Properties of TiO_2-SiO_2 Mixed Oxides and Photocatalytic Oxidation of Heptane and Sulfur Dioxide

A series of TiO 2-XSiO 2[X denotes the molar fraction(%) of silica in the mixed oxides] with different \{n(Ti)\}/n(Si) ratios was prepared with ammonia water as a hydrolysis catalyst. The photocatalysts prepared were characterized by XRD, thermal analysis, FTIR, UV-Vis and SPS. The characterization results of FTIR and UV-Vis spectra show that Ti atoms were gradually changed from octahedral coordination to tetrahedral coordination with the addition of silica, which is not beneficial for obtaining strong Brnsted acidity and higher photocatalytic activity. The photocatalytic activity experiments, which were conducted by using heptane(or SO 2) as the model reactant, showed that TiO 2-SiO 2 containing a suitable amount of silica can exhibit much higher photocatalytic activity than pure TiO 2. The enhanced photocatalytic activity can be attributed to three following factors: (1) smaller crystalline size; (2) higher thermal stability; (3) the new strong Brnsted acidity.

A rationale for the development of thermally stable nanostructured CeO_2-ZrO_2-containing mixed oxides

CeO2-ZeO2 solid solutions are extensively used as oxygen storage promoters in the current automotive three-way catalysts. High thermal stability of the textural properties is one of the most important requirements for practical application since temperatures up to 1273 K are easily experienced by these materials under real working conditions. In the present paper, we investigated how hydrothermal treatments applied to cakes of doped and undoped ZrO2-rich CeO2-ZrO2 precursors might improve the thermal stability of the final CeO2-ZrO2 solid solution. A rationale was developed that allowed to correlate the morphology of the hydrothermaUy treated cake with the thermal stability at 1273 K of the final product, which did not depend on the composition of the mixed oxides.

Highly Dispersed Pd Nanoparticles Supported on Zr-Doped MgAl Mixed Metal Oxides for 2-Ethylanthraquinone Hydrogenation

In this study,Pd-Mg(Al)-LDH/γ-Al2O3 and Pd-Mg(Al)Zr-LDH/γ-Al2O3 precursors were synthesized by impregnating Na2PdCl4 on Mg(Al)-LDH/γ-Al2O3 and Mg(Al)Zr-LDH/γ-Al2O3,and then the precursors were calcinated and reduced to obtain Pd-Mg(Al)-MMO/γ-Al2O3 and Pd-Mg(Al)Zr-MMO/γ-Al2O3 catalysts.Compared with Pd/γ-Al2O3 catalyst,the hydrogenation efficiency of Pd-Mg(Al)-MMO/γ-Al2O3 and Pd-Mg(Al)Zr-MMO/γ-Al2O3 increased by 15.7%and 24.0%,respectively.Moreover,the stability of Pd-Mg(Al)Zr-MMO/γ-Al2O3 catalyst was also higher than that of Pd/γ-Al2O3.After four runs,the hydrogenation efficiency of Pd/γ-Al2O3 decreased from 12.1 to 10.0 g/L,while that of Pd-Mg(Al)Zr-MMO/γ-Al2O3 decreased from 15.0 to 14.3 g/L.The active aquinones selectivities of all catalysts were almost 99%.The structures of the catalysts were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),N2 adsorption–desorption,inductively coupled plasma-atomic emission spectrometry(ICP-AES),CO chemisorption analysis,transmission electron microscopy(TEM),temperature-programmed reduction with hydrogen(H2-TPR),and X-ray photoelectron spectroscopy(XPS).The results indicate that the improved catalytic performance is attributed to the stronger interaction between Pd and Mg(Al)Zr-MMO/γ-Al2O3,smaller Pd particle size and higher Pd dispersion.This work develops an effective method to synthesize highly dispersed Pd nanoparticles based on the layered double hydroxides(LDHs)precursor.

Ce_xTi_(1-x)O_2 Mixed Oxides Supported CuO Catalyst for NO Reduction by CO

Ce x Ti 1- x O 2 mixed oxides of different mole ratios ( x =0, 0.1, 0.2～0.9, 1.0) were prepared by co precipitation of TiCl 4 with Ce(NO 3) 3 and then loaded with different amounts of CuO. The effects of CuO on NO+CO reaction were investigated, and the structure and reductive properties of various CuO/Ce x Ti 1- x O 2 were characterized by the methodologies of BET, TPR and XRD. The results show that different Ce/Ti mole ratios and calcination temperatures induce changes of structure and reductive properties of the Ce x Ti 1- x O 2 mixed oxides. When x =0.1～0.5, amorphous CeTi 2O 6 phase mainly forms at 650 ℃ compared to the formation of CeTi 2O 6 which crystallizes at 800 ℃. When x >0.6, some TiO 2 enters the CeO 2 lattice and a CeO 2 TiO 2 solid solution is formed. The activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 650 ℃ is largely affected by the x values, which is the highest when x =0.3, 0.4 and 0.9. The NO conversion reaches 70% at a reaction temperature of 150 ℃. By comparison, the x values have little effect on the activity of 6%CuO/Ce x Ti 1- x O 2 calcined at 800 ℃ . There are strong interactions between CuO and CeTi 2O 6, i.e., formation of the CeTi 2O 6 phase shifts the CuO reduction peak temperature from 380 to 200 ℃, and CuO, in turn, shifts the CeTi 2O 6 reduction peak temperature from 600 to 300 ℃.

Comparative structural and electrochemical properties of mixed P2/O′3-layered sodium nickel manganese oxide prepared by sol-gel and electrospinning methods:Effect of Na-excess content

The effect of Na-excess content in the precursor on the structural and electrochemical performances of sodium nickel manganese oxide(NNMO)prepared by sol-gel and electrospinning methods is investigated in this paper.X-ray diffraction results of the prepared NNMO without adding Na-excess content indicate sodium loss,while the mixed phase of P2/O′3-type layered NNMO presented after adding Na-excess content.Compared with the sol-gel method,the secondary phase of NiO is more suppressed by using the electrospinning method,which is further confirmed by field emission scanning electron microscope images.N_(2) adsorption-desorption isotherms show no remarkably difference in specific surface areas between different preparation methods and Na-excess contents.The analysis of X-ray absorption near edge structure indicates that the oxidation states of Ni and Mn are+2 and+4,respectively.For the electrochemical properties,superior electrochemical performance is observed in the NNMO electrode with a low Na-excess content of 5wt%.The highest specific capacitance is 36.07 F·g^(-1)at0.1 A·g^(-1)in the NNMO electrode prepared by using the sol-gel method.By contrast,the NNMO electrode prepared using the electrospinning method with decreased Na-excess content shows excellent cycling stability of 100%after charge-discharge measurements for 300 cycles.Therefore,controlling the Na excess in the precursor together with the preparation method is important for improving the electrochemical performance of Na-based electrode materials in supercapacitors.

Electrical Conductivity of Sintered Chromia Mixed with TiO_2,CuO and Mn-Oxides

The electrical conductivity of sintered Cr2O3 mixed with 2% and 5% （in molar fraction） TiO2 or CuO was investigated in the temperature range 500-900℃ in air and in At/4 vol. pct H2 atmospheres. The effect of different Mn-oxides on the electrical conductivity of Cr2O3 was also studied under the same conditions. From the conductivity measurements it is established that additions of TiO2 change the defect structure of Cr2O3 and the effect of TiO2 on the electrical conductivity is controlled by TiO2 concentration as well as temperature and O2 partial pressure of the surrounding atmosphere. The conductivity of Cr2O3 increased in air and decreased in the At/H2 atmosphere by CuO additions. The effect of CuO was discussed with possible changes in the defect concentration in Cr2O3. Mixing of Cr2O3 with different Mn-oxides at the same Mn to metal atom fraction decreased the conductivity in air and in Ar/H2 atmospheres. No clear correlation between the spinel fraction and the changes in conductivity could be found.

Effect of Calcination Temperature on Structure and O_2 Desorption Properties of Ce_xPr_(1-x)O_(2-δ) Mixed Oxides

A series of CexPr1-xO2-δ (x=0, 0.5, 0.9, 1.0) mixed oxide calcined at different temperatures were synthesized by sol-gel method and characterized by Raman, XRD and O2-TPD techniques. When x=0.9, only a cubic phase CeO2 is observed. When x=0.5, the compound was combined by Pr6O11 and CeO2 mixed oxides. For CexPr1-xO2-δ (x=0.5, 0.9)samples 465 cm-1 Raman peak is attributed to the Raman active F2g mode of CeO2. The broad peak at about 570 cm-1 can be linked to lattice defects resulting in oxygen vacancies. The crystallite size of the samples increased as increasing the calcined temperature. But the increased value of Ce0.9Pr0.1O2-δ and Ce0.5Pr0.5O2-δ is smaller than single CeO2 and Pr6O11 obviously. It reveals that the insertion of Pr atom into the ceria lattice could enhance the sintering resistance and thermal stability of the mixed oxides. Calcination temperatures had great effect on the peak intensity for CeO2 but less effect on Ce0.8Pr0.2O2-δ in Raman spectra, and it may be caused by the colors transformation of the mixed oxides. The result of O2-TPD experiment indicates that the formation of solid solution has elevation the stabilization and thermal stability of the mixed oxides.

Preparation of Mesoporous Ce_(0.5)Zr_(0.5)O_2 Mixed Oxide by Hydrothermal Templating Method

Mesoporous Ce0.5Zr0.5O2 mixed oxide with high specific surface area was synthesized under basic condition in the presence of non-ionic surfactant PEG-4000. The effect of synthesis conditions, such as synthesis temperature and the molar ratio of PEG-4000/（[ Ce] ＋ [ Zr] ）, on specific surface area were investigated. The products were characterized by transmission electron microscopy, powder X-ray diffraction, and nitrogen adsorption-desorption measurements, respectively. The results showed that synthesis temperature and the molar ratio of PEG-4000/（[ Ce] ＋ [ Zr] ） had great influence on specific surface area. Under the optimum synthesis conditions, the prepared Ce0.5Zr0.5O2 mixed oxide presented cubic fluorite-type structure and possessed high surface area of 148.6 m2·g^-1 with wormlike pores.

MOLECULAR BEAM STUDIES ON OXIDATION OF CO ON Pd WITH DIFFERENT MIXED RATIOS OF P_(CO) TO P_(O2) ~*

Here some steady-state experiments on oxidation of CO on Pd were performed on a molecular beam apparatus. It is found that the characteristics of the rate of CO_2 formation r versus substrate temperature T are dependent on the ratio P=P_(CO)/P_(O2) in the mixed beam. These characteristics are related to the complicated interactions of co-adsorbed CO and O particles on Pd surface.

TiO_2-SiO_2双组分膜结构与光催化性能的研究

采用溶胶-凝胶法制备了不同Si/Ti比的TiO2-SiO2双组分膜.用紫外光照射亚甲基蓝的分解实验比较薄膜的光催化性能.通过XRD、FTIR、HRTEM、FE-SEM、AFM以及UV-VS-NIR分光光度计等分析手段对薄膜的结构和光学性能进行了表征.结果表明:适量SiO2的引入,显著提高了TiO2薄膜的光催化活性,Si/Ti比为0.2时薄膜的光催化活性为最佳. SiO2引入TiO2薄膜后,生成了Ti-O-Si玻璃相和无定形SiO2,这两种物相聚集在TiO2 晶界周围,有效地阻止了TiO2的晶粒长大,提高了锐钛矿相向金红石相的转变温度,使复合薄膜经过500℃热处理后,只有锐钛矿相存在,有利于薄膜的光催化活性的提高.

SO_4^(2-)/TiO_2-SiO_2的制备及对甲基橙的光催化降解

0引言 水中难降解有机物的治理已成为当今重要的环境问题,对新型高效水处理剂的需求也愈加迫切.

La／TiO_2-SiO_2薄膜的光催化性能研究

采用溶胶-凝胶法制备了不同掺杂量的La／TiO2-SiO2复合薄膜．通过XRD、 FE-SEM和AFM研究了复合薄膜的微观结构,采用紫外光照射下亚甲基蓝的分解实验比较薄膜的光催化性能．结果表明:La掺杂可显著提高TiO2-SiO2复合薄膜的光催化活性,以5％掺杂量为最佳,其光降解率比掺杂前提高了约23％．薄膜活性提高的主要原因是La掺杂后细化了TiO2的晶粒,提高了薄膜的比表面积,使其具有更高的氧化还原电势,La2+取代Ti4+ 进入到TiO2晶格,引起晶格膨胀,这种不同价离子的取代导致TiO2粒子表面电荷分布不平衡,从而提高了光生电子-空穴的分离效率．

TiO_2-SiO_2复合气凝胶:常压干燥制备及性能表征

以廉价的四氯化钛和工业水玻璃为原料,通过溶胶-凝胶法制得TiO2-SiO2复合湿凝胶,用三甲基氯硅烷(TMCS)/乙醇(EtOH)/正己烷(Hexane)混合溶液对湿凝胶进行改性,常压干燥制备了TiO2-SiO2复合气凝胶。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、红外光谱(FTIR)、X射线衍射(XRD)及N2吸附/脱附法对复合气凝胶的形貌和性质进行了分析。结果表明,TiO2-SiO2复合气凝胶具有连续多孔结构,150℃干燥后复合气凝胶的比表面积为1 076 m2.g-1,孔体积为4.96 cm3.g-1;经550℃热处理后,复合气凝胶仍然具有高的孔隙率,比表面积为856 m2.g-1,孔体积为3.46 cm3.g-1。吸附和光催化降解罗丹明B的结果表明,复合气凝胶同时具有较好的吸附和光催化性能,其吸附/光催化协同作用活性优于纯SiO2气凝胶和锐钛矿TiO2粉末;且重复利用四次降解率仍然可达到89%。

SO_4^(2-)/TiO_2-SiO_2固体超强酸的结构及其光催化性能

A series of SO 2- 4/TiO 2 SiO 2 catalysts with different mass fractions of SiO 2 were prepared by sol gel method. The effect of adding SiO 2 on the crystal structure, specific surface area, oxygen adsorption, and acidity of SO 2- 4/TiO 2 catalyst and its photocatalytic property for degradation of bromomethane was studied. The results showed that the specific surface area and amount of oxygen adsorption of catalyst were increased by addition of SiO 2, leading to the obvious increase on photocatalytic activity of SO 2- 4/TiO 2 SiO 2 catalysts and mineralization ratio of bromomethane. Comparing with SO 2- 4/TiO 2, the acidic strength and anti moisture ability of SO 2- 4/TiO 2 SiO 2 catalyst were decreased.

超细CuO/ZnO/TiO_2-SiO_2的表征和CO_2加氢合成甲醇性能研究

用溶胶 凝胶法制备了铜、锌质量分数不同的超细Cu/ZnO/TiO2 SiO2催化剂。通过BET、TPR、XRD及FT IR等方法对催化剂前驱体CuO/ZnO/TiO2 SiO2的物化性能进行表征。用固定床连续流动微反装置,考察催化剂CO2加氢合成甲醇的催化性能。研究结果表明,溶胶 凝胶法制备的CuO/ZnO/TiO2 SiO2催化剂比表面较大(240m2/g～590m2/g),孔径分布单一,晶相组成为CuO。随着铜、锌质量分数的增大,催化剂的比表面积减小,最可几孔径增大;CuO微晶结晶度增大,同时微晶尺寸逐渐增大至20nm。催化剂具有较高的反应活性和选择性,当氧化铜、氧化锌质量分数各为25%时,在260℃,2500h-1,CO2∶H2=1∶3(mol比),2.0MPa的反应条件下,甲醇时空收率为0.126g/(h·g)。

稀土Eu^3＋掺杂纳米TiO2-SiO2发光材料的制备和发光性质的研究

采用溶胶-凝胶法制备了稀土Eu3+掺杂于不同比例的纳米TiO2—SiO2复合体系,研究了基质中钛、硅摩尔配比对发光性能的影响。样品的FTIR谱图显示:纳米复合氧化物SiO2—TiO2之间发生了键合作用,形成了Ti—O—Si键;TEM显示样品的颗粒大小约为35 nm,是具有一定的单分散性的球形颗粒;XRD和SAED结果表明,样品退火至700℃后仍为单一的锐钛矿相,这说明微量硅的加入对二氧化钛的锐钛矿相有热稳定的作用。当微量的Si4+进入TiO2的晶格,取代部分Ti4+的位置时,形成了结构等电子陷阱。通过对样品的激发光谱、发射光谱分析,发现这种结构有利于将基质吸收的能量传递到发光中心,使Eu3+的465nm处7F0→5D2激发效率最高,成为最灵敏的激发线。

溶胶-凝胶法制备TiO2-SiO2多层增透膜

在酸催化体系中以钛酸丁酯为前驱体制得TiO2溶胶，以正硅酸乙酯（TEOS）为前驱体制得SiO2溶胶，采用提拉法在普通载玻片上镀膜．辅助MASS膜系设计软件进行模拟计算，得到了透射比为99％的膜片．根据理论模拟结果，实验采用交叉镀膜，制备出了宽带增透TiO2-SiO2多层膜．用紫外可见分光光度计测量了样品的透射光谱．实验发现，样品具有明显的宽带增透效果：在400～700nm波段，当光线垂直入射时，增透5．5％左右；45°角入射时，可增透10％．

V_2O_5-WO_3/TiO_2-SiO_2制备及其选择性催化还原脱硝活性

以硫酸氧钛和硅溶胶为原料,通过共沉淀法制备得到高比表面积的TiO2-SiO2复合氧化物(Ti/Si=1:1atom),并以此复合氧化物为载体用浸渍法制备了V2O5-WO3/TiO2-SiO2脱硝催化剂,考察了催化剂脱硝性能。结果表明,TiO2-SiO2复合氧化物载体出现较多的隧道孔,提高了载体的比表面积,同时Ti元素更易分布在复合氧化物的表面。相比较于纯TiO2,以复合氧化物为载体的V2O5-WO3催化剂表现出更好的活性温度窗口,催化剂表面酸性更强,催化剂对NH3的吸附性能更好,在低的NH3/NO摩尔比情况下(0.8～1.0mol?mol?1),仍然具有较好的脱硝活性,反应温度280～350℃时,脱硝率可达到98%。

TiO_2-SiO_2载体的酸性对催化剂加氢脱硫性能的影响

采用溶胶 凝胶方法制备了 TiO2 SiO2 复合氧化物, 分析表征了其酸性, 以复合氧化物为载体制备了重油催化裂化(RFCC)柴油加氢精制催化剂。结果表明, TiO2 SiO2 复合氧化物的酸性与 Ti/Si摩尔比有关。酸的类型对催化剂的脱硫性能有显著的影响, 以 TiO2 SiO2 复合氧化物载体制得的 Br sted酸(B酸)较高的催化剂, 对分子结构相对简单的苯并噻吩类硫化物有较好的脱除性能; Lewis 酸(L 酸)较高的催化剂则有利于芳烃的加氢饱和与取代二苯并噻吩的脱除。采用F改性的方法可以提高载体的强 L酸量和催化剂初始阶段的加氢脱硫性能及对二苯并噻吩的脱除性能, 但 RFCC 柴油中存在的烯烃及碱性氮化物易使催化剂的活性下降。

医用NiTi合金表面溶胶-凝胶法制备TiO_2-SiO_2薄膜

采用溶胶－凝胶法在ＮｉＴｉ形状记忆合金表面制备了ＴｉＯ２－ＳｉＯ２复合薄膜，在提高医用ＮｉＴｉ合金的抗腐蚀性方面，收到了显著的效果．运用电化学方法对不同组成的ＴｉＯ２－ＳｉＯ２薄膜在模拟体液中的腐蚀行为进行了研究，结果表明，随薄膜中 Ｔｉ／Ｓｉ比的增加，ＴｉＯ２－ＳｉＯ２薄膜的抗腐蚀性增强．划痕试验表明 ＴｉＯ２－ＳｉＯ２（Ｔｉ／Ｓｉ＝４：１）膜与ＮｉＴｉ合金基体具有较高的界面结合强度．用原子力显微镜（ＡＦＭ）对ＴｉＯ２－ＳｉＯ２薄膜的表面形貌及表面粗糙度进行观察和分析，解释并讨论了ＴｉＯ２－ＳｉＯ２薄膜的配方组成与其抗腐蚀性的关系，ＳｉＯ２含量较少时，薄膜结构致密，膜层均匀平滑，且膜基结合力好，作为医用ＮｉＴｉ合金的表面保护层，可以使其耐腐蚀性有显著提高．