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1.
Titanium silicalite (TS) and TiO2 nanocomposites were prepared by mixing TS and TiO2 with different ratios in ethanol. They were impregnated with 15 wt% Co loading to afford Co‐based catalysts. Fischer–Tropsch synthesis (FTS) performance of these TS–TiO2 nanocomposite‐supported Co‐based catalysts was studied in a fixed‐bed tubular reactor. The results reveal that the Co/TS–TiO2 catalysts have better catalytic performance than Co/TS or Co/TiO2 each with a single support, showing the synergistic effect of the binary TS–TiO2 support. Among the TS–TiO2 nanocomposite‐supported Co‐based catalysts, Co/TS–TiO2‐1 presents the highest activity. These catalysts were characterized using N2 adsorption–desorption measurements, X‐ray diffraction, X‐ray photoelectron spectroscopy, H2 temperature‐programmed reduction, H2 temperature‐programmed desorption and transmission electron microscopy. It was found that the position of the active component has a significant effect on the catalytic activity. In the TS–TiO2 nanocomposites, cobalt oxides located at the new pores developed between TS and TiO2 can exhibit better catalytic activity. Also, a positive relationship is observed between Co dispersion and FTS catalytic performance for all catalysts. The catalytic activity is improved on increasing the dispersion of Co.  相似文献   

2.
刘华  许珊  王晓来 《分子催化》2005,(4):301-307
以硝酸钴和硝酸铈为前驱物,SBA-15为硬模板,利用双溶剂法制备了Co3O4-CeO2介孔复合氧化物,通过X-射线衍射、N2吸脱附测试、程序升温还原和透射电子显微镜等技术对活性组分及载体进行了表征,并且与浸渍法和共沉淀法所制备的催化剂进行了对比分析。结果表明,相比于浸渍法和共沉淀法,采用双溶剂法制备的介孔Co3O4-CeO2复合氧化物具有均匀的介孔结构、较小的颗粒尺寸、较大的比表面积和较高的活性组分分散度。此外,CO氧化脱除评价显示与常规的共沉淀法和浸渍法所制备的催化剂相比该介孔复合氧化物具有较高的反应活性和选择性,其高活性主要归因于较高的比表面积和活性组分的高分散度。  相似文献   

3.
Catalytic hydrodeoxygenation (HDO) of anisole, a methoxy-rich lignin-derived bio-oil model compound, was carried out over a series of Ni-containing (5, 10, 20, and 30 wt%) catalysts with commercial silica and ordered mesoporous silica SBA-15 as support. Both supports and catalysts were characterized by N2 adsorption–desorption isotherms, X-ray diffraction, CO chemisorption, and transmission electron microscopy (TEM). Catalytic reaction was performed at 250 °C and 10 bar H2 pressure. Depending on the catalyst support used and the content of active metal, the catalytic activity and product distribution changed drastically. Increase of the nickel loading resulted in increased anisole conversion and C6 hydrocarbon (benzene and cyclohexane) yield. However, loading more Ni than 20 wt% resulted in a decrease of both conversion and C6 yield due to agglomeration of Ni particles. In addition, Ni/SBA-15 samples exhibited much stronger catalytic activity and selectivity toward C6 hydrocarbon products compared with Ni/silica catalysts. The differences in catalytic activity among these catalysts can be attributed to the effect of the pore size and pore structure of mesoporous SBA-15. SBA-15 can accommodate more Ni species inside channels than conventional silica due to its high pore volume with uniform pore structure, leading to high HDO catalytic activity.  相似文献   

4.
Microporous NaY zeolite is a common support of Cu catalysts for oxidative carbonylation of methanol, but the dispersion of Cu species on NaY is usually subjected to its micropore size. Here, ordered mesoporous KIT-6 was employed as the support for Cu catalyst and Al was incorporated into its framework to increase the surface acidity, which eventually improves the surface exchange capacity and Cu dispersion. The evolution of the state of Cu species on KIT-6 was analyzed combined with control of Cu loading. The physicochemical properties of the supports and corresponding catalysts were characterized by N2 adsorption–desorption, X-ray diffraction, ammonia temperature programmed desorption, Fourier transform infrared spectra, transmission electron microscopy, hydrogen temperature programmed reduction, and X-ray photoelectron spectroscopy. It was found that mesoporous KIT-6 showed better Cu dispersion than microporous NaY zeolite. Agglomerated CuO, dispersed CuO, and Cu2+ are the major Cu species observed on the catalyst surface. The increased surface acidic sites of KIT-6 by Al incorporation promoted the formation of Cu2+ and dispersion of CuO. With the increase in Cu loading, the Cu2+ content in the catalyst was decreased gradually along with increase in the bulk CuO. It was speculated that some exchanged Cu2+ could be transformed into highly dispersed CuO and even bulk CuO after calcination at a high Cu loading. Combined with the catalyst evaluation results, it was deduced that highly dispersed Cu2+ and CuO particles play significant roles in catalytic activity. The catalyst Cu/Al-K-10 achieved the highest space time yield of dimethyl carbonate of 135.4 mg/(g·h), which is 2.7 times the Cu/K-10 owing to its more dispersed Cu species. This laid the basis for preparing highly dispersed Cu species on mesoporous silica supports.  相似文献   

5.
The effect of ethylene diamine tetraacetic acid(EDTA) modification on the physico-chemical properties and catalytic performance of silica nanosprings(NS) supported cobalt(Co) catalyst was investigated in the conversion of syngas(H~(2+) CO) to hydrocarbons by Fischer-Tropsch synthesis(FTS). The unmodified Co/NS and modified Co/NS-EDTA catalysts were synthesized via an impregnation method. The prepared Co/NS and Co/NS-EDTA catalysts were characterized before the FTS reaction by BET surface area,X-ray diffraction(XRD),transmission electron microscopy(TEM),temperature programmed reduction(TPR),X-ray photoelectron spectroscopy(XPS),differential thermal analysis(DTA) and thermogravimetric analysis(TGA) in order to find correlations between physico-chemical properties of catalysts and catalytic performance. FTS was carried out in a quartz fixedbed microreactor(H_2/CO of 2 ∶1,230 ℃ and atmospheric pressure) and the products trapped and analyzed by GC-TCD and GC-MS to determine CO conversion and reaction selectivity. The experimental results indicated that the modified Co/NS-EDTA catalyst displayed a more-dispersed phase of Co_3O_4 nanoparticles(10.9%) and the Co_3O_4 average crystallite size was about 12.4 nm. The EDTA modified catalyst showed relatively higher CO conversion(70.3%) and selectivity toward C_(6-18)(JP-8,Jet A and diesel) than the Co/NS catalyst(C_(6-14))(JP-4).  相似文献   

6.
The catalytic activity of MIMII 2O3 spinel-type complex oxides (MI = Cu, Ni, Mn, Zn, Mg, Co, MII = Co, Cr, Al) in the oxidation of CO and ethylbenzene has been investigated. The Co-containing catalysts were more active than the Cr- and Al-containing catalysts. The nature of the cation influenced the catalytic activity. Higher activities were observed for the catalysts containing two transition elements. A correlation between the catalytic and adsorption properties was established.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1730–1732, October, 1994.  相似文献   

7.
A series of Fe?Ni mixed‐oxide catalysts were synthesized by using the sol–gel method for the reduction of NO by CO. These Fe?Ni mixed‐oxide catalysts exhibited tremendously enhanced catalytic performance compared to monometallic catalysts that were prepared by using the same method. The effects of Fe/Ni molar ratio and calcination temperature on the catalytic activity were examined and the physicochemical properties of the catalysts were characterized by using XRD, Raman spectroscopy, N2‐adsorption/‐desorption isotherms, temperature‐programmed reduction with hydrogen (H2‐TPR), temperature‐programmed desorption of nitric oxide (NO‐TPD), and X‐ray photoelectron spectroscopy (XPS). The results indicated that the reduction behavior, surface oxygen species, and surface chemical valence states of iron and nickel in the catalysts were the key factors in the NO elimination. Fe0.5Ni0.5Ox that was calcined at 250 °C exhibited excellent catalytic activity of 100 % NO conversion at 130 °C and a lifetime of more than 40 hours. A plausible mechanism for the reduction of NO by CO over the Fe?Ni mixed‐oxide catalysts is proposed, based on XPS and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analyses.  相似文献   

8.
The effect of calcination temperature on the catalytic activity for the dimethyl ether (DME) carbonylation into methyl acetate (MA) was investigated over mordenite supported copper (Cu/HMOR) prepared by ion-exchange process. The results showed that the catalytic activ-ity was obviously affected by the calcination temperature. The maximal DME conversion of 97.2% and the MA selectivity of 97.9% were obtained over the Cu/HMOR calcined at 430 oC under conditions of 210 oC, 1.5 MPa, and GSHV of 4883 h-1. The obtained Cu/HMOR catalysts were characterized by powder X-ray diffraction, N2 absorption, NH3 temperature program desorption, CO temperature program desorption, and Raman techniques. Proper calcination temperature was effective to promote copper ions migration and diffusion, and led the support HMOR to possess more acid activity sites, which exhibited the complete decomposing of copper nitrate, large surface area and optimum micropore structure, more amount of CO adsorption site and proper amount of weak acid centers.  相似文献   

9.
Ce0.65Zr0.35O2 was prepared by co-precipitation method and a series of Mn1-yCoy/Ce0.65Zr0.35O2 catalysts with different Mn/Co molar ratio were synthesized via the co-impregnation method. These catalysts were applied for gaseous toluene oxidation, which showed that the catalytic activity was significantly improved by the addition of Mn and Co. In particular, Mn–Co(1:1)/Ce0.65Zr0.35O2 with Mn/Co molar ratio of 1:1 displayed the best result with the lowest complete conversion temperature of 242 °C under a GHSV of 12,000 h?1. The as-prepared catalysts were characterized by X-ray diffraction, H2 temperature-programmed reduction, N2 adsorption–desorption, X-ray photoelectron spectroscopy and O2 temperature-programmed desorption. These characteristics revealed that the coexistence of Mn and Co could enhance the redox property and generate more surface adsorbed oxygen, thereby improving the performance of the catalysts for toluene low-temperature oxidation. The Mn–Co(1:1)/Ce0.65Zr0.35O2 exhibited the best catalytic activity and high stability. The excellent catalytic activity of the Mn–Co(1:1)/Ce0.65Zr0.35O2 could be ascribed to a greater amount of surface adsorbed oxygen species and Mn4+ on the catalyst surface.  相似文献   

10.
Mesoporous oxides TiO2 and ZrO2, synthesized by surfactant templating via a neutral C13(EO)6–Zr(OC3H7)4 assembly pathway, and ceria‐modified TiO2 and ZrO2, prepared by a deposi‐tion–precipitation (DP) method, featuring high surface areas and uniform pore size distributions were used as supports for gold catalysts. The supported gold catalysts were assessed for the cata‐lytic abatement of air pollutants, i.e., CO, CH3OH, and (CH3)2O. The gold was supported on the mes‐oporous oxides by a DP method. The supports and catalysts were characterized by powder X‐ray diffraction, high‐resolution transmission electron microscopy, N2 adsorption–desorption analysis, and temperature‐programmed reduction technique. A high degree of synergistic interaction be‐tween ceria and mesoporous ZrO2 and TiO2 as well as a positive modification of the structural and catalytic properties by ceria was observed. The ceria additive interacts with the mesoporous oxides and induces a strong effect on the reducibility of the supports. The catalytic behavior of the catalysts was discussed to determine the role of the ceria modifying additive and possible interaction be‐tween the gold nanoparticles and ceria‐mesoporous oxide supports. The gold catalysts supported on ceria‐modified mesoporous ZrO2 displayed superior catalytic activity (~100%conversion of CO at 10 °C and CH3OH at 60 °C). The high catalytic activity can be attributed to the ability of the sup‐port to assist oxygen vacancies formation. The studies indicate that the ceria‐modified mesoporous oxide supports have potential as supports for gold‐based catalysts.  相似文献   

11.
Mn-Al和Cu-Mn-Al复合氧化物催化苯甲醇选择氧化反应   总被引:3,自引:3,他引:0  
吴藏藏  郑丽  徐秀峰 《分子催化》2016,30(6):532-539
用溶胶-凝胶法制备了不同组成的Mn-Al和Cu-Mn-Al复合氧化物两组催化剂,用于苯甲醇选择氧化反应.用X射线衍射(XRD)、N2物理吸附(BET)、扫描电镜(SEM)、H_2程序升温还原(H_2-TPR)、O_2程序升温脱附(O_2-TPD)和X射线光电子能谱(XPS)技术对催化剂进行了结构表征,考察了催化剂组成对催化活性的影响.结果表明:以甲苯为溶剂,O_2为氧化剂,353 K反应5 h,Mn_2Al和Cu_(0.3)Mn_(0.7)Al_2催化剂上的苯甲醇转化率分别为36.6%和40.9%,苯甲醛选择性均为100%.进一步研究表明:催化剂活性与其H2还原性和O_2吸附性有关,高活性的催化剂吸附氧多,生成的活性氧易参与反应.  相似文献   

12.
Dimethyl ether carbonylation to methyl acetate was comparatively investigated over mor-denite supported copper (Cu/HMOR) catalysts prepared by different methods including evaporation, urea hydrolysis, incipient wetness impregnation and ion-exchange. The resultsshowed that Cu/HMOR prepared via iron-exchange method exhibited the highest catalytic activity due to the synergistic effect of active-site metal and acidic molecular sieve support. Conversion of 95.3% and methyl acetate selectivity of 94.9% were achieved under conditions of 210 oC, 1.5 MPa, and GSHV of 4883 h-1. The catalysts were characterized by nitrogen absorption, X-ray diffraction, NH3 temperature program desorption, and CO temperature program desorption techniques. It was found that Cu/HMOR prepared by ion-exchange method possessed high surface area, moderate strong acid centers, and CO adsorption cen-ters, which improved catalytic performance for the reaction of CO insertion to dimethyl ether.  相似文献   

13.
Transition metal oxides (TMOs) applied as catalysts whose catalytic activities are directly affected by their pores size and pores distributions. Herein, two-dimensional Cu-doped CeO2 (2D@Cu–CeO2) and three-dimensional Cu-doped CeO2 (3D@Cu–CeO2) were prepared by adopting the mesoporous silica SBA-15 and KIT-6 as templates, respectively. Nanometer Cu-doped CeO2 (nano@Cu–CeO2) was synthesized by the method of precipitation. All catalysts were evaluated for the catalytic oxidation of CO, and the 3D@Cu–CeO2 catalyst exhibited the highest catalytic activity (complete conversion temperature T100?=?50?°C), which can be ascribed to the three-dimensional porous channel structure, larger specific surface area and abundant active surface oxygen species. In addition, complete conversion of CO had remained the same after 3D@Cu–CeO2 was observed for 12 h, indicating it has the best catalytic stability for CO.  相似文献   

14.
TiO2负载Mn-Co复合氧化物催化剂上NO催化氧化性能   总被引:2,自引:0,他引:2  
氮氧化物(NOx)是大气主要污染物之一, 主要来源于化石燃料的燃烧, 其中NO不溶于水难以去除, 催化氧化技术可以将NO氧化为易溶于水可被脱硫装置去除的NO2, 具有十分重要的实际意义. 本文采用浸渍法制备了不同Mn掺杂量的Mn-Co/TiO2复合金属氧化物催化剂, 考察了其催化NO氧化的活性. 结果表明, Mn的掺杂对Co/TiO2催化剂催化NO氧化的活性有明显促进作用, 掺杂量为6%时, Mn(0.3)-Co(0.7)/TiO2催化剂NO的转化效率最高, 300℃达到88%. 采用X射线衍射(XRD)、N2吸附/脱附、H2程序升温还原(H2-TPR)、O2程序升温脱附(O2-TPD)和原位漫反射傅里叶变换红外(in-situ DRFTIR)光谱等技术对催化剂的物理化学特征进行了表征. 结果发现, 当掺杂量为6%时, Mn一方面促进了催化剂表面活性组分的分散, 增加了催化剂的比表面积和孔径; 另一方面提高了催化剂的还原性能, 促进氧的低温脱附, 此外还促进了反应中间产物桥式NO-3向NO2的反应, 从而提高了Co/TiO2催化剂的NO氧化活性.  相似文献   

15.
Oxide catalysts with the spinel structure with the molar ratios between components Co/Mn = 1: 2, Cu/Mn = 1: 2, and Cu/Co/Mn = 2: 2: 3 (samples I–III, respectively) have been prepared by the decomposition of metal nitrate hydrate solutions in an ammonium nitrate melt. Sample IV with the ratio Cu/Co/Mn = 2: 2: 3 containing 80% γ-Al2O3 is obtained by the addition of γ-Al2O3 powder to the initial melt. The catalysts are characterized using X-ray diffraction analysis, electron microscopy, and local X-ray analysis. Catalytic activity in the reaction of CO oxidation increased in the order I < II < III < IV. The proposed method is simple, and the synthesis is rapid. Oxides with the spinel structure homogeneous in composition and morphology without any impurities can be prepared by this method. These oxides exhibited high catalytic activity in the reaction of carbon monoxide oxidation.  相似文献   

16.
采用超声处理辅助浸渍法制备了多壁碳纳米管负载的Cu-Co复合氧化物催化剂. 利用XRD、TEM、H2-TPR、XPS和Raman光谱等表征了催化剂的结构性质. 在Cu和Co氧化物以及金属氧化物与碳纳米管载体间存在强相互作用. 催化剂在富氢气氛中CO催化消除反应中,与单一Cu或Co催化剂相比,Cu-Co复合氧化物催化剂表现出独特的反应特性,特别是在较高反应温度下可同时结合CO优先氧化和CO甲烷化的反应途径来实现高效CO消除. 当Cu/Co比为1/8时活性最优,可以实现在150-250℃和高反应空速 (120 L/(h·g))富氢气氛中CO的完全消除.  相似文献   

17.
The selective oxidation of CO in the presence of hydrogen on CuO/CeO2 systems containing Fe and Ni oxides as promoters was studied. The catalysts containing 1–5 wt % CuO and 1–2.5 wt % Fe2O3 supported on CeO2 and the CuO/CeO2 systems containing 1–2.5 wt % NiO were synthesized, and their catalytic activity as a function of temperature was determined. It was found that the additives of Fe and Ni oxides increased the activity of the CuO/CeO2 catalysts with a low concentration of CuO. In this case, the conversion of CO at 150°C approached 100%. At the same time, these additives had no effect on the activity of the CuO/CeO2 systems at a CuO concentration of 5 wt % or higher, which exhibited an initially high activity in the above temperature region. The forms of CO adsorption and the amounts of active sites for CO adsorption and oxidation were studied using temperature-programmed desorption. It was found that the introduction of Fe and Ni additives in a certain preparation procedure facilitated the formation of an additional amount of active centers associated with CuO. Data on the temperature-programmed reduction of samples (the amount of absorbed hydrogen and the maximum temperature of hydrogen absorption) suggested the interaction of all catalyst components, and the magnitude of this interaction depended on the sample preparation procedure. With the use of Mössbauer spectroscopy, it was found that the procedure of iron oxide introduction into the CuO/CeO2 system was responsible for the electron-ion interactions of catalyst components and the reaction mixture.  相似文献   

18.
A series of Ti-promoted (6 wt%) Co/SiO2 catalysts with titania content of 0 to 10 wt% were sequentially prepared by incipient wetness impregnation, and characterized with X-ray diffraction, thermogravimetric analysis, chemisorption, temperature-programmed desorption and infrared spectroscopy. The influences of Ti addition and reduction temperature (400–700 °C) on the adsorptive behavior and the catalytic properties for CO hydrogenation were investigated. The presence of Ti decreases the adsorption capacity of the cobalt surface for H2, but enhances activity per gram cobalt. In addition, the turnover frequency increases 2–4 times upon Ti addition at reduction temperatures of 400–700 °C. The promotion in activity is accompanied by an enhanced selectivity for higher hydrocarbons and olefins. These modifications can be rationalized by the creation of active sites for CO dissociation. The desorption of CO2 at 100 °C during temperature-programmed desorption of CO indicates the formation of active sites for CO disproportionation. Infrared spectroscopy indicates an increase in the relative absorbance of 2060–2075 cm?1 bands upon Ti addition, which are attributed to CO adsorbed on the defect sites of the cobalt surface. Therefore, the promotion effect of Ti may be directly related to the formation of defect sites on the cobalt surface induced by the decorated titania moieties.  相似文献   

19.
《印度化学会志》2021,98(8):100116
Co3O4–SrCO3 catalysts with various Sr/Co ratios were synthesized by the coprecipitation method, and their properties were tuned by adjusting the Sr/Co molar ratio. Furthermore, the catalytic combustion of vinyl chloride (VC) was used to evaluate the catalytic activity of the Co3O4–SrCO3 catalysts. The physicochemical properties of the catalysts were studied by X-ray diffraction (XRD), infrared spectroscopy (IR), N2 sorption, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), H2 temperature-programmed reduction (H2-TPR) and VC temperature-programmed desorption (VC-TPD). The results showed that the Co3O4–SrCO3 catalysts exhibited composite phases of Co3O4 and SrCO3 and the presence of interactions between them. As a result, the crystallization of the Co3O4 phase for the Co3O4–SrCO3 catalysts was restrained, and the state of Co on the catalyst surface was adjusted. Furthermore, the reducibility and VC adsorption capacity of the Co3O4–SrCO3 catalysts with Sr/Co molar ratios of 0.2 and 0.4 were enhanced compared with those of the Co3O4 catalyst. Otherwise, catalyst SrCo-0.4 exhibited excellent catalytic performance, accompanied by the highest reaction rate and the lowest apparent activation energy. More importantly, the optimized SrCO3–Co3O4 catalyst showed superior catalytic performance compared with other transition metal oxides in previous literature. These results brought a new idea for promoting the activity of transition metal catalysts for the deep oxidation of chlorinated volatile organic compounds (CVOCs) by introducing alkaline-earth metal salts.  相似文献   

20.
Two series of Co and Ni based catalysts supported over commercial (ZrO2, CeO2, and Al2O3) nano supports were investigated for dry reforming of methane. The catalytic activity of both Co and Ni based catalysts were assessed at different reaction temperatures ranging from 500—800 °C; however, for stability the time on stream experiments were conducted at 700 °C for 6 h. Various techniques such as N2 adsorption‐desorption isotherm, temperature‐programmed reduction (H2‐TPR), temperature‐programmed desorption (CO2‐TPD), temperature‐programmed oxidation (TPO), X‐ray diffraction (XRD), thermogravimetric analysis (TGA) were applied for characterization of fresh and spent catalysts. The catalytic activity and stability tests clearly showed that the performance of catalyst is strongly dependent on type of active metal and support. Furthermore, active metal particle size and Lewis basicity are key factors which have significant influence on catalytic performance. The results indicated that Ni supported over nano ZrO2 exhibited highest activity among all tested catalysts due to its unique properties including thermal stability and reducibility. The minimum carbon deposition and thus relatively stable performance was observed in case of Co‐Al catalyst, since this catalyst has shown highest Lewis basicity.  相似文献   

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