不同制备工艺钒系SCR催化剂理化及催化性能研究

本文研究了制备工艺对 TiO2-WO3-V2O5- 载体型催化剂理化特性及其在 NH3-SCR 反应中催化性能的影响.通过 XRD、TG/DTA 等分析方法考察了煅烧温度等对催化剂中各组分晶体结构的影响,确定了制备负载型催化剂的最佳煅烧温度为 500℃.不同制备工艺催化剂理化性能的对比表明,多步浸渍法不仅提高了锐钛矿型 TiO2 向金红石型 TiO2 的转变温度,而且使更多的钒氧化物处于较低的价态,有利于提高还原反应的催化性能;催化活性评价试验也表明使用多步浸渍法制备的 SCR 催化剂具有较高的催化活性和更宽的高活性反应温度窗口.最后考察了反应空速对多步浸渍法所制备催化剂 NOx 转化效率的影响,结果表明:随空速的增加,NOx 转化效率逐渐降低.     

Role of Au(+) in supporting and activating Au(7) on TiO(2)(110)

The adhesion properties and catalytic activity of rutile TiO(2)(110)-supported Au(7) nanoclusters in different oxidation states are investigated by means of density functional theory. The calculations cover both surface science conditions of reduced TiO(2) and real catalyst conditions of oxidized (alkaline) TiO(2) supports. Large adhesion energies of Au(7) are found only when modeling real catalysts where the cluster becomes cationic with Au(+) ions in Au-O or Au-OH bonds. The full catalytic cycle for oxidation of CO by O(2) over Au(7) on alkaline TiO(2)(110) is calculated and found to involve only small activation barriers. In the presence of the CO reductant, the Au(+) sites are capable of cycling between bonding of atomic and molecular oxygen. We confirm our findings by comparison of calculated and experimental infrared stretch frequency data for adsorbed CO.     

稀土改性的氧化镍基低温乙烷氧化脱氢催化剂活性氧物种的Raman光谱研究

利用共沉淀法制备了几种稀土金属氧化物改性的氧化镍催化剂 ,考察了其乙烷氧化脱氢 (ODE)制乙烯的催化性能 ,讨论了不同稀土金属氧化物掺杂浓度对催化剂催化性能的影响 ,利用Raman光谱技术初步表征反应在该类催化剂上的活性氧物种为Raman谱带出现在 1 0 60cm- 1 的表面双原子超氧物种O-2 ,该谱峰的大小与催化剂的ODE性能有很好的对应关系。     

Synthesis of Pt modified ZSM-5 and beta zeolite catalysts: influence of ultrasonic irradiation and preparation methods on physico-chemical and catalytic properties in pentane isomerization

Influence of preparation methods and ultrasound irradiation on physico-chemical and catalytic properties was investigated by synthesizing Pt-ZSM-5 and Pt-Beta catalysts by in-situ and impregnation methods and applying ultrasound irradiation to synthesis gel mixture of ZSM-5 and Beta zeolites. It was concluded from the X-ray powder diffraction patterns of Pt-ZSM-5 and Pt-Beta zeolite catalysts that introduction of Pt by in-situ method and ultrasound irradiation did not influence the structures of ZSM-5 and Beta zeolites. Morphology of ZSM-5 and Beta zeolites were investigated by scanning electron microscopy. SEM micrographs showed that the Pt-ZSM-5-IS-US catalyst synthesized by in-situ method with ultrasound irradiation resulted in smaller crystals of ZSM-5 than Pt-ZSM-5-IS catalyst prepared without ultrasound irradiation. Furthermore SEM micrographs of Pt-Beta-11-IS-US zeolite synthesized using ultrasound irradiation showed much smaller crystals than Pt-Beta-11-IM indicating that ultrasound irradiation had a significant effect on the morphology of Beta zeolite. Conversion of n-pentane and selectivity to iso-pentane over the Pt-ZSM-5-IS-US zeolite catalysts prepared by ultrasound irradiation during in-situ introduction of platinum was higher than the catalysts prepared without the ultrasound irradiation. Furthermore ultrasound irradiated and in-situ synthesized Pt-Beta-11-IS-US catalyst also showed higher selectivity to iso-pentane than Pt-H-Beta-11-IM prepared by impregnation method.     

Selective oxidation of CO in the presence of air over gold-based catalysts Au/TiO2/C (sonochemistry) and Au/TiO2/C (microwave)

Two model catalysts, Au/TiO2/C (S) (sonochemically derived) and Au/TiO2/C (M) (microwave derived), were produced by employing ultrasound irradiation and microwave irradiation, respectively. The deposition of gold colloids onto the support powders, TiO2/C, was accomplished by using a solvated metal atom impregnation (SMAI) method. The SMAI technique provides highly-dispersed gold particles on the TiO2/C support. The catalytic performance of Au based catalysts 1 wt% Au-TiO2/C (S) and 1 wt%Au-TiO2(M)/C (M) have been tested for the oxidation of CO in the temperature range of 0-300 degrees C and compared to that of 1 wt% Au-TiO2 (Degussa-P25). A boost in the conversion of CO was observed for the sonochemically-derived catalyst, Au/TiO2/C (S), at low temperature. Hence, the reactivity order found for CO oxidation is (Au/TiO2/C (S)>Au/TiO2 (P25)>Au/TiO2/C (M)).     

Role of nanostructured dual-oxide supports in enhanced catalytic activity: theory of CO oxidation over Au/IrO2/TiO2

The synergetic effect in multicomponent catalysts is a topic of profound industrial importance and intense academic interest. On a newly identified multicomponent catalyst, Au/IrO(2)/TiO(2), first-principles density-functional theory is analyzed to clarify the outstanding catalytic activity of the system for oxidative reactions at high temperatures. By comparing CO oxidation on interfaces and single-component surfaces, it is revealed that a high dispersion of a more active oxide (IrO2), on a more inert oxide (TiO2) is the key. It preserves the sintering resistance of Au supported on less active oxides, while at the same time promoting oxidative reactions that occur at the Au/active-oxide interface.     

A comparative study for the electrocatalytic oxidation of alcohol on Pt-Au nanoparticle-supported copolymer-grafted graphene oxide composite for fuel cell application

The platinum-gold bimetallic nanoparticles supported poly(cyclotriphosphazene-co-benzidine)-grafted graphene oxide (poly(CP-co-BZ)-g-GO) composite has been prepared for electrochemical performance studies. Cyclic voltammetry and chronoamperometric studies were carried out to check the electrochemical properties of Pt-Au/poly(CP-co-BZ)-g-GO and Pt/poly(CP-co-BZ)-g-GO catalysts for methanol, ethylene glycol and glycerol in alkaline medium. The morphology and crystalline structure of the prepared Pt-Au/poly(CP-co-BZ)-g-GO and Pt/poly(CP-co-BZ)-g-GO and catalysts have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and fourier transform infrared spectroscopy (FT-IR). From the electrochemical results, it was concluded that Pt-Au/poly(CP-co-BZ)-g-GO catalyst shows higher catalytic activity and stability compared to Pt/poly(CP-co-BZ)-g-GO catalyst. The catalytic activity of Pt/poly(CP-co-BZ)-g-GO catalyst has been compared with Pt/poly(CP-co-BZ), Pt/GO and Pt/C catalysts. In addition, oxidation current of ethylene glycol is higher than the methanol and glycerol in alkaline medium on the prepared catalyst.     

Ultrasound assisted co-precipitation synthesis and catalytic performance of mesoporous nanocrystalline NiO-Al2O3 powders

Mesoporous nanocrystalline NiO-Al₂O₃ powders with high surface area were synthesized via ultrasound assisted co-precipitation method and the potential of the selected samples as catalyst was investigated in dry reforming reaction for preparation of synthesis gas. The prepared samples were characterized by N₂ adsorption (BET), X-ray diffraction (XRD), Temperature programmed reduction and oxidation (TPR, TPO) and scanning electron microscopy (SEM) techniques. The effects of pH, power of ultrasound irradiation, aging time and calcination temperature on the textural properties of the catalysts were studied. The sample prepared under specified conditions (pH10, 70 W, without aging time and calcined at 600 °C) exhibited the highest surface area (249.7 m² g⁻¹). This catalyst was calcined at different temperature and employed in dry reforming of methane and the catalytic results were compared with those obtained over the catalysts prepared by impregnation and co-precipitation methods. The results showed that the catalyst prepared by ultrasound assisted co-precipitation method exhibited higher activity and stability with lower degree of carbon formation compared to catalysts prepared by co-precipitation and impregnation methods.     

Sonochemically synthesized mono and bimetallic Au–Ag reduced graphene oxide based nanocomposites with enhanced catalytic activity

Graphene oxide (GO) supported Ag and Au mono-metallic and Au–Ag bimetallic catalysts were synthesized using a sonochemical method. Bimetallic catalysts containing different weight ratios of Au and Ag were loaded onto GO utilizing a low frequency horn-type ultrasonicator. High frequency ultrasonication was used to efficiently reduce Ag(I) and Au(III) ions in the presence of polyethylene glycol and 2-propanol. Transmission electron microscopy (TEM–EDX) and X-ray photoelectron spectroscopy were used to analyze the morphology, size, shape and chemical oxidation states of the prepared metallic catalysts on GO. The catalytic efficiency of the prepared catalysts were compared using 4-nitrophenol (4-NP) reduction reaction and the subsequent formation of 4-aminophenol (4-AP) that was also monitored using UV–vis spectrophotometry. The results revealed that Au–Ag–GO bimetallic catalysts showed high activity for the conversion of 4-NP to 4-AP than their monometallic counterparts. Amongst different weight ratios (1:1, 1:2 and 2:1) between Au and Ag, the 1:2 (Au:Ag) catalyst exhibited very good catalytic performance for the conversion of 4-NP to 4-AP. A total reduction of 4-NP took place within a short period of time if Au–GO was reduced first followed by Ag reduction, whereas a lower reduction rate was observed if Ag–GO was reduced first. The same trend was observed for all the ratios of bimetallic catalysts prepared by this method. The initial unfavorable reduction potential of Ag(I) is likely to be responsible for the above order. It was found that applying dual frequency ultrasonication was a highly effective way of preparing bimetallic catalysts requiring relatively low levels of added chemicals and producing bimetallic catalysts with GO with improved catalytic efficiency.     

Reactivation of Promoted Nickel Catalysts for Deuterium Exchange between Hydrogen and Water in the Vapour Phase

Binary promoted nickel – chromium oxide and ternary promoted nickel – chromium oxide – aluminium oxide mixed catalysts were prepared for use in the present study. The catalysts were prepared by co-precipitation of the corresponding metal nitrates as carbonates followed by calcination in nitrogen atmosphere at 350 °C and reduction in hydrogen atmosphere at 320 °C. To prevent spontaneous oxidation of the catalysts, bidistilled water was added followed by heating of the catalyst mixtures at about 110 °C in hydrogen atmosphere for few hours. Deactivation of catalysts was studied by measurements of the variation of their activities with the time of contact of the reacting gas mixtures with the catalyst surface in the reaction chamber. It was found that while the catalytic activity of ternary catalysts for the isotopic exchange of deuterium between hydrogen and water vapour was higher than that of the binary one, the loss in activity of the former teas faster than the latter. Reactivation of the catalysts were carried out at different temperatures between 110–160°C in hydrogen atmosphere. Catalytic activity measurements indicated that higher temperatures are better for the reactivation process.     

TiO2光催化剂的光谱研究

采用sol-gel法制备了纳米TiO2光催化剂,运用FTIR,FT－Ranam,DSR等光谱技术对催化剂进行了表征,以光催化解油酸作为模型反应考察光催化活性。实验结果表明,催化剂的烧结温度对催化剂的晶相结构、半导体能带结构、光吸收性能及光催化活性均产生显著的影响,当烧结温度为400℃时,TiO2光催化剂具有最好的表观吸光度,最大的吸收带边,以及最佳的光催化活性。     

Successive electrodeposition of polydopamine and PtPd metal on a graphene oxide support for use as anode fuel cell catalysts

Successive electropolymerization of dopamine and electrodeposition of Pd and/or Pt on a graphene oxide (GO) support were used to prepare anode catalysts for low-temperature fuel cells. Transmission electron microscopy images were used to investigate the morphologies and distribution of the prepared catalysts, which showed the metal formed as nanoparticles on the catalysts. The GO surface was favorable for the modification with electropolymerized polydopamine (PDA) and the electrodeposition of metal catalyst nanoparticles using a simple preparation process. The PDA-loaded GO composite was used as a matrix for the dispersion of Pt and Pd nanoparticles. GO could be simultaneously modified by PDA and reduced without using reducing agents. The electrocatalytic performance of the catalysts for the oxidation of selected small molecule fuels (e.g., methanol, ethanol and formic acid) was examined. An outstanding catalytic activity and stability was found for the prepared Pt/Pd/PDA/GO composite, which was attributed to the high active surface area.     

CuO based catalysts on modified acidic silica supports tested in the de-NOx reduction

A series of dispersed CuO catalysts supported on modified silica supports with Al2O3 (SA), TiO2 (ST), and ZrO2 (SZ) were prepared optimising the adsorption method of copper deposition assisted by ultrasound treatment, already reported in a previous paper (S. Bennici, A. Gervasini, V. Ragaini, Ultrason. Sonochem. 10 (2003) 61). The obtained catalysts were characterized in their bulk (atomic absorption, X-ray diffraction, temperature programmed reduction) and surface (N2 adsorption, X-ray photoelectron spectroscopy, scanning electron microscopy) properties. The morphology of the finished materials was not deeply modified compared with that of the relevant supports. The employed complemented techniques evidenced a well dispersed CuO phase with a copper-support interaction on the most acidic supports (SA and SZ). The catalyst performances were studied in the reaction of selective catalytic reduction of NOx with ethene in oxidizing atmosphere in a flow apparatus under variable times (0.360-0.072 s) and temperatures (200-450 degrees C). The catalysts prepared on the most acidic supports (SA and SZ) were the most active and selective towards N2 formation. They showed a particular interesting activity in the reaction of NO2 reduction besides that of NO reduction.     

草酸二甲酯加氢制乙二醇催化剂的研究

常规方法制备的草酸二甲酯加氢催化剂活性和选择性较差,通过化学还原沉积法制备了Cu-B/γ-Al2O3、Cu-B/SiO2非晶态合金催化剂并进行了XRD、TDA的表征。在2.0MPa,摩尔氢酯比50:1,体积空速2h-1,反应温度200℃时进行催化剂评价。结果表明,Cu-B/γ-Al2O3、Cu-B/SiO2非晶态合金催化剂的活性和选择性较好,显示出良好的应用前景。     

Preparing copper catalyst by ultrasound-assisted chemical precipitation method

In this paper, preparing copper catalyst by ultrasound-assisted chemical precipitation method is investigated. The used equipment is JP-020 ultrasonic cleaner, power and frequency are 180 W and 40 kHz respectively. Under the action of ultrasound, CuSO₄·5H₂O is reduced by ascorbic acid to obtain copper. The products are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and catalytic performance test. The results show that the morphology of copper products is rod-like and irregular granular. Copper catalyst has good catalytic oxidation performance for dyes methylene blue, crystal violet, alizarin red and Rhodamine B. The catalytic efficiency of 10 mg catalyst copper to 6 mg/L methylene blue reaches 98.1%, and the catalytic efficiency of the catalyst increases with the increase of catalyst dosage and the decrease of dye solution concentration. In addition, the new preparation techniques for Cu-based catalysts based on coprecipitation method are compared. Finally, the development trend of the new technology of copper-based catalyst preparation based on coprecipitation method is pointed out.     

Investigation on the transition crystal of ordinary rutile TiO2 powder by microwave irradiation in hydrogen peroxide solution and its sonocatalytic activity

The transition crystal TiO(2) catalyst with high sonocatalytic activity was obtained utilizing the microwave irradiation in hydrogen peroxide solution. At the same time a series of affecting factors (microwave irradiation time, heat-treated time and heat-treated temperature) to prepare the TiO(2) catalyst on the sonocatalytic degradation of parathion were considered in this paper. The ultrasound of low power was used as an irradiation source to induce treated TiO(2) particles to perform catalytic activity. The results show that the sonocatalytic activity of the transition crystal TiO(2) powder is obviously higher than those of pure ordinary rutile and anatase TiO(2) powders. At last, the parathion in aqueous solution was degraded completely and became some simple inorganic ions such as NO(3)(-), PO(4)(3-), SO(4)(2-), etc. The degradation ratio of parathion in the presence of the transition crystal TiO(2) catalyst attains nearly 80% within 60 min ultrasonic irradiation, while corresponding ones are only 65.23% and 53.88%, respectively, for pure ordinary rutile and anatase TiO(2) powders.     

Preparation and Acid Catalytic Activity of TiO2 Grafted Silica MCM-41 with Sulfate Treatment

采用连续嫁接方法对纯硅MCM-41孔道表面分别进行一次和两次TiO2修饰,并进行了硫酸根促进,制备了具有规整介孔结构的硫酸根促进型复合金属氧化物ST/MCM-41和d-ST/MCM-41;同时制备了经一次钛修饰但未经硫酸根促进的样品T/MCM-41作为对比. 利用XRD、氮吸附-脱附、元素分析、拉曼光谱和红外光谱等表征手段,对所制样品的结构和表面酸性进行考察;利用假性紫罗兰酮环化这一典型的酸催化反应对其催化活性进行评价,并与工业应用的大孔磺酸树脂Amberlyst-15进行催化性能比较. 表征结果显示,纯     

Comparison of catalytic activities for photocatalytic and sonocatalytic degradation of methylene blue in present of anatase TiO2-CNT catalysts

Anatase TiO(2)-CNT catalysts with high specific surface areas were prepared by depositing TiO(2) particles on the surface of carbon nanotubes (CNTs) using a modified sol-gel technique. These catalysts prepared with different amounts of CNTs were characterized by nitrogen adsorption, Fourier Transform infrared (FT-IR) spectroscopy, scanning electron microscope (SEM), Transmission Electron Microscope (TEM), X-ray diffraction (XRD), Raman spectroscopy, energy dispersive X-ray (EDX) and ultraviolet-visible (UV-Vis) spectroscopy. The catalytic activity of the anatase TiO(2)-CNT catalysts was assessed by examining the degradation of methylene blue (MB) from model aqueous solutions as a probe reaction under visible light and ultrasonic irradiation. The synergistic effect of the greater surface area and catalytic activities of the composite catalysts was examined in terms of the strong adsorption ability and interphase interaction by comparing the different amounts and roles of CNTs in the catalysts.     

Carbonization of Chitosan in Palladium-Chitosan/ Montmorillonite Composites to Prepare Novel Heterogeneous Catalysts for Heck Reactions

Palladium-carbon/montmorillonite (Pd-C/MMT) heterogeneous catalysts were prepared by carbonization of chitosan in palladium-chitosan/montmorillonite (Pd-CS/MMT) composites under a N₂ atmosphere. The main purpose of this study was to determine the effects of the carbonization temperature (250, 450, and 650°C) on the material microstructure and its catalytic performance. X-ray diffraction patterns revealed that the formation of an intercalation of the carbonaceous material between the clay mineral layers which was also confirmed by Fourier transform infrared spectra results. The N content of the Pd-C/MMT catalyst decreased as the carbonization temperature was increased. Thermogravimetry curves revealed that the thermal stability of the Pd-C/MMT catalyst increased obviously as the carbonization temperature was increased. Pd nanoparticles, sized at about 20 nm, were mainly dispersed on the surface of the MMT, as observed by high-resolution transmission electron microscopy (HR-TEM). The prepared Pd-C/MMT catalysts had good catalytic activity when applied in Heck coupling reactions of aromatic halides and alkenes to produce aryl olefins. The relations between the recyclability and the material composition are discussed.     

Effect of Preparation Method on the SCR Activity of Fe-Doped CoCr Oxide Catalysts

Fe-doped CoCr oxide catalysts are prepared by solid-phase mixing method, coprecipitation method, mechanical mixing method, and citric acid method, respectively, and their catalytic activity in the selective catalytic reduction of nitrogen oxides with NH₃ (NH₃-SCR) is tested. The Fe_0.5CoCrO_x catalysts prepared by all preparation methods have good water resistance and sulfur resistance when the calcination temperature is 400 °C. Fe_0.5CoCrO_x prepared by coprecipitation method by calcination at 400 °C (CP-400) is shown to have the optimum catalyst activity. In addition, the catalysts are characterized by a series of characterizations. The characterization results show that CP-400 has the largest specific surface area, which makes the active and acidic sites highly dispersed on the surface of CP-400, resulting in stronger redox and acidity and improved SCR activity. The removal of NO by NH₃-SCR over CP-400 at 150 °C follows the Eley-Rideal (E R) and Langmuir-Hinshelwood (L H) mechanisms.