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1.
王凌翔  王亮  张建  王海  肖丰收 《催化学报》2018,39(10):1608-1614
CO催化氧化是一个重要的经典反应,与许多应用息息相关,包括痕量CO气体检测、汽车尾气净化和安全防护等,吸引了人们广泛的研究兴趣.负载型Au纳米颗粒在CO氧化等许多反应中有着与众不同的催化活性,具有广泛的应用前景,但依然存在着稳定性差、易团聚失活的问题.人们通过应用多孔载体隔离Au纳米颗粒,在Au纳米颗粒表面覆盖金属氧化物、二氧化硅或碳,以及对Au纳米粒子进行封装等方法解决这些问题.尤其是利用金属氧化物与Au纳米粒子间的强相互作用对其进行覆盖或封装,有效地提高了Au催化材料的稳定性.但以上策略操作流程复杂,不利于应用.本文发展了一种简单有效的方法,通过EDTA的络合作用引入CeOx对Au纳米粒子进行修饰,得到的CeOx@Au/SiO2催化剂活性和耐久性明显提升.采用X射线衍射(XRD)和高分辨透射电子显微镜(HRTEM)证明了CeOx成功地修饰在Au纳米颗粒上.且通过EDTA引入CeOx所制备的CeOx@Au/SiO2催化剂结构明显不同于直接加入纳米CeO2所得到的CeOx-Au/SiO2的结构.EDTA的络合作用能有效地连结Ce与Au物种,经焙烧消除EDTA后,加强了CeOx与Au间相互作用,最终在Au纳米粒子表面形成丰富的CeOx颗粒与原子级厚度的CeOx层.进一步应用X射线光电子能谱(XPS)和氢气程序升温还原(H2-TPR)等手段研究了CeOx修饰对Au纳米粒子的影响.XPS结果表明,CeOx@Au/SiO2催化剂带正电的Au+和Au3+的浓度明显高于一般的Au/SiO2和直接加入CeO2制备得到的CeOx-Au/SiO2催化剂.H2-TPR同样表明,CeOx修饰调变了Au纳米粒子的氧化还原性.这些均对其在CO催化氧化反应中的催化活性具有重要影响将CeOx@Au/SiO2催化剂用于CO催化氧化反应中,160°C时,CO转化率达98.8%,至180°C后实现了CO的完全转化.而一般的Au/SiO2催化剂在160°C时CO转化率仅为4.0%,CO的完全转化则需340°C.直接加入纳米CeO2所得到的CeOx-Au/SiO2催化剂,其催化活性略有提升,CO完全转化所需的温度为300°C.这充分证明了通过CeOx修饰Au纳米粒子,能有效提升其催化活性.原位漫反射红外光谱(DRIFT)结果表明,CeOx修饰促进了CO在Au表面的吸附,并能形成[Au(CO)2]δ+物种;同时还观察到大量的单齿CO32? 物种信号,反映了CeOx@Au/SiO2催化剂表面存在丰富的活性氧物种.通入O2后,观察到了大量CO32?物种信号和气相CO2,印证了催化剂表面发生的CO催化氧化过程,也表明其具有非常高的催化活性.考察了CeOx@Au/SiO2催化剂的耐久性,发现经50 h CO氧化反应,催化剂依然能有效保持活性.相比之下,Au/SiO2催化剂经10 h反应后,开始明显失活.由此可见,CeOx@Au/SiO2催化剂具有相当高的耐久性.在600°C将催化剂焙烧3 h,发现Au/SiO2催化剂中Au纳米粒子存在明显团聚现象,而CeOx@Au/SiO2催化剂的Au纳米粒子依然均匀分布在载体表面,且粒径未发生明显变化.  相似文献   

2.
Undoped and silver-doped TiO2 nanoparticles (Ti1?x Ag x O2, where x?=?0.00?C0.10) were synthesized by a sol?Cgel method. The synthesized products were characterized by X-ray diffraction (XRD), particle size analyzer (PSA), scanning electron microscope (SEM), and UV?CVisible spectrophotometer. XRD pattern confirmed the tetragonal structure of synthesized samples. Average crystallite size of synthesized nanoparticles was determined from X-ray line broadening using the Debye?CScherrer formula. The crystallite size was varied from 8 to 33?nm as the calcination temperature was increased from 300 to 800?°C. The incorporation of 3 to 5% Ag+ in place of Ti4+ provoked a decrease in the size of nanocrystals as compared to undoped TiO2. The SEM micrographs revealed the agglomerated spherical-like morphology of particles. SEM, PSA, and XRD measurements show that the particles size of the powder is in nanoscale. Optical absorption measurements indicated a red shift in the absorption band edge upon silver doping. Direct allowed band gap of undoped and Ag-doped TiO2 nanoparticles measured by UV?CVis spectrometer were 3.00 and 2.80?eV, respectively, at 500?°C.  相似文献   

3.
Ag nanoparticles grown on reduced CeO2-x thin films have been studied by X-ray photoelec-tron spectroscopy and resonant photoelectron spectroscopy of the valence band to understand the effect of oxygen vacancies in the CeO2-x thin films on the growth and interfacial elec-tronic properties of Ag. Ag grows as three-dimensional particles on the CeO2-x(111) surface at 300 K. Compared to the fully oxidized ceria substrate surface, Ag favors the growth of smaller particles with a larger particle density on the reduced ceria substrate surface, which can be attributed to the nucleation of Ag on oxygen vacancies. The binding energy of Ag3d increases when the Ag particle size decreases, which is mainly attributed to the final-state screening. The interfacial interaction between Ag and CeO2-x(111) is weak. The resonant enhancement of the 4f level of Ce3+ species in RPES indicates a partial Ce4+→Ce3+ re-duction after Ag deposited on reduced ceria surface. The sintering temperature of Ag on CeO1.85(111) surface during annealing is a little higher than that of Ag on CeO2(111) surface, indicating that Ag nanoparticles are more stable on the reduced ceria surface.  相似文献   

4.
The model RhOx/CeO2 systems were prepared by radio-frequency (RF) plasma sputtering of Rh electrode in O2 or Ar/O2 atmosphere. Thermal stability of the systems and their reaction probability towards CO oxidation were studied by X-ray photoelectron spectroscopy. It was shown that the small oxidized Rh nanoparticles on the CeO2 surface (RhOx/CeO2) obtained by RF sputtering in O2 have spectroscopic characteristics close to those of Rh3+ ions highly dispersed in ceria lattice. The RhOx/CeO2 system remains stable upon heating in vacuum at 450°C and shows reactivity towards CO oxidation at T > 200°C. RF sputtering in Ar/O2 atmosphere results in the formation of larger rhodium nanoparticles that are close to Rh2O3 oxide. The Rh2O3/CeO2 system demonstrates lower activity in CO oxidation and cannot be reduced at a temperature below 300°C.  相似文献   

5.
采用不同方法制备了铈锆复合氧化物催化剂用于催化HCl氧化反应。自发沉积策略制备的CeO2@ZrO2催化剂中,超细CeO2纳米粒子均匀的镶嵌于非晶态ZrO2中。CeO2粒子显著的“尺寸效应”使得该催化剂具有更高的Ce3+和氧空位浓度,而较高的Ce3+和氧空位浓度使得催化剂具有优异的低温氧化还原性能和储释氧能力。催化性能测试表明,CeO2@ZrO2催化剂展现出最好的催化活性(1.90 gCl2·gcat-1·h-1),同时CeO2粒子周围非晶态的ZrO2阻碍CeO2的高温烧结,提高了该催化剂的稳定性。  相似文献   

6.
研究了低于300 ℃时两种氧化铈对稀燃阶段NOx存储性能的影响,催化剂由2%(w)Pt/Al2O3(PA)与CeO2-X(X=S,I)机械混合制备. X射线衍射(XRD),BET表面积和扫描电子显微镜(SEM)用于表征材料的物理结构. X射线光电子能谱(XPS)和H2程序升温还原(H2-TPR)用于表面Ce3+和活性氧定量. 原位漫反射傅里叶变换红外光谱(in-situ DRIFTS)用于分析表面NOx吸附物种. 相比于CeO2-I,CeO2-S 具有优良的物理化学性能,包括高比表面积、丰富的空隙结构、较高的抗老化能力及表面Ce3+浓度. 因而,Pt/Al2O3+CeO2-S 表现出优异的NOx存储能力. 此外,PA+CeO2-X(X=S,I)上存在Pt 与CeO2之间的相互作用,可提高表面氧物种的活性进而促进NO氧化及NOx存储. PA+CeO2-S上的这种相互作用要强于PA+CeO2-I. 研究表明,表面Ce3+浓度和活性氧含量对NOx存储起到重要作用. 然而经过水热处理后,Pt 与老化的氧化铈(ACS,ACI)之间的相互作用降低,并且两种氧化铈NOx存储性能显著下降. 另外,与PA+ACS(ACI)相比,PA+PACS(PACI)样品NOx存储能力得到改善,这归因于表面氧物种活性增加能促进硝酸盐的形成.  相似文献   

7.
采用不同方法制备了铈锆复合氧化物催化剂用于催化HCl氧化反应。自发沉积策略制备的CeO_2@ZrO_2催化剂中,超细CeO_2纳米粒子均匀的镶嵌于非晶态ZrO_2中。CeO_2粒子显著的"尺寸效应"使得该催化剂具有更高的Ce~(3+)和氧空位浓度,而较高的Ce~(3+)和氧空位浓度使得催化剂具有优异的低温氧化还原性能和储释氧能力。催化性能测试表明,CeO_2@ZrO_2催化剂展现出最好的催化活性(1.90 gCl2·gcat~(-1)·h~(-1)),同时CeO_2粒子周围非晶态的ZrO_2阻碍CeO_2的高温烧结,提高了该催化剂的稳定性。  相似文献   

8.
CeO2 nanoparticles have been proven to be competent photocatalysts for environmental applications because of their strong redox ability, nontoxicity, long-term stability, and low cost. We have synthesized CeO2 nanoparticles via solution combustion method using ceric ammonium nitrate as an oxidizer and ethylenediaminetetraacetic acid (EDTA) as fuel at 450 °C. These nanoparticles exhibit good photocatalytic degradation and antibacterial activity. The obtained product was characterized by various techniques. X-ray diffraction data confirms a cerianite structure: a cubic phase CeO2 having crystallite size of 35 nm. The infrared spectrum shows a strong band below 700 cm−1 due to the Ce−O−Ce stretching vibrations. The UV/Vis spectrum shows maximum absorption at 302 nm. The photoluminescence spectrum shows characteristic peaks of CeO2 nanoparticles. Scanning electron microscopy (SEM) images clearly show the presence of a porous network with a lot of voids. From transmission electron microscopy (TEM) images, it is clear that the particles are almost spherical, and the average size of the nanoparticles is found to be 42 nm. CeO2 nanoparticles exhibit photocatalytic activity against trypan blue at pH 10 in UV light, and the reaction follows pseudo first-order kinetics. Finally, CeO2 nanoparticles also reduce CrVI to CrIII and show antibacterial activity against Pseudomonas aeruginosa.  相似文献   

9.
A novel carbonate (co)precipitation method, employing nitrates as the starting salts and ammonium carbonate as the precipitant, has been used to synthesize nanocrystalline CeO2 and Ce1−xYxO2−x/2 (x≤0.35) solid-solutions. The resultant powders are characterized by elemental analysis, differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffractometry (XRD), Brunauer-Emmett-Teller (BET) analysis, and high-resolution scanning electron microscopy (HRSEM). Due to the direct formation of carbonate solid-solutions during precipitation, Ce1−xYxO2−x/2 solid-solution oxides are formed directly during calcination at a very low temperature of ∼300°C for 2 h. The thus-produced oxide nanopowders are essentially non-agglomerated, as revealed by BET in conjunction with XRD analysis. The solubility of YO1.5 in CeO2 is determined via XRD to be somewhere in the range from 27 to 35 mol%, from which a Y2O3-related type-C phase appears in the final product. Y3+-doping promotes the formation of spherical nanoparticles, retards thermal decomposition of the precursors, and suppresses significantly crystallite coarsening of the oxides during calcination. The activation energy for crystallite coarsening increases gradually from 68.7 kJ mol−1 for pure CeO2 to 138.6 kJ mol−1 for CeO2 doped with 35 mol% YO1.5. The dopant effects on crystallite coarsening is elaborated from the view point of solid-state chemistry.  相似文献   

10.
MnxZn1−xFe2O4 (x = 0.05…0.9) nanoparticles prepared via sol–gel hydrothermal process were investigated by X-ray powder diffractometry (XRPD), transmission electron microscopy (TEM), 57Fe Mössbauer spectroscopy (MS), electron paramagnetic resonance spectroscopy (EPR), X-ray absorption near edge structure spectroscopy (XANES) and magnetic hysteresis measurements. XRPD measurements revealed a non-monotonic dependence of the cubic lattice parameter on the Mn concentration, which is interpreted as being the result of a corresponding variation in the inversion degree (concentration of Fe ions on the occupied tetrahedral lattice sites) of the studied spinels. XANES measurements indicated that the average oxidation state of Mn ions decreases with the applied Mn concentration, in contrast with Fe ions that were found to be exclusively in the 3+ oxidation state by MS measurements. EPR spectra recorded as a function of temperature enabled the determination of the characteristic anisotropy energy barrier of the superparamagnetic particles, and contributed to the clarification of peculiarities of the corresponding 57Fe Mössbauer spectra. On the basis of the observed results the interdependences among the sample stoichiometry, the cubic cell parameter, the particle size, the inversion degree, the magnetic ordering temperature and the effective magnetic anisotropy are discussed.  相似文献   

11.
The effect of CeO2 preparation procedure on the electronic and structural states of the active component of Pd/CeO2 catalysts and their activity in the low-temperature reaction of CO oxidation was studied. The following two nonequivalent states of palladium were detected in the catalysts having low-temperature activity using XPS and IR spectroscopy: Pd0(Pdδ+) as the constituent of a palladium-reduced interaction phase and Pd2+ as the constituent of a palladium-oxidized interaction phase Pd x CeO2 ?δ. It was found that the procedure used for preparing a CeO2 support considerably affected the formation of these phases and quantitative ratios between them. It was demonstrated that the palladium-oxidized interaction phase was responsible for low-temperature activity, whereas the palladium-reduced interaction phase was responsible for activity in the region of medium and high temperatures.  相似文献   

12.
By carefully mixing Pd metal nanoparticles with CeO2 polycrystalline powder under dry conditions, an unpredicted arrangement of the Pd‐O‐Ce interface is obtained in which an amorphous shell containing palladium species dissolved in ceria is covering a core of CeO2 particles. The robust contact that is generated at the nanoscale, along with mechanical forces generated during mixing, promotes the redox exchange between Pd and CeO2 and creates highly reactive and stable sites constituted by PdOx embedded into CeO2 surface layers. This specific arrangement outperforms conventional Pd/CeO2 reference catalysts in methane oxidation by lowering light‐off temperature by more than 50°C and boosting the reaction rate. The origin of the outstanding activity is traced to the structural properties of the interface, modified at the nanoscale by mechanochemical interaction.  相似文献   

13.
Metal–support interactions (MSIs) and particle size play important roles in catalytic reactions. For the first time, silver nanoparticles supported on CeO2‐SBA‐15 supports are reported that possess tunable particle size and MSIs, as prepared by microwave (MW) irradiation, owing to strong charge polarization of CeO2 clusters (i.e., MW absorption). Characterizations, including TEM, X‐ray photoelectron spectroscopy, and extended X‐ray absorption fine structure, were carried out to disclose the influence of CeO2 contents on the Ag particle size, MSI effect between Ag nanoparticles and CeO2‐SBA‐15 supports, and the strong MW absorption of CeO2 clusters that contribute to the MSIs during Ag deposition. The Ag particle sizes were controllably tuned from 1.9 to 3.9 nm by changing the loading amounts of CeO2 from 0.5 to 2.0 wt %. The Ag nanoparticle size was predominantly responsible for the high turnover frequency (TOF) of 0.41 min?1 in ammonia borane dehydrogenation, whereas both particle size and MSIs contributed to the high TOF of 555 min?1 in 4‐nitrophenol reduction for Ag/0.5CeO2‐SBA‐15, which were twice as large as those of Ag/SBA‐15 without CeO2 and Ag/CeO2‐SBA‐15 prepared by conventional oil‐bath heating.  相似文献   

14.

Cr/MgO(x)–CeO2(100?x) nanocatalysts were synthesized by a coprecipitation method and characterized by X-ray diffraction (XRD) analysis, field-emission scanning electron microscopy (FESEM), energy-dispersive x-ray (EDX) spectroscopy, diffuse reflectance spectroscopy (DRS), and Brunauer–Emmett–Teller (BET) analysis. The effect of ceria addition on their physicochemical characteristics was investigated, and the results were correlated with their catalytic performance in oxidative dehydrogenation of ethane. A decrease in the size of the metal particles was found when adding a suitable content of ceria to the support. Crystalline Cr2O3 was not found in the calcined samples, indicating good dispersion of Cr species on the support. All samples showed nanosized particles with uniform morphology, with the best surface morphology for the Cr/MgO(50)–CeO2(50) sample, on which the particle distribution mainly lay in the range of 40–60 nm. Variation of the amount of Ce in the support led to an enhancement of the Cr6+/Cr3+ ratio, with the highest value for the Cr/MgO(50)–CeO2(50) sample. This catalyst effectively dehydrogenated ethane to ethylene with CO2 at 700 °C even after 5 h on-stream, giving 42.76 % ethylene yield.

  相似文献   

15.
Nanocrystals of Ce1?xPbxO2?δ (x = 0.00, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, and 0.35) were prepared by a hydrothermal reaction route. During the formation reaction, buffer solutions were explored as an effective additive to retain the initial molar ratio. With increasing the Pb2+ content, the average crystallite size was slightly retarded. Morphologies observed by transmission electron microscope indicated that the particles were spherical-like and highly uniformed. Pb2+ ions are homogenously distributed in the solid solutions. Analyses using X-ray diffraction, Raman and UV spectroscopies showed that the solid solubility limit of Pb2+ in CeO2 was about x = 0.20. For x < 0.20, with increasing the Pb2+ content, the bulk conductivity increased, and the oxygen storage capacity was enhanced as followed by a decrease in reduction temperature.  相似文献   

16.
The effect of Sm doping on CeO2 for its use as a solid electrolyte material for intermediate temperature solid oxide fuel cells (IT-SOFCs) has been explored here. Ce1−xSmxO2−δ (x = 0.1–0.3) samples are successfully synthesized by carbonate co-precipitation method. TG–DTA, XRD, Raman, UV–Vis, FT-IR, SEM and ac-impedance are used for structural and electrical characterization. From the XRD patterns, well-crystalline cubic fluorite structured solid solution is confirmed. Lattice parameters increased with increase in Sm3+ while the crystallite size decreased. The optical absorption spectra exhibits a red shift for Sm3+ doped CeO2. Raman spectra show an intense peak at 463 cm−1, a characteristic peak for doped ceria. SEM shows cluster like particles. Based on ac-impedance data, the total oxygen ionic conductivity is highest for Ce0.8Sm0.2O2−δ in the temperature range of 473–623 K.  相似文献   

17.
Transition‐metal sulfides (TMSs) have emerged as important candidates for oxygen evolution reaction (OER) electrocatalysts. Now a hybrid nanostructure has been decorated with CeOx nanoparticles on the surface of ZIF‐67‐derived hollow CoS through in situ generation. Proper control of the amount of CeOx on the surface of CoS can achieve precise tuning of Co2+/Co3+ ratio, especially for the induced defects, further boosting the OER activity. Meanwhile, the formation of protective CeOx thin layer effectively inhibits the corrosion by losing cobalt ion species from the active surface into the solution. It is thus a rare example of a hybrid hetero‐structural electrocatalyst with CeOx NPs to improve the performance of the hollow TMS nanocage.  相似文献   

18.
Ce1?x Ti x O2 nanocomposites supported on attapulgite clay (Ce1?x Ti x O2/ATP) were prepared by a facile sol–gel route. The textural and structural properties of the prepared products were characterized by thermogravimetric-differential scanning calormetry analysis, X-ray diffraction, transmission electron microscopy, energy-dispersive spectrometry, Fourier transform infrared spectroscopy and Nitrogen adsorption-desorption measurements. The catalytic activity of the prepared Ce1?x Ti x O2/ATP catalysts for rhodamine B degradation was investigated. Results indicate that the particle size of Ce1?x Ti x O2 nanoparticles evenly attached onto the surface of ATP is approximately 10 nm. The Ti4+ doping ratios exhibit considerable impact on the redox ability and catalytic activity of Ce1?x Ti x O2/ATP composites. The introduction of an optimal amount of Ti4+ contributes to forming structure defects and electronic defects in the oxide lattice, increasing concentration of oxygen vacancies, consequently improving low-temperature redox ability of Ce4+ and enhancing catalytic activity of the composites. Ce1?x Ti x O2/ATP (x = 0.5) catalyst has the best catalytic degradation efficiency, which can reach as high as 97 % after reaction for 240 min. It is also found that attapulgite clay exhibit a positive synergistic effect to the Ce1?x Ti x O2 nanoparticles.  相似文献   

19.
用沉积沉淀法合成两种不同系列的CeO2-ZrO2-La2O3混合氧化物(ZrO2和La2O3沉积CeO2粒子(标记为A-x)以及CeO2和La2O3沉积ZrO2粒子(标记为B-x)),并用作Rh催化剂的载体。XRD、拉曼、TPR、XPS和O2脉冲等表征结果显示出不同的沉积顺序将导致不同的结构和氧化还原性能,且B-x具有更高的氧迁移性、储氧能力和表面Ce浓度。当其负载Rh后,Rh/B-x催化剂具有更高的NO和CO转化率及N2选择性,且Ce的最佳含量为50at%。这可能归因于Rh负载于富铈表面形成更多有利于NO分解的表面Ce3+活性位。  相似文献   

20.
Gold-palladium catalysts supported on cerium oxide were synthesized with the double complex salts. X-ray photoelectron spectroscopy (XPS) and other physicochemical methods (TEM, TPR) were used to demonstrate that synthesis of highly active palladium catalysts requires the oxidative treatment stimulating the formation of a catalytically active surface solid solution Pd x Ce1?x O2, which is responsible for the lowtemperature activity (LTA) in the reaction CO + O2. In the case of gold catalysts, active sites for the lowtemperature oxidation of CO are represented by gold nanoparticles and its cationic interface species. Simultaneous deposition of two metals increases the catalyst LTA due to interaction of both gold and palladium with the support surface to form a Pd1?x CexO2 solid solution and cationic interface species of palladium and gold on the boundary of Pd-Au alloy particles anchored on the solid solution surface.  相似文献   

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