重点分析了ZrO2的热性质、化学稳定性和其理论基础。ZrO2的导热系数极低,可用于热障涂层,介绍了热障涂层的结构和制备方法,说明了ZrO2作为热障涂层材料的优异特性。分析了ZrO2的表面能与表面酸性强度,表面酸位来源、固体超强酸的原理、性质、制备方法和应用领域。ZrO2的化学稳定性好,可作为催化剂材料基体,ZrO2基催化材料分类为纯ZrO2催化剂、负载型催化剂和复合型催化剂,列举了ZrO2基固体超强酸的反应方程式,ZrO2复合型催化剂具有更好的催化性能,论述了以CeO2-ZrO2固溶体作为三效催化剂的机理和进展。相关方法和原理可为ZrO2的热学性质研究提供系统的理论知识,将有助于理解和应用ZrO2的催化原理和表面性质。

Thermal properties, chemical stability of ZrO2 and their mechanisms are reviewed.The ultra-low thermal con-ducting coefficient of ZrO2 is the key for its application in thermal barrier coatings , the structure and synthesis methodology are introduced, and advantages of ZrO2 based thermal barrier coatings are described.The surface energy, acidic positions and their originations in ZrO2 , the principle, nature, preparation and application areas of ZrO2 based super-acids are ana-lyzed.The fairly good chemical stability of ZrO2 is the basic for catalytic application.ZrO2 based catalysts can be classi-fied into pure ZrO2 , loaded and composite ones.The composites-based ZrO2 has better catalytic performance and some typical catalytic reactions are also listed.Mechanisms and research progress of CeO2 -ZrO2 solid solutions as three way catalysts are also introduced.This review provides the systematic knowledge of thermal and catalytic applications of ZrO 2 , which can help understanding their

通过对PAA-g-ZrO2复合膜过滤牛血清蛋白过程的污染阻力及其分布分析揭示接枝聚丙烯酸(PAA)对ZrO2膜抗污染性能的影响规律。结果表明:PAA-g-ZrO2复合膜和ZrO2膜的总阻力均随着过滤时间的延长而增加,但是PAA-g-ZrO2复合膜总阻力的增加趋势明显低于原ZrO2膜,同时,PAA-g-ZrO2复合膜的内部污染阻力Rif所占比例下降为原ZrO2膜的一半,这表明PAA接枝到ZrO2膜表面明显降低了膜孔内堵塞的内部污染,提高了膜的抗污染和易清洗性能。此外,溶液的pH值对PAA-g-ZrO2复合膜的污染阻力及其分布有着明显影响,当溶液pH值为8.0时,PAA-g-ZrO2复合膜几乎不存在膜孔堵塞污染。

Fouling of PAA-g-ZrO2 composite membrane by BSA solution was investigated in conjunction with analysis of membrane total resistances and resistances distribution. The total resistances of the PAA-g-ZrO2 composite membrane and ZrO2 membrane increased with increasing filtration time, but the growth trend of the PAA-g-ZrO2 composite membrane total resistances was lower than that of the ZrO2 membrane. The fouling resistance of the ZrO2 membrane was Rcp (concentration polarization resistance)-dominant, while Rcp and Rm (membrane resistance) controlled the PAA-g-ZrO2 composite membrane separation process. The internal plugging resistance (Rif) of the PAA-g-ZrO2 composite membrane was just half of that of the ZrO2 membrane. Themembrane resistance of PAA-g-ZrO2 composite membrane increased with increasing pH. The densely packed brush-shaped structure of the PAA chains was considered to be responsible for reducing the protein adsorption on the membrane surface. Furthermore, the PAA-g-ZrO2 compo

以ZrO2-Al2O3作为催化剂载体,分别制备了SO2-4/ZrO2-Al2O3、NaOH/ZrO2-Al2O3、ZrO2-Al2O33种固体催化剂,并采用酯化后3A分子筛除水和减压反应精馏两种方法精制生物质裂解油。结果表明,在分别使用SO2-4/ZrO2-Al2O3,NaOH/ZrO2-Al2O3,ZrO2-Al2O33种催化剂的条件下,酯化后3A分子筛除水的方式,可以将产品的含水率降至19.6%、18.3%和15.6%,而反应精馏可以将产品含水率分别降低至4.8%、5.4%和3.8%,较之前者效果更加明显。另外,对于3种不同性质的催化剂,结合酯化度计算式,对催化生物油酯化效果进行评价,可知其催化活性为:SO2-4/ZrO2-Al2O3NaOH/ZrO2-Al2O3ZrO2-Al2O3。最后,将得到的油品性质进行检测(包括黏度、pH值、密度和热值等),各项结果表明,使用硫酸化催化剂,并采用减压反应精馏的酯化方式可以制备出一种性能优良的液体燃料。

The ZrO2-Al2 O3 was used as a carrier for preparing the catalysts SO2-4 /ZrO2-Al2 O3 , NaOH/ZrO2-Al2 O3 and ZrO2-Al2 O3 in the process of upgrading bio-oil by the methods of dehydration after esterification and reaction recification. Compared these two methods, we could conclude that dehyrating after esterification over 3A molecular sieve could decrease the moisture content to 19. 6%, 18. 3% and 15. 6%, while reaction recification were 4. 8%, 5. 4% and 3. 8% which were better than before under the condition of SO2-4 /ZrO2-Al2 O3 , NaOH/ZrO2-Al2 O3 , ZrO2-Al2 O3 catalyzed, respectively. Meanwhile, according to the evaluation of the bio-oil catalyzed by the modified ZrO2-Al2 O3 with the formula of esterification degree, it indicated the activation of catalysts are SO2-4 /ZrO2-Al2 O3 >NaOH/ZrO2-Al2 O3 >ZrO2-Al2 O3 . Moreover, the quality of the upgraded oil ( kinematics viscosity, pH value, density and heating value ) showed that the bio-oil upgraded by reaction rectification and catalyze

本文以胶原纤维为模板,制备了多孔纤维状TiO2-ZrO2复合氧化物,并以此为载体制备了多孔纤维状SO42-/TiO2-ZrO2固体酸。 SEM观察发现TiO2-ZrO2和SO42-/TiO2-ZrO2均复制了胶原纤维独特的纤维结构, TiO2-ZrO2氧化物的比表面积达到77．51 m2·g-1；XRD分析发现,Ti-Zr摩尔比对TiO2-ZrO2的晶相结构有重要影响,当Ti/Zr摩尔比为0．67∶1时,TiO2-ZrO2以TiZrO4晶相为主；NH3-TPD分析表明SO42-/TiO2-ZrO2的酸量及酸强度与Ti-Zr摩尔比以及活化温度有着密切关系。在乙酸与正丁醇的酯化反应中,多孔纤维状SO42-/TiO2-ZrO2固体酸表现出优良的催化性能。当催化剂用量为6．5wt%,反应时间为60min时,乙酸的转化率高达98．1%；该固体酸催化剂重复使用性优良,循环使用5次时,转化率仍然保持在85%以上。

In the present study,a novel porous and fibrous composite oxide of TiO2-ZrO2 was prepared using collagen fiber as tem-plate,and the composite oxide was further used as support to prepare SO4 2-/TiO2-ZrO2 solid acid. SEM observation showed that the morphology of collagen fiber has been successfully duplicated by TiO2-ZrO2 and SO4 2-/TiO2-ZrO2 ,and the specific surface area of as-prepared TiO2-ZrO2 was as high as 77. 51 m2·g-1 . XRD analysis indicated that the mole ratio of Ti/Zr would greatly influence the crystalline phases of TiO2-ZrO2. When the mole ratio of Ti/Zr was 0. 67∶1,TiZrO4 was the main crystalline phase of TiO2-ZrO2 composite oxide. NH3-TPD determination results showed that the acid content and acid strength of porous fibrous SO4 2-/TiO2-ZrO2 solid acid was greatly related with mole ratio of Ti/Zr and activation temperature. In the esterification reaction of acetic acid and n-butyl alcohol,porous and fibrous SO4 2-/TiO2-ZrO2 solid acid exhibited excellent cataly

重点分析了ZrO2的电子结构与能带特点、光学吸收、发射谱等,介绍了第一原理法计算不同晶相ZrO2的能带结构和电子能量状态密度图（DOS）的结果,在计算能级结构的基础上,归纳了不同晶相的ZrO2在禁带附近可能的电子跃迁机理及其相应的能量,说明了无论是高纯ZrO2还是掺杂ZrO2,在室温下均表现出高的绝缘性能。分析了高温下ZrO2导电能力提高的原因,高温导电性可应用于氧传感器和燃料电池中的电极隔膜材料。掺杂后的ZrO2晶体的透光性非常好,且在较高温度的环境中,如果不发生晶体结构转变或失透等,则温度对提高晶体的折射率有积极的作用。ZrO2粉体的白色外观是由于粉体的表面对可见光的散射以及晶体内部的大量缺陷对光的散射作用。介绍了纯ZrO2材料的发光效应来源在于捕获了电子的氧空位形成的新能级与基态能级间的跃迁,氧空位形成的F-色心或缔合中心而产生。指出ZrO2可以作为发光离子基质的原因在于作为宽禁带的ZrO2的声子能量较低,可为发光中心的稳定发光提供刚性场所。

This review analyzed the band structure,optical absorption and emission spectra of ZrO2 .The DOS and band structures of ZrO2 with different crystallographic types are introduced based on the first principal calculating to the energy structures.Possible transition mechanisms and energy gaps of electrons near the forbidden band of ZrO2 with different structures are analyzed based on the DOS calculations.Either pure or doped ZrO2 has a high insulation performance at room temperature.Conductivity of ZrO2 at high temperature is analyzed,and the applications in the fields such as oxygen sensor and the fuel cell separator materials are introduced.Doped ZrO2 crystal is highly light translucency,the high tem-perature has a positive effect to improve the refractive index of ZrO2 if the crystal does not occur structural changing or de-vitrification.The white appearance of ZrO2 powder is due to the light scattering on the surface and by the intrinsic defects. Luminescence in ZrO2 is orig