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1.
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.  相似文献   

2.
The compositionally graded and homogeneous Ba(ZrxTi1−x)O3 (BZT) thin films were fabricated on LaNiO3 (LNO) buffered Pt/Ti/SiO2/Si and Pt/Ti/SiO2/Si substrates by a sol–gel deposition method, respectively. These films crystallized into a single perovskite phase. The BZT thin films deposited on LaNiO3/Pt/Ti/SiO2/Si substrates had a highly (1 0 0) preferred orientation and exhibited a preferred (1 1 0) orientation when the thin films were deposited on Pt/Ti/SiO2/Si substrates. The LNO and Ba(Zr0.30Ti0.70) served as seed layer on Pt/Ti/SiO2/Si substrates and analyze the relationship of seed layer, microstructure and dielectric behavior of the thin films. The compositionally graded thin films from BaTiO3 to BaZr0.35Ti0.65O3 were fabricated on LNO/Pt/Ti/SiO2/Si substrates. The tunability behavior of compositionally graded films was analyzed in order to produce optimum effective dielectric properties. The dielectric constant of BaZrxTi1−xO3 compositionally graded thin films showed weak temperature dependence. This kind of thin films has a potential in a fabrication of a temperature stable tunable device.  相似文献   

3.
The surface properties of a series of V2O5 catalysts supported on different oxides (Al2O3, H–Na/Y zeolite, MgO, SiO2, TiO2 and ZrO2) were investigated by transmission electron microscopy and FTIR spectroscopy augmented by CO and NH3 adsorption. In the case of the V2O5/SiO2 system TEM images evidenced the presence of V2O5 crystallites, whereas such segregated phase was not observed for the other samples. VOx species resulted widely spread on the surface of Al2O3, H–Na/Y zeolite, MgO and SiO2, whereas on TiO2 and ZrO2 they are assembled in a layer covering almost completely the support. Furthermore, evidences for the presence in this layer of V–OH Brønsted acid sites close to the active centres were found. It is proposed that propene molecules primarily produced by oxydehydrogenation of propane can be adsorbed on this acid centres and then undergo an overoxidation by reaction with redox centres in the neighbourhood. This features could account for the low selectivity of V2O5/TiO2 and V2O5/ZrO2 catalysts.  相似文献   

4.
Developing catalysts with not only hydrogenation activity but also cracking activity is very important for the advancement of suspended-bed hydrocracking technology. Within this respect, MoS2/SiO2-Al2O3 bifunctional catalyst is a kind of typical catalysts with both hydrogenation and cracking activity. Herein, a series of Zr-doped SiO2-Al2O3 mixed oxides were synthesized by a sol-gel coupled with hydrothermal method. The synthesized mixed oxides were characterized for chemical structures and acidic properties. It is found that doping SiO2-Al2O3 with Zr atoms significantly increases the numbers of acidic sites. The Zr-doped SiO2-Al2O3mixed oxides were then combined with dispersed MoS2, which was in-situ produced from oil-soluble Mo precursors, to fabricate a novel kind of bifunctional catalysts for suspended-bed hydrocracking of heavy oils. Owing to the significantly increased numbers of acidic sites in Zr-doped SiO2-Al2O3 mixed oxides, corresponding bifunctional catalysts demonstrate much enhanced activity for suspended-bed hydrocracking of heavy oils in relative to MoS2/SiO2-Al2O3 bifunctional catalysts.  相似文献   

5.
Ag-based catalysts supported on various metal oxides, Al2O3, TiO2, and TiO2–Al2O3, were prepared by the sol–gel method. The effect of SO2 on catalytic activity was investigated for NO reduction with propene under lean burn condition. The results showed the catalytic activities were greatly enhanced on Ag/TiO2–Al2O3 in comparison to Ag/Al2O3 and Ag/TiO2, especially in the low temperature region. Application of different characterization techniques revealed that the activity enhancement was correlated with the properties of the support material. Silver was highly dispersed over the amorphous system of TiO2–Al2O3. NO3 rather than NO2 or NOx reacted with the carboxylate species to form CN or NCO. NO2 was the predominant desorption species in the temperature programmed desorption (TPD) of NO on Ag/TiO2–Al2O3. More amount of formate (HCOO) and CN were generated on the Ag/TiO2–Al2O3 catalyst than the Ag/Al2O3 catalyst, due to an increased number of Lewis acid sites. Sulfate species, resulted from SO2 oxidation, played dual roles on catalytic activity. On aged samples, the slow decomposition of accumulated sulfate species on catalyst surface led to poor NO conversion due to the blockage of these species on active sites. On the other hand, catalytic activity was greatly enhanced in the low temperature region because of the enhanced intensity of Lewis acid site caused by the adsorbed sulfate species. The rate of sulfate accumulation on the Ag/TiO2–Al2O3 system was relatively slow. As a consequence, the system showed superior capability for selective adsorption of NO and SO2 toleration to the Ag/Al2O3 catalyst.  相似文献   

6.
The physico-chemical characteristics and the reactivity of sub-monolayer V2O5-WO3/TiO2 deNOx catalysts is investigated in this work by EPR, FT-IR and reactivity tests under transient conditions. EPR indicates that tetravalent vanadium ions both in magnetically isolated form and in clustered, magnetically interacting form are present over the TiO2 surface. The presence of tungsten oxide stabilizes the surface VIV and modifies the redox properties of V2O5/TiO2 samples. Ammonia adsorbs on the catalysts surface in the form of molecularly coordinated species and of ammonium ions. Upon heating, activation of ammonia via an amide species is apparent. V2O5-WO3/TiO2 catalysts exhibits higher activity than the binary V2O5/TiO2 and WO3/TiO2 reference sample. This is related to both higher redox properties and higher surface acidity of the ternary catalysts. Results suggest that the catalyst redox properties control the reactivity of the samples at low temperatures whereas the surface acidity plays an important role in the adsorption and activation of ammonia at high temperatures.  相似文献   

7.
The direct decomposition of nitric oxide (NO) over barium catalysts supported on various metal oxides was examined in the absence and presence of O2. Among the Ba catalysts supported on single-component metal oxides, Ba/Co3O4 and Ba/CeO2 showed high NO decomposition activities, while Ba/Al2O3, Ba/SiO2, and Ba/TiO2 exhibited quite low activities. The effect of an addition of second components to Co and Ce oxides was further examined, and it was found that the activities were significantly enhanced using Ce–Mn mixed oxides as support materials. XRD results indicated the formation of CeO2–MnOx solid solutions with the cubic fluorite structure. O2-TPD of the CeO2–MnOx solid solutions showed a large desorption peak in a range of relatively low temperature. The BET surface areas of the CeO2–MnOx solid solutions were larger than those of pure CeO2 and Mn2O3. These effects caused by the addition of Mn are responsible for the enhanced activities of the Ba catalysts supported on Ce–Mn mixed oxides.  相似文献   

8.
Mesostructured SiO2–TiO2 mixed oxides have been prepared by a soft-templating sol–gel route, using a non-ionic triblock copolymer as structure-directing agent. Tetraethylorthosilicate (TEOS) and titanium tetraisopropoxide (TTIP) have been employed as Si and Ti sources, respectively. Using a prehydrolysis TEOS step allows mixed oxides to be produced with a homogeneous porosity and with no phase segregation, in a wide range of Si/Ti compositions. Both the hydrolysis molar ratio and the silicon content have been found to be important factors determining the final properties of these materials. For instance, mixed oxides containing low silicon concentrations exhibit N2 physisorption isotherms typical of mesoporous materials, although with an important contribution of microporosity. On the other hand, increasing the hydrolysis molar ratio makes more difficult to reach a total dispersion of SiO2 through the TiO2 matrix. Even with low SiO2 loadings, the thermal stability is effectively enhanced, when compared to the equivalent pure TiO2 materials, as a consequence of a delay in the titania crystallization to anatase. Thus, after calcination at 300 °C for 3 h, mixed oxides containing low Si/Ti ratios (20/80) show BET surface area in the range 290–346 m2/g, while pure TiO2 materials largely collapse under the same treatment and their BET surface area drop strongly to values around 125 m2/g. This synthesis route, therefore, provides mesoporous TiO2-rich materials with enhanced stability and textural properties, which is of high interest for applications as catalysts and supports.  相似文献   

9.
Hu Chun  Tang Yuchao  Tang Hongxiao 《Catalysis Today》2004,90(3-4):325-materials
TM/TiO2/SiO2 photocatalysts were prepared by the photodeposition method using transition metal salts (TM=Fe3+, Co2+, Ni2+ and Cu2+) as precursors and the surface bond-conjugated TiO2/SiO2 as supporter in N2 atmosphere, and were characterized by XRD, XPS, UV-Vis diffuse reflection and zeta-potential. Their photocatalytic activities were evaluated using reactive brilliant red K-2G (K-2G) and cationic blue X-GRL (CBX) showing different adsorption behavior on the oxides. Fe, Cu supported TiO2/SiO2 can efficiently extend the light absorption to the visible region. XPS analysis verified that the introduction of transition metal lead to the changes of the electronic environmental of Ti cations and the zeta-potential of oxides. As a result, K-2G has higher adsorption on the modified TiO2/SiO2 than that on the baked one, while the adsorption of CBX has a little change on the both oxides. At the same time, for the photodegradation of K-2G, Fe3+, Co2+, Ni2+-modified catalysts show that their photoactivities are 3.3–2.2 times higher than the bare one. On the contrast, all transition-metal-supported catalysts have no significant activity improvement except that Fe/TiO2/SiO2 shows 1.68 times higher activity for the photodegradation of CBX. The results indicate that the photoactivity could be increased in photodegradation of dyes by changing the performances of adsorption to dyes and absorption to light of photocatalyst.  相似文献   

10.
采用浸渍法将不同含量的Cr2O3负载在工业V-Mo/Ti脱硝催化剂上,并通过XRD、NH3-TPD、H2-TPR、XPS、N2-吸附脱附、拉曼光谱等手段对催化剂进行表征分析。使用固定床微型反应评价装置对不同催化剂进行了脱硝性能检测。结果表明:工业V-Mo/Ti脱硝催化剂上负载Cr2O3,对催化剂的孔结构影响较小;V-Mo-Cr/Ti催化剂与V-Mo/Ti催化剂相比具备更多的表面酸量。但由于受Cr2O3的影响,催化剂的还原性能较低,化学吸附氧含量较少。与V-Mo/Ti催化剂相比,V-Mo-Cr/Ti催化剂在250~430 ℃温度区间内的脱硝效率较低,N2O生成量较多。  相似文献   

11.
The catalytic oxidation of sulfur dioxide to sulfur trioxide over several binary (MxOy/TiO2) and ternary (V2O5/MXOY/TiO2) supported metal oxide catalysts was systematically investigated. The supported metal oxide components were essentially 100% dispersed as surface metal oxide species, as confirmed by Raman spectroscopy characterization. The sulfur dioxide oxidation turnover frequencies of the binary catalysts were all within an order of magnitude (V2O5/TiO2>Fe2O3/TiO2>Re2O7/TiO2  CrO3/TiO2  Nb2O5/TiO2>MoO3/TiO2  WO3/TiO2). An exception was the K2O/TiO2 catalysts, which is essentially inactive for sulfur dioxide oxidation. With the exception of K2O, all of the surface metal oxide species present in the ternary catalysts (i.e., oxides of V, Fe, Re, Cr, Nb, Mo and W) can undergo redox cycles and oxidize SO2 to SO3. The turnover frequency for sulfur dioxide oxidation over all of these catalysts is approximately the same at both low and high surface coverages. This indicates that the mechanism of sulfur dioxide oxidation is not sensitive to the coordination of the surface metal oxide species. A comparison of the activities of the ternary catalysts with the corresponding binary catalysts suggests that the surface vanadium oxide and the additive surface metal oxide redox sites act independently without synergistic interactions. The V2O5/K2O/TiO2 catalyst showed a dramatic reduction in the catalytic activity in comparison to the unpromoted V2O5/TiO2 catalyst. The ability of K2O to significantly retard the redox potential of the surface vanadia species is primarily responsible for the lower catalytic activity of the ternary catalytic system. The fundamental insights generated from this research can potentially assist in the molecular design of the air pollution control catalysts: (1) the development of catalysts for low temperature oxidation of SO2 to SO3 during sulfuric acid manufacture (2) the design of efficient SCR DeNOx catalysts with minimal SO2 oxidation activity and (3) improvements in additives for the simultaneous oxidation/sorption of sulfur oxides in petroleum refinery operations.  相似文献   

12.
TiO2 nanocrystalline particles dispersed in SiO2 have been prepared by the sol-gel method using titanium- and silicon-alkoxides as precursors. Nano-composite thin films were formed on the glass substrates by dip-coating technique and heat treated at temperatures up to 500 °C for 1 h. The size of the TiO2 nanocrystalline particles in the TiO2–SiO2 solution ranged from 5 to 8 nm. The crystalline structure of TiO2 powders was identified as the anatase phase. As the content of SiO2 increased, the anatase phase tended to be stabilized to higher temperature. TEM results revealed the presence of spherical TiO2 particles dispersed in a disk-shaped glassy matrix. Photocatalytic activity of the TiO2–SiO2 (1:1) thin films showed decomposition of 95% of methylene blue solution in 2 h and a contact angle of 10°. The photocatalytic decomposition of methylene blue increased and the contact angle decreased with the content of TiO2 phase. TiO2–SiO2 with the molar ratio of 1:1 showed a reasonable combination of adhesion, film strength, and the photocatalytic activity.  相似文献   

13.
The water-gas shift (WGS) activity of platinum catalysts dispersed on a variety of single metal oxides as well as on composite MOx/Al2O3 and MOx/TiO2 supports (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Y, Zr, La, Ce, Nd, Sm, Eu, Gd, Ho, Er, Tm) has been investigated in the temperature range of 150–500 °C, using a feed composition consisting of 3% CO an 10% H2O. For Pt catalysts supported on single metal oxides, it has been found that both the apparent activation energy of the reaction and the intrinsic rate depend strongly on the nature of the support. In particular, specific activity of Pt at 250 °C is 1–2 orders of magnitude higher when supported on “reducible” compared to “irreducible” metal oxides. For composite Pt/MOx/Al2O3 and Pt/MOx/TiO2 catalysts, it is shown that the presence of MOx results in a shift of the CO conversion curve toward lower reaction temperatures, compared to that obtained for Pt/Al2O3 or Pt/TiO2, respectively. The specific reaction rate is in most cases higher for composite catalysts and varies in a manner which depends on the nature, loading, and primary crystallite size of dispersed MOx. Results are explained by considering that reducibility of small oxide particles increases with decreasing crystallite size, thereby resulting in enhanced WGS activity. Therefore, evidence is provided that the metal oxide support is directly involved in the WGS reaction mechanism and determines to a significant extent the catalytic performance of supported noble metal catalysts. Results of catalytic performance tests obtained under realistic feed composition, consisting of 3% CO, 10% H2O, 20% H2 and 6% CO2, showed that certain composite Pt/MOx/Al2O3 and Pt/MOx/TiO2 catalysts are promising candidates for the development of active WGS catalysts suitable for fuel cell applications.  相似文献   

14.
The interactions between metalogranically derived bismuth oxide films and Pt/Ti/SiO2/Si substrates have been investigated in this study. The diffusion of bismuth species to the substrate and that of titanium species to the film surface occur during the heating processes, and pluralistic Bi-Ti-O phases are formed. With an increase in the heating temperature, the diffusion of titanium species is enhanced, thereby forming the compounds with a high Ti/Bi ratio in films. Based on analysis of SEM and AFM, the microstructure of films are significantly varied by the diffusion of titanium species, which results in the formation of large grains on film surface and causes a significant increase in roughness of films. The above results imply that the interface between bismuth-layered perovskite films and Pt/Ti/SiO2/Si substrates would be influenced by the interdiffusion of bismuth and titanium species.  相似文献   

15.
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.  相似文献   


16.
《Catalysis Today》2002,75(1-4):203-209
A new environmentally friendly method for the production of 2,3,5-trimethyl-1,4-benzoquinone (TMBQ, Vitamin E precursor) based on the oxidation of 2,3,6-trimethylphenol (TMP) with aqueous H2O2 over various Ti-containing mesoporous silicate materials is reported. Both well-organized Ti-containing mesoporous mesophase silicate (Ti-MMM), having hexagonal arrangement of uniform mesopores, and amorphous TiO2–SiO2 mixed oxides (aerogels and xerogels) produced TMBQ with good to high yield. All the materials studied have been proved to operate as truly heterogeneous catalysts. No titanium leaching occurred from the solid matrixes during the oxidation process. Titanium dispersion and its accessibility were found to be crucial factors determining the catalytic properties. For samples with similar titanium loading, both the catalytic activity and TMBQ yield appeared to fall in the order TiO2–SiO2 aerogel>Ti-MMM>TiO2–SiO2 xerogel and correlate with average mesopore diameter and mesopore volume. The best results (96–98% selectivity to TMBQ at 99–100% TMP conversion) were obtained with TiO2–SiO2 aerogels, containing 1.7–6.5 wt.% Ti.  相似文献   

17.
Mo/TiO2 catalysts were modified with Nb by two different methods, sol–gel and surface deposition, in order to study the effect of Nb incorporation on the thiophene HDS activity. The results show that the formation of Nb–Ti mixed oxides leads to catalysts with poor HDS activity while the deposition of Nb oxide species on the surface of TiO2 leads to catalysts with activities larger than those of Mo/Al2O3 and Mo/TiO2. This increase in activity was attributed to the formation of a larger population of Mo sulfur anionic vacancies when Nb was surface deposited on the TiO2.  相似文献   

18.
从研究应用角度出发, 综述了近年来H2O2/固体催化剂氧化脱硫体系中载体的研究进展和发展趋势, 分别从单一氧化物载体、复合氧化物载体、活性炭载体、分子筛及复合分子筛载体4个方面论述了氧化脱硫催化剂载体各自的优缺点及应用成果。单一氧化物载体重点介绍了Al2O3、TiO2、SiO2、ZrO2;复合氧化物载体主要对二元复合氧化物进行了综述;重点介绍了以ZSM-5、SBA-15、MCM-41、HMS为代表的分子筛及复合分子筛载体。最后将不同类型载体的结构特点、反应优缺点等进行了归纳总结, 展望了氧化脱硫催化剂载体未来的研究方向, 并提出分子筛及复合分子筛载体将是氧化脱硫催化剂载体研究的焦点。  相似文献   

19.
通过球磨混合法,制备TiO2、SiO2和TiO2+SiO2掺杂的Al2 O3粉体,经不同温度煅烧后进行X射线衍射(XRD)测试,比较研究这三种掺杂对Al2 O3粉体相转变温度的影响.研究结果表明,TiO2、SiO2掺杂对γ-Al2 O3向α-Al2 O3的相转变均有促进作用.在掺杂质量分数为0.5%的情况下,二者可分别...  相似文献   

20.
金其奇  谢峻林  李凤祥  齐凯  方德  何峰 《化工进展》2019,38(3):1411-1418
为了探究涂层组分对整体式低温选择性催化还原(SCR)脱硝催化剂性能的影响,本文使用锰氧化物(MnO x )、氧化物涂层(TiO2、SiO2及Al2O3)、堇青石(CC)基体制备整体式涂层催化剂,考察催化剂牢固度以及脱硝活性。结果表明:在200℃ 时,对于MnO x /Al2O3/CC催化剂,MnO x 负载率为6%(质量分数)时脱硝效率最高为95%;对于MnO x /TiO2/CC,负载率为6%~12%时脱硝效率相差不大,为75%左右;对于MnO x /SiO2/CC,负载率12%时脱硝效率80%。样品牢固度排列顺序如下:MnO x /Al2O3/CC > MnO x /SiO2/CC > MnO x / TiO2 /CC。通过BET、SEM、TG、Raman、H2-TPR等测试与分析方法发现:影响催化剂性能的因素主要为活性组分MnO x 状态以及载体性能的差异。Al2O3涂层比表面积适中,作为载体活性好;SiO2涂层虽然比表面积大、牢固度好,但作为载体活性差;TiO2作为涂层比表面积较小,溶胶中溶剂挥发快使得涂层表面不均匀。  相似文献   

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