Water Formation in Non-Hydrolytic Sol–Gel Routes: Selective Synthesis of Tetragonal and Monoclinic Mesoporous Zirconia as a Case Study

Several non-hydrolytic sol–gel syntheses involving different precursors, oxygen donors, and conditions have been screened aiming to selectively produce mesoporous t-ZrO₂ or m-ZrO₂ with significant specific surface areas. The in situ water formation was systematically investigated by Karl Fisher titration of the syneresis liquids. XRD and nitrogen physisorption were employed to characterize the structure and texture of the ZrO₂ samples. Significant amounts of water were found in several cases, notably in the reactions of Zr(OnPr)₄ with ketones (acetone, 2-pentanone, acetophenone), and of ZrCl₄ with alcohols (benzyl alcohol, ethanol) or acetone. Conversely, the reactions of Zr(OnPr)₄ with acetic anhydride or benzyl alcohol at moderate temperature (200 °C) and of ZrCl₄ with diisopropyl ether appear strictly non-hydrolytic. Although reaction time and reaction temperature were also important parameters, the presence of water played a crucial role on the structure of the final zirconia: t-ZrO₂ is favored in strictly non-hydrolytic routes, while m-ZrO₂ is favored in the presence of significant amounts of water. ¹H and ¹³C NMR analysis of the syneresis liquids allowed us to identify the main reactions responsible for the formation of water and of the oxide network. The morphology of the most interesting ZrO₂ samples was further investigated by electron microscopy (SEM, TEM).     

铜基/氧化锆催化剂的应用及改性研究进展

ZrO2具有弱酸碱性、氧化还原性、良好的热稳定性和机械强度,在催化领域得到广泛应用。以Zr O2为载体的铜基催化剂因其活性高,选择性好,性能稳定,受到越来越多的关注。本文介绍了Cu/Zr O2催化剂在醇类的水蒸气重整制氢、CO/CO2加氢合成低碳醇、二乙醇胺脱氢、乙醇直接合成乙酸乙酯和低温水煤气变换方面的应用。综述了添加不同助剂对Cu/Zr O2催化剂物化及催化性能的影响。     

旋涂法制备氧化锆介质层及其在薄膜晶体管中的应用

采用旋涂法制备了氧化锆介质层薄膜，重点讨论了退火温度以及旋涂转速对薄膜性能的影响及作用机制。研究发现高温后退火一方面使得氧化锆水合物脱水形成氧化锆，另一方面促使氧化锆薄膜结晶。此外，转速较高时，其变化对薄膜厚度及粗糙度无显著影响。当转速为5 000 r/min、退火温度为300℃时，制备的绝缘层厚度具有良好的厚度均匀性，粗糙度为0.7 nm，漏电流为3.13×10^-5 A/cm²（电场强度1 MV/cm）。最终，利用ZrO₂薄膜作为栅极绝缘层，在玻璃基板上制备了铟镓锌氧化物-薄膜晶体管（IGZO-TFT），其迁移率为6.5 cm²/（V·s），开关比为2×10⁴。     

多级孔WO3/ZrO2固体酸催化剂的制备与表征

采用复合模板表面活性剂辅助水热法一步合成了WO3/ZrO2多级孔固体酸催化剂,并应用X射线衍射、低温N2吸附-脱附、拉曼光谱及NH3程序升温脱附对催化剂进行了表征.结果表明,WO3的引入使得WO3/ZrO2催化剂的比表面积增大,表面的酸中心明显增加.在乙酸和正丁醇的酯化反应中,WO3/ZrO2多级孔固体酸催化剂表现出较...     

Metal-reinforced sulfonic-acid-modified zirconia for the removal of trace olefins from aromatics

Metal-reinforced sulfonic-acid-modified zirconia catalysts were successfully prepared and used to remove trace olefins from aromatics in a fixed-bed reactor. Catalysts were characterized by ICP-OES, N₂ adsorption–desorption, X-ray diffraction, thermogravimetric analysis (TGA), and pyridine-FTIR spectroscopy. Different metals and calcination temperatures had great influence on the catalytic activity. Alumina-reinforced sulfated zirconia exhibited outstanding catalytic performance, stable regeneration activity, and giant surface area, and are promising in industrial catalysis. TGA showed that the decomposition of methyl could be attributed to Brønsted acid sites, and pyridine-FTIR spectroscopy proved the weak Brønsted sites on these synthesized metal-reinforced sulfated zirconia. Also, a relation between the reaction rate and weak Brønsted acid density is proposed.     

高热稳定性介孔氧化锆的合成及表征

利用阴离子表面活性剂作模板,通过水热均匀沉淀方法成功合成了具有高热稳定性的介孔氧化锆.该方法以十二烷基苯磺酸钠(SDBS)作为介孔结构的导向剂,其含S基团在煅烧时起到了稳定剂的作用.采用透射电镜、氮气吸附-脱附、X射线粉末衍射、红外光谱测试手段对样品进行了表征.研究表明,以SD-BS为模板剂合成的介孔氧化锆具有蠕虫状介...     

Characterization of laser sealed coatings of yttria partially stabilized zirconia

The present paper reports an experimental investigation based on X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), and wavelength dispersive spectroscopy (WDS) analyses of phases formed after laser sealing of plasma sprayed coatings of 8.5 wt% yttria partially stabilized zirconia (YPSZ). X-ray diffraction and X-ray step-scanning analyses showed that the plasma sprayed and sealed coatings consisted mainly of t′ phase with a very small amount of monoclinic phase (m phase) in the plasma sprayed coatings. It was also found that the small amounts of m and cubic phases (c phase) present in the sealed coatings were dependent on laser processing specific energies (specific energy is equal to laser power/traverse speed x beam diameter). It was also found that rhombohedral (r) phase formed after laser sealing of coatings at higher specific energies. A direct relationship between c/a ratio of transformable tetragonal phase (t phase) produced by thermal treatment of sealed coatings and nontransformable tetragonal phase (t′ phase) and the amount of Yttria was obtained. A new equation was derived, which describes the relationship between Yttria concentration and the c/a ratio of tetragonal phases (t or t′).     

Effect of Sulfation of Zirconia on Catalytic Performance in the Dehydration of Aliphatic Alcohols

Catalytic dehydration of 2‐propanol and that of 1‐butanol were performed at atmospheric pressure and 150–300°C over ZrO₂ and sulfated ZrO₂ (S/ZrO₂) in a fixed‐bed, tubular reactor. The catalysts were characterized with XRD, elemental analysis, FT‐IR, N₂ physisorption, TG/DTA, TPD, and TPR. The main structures of ZrO₂ and S/ZrO₂ were monoclinic and tetragonal, respectively. As ZrO₂ was modified with sulfuric acid, its surface area and acid amount were greatly increased, whereas the pore volume, the pore diameter, and the particle size were reduced. Both samples owned weak basicity. For both reactions, only dehydration products of alkene and ether were obtained. The alcohol conversion enhanced remarkably with the catalyst acid amount and the surface area as well as the reaction temperature. In addition, the ether selectivity on S/ZrO₂ decreased with raising the reaction temperature. The activation energy was 81.0 kJ/mol in the propene formation from 2‐propanol over S/ZrO₂. The corresponding value was 94.4 kJ/mol for the dehydration of 1‐butanol.     

热屏结构对泡生法蓝宝石单晶炉功率影响研究

蓝宝石晶体因优异的综合性能被广泛用于航空航天等高性能要求领域。泡生法是目前生产大直径蓝宝石单晶的主要方法,热场对生产工艺、产品质量和单晶炉功率具有重要影响;并将影响生产成本。本文对氧化锆及钼金属组合式热屏中氧化锆材料内置、外置及材料不同组合方式对泡生法蓝宝石单晶炉功率的影响进行研究,得到合理的热场结构;并与实际生产结果进行验证。结果表明:相比于传统的15层钼保温结构,加入氧化锆保温层会明显降低单晶炉能耗,其中氧化锆内置的热场结构对单晶炉能耗降低影响更为明显;随着氧化锆层由0增加至15层,单晶炉能耗显著降低,相比传统15层钼保温结构,15层氧化锆保温结构炉体功率降低了38%。     

硫酸化氧化锆固体超强酸

硫酸化氧化锆(SZ)是一种固体超强酸催化剂,它能高效催化异构化、烷化、酰化、环化、裂解、酯化和酯交换等多种类型的催化反应。1979年,日本科学家Hino和Arata发现SZ能在室温催化丁烷异构化反应,首次提出了SZ是一种酸性比100%浓硫酸还强一万倍的固体超强酸,从而引起了科学家们对SZ研究的浓厚兴趣。经过了三十多年发展,研究者们在SZ的合成、改性、表征和应用等方面取得了许多新的研究成果。本文综述了SZ几十年来的研究进展,内容主要包括SZ的合成方法,表面结构和酸性机理,研究者们对SZ性质的不同看法,SZ的改性及应用。