层序空间多孔结构TiO2实现高效光催化CO2还原

以葡萄糖为原料，经一步水热法生成葡萄糖基碳球(GCs)，粒径约500nm，利用微乳液聚合法合成粒径约270nm的聚苯乙烯微球(PSs)。通过真空抽滤，制备了GCs和PSs层层组装的多级模板，TiCl₄完全浸润模板并经干燥和高温煅烧，获得了空间层序多级孔结构的TiO₂。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、N₂吸附-脱附等手段表征了所制备催化剂的形貌、组分和孔结构。在饱和CO₂气氛下加入H₂O，利用催化剂在模拟太阳光条件进行光催化还原试验。结果表明：经过7h的光催化测试，相较于商用P25和无空间结构的TiO₂，层序空间多孔TiO₂生成还原产物CO的产率均得到明显提高。其中，空间复合多级孔TiO₂在结构失配的情况下仍表现出较高的CO产率。结合实验结果和表征证实：纳米微球层所形成的层序空间多孔TiO₂具有较高的比表面积和丰富的孔结构，有利于形成大量表面活性位点。三维网状多孔结构暴露出...     

TiO2·Al2O3复合氧化物载体研究进展

TiO2.Al2O3多孔复合氧化物是新型的催化剂载体材料,因其在加氢精制工艺上能够显著增加催化剂的脱硫、脱氮活性而逐渐受到重视。本文综述了国内外关于TiO2·Al2O3多孔材料的制备方法,分析了制备方法对材料的比表面积、孔结构、表面酸性等载体性能影响的一般规律。通过对国内外研究者的TiO2·Al2O3合成方法的综合评述...     

MgCl2负载β-二酮-茂型钛配合物催化乙烯聚合的研究

研究开发了一种新型非茂负载聚烯烃催化剂——CpTi(dbm)Cl2/MgCl2／THF,分析了该催化剂的结构特征，研究了该催化剂的乙烯聚合活性与催化剂的组成和结构间的关系。结果表明，用共沉淀方法制备的MgCl2具有较大的比表面积和孔体积。CpTi(dbm)Cl2同MgCl2作用后，催化剂中的CpTi(dbm)Cl2仍保持了原来的化学结构，而活化了的MgCl2也仍然基本保持原有的晶型；载体型催化剂的孔体积和比表面积随着Mg／Ti比的增加而增加；Mg/Ti比影响栽体型催化剂粒子形态、分散性以及催化活性随着Mg／Ti比增加，催化剂的粒子形态和分散性提高，催化活性线性地增加，MgCl2对Ti生成活性中心起良好的化学改性作用。     

Ni含量对介孔Ni-CaO-ZrO2催化剂上CH4-CO2重整反应的影响研究

采用并流共沉淀法制备了Ni含量不同的介孔Ni-CaO-ZrO2纳米复合氧化物催化剂,研究了其在CH4-CO2重整反应中的催化性能。利用N2吸附-脱附(BET)、X射线粉末衍射(XRD)、程序升温还原(TPR)以及程序升温氧化(TPO)等手段对催化剂进行了表征。结果表明,Ni含量对催化剂的物化性质和催化性能有较大影响,低Ni含量的催化剂具备较完善的介孔结构,该种结构非常有利于Ni物种的分散及其在高温下的抗烧结能力,从而提高了催化剂的稳定性;但过低的Ni负载量会造成催化剂表面Ni活性位过少,进而影响催化剂的活性;另一方面,Ni含量过高会导致催化剂介孔结构的坍塌,Ni在反应条件下烧结严重,大尺寸的Ni颗粒会大大增加积炭的生成,从而造成催化剂失活。     

K_2WO_4负载量对γ-Al_2O_3催化合成甲硫醇的影响

利用浸渍法,以γ-Al2O3为载体,K2WO4为活性组分,考察了不同K2WO4负载量对γ-Al2O3晶相组成、孔结构及催化性能的影响。采用XRD和BET等手段对催化剂的晶相组成和孔结构特征进行了分析表征,催化剂于甲醇-硫化氢体系进行催化性能评价。研究结果表明,不同K2WO4负载量对γ-Al2O3晶相组成、孔结构及催化性能具有较大的影响;以γ-Al2O3为载体,活性组分K2WO4负载质量分数6%时,制得K2WO4(6%)/γ-Al2O3催化剂比表面积215.412 m2·g-1、孔容0.6345 cm3·g-1、CH3SH选择性和收率分别为达90.12%和72.65%。     

介孔CuO-ZnO/SiO_2催化剂用于二氧化碳加氢合成甲醇的研究

采用原位溶胶-凝胶法制备了介孔CuO-ZnO/SiO_2催化剂,考察了表面活性剂类型和焙烧温度对催化剂结构和催化性能的影响。以二氧化碳加氢合成甲醇为探针反应,并结合TG-DTG、BET表征手段对催化剂结构和性能进行了分析。结果表明,采用CTAB为表面活性剂并经450℃焙烧所得的介孔CuO-ZnO/SiO_2催化剂具有高的比表面积和最佳的催化性能;反应条件250℃、3.0 MPa时,该催化剂的CO_2转化率、甲醇选择性分别为21.6%和35.6%。     

V2O5负载量对V2O5／TiO2催化剂SCR法脱硝的影响

以TiO2载体,采用浸渍法制备了不同V2O5负载量的用于选择性催化还原NOx的V2O5／TiO2催化剂。利用BET,SEM和Ⅺ①,对不同V2O5负载量的催化剂组成、结构、形貌和性能进行了表征,考察不同V2O5负载量对催化剂制备的影响。结果表明制备的催化剂具有较多的中孔和微孔,催化剂中V2O5含量的增加,会降低催化剂的表面积;V2O5含量为2％的V2O5／TiO2催化剂样品比表面积最大,但是其活性非常低;V2O5含量为4％催化剂比表面积较大,NOx脱转化率高;V2O5的负载量小时,V2O5主要以等轴聚合的钒基型式（V3O7和V6O13）存在,这些钒基是催化剂的活性中心;当负载量超过6％,V2O5主要以结晶相存在,占据大量活性位,降低催化效果。     

CuO-ZnO-Al_2O_3环乙醇脱氢催化剂的制备及性能

本文对用于环己醇脱红制环已酮的Cuo－Zno－Al_20_3催化剂的制备及性能进行研究，采用BET、DTA、XRD对催化剂结构如比表面、孔结构、晶相组成及晶粒大小进行了表征，并对结构与催化剂的制备和性能进行了关联。     

非负载介孔Co-Mo-Al2O3催化剂的制备及其加氢脱氧性能

采用热沉淀法制备了非负载介孔Co-Mo-Al2O3复合氧化物催化剂,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和N2吸附-脱附等方法分析了焙烧温度和超声振荡对催化剂微观结构的影响,并以苯酚为探针分子,在连续流动固定床反应器上考察了催化剂的加氢脱氧性能.结果表明:非负载介孔Co-Mo-Al2O3复合氧化物催化剂具有较窄的孔径分布(最可几孔径3.9 nm)和良好的苯酚加氢脱氧活性;在热沉淀过程中辅以超声振荡可有效控制催化剂的粒径尺寸、均匀度和介孔结构,可使催化剂的比表面积提高约50%,使苯酚的加氢脱氧活性提高约45%.     

整体式Fe-β分子筛成型方法及其催化N_2O分解反应性能

为了降低催化剂床层压降,提高Fe-β分子筛催化剂用于N_2O催化分解的能力,通过研究整体式分子筛催化剂制备方法,优化出最优原料配比为ω(拟薄水铝石)=40%,ω(硝酸)=8%,水粉比为0.6 m L·g~(-1)。研究了成型过程对分子筛催化剂结构及性能的影响,并在不同孔密度分子筛催化剂、N_2O浓度和空速条件下考察N_2O分解反应性能。结果表明,在相同温度、空速和N_2O浓度下,分子筛催化剂的孔密度越高,催化活性呈增强趋势;对于相同孔密度的分子筛催化剂,随着空速的增加,相同温度下的N_2O转化率逐渐下降;对于相同孔密度的分子筛催化剂,在相同反应空速和温度下,随着N_2O浓度的增大,N_2O转化率呈上升趋势。     

Local structure and photocatalytic activity of B2O3–SiO2/TiO2 ternary mixed oxides prepared by sol–gel method

The local structure and the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides (SiO₂ content was fixed as 30 at.% with respect to TiO₂) was investigated by using XRD, FT-IR, BET, UV-vis spectra, and electron paramagnetic resonance (EPR) measurement. In FT-IR analysis, boron was incorporated into the framework of titania matrix with replacing Ti---O---Si with Si---O---B or Ti---O---B bonds. Also, paramagnetic species such as O⁻ and Ti³⁺ defects were formed by the boron incorporation. In SiO₂/TiO₂ mixed oxides, a blue shift in the light absorption band was observed due to the quantization of band structure. All B₂O₃–SiO₂/TiO₂ samples had pure anatase phase and no rutile phase was formed even though the calcination temperature was over 900 °C. Incorporating boron oxides of more than 10% enlarges the grain size of anatase phase and causes a red shift of the light absorption spectrum. The surface area was monotonically decreased with increasing the content of boron content. As a result, the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides was greatly influenced by the content of boron oxide. The highest photoactivity (g moles/min l) was obtained when the boron content was 5% and seven times higher than that of silica/titania binary mixed oxide. In addition, the specific photoactivity (g moles/m² l) was maximum still at 5%. It was concluded that the large reduction of surface area, the change of band structure, and more formation of bulk Ti³⁺ sites are responsible for the deterioration in the photoactivity of B₂O₃–SiO₂/TiO₂ ternary mixed oxides when the content of boron is over 10%, although their crystallinity was enhanced by increasing the calcination temperature with keeping anatase phase.     

晶核剂对MgO－B_2O_3－SiO_2渣系析晶行为的影响

本文运用偏光显微镜、Ｘ射线衍射分析、差热分析和化学分析等手段，研究了用ＴｉＯ＿２和复合氧化物作晶核剂对ＭｇＯ－Ｂ＿２Ｏ＿３－ＳｉＯ＿２渣系析晶行为和硼提取率的影响。结果表明：硼提取率随硼渣结晶程度的提高而增大；ＴｉＯ＿２的加入降低了硼渣粘度，因此提高了总成核速率和晶体生长速率，加快析晶速度，使渣中含硼组分容易以结晶相析出，从而改善了硼提取率。复合氧化物改善硼提取率和提高硼渣结晶程度比ＴｉＯ＿２显著。     

Catalytic hydrolysis of dichlorodifluoromethane (CFC-12) on unpromoted and sulfate promoted TiO2–ZrO2 mixed oxide catalysts

The mixed oxide of zirconium and titanium was investigated for the catalytic hydrolysis of dichlorodifluoromethane. The mixed oxide was further promoted by doping with sulfate ions. It was found by both powder X-ray diffraction and Raman spectroscopy that addition of hydrogen peroxide to the methanol solution of ZrOCl₂ and TiCl₄ before gelation was induced by ammonia addition promoted the formation of the mixed oxide phase with the anatase structure in addition to the expected phase of columbite structure. This increased the surface area and activity of the mixed oxide. Promotion with sulfate enhanced the acidity and activity of the catalysts. When sulfate was added by treatment with sulfuric acid, phase transformation, depending on the concentration of the acid used, in addition to sulfate deposition on the oxide surface, occurred. The treatment with 96% sulfuric acid resulted in a catalyst with nearly entirely the anatase structure. This catalyst was found to be the most active, capable of complete conversion of CFC-12 and 100% selectivity to carbon dioxide at 280°C. Prolonged reaction of this catalyst at 280°C for 211 h resulted neither in reduction of activity nor reduction in CO₂ selectivity. The performance of this catalyst is among the highest reported in the literature.     

Sm2O3掺杂对BaO-B2O3-Al2O3-SiO2玻璃形成及结构的影响

借助魔角旋转核磁共振技术,探讨掺Sm2O3后BaO-B2O3-Al2O3-SiO2(BBAS)玻璃(BBASS玻璃)的形成、结构及热处理条件下玻璃结构的变化情况.研究表明:随着稀土掺量的增加,BBASS玻璃的形成区域先扩大后缩小.在Sm2O3外掺摩尔分数为30%时BBASS玻璃具有最大的形成区域.在BBAS玻璃结构中,随着BaO含量的增加,硼氧三角体[BO3]逐渐向[BO4]转变,原先[AlO4],[AlO5],[AlO6]共存的铝氧多面体结构逐渐转变为大量[AlO4]和少量[AlO5]共存的结构.在BBASS玻璃结构中,随着5m2O3掺入量的增加,Sm2O3对铝氧多面体结构变化的影响与BaO类似;对硼氧多面体而言,Sm3 强大的积聚作用使玻璃结构中硼氧多面体形成了巨大的网络.以上差异说明了Al3 比B3 更容易进入稳定的四面体结构.热处理对玻璃结构影响甚微.     

Characterization of titanium-boron binary oxides and their photocatalytic activity for stoichiometric decomposition of water

A titanium-boron binary oxide has been prepared by sol–gel method and used as a photocatalyst for the decomposition of water. The structure of titanium oxide species in the Ti/B binary oxide was amorphous before and crystal after calcination in O₂, while the boron oxide species maintained its amorphous state. With increasing calcination temperature, the crystalline structure of titanium oxides changed from an anatase phase to a rutile phase. Pt-loaded Ti/B photocatalysts decomposed water stoichiometrically in aqueous suspension system. Their photocatalytic activity decreased markedly with increase in the calcination temperature, indicating that the photocatalytic activity of the Ti/B binary oxide was strongly dependent on the crystal phase of the titanium oxide in the Ti/B binary oxide. A remarkable yield in the reaction of water decomposition was obtained when Na₂CO₃ was added in the Pt-loaded Ti/B binary oxide suspension.     

B_2O_3／Al_2O_3催化剂结构和性能的研究

采用溶胶凝胶法和浸渍法,在500℃下焙烧2 h,制备不同组成的B2O3／Al2O3催化剂。通过X射线衍射、热失重、傅立叶红外光谱等测试方法对所制备的催化剂的结构进行表征。通过催化剂与二苯甲酰基甲烷(DBM)配位情况对催化剂的性能表征。研究表明:焙烧获得的主催化剂晶型为γ-Al2O3,添加第二组分B2O3,可以提高与DBM的配位能力,以改善Al2O3的催化活性。     

Influence of structure and temperature on the thermal conductivity of molten CaO–B2O3

The effect of the temperature and borate structure on the thermal conductivity of the molten CaO–B₂O₃ binary system was investigated. The thermal conductivity was measured from 1573 K to approximately the liquidus temperature using a transient hot‐wire method, and was found to decrease with increasing temperature. The temperature dependence of the thermal conductivity in the molten oxide system was interpreted in terms of the lifetime of phonon‐like excitations and Maxwell relaxation times. The short‐range order borate structure was investigated through magic angle spinning (MAS) and triple‐quantum MAS (3Q‐MAS) NMR. Although the content of 4‐coordinated boron was not significantly affected by the addition of CaO, structural changes associated with the fraction of 3‐coordinated boron in ring and non‐ring sites were observed. The Raman spectra showed that the intermediate range order borate structure was changed from boroxyl rings to chain‐type metaborate units at higher CaO concentrations. The thermal conductivity decreased with decreasing BO_1.5/CaO ratio, owing to the depolymerization of the borate network.     

铝硼硅酸盐硼挥发抑制的初步研究

通过热分析手段研究氧化镧对铝硼硅酸盐玻璃熔制过程中硼挥发量的影响。TG测试结果表明,随着玻璃配合料中氧化镧质量分数的增加,硼挥发量逐渐降低。当La2O3与B2O3摩尔比超过0.2时,这种趋势变化不明显。同时通过XRD分析出了不同热处理机制下,氧化镧和硼酸的混合物的产物在650,℃时,除了La2O3和H3BO3之外,还有新相LaBO3生成;800,℃时,产物为La（BO2）3。与碱土金属硼酸盐相比,La（BO2）3和LaBO3具有更低的饱和蒸汽压,这是硼的挥发量降低的根本原因。     

Vibrational Spectra of Vitreous B2O3.xH2O

The infrared absorption spectra of boron oxide glasses of low and high water content have been obtained in the 400- to 4000-cm.⁻¹ region using thin films or fine powders dispersed in a liquid. A structural interpretation of the glass spectra has been made with the aid of the spectra of the closely related materials boric acid, orthorhombic metaboric acid, and partly deuterated boron oxide glass of high water content. It has been shown that the glass spectra are consistent with a random-network structure in which each boron is triangularly coordinated by three oxygens and that the presence of water leads to weak hydrogen bonding between oxygen atoms. No evidence for a substantial amount of tetrahedral coordination of boron by oxygen has been found in glasses of either low or high water content.     

Sintering of Silicon Carbide/Molybdenum Disilicide Composites Using Boron Oxide as an Additive

Sintering of silicon carbide reinforced molybdenum disilicide-Composites using boron oxide as an additive was performed. The addition of boron oxide to the composites was found to be beneficial. It reduced the processing temperature, resulted in smaller grain sizes, and increased the flexural strength of the composites. Formation of glassy boundary phase was also found.