inert solvent at 30 and 60 °C. Selectivity between toluene and thiophene at saturation capacities were also measured at 30 °C. The adsorption capacity for thiophene increased for the studied adsorbents as follows: NaY < ZnY < NiY < AgY at 30 °C and NaY < NiY < ZnY < AgY at 60 °C. Toluene is less adsorbed, but within the same order of magnitude as thiophene and following the same sorbent order. All adsorbents were moderately selectivity for toluene. Nevertheless, the sulfur content was successfully reduced in the presence of aromatics and olefins in immersion tests with a model fuel mixture. These results show the importance of inserting transitions metals in the zeolitic structure to enhance the adsorption of both aromatic and sulfur containing compounds in organic liquid mixtures, which shows promise to meet environmental standards in transportation fuels.     

Isobutane/2-butene alkylation on faujasite-type zeolites (H EMT and H FAU)

The alkylation of isobutane with 2-butene on hexagonal (protonated form = H EMT, investigated, for the first time on this reaction) and cubic faujasite (protonated form = H FAU) with Si/Al ratios of 3.5 was studied at 80°C and compared with the results obtained for a cerium exchanged Y zeolite (Ce Y). The alkylate composition consisted of 90% and about 80% C₈ paraffins for H EMT and H FAU/Ce Y, respectively. Within the C₈ fractions the three trimethylpentanes (TMP) 2,2,4-, 2,3,3- and 2,3,4-TMP were the dominating product compounds in all tests, whereas a higher content of dimethylhexanes (DMH) was observed for the H FAU and Ce Y. However, among the four trimethylpentanes 2,3,3,-TMP and 2,3,4-TMP were always the main compounds formed. Oligomerization was favoured only by the H FAU and Ce Y, with a strong increase of C₈ olefins after about one third of the observed reaction time. On the contrary, H EMT exhibited much less formation of C₈ olefins (and on a constant level) even after 300 min reaction time. The deactivated samples showed only formation of non-aromatic coke. The differences in the product pattern were attributed to the slightly larger size of the second type of supercage in EMT and to the stronger Bronsted acid sites in the hexagonal faujasite.Dedicated to Professor Dr. Martin Klessinger on the occasion of his 60th birthday.     

Atom transfer radical polymerization (ATRP) of styrene and acrylonitrile with monofunctional and bifunctional initiators

A bifunctional initiator (benzal bromide) was used to initiate the bulk atom transfer radical polymerization of styrene and acrylonitrile at 90 °C with CuBr/2,2-bipyridyl. We compared these results with those of a monofunctional initiator of similar structure (1-bromoethyl benzene) under the same polymerization conditions. The monofunctional initiator worked better than the bifunctional initiator when both comonomers were added simultaneously at the beginning of the copolymerization; the bifunctional initiator was only effective when acrylonitrile was added after 20 min of polymerization with styrene. The styrene-acrylonitrile copolymers were characterized by gel permeation chromatography, ¹³C nuclear magnetic resonance spectroscopy, Fourier-transform infrared spectroscopy, and refractometry. Copolymer composition was monitored by both ¹³C NMR and by the change in the specific refractive index increment.     

The Unpredictability of Research Directions and the Synergy between Theory and Experiment in Physical-Organic Chemistry

Research projects in physical-organic chemistry can go in unpredictable directions. One such project, described herein, began with the discovery of a large, imaginary, calculated vibrational frequency and soon led to the prediction that cyclobutanetetraone (CO)₄ had a triplet ground state. Molecular orbital (MO) theory provided the understanding of why (CO)₄ was calculated to have a planar triplet ground state and why, in contrast, (SiO)₄ was calculated to have a tetrahedral singlet ground state. Qualitative MO theory, as well as calculations, also predicted that (CO)₃, (CO)₅, and (CO)₆ should all be found to have singlet ground states. Testing experimentally these predictions about (CO)_n molecules, n=3–6, led to a very fruitful collaboration with Dr. Xuebin Wang, who obtained the negative ion photoelectron (NIPE) spectra of the radical anions of these four molecules and also of (CS)₄. Assignments of the signals in these five NIPE spectra required computing the vibrational progressions in them. The necessary acquisition of the ability to simulate the signals in NIPE spectra resulted in the successful analysis of the very complex spectrum of meta-benzoquinone (MBQ) radical anion, which Dr. Wang had already obtained and published. Analysis of this spectrum confirmed the prediction, made more than 20 years previously, that the ordering of the two lowest singlet states in MBQ was reversed from that in meta-benzoquinodimethane (MBQDM). The research described herein illustrates not only the unpredictability of where some research projects will eventually lead, but also the synergy between calculations and experiments in physical-organic chemistry.     

Correlation between Cu (I)-complexes and filling of via cross sections by copper electrodeposition

In the manufacture of metal interconnects for semiconductor devices, trenches and vias in dielectric layers on the Si wafer are filled by copper electrodeposition. The acceleration of deposition at the bottom of trenches and vias is a key to the bottom-up filling of these high aspect ratio cavities. We report the detection of this acceleration effect by rotating ring disk electrode experiments. The Cu (I)-complex, which forms on the disk electrode, was captured as a current (I_ring) on the ring electrode. I_ring increased in periodic reverse pulse current mode, as compared to direct or pulse current. The periodic reverse pulse current produced the most bottom-up filling based on microscopic observations of via cross sections. I_ring increased with the additions of Cl⁻, which also produced greater bottom-up filling. I_ring increased with additions of SPS, which were also found to improve bottom-up filling.     

Lattice parameter accommodation between GaAs(111) nanowires and Si(111) substrate after growth via Au-assisted molecular beam epitaxy

Using out-of-plane and in-plane X-ray diffraction techniques, we have investigated the structure at the interface between GaAs nanowires [NWs] grown by Au-assisted molecular beam epitaxy and the underlying Si(111) substrate. Comparing the diffraction pattern measured at samples grown for 5, 60, and 1,800 s, we find a plastic strain release of about 75% close to the NW-to-substrate interface even at the initial state of growth, probably caused by the formation of a dislocation network at the Si-to-GaAs interface. In detail, we deduce that during the initial stage, zinc-blende structure GaAs islands grow with a gradually increasing lattice parameter over a transition region of several 10 nm in the growth direction. In contrast, accommodation of the in-plane lattice parameter takes place within a thickness of about 10 nm. As a consequence, the ratio between out-of-plane and in-plane lattice parameters is smaller than the unity in the initial state of growth. Finally the wurtzite-type NWs grow on top of the islands and are free of strain.     

Preparation of bifunctional chelating fiber containing iminodi(methylphosphonate) and sulfonate and its performances in column-mode uptake of Cu(II) and Zn(II)

The bifunctional chelating fiber, FNPS, was prepared from vinylbenzyl chloride (CMS) grafted polyethylene-coated polypropylene fiber (PPPEf-g-CMS). In addition to the primary iminodi(methylphosphonate) chelating groups, FNPS has sulfonate groups as secondary functional group. FNPS was prepared by the following four steps. First, PPPEf-g-CMS was reacted with potassium phthalimide to substitute chlorine atoms in PPPEf-g-CMS with phthalimide groups. Second, sulfonate groups were introduced into the phenyl groups of benzyl moieties on the grafted polymer chains by the reaction with 95% sulfuric acid. Third, phthalimide moieties were hydrolyzed with ethanol solution of hydrazine hydrate to give the primary amino groups at the end of benzyl moieties on the grafted chains. Finally, these primary amino groups were converted into iminodi(methylphosphonate) groups by Mannich condensation reaction, in which the precursory fiber was reacted with large excess phosphorous acid and paraformaldehyde in 6 M hydrochloric acid media under the refluxed conditions for 6 h. The sulfonate and iminodi(methylphosphonate) groups in the resulting FNPS were identified by FT-IR spectroscopy. Contents of nitrogen, phosphorus, and sulfur in FNPS were found to be 1.53, 2.80, and 0.99 mmol/g, respectively. The phosphorus to nitrogen molar ratio was 1.83. This is very close to the ideal value of 2. The sulfur to nitrogen molar ratio was 0.65. The column-mode test on the Cu(II) uptake from a 0.1 mM Cu(II) aqueous solution revealed that FNPS can take up Cu(II) rapidly even in the extremely high feed flow rate range from 1000 to 7000 h^?1 in space velocity. The breakthrough capacity of FNPS for Cu(II) is as high as ca. 0.8 mmol/g at the flow rate of 7000 h^?1. In addition, it is expected that the FNPS packed column will make it possible to purify huge volumes of waters contaminated with 10^?4 M levels of Zn(II), as long as the concentrations of the co-existing Ca(II) and Mg(II) are nearly equal to those in river waters.     

Synergy between tungsten and palladium supported on titania for the catalytic total oxidation of propane

Titania-supported palladium catalysts modified by tungsten have been tested for the total oxidation of propane. The addition of tungsten significantly enhanced the catalytic activity. Highly active catalysts were prepared containing a low loading of 0.5 wt.% palladium, and activity increased as the tungsten loading was increased up to 6 wt.%. Catalysts were characterised using a variety of techniques, including powder X-ray diffraction, laser Raman spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction and aberration-corrected scanning transmission electron microscopy. Highly dispersed palladium nanoparticles were present on the catalyst with and without the addition of WO_x. However, the addition of WO_x slightly increases the average palladium particle size, and there was some evidence for the Pd forming epitaxial islands on the support in the tungsten-doped samples. Surface analysis identified a combination of Pd⁰ and Pd²⁺ on a Pd/TiO₂ catalyst, whereas all of the Pd loading was found in the form of Pd²⁺ with the addition of tungsten into the catalysts. At low tungsten loadings, isolated monotungstate and some polytungstate species were highly dispersed over the titania support. The concentration of polytungstate species increased as the loading was increased, and it was also promoted by the presence of palladium. The coverage of the highly dispersed tungstate species over the titania also increased as the tungsten loading increased. Some tungstate species were also found to be associated with the palladium oxide particles, and there was an enrichment of oxidised tungsten species at the peripheral interface of the palladium oxide nanoparticles and the titania. Sub-ambient temperature–programmed reduction experiments identified an increased concentration of highly reactive species on catalysts with palladium and tungsten present together, and we propose that the new WO_x-decorated interface between PdO_x and TiO₂ particles may be responsible for the enhanced catalytic activity in the co-impregnated catalysts.     

烃分子动力学直径与分子筛择形催化性能的相关性

作为分子筛研究领域的一个热点,择形催化理论在工业上已经被研究了近60年。尽管在理论上很多研究还不够深入,但随着对催化反应类型、新型催化材料合成、分子筛结构测定、催化性能表征、催化反应作用机理等方面研究的深入,对择形催化反应的认识仍取得了令人欣慰的进步。本文在现有的研究基础上,对不同尺寸的烃分子在分子筛孔道内的吸附和扩散行为进行了总结,并对烃分子反应动力学直径与分子筛的择形相关性做了一定的探究。分析表明,烃分子的反应动力学直径与分子筛择形催化相关性存在一个适用规律区间,当其略小于或接近分子筛孔径时,分子筛的择形催化性能表现最好。此外,分子筛本身的拓扑结构等因素也会对分子筛催化性能造成影响。