Active sites in Cu/ZnO/ZrO2 catalysts for methanol synthesis from CO/H2

Among various Cu/ZnO/ZrO₂ catalysts with the Cu/Zn ratio of 3/7, the one with 15 wt.% of ZrO₂ obtains the best activity for methanol synthesis by hydrogenation of CO. The TPR, TPO and XPS analyses reveal that a new copper oxide phase is formed in the calcined Cu/ZnO/ZrO₂ catalysts by the dissolution of zirconium ions in copper oxide. In addition, the Cu/ZnO/ZrO₂ catalyst with 15 wt.% of ZrO₂ turns out to contain the largest amount of the new copper oxide phase. When the Cu/ZnO/ZrO₂ catalysts is reduced, the Cu²⁺ species present in the ZrO₂ lattice is transformed to Cu⁺ species. This leads to the speculation that the addition of ZrO₂ to Cu/ZnO catalysts gives rise to the formation of Cu⁺ species, which is related to the methanol synthesis activity of Cu/ZnO/ZrO₂ catalyst in addition to Cu metal particles. Consequently, the ratio of Cu⁺/Cu⁰ is an important factor for the specific activity of Cu/ZnO/ZrO₂ catalyst for methanol synthesis.     

纳米氧化锆/氧化锌光催化降解酸性红B的研究

以醋酸锌和氯氧化锆为原料，采用化学沉淀法制备了纳米氧化锆／氧化锌光催化剂。在中性条件下研究了催化剂煅烧温度，锆复合量，催化剂用量，染料初始质量浓度，过氧化氢质量浓度，各种阴、阳离子等条件对酸性红B脱色反应的影响。结果表明，该催化剂最佳制备条件为煅烧温度350℃，锆复合量2．5％（物质的量分数）。催化剂最佳用量0．9g／L。提高染料初始质量浓度会降低反应脱色率。适量过氧化氢可提高反应脱色率，当其质量浓度超过300mg／L会起负作用。NO3^-对反应影响不大；Fe^3＋和Ag^＋对反应起促进作用；SO4^2-，Cl^-，NO2^-等阴离子和Fe^2＋，Mn^2＋等阳离子对反应起抑制作用。     

Deoxygenation of benzoic acid on metal oxides: 1. The selective pathway to benzaldehyde

The mechanism of the selective deoxygenation of benzoic acid to benzaldehyde was studied on ZnO and ZrO₂. The results show conclusively that the reaction proceeds as a reverse type of Mars and van Krevelen mechanism consisting of two steps: hydrogen activates the oxide by reduction resulting in the formation of oxygen vacancies. Subsequent re-oxidation of these vacancy sites by benzoic acid yields benzaldehyde. Inhibition of the deoxygenation reaction can be achieved by addition of suitable polar compounds with a high affinity for the oxygen vacancy sites such as carbon dioxide or water. Differences in the catalytic activity and selectivity of ZnO and ZrO₂ can be attributed to differences in hydrogen activation, redox properties and extent of benzoic acid coverage.     

ZrO2增韧陶瓷的研究进展

综述了ZrO2陶瓷及添加氧化物稳定剂对四方相氧化锆的稳定性影响，以及ZrO2陶瓷材料的种类，增韧机理及其主要应用领域，并展望了氧化锆增韧陶瓷的研究发展趋势。     

不同烧结法对3Y-TZP陶瓷力学性能的影响

本文研究了低温烧结含3mol%氧化钇的四方多晶氧化锆(3Y-TZP)的烧结性能和力学性能,以及进行热等静压(HIP)后其力学性能的变化。成形后的3Y-TZP在常压、1300～1450℃温度下进行烧结。由于该粉料有很高的烧结活性,在1300℃低温烧成下就可获得相对密度大于94%的烧结体;在1350℃烧成温度下3Y-TZP获得了最佳的力学性能。其断裂韧性(KIC)和维氏硬度(HV)分别达到18.7MPa.m1/2和13.7GPa,其中应力诱导相变是其主要的增韧机理。对低温烧成的3Y-TZP陶瓷进行热等静压烧结后发现,HIP增大3Y-TZP陶瓷HV的作用显著,可使其增至14.3GPa。     

Porous Ni/ZrO2 Cermet from Highly Concentrated Composite Colloid

Rheology and shaping of concentrated cermet suspensions consisting of nickel (Ni) and yttria‐stabilized zirconia (YSZ) nanoparticles in water have been examined over a broad range of volumetric solids concentration (? = 0.1–0.4) and Ni fraction (f_Ni = 0.15–0.45). Preferential adsorption of pyrogallol‐poly(ethylene glycol) polymer (i.e., Gallol‐PEG) on surface of the Ni and YSZ particles imparts steric hindrance between the suspending particles so that fluidity can be obtained under shear stress. The cermet suspensions exhibit shear‐thinning flow behavior under steady‐shear measurement over shear rates of 10⁰–10³ s^?1. Yield stress and yield strain of the suspensions appear to vary pronouncedly with ? and f_Ni under oscillatory shear over a shear‐strain range of 10^?1–10³%. With the Gallol‐PEG adsorption, an apparent viscosity less than 6 × 10^?1 Pa.s at a shear rate of 10² s^?1 has been obtained for the highly concentrated composite suspension with ? of 0.40 and f_Ni of 0.25. A high solids concentration effectively prohibits phase segregation during wet‐shaping processes. Uniform green compacts have been obtained from slip casting of the concentrated cermet mixture (? = 0.30) without use of binder and are then fired at 1200°C under reducing atmosphere to form porous Ni/YSZ compacts. Relative sintered density increases from 65% to 75% of the theoretical value when f_Ni was increased from 0.15 to 0.45, due mainly to the lower sintering temperature required for the Ni phase.     

氧化物陶瓷的微波烧结机理

本文是综述文章,介绍了近十几年来发展较快的微波烧结技术,及微波烧结时 Ａｌ２ Ｏ３ 、 Ｚｒ Ｏ２ 等材料的微波烧结机理。研究发现, Ａｌ２ Ｏ３ 、 Ｚｒ Ｏ２ 陶瓷的微波烧结机理与常规烧结基本相同,微波烧结条件下的烧结及晶粒长大的活化能比常规烧结条件下低、速度较常规烧结条件下快,说明微波烧结条件下起决定作用的传质过程不同,微波烧结中体积扩散占主要地位,但产生这一现象的原因尚待研究。     

石墨烯纳米片复合氧化锆陶瓷的制备与性能研究

放电等离子体烧结(SPS)技术作为一种比较新的烧结技术已经被广泛用于制备各种材料。本文以3Y-ZrO_2粉体和石墨烯纳米片为原料,采用SPS技术制备了石墨烯纳米片复合ZrO_2陶瓷,利用扫描电镜、透射电镜和X射线衍射仪等对烧结样品的显微结构和晶相进行了表征,同时对所制备材料的密度、显微硬度和断裂韧性进行了测试。结果表明,烧结温度和石墨烯纳米片对所制备样品的显微结构和性能都有显著的影响。随着烧结温度的增加,样品的密度提高,晶粒生长明显。而石墨烯纳米片的引入则显著抑制了ZrO_2晶粒的生长,但是由于分散性问题,其显微硬度和断裂韧性反而略有降低。     

添加物对ZrO2系快离子导体烧结性能的影响

本文介绍了１３２０℃下，ＣａＯ，Ｙ２Ｏ３等稳定剂，低融物组成及１－６价阳离子化合物对ＺｒＯ２烧结性能的影响并列举出材料的晶型及某些主要性能。     

纳米SiO_2和ZrO_2共同作用硅酸盐水泥水化机理

利用XRD和SEM表征了纳米S iO2和ZrO2对硅酸盐水泥砂浆改性后的试样。研究发现,在固定水灰比为0.5时,复掺2%纳米S iO2和0.25%ZrO2共同发挥纳米诱导水化作用,生成更多的C—S—H凝胶并向着针柱状形貌生长,细化了Ca(OH)2,使其镶嵌在C—S—H凝胶和钙钒石中,使得C—S—H与凝胶与钙矾石紧密交织,减少水泥石中总孔隙率,水泥石的结构更加细化密实,使抗压强度明显高于同龄期标准试样。     

微波闪速合成纳米ZrO_2/ZnO复合材料及其光催化性能研究

以硝酸锆和硝酸锌为原料,尿素为助燃剂,采用微波闪速法合成纳米ZrO2/ZnO复合材料,研究了纳米ZrO2/ZnO复合材料分别对甲基橙和罗丹明B的光催化降解性能。结果表明,在紫外光条件下,纳米ZrO2/ZnO复合材料光催化降解甲基橙效果明显优于罗丹明B。     

Ni/ZnO-ZrO2催化低温乙醇水蒸气重整制氢

以草酸钠为共沉淀剂,采用共沉淀法制备了以ZnO-ZrO2为载体的镍基乙醇水蒸气重整制氢催化剂(Ni/ZnO-ZrO2)。考察了不同锌锆摩尔比的ZnO-ZrO2负载的镍基催化剂在300～450℃催化乙醇水蒸气重整制氢的反应性能。用TPR、TPO、XRD对催化剂试样进行了表征。结果表明,当n(Zn)∶n(Zr)=1∶1,Ni负载质量分数10%时,催化剂中有镍锌复合氧化物生成,350℃时乙醇转化率达100%,450℃氢气选择性接近90%;TPO结果表明,ZnO-ZrO2复合载体可以降低催化剂上的积炭量。     

烧结温度对不锈钢表面溶胶-凝胶ZrO2纳米薄膜摩擦学性能的影响

采用溶胶-凝胶法,在304不锈钢表面制备了分别经500℃、600℃和700℃下热处理的ZrO2薄膜.利用X射线衍射仪(XRD)、原子力显微镜(AFM)、扫描电镜(SEM)和摩擦磨损测试仪,研究了热处理温度对ZrO2薄膜的表面结构和摩擦学性能的影响.结果表明:随着温度的升高,ZrO2晶体结构逐渐由四方相(t-ZrO2)向单斜相(mZrO2)转变;当热处理温度从500℃升高到700℃时,ZrO2薄膜的平均晶粒度略有增大,但都在80 nm左右,晶粒分布趋于均匀致密,且其表面粗糙度由6.3 nm降低至4.6 nm左右.同时ZrO2薄膜的摩擦系数和磨损率分别从0.22和2.24×10-4mm3/Nm逐渐减小为0.19和1.95×10-4 mm3/Nm,因而薄膜的抗磨减摩性能也显著提高.     

ZrO2含量对Al2O3/ZrO2复相陶瓷微观结构和力学性能的影响

本研究以耐磨结构陶瓷的应用为目标,研究了Al2O3-ZrO2复相陶瓷中加入不同的ZrO2陶瓷材料对微观结构及其力学性能的影响,分析了ZrO2在复相陶瓷中所起的作用.结果表明:随ZrO2含量的增加,在相同烧结温度下,晶粒变小,材料的力学性能提高.当ZrO2加入量为55％时,复相材料的抗折强度503MPa,断裂韧性12.80 MPa·m1/2,密度4.88 g·cm-3,硬度(HV)为1432 kg ·mm-2.探讨了Al2O3/ZrO2复相陶瓷的增韧机理.     

ZrO2/TCP协效阻燃聚甲基丙烯酸丁酯包覆材料研究

为获得阻燃聚甲基丙烯酸丁酯包覆材料,进行了ZrO2和磷酸三甲苯酯(TCP)改进聚甲基丙烯酸丁酯阻燃性能的研究.结果表明,ZrO2和TCP的不同添加总量、ZrO2与TCP的配比对其协同效果都有影响.当ZrO2/TCP的添加量为10%(质量分数)、配比为3∶7(质量比,下同)时,材料的氧指数达到24.6,协同效果最佳.采用热分析、数码照相、拉曼光谱和红外光谱等对成炭机理和协同效应进行了分析.结果表明,当ZrO2/TCP协效体系的总质量分数为10%、配比为3∶7时,500 ℃时体系的成炭量为14.7%,ZrO2能通过催化和交联作用而影响成炭量和炭层结构.     

ZrO2微粒与基质金属及溶液间相互作用的研究

介绍了Ni-ZrO2复合镀工艺配方。通过镀液中ZrO2微粒的Zeta电位分析以及ZrO2微粒质量浓度对镀液pH的影响研究,探讨了微粒与镀液间的相互作用。分别通过纯镍镀层和Ni-ZrO2复合镀层的X-射线衍射实验及SEM形貌分析,研究了微粒与基质金属间的相互作用。结果表明,镀液中的pH随着ZrO2质量浓度的增加而增大;ZrO2微粒因吸附镀液中的H^＋而带正电,有益于其阴极扩散,从而增加镀层中粉体的含量;ZrO2微粒与基质金属间不是简单的机械混合,而是存在相互作用。而且,它的存在改变了基质金属镍的择优取向,也细化了金属镍的晶粒。     

制备条件对ZrO_2结构的影响

本文对以工业ZrOCl2为原料,NH3·H2O为沉淀剂合成ZrO2进行了研究,重点考察了ZrOCl2溶液浓度、NH3·H2O浓度、沉淀pH值、沉淀及老化温度等因素对所制备的ZrO2表面积和孔容的影响,从而得出了一定的规律。     

ZrO_2含量对镁锆不烧砖性能的影响

以w(MgO)=97%的电熔镁砂和w(ZrO2)=14.33%的预合成电熔镁锆料为原料,以酚醛树脂为结合荆,用400 t摩擦压砖机机压成型制备了w(ZrO2)分别为0、2%、4%、6%和8%的镁锆不烧砖,研究了ZrO2含量对镁锆不烧砖的常温性能、高温强度、抗热震性的影响,同时还重点研究了其抗渣性能(采用回转抗渣法,渣为碱度3.6的精炼炉渣,侵蚀温度1 650℃),并借助SEM和EDAX分析了部分抗渣后试样的显微结构.结果表明:(1)随着引入的ZrO2含量提高,镁锆不烧砖的常温力学性能总体呈上升趋势,w(zrO2)由0增加到8%时,1 600℃3 h处理后镁锆不烧砖的高温抗折强度(1 500℃下)从0.5 MPa提高到2 MPa.(2)引入的ZrO2改善了不烧砖的抗热震性,w(ZrO2)由0增加到8%时,试样经1 000℃风冷1次后的抗折强度保持率由20%提高至70%以上.(3)ZrO2的引入可以改善镁质材料的抗渣渗透性,尤其是电熔钱锆合成料以细粉形式引入时效果更佳;但ZrO2的引入又对抗渣侵蚀性有所不利,尤其是引入w(ZrO2)达6%～8%时,会造成主晶相方镁石和c-ZrO2,的热膨胀不匹配效应加剧,使材料产生较大裂纹甚至剥落,导致抗渣渗透性随之恶化.当引入的w(ZrO2,)≤4%时,材料以侵蚀损毁为主,蚀损深度约12 mm;而w(ZrO2)>4%时,以渗透和剥落损毁为主,最高蚀损深度达到30 mm左右.因此,综合考虑,镁锆不烧砖中ZrO2,含量以4%(质量分数)为宜.     

Far from equilibrium ultrafast high-temperature sintering of ZrO2–SiO2 nanocrystalline glass–ceramics

Ultrafast high-temperature sintering (UHS) is a novel sintering technique with ultrashort firing cycles (e.g., a few tens of seconds). The feasibility of UHS has been validated on several ceramics and metals; however, its potential in consolidating glass–ceramics has not yet been demonstrated. In this work, an optimized carbon-free UHS was utilized to prepare ZrO₂–SiO₂ nanocrystalline glass–ceramics (NCGCs). The phase composition, grain size, densification behavior, and microstructures of NCGCs prepared by UHS were investigated and compared with those of samples sintered by pressureless sintering. Results showed that NCGCs with a high relative density (～95%) can be obtained within ～50 s discharge time by UHS. The UHS processing not only hindered the formation of ZrSiO₄ and cristobalite but also enhanced the stabilization of t-ZrO₂. Meanwhile, owing to the ultrashort firing cycles, the UHS technology allowed the NCGCs to be consolidated in a far from equilibrium state. The NCGCs showed a microstructure of spherical monocrystalline ZrO₂ nanocrystallites embedded in an amorphous SiO₂ matrix.