Effect of electronic interaction between metal and support, II. TPD, TPR and chemisorption studies on Ru/Al2O3?MgO catalysts

TPD, TPR and chemisorption were used to characterize Ru/Al₂O₃–MgO catalysts. It is suggested that the acidity of support may influence the properties of catalysts significantly.

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, Ru/Al₂O₃–MgO. , .

     

TPR studies on steam reforming of 2-propanol on Rh/Al2O3, Ru/Al2O3 and Pd/Al2O3

Reaction pathways for steam reforming of 2-propanol (isopropyl alcohol, IPA) on Rh/Al₂O₃, Ru/Al₂O₃ and Pd/Al₂O₃ have been studied by temperature-programmed reactions (TPRs) of IPA and acetone in the presence of steam. The results of TPRs suggest that that of IPA on Rh/Al₂O₃ and Ru/Al₂O₃ proceeds via acetone, while the steam reforming of IPA on Pd/Al₂O₃ takes place via propene from acetone. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fischer-Tropsch synthesis over Ru/Al2O3 catalysts

Fischer-Tropsch syntheses (FTS) were carried out in a slurry phase over Ru/Al₂O₃ catalysts using hexadecane as a solvent. The outcome of the FTS was dependent on the oxide support, calcination temperature, synthesis gas composition and sulfur content. The addition of Mn/Na to Ru/Al₂O₃ was effective in raising the initial activity and C5+ selectivity, but after 20 hours, the performance of the modified catalyst was similar to that of the unmodified catalyst. An additional investigation involving the use of fresh vs used catalysts demonstrated that an agglomeration of the metallic Ru, at least in part, does occur during the reaction.     

氧化铝载体硫酸化对锰铈催化剂SCR脱硝性能的影响

分别以硫酸改性前后的氧化铝为载体,采用浸渍法制备了锰铈催化剂,对其NH_3-SCR脱硝性能进行评价,并采用XRD、BET、NH_3-TPD、H_2-TPR以及FT-IR对催化剂进行了表征。结果表明,改性降低了金属的分散性和氧化性,增加了酸量,特别是B酸量;催化剂的最佳脱硝温度窗口向高温扩展,活性温度窗口范围变宽,并且,改性液浓度越大变化幅度越大。当反应温度在200-250℃时,未改性催化剂与采用0.2 mol/L硫酸改性的催化剂具有接近的催化活性,但改性后的催化剂具有更高的抗水抗硫活性,250℃时脱硝率可达70%。     

PREPARATION OF Ru/Al2O3 CATALYSTS FROM RuCl3

Increasing reduction time increases ruthenium reduction, but even after 6 h, ruthenium is not completely reduced and chlorine is not completely eliminated in Ru/Al₂O₃ prepared from RuCl₃.     

Carbon monoxide adsorption and hydrogen-oxygen titration on Ru/Al2O3

Hydrogen-oxygen titration and carbon monoxide adsorption on Ru/Al₂O₃ samples were employed to determine metal dispersity values. To avoid Ru–CO polycarbonyl formation, before CO adsorption, the ruthenium surface was precovered with hydrogen. By this procedure, good agreement between H₂–O₂ titration, CO adsorption and electron microscopy is obtained.

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Ru/Al₂O₃ H₂–O₂ CO. Ru–CO, . H₂–O₂, CO .

     

Sulfuration of Pt/Al2O3, Pt?Re/Al2O3 and Pt?Ir/Al2O3 catalysts

Three reforming catalysts Pt/Al₂O₃, Pt–Ir/Al₂O₃ and Pt–Re/Al₂O₃ have been sulfurated by H₂S and tested by their activities in benzene hydrogenation. By treatment at 500°C under hydrogen flow only a part of the initial activity of the non-sulfurated catalyst is retained. So only a part of the adsorbed sulfur is easily removed in these conditions. The remaining sulfur for each of the catalysts (Pt/Al₂O₃, Pt–Ir/Al₂O₃ and Pt–Re/Al₂O₃) gives the same atomic ratio of 0.5 sulfur atom per accessible metallic atom.

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Pt/Al₂O₃, Pt–Ir/Al₂O₃ Pt–Pe/Al₂O₃ . 500°C H₂ . . ., . (Pt/Al₂O₃, Pt–Ir/Al₂O₃ Pt–Pe/Al₂O₃) 0,5.

     

Sulfurization of Pt/Al2O3?Cl catalysts. IV. Adsorption sites of H2S on Al2O3, Al2O3?Cl and Pt/Al2O3?Cl

Chemisorption of H₂S on Al₂O₃, Al₂O₃–Cl and Pt/Al₂O₃–Cl has been studied by gravimetry and IR spectroscopy. The influence of the amount of Cl on the H₂S adsorption equilibrium value and the nature of the adsorption sites at low and high coverages are discussed.

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H₂S Al₂O₃, Al₂O₃–Cl Pt/Al₂O₃–Cl . Cl H₂S, .

     

Toluene steam dealkylation over Rh/Al2O3. Effect of the support

Rh catalysts supported on different -aluminas were prepared and tested under identical conditions. Both catalytic activity and selectivity seem to depend on the surface concentration of acid sites. The bifunctional character of the catalyst and the role played by the support in activating the reactants are confirmed.

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, - . , . , .

     

Preparation of crack-free ZrO2 membrane on Al2O3 support with ZrO2–Al2O3 composite intermediate layers

To develop porous alumina supported MF ZrO₂ membranes, ZrO₂–Al₂O₃ composite intermediate layers are considered in order to decrease stress creation during the processing and avoid cracks formation. The relation between distortion stress and sintering shrinkage was experimentally studied. And the cracks formation mechanism was qualitatively evaluated and discussed. Finally, crack-free YSZ membrane with pore size of 0.16 μm on the two ZrO₂–Al₂O₃ intermediate layers possessing a gradient composition was successfully prepared and characterized.     

Investigation of the acidity of Ni/Al2O3 and Ni/SiO2?Al2O3 catalysts

Acidity of Ni-modified alumina and silica-alumina catalysts was determined using n-butylamine titration and pyridine adsorption methods. Strong influence of Ni²⁺ ions on the Brönsted acidity of silicaalumina was observed. Improved Brönsted acidity of such system was confirmed by the results of the test reaction.     

The support and characterization of C60 and MoO3 on Al2O3

A new type of catalyst from supporting C₆₀ on MoO₃ and Al₂O₃ has been prepared. The effect of different order of impregnation and calcination atmosphere on catalyst are investigated by the solution test in toluene, UV-VIS spectroscopy and temperature programmed reduction (TPR). The results show that when the catalyst was prepared by supporting MoO₃ on C₆₀/Al₂O₃ and calcined in N₂, there is a stronger interaction between C₆₀, MoO₃ and Al₂O₃, but when supporting C₆₀ on MoO₃/Al₂O₃, the interaction is relatively weak. We consider that in the former method a new complex, Mo–C₆₀–O–Al, is formed.     

Surface acidity of the La2O3/Al2O3 system

Surface acidity of aluminium oxide containing 5 wt. % lanthanum oxide has been determined by IR spectroscopy. Strength of Lewis sites of the La₂O₃/Al₂O₃ system was lower than that of pure aluminium oxide. However, the presence of La₂O₃ in aluminium oxide increased the thermostability of these sites in the mixed system.     

过渡金属修饰Fe2O3/Al2O3氧载体的Redox性能研究

采用冷冻干燥法分别制备了经Cu、Co、Mn、Ni修饰的Fe₂O₃/Al₂O₃氧载体。利用化学吸附仪,通过程序升温还原(H₂-TPR)和程序升温氧化(TPO)来研究经不同过渡金属修饰的Fe₂O₃/Al₂O₃与H₂和O₂的反应性能。实验发现,在Fe₂O₃/Al₂O₃中加入Cu、Co、Ni以后,氧载体与H₂的反应性都有提高,但是当在Fe₂O₃/Al₂O₃中加入Mn以后,氧载体的反应性和载氧能力反而下降。经Cu修饰的Fe₂O₃/Al₂O₃与H₂的反应性最高,且具有很好的反应稳定性,适合用于化学链燃烧。     

Characterization of paramagnetic hole-centers in Al2O3 and Al2O3:Fe by optical and EPR absorption

The electron paramagnetic resonance (EPR) and optical absorption spectra of nominally pure and Fe-doped single crystals of Al₂O₃ have been examined before and after gamma-ray irradiation at 77°K. The EPR spectra for doped and irradiated crystals were found to be a function of the iron concentration. Analysis of the optical and EPR spectra observed on the same Fe-doped crystals which had been subjected to gamma-ray irradiations suggests that the center which accounts most satisfactorily for the details of these spectra is: a single trapped-hole localized on an anion which is adjacent to a substitutional divalent iron impurity atom. The optical absorption band ascribed to this center occurs at 3.08 eV.     

Ru/Al2O3-catalyzed transfer dehydrogenation of alcohols

Summary Primary and secondary alcohols were oxidized to their corresponding aldehydes or ketones in good yields using Ru/Al₂O₃ as catalyst in the presence of acetone. The catalyst can be recovered by simple filtration and reused after washing with acetone.     

Reactivity of sites on Al2O3 surface modified by Ni

It has been established that CO oxidation with excess O₂ on Ni/Al₂O₃ forms an inhomogeneous NiO contact surface that smoothes critical effects in the sharp reactivity change.     

Partial oxidation of methane on Cr2O3/Al2O3

The oxidation of methane on supported chromia was studied at temperatures varying between 423 and 743 K and CH₄/O₂ ratios between 1 and 9 in a differential reactor. The main reaction products observed were carbon monoxide and formaldehyde. The rates of reaction obey a power law expression.

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, 423 743 CH₄/O₂ 1 9, . . .

     

Fe改性对Ru/Al_2O_3催化剂的马来酸二甲酯加氢性能影响

以Al2O3为载体,采用吸附-沉淀法制备一系列Ru-Fe/Al2O3催化剂,并进行了H2-TPR、XRD及XPS表征。以马来酸二甲酯(DMM)催化加氢合成丁二酸二甲酯(DMS)为探针反应,考察了Fe的加入对Ru/Al2O3催化性能的影响。评价结果表明,当Fe/Ru原子比小于2时,催化剂活性变化不大;但Fe/Ru原子比大于或等于2时,催化剂活性明显增加;与Ru/Al2O3催化剂相比,Fe的加入改善了催化剂的高温氧化还原处理稳定性。以甲醇为溶剂,在70℃、1.0 MPa压力、600 r/min转速下,Ru-Fe/Al2O3催化DMM的转化率与生成DMS的选择性均接近100%。XPS和H2-TPR表征结果表明,Ru-Fe/Al2O3中Fe与Ru产生较强的相互作用,促进Ru的分散且调变了Ru的电子特性。     

Structural changes resulting from doping Ti2O3 with Sc2O3 or Al2O3

The crystal structures of (Ti_1?xSc_x)₂O₃, x = 0.0038, 0.0109, and 0.0413, and of (Ti_0.99Al_0.01)₂O₃, have been determined from X-ray diffraction data collected from single crystals using an automated diffractometer, and have been refined to weighted residuals of 25–34. Cell constants have also been determined for x = 0.0005, 0.0019, and 0.0232. The compounds are rhombohedral, space group $\text{R}\text{3}\text{c}$, and are isomorphous with α-Al₂O₃. The hexagonal cell dimensions range from a = 5.1573(2)Å, c = 13.613(1)Å for (Ti_0.9995Sc_0.0005)₂O₃ to a = 5.1659(4)Å, c = 13.644(1)Å for (Ti_0.9587Sc_0.0413)₂O₃, and a = 5.1526(2)Å, c = 13.609(1)Å for (Ti_0.99Al_0.01)₂O₃. Sc and Al substitution cause similar increases in the short near-neighbor metal-metal distance across the shared octahedral face; for Sc doping the increase is from 2.578(1) Å in pure Ti₂O₃ to 2.597(1) Å in (Ti_0.9587Sc_0.0413)₂O₃. By contrast, changes in the metal-metal distance across the shared octahedral edge appear to be governed by ionic size effects. The distance increases from 2.994(1) Å in Ti₂O₃ to 3.000(1) Å in (Ti_0.9587Sc_0.0413)₂O₃ and decreases to 2.991(1) Å in (Ti_0.99Al_0.01)₂O₃.