Well-Dispersed Gallium-Promoted Sulfated Zirconia on Mesoporous MCM-41 Silica

Gallium-promoted sulfated zirconia (SZ) was confined inside pure-silica MCM-41 (abbreviated as SZGa/MCM-41), where the latter served as a host material. It was prepared by direct dispersion of metal sulfate in the as-synthesized MCM-41 materials, followed by thermal decomposition. The SZGa/MCM-41 catalysts were characterized by XRD, N₂ adsorption, HRTEM, DRIFT, NH₃-TPD, and TPR. The experimental results showed that the ordered porous host structure was still maintained in the catalyst. SZ was in meta-stable tetragonal phase and highly dispersed on the interior surface of MCM-41 even at a high loading of 50 wt%. Additionally, a small fraction of SZ nanoparticles on the external surface of MCM-41 was obtained. The catalytic activity of SZGa/MCM-41 was examined in n-butane isomerization. In comparison to SZ/MCM-41 without promoter, the catalytic activities of the Ga-promoted catalysts were greatly improved. The reason proposed for the higher activity of the Ga-promoted catalysts was that Ga enhances the oxidizing ability of the catalysts.     

A Convenient Preparation Method for Synthesizing Formamidine Utilizing Sulfated Zirconia

Sulfated zirconia is able to effectively catalyze the reaction between aniline and trimethyl orthoformate to produce formamidine with a product yield of 97% at 313 K. N-phenylformimidate is proposed as the reaction intermediate, which reacts further with aniline to produce formamidine. Less degree of acid sites poisoning by the reaction mixture due to the weaker acidity of sulfated zirconia as well as its mesoporosity seem to play important role in this catalyzed reaction.     

Different Acylating Agents in the Synthesis of Aromatic Ketones on Sulfated Zirconia

Sulfated zirconia (SZ) has been used as a heterogeneous catalyst in the synthesis of aromatic ketones. A number of carboxylic anhydrides and acid chlorides proved to be appropriate acylating agents in the reaction with anisole and chlorobenzene. The rate of anisole acylation was found to be dependent on the type of acylating agent used. Thus, acetic anhydride and benzoic anhydride reacted faster on SZ with anisole than benzoyl chloride. Successful SZ-catalyzed acylations of chlorobenzene were limited to acceptor substituted benzoyl chlorides as acylating agents. Acetic anhydride and benzoic anhydride did not react with chlorobenzene in the presence of SZ.     

Mesostructured Sulfated Zirconia with High Catalytic Activity in n-Butane Isomerization

A mesostructured sulfated zirconia with a large surface area (189 m²/g) has been successfully prepared using a triblock copolymer as a structure-directing agent. The resulting material was characterized by XRD, TEM, nitrogen adsorption, FTIR and TG/DTA, which suggested that the mesostructured sulfated zirconia was tetragonal crystalline. Catalytic testing showed that the mesostructured sulfated zirconia was much more active than conventional sulfated zirconia for n-butane isomerization.     

介孔SO_4~(2-)/ZrO_2的制备、表征及性能

以正丙醇锆为锆前躯体,硫酸铵为硫源,十六烷基三甲基溴化铵(CTAB)为模板剂,溴化钾为添加剂,按n(Zr4+)∶n(CTAB)∶n(SO24-)=2∶1∶2,在水热条件、酸性介质中合成了介孔ZrO2/SO24-。通过X射线衍射(XRD),N2物理吸附,扫描电镜(SEM),FTIR分析手段对其结构进行了表征;并以乙酸正丁酯的酯化反应为探针反应,考察了其催化活性。结果表明,采用两步焙烧法去除模板剂后,该样品的介孔结构类似于MCM-41,d值为3.85nm;在500℃焙烧后,该样品仍具有274m2/g的比表面积及3.2nm的平均孔径;SEM显示焙烧后的样品形貌为球形颗粒;FTIR分析得出,焙烧产物ZrO2/SO42-中S=O键对Zr4+有强的吸电子作用,产生强的Lewis酸中心。当催化剂用量为正丁醇质量的2.5%,n(乙酸)∶n(正丁醇)=1∶2,反应3h后,乙酸的转化率达91.48%。     

Catalytic Behavior of Alumina-Promoted Sulfated Zirconia Supported on Mesoporous Silica in Butane Isomerization

Alumina-promoted sulfated zirconia was supported on mesoporous molecular sieves of pure-silica MCM-41 and SBA-15. The catalysts were prepared by direct impregnation of metal sulfate onto the as-synthesized MCM-41 and SBA-15 materials, followed by solid state dispersion and thermal decomposition. Measurements of XRD and nitrogen adsorption isotherms showed that the structures of resultant materials retain well-ordered pores, even with ZrO₂ loading as high as 50 wt%. The characterization results indicated that most of the promoted sulfated zirconia were well dispersed on the internal surface of the ordered mesopores. The catalytic behavior of the alumina-promoted sulfated zirconia supported on mesoporous silica was studied in n-butane isomerization. The supports of mesoporous structures led to high dispersion of sulfated zirconia in the meta-stable tetragonal phase, which was the catalytic active phase. The high performance of alumina-promoted catalysts was ascribed to the sulfur retention by alumina.     

Isomerizations of Cycloheptane to Methylcyclohexane and Cyclooctane to Ethylcyclohexane Catalyzed by Sulfated Zirconia

Reactions of cycloheptane and cyclooctane were performed over the superacid of sulfated zirconia in liquid phase at 50 °C a main product was methylcyclohexane from cycloheptane through a protonated bicyclo[4.1.0]heptane and ethylcyclohexane from cyclooctane via a protonated bicyclo[4.2.0]octane. Cyclodecane was dehydrogenated into decalines; cyclododecane was converted into many products, more than 30 species.     

再铸全氟磺酸-聚四氟乙烯共聚物/磺化氧化锆复合膜的制备与性能研究

利用溶液再铸法制备了全氟磺酸－聚四氟乙烯共聚物 （Nafion?）/磺化氧化锆（SZ）复合膜,借助X射线衍射、扫描电子显微镜、热失重分析仪等研究了所制备复合膜的微观结构、形貌以及性能。结果表明,棒状SZ颗粒以平行于膜表面的方向排列,均匀分布在Nafion?膜的骨架中,改善了膜在中温区的热稳定性;将复合膜用于直接甲醇燃料电池（DMFC）的电解质膜时,使用了3 ％ 和6 ％SZ的Nafion?/SZ复合膜的DMFC在45 ℃和5 mol/L甲醇进料时的峰值输出功率密度分别为46.27、59.47 mW/cm2,明显高于同样条件下Nafion?膜的38.2 mW/cm2。     

Effect of the Sulfated Zirconia Nanostructure Characteristics on Physicochemical and Electrochemical Properties of SPEEK Nanocomposite Membranes for PEM Fuel Cell Applications

This study expresses that the characteristics of sulfated zirconia (SZ) nanostructure in sulfonated poly(ether ether ketone) (SPEEK)‐based membranes is the key to optimize their properties for fuel cell applications. Two types of SZ treating in different thermal conditions are produced by precipitation and analyzed by X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, energy‐dispersive X‐ray analysis, and transmission electron microscopy. Sulfate concentration on both types of SZ is changing from 0.54 to 1.45 wt% and thus the SZ samples differ in particle size and sulfate content. The nanocomposite membranes are prepared by incorporating 6 wt% of SZ samples into SPEEK matrix in casting procedure followed by performing electrochemical characterizations and impedance spectroscopy. Moreover, morphology, mechanical, and chemical stability of the membranes are investigated by field emission scanning electron microscopy, stress–strain, and ex situ Fenton's tests. The incorporation of SZ sample having more surface sulfate groups in the SPEEK matrix results in not only excessive oxidative stability and tensile strength but also more acidic sites for ion transport, promoting conductivity. Furthermore, both types of nanocomposite membranes show improved ionic conductivity and water affinity with a lower tendency to swell rather than the plain SPEEK membrane. It is proved that desired consequences of doping SZ into SPEEK matrix can be intensified by changing the physicochemical properties of sulfated zirconia nanoparticles.     

Sulfated zirconia catalysts promoted with Fe and Mn: Mn effect in the Fe dispersion

n-Butane conversion was studied over Fe- and Mn-promoted sulfated zirconia by pulse reaction over the temperature range of 423–503 K to explore the role of Mn in the catalytic activity of Fe-promoted sulfated zirconia. On a sample containing 2 wt.% Fe, the n-butane isomerization activity was found to decrease with decreasing Fe/Mn molar ratio beyond 0.65 wt.% Mn. Concomitantly, XPS showed that the surface Fe/Zr intensity ratio increases with the Mn content until it reaches a maximum at 0.65 wt.% Mn, and then decreases. This behavior reflects a higher Fe dispersion at relatively low Mn content. Thus, low concentrations of Mn disperse the iron on the surface.

Temperature programmed reduction data indicate that more sulfate species are accessible to reduction when metal promoters are present over sulfated zirconia. However, increasing Mn amount decreases the fraction of sulfate being reducible.     

Well-dispersed Ceria-promoted Sulfated Zirconia Supported on Mesoporous Silica

Ceria-promoted sulfated zirconia (CeSZ) was supported on mesoporous molecular sieve of pure-silica MCM-41 (abbreviated as CeSZ/MCM-41). It was prepared by direct impregnation of metal sulfate onto the as-synthesized MCM-41, followed by solid state dispersion and thermal decomposition. The resultant catalysts were characterized by TG, XRD, nitrogen physisorption and TEM. It was showed that the hollow tubular structure of MCM-41 was retained, even with ZrO₂ loading as high as 60 wt.%. Most of CeSZ was well dispersed on the interior surface of the ordered mesopores, following a slight twist of the channels. The catalytic activity of CeSZ/MCM-41 was studied in the octadecanol oxidation. The improved performance of CeO₂-promoted catalysts was attributed to the high dispersion of sulfated zirconia (SZ) and the introduction of CeO₂ enhancing the oxidation ability of catalysts by retarding the transformation of zirconia from highly catalytic active metastable tetragonal phase to monoclinic phase.     

n-Butane Isomerization Catalyzed by Sulfated Zirconia Nanocrystals Supported on Silica or γ-Alumina

Supported sulfated zirconia catalysts with zirconia contents of 10, 20 and 50 wt% were prepared by impregnation of SiO₂ and γ-Al₂O₃ supports with H₂SO₄/ Zr(SO₄)₂ solutions followed by calcination at 923 K. The catalysts were characterized by X-ray diffraction, extended X-ray absorption fine structure measurements, thermal analysis, UV–vis spectroscopy, and electron microscopy. Tetragonal zirconia was detected in all silica-supported samples but only in the 50 wt% zirconia-containing alumina-supported sample, indicating high dispersion of zirconia on alumina. Alumina-supported samples retained additional sulfate, at least in part as Al₂(SO₄)₃. All samples were active in n-butane isomerization (1 kPa n-butane, 378 K). There was no relation between the presence of tetragonal zirconia in these samples and the catalytic performance.     

Sulfated Zirconia with Ordered Mesopores as an Active Catalyst for n-Butane Isomerization

Zirconia/surfactant composites were hydrothermally synthesized in aqueous sulfuric acid at 373 K using Zr(O-nPr)₄ as oxide precursor and hexadecyl-trimethyl-ammonium bromide as template. Mesostructural features similar to those of MCM-41 were detected by X-ray diffractometry, with d=4.6 nm. A sample obtained from a starting mixture with Zr:S:CTAB = 2:2:1 was stable enough for removal of occluded organics. After calcination at 813 K, the d-value was 3.6 nm, the surface area 200 m²/g, and the mean pore diameter estimated by the BJH method 2.2 nm. Extended X-ray absorption fine structure analysis suggests Zr to be in a short-range structure (<4 Å) similar to that of Zr in monoclinic ZrO₂. Scanning electron microscopy including energy dispersive X-ray analysis showed 1-5 m sulfur-containing ZrO₂ spheres. The material catalyzes the isomerization of n-butane to i-butane at 378 K with a steady activity in the order of magnitude of commercial sulfated ZrO₂.     

Effect of Iron Addition on the Durability of Pd–Pt-Loaded Sulfated Zirconia for the Selective Reduction of Nitrogen Oxides by Methane

The effects of adding iron to Pd–Pt/sulfated zirconia (SZ) on the selective NO _x reduction by methane were examined based on durability tests under conditions simulating natural gas combustion exhaust. While Pd–Pt/SZ was severely deactivated at 500 °C, Pd–Pt/Fe-SZ maintained a NO _x conversion higher than 70% for over 2400 h under the same conditions. Methane conversion on Pd–Pt/Fe-SZ was significantly lower than that on Pd–Pt/SZ. XRD analysis of fresh and used catalysts showed that a part of the SZ had transformed to monoclinic ZrO₂ and that adding Fe suppressed the transformation. These results suggested that the improvement in NO _x conversion by adding Fe was due to the suppression of methane combustion and the stabilization of SZ against transformation to ZrO₂.     

The Effect of Immersion on the Breaking Force and Failure Locus in an Epoxy/Mild Steel System

This paper presents the effects of immersion on the adhesion behavior in a polyamide-cured epoxy system immersed in sodium chloride electrolyte adjusted to three different pH values. The strength of lap shear joints was measured before and after exposure and after redrying. The failure locus was determined on a macroscopic and microscopic level. It was found that a large adhesion loss occurred upon immersion. Most of that loss was recovered upon redrying. All of the breaking force was recovered when the immersion fluid was distilled water. The locus of failure was primarily through the bulk of the adhesive before immersion. After immersion the failure was interfacial with a thin residue of polymer remaining on the metal surface. These results are discussed with respect to earlier work on the water absorption properties of the system.     

Sulfated zirconia catalysts: Are Brønsted acid sites the source of the activity?

The thermal decomposition products of pyridinium sulfate differ from those of pyridinium sulfate supported on zirconia which in turn differs from that of pyridine adsorbed on a sulfated zirconia. Unsupported pyridinium sulfate decomposes to produce pyridine and sulfuric acid, and these subsequently react to produce oxides of carbon and sulfur. Zirconia that is sulfated and then exposed to pyridine does not release detectable amount of pyridine during heating in an inert gas; rather the pyridine undergoes oxidation reduction reactions simultaneously to release CO₂ and sulfur compounds. Pyridinium sulfate supported on zirconia decomposes upon heating to release pyridine and sulfuric acid, which reacts with the zirconia. The desorption of pyridine in one case and only CO₂/SO_x in the other case suggests that sulfated zirconia does not contain Brønsted acidity that can form pyridinium sulfate.     

Qualitative X-ray Diffraction Analysis of Metastable Tetragonal (t') Zirconia

The identification and discrimination of cubic ( c ) and metastable t '-zirconia phases by conventional X-ray diffraction has proved to be a difficult problem because of the crystallographic similarities of the two phases. In this study, the c -phase and t '-phase in biphasic metastable zirconia samples have been successfully distinguished by X-ray diffraction; data were collected using a high-resolution powder diffractometer with monochromatic radiation and the peak shapes were fitted using a peak-fitting program to distinguish the different phases. From this study, the minimum temperature, T ₀, at which the t '-phase can be obtained on cooling rapidly compositions in the range 3–7 mol% Y₂O₃–ZrO₂ to room temperature was estimated as ∼1425°C. For a constant temperature above 1425°C, the lattice parameters of the t '-phase of 3–7 mol% Y₂O₃–ZrO₂ compositions within the two-phase region of the phase diagram were unaffected by the yttria content; only the amount of t '-phase formed was affected by the yttria content.     

The Effect of Immersion on the Breaking Force and Failure Locus in an Epoxy/Mild Steel System

This paper presents the effects of immersion on the adhesion behavior in a polyamide-cured epoxy system immersed in sodium chloride electrolyte adjusted to three different pH values. The strength of lap shear joints was measured before and after exposure and after redrying. The failure locus was determined on a macroscopic and microscopic level. It was found that a large adhesion loss occurred upon immersion. Most of that loss was recovered upon redrying. All of the breaking force was recovered when the immersion fluid was distilled water. The locus of failure was primarily through the bulk of the adhesive before immersion. After immersion the failure was interfacial with a thin residue of polymer remaining on the metal surface. These results are discussed with respect to earlier work on the water absorption properties of the system.     

Effect of Sulfation on the Acid-Base Properties of Tetragonal Zirconia. A Calorimetric and IR Spectroscopic Study

The RT adsorption of CO₂ was studied in order to compare the surface acid-base properties of yttria-stabilized tetragonal ZrO₂, either plain or variously sulfated. The nature of the species formed upon CO₂ adsorption, as well as their stability upon outgassing, was monitored by IR spectroscopy, whereas the population of the sites and their energy distribution was studied by microcalorimetry. The effect of sulfation on the basicity of cus Zr⁴⁺/O^2- pairs and on the Lewis acidic strength of cus Zr⁴⁺ cations, as well as the influence of calcination on the amount and nature of surface sulfates were studied and correlated with the catalytic activity of SZ systems.     

IR characterization of sulfated zirconia derived from zirconium sulfate

Surface characterization of a sulfate-derived zirconia sample containing approximately 1 wt% S was performed by IR spectroscopy. Several types of sulfate groups were detected which are resistant to heating in vacuo up to 973 K. By using CO as a spectroscopic probe, two kinds of Lewis acid sites were identified which were assigned to surface Zr⁴⁺ ions in different environments. Comparison with corresponding data for a nearly sulfate-free zirconia sample showed that sulfated zirconia has an enhanced Lewis acidity.