焙烧温度对柴油车氧化催化剂Pt-Pd-（x）ZrO2/Ce0.3Zr0.7O2-Al2O3性能的影响

制备了氧化铝、铈锆固溶体复合氧化物负载铂、钯的双金属催化剂Pt-Pd/ Ce0.3Zr0.7O2-Al2O3,并添加3% ZrO2助剂改性,用于柴油车尾气中CO、HC和NO的催化氧化,其中贵金属负载量仅为0.68 wt%。考察了制备过程中焙烧温度对催化剂性能的影响。催化剂活性评价结果表明,与未添加ZrO2的催化剂比较。添加ZrO2明显提高了催化剂的低温氧化活性,而且焙烧温度对催化剂的氧化性能有较大影响。焙烧温度为800 ?C时,CO和C3H6的起燃温度最低,分别为168、189 ?C,焙烧温度为700 ?C时,NO转化为NO2的转化率最高,最大转化率为36%,具有较好的热稳定性。通过XRD、N2吸附-脱附、CO化学吸附、XPS、H2-TPR等表征手段考察了催化剂物理化学性质随焙烧温度的变化情况,并分析了与催化剂活性之间的关系,得到贵金属分散度、表面化学吸附氧含量、催化剂的还原性质对氧化性能有重要影响,发挥协同作用。进而可以通过优化焙烧温度提升柴油车氧化催化剂性能,对提高工业应用柴油车尾气后处理系统的净化效率有重要意义。     

Nanofibers of barium strontium titanate (BST) by sol-gel processing and electrospinning

This paper describes the fabrication of barium strontium titanate (Ba0.6Sr0.4TiO3 or BST) nanofibers by electrospinning method using a solution that contained poly(vinylpyrrolidone) and a sol-gel solution of BST. The as-spun and calcined BST/PVP composite nanofibers were characterized by TG-DTA, X-ray diffraction, FT-IR, SEM and TEM, respectively. After calcination of the as-spun BST/PVP composite nanofibers at above 700 degrees C in air for 2 h, BST nanofibers of 188+/-25 nm in diameter having well-developed cubic-perovskite structure were successfully obtained. The crystal structure and morphology of the nanofibers were influenced by the calcination temperature. Calcination at below 700 degrees C resulted in amorphous phase whereas BST with second phase such as barium titanate were formed at above 700 degrees C. Diameters of the nanofibers decreased from 208+/-35 to 161+/-18 nm with increasing calcination temperature between 600 and 800 degrees C.     

WOx/ZrO2 catalysts prepared by anionic exchange: in situ Raman investigation from the precursor solutions to the calcined catalysts

W/ZrO(2) catalysts were prepared using anionic exchange of peroxotungstate species with hydroxyl groups of zirconium hydroxide at low pH. The solids were dried and calcined under air at 700 degrees C. Each step of this novel method of preparation was investigated by Raman spectroscopy. A reference sample was also prepared by incipient wetness impregnation of ZrO(2).n(H2O) with an ammonium tungstate solution and characterized throughout its preparation process. Complementary data were collected from X-ray diffraction, chemical analysis, surface area measurements, and thermal analysis. The Raman spectra of the H2WO4-H2O2 precursor solutions evidenced the presence of (W2O3(O2)4(H2O)2)(2-) dimers. These low-nuclearity species were exchanged with zirconium hydroxide at low pH. The Raman spectra of the dried solids did not reveal peroxotungstate species but were typical of tetrahedral (WO4)(2-) species. A slight agglomeration of W species was observed with an increase in the W content. However, for an equivalent W loading, a higher W dispersion was obtained by anionic exchange, compared to the impregnation method. Furthermore, a remarkable homogeneity of the exchanged samples was evidenced by the micro-Raman spectra. The in situ Raman spectra recorded during calcination characterized both crystalline phases and supported tungsten species. Significant modifications were observed during the calcination process. The exchanged and the impregnated samples, with the same W loading, evidenced a similar type of tungsten species with one W=O bond. However, their behavior during calcination up to 700 degrees C was different. This was attributed to different strengths of interaction with the support. Moreover, the spectra recorded after calcination on various points of the exchanged sample with a high W content revealed a better spatial homogeneity than the impregnated one.     

Preparation of nanometer-sized In2O3 particles by a reverse microemulsion method

Nanometer-sized indium oxide (In(2)O(3)) particles have been prepared by chemical reaction of inorganic indium compounds and ammonia gas in a reverse microemulsion system consisting of water, Triton X-100 (surfactant), n-heptanol (co-surfactant), and n-octane (oil). Precursor hydroxides precipitated in the droplets of water-in-oil (W/O) microemulsion were calcined at different temperatures to form indium oxide powder. The factors affecting the particle size have been discussed; the calcination temperature is considered to be the important factor for controlling the size. In(2)O(3) calcined at 400 degrees C had a spherical form and a narrow size distribution. Calcination at 800 degrees C led to the formation of particles not only of irregular shape, but also of a wide size distribution. With the increase in calcination temperature from 400 to 800 degrees C, the average size of the particles grew from 7 to about 40 nm. The species of reactants used in the aqueous phase had a significant effect on the size of the particles. The average diameter of In(2)O(3) particles derived from reactant InCl(3) was 7 nm; that of particles derived from In(NO(3))(3) was 15 nm. The In(2)O(3) nanoparticles were characterized by transmission electron microscopy and X-ray diffraction. The phase behavior of the microemulsions is discussed.     

Direct formation of thermally stabilized amorphous mesoporous Fe2O3/SiO2 nanocomposites by hydrolysis of aqueous iron III nitrate in sols of spherical silica particles

Nanocomposite materials containing 10% and 20% iron oxide/silica, Fe2O3/SiO2 (w/w), were prepared by direct hydrolysis of aqueous iron III nitrate solution in sols of freshly prepared spherical silica particles (St?ber particles) present in their mother liquors. This was followed by aging, drying, calcination up to 600 degrees C through two different ramp rates, and then isothermal calcinations at 600 degrees C for 3 h. The calcined and the uncalcined (dried at 120 degrees C) composites were characterized by thermogravimetric analysis, differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction (XRD), N2 adsorption/desorption techniques, and scanning electron microscopy as required. XRD patterns of the calcined composites showed no line broadening at any d-spacing positions of iron oxide phases, thereby reflecting the amorphous nature of Fe2O3 in the composite. The calcined composites showed nitrogen adsorption isotherms characterizing type IV isotherms with high surface area. Moreover, surface area increased with the increasing of the iron oxide ratio and lowering of the calcination ramp rate. Results indicated that iron oxide particles were dispersed on the exterior of silica particles as isolated and/or aggregated nanoparticles. The formation of the title composite was discussed in terms of the hydrolysis and condensation mechanisms of the inorganic FeIII precursor in the silica sols. Thereby, fast nucleation and limited growth of hydrous iron oxide led to the formation of nanoparticles that spread interactively on the hydroxylated surface of spherical silica particles. Therefore, a nanostructured composite of amorphous nanoparticles of iron oxide (as a shell) spreading on the surface of silica particles (as a core) was formed. This morphology limited the aggregation of Fe2O3 nanoparticles, prevented silica particle coalescence at high temperatures, and enhanced thermal stability.     

Preparation and characterization of Zn(0.9)Mg(0.1)TiO3via electrospinning

Hexagonal Zn(0.9)Mg(0.1)TiO(3) (ZMT) composite fibers were successfully prepared by combining sol-gel with an electrospinning and calcination technique. The crystalline phase and microstructures of Zn(0.9)Mg(0.1)TiO(3) fibers, calcined at various temperatures for 1 h, were examined by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Fourier transform infrared (FT-IR) spectroscopy and thermogravimetry differential thermal analysis (TG-DTA) techniques. The results showed that the crystalline phase, morphology and grain size of the ZMT fibers were influenced by the calcination temperature and the doped magnesium improved the stability of the ilmenite ZnTiO(3)-based ceramic. Fibrous, linked particles and separated hexagonal particles were obtained after being calcined at 500, 700 and 900 °C, respectively. The single phase Zn(0.9)Mg(0.1)TiO(3) was formed from 700 °C to 900 °C and the possible formation mechanism was proposed. The as-prepared samples exhibited low activities for Methylene blue (MB) photodegradation under visible-light irradiation.     

Effect of calcination temperature on structure and performance of Ni/TiO2-SiO2 catalyst for CO2 reforming of methane

The influence of calcination temperature on the structure and catalytic behavior of Ni/TiO2-SiO2 catalyst, for CO2 reforming of methane to synthesis gas under atmospheric pressure, was investigated. The results showed that the Ni/TiO2-SiO2 catalyst calcined at 700 ℃ had high and stable activity while the catalysts calcined at 550 and 850 ℃ had low and unstable activity. Depending on the calcination temperature, one, two, or three of the following Ni-containing species, NiO, Ni2.44Ti0.72Si0.07O4, and NiTiO3 were identified by combining the temperature programmed reduction （TPR） and X-ray diffraction （XRD） results. Their reducibility decreased in the sequence： NiO〉Ni2.44Ti0.72Si0.07O4〉NiTiO3. It suggests that high and stable activities observed over the Ni/TiO2-SiO2 catalyst calcined at 700 ~C were induced by the formation of Ni2.44Ti0.72Si0.07O4 and smaller NiO species crystallite size.     

Synthesis and characterization of mesoporous ceria/alumina nanocomposite materials via mixing of the corresponding ceria and alumina gel precursors

Mesoporous ceria/alumina, CeO(2)/Al(2)O(3), composites containing 10, 20 and 30% (w/w) ceria were prepared by a novel gel mixing method. In the method, ceria gel (formed via hydrolysis of ammonium cerium(IV) nitrate by aqueous ammonium carbonate solution) and alumina gel (formed via controlled hydrolysis of aluminum tri-isopropoxide) were mixed together. The mixed gel was subjected to subsequent drying and calcination for 3 h at 400, 600, 800 and 1000 degrees C. The uncalcined (dried at 110 degrees C) and the calcined composites were investigated by different techniques including TGA, DSC, FTIR, XRD, SEM and nitrogen adsorption/desorption isotherms. Results indicated that composites calcined for 3 h at 800 degrees C mainly kept amorphous alumina structure and gamma-alumina formed only upon calcinations at 1000 degrees C. On the other hand, CeO(2) was found to crystallize in the common ceria, cerinite, phase and it kept this structure over the entire calcination range (400-1000 degrees C). Therefore, high surface areas, stable surface textures, and non-aggregated nano-sized ceria dispersions were obtained. A systematic texture change based on ceria ratio was observed, however in all cases mesoporous composite materials exposing thermally stable texture and structure were obtained. The presented method produces composite ceria/alumina materials that suit different applications in the field of catalysis and membranes technology, and throw some light on physicochemical factors that determine textural morphology and thermal stability of such important composite.     

甲烷氧化偶联:Mn2O3-Na2WO4/SiO2催化剂的金属氧化物MOx(M=Ti,Mg,Ga,Zr)改性及掺杂效应研究

甲烷 (页岩气、天然气、可燃冰和煤层气的主要成分) 是地球上储量巨大的优质能源和高品味的碳氢资源, 我国也拥有储量居全球前列的页岩气、可燃冰和煤层气. 虽然甲烷经由合成气可以间接转化为乙烯等产品, 但工艺流程长以及合成气造气高温、高能耗和高物耗也是不争的事实, 这在一定程度上降低了间接合成路线的竞争优势. 特别是, 甲烷的间接转化需要将本应部分保留于产品的 C-H 键全部打断生成合成气, 然后再在催化剂作用下重组得到烃类产品, 故而并不完美.因此, 甲烷的直接转化一直是科学家孜孜以求的理想路径, 甲烷氧化偶联制乙烯 (OCM 反应) 也再一次引起关注.目前, Mn2O3-Na2WO4/SiO2是最富有应用前景的催化剂, 但其适宜反应温度仍高达 800 ℃ 以上, 极大地制约了其工业化应用. 为提高其低温催化性能, 本文采用金属氧化物 MOx(TiO2, MgO, Ga2O3或 ZrO2) 对 Mn2O3-Na2WO4/SiO2催化剂进行了掺杂改性, 利用扫描电子显微镜、N2吸附-脱附等温曲线、X 射线衍射、拉曼光谱、电感耦合等离子体原子发射光谱等手段对改性后的催化剂进行了系统表征. 结果表明, TiO2掺杂的 Mn2O3-Na2WO4/SiO2催化剂在 700 ℃(催化剂床层温度)下, CH4转化率可达 23%, 同时 C2-C3烃类选择性约为 73%, 且能够稳定运行 300 h 无失活迹象; MnTiO3的形成对提高OCM 反应的低温活性和选择性至关重要, 本质在于低温 (≤ 700 ℃) 化学循环"MnTiO3?Mn2O3"的形成替代了未改性催化剂的高温 (＞ 800 ℃) 化学循环"MnWO4?Mn2O3". 对于 MgO 改性的 Mn2O3-Na2WO4/SiO2催化剂, 其催化性能与未改性催化剂相当, 反应过程中 Mn2O3与 MgO 生成了新物相 Mg2MnO4; 虽然也形成了新的 MnWO4?Mg2MnO4氧化还原循环, 但是该循环与 MnWO4?Mn2O3循环类似, 需在高温下才可高效进行. 对于 Ga2O3或 ZrO2改性的催化剂, 其催化性能低于未改性催化剂, 原因在于反应过程中 Ga2O3或 ZrO2的引入促进了 MnWO4物相的生成并对其有稳定作用, 反应后的催化剂无论是体相还是表面都只能检测到 MnWO4, 推测认为α-方石英、Na2WO4和 Mn2O3的缺失是导致 Ga2O3或 ZrO2改性催化剂性能下降的主要原因.     

The effect of calcination on morphology of phosphate coating and microstructure of sintered iron phosphated powder

Carbonyl iron powder was coated with phosphate layer using phosphating precipitation method. The phosphated powder was dried at 60 °C for 2 h in air and heat treated by calcination at 400 and 800 °C for 3 h in air. Cylindrical specimens density of ~6.5 g.cm^?3 based on iron phosphated powder calcined at 400 °C were sintered at 820, 900, 1110 °C in N₂ + 10%H₂ atmosphere and 1240 °C in vacuum for 30 min. The morphology and phase composition of the phosphate coating and sintered compacts were studied by scanning electron microscopy, atomic force microscopy (AFM) and X‐ray diffraction (XRD) analysis. Gelatinous morphology of dried phosphate coating (thickness of ~100 nm) containing nanoparticles of iron oxyhydroxides and hydrated iron phosphate was observed. From XRD, diffractogram indicated the presence of goethite α‐FeOOH, lepidocrocite γ‐FeOOH and ludlamite Fe₃(PO₄)₂.4H₂O. The calcined phosphate coating (thickness of ~ 400 nm) contained non‐homogeneous consistency of α‐Fe₂O₃ layer on iron particles, an inter‐layer of amorphous FePO₄ and Fe₃O₄ top layer. The transformation to crystalline FePO₄ structure occurred during calcination at 800 °C with the presence of α‐Fe₂O₃ forming a light top zone (rough morphology). The microstructure of compacts sintered in solid state at temperatures up to 900 °C has retained composite network character. A fundamental change in microstructure due to the liquid phase sintering occurred after sintering at temperatures of 1100 and 1240 °C. It was confirmed that the microstructure complex consists of spheroidized α‐Fe and α‐Fe₂O₃ phases surrounded by solidified liquid phase consisting various phosphate compounds. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis of titanium dioxide nanoparticles with mesoporous anatase wall and high photocatalytic activity

Mesoporous titanium dioxide nanosized powder with high specific surface area and anatase wall was synthesized via hydrothermal process by using cetyltrimethylammonium bromide (CTAB) as surfactant-directing agent and pore-forming agent. The resulting materials were characterized by XRD, nitrogen adsorption, FESEM, TEM, and FT-IR spectroscopy. The as-synthesized mesoporous TiO2 nanoparticles have mean diameter of 17.6 nm with mean pore size of 2.1 nm. The specific surface area of the as-synthesized mesoporous nanosized TiO2 exceeded 430 m2/g and that of the samples after calcination at 600 degrees C still have 221.9 m2/g. The mesoporous TiO2 nanoparticles show significant activities on the oxidation of Rhodamine B (RB). The large surface area, small crystalline size, and well-crystallized anatase mesostructure can explain the high photocatalytic activity of mesoporous TiO2 nanoparticles calcined at 400 degrees C.     

碱液回流老化ZrO(OH)_2制备纳米晶ZrO_2的影响因素

通过考察回流老化所用的碱液（NH_4OH, NaOH和KOH）介质和容器材质（玻璃 和Teflon）对ZrO(OH)_2凝胶及其焙烧产物ZrO_2的织构／结构和热稳定性的影响， 研究了杂质元素掺杂和凝胶溶解－再沉淀等因素在形成高表面积纳米晶ZrO(OH) _2/ZrO_2过程中的作用。在Teflon容器中，以NH_4OH为介质（pH = 11.5）的回流 老化对ZrO(OH)_2/ZrO_2的性质无明显影响。而使用玻璃容器则可显著提高ZrO(OH) _2/ZrO_2的表面积、孔容和抗烧结性质，并在800℃获得小晶粒（5～7 nm）四方晶 相ZrO_2纳米晶材料；在DTA曲线上ZrO(OH)_2转变成ZrO_2晶体的温度由回流老化前 的463℃提高到810～840℃。在以KOH和NaOH为介质(pH = 13)的实验中，使用玻璃 容器得到与经NH_4OH为介质时相类似的结果；但在Teflon容器中只形成低表面积和 较大尺寸（约20 nm）以单斜相为主的混合晶相ZrO(OH)_2，其在800℃焙烧后形成 大晶粒（35 nm）单斜相ZrO_2。样晶的元素分析结果清楚地揭示出使用玻璃容器时 有SiO_2从器壁溶解掺杂进入ZrO(OH)_2凝胶。样品的表面积和孔容与杂质Si~(4+) 含量之间有顺变关系，表明Si~(4+)掺杂是形成高表面积和大孔容ZrO(OH) _2/ZrO_2、提高ZrO_2晶化温度以及稳定小晶粒四方晶相ZrO_2的最主要因素。在不 发生Si~(4+)掺杂前提下，K~+和Na~+的存在可促进ZrO(OH)_2形成结晶，但对高温 下ZrO_2织构的稳定性影响不大。此外，ZrO(OH)_2凝胶的溶解－再沉淀和骨架网络 有序化也是回流老化影响ZrO(OH)_2/ZrO_2织构的重要因素。     

Synthesis, structure, texture, and CO sensing behavior of nanocrystalline tin oxide doped with scandia

Weakly agglomerated nanocrystalline scandia doped tin oxide powders with high surface area (170-220 m(2)/g) and uniform size (3-4 nm) were synthesized for the first time by a two-step hydrothermal process in the presence of urea, followed by the calcination between 500 and 1200 degrees C. The structure and texture of the binary oxide system were characterized by thermogravimetry and differential thermal analysis, Brunauer-Emmett-Teller-specific surface area analysis, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. A metastable scandium tin oxide solid solution in tetragonal structure was formed for the scandia content lower than 6 mol % as the samples were calcined at 800 degrees C, and the excess Sc atoms were dispersed at the surface of the crystallites above this limit. The solid solution was metastable, so scandium migrated toward the surface region of the crystallites and produced a second phase of Sc(4)Sn(3)O(12) during calcining at high temperatures over 1000-1200 degrees C. In the case of the samples with higher dopant concentration (>15 mol %), the calcination at the temperature between 500 and 800 degrees C caused the precipitation of Sc(2)O(3), and the calcination over 1000-1200 degrees C led to the formation of more Sc(4)Sn(3)O(12). Textural analysis showed that doping an appropriate amount of Sc(2)O(3) into nanosized SnO(2) could effectively inhibit the grain growth and stabilize the surface area against high-temperature calcinations below 1000 degrees C. CO gas-sensing property measurements revealed that the dispersion of Sc at the surfaces of the SnO(2) nanocrystallites could improve the CO sensitivity significantly, and the pellet sample with scandia content of 10 mol % sintered at 800 degrees C showed the best CO gas-sensing property in the operation temperature range of 300-400 degrees C. On the basis of the structural and textural analysis, the correlation between the structure/texture and the sensitivity to CO for the as-calcined (SnO(2))(1-x)(Sc(2)O(3))(x) nanocrystallites has been established and explained.     

Thermal decomposition of monocalcium aluminate decahydrate (CaAl2O4.10H2O) investigated by in-situ synchrotron X-ray powder diffraction, thermal analysis and 27Al, 2H MAS NMR spectroscopy

The stability of monocalcium aluminate decahydrate, with the nominal composition CaAl(2)O(4).10H(2)O (CAH(10)), has a decisive role for the strength development and durability of cementitious materials based on high alumina cements. This has prompted an investigation of the thermal transformation of crystalline monocalcium aluminate decahydrate in air to an amorphous phase by in-situ synchrotron X-ray powder diffraction in the temperature range from 25 to 500 degrees C, by DTA/TGA, and (2)H, (27)Al MAS NMR spectroscopy. The decomposition includes the loss of hydrogen-bonded water molecules in the temperature range up to 175 degrees C, coupled with a reduction of the unit cell volume from 1928 A(3) at 25 degrees C, to 1674 A(3) at 185 degrees C. Furthermore, X-ray diffraction shows that CaAl(2)O(4).10H(2)O starts to transform to an amorphous phase at approximately 65 degrees C. This phase is fully developed at approximately 175 degrees C and it converts to crystalline CaAl(2)O(4) when heated to 1300 degrees C. The thermal decomposition in the temperature range from approximately 65 to approximately 175 degrees C involves both formation of an amorphous phase including AlO(4) tetrahedra and structural changes in the remaining crystalline phase.     

ZrO_2表面 B_2O_3的分散及其作用状态

用 XPS、 FT IR和 FT Raman等技术研究了 ZrO2表面 B2O3的分散及其作用状态,测定了 B2O3在 ZrO2表面的分散阈值 .结果表明： B2O3在 ZrO2表面可以三配位 BO3和四配位 BO4结构单元存在;载体 ZrO2的预焙烧温度和硼含量对 B2O3的分散及作用状态有较大影响,并改变 BO3与 BO4结构单元之间的比例 .实验测得 B2O3在 ZrO2载体上的单层分散阈值为 0.05 gB2O3/gZrO2(或 B2O3的质量分数 w=4.76％),处在此单层中的硼原子以 BO4为结构单元直接与 ZrO2表面相作用 .只有当 B2O3的负载量超过此(单层)分散阈值时, BO3结构单元才会形成 .     

Synthesis and Characterization of Hydrotalcite-like Compounds Containing V(3+) in the Layers and of Their Calcination Products

The synthesis and full characterization of a new hydrotalcite-like compound with the formula [Mg(0.71)V(0.29)(OH)(2)](CO(3))(0.145).0.72H(2)O and with V(3+) in the layers are described. The influence of hydrothermal treatment and drying rate on the crystallinity of the materials obtained is discussed. The evolution to mixed oxides upon calcination at different temperatures (448, 548, 773, 1023, and 1273 K) under different atmosphere environments (air or nitrogen) for 2 h has been studied. Characterization of the original layered materials and of the calcination products has been carried out by X-ray diffraction, thermal analysis, Fourier-transform infrared spectroscopy, BET specific surface area determination, temperature-programmed reduction, and transmission electron microscopy. X-ray absorption spectroscopies (XANES and EXAFS) have also been used to assess the local geometry of vanadium ions in the different compounds prepared. All experimental data agree with a well-crystallized hydrotalcite-like compound after thermal treatment, and also a minor effect of the drying rate on the crystallinity has been found. Thermal decomposition yields poorly crystalline layered compound at 448 K that undergoes transformation to mostly amorphous materials when calcined at 548-773 K, finally leading to a mixture of MgO and Mg(3)V(2)O(8), which has increasing crystallinity as the calcination temperature increases. XAS results indicate the presence of V(3+) ions in an octahedral coordination in the parent sample calcined at 448 K and tetrahedrally coordinated V(5+) species for samples calcined at higher temperatures, calcination giving rise to a better ordering of the second coordination sphere. Similar results were found when calcination was performed in nitrogen, although higher temperatures were needed to achieve the same result.     

ZrO2表面B2O3的分散及其作用状态

用XPS、FT IR和FT Raman等技术研究了ZrO2表面B2O3的分散及其作用状态,测定了B2O3在ZrO2表面的分散阈值.结果表明：B2O3在ZrO2表面可以三配位BO3和四配位BO4结构单元存在;载体ZrO2的预焙烧温度和硼含量对B2O3的分散及作用状态有较大影响,并改变BO3与BO4结构单元之间的比例.实验测得B2O3在ZrO2载体上的单层分散阈值为0.05 gB2O3/gZrO2（或B2O3的质量分数w=4.76％）,处在此单层中的硼原子以BO4为结构单元直接与ZrO2表面相作用.只有当B2O3的负载量超过此（单层）分散阈值时, BO3结构单元才会形成.     

预处理条件对La_2O_3上过氧物种光诱导生成的影响

采用原位显微Raman光谱技术详细考察了焙烧温度和焙烧时间对La(OH)3分解制备的La2O3结构以及过氧物种光诱导生成性能的影响,结果表明,经700℃焙烧所得La2O3样品较经800℃以上长时间焙烧的样品更有利于过氧物种的生成.对La(OH)3热分解过程的原位XRD测试结果表明,焙烧温度需达到近700℃才可使La(OH)3完全转化为La2O3.在700℃焙烧的样品上,除了六方相的La2O3外,还可检出介稳态的立方相La2O3.经800℃以上长时间(≥5 h)焙烧后,介稳态的立方相La2O3将转化为稳定的六方相La2O3物种.在相同的实验条件下,立方相的稀土倍半氧化物较六方相更有利于过氧物种的光诱导生成,其原因可能源于前者含更多氧空位,因而更有利于对分子氧的吸附和活化.     

Effect of calcination temperature on the surface morphology and crystallinity of tungsten (VI) oxide nanorods prepared using colloidal gas aphrons method

The effect of calcination temperature on the surface morphology and crystallinity of tungsten (VI) oxide, WO₃ nanorods prepared using colloidal gas aphrons (CGAs) as template was studied. The synthesized WO₃ nanorods were calcined in a furnace for 4 h at four different temperatures, i.e., 400, 500, 600 and 700 °C. The morphology of the calcined WO₃ nanorods have been characterized by both transmission electron microscope (TEM) and variable pressure scanning electron microscope (SEM) equipped with energy dispersive X-ray analysis (EDAX). The results showed that the calcination temperature influenced the shape and size of the WO₃ nanorods produced. It is also found that the calcination at various temperature do not effect the composition and the purity of the WO₃ nanorods. In order to characterize the crystalinity of WO₃, X-ray diffraction (XRD) has been used. It shows that all the calcined WO₃ produced are in crystalline form compared to the as-prepared WO₃ nanorods, which is in amorphous form.     

固体超强酸SO2-4/ZrO2的制备及其催化性能研究

以氧氯化锆为锆原,氨水为沉淀剂,硫酸溶液为浸渍液,通过沉淀-浸渍法制备SO2-4/ZrO2(SZ)酯化催化剂,其结构经BET、X-射线衍射(XRD)、傅立叶变换红外光谱(FT-IR)及扫描电子显微镜(SEM)表征.结果表明:随着焙烧温度升高,催化剂的比表面积依次降低,孔径增大,氧化锆的晶态由无定形态转化为四方晶态再转化为单斜晶态;于600℃焙烧时,催化剂形成的S=O键红外吸收峰最强;于700℃焙烧时,催化剂结构被破坏.在丙烯酸与十八醇的酯化反应中对催化剂进行活性测试.结果表明:600℃焙烧的催化剂产率最高(96.4%).