洁净冶炼用SiAlON耐火材料的制备技术进展

碳热还原氮化工艺具有低成本且有产业化生产的潜力等特点,因而被认为是制备洁净冶炼用SiAlON耐火材料的实用方法.本文对碳热还原氮化法制备SiAlON的进展进行了综述,归纳分析了不同条件对生成物相和性能的影响.并对今后的研究进行了展望.     

Pt0.01Fe0.05-g-C3N4催化剂高效光热催化二氧化碳还原

光热催化是一种高效利用太阳光, 将二氧化碳转化为高价值产物的方法. 本工作以石墨相氮化碳为载体, 通过水热-浸渍两步法制备了负载铂、铁氧化物的石墨相氮化碳催化剂. 该催化剂具备优异的光热转换性能, 可实现7.36 mmol•h^-1•g_cat^-1的二氧化碳还原活性和97%的一氧化碳选择性. 使用X射线晶体衍射(XRD)、配备能量色散X射线谱(EDS)的球差校正扫描透射电子显微镜(Cs-S/TEM)、X射线光电子能谱(XPS)、紫外可见漫反射光谱(DRS)等表征手段从催化剂物相、微观结构、表面状态、光学性能等方面对催化剂进行了表征. 结果显示, 催化剂能吸收全谱太阳光, 且具备较高的载流子分离效率. 基于原位傅里叶变换红外光谱(DRIFTS)表征结果, 提出了二氧化碳在催化剂表面的可能的反应机理, 并对铂在铁氧化物表面的氢溢流效应进行了表征. 结果表明二氧化碳和氢气分别在铁氧化物、铂位点被活化, 参与催化反应. 本工作对后续光热二氧化碳还原催化剂的设计、合成与机理研究具有一定的参考作用.     

石墨相氮化碳的液相合成及光催化性能研究进展

石墨相氮化碳是类石墨层状聚合物材料,因其特殊的能带和电子结构,近年来成为功能材料研究领域的热点.液相合成法具有温和多变的特性,是石墨相氮化碳合成的重要途径.本文作者就现阶段液相介质合成氮化碳的主要方法进行了介绍,主要包括液相电沉积、脉冲激光烧蚀、溶剂热合成法等.介绍了不同液相介质和合成参数对制备氮化碳材料晶型、形貌等的影响.同时就溶剂热合成氮化碳在光催化领域的研究进展进行了总结.在未来的研究中,液相合成法将极大的丰富氮化碳材料结构优化的途径,有助于推动多功能聚合物材料的深入研究.     

稀土对SiO2碳热还原氮化制备Si3N4机理研究

研究了不同稀土氧化物添加剂对ＳｉＯ２碳热还原氮化制备Ｓｉ３Ｎ４粉料作用机理。结果表明，稀土氧化物添加剂促进氧化，且制备的Ｓｉ３Ｎ４粉料，颗粒细，含α－Ｓｉ３４Ｎ４较高，是一种有开发前景的添加剂。     

Ni-Mo氮化物催化剂:合成及其丙烷氨氧化催化性能简

分别采用溶胶-凝胶法、旋转蒸发微波干燥法、共沉淀法、浸渍法和机械混合法制备Ni-Mo氧化物前驱体. 以H₂和N₂的混合气为氮化气体,采用程序升温氮化法合成了镍钼氮化物催化剂. 利用X射线衍射、总氮含量分析、X射线光电子能谱及H₂程序升温还原对Ni-Mo氧化物前体及氮化物催化剂进行了表征. 将上述Ni-Mo氮化物催化剂用于丙烷氨氧化反应中. 结果表明,Ni-Mo氧化物前驱体的制备方法影响其氮化物催化剂上丙烷氨氧化反应性能. Ni-Mo氮化物催化剂中氮物种的移动性及反应性对产物丙烯腈选择性的影响较大,共沉淀法制备的催化剂存在大量的活性氮物种,因而具有良好的催化丙烷氨氧化反应活性.     

稀土氧化物作为邻苯二酸酐和辛醇酯化催化剂的研究

稀土氧化物可用作催化剂,如用于烷烃的裂解、烯烃的异构化、醇类脱水等.但稀土氧化物作为酯化催化剂迄今未见报道.我们在研究酯化催化时,选择了邻苯二甲酸二辛酯的合成.它是一种优良增塑剂.为了提高产品质量,近年来已由非酸催化代替了老法酸催化.其中用金属氧化物(如ZnO,SnO等)做催化剂已有报道.我们参照他们的实验方法,用稀土氧化物作催化剂进行了研究.     

RGO/C_3N_4复合材料的制备及可见光催化性能

通过半封闭一步热裂解法和改进的Hummers法分别制备了类石墨氮化碳(C3N4)和氧化石墨烯(GO),再利用光还原方法制得还原氧化石墨烯/氮化碳(RGO/C3N4)复合材料。采用X射线衍射(XRD),场发射扫描电镜(FESEM),X射线光电子能谱(XPS),紫外-可见漫反射吸收光谱(DRS),光致荧光(PL)和傅里叶变换红外光谱(FTIR)等测试技术对复合材料进行表征。以罗丹明B(RhB)为探针分子在可见光下考察RGO/C3N4复合材料的光催化活性,结果表明:RGO的引入显著提高了C3N4的光催化活性,且6.0%RGO/C3N4复合物的光催化活性最高,可能的原因是RGO具有优良的接受和传导电子性能,抑制了C3N4光生电子-空穴的复合机率,进而提高了光催化活性。     

溶剂热插层法制备荧光石墨相氮化碳量子点及其在Fe3+检测中的应用

利用溶剂热法, 基于氢氧化钾的插层作用制备了荧光氮化碳量子点(g-C₃N₄ QDs). 所获得的氮化碳量子点具有良好的水溶性和荧光稳定性. 透射电子显微镜(TEM)照片显示, 氮化碳量子点的粒径约为2.3 nm; X射线光电子能谱(XPS)和红外光谱(FTIR)结果表明, 氮化碳量子点表面存在大量的亲水基团; 荧光发射光谱(PL)结果表明, 氮化碳量子点具有激发波长依赖性. 基于三价铁离子(Fe³⁺)对荧光氮化碳量子点荧光的猝灭现象, 构建了一种用于检测Fe³⁺的荧光传感器, 在Fe³⁺浓度为5~100 μmol/L范围内, 检测体系表现出良好的线性关系, 检出限约为0.5 μmol/L, 实现了对Fe³⁺的高效、 灵敏、 选择性检测.     

钕铁硼废料焙砂的碳热还原试验研究

钕铁硼废料中含有大量的铁,现有回转窑焙烧-HCl浸出预处理工艺难于将其回收利用。基于稀土氧化物和铁氧化物还原性质差异,以钕铁硼废料焙烧产物(简称为焙砂)为对象,在高温井式窑炉中开展焙砂碳热还原试验研究,考察了还原介质(焦炭、石墨和块煤)、介质粒度、还原温度、还原时间、配碳比、物料厚度等条件对铁还原率的影响。结果表明,焦炭具有较好的还原效果,在还原温度为1200℃,还原时间为4 h,配碳比为30%,物料厚度为22 mm的条件下,焙砂中铁的还原度高达88.08%,为综合回收利用钕铁硼废料中铁资源提供了理论基础和方法途径。     

新型生态耐火材料的制备工艺与再循环技术

本文回顾了目前工业粉煤灰的资源综合利用与再循环技术,提出拟利用电厂粉煤灰,合成具有环境友好功能的新型生态赛隆耐火材料/陶瓷新思路.研究结果表明,通过酸洗工艺参数的控制,可实现粉煤灰中杂质铁的去除,有利于合成材料的体积密度的改善.采用胶态成型工艺与碳热还原氮化工艺,可实现与环境友好的生态环境材料的研制.     

Polymer derived non-oxide ceramics modified with late transition metals

This tutorial review highlights the methods for the preparation of metal modified precursor derived ceramics (PDCs) and concentrates on the rare non-oxide systems enhanced with late transition metals. In addition to the main synthetic strategies for modified SiC and SiCN ceramics, an overview of the morphologies, structures and compositions of both, ceramic materials and metal (nano) particles, is presented. Potential magnetic and catalytic applications have been discussed for the so manufactured metal containing non-oxide ceramics.     

Preparation of titanium carbide powders by sol–gel and microwave carbothermal reduction methods at low temperature

Titanium carbide ultrafine powders were prepared from tetrabutyl titanate and sucrose by sol–gel and microwave carbothermal reduction. The influences of reaction temperature and molar ratio of Ti to C on the synthesis of titanium carbide were studied. The results show that excess amount of carbon plays a positive effect on the carbothermal reduction of TiO₂ at low temperature. The inceptive carbothermal reduction temperature of TiO₂ and formation of titanium oxycarbide was below 900 °C, and pure TiC can be prepared at 1,200 °C, which was considerably lower compared to that by conventional carbothermal reduction using a mixture of TiO₂ and carbon powders as raw materials. The morphology and particle size of synthesized TiC powder were examined by field emission-scanning electron microscopy (FE-SEM) and the quantities of the phases of the powders were analyzed by Rietveld refinement method, the particle sizes of the TiC powders synthesized at 1,300 °C distribute over 0.1–0.5 μm.     

Ordered mesoporous non-oxide materials

Ordered mesoporous inorganic non-oxide materials attract increasing interest due to their plenty of unique properties and functionalities and potential applications. Lots of achievements have been made on their synthesis and structural characterization, especially in the last five years. In this critical review, the ordered mesoporous non-oxide materials are categorized by compositions, including non-oxide ceramics, metal chalcogenides, metal nitrides, carbides and fluorides, and systematically summarized on the basis of their synthesis approaches and mechanisms, as well as properties. Two synthesis routes such as hard-templating (nanocasting) and soft-templating (surfactant assembly) routes are demonstrated. The principal issues in the nanocasting synthesis including the template composition and mesostructure, pore surface chemistry, precursor selection, processing and template removal are emphatically described. A great number of successful cases from the soft-templating method are focused on the surfactant liquid-crystal mesophases to synthesize mesostructured metal chalcogenide composites and the inorganic-block-organic copolymer self-assembly to obtain non-oxide ceramics (296 references).     

The influence of processing parameters on the fabrication of Si3N4 wires

Silicon nitride (Si₃N₄) wires have been prepared by means of carbothermal reduction followed by the nitridation (CTRN) of silica gel containing ultrafine decomposed saccharose. The influence of temperature of reaction and mass ratio of carbon to silicon $ \left( \frac{C}{Si} \right) $ on the synthesis of Si₃N₄ wires were studied. The presence of nitrogen gas in the pores of gel at high temperature starts the CTRN reaction leading to the formation of Si₃N₄ wires. The results show that the Si₃N₄ was fully formed with two kinds of morphologies including globular and wire with a width of 100–500 nm and length of several microns at sintering temperature of 1,400 °C by employing the mass ratio of $ \frac{C}{Si} \; = \;0.5 $ . The infrared adsorption of the wires exhibits absorption bands related to the absorption peaks of Si–N bond of Si₃N₄. The thermal analysis results reveal that carbothermal nitridation reaction was completed at temperature of 1,400 °C.     

Changes to the physicochemical characteristics of wheat straw by mechanical ultrafine grinding

To investigate changes on the physicochemical characteristics of wheat straw by mechanical ultrafine grinding, wheat straw powders of four different particle sizes and distributions were produced using a sieve-based Retsch ZM100 grind mill and CJM-SY-B ultrafine vibration grind mill. Changes on the microstructure and physicochemical characteristics of the different powders were assessed by scanning electron microscopy, X-ray diffractometry, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and relevant standard laboratory analysis methods. Ultrafine grinding reduced the crystallite size and crystallinity of the wheat straw. New surfaces were exposed on the ultrafine powder with high levels of cellulose/hemicelluloses components but there was no apparent change in chemical structure. Wheat straw powders were smaller in size but had a higher bulk density (from 0.19 to 0.54 g/mL) and angle of repose (from 46.02° to 55.61°) and slide (from 37.26° to 41.00°). The hydration properties (water-holding capacity and swelling capacity) decreased with reduction in particle size of the wheat straw. Both the sieve-based and ultrafine powder exhibited a good ability to remove Pb²⁺ and Cd²⁺ and there was marginal improvement when using the ultrafine powder. The thermal stability of the ultrafine powder measured by thermogravimetric analysis decreased significantly because of the low cellulose crystallinity.     

Preparation and microstructure evolution of diboride ultrafine powder by sol–gel and microwave carbothermal reduction method

Titanium diboride ultrafine powder was prepared from sucrose, tetrabutyl titanate and boric acid by the sol–gel and microwave carbothermal reduction method. The influence of reaction temperature, ratio of Ti to C and Ti to B on the synthesis of titanium diboride was studied. The results indicated that the carbothermal temperature, the content of carbon and the amount of H₃BO₃ show obvious effects on the formation of TiB₂. 1,300 °C was the optimum synthesis temperature and pure TiB₂ could be prepared. The microstructure of prepared TiB₂ was investigated by field emission-scanning electron microscopy (FE-SEM), which results showed that the crystalline size of the prepared titanium diboride at 1,300 °C was about 3–5 μm. The quantities of the crystalline phases of the powders prepared at different temperatures were analyzed by Rietveld refinement method. An erratum to this article can be found at     

RuO2-loaded beta-Ge3N4 as a non-oxide photocatalyst for overall water splitting

Germanium nitride beta-Ge3N4 dispersed with RuO2 nanoparticles is presented as the first example of a non-oxide photocatalyst for the stoichiometric decomposition of H2O into H2 and O2. All of the successful photocatalysts developed for overall water splitting over the past 30 years have been based on oxides of metals. The discovery of a non-oxide photocatalyst, such as nitrides and oxynitrides, achieving the same function is therefore expected to stimulate research on non-oxide photocatalysts. New opportunities for progress in the development of visible light-driven photocatalysis can thus be expected, as the higher valence band positions of metal nitrides compared to the corresponding metal oxides provide narrower band gaps, which are suitable for visible light activity.     

Structural and functional diagnostics of ultrafine components in condensed high-energy systems

The study deals with octogen (HMX) and aluminum, which are among the most widely used components of condensed high-energy systems. The structure, thermal behavior and combustion parameters were determined for the octogen-based monofuels and octogen-aluminum binary systems at different dispersity of components. Irrespective of differences in thermal behavior, monofuels obtained with standard and ultrafine octogen powders were shown to have virtually identical combustion parameters. In the binary systems, replacement of standard microsized aluminum by ultrafine one increases the combustion rate by a factor of 2.5, and completeness of the metal reaction (oxidation) by a factor of 4.     

Preparation and Characterization of CeO2 Nanoparticles

The preparation and characterization of cerium oxide nano-powder has attracted much attention over the past few years due to their great potential in many fields. It is commonly used in glass, ceramics, fluorescence powder and catalyst etc.1. Cerium oxide was produced by oxalic acid decomposition in industry. Take this way, the products are pure but the size of powder is large ( ＞3 μ m )2. Up to now,various methods have been reported to synthesize ultra fine cerium oxide powders, such as homogeneous deposition method, hydrothermal method, sol-gel method and spray deposition method etc. 3-6. However, these methods are not convenient for synthesis of large amounts of powders because of the difficulty of technique and expensive equipment involved. Although sol-gel method is well suited to synthesize ultrafine powders, this reaction is always in high temperature.