Synthesis of chromium containing pigments from chromium galvanic sludges

In this work the screening results of the scientific activity conducted on laboratory scale to valorise chromium(III) contained in the galvanic sludge as chromium precursor for ceramic pigments are reported. The valorisation of this waste as a secondary raw material (SRM) is obtained by achievement of thermal and chemical stable crystal structures able to color ceramic material. Two different pigments pink CaCr(0.04)Sn(0.97)SiO(5) and green Ca(3)Cr(2)(SiO(4))(3) were synthesized by solid-state reactions using dried Cr sludge as chromium oxide precursor. The obtained pigments were characterized by X-ray diffraction and SEM analysis. Furthermore the color developed in a suitable ceramic glaze was investigated in comparison with the color developed by the pigments prepared from pure Cr(2)O(3). The characterization carried out corroborates the thermal and chemical stability of the synthesized pigments and, especially for the Cr-Sn pink pigment, the powders develop an intense color that is very similar to the color developed by the pigments obtained starting from pure Cr(2)O(3).     

Catalytic pyrolysis of oil fractions separated from food waste leachate over nanoporous acid catalysts

Oil fractions, separated from food waste leachate, can be used as an energy source. Especially, high quality oil can be obtained by catalytic cracking. In this study, nanoporous catalysts such as Al-MCM-41 and mesoporous MFI type zeolite were applied to the catalytic cracking of oil fractions using the pyrolysis gas chromatography/mass spectrometry. Mesoporous MFI type zeolite showed better textural porosity than Al-MCM-41. In addition, mesoporous MFI type zeolite had strong Br?nsted acidity while Al-MCM-41 had weak acidity. Significant amount of acid components in the food waste oil fractions were converted to mainly oxygenates and aromatics. As a result of its well-defined nanopores and strong acidity, the use of a mesoporous MFI type zeolite produced large amounts of gaseous and aromatic compounds. High yields of hydrocarbons within the gasoline range were also obtained in the case of mesoporous MFI type zeolite, whereas the use of Al-MCM-41, which exhibits relatively weak acidity, resulted in high yields of oxygenates and diesel range hydrocarbons.     

Catalytic decomposition of 1,2-dichlorobenzene using Pt-loaded nanoporous zeolite MFI catalyst

Nanoporous zeolite MFI was prepared by using HClO4 as a promoter. A significant proportion of the synthesized zeolite MFI nanoparticles exhibited nanoporous characteristics. Although the synthesis of the zeolite MFI was completed within 6 h, the crystallinity of all the zeolite MFI was shown to be high. The synthesis time of approximately 6 h used in this study was much shorter than the conventional hydrothermal method. The feasibility of the new nanoporous zeolite MFI towards the gas phase catalytic oxidation of a model for dioxin, 1,2-dichlorobenzene, was tested by comparing the catalytic activity of Pt/nanoporous zeolite MFI with that of a Pt/gamma-Al2O3 catalyst. The catalytic activity of the Pt/nanoporous zeolite MFI was higher than that of the Pt/gamma-Al2O3 catalyst. The internal surface area and acidity appears to be a major factor for the decomposition of 1,2-dichlorobenzene.     

Langmuir-Blodgett法制备b-轴取向MFI型分子筛膜

实验利用Langmuir-Blodgett(LB)技术大面积有序组装分子筛晶粒, 进而制备连续致密且高度b-轴取向MFI型分子筛膜。首先, 采用LB技术在表面性质不同的不锈钢载体和铂电极载体上实现了b-轴取向MFI分子筛晶粒的高度有序组装; 其次, 采用合成液预处理法对LB法制备的高度b-轴取向的MFI晶种层进行二次合成。XRD和SEM表征结果显示: 采用合成液预处理法可以有效抑制分子筛晶粒在二次生长过程中生成孪晶, 进而获得高度b-轴取向MFI分子筛膜; 最后, 电化学测试结果证实采用LB技术制备的b-轴取向MFI分子筛膜致密, 无缺陷。     

水性光油中珠光颜料显色性的比较

目的研究不同参数下珠光颜料在水性光油中的显色效果。方法将珠光颜料均匀分散加入到水性光油中,在胶印色样表面进行上光涂布,测量上光前后色样的色度值,计算色差,研究珠光颜料质量分数和印版加网线数对其呈色效果的影响。结果黄绿、蓝色、金色这3种珠光颜料的主密度和色差都随着质量分数的增加而增大;相同质量分数下,5~25,10~60,40~100μm 3种粒径大小的青色颜料分别对应凹印版辊70,60,50 lpi/cm加网线数时,颜色的主密度和色差值最大。结论研究表明质量分数是影响珠光颜料显色效果的最主要因素,颜料的粒径大小和凹印版辊的加网线数相匹配时珠光颜料的显色效果最好。     

A study on the synthesis,characterization and catalytic activity of ruthenium-substituted MFI (Mobil Five) zeolite

Hydrothermal synthesis was adapted to prepare a series of ruthenium (Ru)-incorporated Mobil Five (MFI) zeolite materials with silicon (Si) to aluminium (Al) ratio of 100 and with Al to Ru ratios 1:1, 2:1 and 3:1. An X-ray diffractometer (XRD) and FT-IR were employed to identify the formation of the zeolite phase. A favourable environment was maintained in the gel to overcome the difficulties of isomorphous substitution of ruthenium into the MFI framework. The unit cell volume change and the shift in XRD reflection positions showed a positive correlation with increased ruthenium content in the samples. UV–Vis (DRS) spectra confirmed the position of ruthenium in the T-site in the MFI structure. Thermogravimetric analysis was carried out for studying water and template removal patterns and also for studying the thermal stability of the synthesized samples. Formation of uniform rectangle- and twinned-rectangle-shaped MFI particles with particle size approaching \(27\,\upmu \hbox {m}\) was confirmed by scanning electron microscopy. Energy-dispersive X-ray analysis was carried out for quantification of Si, Al and Ru. The catalytic activities of the synthesized samples for the hydroxylation of phenol was investigated, the major products being catechol and hydroquinone.     

MFI分子筛膜在光纤微谐振器上的合成及表征

采用原位水热合成法,分别采用四丙基氢氧化铵(TPAOH)和正丁胺(NBA)为模板剂,在光纤微谐振器表面成功制备出MFI沸石分子筛膜.用X射线衍射(XRD)和扫描电镜(SEM)对膜的物相结构和晶体形貌表征分析可以看出,用四丙基氢氧化铵(TPAOH)为模板剂合成出的沸石晶体具有规则的六棱柱外形,晶粒大小约2 μm,而用正丁胺(NBA)为模板剂合成出的沸石晶体没有规则外形,晶粒大小约为500 nm.采用镀有沸石的长周期光栅(LPFG)检测体积分数为5％丙酮气体,长周期光栅的谐振波长蓝移了2 nm.沸石膜在光纤微谐振表面的合成可用于精密传感器的开发.     

乙酸乙酯作潜伏性酸对铁黄表面改性处理的研究

为了改善铁黄颜料的耐热性,运用乙酸乙酯作为潜伏性酸试剂,研究了一种新的铁黄表面均匀包覆二氧化硅的方法,即通过控制乙酸乙酯的水解速率来实现在铁黄表面均匀包覆二氧化硅。对表面均匀包覆二氧化硅后的铁黄颜料的颜色变化、分散稳定性、吸油量进行了表征。结果表明,均匀包覆二氧化硅可有效改善铁黄颜料的综合性能。     

天然色素在卷烟纸染色中的影响因素

简述了彩色卷烟纸的现状和前景,并采用天然色素对卷烟纸进行了染色,主要研究染色时的特性.结果表明,pH值的变化对颜色的影响很小,钠盐、锌盐、铝盐、镁盐的加入量对卷烟纸颜色变化影响不大,铁盐的加入对卷烟纸颜色影响较大.抗氧化剂L-抗坏血酸的加入提高了彩色卷烟纸颜色的光稳定性,对湿稳定性也有一定的提高.     

Metal encapsulation in zeolite particles: A rational design of zeolite-supported catalyst with maximum site activity

Zeolite-supported metal catalysts have been proven effective in many important catalytic reactions, such as hydrogenation, Fisher-Tropsch synthesis, automobile exhaust catalysis, selective catalytic reduction and many others. Despite the successful preparation of the catalyst through widely adopted methods, including ion exchange and impregnation, the metal dispersion over the zeolite is lack of control with high randomness. This renders the so-called “catalytic performance” an overall contribution from the metal sites located inside the zeolite micropores and those located on the external surface. This is exceptionally true for small to medium pore zeolites with typical free apertures of 0.3–0.6 nm (such as LTA and MFI). A more rational design of zeolite-supported metal catalysts is by encapsulating the metal nanoparticles or clusters within zeolite pores prior to the zeolite formation. Encapsulation of metals in zeolite prevents them from sintering and sulphur poisoning by cage confinement and molecular exclusion (via well-defined pore size and shape), respectively. This paper gives a new perspective on using metal clusters and nanoparticles as catalysts and the design of an effective zeolite-supported catalytic system.     

Synthesis of iron red hybrid pigments from oil shale semi-coke waste

Oil shale semi-coke (SC) is a bulk solid waste produced after shale oil being extracted from oil shale. It is abundant on the earth, but most of them are discarded or piled up as solid waste, and their reuse as resources is very limited. In this paper, adhering to the concept of “waste to materials“, the α-Fe₂O₃/SC hybrid pigments with the red color (a* = 29.68) better than commercial iron red pigments (a* = 26.92) were synthesized by an one-pot hydrothermal reaction of pretreated SC with Fe(III), using SC as a cheap starting material. The microscopic structure, chemical composition and color of the hybrid pigments were studied, and the reaction parameters for synthesizing the best hybrid pigments from SC were optimized. The results indicate that the hybrid pigments are mainly composed of SiO₂ and Fe₂O₃, where α-Fe₂O₃ particles grow on the surface of SC-derived silicate substrate with a better dispersion. The hybrid pigments showed a good stability, especially an outstanding high temperature-resistant stability. The secondary heat treatment induced the further improvement of red color value of the hybrid pigments. This work provides a new way and solution for the rational disposal and functional application of SC waste.     

Steam-assisted crystallization of TPA+-exchanged MCM-41 type mesoporous materials with thick pore walls

Hierarchical MCM-41/MFI composites were synthesized through ion-exchange of as-made MCM-41 type mesoporous materials with tetrapropylammonium bromide and subsequent steam-assisted recrystallization. The obtained samples were characterized by powder X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis, FT-IR, ¹H–¹³C CP/MAS and nitrogen adsorption–desorption. The XRD patterns show that the MCM-41/MFI composite possesses both ordered MCM-41 phase and zeolite MFI phase. SEM and TEM images indicate that the recrystallized materials retained the mesoporous characteristics and the morphology of as-made mesoporous materials without the formation of bulky zeolite, quite different from the mechanical mixture of MCM-41 and MFI structured zeolite. Among others, lower recrystallization temperature and the introduction of the titanium to the parent materials are beneficial to preserve the mesoporous structure during the recrystallization process.     

Zeolite Nanosheets Stabilize Catalyst Particles to Promote the Growth of Thermodynamically Unfavorable,Small‐Diameter Carbon Nanotubes

A challenge in the synthesis of single‐wall carbon nanotubes (SWCNTs) is the lack of control over the formation and evolution of catalyst nanoparticles and the lack of control over their size or chirality. Here, zeolite MFI nanosheets (MFI‐Ns) are used to keep cobalt (Co) nanoparticles stable during prolonged annealing conditions. Environmental transmission electron microscopy (ETEM) shows that the MFI‐Ns can influence the size and shape of nanoparticles via particle/support registry, which leads to the preferential docking of nanoparticles to four or fewer pores and to the regulation of the SWCNT synthesis products. The resulting SWCNT population exhibits a narrow diameter distribution and SWCNTs of nearly all chiral angles, including sub‐nm zigzag (ZZ) and near‐ZZ tubes. Theoretical simulations reveal that the growth of these unfavorable tubes from unsupported catalysts leads to the rapid encapsulation of catalyst nanoparticles bearing them; their presence in the growth products suggests that the MFI‐Ns prevent nanoparticle encapsulation and prologue ZZ and near‐ZZ SWCNT growth. These results thus present a path forward for controlling nanoparticle formation and evolution, for achieving size‐ and shape‐selectivity at high temperature, and for controlling SWCNT synthesis.     

Synthesis of MFI-type zeolite membranes on porous α-alumina supports by wet gel crystallization in the vapor phase

A new method has been developed for synthesis of MFI-type zeolite membranes on porous -alumina supports. Using this method, a thin layer of wet-gel precursor precoated from a synthesis sol containing SiO₂, tetrapropylammonium hydroxide (TPAOH), NaOH, and H₂O was converted to an MFI zeolite film by vapor-phase treatment at elevated temperatures. MFI zeolite films were formed on the -alumina substrates, respectively, in the vapor phases of TPAOH solution and an ethylenediamine(EDA)/triethylamine (TEA)/water mixture, but an amorphous material was obtained in the vapor phase of pure water. Scanning electron microscopy and helium permeation examinations before calcination showed that the MFI membrane obtained in the vapor phase of the TPAOH solution was of higher quality than that synthesized in the vapor phase of the EDA/TEA/water mixture in terms of zeolite film integrity and compactness. It was also found that the existence of the template TPA⁺ in the parental synthesis sol was critical to the formation of MFI zeolite under the investigated conditions. When precursor layers coated from a template-free colloidal silica system were used, the vapor-phase treatment resulted in formation of Na-P1 and ANA zeolite films, respectively, in the vapors of TPAOH solution and the EDA/TEA/water mixture. The method developed in this work has the advantages of improved controllability, minimal waste generation, and reduced chemical consumption that are desirable for large-scale production of zeolite membranes.     

Zeolite (In)Stability under Aqueous or Steaming Conditions

Zeolites are among the most environmentally friendly materials produced industrially at the Megaton scale. They find numerous commercial applications, particularly in catalysis, adsorption, and separation. Under ambient conditions aluminosilicate zeolites are stable when exposed to water or water vapor. However, at extreme conditions as high temperature, high water vapor pressure or increased acidity/basicity, their crystalline framework can be destroyed. The stability of the zeolite framework under aqueous conditions also depends on the concentration and character of heteroatoms (other than Al) and the topology of the zeolite. The factors critical for zeolite (in)stability in the presence of water under various conditions are reviewed from the experimental as well as computational sides. Nonreactive and reactive interactions of water with zeolites are addressed. The goal of this review is to provide a comparative overview of all-silica zeolites, aluminosilicates and zeolites with other heteroatoms (Ti, Sn, and Ge) when contacted with water. Due attention is also devoted to the situation when partial zeolite hydrolysis is used beneficially, such as the formation of hierarchical zeolites, synthesis of new zeolites or fine-tuning catalytic or adsorption characteristics of zeolites.     

表面胶转化法合成亚微米厚度MFI型分子筛薄膜应用于快速择形分离己烷异构体

在膜分离中,薄膜超薄化对促进气体传输至关重要,而将膜厚降至亚微米级则极具挑战性.本文中,我们提出表面胶转化法来合成亚微米厚度的纯硅MFI分子筛膜.通过精细调控前驱体化学组成制备了低浸润性的黏性胶,有效防止凝胶从氧化铝载体表面渗透至空隙中.在晶种的诱导下,辅以少量水蒸气,表面凝胶经历了直接和完全晶化过程,形成了厚度为~5...     

25th Anniversary Article: Progress in Chemistry and Applications of Functional Indigos for Organic Electronics

Indigo and its derivatives are dyes and pigments with a long and distinguished history in organic chemistry. Recently, applications of this ‘old’ structure as a functional organic building block for organic electronics applications have renewed interest in these molecules and their remarkable chemical and physical properties. Natural‐origin indigos have been processed in fully bio‐compatible field effect transistors, operating with ambipolar mobilities up to 0.5 cm²/Vs and air‐stability. The synthetic derivative isoindigo has emerged as one of the most successful building‐blocks for semiconducting polymers for plastic solar cells with efficiencies > 5%. Another isomer of indigo, epindolidione, has also been shown to be one of the best reported organic transistor materials in terms of mobility (～2 cm²/Vs) and stability. This progress report aims to review very recent applications of indigoids in organic electronics, but especially to logically bridge together the hereto independent research directions on indigo, isoindigo, and other materials inspired by historical dye chemistry: a field which was the root of the development of modern chemistry in the first place.     

An efficient synthesis of nanocrystalline MFI zeolite using different silica sources: A green approach

Nanocrystalline MFI zeolite was synthesized with a very broad range of silica to alumina ratios using an autoclave for periods of 7 h at 473 K under autogeneous pressure without seeding gel, promoter, organic solvent or sulfuric acid. The procedure has been successfully employed for the synthesis of MFI samples using fumed silica, colloidal silica, aerosil and tetraethylorthosilicate as silica sources. The synthesized samples were characterized by different techniques such as X-ray diffraction, Fourier transform infrared spectroscopy, Scanning electron microscopy. Their average crystallite size ranges from about 26 to 55 nm and they exhibit high crystallinity.     

Blue pigment colors from wall painting churches in danger (Portugal 15th to 18th century): identification, diagnosis, and color evaluation

Samples of blue wall paint layers from selected 15th to 18th century religious mural paintings from southern Portugal (Alentejo) have been analyzed using a multi-analytical methodology involving the combination of in situ visible spectro-colorimetry with microanalytical techniques such as optical and scanning electron microscopy and Raman spectroscopy. In situ analyses and micro-sampling were carried out in nine different churches, many in an advanced state of deterioration. The objectives of this study were: (a) to identify and compare the pigments that were used in the blue paint layers across the Alentejo region and through time by analysis of the elemental and mineralogical composition and pictorial techniques, and (b) to correlate the data between the actual color of the paint layer and the state of conservation of the pigments. For the paintings dated from the 16th century forward, the results show a generalized use of smalt blue. To a lesser extent, natural azurite was used despite the geological richness of the region in copper and pyrite ores. In only one painting was an optical blue made of carbon black and lime found. The pigments, pure or mixed with red and yellow ochres, were coarsely ground and used in different concentrations to create three-dimensional effects. These parameters as well as the presence of iron oxides in underlayer paints influence the colorimetric coordinates in the more transparent smalt blue paint layers. The state of conservation of the pigments plays an important role in the alteration of the paint color. A clear example of this is the fading of the smalt blue in several paintings due to lixiviation processes.     

汽相转化法制备纳米晶组成的块状ZSM-5多孔沸石

在ZSM-5沸石前驱体中加入羧甲基纤维素钠并制得干胶, 然后通过蒸汽相转化制得了大块状ZSM-5沸石。由于羧甲基纤维素钠与硅铝物种之间的相互作用干扰了沸石晶体的正常生长, 这种干扰所产生的“键阻断”作用导致合成的大块状ZSM-5沸石由100~150 nm的初级ZSM-5沸石晶体组成, 在这些初级粒子之间存在2~20 nm的二次介孔结构。异丙苯催化裂化结果表明, 由于纳米沸石具有较高的外表面积和较大的介孔孔容, 比参比催化剂表现出更高的异丙苯转化率。