Nd2O3／TiO2光催化剂的光生羟基自由基和光活性

以硝酸钕和钛酸四正丁酯作为前驱体,采用溶胶-凝胶法制备了Nd2O3/TiO2纳米光催化剂,并通过XRD和BET等手段进行了表征.以对苯二甲酸作为探针分子,结合化学荧光技术研究了光催化剂表面羟基自由基的生成;并以甲基橙为光催化降解反应模型化合物,考察了光催化剂的活性.测定了甲基橙在TiO2和Nd2O3/TiO2(1.0%)光催化剂上的吸附常数.结果表明:Nd2O3掺杂使TiO2的粒径减小,比表面积增大;羟基自由基的生成速率越大,催化剂的催化活性越高.Nd2O3掺杂有利于反应底物在催化剂表面的吸附,Nd2O3的最佳掺入量为Nd/Ti(摩尔比)=1.0%.     

TiO_2（B）的合成及其光催化性能的研究

以硫酸钛和过氧化钠为原料,合成了过氧钛酸复合物作为前躯体,进而通过水热法制备出单斜结构二氧化钛TiO2（B）,采用XRD、TEM、FTIR和BET等技术对样品进行了表征。结果表明,TiO2（B）的比表面积为98.15 m2/g,对甲基橙的光催化降解表现出比P25更高的活性和良好的稳定性。     

ZnO/C/TiO2复合纳米材料制备及其光催化性能

以金属有机骨架MOF-5为前驱体,在氮气气氛下高温处理得ZnO/C,通过水热法将ZnO/C负载到TiO2中获得ZnO/C/TiO2纳米复合光催化剂,对其晶体结构、形貌特征、成分等进行了表征,采用正交实验法考察了MOF-5处理温度、ZnO/C负载量、钛酸丁酯加入量对复合光催化剂催化降解甲基橙性能的影响. 结果表明,TiO2的比表面积为87.5 m2/g, ZnO/C/TiO2的比表面积为109.0 m2/g. 制备ZnO/C/TiO2的最佳条件为MOF-5处理温度600℃,ZnO/C负载量0.07 g,钛酸丁酯加入量1.5 mL. 甲基橙用紫外灯照射90 min,以TiO2为催化剂时降解率为62.1%,以ZnO/C/TiO2为催化剂时降解率达99.5%,光催化活性大大提高.     

TiO2（B）的合成及其光催化性能的研究

以硫酸钛和过氧化钠为原料,合成了过氧钛酸复合物作为前躯体,进而通过水热法制备出单斜结构二氧化钛TiO2(B),采用XRD、TEM、FTIR和BET等技术对样品进行了表征。结果表明,TiO2(B)的比表面积为98.15 m2/g,对甲基橙的光催化降解表现出比P25更高的活性和良好的稳定性。     

钕和镨共掺杂TiO2光催化性能的研究

采用溶胶—凝胶法制备纯纳米TiO2、钕和镨掺杂的纳米TiO2光催化剂,以甲基橙为目标降解物,研究了催化剂加入量、染料初始质量浓度、溶液pH值对甲基橙降解率的影响.实验结果表明,钕掺杂的纳米TiO2光催化活性高于纯纳米TiO2的光催化活性,而适量钕镨共掺杂纳米TiO2光催化活性可进一步提高,最佳掺杂浓度为0.5％的钕和0.2％的镨.当钕和镨共掺杂纳米TiO2催化剂加入量为2.0g/L,甲基橙溶液的初始质量浓度为30 mg/L,pH值为10.5时,在40 W紫外灯光照射35 min后降解率最好,可达到93％.     

TiO2光催化处理含甲基橙微污染水的动力学研究

通过溶胶-凝胶和浸渍相结合的方法制备出负载型纳米TiO2光催化剂,在光催化氧化反应器中对含有甲基橙的微污染水进行了光催化氧化研究.确定影响甲基橙光催化氧化的主要影响因素为TiO2光催化剂投加量、氧化剂投加量.结果表明,光催化氧化要比无催化剂的光氧化效果好,甲基橙的降解过程符合一级反应动力学模型;最佳的催化剂投加质量浓度为0.40 g/L;增加H2O2的投加量有助于甲基橙的去除.     

双效功能型复合光催化剂Ag/TiO2/AC的制备及光催化活性

以硝酸银、四氯化钛及活性炭为原料,采用溶胶-凝胶法和浸渍法制备了3种复合光催化剂。通过TEM、XRD、BET和UV-Vis光谱对复合光催化剂的形貌、物相组成、比表面积和吸光性能进行了表征,并以甲基橙的脱色降解为模型反应,考察了样品的光催化性能。结果表明:其光催化活性大小顺序为Ag/Ti O2/ACAg/Ti O2Ti O2,其中,Ag/Ti O2/AC由于具有895.21 m2/g的比表面积和Ag的负载改性而具有吸附、光催化双效功能,且对光的吸收扩展到可见光区,对甲基橙的最大降解率能达到95.2%。催化剂连续重复使用5次,Ag/Ti O2/AC对甲基橙溶液的脱色降解率均保持在90%以上。     

钛柱撑蒙脱石光催化降解甲基橙的性能研究

以钛酸丁酯为前驱体、钠基蒙脱石为载体,采用溶胶-凝胶法制备了二氧化钛柱撑蒙脱石（TiO2—MMT）纳米复合材料。采用X-射线衍射仪、透射电子显微镜、全自动比表面积及中孔、微孔分析仪（BET）等分析手段对TiO2—MMT进行了表征,并研究了其对甲基橙的光催化降解活性。结果表明：TiO2—MMT主要由锐钛矿型TiO2和蒙脱石组成,呈层片状结构,TiO2柱撑到蒙脱石层间,并使其（001）晶面间距明显增大。在中性和碱性奈件下,TiO2-MMT对甲基橙的光催化降解能力较弱;在酸性条件下,TiO2-MMT对甲基橙的降解率远远高于中性和碱性条件下的降解率。TiO2—MMT光催化降解甲基橙的优化条件为：pH值4、甲基橙初始浓度30mg·L-1、TiO2-MMT投加量10g·L-1,在优化条件下光照2h,TiO2-MMT对甲基橙的催化降解率为99．4％。     

锆-钕-氧纳米材料的合成及其可见光响应的光催化性能

采用熔盐辅助的溶胶–凝胶法成功合成了锆–钕–氧(Zr–Nd–O)系列纳米材料。利用 X 射线衍射、X 射线能量散射谱以及扫描电子显微镜对所得产物的物相、组成以及形貌进行了表征。通过染料水溶液在可见光条件下的光催化降解实验对 Zr–Nd–O 系列纳米材料的光催化性能进行了评价。结果表明：所得Zr0.8Nd0.2O2–δ纳米材料对罗丹明B和亚甲基蓝水溶液具有很好的可见光催化降解性能，在可见光照射150 min后的最大降解率分别为93.4%和83.0%。反应机理研究表明，其优异的光催化性能来源于其特殊的缺陷结构、较小的颗粒尺寸(25～65 nm)和较大的比表面积(54.88 m2/g)。     

超声制备纳米TiO2及其光催化活性研究

在超声条件下采用溶胶凝胶法制备了纳米TiO2光催化剂,以甲基橙的光催化降解为探针反应评价了其光催化活性,运用XRD、BET、TEM等技术对制备的TiO2进行表征,结果表明,低频超声可以抑制TiO2晶粒的聚集和长大,提高分散度,增大比表面积,TiO2样品在紫外光下光催化降解甲基橙的能力显著增强,其中28 kHz超声频率下制备的样品效果最好,降解速率比未超声得到的TiO2提高了15％.     

Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions

Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions were studied for potential applications in water decontamination technology and their capacity to induce an oxidation process under VIS light. UV–vis spectroscopy analysis showed that the junctions-based Cu₂O, Bi₂O₃ and ZnMn₂O₄ are able to absorb a large part of visible light (respectively, up to 650, 460 and 1000 nm). This fact was confirmed in the case of Cu₂O/TiO₂ and Bi₂O₃/TiO₂ by photocatalytic experiments performed under visible light. A part of the charge recombination that can take place when both semiconductors are excited was observed when a photocatalytic experiment was performed under UV–vis illumination. Orange II, 4-hydroxybenzoic and benzamide were used as pollutants in the experiment. Photoactivity of the junctions was found to be strongly dependent on the substrate. The different phenomena that were observed in each case are discussed.     

ZrB2质与TiB2质耐火材料

介绍了ZrB     

Properties of char particles obtained under O2/N2 and O2/CO2 combustion environments

Pulverized coal combustion in O₂/N₂ and O₂/CO₂ environments was investigated with a drop tube furnace. Results present that the reaction rate and burn-out degree of O₂/CO₂ chars (obtained in O₂/CO₂ environments) are lower than that of O₂/N₂ chars (obtained in O₂/N₂ environments) under the same experimental condition. It indicates that a higher O₂ concentration in O₂/CO₂ environment is needed to achieve the similar combustion characteristic to that in O₂/N₂ environment. The main differences between O₂/N₂ and O₂/CO₂ chars rely on the pore structure determined by N₂ adsorption and chemical structure measured by FT-IR. For O₂/CO₂ char, the surface is thick and the pores are compact which contribute to the fragmentation reduction of particles burning in O₂/CO₂ environment. The organic functional group elimination rate from the surface of O₂/CO₂ chars is slower or delayed. The present research results might have important implications for further understanding the intrinsic kinetics of pulverized coal combustion in O₂/CO₂ environment.     

ZrO2/SiO2- and La2O3/Al2O3-supported platinum catalysts for CH4/CO2 reforming

Surface-phase ZrO₂ on SiO₂ (SZrOs) and surface-phase La₂O₃ on Al₂O₃ (SLaOs) were prepared with various loadings of ZrO₂ and La₂O₃, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH₄/CO₂ reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al₂O₃ and Pt/SiO₂ catalysts. CO₂ or CH₄ pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO₂ to form a stable surface-phase oxide. The lanthana cannot be spread well on Al₂O₃, but it forms a stable amorphous oxide with Al₂O₃. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO₂ and Pt/Al₂O₃ by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO₂ and Pt/Al₂O₃ catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO₂ adsorbed on the basic sites of SZrOs and SLaOs.     

Modeling char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of this investigation has been to model combustion under suspension fired conditions in O₂/N₂ and O₂/CO₂ mixtures. Experiments used for model validation have been carried out in an electrically heated Entrained Flow Reactor (EFR) at temperatures between 1173 K and 1673 K with inlet O₂ concentrations between 5 and 28 vol.%. The COal COmbustion MOdel, COCOMO, includes the three char morphologies: cenospheric char, network char and dense char each divided between six discrete particle sizes. Both combustion and gasification with CO₂ are accounted for and reaction rates include thermal char deactivation, which was found to be important for combustion at high reactor temperatures and high O₂ concentrations. COCOMO show in general good agreement with experimental char conversion profiles at conditions covering zone I-III. From the experimental profiles no effect of CO₂ gasification on char conversion has been found. COCOMO does however suggest that CO₂ gasification in oxy-fuel combustion at low O₂ concentrations can account for as much as 70% of the overall char consumption rate during combustion in zone III.     

Partial oxidation of methane to CO and H2 over nickel and/or cobalt containing ZrO2, ThO2, UO2, TiO2 and SiO2 catalysts

The influence of different metal oxide supports (i.e. ZrO₂, ThO₂, UO₂, TiO₂ and SiO₂) on the performance of Ni- and/or Co-containing catalysts [Ni and/or Co/MO₂ mole ratio (where M=Zr, Th, U, Ti or Si)=1.0] in the oxidative methane-to-syngas conversion at very low contact time (GHSV=5.2×10⁵ cm³ g⁻¹ h⁻¹ at STP) was investigated. The nickel-containing ZrO₂, ThO₂ and UO₂ catalysts (with or without pre-reduction by hydrogen at 500°C) showed good performance in the process; the order of their performance is NiO–ThO₂>NiO–UO₂>NiO–ZrO₂. The NiO–TiO₂ showed appreciable catalytic activity only after its reduction at 800°C. However, this catalyst and the NiO–SiO₂ catalyst showed poor performance in the process. These two catalysts are also deactivated very fast, mostly because of sintering of Ni and/or formation of catalytically inactive binary metal oxide phases by solid–solid reaction at the high catalyst calcination and/or catalytic reaction temperature. Although the Ni-containing ThO₂, UO₂ and ZrO₂ catalysts showed good performance, carbon deposition on them during the process is fast. However, because of the addition of cobalt to these catalysts (with Co/Ni=1.0), the rate of carbon deposition on them in the process is drastically reduced. This Co addition however resulted in a significant decrease in both the conversion and selectivity; the decrease in the selectivity was small.     

Gas-solid oxidations with RuO2---TiO2 and RuO2---SiO2 membranes

The activity of the RuO₂---TiO₂ and RuO₂---SiO₂ membrane catalysts in oxidation with air of the isopropylic alcohol was determined at temperatures ranging from 40 to 120°C. The RuO₂---TiO₂ and RuO₂---SiO₂ membranes were prepared by the sol-gel process and supported on microporous glass membranes. The catalysts were characterized by scanning electron microscopy, IR spectroscopy and X-ray diffraction studies.     

Adsorption of CO2 from dry gases on MCM-41 silica at ambient temperature and high pressure. 2: Adsorption of CO2/N2, CO2/CH4 and CO2/H2 binary mixtures

Adsorption equilibrium capacity of CO₂, CH₄, N₂, H₂ and O₂ on periodic mesoporous MCM-41 silica was measured gravimetrically at room temperature and pressure up to 25 bar. The ideal adsorption solution theory (IAST) was validated and used for the prediction of CO₂/N₂, CO₂/CH₄, CO₂/H₂ binary mixture adsorption equilibria on MCM-41 using single components adsorption data. In all cases, MCM-41 showed preferential CO₂ adsorption in comparison to the other gases, in agreement with CO₂/N₂, CO₂/CH₄, CO₂/H₂ selectivity determined using IAST. In comparison to well known benchmark CO₂ adsorbents like activated carbons, zeolites and metal-organic frameworks (MOFs), MCM-41 showed good CO₂ separation performances from CO₂/N₂, CO₂/CH₄ and CO₂/H₂ binary mixtures at high pressure, via pressure swing adsorption by utilizing a medium pressure desorption process (PSA-H/M). The working CO₂ capacity of MCM-41 in the aforementioned binary mixtures using PSA-H/M is generally higher than 13X zeolite and comparable to different activated carbons.     

Kinetics of CO and H2 oxidation over CuO-CeO2 catalyst in H2 mixtures with CO2 and H2O

The kinetics of CO and H₂ oxidation over a CuO-CeO₂ catalyst were simultaneously investigated under reaction conditions of preferential CO oxidation (PROX) in hydrogen-rich mixtures with CO₂ and H₂O. An integral packed-bed tubular reactor was used to produce kinetic data for power-law kinetics for both CO and H₂ oxidations. The experimental results showed that the CO oxidation rate was essentially independent of H₂ and O₂ concentrations, while the H₂ oxidation rate was practically independent of CO and O₂ concentrations. In the CO oxidation, the reaction orders were 0.91, −0.37 and −0.62 with respect to the partial pressure of CO, CO₂ and H₂O, respectively. In the H₂ oxidation, the orders were 1.0, −0.48 and −0.69 with respect to the partial pressure of H₂, CO₂ and H₂O, respectively. The activation energies of the CO oxidation and the H₂ oxidation were 94.4 and 142 kJ/mol, respectively. The rate expressions of both oxidations were able to predict the performance of the PROX reactor with accuracy. The independence between the CO and the H₂ oxidation suggested different sites for CO and H₂ adsorption on the CuO-CeO₂ catalyst. Based on the results, we proposed a new reaction model for the preferential CO oxidation. The model assumes that CO adsorbs selectively on the Cu⁺ sites; H₂ dissociates and adsorbs on the Cu⁰ sites; the adsorbed species migrates to the interface between the copper components and the ceria support, and reacts there with the oxygen supplied by the ceria support; and the oxygen deficiency on the support is replenished by the oxygen in the reaction mixture.     

New acrylic monolithic carbon molecular sieves for O2/N2 and CO2/CH4 separations

The modification of activated carbon fibres prepared from a commercial textile acrylic fibre into materials with monolithic shape using phenolic resin as binder was studied. The molecular sieving properties for the gas separations CO₂/CH₄ and O₂/N₂ were evaluated from the gas uptake volume and selectivity at 100 s contact time taken from the kinetic adsorption curves of the individual gases. The pseudo-first order rate constant was also determined by the application of the LDF model. The samples produced show high CO₂ and O₂ rates of adsorption, in the range 3-35 × 10⁻³ s⁻¹, and in most cases null or very low adsorption of CH₄ and N₂ which make them very promising samples to use in PSA systems, or similar. Although the selectivity was very high, the adsorption capacity was low in certain cases. However, the gas uptake in two samples reached 23 cm³ g⁻¹ for CO₂ and 5 cm³ g⁻¹ for O₂, which can be considered very good. The materials were heat-treated using a microwave furnace, which is a novel and more economic method, when compared with conventional furnaces, to improve the molecular sieves properties.