Polymers oxidation with VO(acac)2 complex

The introduction of epoxy groups in the polymer backbone is one of the most promising methods of modifying polydienes. In this work the performance of the classical catalytic system VO(acac)₂/tert-butylhydroperoxide was evaluated for the epoxidation of polydienes. The polymers investigated were a hydroxylated poly(butadiene), two polybutadienes with high and with low 1,4-content, a poly(isoprene), and a styrene–butadiene copolymer. The epoxidized polymers were characterized by IR, ¹H and ¹³C NMR and GPC techniques. The vanadium system was active for the epoxidation reaction and the reactivity decreases in the order HTPB>PI>1,4-PB>1,2-PBSBR. The occurrence of secondary reactions to low extension could be detected by the presence of hydroxyl, carbonyl and alcohol signals in the spectra of epoxidized polymers. Incomplete mass recovery (70–90%) was observed probably due to the chain degradation or modification of the polymer polarity.     

Synthesis and H2 uptake of Cu2(OH)3Cl, Cu(OH)2 and CuO nanocrystal aggregate

Monodispersed Cu₂(OH)₃Cl nanoplatelets, Cu(OH)₂ nanowires, CuO nanoparticles and nanoribbons with a spherical morphology were synthesized using hydrothermal and heat-treatment reactions, and their H₂ storage characteristics were examined. The Cu₂(OH)₃Cl nanoplatelets particles formed immediately after mixing the reactant, which subsequently formed larger uniform spherical particles in the submicron range. This procedure highlights a practical strategy for producing spherical Cu(OH)₂ and CuO materials consisting of monodispersed nanocrystals. The spherical aggregates of Cu₂(OH)₃Cl nanoplatelets heat-treated at 473 K could reversibly store up to 2.35 wt.% H₂ at 38 bar and 293 K.     

Reaction of 4-(naphthylmethyl)bibenzyl, thermally and in the presence of fe ( co )3 ( Pph3 )2

The reaction pathways, kinetics and mechanisms of 4-(naphthylmethyl)bibenzyl (NBBM) have been studied in order to resolve the fundamentals underlying the catalysis of coal liquefaction by Fe-based catalysts. Reactions of NBBM: ( 1 ) under nitrogen in the absence of catalyst, (2) under hydrogen in the absence of catalyst, (3) under nitrogen in the presence of the catalyst precursor Fe(CO)₃(PPh₃)₂, and (4) under hydrogen in the presence of the catalyst precursor Fe(CO)₃(PPh₃)₂ were accomplished. Thermolysis was selective for cleavage of the weak bibenzyl bond, whereas the catalyst precursor effected cleavage at the naphthyl moiety. The catalyst precursor was most effective in the presence of hydrogen, where the rate of consumption of NBBM and the selectivity of breaking the bond at the naphthalene ring both increased. Hydrogenation activity was also observed. Possible mechanisms are proposed to describe the pyrolytic and catalytic reactions of NBBM.     

Solid state protonic conductor NH4PO3–(NH4)2Mn(PO3)4 for intermediate temperature fuel cells

A new proton-conductive composite of NH₄PO₃–(NH₄)₂Mn(PO₃)₄ was synthesized and characterized as a potential electrolyte for intermediate temperature fuel cells that operated around 250 °C. Thermal gravimetric analysis and X-ray diffraction investigation showed that (NH₄)₂Mn(PO₃)₄ was stable as a supporting matrix for NH₄PO₃. The composite conductivity, measured using impedance spectroscopy, improved with increasing the molar ratio of NH₄PO₃ in both dry and wet atmospheres. A conductivity of 7 mS cm⁻¹ was obtained at 250 °C in wet hydrogen. Electromotive forces measured by hydrogen concentration cells showed that the composite was nearly a pure protonic conductor with hydrogen partial pressure in the range of 10²–10⁵ Pa. The proton transference number was determined to be 0.95 at 250 °C for 2NH₄PO₃–(NH₄)₂Mn(PO₃)₄ electrolyte. Fuel cells using 2NH₄PO₃–(NH₄)₂Mn(PO₃)₄ as an electrolyte and the Pt–C catalyst as an electrode were fabricated. Maximum power density of 16.8 mW/cm² was achieved at 250 °C with dry hydrogen and dry oxygen as the fuel and oxidant, respectively. However, the NH₄PO₃–(NH₄)₂Mn(PO₃)₄ electrolyte is not compatible with the Pt–C catalyst, indicating that it is critical to develop new electrode materials for the intermediate temperature fuel cells.     

Preparation and characterization of a PMMA/Ce(OH)3, Pr2O3/graphite nanosheet composite

An easy process for the synthesis of poly(methyl methacrylate)/Ce(OH)₃, Pr₂O₃/graphite nanosheet (PMMA/Ce(OH)₃, Pr₂O₃/NanoG) composite was developed. Graphite nanosheets (NanoG) were prepared by treating the expanded graphite with sonication in aqueous alcohol solution. The PMMA/Ce(OH)₃, Pr₂O₃/NanoG composites were prepared via in situ polymerization of MMA monomer in the presence of graphite nanosheets and Ce(OH)₃, Pr₂O₃ through reverse micelle template, in which the methyl methacrylate was designated as the oily phase. The composites were then dispersed with chloroform and coated on glass slides to form films. Scanning and transmission electron microscopy were used to characterize the structure and dispersion of the graphite nanosheets and the composites. The results showed that the high-aspect-ratio structure of the nanosheets played an important role in forming a conducting network in the PMMA matrix. From thermogravimetric analysis, the introduction of graphite nanosheets and inorganic nanopartices exhibited a beneficial effect on the thermal stability of PMMA.     

Optimization of electrochemically synthesized Cu3(BTC)2 by Taguchi method for CO2/N2 separation and data validation through artificial neural network modeling

Cu₃(BTC)₂, a common type of metal organic framework (MOF), was synthesized through electrochemical route for CO₂ capture and its separation from N₂. Taguchi method was employed for optimization of key parameters affecting the synthesis of Cu₃(BTC)₂. The results indicated that the optimum synthesis conditions with the highest CO₂ selectivity can be obtained using 1 g of ligand, applied voltage of 25 V, synthesis time of 2 h, and electrode length of 3 cm. The single gas sorption capacity of the synthetized microstructure Cu₃(BTC)₂ for CO₂ (at 298 K and 1 bar) was a considerable value of 4.40 mmol·g⁻¹. The isosteric heat of adsorption of both gases was calculated by inserting temperature-dependent form of Langmuir isotherm model in the Clausius-Clapeyron equation. The adsorption of CO₂/N₂ binary mixture with a concentration ratio of 15/85 vol-% was also studied experimentally and the result was in a good agreement with the predicted value of IAST method. Moreover, Cu₃(BTC)₂ showed no considerable loss in CO₂ adsorption after six sequential cycles. In addition, artificial neural networks (ANNs) were also applied to predict the separation behavior of CO₂/N₂ mixture by MOFs and the results revealed that ANNs could serve as an appropriate tool to predict the adsorptive selectivity of the binary gas mixture in the absence of experimental data.     

Water-induced bulk Ba(NO3)2 formation from NO2 exposed thermally aged BaO/Al2O3

Phase changes in high temperature treated (>900 °C) 8 or 20 wt% BaO supported on γ-Al₂O₃ model lean NO_x trap (LNT) catalysts, induced by NO₂ and/or H₂O adsorption, were investigated with powder X-ray diffraction (XRD), solid state ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, and NO₂ temperature programmed desorption (TPD) experiments. After calcination in dry air at 1000 °C, the XRD and solid state ²⁷Al MAS NMR results confirm that stable surface BaO and bulk BaAl₂O₄ phases are formed for 8 and 20 wt% BaO/Al₂O₃, respectively. Following NO₂ adsorption over these thermally treated samples, some evidence for nanosized Ba(NO₃)₂ particles are observed in the XRD results, although this may represent a minority phase. However, when water was added to the thermally aged samples after NO₂ exposure, the formation of bulk crystalline Ba(NO₃)₂ particles was observed in both samples. Solid state ²⁷Al MAS NMR is shown to be a good technique for identifying the various Al species present in the materials during the processes studied here. NO₂ TPD results demonstrate a significant loss of uptake for the 20 wt% model catalysts upon thermal treatment. However, the described phase transformations upon subsequent water treatment gave rise to the partial recovery of NO_x uptake, demonstrating that such a water treatment of thermally aged catalysts can provide a potential method to regenerate LNT materials.     

Electrochemical performance of nanocrystalline Li3V2(PO4)3/carbon composite material synthesized by a novel sol–gel method

A novel sol–gel method based on V₂O₅·nH₂O hydro-gel was developed to synthesize nanocrystalline Li₃V₂(PO₄)₃/carbon composite material. In this route, V₂O₅·nH₂O hydro-gel, NH₄H₂PO₄, Li₂CO₃ and high-surface-area carbon were used as starting materials to prepare precursor, and the Li₃V₂(PO₄)₃/carbon was obtained by sintering precursor at 750 °C for 4 h in flowing argon. The sol–gel synthesis ensures homogeneity of the precursors and improved reactivity. The sample was characterized by XRD, SEM and TEM. X-ray diffraction results show Li₃V₂(PO₄)₃ sample is monoclinic structure with the space group of P2₁/n. The TEM image indicates that the Li₃V₂(PO₄)₃ particles modified by conductive carbon are about 70 nm in diameter. The Li₃V₂(PO₄)₃/carbon system showed that the discharge capacities in the first and 50th cycle are about 155.3 and 143.6 mAh/g, respectively, in the range of 3.0–4.8 V. The sol–gel method is fit for the preparation of Li₃V₂(PO₄)₃/carbon composite material which may offer some favorable properties for commercial application.     

Al（OH）3@Zn（OH）2双层包覆氧化铁黄合成及其耐热性能研究

采用共沉淀法对铁黄颜料进行Al（OH）₃/Zn（OH）₂双层异相包覆,提升其耐热性能,并通过XRD、TG-DTA、FT-IR、SEM&EDS等手段对包覆前后铁黄颜料的微观结构进行表征。研究结果表明,包覆质量分数为40%的Al（OH）₃时铁黄颜料的耐热性能较好;第二层包覆Zn（OH）₂,最优包覆质量分数为30%,样品在240 ℃时色差值为1.84。XRD测试结果表明,Al（OH）₃和Zn（OH）₂包覆并没有改变氧化铁黄的特征峰,两者可能以无定形态包覆在铁黄粒子表面。SEM、EDS、FT-IR测试表明,Al（OH）₃/Zn（OH）₂已成功对铁黄颜料进行了包覆;此外,还出现了片状结构对应Al（OH）₃自身成核现象,包锌后出现了团聚现象。TG-DTA表征显示,包覆后样品升温脱水分两步,低温吸热峰对应包覆层物质的脱水,高温吸热峰偏向更高温度,对应包覆颜料耐热性能的提升。     

Dehydrogenation of i-butane on CrOx/Al2O3 catalysts prepared by ALE and impregnation techniques

Atomic layer epitaxy (ALE), a technique relying on saturating gas–solid reactions, was applied in the preparation of CrO_x/Al₂O₃ catalysts using Cr(acac)₃ vapor and air as source materials for CrO_x. Vaporized Cr(acac)₃ was reacted with preheated Al₂O₃, and the surface complex formed was treated with air to remove the ligand residues. The Cr loading increased from 1.3 to 12.5 wt.% as the number of saturating Cr(acac)₃ and air reactions was increased from one to 10. CrO_x/Al₂O₃ catalysts were also prepared from solution by incipient wetness impregnation (0.3–21 wt.%). XPS and UV–VIS measurements of the catalysts revealed the presence of both Cr⁶⁺ and Cr³⁺. Although the oxidation state distribution was similar, H₂-temperature programmed reduction (TPR) and solubility measurements indicated that Cr⁶⁺ surface sites were in stronger interaction with Al₂O₃ and more uniformly distributed in the catalysts prepared by ALE than by impregnation. On the basis of the activity of the catalysts in the dehydrogenation of i-butane, we propose that the dehydrogenation reaction uses both reduced Cr⁶⁺, i.e. redox Cr³⁺, and exposed non-redox Cr³⁺ sites. Furthermore, the dehydrogenation reaction must be insensitive to the size of the CrO_x ensembles since activities were similar for the catalysts prepared by ALE and impregnation. The decay of the dehydrogenation activity in successive prereduction–reaction–regeneration cycles was attributed to a decrease in the number of redox Cr³⁺ sites.     

Study of [Fe(bpy)3] complex encapsulated in zeolite Y

Tris complex of Fe^II with 2,2′ bipyridine (bpy) ligand, has been encapsulated in the supercages of zeolite Y and characterized by powder X-ray diffraction, Infrared spectroscopy, ⁵⁷Fe Mössbauer, effect measurements and multinuclear NMR spectroscopy. The complex was prepared in the supercages of Zeolite Y by exchanging the cations of zeolite Y with Fe^II and its subsequent complexing with bpy ligand. Based on the comparison of the results obtained for [Fe^II(bpy)₃](ClO₄)₂ and the [Fe(bpy)₃]Y complexes, it has been inferred that there is significant structural distortion for the encapsulated complex and all Fe is present as Fe^II in low spin state, which is characterized by isomer shift, δ = 0.37 mm s⁻¹ and quadrupole splitting, ΔE_q = 0.81 mm s⁻¹ as revealed by ⁵⁷Fe Mössbauer spectroscopic measurements.     

乙酰丙酮氧钒的绿色合成工艺研究

以三氧化二钒为钒源,在体系中引入氧化剂和水夹带剂,合成了乙酰丙酮氧钒,实现了乙酰丙氧钒的绿色连续合成。探讨了空气、过氧化氢和氧气三种氧化剂对乙酰丙酮氧钒合成的影响,对产物进行表征并与商业乙酰丙酮氧钒对比。结果表明,引入氧化剂之后,乙酰丙酮氧钒的产率显著提高,三种氧化剂制得的乙酰丙酮氧钒产率均可达到80%以上,其中氧气氧化效果最好,当氧气流量为200 mL/min,回流2 h时,乙酰丙酮氧钒产率可达90%。XRD、FTIR和TG结果显示,本研究合成的乙酰丙酮氧钒纯度较高,与商业乙酰丙酮氧钒可比。     

Al_2(SO_4)_3/FeCl_3催化合成乙酸异戊酯

以冰乙酸和异戊醇为原料,Al_2(SO_4)_3/FeCl_3为催化剂,对催化合成乙酸异戊酯的条件进行研究。考察催化剂用量、乙酸与异戊醇物质的量比以及反应时间对乙酸酯化率的影响。结果表明,Al_2(SO_4)_3/FeCl_3具有良好的催化活性,在乙酸物质的量为0.1 mol、乙酸与异戊醇物质的量比为1∶4、催化剂用量1.0 g、反应时间2.0 h和带水剂环己烷用量10 m L反应条件下,重复实验3次,平均乙酸酯化率为93.50%。     

Nb2O5-supported WO3: a comparative study with WO3/Al2O3

WO₃/Nb₂O₅-supported samples prepared by impregnation are characterised by X-ray diffraction (XRD), Raman spectroscopy and X-ray absorption spectroscopy (XAS) at the W–L₃ absorption edge, as well as temperature programmed reduction (TPR) and FT-IR monitoring of pyridine adsorption. Results are compared with those obtained for WO₃/Al₂O₃ samples prepared in the same conditions, showing that niobia is able to disperse tungsta better than alumina does. Formation of a crystalline WO₃ needs larger tungsten contents on niobia than on alumina, since tungsten solution into niobia is easier than into alumina. Raman and XAS spectra recorded under ambient conditions suggest that similar WO_x species are formed on both supports at tungsten contents 0.5–1 theoretical monolayers; however, TPR results for the low tungsten loaded samples indicate that, when reduction starts (always at temperatures higher than 700 K under H₂/Ar flow) there is a larger concentration of tetrahedral [WO₄] species on alumina, than on niobia. Samples with low tungsten loading have been tested in isopropanol decomposition and ethylene oxidation, following both processes by FT-IR of adsorbed species up to 673 K. Results show that adsorption of ethylene on WO₃/Nb₂O₅ yields acetaldehyde and acetate at 473 K, while this adsorption is non-reactive either on the supports or on WO₃/Al₂O₃. Isopropanol adsorbs dissociatively on both supports, leading to acetone and propene formation on tungsta–niobia, but only propene on tungsta–alumina, probably due to the larger reducibility of the tungsten-containing phases.     

Underlying mechanism of the hydrothermal instability of Cu3(BTC)2 metal-organic framework

Water induced decomposition of Cu₃(BTC)₂ (BTC= benzene-1,3,5-tricarboxylate) metal-organic framework (MOF) was studied using dynamic water vapour adsorption. Small-angle X-ray scattering, Fourier transform infrared spectroscopy and differential scanning calorimetry analyses revealed that the underlying mechanism of Cu₃(BTC)₂ MOF decomposition under humid streams is the interpenetration of water molecules into Cu-BTC coordination to displace organic linkers (BTC) from Cu centres.     

Synthesis, structure and photocatalytic properties of Fe(III)-doped TiO2 prepared from TiCl3

Iron(III)-doped titanium dioxide photocatalysts were prepared from aqueous titanium(III) chloride solution in the presence of dissolved FeCl₃ (0–10.0 at.% relative to TiCl₃) by co-precipitation method. The precipitate was completely oxidized in the aerated suspension, hydrothermally treated, washed and calcinated. The structure of the powders was characterized by thermoanalysis (TG-DTA), diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), nitrogen adsorption and transmission electron microscopy (TEM). The light absorption of the iron-containing powders is red shifted relative to the bare sample. The particle size and anatase content were found to significantly decrease at iron contents ≥6.0 at.% which is accompanied with the increase of their specific surface area. XANES measurements showed that the local structure of iron systematically changes with the variation of the dopant concentrations: at higher Fe-contents, hematite- or goethite-like environments were observed, consistent with the formation of separate X-ray amorphous Fe(III)-containing phases. The local structure of iron gradually transformed with decreasing dopant concentrations, possibly due to substitution of Fe(III) in the titania (TiO₂) crystal lattice. Energy dispersive X-ray analysis (EDX) and chemical analysis was used to characterize the iron content of the samples in the bulk and X-ray photoelectron spectroscopy (XPS) in the surface layer of the particles. The photocatalytic performance of the prepared photocatalysts was compared with the activity of Aldrich anatase under UV–vis and VIS irradiation in two different photoreactors. Maximum photocatalytic performance was found at 3.0 at.% iron concentration for UV–vis and at 1.2 at.% for VIS irradiation. Doping with iron(III) ions increased the photodegradation rate of phenol by a factor of three for UV–vis irradiation and by a factor of two for VIS irradiation, relative to the bare photocatalyst.     

乙酰丙酮钴(Ⅱ)对甲苯液相空气氧化反应的催化性能

以乙酰丙酮钴(Co(acac)₂)为催化剂,在1 L高压搅拌反应釜中研究了其对甲苯液相空气氧化反应的催化性能和反应产物分布,考察了催化剂用量对甲苯转化率和苯甲酸收率的影响,并考察了不同温度下不同催化剂用量时的催化剂寿命。结果表明,Co(acac)₂催化甲苯液相氧化是平行连串的复杂反应,Co(acac)₂的催化活性存在"催化-抑制转换"现象,适宜的催化剂用量为0.0044%(质量分数);催化剂的寿命随反应温度变化存在一个最大值,165℃时催化剂寿命最长,反应温度较低(<165℃)时催化剂更容易失活;在165℃、Co(acac)₂用量为0.0044%时,反应4 h,甲苯转化率为19%,苯甲酸收率为80%;与醋酸钴、环烷酸钴等钴盐催化剂相比,Co(acac)₂催化剂具有用量少、催化活性时间长的优点,可有效地减缓钴盐结垢现象,Co(acac)₂催化剂对甲苯液相空气氧化反应具有良好的催化性能。     

Ni(OH)2修饰对a-Fe2O3薄膜光电化学性能的增强效应

利用一种简便的电沉积方法制备氧化铁薄膜,并在过程中引入Ni(OH)₂进行修饰,对具体电沉积实验参数进行优化,从而建立最佳制备条件。利用场发射扫描电子显微镜、X射线粉末衍射对Fe₂O₃/Ni(OH)₂光电极膜的结构进行表征。利用循环伏安和计时电流测量析氧过电位和光电流密度。结果表明,Ni(OH)₂修饰的α-Fe₂O₃薄膜可提高光生电子与空穴的分离效率,从而显著提高光电催化活性。     

Lean reduction of NO by C3H6 over Ag/alumina derived from Al2O3, AlOOH and Al(OH)3

The effectiveness of Ag/Al₂O₃ catalyst depends greatly on the alumina source used for preparation. A series of alumina-supported catalysts derived from AlOOH, Al₂O₃, and Al(OH)₃ was studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet–visible (UV–vis) spectroscopy, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, O₂, NO + O₂-temperature programmed desorption (TPD), H₂-temperature programmed reduction (TPR), thermal gravimetric analysis (TGA) and activity test, with a focus on the correlation between their redox properties and catalytic behavior towards C₃H₆-selective catalytic reduction (SCR) of NO reaction. The best SCR activity along with a moderated C₃H₆ conversion was achieved over Ag/Al₂O₃ (I) employing AlOOH source. The high density of Ag–O–Al species in Ag/Al₂O₃ (I) is deemed to be crucial for NO selective reduction into N₂. By contrast, a high C₃H₆ conversion simultaneously with a moderate N₂ yield was observed over Ag/Al₂O₃ (II) prepared from a γ-Al₂O₃ source. The larger particles of Ag_mO (m > 2) crystallites were believed to facilitate the propene oxidation therefore leading to a scarcity of reductant for SCR of NO. An amorphous Ag/Al₂O₃ (III) was obtained via employing a Al(OH)₃ source and 500 °C calcination exhibiting a poor SCR performance similar to that for Ag-free Al₂O₃ (I). A subsequent calcination of Ag/Al₂O₃ (III) at 800 °C led to the generation of Ag/Al₂O₃ (IV) catalyst yielding a significant enhancement in both N₂ yield and C₃H₆ conversion, which was attributed to the appearance of γ-phase structure and an increase in surface area. Further thermo treatment at 950 °C for the preparation of Ag/Al₂O₃ (V) accelerated the sintering of Ag clusters resulting in a severe unselective combustion, which competes with SCR of NO reaction. In view of the transient studies, the redox properties of the prepared catalysts were investigated showing an oxidation capability of Ag/Al₂O₃ (II and V) > Ag/Al₂O₃ (IV) > Ag/Al₂O₃ (I) > Ag/Al₂O₃ (III) and Al₂O₃ (I). The formation of nitrate species is an important step for the deNO_x process, which can be promoted by increasing O₂ feed concentration as evidenced by NO + O₂-TPD study for Ag/Al₂O₃ (I), achieving a better catalytic performance.     

Ag-Zn_3(VO_4)_2光催化剂催化降解甲基橙溶液

采用水热法结合高温热处理制备Ag-Zn_3(VO_4)_2光催化剂,研究催化剂在可见光下降解甲基橙溶液的性能,并考察催化剂用量、甲基橙溶液初始浓度、pH值、盐效应和H_2O_2用量对光催化性能的影响,评价Ag-Zn_3(VO_4)_2光催化剂的重复使用性能。结果表明,在催化剂用量2.0 g·L~(-1)、甲基橙溶液初始浓度20 mg·L~(-1)和溶液pH=6.2条件下光照反应5 h,甲基橙溶液脱色率可达99.18%,Na_2SO_4对光催化降解甲基橙起抑制作用,且随着溶液中盐浓度增加,抑制作用更明显。H_2O_2在一定浓度范围可促进光催化降解甲基橙,100 mL甲基橙溶液中30%H_2O_2加入量为1.0 mL时,甲基橙溶液脱色率可提高21.68个百分点。催化剂重复使用5次后,光照5 h的甲基橙溶液脱色率仍可达到75.99%。