Supercritical hydrothermal synthesis of nano-zinc oxide: Process and mechanism

Nano-zinc oxide is a type of multifunctional inorganic material, which had been extensively used due to the excellent properties such as piezoelectricity, sterilization, and UV shielding. The methods used for preparing nano-zinc oxides include precipitation, low-temperature hydrothermal, sol-gel, spray pyrolysis, and gas-phase synthesis. All of the current methods share the same problems of long reaction time, large particle sizes, and uneven distribution of particle sizes. The supercritical hydrothermal synthesis is a promising method for nano-ZnO preparation, which has the advantages of fast reaction rates and uniform particle size distribution. In this paper, the mechanism of supercritical hydrothermal synthesis of ZnO (including reaction, crystallization, and growth mechanism) is introduced. Then the effects of key parameters (materials and process parameters) are summarized. Moreover, the effects of surface modification and doping on ZnO are analyzed. Some suggestions for improving the particle quality by supercritical hydrothermal synthesis are also presented, as well as the future research directions.     

A review: Conventional and supercritical hydro/solvothermal synthesis of ultrafine particles as cathode in lithium battery

Olivine LiMPO₄ (M = Mn, Fe, Co and Ni, LMP) materials are considered to be the most promising cathode candidates for high energy storage devices. In this work, the feasibility of the thermodynamics of powder formation is discussed for explaining such a reaction mechanism, as well as the recent progress of conventional and supercritical hydro/solvothermal syntheses, are summarized. The association among synthesis conditions, structure, morphology and electrochemical properties, especially for rate capability and tap density under hydro/solvothermal condition, are highlighted. Notably, this work primarily concentrates on the processes in which additives participate in the hydrothermal synthesis of LMP and considers less the subsequent treatments of synthesized LMP with extra additives. In other words, the modifications during the synthesis process with additives are the primary topic. Recently, supercritical hydro/solvothermal synthesis has been demonstrated to be a promising approach for generating high-crystalline micro-nanoparticles with short reaction times (less than 2 min) and high crystallization rates affected by the specific characteristics in supercritical fluids. Additionally, the smallest powders among the reported LFP nanoparticles (less than 15 nm) had been synthesized via SHS (supercritical hydrothermal synthesis). Inspired by the structure-function relationships that are gained by hydro/solvothermal synthesis, rapid and continuous supercritical hydro/solvothermal synthesis is of interest for the commercial production of high-performance micro/nanocrystals due to its environmental friendliness and easy scale-up.     

Continuous hydrothermal synthesis of HT-LiCoO2 in supercritical water

A detailed investigation was made into the production of high temperature lithium cobalt oxide (HT-LiCoO₂) particles by continuous hydrothermal synthesis via the reaction of cobalt nitrate, lithium hydroxide, and hydrogen peroxide. The experiments were carried out in both subcritical and supercritical water, at temperatures ranging from 300 to 411 °C, with residence times less than 1 min in all instances. Although Co₃O₄ particles were synthesized in subcritical water at similar reaction conditions designed for comparison, well-ordered particles of HT-LiCoO₂ were obtained in supercritical water. In supercritical conditions, the variations in temperature and residence time did not have significant impacts on the average particle size, particle size distribution, or morphology of obtained HT-LiCoO₂. However, it was important to supply excessive lithium hydroxide and hydrogen peroxide in order to synthesize single-phased HT-LiCoO₂ particles without undesired by-products. The hydrothermal synthetic route for LiCoO₂, CoO, and Co₃O₄ in both subcritical and supercritical conditions was postulated.     

超细二氧化锆干燥方式探讨

介绍了几种常用的制备纳米粉体的干燥方法。研究了水热反应制备二氧化锆粉体过程中，直接干燥法、共沸蒸镏和超临界干燥3种常用的干燥方法对最终产品粒子大小和微观形态的影响。通过比较，直接干燥法制备的纳米粒子粒径大于100nm，而采用共沸蒸馏和超临界干燥制得的粉体分散性好，可制备出粒径小于10nm的粉体。因此，共沸蒸馏和超临界干燥法是良好的干燥方法。     

Rapid and Continuous Hydrothermal Synthesis of Boehmite Particles in Subcritical and Supercritical Water

Hydrothermal synthesis of AlOOH particles from an Al(NO₃)₃ aqueous solution was examined in subcritical and supercritical water. Continuous and rapid production of AlOOH fine particles was achieved by mixing a metal salt aqueous solution with preheated water fed from another line. The effects of temperature, pressure, and initial concentration of solution on the particle size, morphology, and crystal structure of the metal (hydrous) oxides were examined. These properties are strongly affected by slight changes in pressure and temperature. This strong effect is attributed to the large changes in the properties of water near its critical point resulting from the slight changes in pressure and temperature. The results suggest the simultaneous control of size, crystal structure, and morphology of the particles by hydrothermal synthesis in supercritical water.     

氢氧化铝活化对水热法制备勃姆石的影响

采用氢氧化铝粉体为原料,活化后通过水热法制备勃姆石。研究了氢氧化铝活化对勃姆石颗粒尺寸的影响,并讨论了相关机理。研究结果表明:未活化氢氧化铝水热反应所得产物颗粒粒径为2 μm,经过加热（160~220 ℃）活化的氢氧化铝,水热反应所得产物的颗粒粒径在0.3~2 μm变化。对活化氢氧化铝和水热反应中间产物进行表征,由结构分析推测作用机制:氢氧化铝加热活化过程中生成少量勃姆石,这些勃姆石在氢氧化铝水热反应转化为勃姆石（AlOOH）的过程中成为晶种,活化温度升高和活化时间延长,勃姆石晶种数量增加,氢氧化铝水热反应所得产物的颗粒粒径减小,并且加快了水热反应速率。该工作有望提供一种氢氧化铝水热法制备勃姆石的新途径和相关基础理论。     

ZrO2制备方法研究进展

以ZrO₂为活性组分或载体的催化剂,在酚类定向催化转化中具有较高的研究价值。总结了ZrO₂的各种制备方法,包括溶胶-凝胶法、共沉淀法、水热法、表面活性剂辅助法、静电纺丝法、热解法、多元醇还原法、反相微乳法和超临界合成法等。阐述了各种方法的反应原理,详细比较了不同制备方法的优劣,并具体分析了制备方法对催化剂结构及性能的影响。     

纳米锑掺杂氧化锡制备中超临界CO_2干燥的工艺优化及动力学

纳米锑掺杂氧化锡(ATO)具有优越的光电性能,在制备过程中前驱体干燥处理至关重要。为掌握ATO前驱体的超临界CO2干燥工艺特性,研究了超临界干燥的时间、温度、压力和CO2流量等工艺参数对纳米ATO粒径、比表面积等的影响,进一步探讨了超临界CO2流量对干燥动力学的影响规律,并拟合了干燥曲线方程。结果表明:温度35~40℃、压力10~14 MPa、CO2流量1.2~1.8 L·h-1、干燥5~6 h,最终能够获得平均粒径20~30 nm、高比表面积的纳米ATO材料;流量对干燥速率有明显影响,醇分比0.4为干燥速率由恒速转为降速的临界点,醇凝胶干燥动力学方程能够很好地描述ATO醇凝胶干燥工艺过程。研究结果可为湿法制备纳米材料的湿凝胶干燥工业化生产和控制提供参考。     

Iron oxide synthesis using a continuous hydrothermal and solvothermal system

Iron oxide synthesis via a continuous hydrothermal and solvothermal reaction were studied. In the hydrothermal synthesis, fine α-Fe₂O₃ (hematite) particles were obtained at 250–420 °C and 30 MPa. The α-Fe₂O₃ crystals were grown in sub-critical water via a dissolution and precipitation process. The growth of α-Fe₂O₃ crystals in supercritical water was suppressed due to the rather low solvent power of water. Crystalline Fe₃O₄ was obtained as the temperature was raised above the supercritical state in the solvothermal preparation. Isopropanol (IPA) was oxidized in acetone which provided a reducing atmosphere. Acetone molecule adsorption onto the Fe₃O₄ particle surface inhibited crystallite growth.     

纳米粒度金属氧化物催化剂制备方法的研究进展

金属氧化物是一类重要的催化剂,在催化领域中已得到广泛的应用,将金属氧化物纳米化后,其催化性能更加优良,可以预见,纳米金属氧化物将是催化剂发展的重要方向。综述了近年来国内外金属氧化物催化剂的研究进展，讨论了纳米金属氧化物催化剂的各种制备方法，如溶胶 凝胶法、水解法、水热合成法、 微乳法、沉淀法、固相反应法、超临界干燥法、微波固相法、热分解法、燃烧合成法和撞击流反应 沉淀法等，并对各种方法的特点作了总结和归纳。     

12-磷钨酸体系水热法制备金颗粒及其表征

利用Keggin结构的12-磷钨酸作为软模板,采用水热法还原氯金酸制备金颗粒. 考察了AuCl4-离子与12-磷钨酸的摩尔比、反应时间及反应温度对Au颗粒的影响. 用TEM, UV-Vis, FESEM, XPS, XRD等手段对所制金纳米颗粒的形貌、组分、粒径和结构进行了表征. 结果表明,HAuCl4与磷钨酸反应速率较快,可获得尺寸范围较大的球形、三角形、多孪晶和六边形等不同形貌的Au颗粒. 对Au颗粒的形成机理进行了探讨.     

火焰合成法制备TiO2的燃烧发生器研究进展

火焰合成法是指前驱物在燃烧器中经过一系列复杂的物理化学反应过程得到产物纳米颗粒的方法,具有一步合成的优点,是现代工业规模化制备高性能材料的一种重要方法。火焰合成过程机理涉及物质的相态变化、颗粒生长团聚和热量质量交换等复杂过程,探究火焰合成过程是实现产物颗粒调控的关键。本文对火焰合成过程中的关键部分,如前驱物、为合成过程提供高温氧化环境的燃烧器、产物颗粒等进行分析,阐述了火焰气溶胶技术中颗粒的生长及转变路径、不同燃烧器的结构及其温度场、流场特点,并分析了不同燃烧器合成的纳米TiO₂进行了粒径及晶型特点的研究进展。指出火焰合成TiO₂生长机理和形态调控的基础研究对工业制备钛白粉具有指导意义。     

Continuous Synthesis of Tin and Indium Oxide Nanoparticles in Sub- and Supercritical Water

Nanocrystalline tin and indium oxides (In₂O₃/SnO₂) were synthesized in sub- and supercritical water at 350°/380°C and 30 MPa in <73 s in a tubular flow reactor from an aqueous solution of {SnCl₄+InCl₃} (0.2 M ). The conversion rate for tin was 100%. Nanoparticles were analyzed by transmission electron microscopy (TEM), emitted X-rays, Raman, differential scanning calorimetry, and X-ray diffraction techniques. The bulk particles were composed of In, Sn, and O atoms, and made up of cubic In₂O₃ (10 nm) and tetragonal SnO₂ (5.5 nm) crystals. After calcination at 500°C for 2 h, little change occurred in the particle size and crystal phase. Traces of tin-doped indium oxide particles were also formed as confirmed by the TEM electron diffraction pattern. Using this one-step, high-temperature hydrothermal process, oxide nanoparticles can be continuously and conveniently produced in a well-controlled process.     

水热法制备纳米分散颗粒和晶须材料进展

纳米分散颗粒和一维晶须材料性能优越、用途广泛,是近年研究热点。液相法尤其是水热法因具有过程简单和能耗低等特点而被广泛用于制备纳米材料。首先介绍了近年来水热技术在纳米分散颗粒制备中的进展,包括超临界水热法、连续水热法以及水热改性法,并分析了其实现纳米颗粒粒径及分散性控制的原理。然后介绍了两种水热制备晶须材料的新思路,包括水热重结晶法和离子诱导-结构重整法,阐述了其实现晶须定向生长的机制。     

碳化物衍生碳的制备及其应用研究进展

碳化物衍生碳（CDC）是除去碳化物中非碳元素后得到的产物,本文综述了卤素刻蚀法、超临界水热法、酸浸泡法、碳化钙反应法、高温热解法、高温熔盐电化学刻蚀法六种制备方法,其中,氯气刻蚀法效率最高。文中指出：CDC因具有轻质、高孔隙率、孔径可调、高比表面积、碳形态多样、生物相容性好等优势,可用于电化学储能（如超级电容器、锂离子电池、燃料电池）、吸附、生物医药和摩擦学领域中;而影响CDC孔结构的因素有很多,如前体类型、反应温度、反应气氛、反应时间、刻蚀方式以及活化方式。通过选择不同的合成参数,可以制备出满足不同应用场景需求的CDC材料。本文还展望了CDC在未来实现商业化的可能性及需要满足的五点要求。     

加压水溶液法制备工艺对α型高强石膏性能的影响

采用加压水溶液法以脱硫石膏为原料制备高强石膏,其工艺参数是决定高强石膏制备品质的关键。通过研究水热温度、水热时间、搅拌转速及料浆浓度四种工艺参数对α型高强石膏性能的影响规律,对不同工艺参数下制备样品的晶体形貌和石膏相组成进行定性及定量分析,并优化出加压水溶液法制备α型高强石膏的最佳工艺。结果表明,水热温度对生成晶体的尺寸及长径比的影响较大,水热时间主要影响晶体的尺寸,对长径比的影响不大,而水热温度和水热时间是影响α型高强石膏相组成的重要因素。搅拌转速和料浆浓度主要影响高强石膏尺寸及长径比,对石膏相组成影响不大。在最佳工艺条件下:水热温度130 ℃、水热时间4 h、搅拌转速250 r/min及料浆浓度30%(质量分数),制备的α型高强石膏2 h抗折强度为5.4 MPa,烘干抗压强度为41.9 MPa。     

Synthesis of in situ functionalized iron oxide nanoparticles presenting alkyne groups via a continuous process using near-critical and supercritical water

The preparation of iron oxide nanoparticle dispersions of varying properties (e.g. color, crystal structure, particle size distribution) in a continuous hydrothermal pilot plant operating under near-critical and supercritical conditions with the aim of producing in situ functionalized nanoparticles suitable for secondary functionalization via click chemistry is reported. The effect of varying the mixing setup, reaction temperature and the starting material (iron salt) in the presence of different carboxylic acids on the resulting nanoparticle dispersions was investigated. The stability of the clickable ligands in the harsh hydrothermal environment was also tested and the clickability of the functionalized particles was demonstrated by means of XPS and fluorescence measurements after model click reactions.     

Palm oil transesterification in sub- and supercritical methanol with heterogeneous base catalyst

An environmentally benign process for the production of methyl ester using γ-alumina supported heterogeneous base catalyst in sub- and supercritical methanol has been developed. The production of methyl ester in refluxed methanol conventionally utilized double promoted γ-alumina heterogeneous base catalyst (CaO/KI/γ-alumina); however, this process requires a large amount of catalyst and a long reaction time to produce a high yield of methyl ester. This study carries out methyl ester production in sub- and supercritical methanol with the introduction of an optimized catalyst used in the previous work for the purpose of improving the process and enhancing efficiency. CaO/KI/γ-Al₂O₃ catalyst was prepared by precipitation and impregnation methods. The effects of catalyst amount, reaction temperature, reaction time, and the ratio of oil to methanol on the yield of biodiesel ester were studied. The reaction was carried out in a batch reactor (8.8 ml capacity, stainless steel, AKICO, Japan). Results show that the use of CaO/KI/γ-Al₂O₃ catalyst effectively reduces both reaction time and required catalyst amount. The optimum process conditions were at a temperature of 290 °C, ratio of oil to methanol of 1:24, and a catalyst amount of 3% over 60 min of reaction time. The highest yield of biodiesel obtained under these optimum conditions was almost 95%.     

Experimental study of gas-dynamically induced nanoparticle synthesis by use of adapted sampling probes

A new process for the synthesis of nanoparticles in the gas-phase is experimentally investigated. The gas-dynamically induced nanoparticle synthesis uses the initiation of the chemical reaction by gasdynamic shock and the quenching of high temperature gas by accelerating the flow from subsonic flow speed to supersonic speed. Therefore, the design of the reactor consists of two Laval nozzles. The process provides high heating and cooling rates, an adjustable reaction time and a particle synthesis at constant thermodynamic conditions to obtain non-aggregated nanoparticles. In order to analyze the synthesized SiO₂ particles during their growth, samples are taken in the reaction volume and downstream of the quenching. The particles from the reaction chamber were extracted with the help of a specially designed water-cooled probe. The geometry of the probe is optimized by CFD simulations. The particles downstream the quenching are extracted by a heated and isolated probe. The particles are collected on TEM grids. The experimental investigations show that the synthesized particles are spherical and non-aggregated in the reaction chamber and after quenching. The possibility to synthesize a non-aggregated product in the novel process is thus demonstrated. The mean particle size is defined by the process conditions and varies from 25 to 37 nm after quenching.     

Solvent effect on microstructure of yttria-stabilized zirconia (YSZ) particles in solvothermal synthesis

Using methanol or methanol/2-propanol mixtures as reaction media, yttria-stabilized zirconia (YSZ) particles were synthesized with a solvothermal route. The particles were characterized with X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), laser diffraction technique, and nitrogen adsorption isotherms. Results indicated that cubic/tetragonal YSZ nanocrystals with crystal size lower than 5 nm were obtained and the crystal size depends on solvent composition, reaction temperature and reaction time. For the same reaction temperature and reaction time, the solvent composition also controls YSZ crystal agglomeration behaviour. According to the DLVO theory and analysis of experimental results, the solvent effect on microstructures of YSZ particles in solvothermal synthesis has been discussed. In addition, the mechanism of particle microstructure evolution during solvothermal synthesis has been suggested.