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1.
Metal oxide-modified ZnO /SiO2 catalysts were studied for the cyclo-dehydrogenation of ethylenediamine with propyleneglycol to 2-methylpyrazine at 633 K. The ZnO/SiO2 catalyst showed fairly good ethylenediamine conversion and quantitative propyleneglycol conversion with about 60 mol% of 2-methylpyrazine selectivity, which is due to the existence of large amount of unconverted intermediate, 2-methylpiperazine. Metal oxide (CuO, NiO, Co3O4)-modified ZnO/SiO2 catalysts were prepared to facilitate the dehydrogenation of 2-methylpiperazine to 2-methylpyrazine. About 82 mol% of 2-methylpyrazine selectivity was achieved on CuO and Co3O4 modified ZnO/SiO2 catalysts, with significant increases of pyrazine selectivity. The catalytic properties of the metal oxidemodified ZnO/SiO2 catalysts, pretreated with hydrogen gas as in the cyclo-dehydrogenation, were compared using the well-known probe reaction, the dehydrogenation/ dehydration of cyclohexanol to cyclohexanone or phenol/cyclohexene. The selectivities of pyrazine in the cyclo-dehydrogenation on the metal oxide-modified ZnO/SiO2 catalysts were correlated with the phenol selectivities of the probe reaction. It is proposed that the metallic site of catalyst is responsible for the formation of pyrazine from ethylenediamine dimerization. The improved 2-methylpyrazine yield on CuO/ZnO/SiO2 catalyst was explained by the proper adjustment of catalytic properties, which could be differentiated by the phenol selectivity in the cyclohexanol probe reaction. Thus, the large enhancement of 2-methylpiperazine dehydrogenation to 2-methylpyrazine and the suppression of excess pyrazine formation are supposed to occur on the metallic Cu formed in situ during the reaction during the cyclo-dehydrogenation of ethylenediamine with propyleneglycol.  相似文献   

2.
Within the framework of the density functional theory (DFT), the electronic structure of monooxodioxovanadium functional groups in tetrahedral coordination, which model the active centers (ACs) of fine supported catalysts V2O5/SiO2 and V2O5/TiO2, has been analyzed. The optimal structures of three ACs as possible models of monomeric and polymeric oxovanadium forms on the carriers with low vanadium content were determined. The modified DFT method involving the time dependence of Kohn-Sham equation (TDDFT) was used for the adopted AC models to calculate the energies of the excited states, and optical spectra of the absorption in 25000–60000 cm?1 region were reconstructed on their base. The spectrum in this region is due to O → V charge transfer. The features of electronic spectra with the charge transfer for V2O5/SiO2 and V2O5/TiO2 catalysts and the vibrational spectra of three AC models corresponding to the monomeric and dimeric oxovanadium forms of the supported catalysts V2O5/SiO2 and V2O5/TiO2 were defined. The detailed interpretation of normal vibration frequencies is given. The frequencies typical of the monomeric and dimeric oxovanadium forms on the carrier surface were identified.  相似文献   

3.
The effect of the microstructure of titanium dioxide on the structure, thermal stability, and catalytic properties of supported CuO/TiO2 and CuO/(CeO2-TiO2) catalysts in CO oxidation was studied. The formation of a nanocrystalline structure was found in the CuO/TiO2 catalysts calcined at 500°C. This nanocrystalline structure consisted of aggregated fine anatase particles about 10 nm in size and interblock boundaries between them, in which Cu2+ ions were stabilized. Heat treatment of this catalyst at 700°C led to a change in its microstructure with the formation of fine CuO particles 2.5–3 nm in size, which were strongly bound to the surface of TiO2 (anatase) with a regular well-ordered crystal structure. In the CuO/(CeO2-TiO2) catalysts, the nanocrystalline structure of anatase was thermally more stable than in the CuO/TiO2 catalyst, and it persisted up to 700°C. The study of the catalytic properties of the resulting catalysts showed that the CuO/(CeO2-TiO2) catalysts with the nanocrystalline structure of anatase were characterized by the high-est activity in CO oxidation to CO2.  相似文献   

4.
TiO2 nanoparticles were produced in the diffusion flame reactor, and the size and anatase/rutile content of TiO2 were examined by a Particle Size Analyzer and X-ray diffraction, respectively. Increase in fuel/O2 ratio, initial concentration of TiCl4 or total gas flow rate causes the larger particle size and the higher rutile composition. The photocatalytic activities of TiO2 powders were tested on the decompositions of phenol and toluene in the aqueous solution under UV irradiation. The degradation rate increases as the TiO2 particle size decreases and as the initial concentration of phenol or toluene increases. The photodegradation rate of phenol by TiO2 particles is higher than that of toluene at the same process conditions. The computational method was used to simulate the gas temperature, velocity and species mass fractions inside the diffusion flame reactor during synthesis of TiO2 nanoparticles. The measured and simulated temperature results were compared on several positions above the burner and both of them show good agreements. The typical contours of TiCl4, TiO2 mass fractions and gas velocities in flame reactor were presented.  相似文献   

5.
In this work, TiO2 and doped TiO2 photocatalysts (Fe/TiO2 and Cu/TiO2) were synthesized by the sol–gel method. The main objective of this study was to investigate the influence of dopants on the structure, morphology, and activity of the catalysts in powder and immobilized states. XRF, XRD, and SEM methods were used to characterize the catalysts. The structure and phase distribution of the nanocrystalline powders were identified by XRD. Nanoparticles crystallite size and the degree of crystallinity were affected by doping. The anatase contents of catalysts were achieved as follows: TiO2 (5.89 %) < Fe/TiO2 (42.17 %) < Cu/TiO2 (70.28 %). It was indicated that the activity of the catalysts strongly depends on the anatase content. Under the same circumstances, copper-modified TiO2 exhibited a twofold higher photocatalytic activity compared with TiO2. The nanostructured catalysts were immobilized on light expanded clay aggregate (LECA) granules in order to investigate the effect of a novel support on the activity of the catalysts. Morphological changes are recognizable in the SEM images. Activity tests indicated that the best catalytic performance was assigned to Cu/TiO2/LECA. After 120 min of irradiation, 61 % degradation of phenol in synthetic wastewater was achieved. The high photocatalytic activity of Cu/TiO2/LECA confirms that LECA is as an excellent support.  相似文献   

6.
A series of Ce–MnO x /TiO2 catalysts were prepared using a novel sol–gel template method and investigated for low-temperature selective catalytic reduction (SCR) of NO with NH3 at temperatures ranging from 353 to 473 K. The 0.07Ce–MnO x /TiO2 catalyst showed the highest activity and best resistance to SO2 poisoning. The structure and properties of the catalysts were characterized using X-ray diffraction (XRD) analysis, thermogravimetric analysis (TGA), thermogravimetry (TG)–differential scanning calorimetry (DSC)–mass spectroscopy (MS), high-resolution transmission electron microscopy (HRTEM), Brunauer–Emmett–Teller (BET) measurements, H2-temperature-programmed reduction (TPR), and NH3-temperature-programmed desorption (TPD). The superior catalytic activity of the 0.07Ce–MnO x /TiO2 catalyst was probably due to a change in the active components, an increase in surface active oxygen and surface acid sites, and lower crystallinity and larger surface area with Ce doping. Furthermore, the reduction ability also became stronger. The SO2 poisoning resistance of the 0.07Ce–MnO x /TiO2 catalyst improved because doping with Ce can effectively decrease the formation of ammonium salt on the catalyst surface and the sulfation of MnO x . In situ diffuse-reflectance infrared Fourier-transform (DRIFT) spectroscopy experiments indicated that addition of Ce could promote adsorption of NH3 and inhibit generation of some nitryl species. The SCR reactions over the catalysts mainly followed the Eley–Rideal mechanism accompanied with a partial Langmuir–Hinshelwood mechanism.  相似文献   

7.
The effects of Ru on the self-reducibility of Ru-doped Ni/MgAl2O4 catalysts, which do not need pre-reduction treatment with H2, were investigated in the steam reforming of methane (SRM). The Ru-promoted Ni/MgAl2O4 catalysts with various amounts of Ru (0–0.5 wt%) were prepared by stepwise impregnation and co-impregnation methods using hydrotalcite-like MgAl2O4 support. For comparison, Ru/MgAl2O4 catalysts with the same amount of Ru were also prepared by the impregnation method. The catalysts were characterized by the N2-sorption, XRD, H2-TPR, H2-chemisorption, and XPS methods. Ni/MgAl2O4 catalyst in the presence of even the trace amount of Ru (Ru content ≥0.05 wt%) showed higher conversion without pre-reduction as compared to Ru/MgAl2O4 catalysts in SRM under the same conditions. The self-activation of Ru–Ni/MgAl2O4 catalysts is mainly attributed to the spillover of hydrogen, which is produced on Ru at first and then reduces NiO species under reaction conditions. Besides, Ru doping makes the reduction of NiO easier. The stepwise impregnated Ru/Ni/MgAl2O4 catalyst produced superior performance as compared to co-impregnated Ru–Ni/MgAl2O4 catalyst for SRM.  相似文献   

8.
Carbon dioxide reforming (CDR) of methane to synthesis gas over supported nickel catalysts has been reviewed. The present review mainly focuses on the advantage of ceria based nickel catalysts for the CDR of methane. Nickel catalysts supported on ceria–zirconia showed the highest activity for CDR than nickel supported on other oxides such as zirconia, ceria and alumina. The addition of zirconia to ceria enhances the catalytic activity as well as the catalyst stability. The catalytic performance also depends on the crystal structure of Ni–Ce–ZrO2. For example, nickel catalysts co-precipitated with Ce0.8Zr0.2O2 having cubic phase gave synthesis gas with CH4 conversion more than 97% at 800 °C and the activity was maintained for 100 h during the reaction. On the contrary, Ni–Ce–ZrO2 having tetragonal phase (Ce0.8Zr0.2O2) or mixed oxide phase (Ce0.5Zr0.5O2) deactivated during the reaction due to carbon formation. The enhanced catalytic performance of co-precipitated catalyst is attributed to a combination effect of nano-crystalline nature of cubic Ce0.8Zr0.2O2 support and the finely dispersed nano size NiO x crystallites, resulting in the intimate contact between Ni and Ce0.8Zr0.2O2 particles. The Ni/Ce–ZrO2/θ–Al2O3 also exhibited high catalytic activity during CDR with a synthesis gas conversion more than 97% at 800 °C without significant deactivation for more than 40 h. The high stability of the catalyst is mainly ascribed to the beneficial pre-coating of Ce–ZrO2 resulting in the existence of stable NiO x species, a strong interaction between Ni and the support, and an abundance of mobile oxygen species in itself. TPR results further confirmed that NiO x formation was more favorable than NiO or NiAl2O4 formation and further results suggested the existence of strong metal-support interaction (SMSI) between Ni and the support. Some of the important factors to optimize the CDR of methane such as reaction temperature, space velocity, feed CO2/CH4 ratio and H2O and/or O2 addition were also examined.  相似文献   

9.
以反相微乳液法和沉淀法相结合制备了核壳结构TiO2@SiO2,首次用于碳酸二甲酯与苯酚酯交换合成碳酸二苯酯反应,显示较好的催化活性. 采用200 ℃焙烧的TiO2@SiO2,用量0.20 g,反应9 h,苯酚转化率达41.8%,酯交换选择性为100%. 透射电镜显示TiO2@SiO2核厚壳薄,TiO2核直径220-300 nm,SiO2壳厚度40-60 nm,具有介孔结构. TiO2@SiO2对碳酸二甲酯与苯酚酯交换反应有好的重复使用性,使用4次苯酚转化率仍保持在40%以上. TiO2与SiO2发生相互作用,Ti进入骨架形成Ti-O-Si键,骨架Ti的形成提高了TiO2@SiO2的催化性能.  相似文献   

10.
The structural properties of Au/TiO2 catalyst were studied by X-ray diffraction, UV-visible diffuse reflectance, photoluminescene, scanning transmission and electron microscope, and temperature programmed reduction. The photocatalytic activity of the catalysts was evaluated for the degradation of various azo-dyes such as methylene blue, methyl orange, reactive blue-4, and eosin-B under solar irradiation. It was found that TiO2 catalyst modified with gold exhibits higher percentage of degradation compared to starting TiO2. For example, TiO2 showed 35% of methyl orange degradation whereas gold modified TiO2 possessed 82%. Effect of different parameters such as pH and dye concentration has been evaluated and the photocatalytic activity was correlated with physico-chemical properties. The dye degradation rate followed first order kinetics.  相似文献   

11.
The samples of the NiO/B2O3-Al2O3 system with NiO contents from 0.48 to 38.30 wt % were synthesized by the impregnation of borate-containing alumina (20 wt % B2O3). It was found that nickel oxide occurred in an X-ray amorphous state in the samples containing to 23.20 wt % NiO. At a NiO content of 4.86 wt % or higher, the support was blocked by the modifier to cause a decrease in the specific surface area from 234 to 176 m2/g and in the amount of acid sites from 409–424 to 333 μmol/g. An extremal character of the dependence of catalyst activity in ethylene oligomerization on NiO content was found with a maximum in the range of 4.86–9.31 wt %. Based on spectroscopic data, it was found that ethylene activation on the NiO/B2O3-Al2O3 catalyst can be associated with the presence of Ni2+ cations, which chemically interact with the support. The catalyst containing 4.86 wt % NiO at 200°C, a pressure of 4 MPa, and an ethylene supply rate of 1.1 h−1 provided almost complete ethylene conversion at the yield of liquid oligomerization products to 90.0 wt %; the total concentration of C8+ alkenes in these products was 89.0 wt %.  相似文献   

12.
Two Au catalysts supported on TiO2 were prepared by impregnation method followed by sodium borohydride reduction or calcination in air (Au/TiO2-R and Au/TiO2-C, respectively). The 1 wt % Au/TiO2-R sample was found to be highly efficient for the oxidation of low concentrated formaldehyde at room temperature. A HCHO conversion of 98.5% was achieved with this catalyst, whereas the Au/TiO2-C sample showed almost no activity under the same conditions. Highly dispersed metallic Au nanoparticles with small size (∼3.5 nm) were identified in the 1 wt % Au/TiO2-R catalyst. A significant negative shift of Au4f peak in XPS spectra with respect to bulk metallic Au was observed for the 1 wt % Au/TiO2-R but no similar phenomena was found for the heat-treated catalyst. More Au nanoparticles and higher content of surface active oxygen were identified on the surface of the Au/TiO2-R in comparison with the Au/TiO2-C, suggesting that the Au/TiO2-R catalyst can enhance the amount of active sites and species involved in for HCHO oxidation. The reduction treatment by sodium borohydride promotes the formation of dispersed metallic Au nanoparticles with small size because it facilitates the electron transfer and increases the content of surface Au nanoparticles and activated oxygen. All these factors are responsible for a high activity of this catalyst in the oxidation of HCHO.  相似文献   

13.
Nanocrystalline TiO2 powders in the anatase, rutile, and mixed phases prepared by hydrolysis of TiCl4 solution were of ultrafine size (<7.2 nm) with high specific surface areas in the range 167 to 388 m2/g. In the photocatalytic degradation of phenol as model reaction, the photocatalytic properties of TiO2 nanoparticles were evaluated by use of UV–vis absorption spectroscopy and total organic carbon (TOC) content. The synthetic mixed-phase TiO2 powder calcined at 400 °C had higher activity than pure anatase or rutile; it degraded more than 90% phenol to CO2 (evaluated by TOC) after irradiation with near UV light for 90 min at a catalyst loading of 0.4 g/L. The TOC results indicated that rutile TiO2 crystallites of particle size 7.2 nm resulted in much better photocatalytic performance than particles of larger size. This result suggested that some intermediates, not determined by UV–vis absorption spectroscopy, existed in the solution after the photocatalytic process over the rutile TiO2 photocatalysts of larger crystallite size.  相似文献   

14.
The influence of NH3-treating temperature on the visible light photocatalytic activity of N-doped P25-TiO2 as well as the relationship between the surface composition structure of TiO2 and its visible light photocatalytic activity were investigated. The results showed that N-doped P25-TiO2 treated at 600°C had the highest activity. The structure of P25-TiO2 was converted from anatase to rutile at 700°C. Moreover, no N-doping was detected at the surface of P25-TiO2. There was no simply linear relationship between the visible light photocatalytic activity and the concentration of doped nitrogen, and visible light absorption. The visible light photocatalytic activity of N-doped P25-TiO2 was mainly influenced by the synergistic action of the following factors: (i) the formation of the single-electron-trapped oxygen vacancies (denoted as Vo·); (ii) the doped nitrogen on the surface of TiO2; (iii) the anatase TiO2 structure.  相似文献   

15.
In this work, NiWO4 nanoparticles were prepared by a novel simple method and loading on the mesoporous TiO2 whiskers (TiO2(w)) carrier as the precursor of NiWS. In addition, the NiWS-TiO2(w) catalysts showing high hydrodesulfurization (HDS) activity is described. The structure and chemical composition of the as-prepared samples were characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction, NH3-temperature programmed desorption and transmission electron microscopy, respectively. Results indicate that smaller crystallite size and better dispersion of active NiWO4 particles could be achieved by using TiO2(w) as the support to disperse NiWO4 nanoparticles. TiO2(w) can also decrease the reduction temperature of Ni–W metal oxide and promote a highly sulfidation degree of Ni and W active sites. The obtained NiWS-TiO2(w) catalysts show much higher dibenzothiop HDS activity than the unsupported NiWS catalyst, and the sulphur content of desulfurated oil can reach 20 ppm at the mild condition of 260 °C and 2 Mpa.  相似文献   

16.
TiO2–SiO2 composite nanoparticles were prepared by a sol–gel process. To obtain the assembly of TiO2–SiO2 composite nanoparticles, different molar ratios of Ti/Si were investigated. Polyurethane (PU)/(TiO2–SiO2) hybrid films were synthesized using the “grafting from” technique by incorporation of modified TiO2–SiO2 composite nanoparticles building blocks into PU matrix. Firstly, 3-aminopropyltriethysilane was employed to encapsulate TiO2–SiO2 composite nanoparticles’ surface. Secondly, the PU shell was tethered to the TiO2–SiO2 core surface via surface functionalized reaction. The particle size of TiO2–SiO2 composite sol was performed on dynamic light scattering, and the microstructure was characterized by X-ray diffraction and Fourier transform infrared. Thermogravimetric analysis and transmission electron microscopy (TEM) employed to study the hybrid films. The average particle size of the TiO2–SiO2 composite particles is about 38 nm when the molar ratio of Ti/Si reaches to1:1. The TEM image indicates that TiO2–SiO2 composite nanoparticles are well dispersed in the PU matrix.  相似文献   

17.
以TiO2纳米粒子为主催化剂,采用"浸渍-还原法"构筑了铜、镍共负载的二氧化钛基光催化系统。以苯为起始原料,H2O2为氧化剂,研究了Cu/Ni助催化剂对TiO2可见光催化制取苯酚性能的影响并对Cu/Ni助催化剂的作用机制进行了探讨。结果表明,在可见光照射下,纯TiO2纳米粒子对苯氧化制取苯酚反应没有催化活性。铜、镍的引入可以明显地增强Ti02可见光催化制取苯酚的活性。当使用负载有铜、镍的TiO2作为催化剂时,苯酚的产率可达到18%。结果还表明Cu、Ni之间存在着很强的协同作用。在该协同作用下,Cu、Ni共负载的TiO2纳米粒子表现出了较单一金属负载的TiO2纳米粒子高得多的光催化活性。  相似文献   

18.
以TiO2纳米粒子为主催化剂, 采用“浸渍-还原法”构筑了铜、镍共负载的二氧化钛基光催化系统。以苯为起始原料, H2O2为氧化剂, 研究了Cu/Ni助催化剂对TiO2可见光催化制取苯酚性能的影响并对Cu/Ni助催化剂的作用机制进行了探讨。结果表明, 在可见光照射下, 纯TiO2纳米粒子对苯氧化制取苯酚反应没有催化活性。铜、镍的引入可以明显地增强TiO2可见光催化制取苯酚的活性。当使用负载有铜、镍的TiO2作为催化剂时, 苯酚的产率可达到18%。结果还表明Cu、Ni之间存在着很强的协同作用。在该协同作用下, Cu、Ni共负载的TiO2纳米粒子表现出了较单一金属负载的TiO2纳米粒子高得多的光催化活性。  相似文献   

19.
Fluorine-modified TiO2 nan oparticles were synthesized by introducing TiF4 as a fluorine source either before or after the sufficient hydrolysis and condensation of Ti(OEt)4. The photocatalytic activity of the fluorine-modified catalysts was found to be greatly affected by the fluorine position in TiO2 nanoparticles. When TiF4 and Ti(OEt)4 hydrolyzed with synchronization, the fluorine tended to be doped in the lattice. The formation of Ti3+ defects could result in charge recombination in bulk and bring down the photocatalytic activity. In contrast, if TiF4 was introduced after the sufficient hydrolysis and condensation of Ti(OEt)4. Ti−F bonds could exist mainly on the TiO2 particles surface, which not only prevented the growth of anatase crystals but also facilitated the transfer of organic compounds from solution to catalyst surface by reducing the hydrophilic properties.  相似文献   

20.
Sumitomo Chemical has developed a low energy consuming and green process for the catalytic oxidation of HCl to Cl2, especially when compared with the electrolysis process. The RuO2/rutile-TiO2 catalyst has high catalytic activity and thermal stability due to ultra-fine RuO2 crystallites that cover the surface of the TiO2 primary particles with strong interaction. In addition, the silica modified RuO2/rutile-TiO2 catalyst shows higher thermal stability by preventing the RuO2 sintering due to using dispersed SiO2 particles. With these catalysts, high reaction rates required for industrial applications are achieved, even at low temperatures.  相似文献   

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