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1.
采用共沉淀的方法制备了不同Fe 掺杂量的SO42-/SnO2-Fe2O3固体超强酸催化剂. 利用傅里叶变换红外(FTIR)光谱, 粉末X射线衍射(XRD), N2吸附-脱附实验(BET), 热重(TG)分析和扫描电镜(SEM)等方法对样品进行了表征. 考察了所得催化剂对4-叔丁基环己酮与乙二醇缩合反应的催化性能. 实验结果表明, 与未经过掺杂改性的SO42-/SnO2固体酸催化剂相比, 改性后催化剂的催化性能得到了改善. 研究了以Fe/Sn 摩尔比为0.5的SO42-/SnO2-Fe2O3固体酸为催化剂, 部分醛酮类化合物与乙二醇及1,2-丙二醇的缩合反应. 考察了反应时间、催化剂用量等因素对反应的影响. 同时, 将所得催化剂应用于环酮Baeyer-Villiger 氧化反应中, 催化剂表现出良好的催化活性, 且催化剂具有一定的循环使用性.  相似文献   

2.
A series of SnO2‐TiO2 binary oxide catalysts prepared by co‐current precipitation method was found to be a novel and good system for the selective catalytic reduction of NO by propene in the presence of oxygen with high activity and good selectivity to N2. The NO conversion to N2 over SnO2‐TiO2 oxide catalysts varied with SnO2 content and attainted a maximum at 65% over the catalyst with SnO2 content at 40wt% for a feed with 1186 ppm NO, 948 ppm propene and 2.23% O2, in He and a space velocity of 15000 h?1 at 350°C. The SnO2TiO2 catalysts could sustain moderate activity in the presence of 10% steam. Because of the identical valence and the similar radius of Sn4+ and Ti4+, SnO2‐TiO2 binary oxides can form solid solution in three different phases as proved by XRD, electron diffraction and TPR. Sn4+ is the main active species in the SnO2‐TiO2 catalysts, and it is enriched on the solid solution surface as tested by XPS analysis. H2‐TPR, NH3‐TPD and BET tests show that SnO2‐TiO2 solid solution can dilute SnO2 and suppress the activity of propene complete oxidation over SnO2. This may be beneficial to the reactivity enhancement of NO conversion.  相似文献   

3.
A carbon supported Pt–Sn electrocatalyst in the Pt/Sn atomic ratio 50:50 was prepared by the reduction of Pt and Sn precursors with formic acid and thermally treated at 200 °C (i.e., in the presence of solid tin) and 500 °C (in the presence of molten tin) in flowing hydrogen. In the absence of thermal treatment, X-ray diffraction (XRD) analysis showed a solid solution of Sn in the face centered cubic (fcc) Pt and SnO2. After thermal treatment, the formation of a main phase of hexagonal PtSn (niggliite) and a secondary phase of cubic Pt3Sn was observed in the Pt50Sn50 catalyst. The relative amount of the PtSn phase increased with increasing thermal treatment temperature. The presence of molten tin gave rise to the formation of some big particles during annealing at 500 °C. The activity for the ethanol oxidation reaction (EOR) of the as-prepared catalyst was higher than that of both thermally treated catalysts and Pt75Sn25/C and Pt50Ru50/C by E-TEK. The higher activity for the EOR of the as-prepared Pt–Sn catalysts was ascribed to the presence of a large amount of SnO2. Dedicated to Teresa Iwasita’s 65th birthday.  相似文献   

4.
Different amounts of Mn and Ce oxides were loaded onto nitric acid-modified activated carbon (ACN) by wet impregnation. The series of catalysts were employed for the selective catalytic reduction of NO x by NH3 at temperatures between 100 and 250 °C. Cerium-modified catalysts exhibited higher de-NO x performance than those modified with Mn/ACN, even with the same total loadings. The precursor solution with a molar ratio for Ce/(Mn + Ce) of 0.4 exhibited the highest catalytic activity. Enhanced resistance to SO2 and H2O and better stability were observed for 10%Mn–Ce(0.4)/ACN relative to 10%Mn/ACN. The catalysts were further characterized by N2 physisorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR), and temperature-programmed desorption of ammonia (NH3-TPD). The N2 physisorption and XRD results suggested that co-doping Ce with Mn increased the surface area and promoted the dispersion of Mn–Ce binary metal oxides. H2-TPR the NH3-TPD results demonstrated that the interaction between manganese oxide and cerium oxide species enhanced the redox and surface acidity of 10%Mn–Ce(0.4)/ACN.  相似文献   

5.
采用固相浸渍法制备了一系列NiO/CeO2催化剂,并通过与常规湿浸渍法比较,考察了制备方法对催化剂和CO氧化反应性能的影响.同时结合X射线衍射(XRD),N2吸附-脱附(BET),透射电镜(TEM),氢气-程序升温还原(H2-TPR),拉曼(Raman)光谱,X射线光电子能谱(XPS)等手段对催化剂的结构和表面物种分散状态进行了表征.CO氧化活性测试结果表明,当镍负载量相同时,固相浸渍法制备的催化剂相比于湿浸渍法表现出更好的催化性能.TEM、XPS、H2-TPR结果表明,固相浸渍法更有利于加强镍铈间的相互作用和得到高分散的镍物种,从而促进镍物种的还原.Raman结果表明固相浸渍法相比于湿浸渍法能产生更多氧空位,这有利于氧气在催化剂表面的活化,使得CO氧化反应更容易进行.  相似文献   

6.
采用共沉淀法制备了不同铈铬比例的CeO2-CrOx复合氧化物(Ce/Cr 摩尔比分别为9/1、4/1、2/1、1/1、1/2、1/4、1/8)以及单纯的CeO2和Cr2O3, 并研究了各催化剂对1,2-二氯乙烷(DCE)的催化氧化性能. 结果表明,相较于单纯的CeO2, 不同铈铬比例的复合氧化物催化剂对DCE的催化氧化活性有明显提高, 其中Ce/Cr 摩尔比为2/1的CeO2-CrOx复合氧化物上DCE的氧化活性最好, 且只有极微量的含氯等副产物产生; 随着Ce/Cr 摩尔比减小, 对HCl的选择性有下降的趋势. 通过X射线衍射(XRD)、N2吸附/脱附(BET)、紫外拉曼(UV-Raman)光谱、H2程序升温还原(H2-TPR)、NH3程序升温脱附(NH3-TPD)等实验技术, 研究了铈铬比例对铈铬复合氧化物的物理化学性质的影响. 结果表明, 适当比例Ce-Cr的复合, 形成了结构较稳定的Ce-Cr-O固溶体, 提高了催化剂活性氧物种的流动性, 催化剂表面酸量及强弱酸比例, 从而有利于DCE的吸附活化, 进一步脱氯降解以及深度氧化.  相似文献   

7.
PtRu/C anode electrocatalysts modified by Sn were prepared for ethanol oxidation reaction (EOR). Their phase structures, surface species, surface compositions, and EOR activities were characterized by XRD, XPS, temperature-programmed reduction (TPR), and CV, respectively. It has been found that in the PtRu/SnxC and PtSn/C alloy catalysts, some Sn alloyed with Pt to form Pt–Sn phase existed as the metallic state, however, the excess Sn existed as the amorphous SnO or crystalline SnO2. Surface analyses and electrochemical measurements suggest that the surface Ru and amorphous SnO instead of the crystalline SnO2 are important species for the promotion of EOR. As a result, compared with PtSn/C, the I06 was enhanced about 200% for the PtRu/C electrocatalyst with 10 wt% of Sn modification.  相似文献   

8.
Nanoclusters of Pt, Pt–Rh, Pt–SnO2 and Pt–Rh–SnO2 were successfully synthesized by polyol method and deposited on high-area carbon. HRTEM and XRD analysis revealed two phases in the ternary Pt–Rh–SnO2/C catalyst: solid solution of Rh in Pt and SnO2. The activity of Pt–Rh–SnO2/C for ethanol oxidation was found to be much higher than Pt/C and Pt–Rh/C and also superior to Pt–SnO2/C. Quasi steady-state measurements at various temperatures (30–60 °C), ethanol concentrations (0.01–1 M) and H2SO4 concentrations (0.02–0.5 M) showed that Pt–Rh–SnO2/C is about 20 times more active than Pt/C in the potential range of interest for the fuel cell application.  相似文献   

9.
A series of Sn-Fe binary oxide catalysts with different Sn/Fe mole ratios were prepared by the combination of redox reactions and coprecipitation methods, and used in CH4 deep oxidation. It is found that Sn-Fe binary catalysts show higher activity than pure SnO2 and Fe2O3. XRD and BET surface area results illustrate that the binary catalysts have lower crystallinity and higher surface areas than the pure samples. Furthermore, TPR and XPS results demonstrate that more active oxygen species are formed in the Sn-Fe binary samples. Indeed, these could be the predominant reasons leading to the enhanced CH4 oxidation activity of the Sn-Fe binary catalysts.  相似文献   

10.
The electrocatalytic carbon dioxide reduction reaction (CO2RR) producing HCOOH and CO is one of the most promising approaches for storing renewable electricity as chemical energy in fuels. SnO2 is a good catalyst for CO2-to-HCOOH or CO2-to-CO conversion, with different crystal planes participating the catalytic process. Among them, (110) surface SnO2 is very stable and easy to synthesisze. By changing the ratio of Sn: O for SnO2(110), we have two typical SnO2 thin films: fully oxidized (stoichiometric) and partially reduced. In this work, we are concerned with different metals (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au)-doped SnO2(110) with different activity and selectivity for CO2RR. All these changes are manipulated by adjusting the ratio of Sn: O in (110) surface. The results show that stochiometric and reduced Cu/Ag doped SnO2(110) have different selectivity for CO2RR. More specifically, stochiometric Cu/Ag-doped SnO2(110) tends to generate CO(g). Meanwhile, the reduced surface tends to generate HCOOH(g). Moreover, we also considered the competitive hydrogen evolution reaction (HER). The catalysts SnO2(110) doped by Ru, Rh, Pd, Os, Ir, and Pt have high activity for HER, and others are good catalysts for CO2RR.  相似文献   

11.
CH4和 CO是两种主要的温室效应气体和空气污染物,催化氧化是最有效的消除 CH4和 CO的方法.研发不含贵金属的金属氧化物催化剂或者减少催化剂中贵金属用量为该领域研究热点. SnO2是一种重要的宽禁带 n型半导体材料,广泛应用于气敏器件、锂离子电池以及光电设备. SnO2表面富含活泼的缺位氧且具有良好的热稳定性,因此其在催化方面的性能近年来逐渐受到人们关注.在过去的5年中,本团队深入研究了 SnO2材料在空气污染治理和绿色能源生产等领域的应用及其催化性质.发现通过其它阳离子如 Fe3+, Cr3+, Ta5+, Ce4+和Nb5+等的掺杂,替换晶格中部分 Sn4+,形成金红石型 SnO2固溶体结构,显著提高了催化剂氧物种的流动性、活性和催化剂本身的热稳定性.固溶体材料是一类重要的催化剂,受到广泛关注.一个典型的例子是铈锆固溶体,其作为储氧材料已广泛应用于汽车尾气净化器.形成固溶体结构后,氧化铈的储氧能力和热稳定性得到显著提高.为有效形成固溶体,两个阳离子需要具有相似的离子半径和电负性.以往,人们基于结构中金属阳离子和氧阴离子的离子半径提出了容忍因子的判别方法,以此来判断固溶体是否能有效形成及所生成固溶体的稳定性.我们在前期工作中,以 Sn-Nb固溶体为例,提出了简单的X射线衍射(XRD)外推法来计算固溶体晶格容量,即形成稳定固溶体时客体阳离子取代主体晶格阳离子的最大值.作为延续工作,本文采用共沉淀法制备了一系列 Sn/M (M = Mn, Zr, Ti, Pb)摩尔比为9/1的 SnO2基催化剂,并用于 CH4和 CO催化氧化.结果表明, Mn3+, Zr4+, Ti4+和 Pb4+均可以掺杂进四方金红石型 SnO2晶格中,形成稳定的固溶体结构.其中 Sn-Mn-O固溶体表现出最高活性.为了深入研究 Mn2O3在 SnO2中的晶格容量及最优催化剂配比,采用共沉淀法制备了一系列不同 Sn/Mn摩尔比的样品,采用 XRD, N2-BET, H2-TPR, SEM和XPS等手段对其物理化学性能进行了表征,并考察了对 CH4的催化氧化性能.通过 XRD外推法测定了 Mn3+离子在 SnO2中的晶格容量为0.135 g Mn2O3/g SnO2,相当于 Sn/Mn摩尔比为79/21.这表明形成稳定的固溶体后, SnO2晶格中最多只有21% Sn4+可以被 Mn3+替代;当 Mn3+含量超过晶格容量时,过量的 Mn3+在催化剂表面形成 Mn2O3,对催化剂活性不利.类似于 Sn-Nb-O固溶体,在 Sn-Mn-O催化剂体系中亦观察到明显的晶格容量效应.纯相的 Sn-Mn-O固溶体比含过量 Mn2O3晶相的 Sn-Mn-O催化剂具有更高活性.  相似文献   

12.
ZnO doped SnO2 has been successfully synthesized by the solvothermal method using methanol as organic solvent. The effect of ZnO/SnO2 molar ratios on the crystal structure, microstructure, optical and photocatalytic properties has been investigated. The synthesized samples are characterized by X-ray diffraction, transmission electron microscopy, N2 physical adsorption, FT-IR spectroscopy and UV–Vis spectroscopy. XRD results revealed that all diffraction peaks positions agree well with the reflection of a tetragonal rutile structure of SnO2 phase without extra peaks at 0.1ZnO:0.9SnO2 and 0.2ZnO:0.8SnO2 molar ratios. However, the secondary phase of ZnO at 0.3ZnO:0.7SnO2 molar ratio was investigated. TEM images revealed that the shape of SnO2 particles was spherical and the particle sizes of SnO2 and 0.3ZnO:0.7SnO2 molar ratio were 6.2 and 16.4 nm, respectively. The newly prepared samples have been tested by the determination of photocatalytic degradation of methylene blue (MB). The results indicated that Zn2+ doping at 0.3ZnO:0.7 SnO2 molar ratio showed the highest photocatalytic activity for the MB photodegradation. The heightened photocatalytic activity of ZnO/SnO2 could be ascribed to the enhanced charge separation derived from the coupling of ZnO with SnO2 due to the potential energy differences between SnO2 and ZnO. The recycling tests demonstrated that 0.3ZnO:0.7 SnO2 photocatalysts were quite stable during that liquid–solid heterogeneous photocatalysis since no decrease in activity in the first four cycles was observed.  相似文献   

13.
The preparation and spectroscopic characterization of [R3Sn(O2CCH2SC5H4N-4)], R == Ph, benzyl (Bz), cyclohexyl (c-Hex) and n-Bu, and of [R3Sn(O2CCH2SC4H3N2-2,6)], R == Me, Ph and n-Bu, are reported. The 2-pyrimidyl compounds feature trigonal bipyramidal tin centres with trans-R3SnO2 geometries as was confirmed by X-ray crystallography for [Ph3Sn(O2CCH2SC4H3N2-2,6)]. ¶ By contrast the 4-pyridyl compounds have trigonal bipyramidal geometries in the solid state (arising from intermolecular Sn…N interaction) and tetrahedral geometries in solution. The biocidal activity of these compounds against the fungi Helminthosporium maydis (ITCC 2675) and H. oryzae (ITCC 2675), both of which damage crops such as maize and rice, shows promise. Encouraging is the observation that the compounds show no adverse phytotoxicity at concentrations to 10?3M.  相似文献   

14.
Cu/SnO2/SiO2 catalysts, prepared with three different copper precursors (copper nitrate, sulfate and chloride), were characterized and investigated for the steam reforming of methanol. Cu/SnO2/SiO2 catalyst, prepared with copper nitrate, showed the highest activity among the tested catalysts. The highest activity of the catalyst prepared with copper nitrate was ascribed to the highly dispersed Cu particles from CO adsorption experiment. The selectivity of methanol to H2 decreased with an increase in the amount of acid on the surface of Cu/SnO2/SiO2 catalysts from FT-IR experiments.This revised version was published online in December 2005 with corrections to the Cover Date.  相似文献   

15.
Nanocomposite samples containing various molar compositions of tin and titanium oxides were synthesized by a sol–gel method using octadecylamine as controlling template agent. The structural and the crystalline features of the samples were investigated with Fourier Transformer Infra-red, X-ray diffraction, Transmission electron microscope (TEM) where the surface area was estimated by BET analysis. The crystalline parameters and the particle size were estimated by Rietveld quantitative phase analysis. It is interesting to mention that a reduction in the lattice parameters was detected upon introduction of various molar compositions of titanium oxide revealing that a part of titania is incorporated into the SnO2 lattice forming Ti1−xSnxO2 solid solution. The quantitative analysis claims that part of titanium oxide is incorporated substitutionally in the crystal lattice of SnO2, forming a solid solution and other parts are either segregated as separate rutile titania phase or dispersed as amorphous phase on the grain boundary of SnO2. The results show a remarkable reduction in particle size from 42 to 5 nm and increasing in the specific surface area up to 176 m2/g upon introduction of various content of titania implying the role of titania particles in preventing SnO2 crystallites from further growing up during the progress of calcination. TEM images show that pure tin oxide particles arranged in large aggregation in wormhole like structure, while the existence of titanium oxide are successfully creates spherical nanoparticles system organized in a definite structure. The optical absorbance spectra indicate a red shift and band gap narrowing upon introduction of titania which increase with increasing in titania contents.  相似文献   

16.
Highly ordered mesoporous cobalt-copper composite oxides were prepared by the nanocasting method with various Co and Cu ratios. The catalysts obtained were characterized by X-ray diffraction, N2 adsorption–desorption, H2-temperature programmed reduction, CO-temperature programmed desorption and X-ray photoelectron spectroscopy. All of the catalysts had uniform mesopores and high surface areas. The distinct catalytic properties of these well-characterized mesoporous materials were demonstrated for preferential CO oxidation. It is found that the mesoporous cobalt-copper composite oxides, exhibited the higher catalytic activity for CO conversion and selectivity compared with the mesoporous Co3O4 and mesoporous CuO. Among these catalysts the mesoporous cobalt-copper catalyst with Co:Cu molar ratio of 70:30, shows the best catalytic activity and the broadest operating temperature “window” for the high CO conversion in the range of 125–200oC. The higher catalytic activity was attributed to the higher CO adsorption and oxygen vacancies.  相似文献   

17.
ZnO–SnO2 nanoparticles were prepared by coprecipitation method; then Mg, with different molar ratios and calcination temperatures, was loaded on the coupled nanoparticles by impregnation method. The synthesized nanoparticles were characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), and Brunauer–Emmett–Teller (BET) techniques. Based on XRD results, the ZnO–SnO2 and Mg/ZnO–SnO2 nanoparticles were made of ZnO and SnO2 nanocrystallites. According to DRS spectra, the band gap energy value of 3.13 and 3.18 eV were obtained for ZnO–SnO2 and Mg/ZnO–SnO2 nanoparticles, respectively. BET analysis revealed a Type III isotherm with a microporous structure and surface area of 32.051 and 49.065 m2 g?1 for ZnO–SnO2 and Mg/ZnO–SnO2, respectively. Also, the spherical shape of nanocrystallites was deduced from TEM and FESEM images. The photocatalytic performance of pure ZnO–SnO2 and Mg/ZnO–SnO2 was analyzed in the photocatalytic removal of methyl orange (MO). The results indicated that Mg/ZnO–SnO2 exhibited superior photocatalytic activity to bare ZnO–SnO2 photocatalyst due to high surface area, increased MO adsorption and larger band gap energy. Maximum photocatalytic activity of Mg/ZnO–SnO2 nanoparticles was obtained with 0.8 mol% Mg and calcination temperature of 350°C.  相似文献   

18.
Pure SnO2, sulfated SnO2-SO4 2- and Pd supported on SnO2 and SnO2-SO4 2- were prepared from SnO2 precursor with high surface area, and used for CH4 deep oxidation. The catalysts were characterized by means of N2-BET, XRD, TG-DTA, XPS and TPD. SnO2-SO4 2- shows higher activity than SnO2, due to the presence of more active oxygen species, superacid sites and its higher BET surface area. Pd/SnO2 and Pd/SnO2-SO4 2- display essentially the same activity to each other, while it is much higher than the activity on SnO2 and SnO2-SO4 2-. The main reason is ascribed to the concerted action between Pd and the supports.  相似文献   

19.
以十六烷基三甲基溴化胺(CTAB)为模板剂,通过调变CTAB浓度水热合成了氧化钴前驱体,焙烧制得棒状形貌的Co3O4,在其表面浸渍K2CO3溶液制得K改性的Co3O4催化剂,用于N2O分解。用X射线衍射(XRD)、N2物理吸附(BET)、扫描电镜(SEM)、X射线光电子能谱(XPS)、H2程序升温还原(H2-TPR)和O2程序升温脱附(O2-TPD)等技术对催化剂进行了表征,考察了CTAB/钴及尿素/钴物质的量比等制备参数对Co3O4催化分解N2O活性的影响。结果表明,CTAB浓度为0.05 mol/L、CTAB/钴离子物质的量比为1、尿素/钴离子物质的量比为4时,所制备的Co3O4催化剂具有较高的N2O分解活性,而K改性可以进一步提升其催化性能。K改性的Co3O4在有氧有水气氛中400℃下进行N2O分解反应,50 h后N2O转化率仍保持在91%以上。  相似文献   

20.
以MCM-41为载体,采用一种简捷、温和法制备了负载型Ni2P/MCM-41催化剂。用H2程序升温还原(H2-TPR)、X射线衍射(XRD)、N2吸附比表面积测定(BET)和X射线光电子能谱(XPS)分析对催化剂进行了表征。以1%(质量分数)二苯并噻吩(DBT)的十氢萘溶液为原料,在连续固定床反应装置上,研究了初始Ni/P物质的量比对催化剂HDS活性的影响,并考察了催化剂的稳定性。结果表明,初始Ni/P物质的量比为1/2和1/3的前驱体,在390 ℃下还原时得到单一的Ni2P相。初始Ni/P物质的量为1/2时,得到的催化剂活性最好。在反应温度340 ℃、压力3.0 MPa、氢/油体积比500、质量空速2.0 h-1时,DBT的转化率接近100%。  相似文献   

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