Characterization of aerogel Ni/Al2O3 catalysts and investigation on their stability for CH4-CO2 reforming in a fluidized bed

The CH₄-CO₂ reforming was investigated in a fluidized bed reactor using nano-sized aerogel Ni/Al₂O₃ catalysts, which were prepared via a sol–gel method combined with a supercritical drying process. The catalysts were characterized with BET, XRD, H₂-TPR and H₂-TPD techniques. Compared with the impregnation catalyst, aerogel catalysts exhibited higher specific surface areas, lower bulk density, smaller Ni particle sizes, stronger metal-support interaction and higher Ni dispersion degrees. All tested aerogel catalysts showed better catalytic activities and stability than the impregnation catalyst. Their catalytic stability tested during 48 h reforming was dependent on their Ni loadings. Characterizations of spent catalysts indicated that only limited graphitic carbon formed on the aerogel catalyst, while massive graphitic carbon with filamentous morphology was observed for the impregnation catalyst, leading to significant catalytic activity degradation. An aerogel catalyst containing 10% Ni showed the best catalytic stability and the lowest rate of carbon deposition among the aerogel catalysts due to its small Ni particle size and strong metal-support interaction.     

Effect of different promoters on Ni/CeZrO2 catalyst for autothermal reforming and partial oxidation of methane

Ni/CeZrO₂ catalysts promoted by Ag, Fe, Pt and Pd were investigated for methane autothermal reforming and partial oxidation of methane. The catalysts properties were determined by BET surface area, X-ray diffraction (XRD), H₂ temperature-programmed reduction (TPR), temperature-programmed desorption of CO₂ (CO₂-TPD) and UV–vis diffuse reflectance spectroscopy (DRS). Nickel dispersions were evaluated using a model reaction, the dehydrogenation of cyclohexane. BET surface area results showed that the catalysts prepared by successive impregnation presented lower surface area which favored the smaller nickel dispersion. XRD analysis showed the formation of a ceria–zirconia solid solution. TPR experiments revealed that the addition of Pt and Pd as promoters increased the reducibility of nickel. CO₂-TPD results indicated that the AgNiCZ catalysts presented the best redox properties among all catalysts. The autothermal reforming of methane showed that, among different promoters, the sample modified with silver, AgNiCZ, presented higher methane conversion and better stability during the reaction. These results are related to the good reducibility and to the higher redox capacity observed in TPR and CO₂-TPD analysis. Samples prepared by successive impregnation technique resulted in a smaller catalytic activity. For partial oxidation of methane, just as happened in autothermal reforming, AgNiCZ also presented the best performance during the 24 h of reaction and the addition of silver by successive impregnation resulted in a lower methane conversion, probably, due to the smaller metal dispersion.     

Metal Exchanged ZSM-5 Zeolite Based Catalysts for Direct Decomposition of N2O

Co+Pt/ZSM-5 and Ag+Pt/ZSM-5 type catalysts were prepared by ion exchange method followed by calcination. These Co and Ag based catalysts, promoted by a small amount of Pt have been studied for their catalytic activity towards N₂O decomposition. Both the catalysts show high catalytic activity, however, cobalt–platinum based catalyst shows relatively better activity at higher temperature. At 550 °C almost 100% conversion of N₂O is achieved over Co+Pt/ZSM-5 with a maximum of 0.08479 mmole of N₂O decomposed per gram of the catalyst per unit time. These catalytic materials have been characterized for their structure, composition, morphology and other details, using XRD, SEM, EDX, ICP, BET techniques. Much improved catalytic activity for the bimetallic zeolite than the mono-metal containing compositions clearly demonstrate the synergistic effect of these transition metals, while high surface area of ZSM-5 is also responsible for the improved N₂O decomposition activity.     

后处理方式对2,2′-二氯氢化偶氮苯合成用铂炭催化剂的影响

对2,2′-二氯氢化偶氮苯合成用3%铂炭催化剂分别进行了热处理、微波处理和超声波处理。通过BET测试和SEM表征技术以及催化反应模拟对其性能进行检测与分析。结果表明,热处理导致金属粒子团聚,催化剂的比表面积减小,邻氯硝基苯催化加氢反应性能下降;微波和超声波处理促进了金属粒子的均匀分散,增大了催化剂的比表面积,提高了催化剂在邻氯硝基苯加氢反应中的催化性能。     

Comparative Study of WS2 and Co(Ni)/WS2 HDS Catalysts Prepared by ex situ/in situ Activation of Ammonium Thiotungstate

A comparative study of the syntheses of unsupported WS₂ and M/WS₂ (M = Co, Ni) catalysts by ex situ/in situ decomposition of ammonium thiotungstate (ATT) is herein reported. Ex situ activation was performed under a H₂S (15% volume)/H₂ flow, whereas in situ activation consists in the direct decomposition of ATT or Co(Ni)/ATT precursors in the presence of a hydrocarbon solvent during the hydrodesulfurization (HDS) of dibenzothiophene (DBT). Precursors were characterized by thermogravimetric analysis and final catalysts by X-ray diffraction (XRD), scanning electron microscopy (SEM) and specific surface area (BET). Catalysts activated using the in situ mode of activation present higher specific surface areas with the noticeable exception of the Ni/ATT precursor. Activity measurements showed that the in situ activated WS₂ and Ni/WS₂ catalysts exhibit higher activity than the ex situ activated catalysts.     

Dibenzothiophene hydrodesulfurization over MoP/SiO<Subscript>2</Subscript> catalyst prepared with sol-gel method

Silica-supported molybdenum phosphide, MoP/SiO₂ catalysts with different Mo weight loadings were prepared by temperature programmed reduction of the oxidic catalyst precursors, which were prepared via sol-gel technique using ethyl silicate-40 as silica source. Samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), BET surface area measurements, and their catalytic activity in hydrodesulfurization (HDS) was tested with dibenzothiophene (DBT) as model compound. XRD analysis revealed the amorphous nature of the catalyst up to 10 wt% Mo loading and the formation of crystalline MoP phase on amorphous silica support with higher Mo loading. BET surface area showed high surface area for catalysts prepared by sol-gel technique with lower Mo content, and the surface area decreased with increasing in Mo loading. The HDS results showed that prepared MoP/SiO₂ exhibited high HDS activity and stability toward the catalytic test. Among the series of catalysts prepared, MoP/SiO₂ containing 20 wt% Mo was found to be the most active catalyst. And the effects of reaction temperature and hydrogen pressure on conversion and product selectivity were investigated.     

Synthesis and characterization of methanol tolerant Pt/TiOx/C nanocomposites for oxygen reduction in direct methanol fuel Cells

Pt/TiO_x/C nanocomposites have been synthesized by depositing hydrated titanium oxide on carbon-supported Pt (Pt/C), reducing H₂PtCl₆ with sodium formate on carbon-supported hydrated titanium oxide (TiO₂/C), and simultaneously depositing hydrated titanium oxide and reducing H₂PtCl₆ with formate on carbon support, followed by heat treatment at 500 and 900 °C in 90% Ar-10% H₂ mixture. The catalytic activity for oxygen reduction was evaluated in half cells with sulfuric acid electrolyte and in single direct methanol fuel cells (DMFC). Tolerance to methanol was studied with half cells containing sulfuric acid mixed with methanol. Charge transfer resistance and electrochemical active surface area of the Pt/TiO_x/C catalysts were studied with impedance and cyclic voltammetry measurements. Both the synthesis methods and heat treatments influence the catalytic activity, and some of the Pt/TiO_x/C composites exhibit higher catalytic activity than Pt/C. The Pt/TiO_x/C catalysts also exhibit better methanol tolerance than Pt/C. The mechanism for the enhanced catalytic activity of Pt/TiO_x/C is discussed.     

The role of nickel in pyridine hydrodenitrogenation over NiMo/Al2O3

Al₂O₃ supported Mo, Ni, and NiMo/Al₂O₃ catalysts with various Ni contents were prepared to investigate the role of Ni as a promoter in a NiMo bimetallic catalyst system. The hydrodenitrogenation (HDN) reaction of pyridine as a catalytic probe was conducted over these catalysts under the same reaction conditions and the catalysts were characterized using BET surface area measurement, infrared spectroscopy, temperature programmed reduction, DRS and ESR. According to the results of reaction experiments, the NiMo/Al₂O₃ catalyst showed higher activity than Mo/Al₂O₃ catalyst in the HDN reaction and particularly the one with atomic ratio [Ni/(Ni+Mo)]=0.3 showed the best activity for the HDN of pyridine. The findings of this study lead us to suggest that the enhancement in the HDN activity with nickel addition could be attributed to the improvement in the reducibility of molybdenum and the formation of Ni-Mo-O phase.     

Performance of Ni catalyst supported on La-hexaaluminate in CO<Subscript>2</Subscript> reforming of CH<Subscript>4</Subscript>

CO₂ reforming of CH₄ was performed using Ni catalyst supported on La-hexaaluminate which has been an well-known material for high-temperature combustion. La-hexaaluminate was synthesized by sol-gel method at various conditions where different amount of Ni (5–20 wt%) was loaded. Ni/La-hexaaluminate experienced 72 h reaction and its catalytic activity was compared with that of Ni/Al₂O₃, Ni/La-hexaaluminate shows higher reforming activity and resistance to coke deposition compared to the Ni/Al₂O₃ model catalyst. Coke deposition increases proportionally to Ni content. Consequently, Ni(5)/La-hexaaluminate(700) is the most efficient catalyst among various Ni/La-hexaaluminate catalysts regarding the cost of Ni in Ni(X)/La-hexaaluminate catalysts. BET surface area, XRD, EA, TGA and TPO were performed for surface characterization. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Na改性Pt/AlOOH对甲醛催化氧化反应活性的影响

具有晶面取向的阳极氧化AlOOH因其低温甲醛催化性能而被用于催化氧化甲醛体系。为丰富AlOOH表面羟基含量,采用Na₂CO₃为Na前体浸渍法改性载体,制备不同Na含量（0.13%、0.19%、0.30%、0.41%,质量分数）的Pt/Na_x/AlOOH催化剂。通过BET、FTIR、XPS、HRTEM等表征分析,发现加入Na后,Na/AlOOH的表面羟基更加丰富,Pt/Na_x/AlOOH催化剂的比表面积增大,拥有更小的Pt颗粒尺寸,表面Pt颗粒分散度提高,Pt0元素价态含量增加。当Na含量为0.41%时,催化剂Pt/0.41Na/AlOOH的Pt分散度高达56%。实验结果证明,Pt/0.41Na/AlOOH展现出最优的HCHO催化活性,60℃时HCHO转化率达100%。     

载体热处理温度对Pt/FeOx催化HCHO氧化性能的影响

以不同温度热处理的FeOx-T为载体，采用胶体沉积法制备了一系列Pt/FeOx-T催化剂用于甲醛室温催化氧化。通过 XRD、BET、H2 -TPR、FTIR和TEM 对Pt/FeOx-T催化剂的结构进行表征，结果表明，热处理温度影响FeOx载体的比表面积、氧化还原性质和Pt/FeOx-T表面羟基的数量，以及Pt物种和FeOx载体之间的相互作用。活性测试表明，100?C热处理的FeOx为载体制备的1.5wt% Pt/FeOx-100催化剂具有较高的催化活性，在25?C，RH=55%的条件下，甲醛的转化率可达到96.2%。     

Electrocatalysis of oxygen reduction on carbon-supported PtCo catalysts prepared by water-in-oil micro-emulsion

Synthesis of carbon-supported PtCo/C using micro-emulsion method including simultaneous procedure and sequential procedures in both acid and alkaline media was reported. UV-vis and electron microscopy were used to characterize the formation, surface morphology and distribution of PtCo nanoparticles. Crystallite structure of catalysts was analyzed from XRD patterns. Catalytic properties of PtCo/C catalysts synthesized were compared with commercial Pt/C using RDE based on both mass activity (MA) and specific activity (SA). PtCo/C catalysts prepared in both acidic and basic conditions showed better performance than commercial Pt/C catalyst. High-temperature heat treatment was found useful only to PtCo/C by sequential procedure. The peroxide yield was also explored using RRDE technique. The H₂O₂ yield results were correlated with SA and R values (ratio of charge transferred about Co and Pt on the surface of catalyst) obtained from CVs in 1 M KOH solution. A sacrificial Co oxidized effect on impediment of adsorption of OH may cause higher catalytic properties and higher H₂O₂ yield to Pt base alloy catalysts.     

Highly active and coking resistant Ni/CeO2-ZrO2 catalyst for partial oxidation of methane

Nickel catalysts over the CeO₂-ZrO₂ solid solution were successfully prepared by the co-precipitation method for partial oxidation of methane. The structures of the catalysts were systematically examined by N₂ adsorption/desorption, CO chemisorption, X-ray diffraction (XRD) and H₂-TPR techniques. The catalytic performance and carbon deposition were investigated for partial oxidation of methane as well. The results showed that the Ni/CeO₂-ZrO₂ catalysts had a large BET area and fine Ni dispersion. By the co-precipitation method, Ni and CeO₂-ZrO₂ solid solution had strong interaction confirmed by the H₂-TPR analysis. The Ni/CeO₂-ZrO₂ catalysts showed high activity and stability and the Ni/Ce_0.25Zr_0.75O₂ exhibited the best activity and coking resistance among these catalysts. The catalytic activities and coking resistant behaviors of catalysts were affected by the surface and structural properties of the catalysts.     

Improving the Stability and Ethanol Electro‐Oxidation Activity of Pt Catalysts by Selectively Anchoring Pt Particles on Carbon‐Nanotubes‐Supported‐SnO2

To improve the stability and activity of Pt catalysts for ethanol electro‐oxidation, Pt nanoparticles were selectively deposited on carbon‐nanotubes (CNTs)‐supported‐SnO₂ to prepare Pt/SnO₂/CNTs and Pt/CNTs was prepared by impregnation method for reference study. X‐ray diffraction (XRD) was used to confirm the crystalline structures of Pt/SnO₂/CNTs and Pt/CNTs. The stabilities of Pt/SnO₂/CNTs and Pt/CNTs were compared by analyzing the Pt size increase amplitude using transmission electron microscopy (TEM) images recorded before and after cyclic voltammetry (CV) sweeping. The results showed that the Pt size increase amplitude is evidently smaller for Pt/SnO₂/CNTs, indicating the higher stability of Pt/SnO₂/CNTs. Although both catalysts exhibit degradation of electrochemical active surface area (EAS) after CV sweeping, the EAS degradation for the former is lower, further confirming the higher stability of Pt/SnO₂/CNTs. CV and potentiostatic current–time curves were recorded for ethanol electro‐oxidation on both catalysts before and after CV sweeping and the results showed that the mass specific activity of Pt/CNTs increases more than that of Pt/SnO₂/CNTs, indicating that Pt/CNTs experiences more severe evolution and is less stable. The calculated area specific activity of Pt/SnO₂/CNTs is larger than that of Pt/CNTs, indicating SnO₂ can co‐catalyze Pt due to plenty of interfaces between SnO₂ and Pt.     

Ni、Pt对柴油车排气颗粒物去除催化剂的修饰作用

以改性整体式堇青石蜂窝陶瓷为载体,用Ni和Pt修饰Cu-K-V/TiO₂/γ-Al₂O₃ /cordierite催化剂,制备了用于消除柴油车排气颗粒物的催化剂;采用DSC/TG方法确定催化剂的活性及BET、TG-IR等方法对催化剂进行了表征,探讨了Ni和Pt对Cu-K-V/TiO₂/γ-Al₂O₃ /cordierite催化剂的修饰作用及老化对催化剂的影响.研究发现经Ni和Pt修饰后的催化剂能有效降低柴油车排气颗粒物的最大燃烧速率时的温度,特别是对颗粒物中最难燃烧的石墨化部分的去除;而且Ni和Pt的添加能提高颗粒物的去除效率.对含Pt催化剂,老化会降低催化剂的活性;而对含Ni的催化剂,老化使催化剂的活性增加,这可能是Ni向催化剂非孔道的外表面迁移的结果.     

Role of Pt in the Activity and Stability of PtNi/CeO2–Al2O3 Catalysts in Ethanol Steam Reforming for H2 Production

Hydrogen production from ethanol reforming was investigated on bimetallic PtNi catalysts supported on CeO₂/Al₂O₃. Pt content was varied from 0.5 to 2.5 %. Physico-chemical characterization of the as-prepared and H₂-reduced catalysts by TPR, XRD and XPS showed that Pt phase interacted with the Ni and Ce species present at the surface of the catalysts. This interaction leads to an enhancement of the reducibility of both Ni and Ce species. Loadings of Pt higher than 1.0 wt% improved the activity and stability of the Ni/CeO₂–Al₂O₃ catalyst in ethanol steam reforming, in terms of lower formation of coke, C₂ secondary products and a constant production of CO₂ and H₂. The amount and type of carbon deposited on the catalyst was analyzed by TG–TPO while the changes in crystalline phases after reaction were studied by XRD. It was found that for Pt contents higher than 1 wt% in the catalysts, a better contact between Pt and Ce species is achieved. This Pt–Ce interaction facilitates the dispersion of small particles of Pt and thereby improves the reducibility of both Ce and Ni components at low temperatures. In this type of catalysts, the cooperative effect between Pt⁰, Ni⁰ and reduced Ce phases leads to an improvement in the stability of the catalysts: Ni provides activity in C–C bond breakage, Pt particles enhance the hydrogenation of coke precursors (C_xH_y) formed in the reaction, and Ce increases the availability of oxygen at the surface and thereby further enhances the gasification of carbon precursors.     

A kinetic and DRIFTS study of supported Pt catalysts for NO oxidation

NO oxidation was studied over Pt/CeO₂ and Pt/SiO₂ catalysts. Apparent activation energies (E _a) of 31.4 and 40.6 kJ/mole were determined for Pt/CeO₂ and Pt/SiO₂, respectively, while reaction orders for NO and O₂ were fractional and positive for both catalysts. Pre-treatment of the catalysts with SO₂ caused a decrease in the E _a values, while the reaction orders were only slightly changed. In situ DRIFTS measurements indicated that high concentrations of nitrate species were formed on the surface of Pt/CeO₂ during NO oxidation, while almost no surface species could be detected on Pt/SiO₂. The addition of SO₂ resulted in the formation of a highly stable sulfate at the expense of nitrate species and caused an irreversible loss of catalytic activity for Pt/CeO₂.     

Deactivation of Supported Copper Catalysts for Methanol Synthesis

Binary Cu/ZnO and Cu/Al₂O₃ as well as ternary Cu/ZnO/Al₂O₃ catalysts were investigated with respect to their catalytic activity and stability in methanol synthesis. In a rapid aging test, activity measurements were carried out in combination with the determination of the specific Cu surface area. A close correlation between the loss of catalytic activity and the decrease in specific Cu surface area was found due to sintering of the Cu particles. Differences in the deactivation behavior and the area-activity relationship of each catalyst system imply that the catalysts should be grouped in different classes.     

Simultaneous oxidative conversion and CO2 reforming of methane to syngas over Ni/vermiculite catalysts

Modified-vermiculite supported Ni catalysts were prepared and characterized by XRD, BET, TGA, TPR and TEM. The catalytic activity of these catalysts for simultaneous oxidative conversion and CO₂ reforming of methane to syngas was evaluated. The results indicated that vermiculite has a great potential as a support of Ni component due to its excellent thermal stability. Among these catalysts, the expanded-vermiculite supported Ni catalyst exhibited the highest catalytic activity and stability. It was found that Ni oxides supported on vermiculite was reduced more easily and also Ni-based vermiculite catalysts suppressed coke depositing in the reaction, in comparison with alumina-supported Ni catalyst.     

Catalytic methanation of syngas over Ni-based catalysts with different supports

Co-precipitation method was selected for the preparation of Ni/Al2O3, Ni/ZrO2 and Ni/CeO2 catalysts, and their performances in methanation were investigated in this study. The structure and surface properties of these catalysts were characterized by BET, XRD, H2-TPD, TEM and H2-TPR. The results showed that the catalytic activity at low temperature followed the order:Ni/Al2O3>Ni/ZrO2>Ni/CeO2. Ni/Al2O3 catalyst presented the best catalytic performance with the highest CH4 selectivity of 94.5%. The characterization results indicated that the dispersion of the active component Ni was the main factor affecting the catalytic activity and the one with higher dispersion gave better performance.