Characterization of Cu/CeO2/γ-Al2O3 Thin Film Catalysts by Thermal Desorption Spectroscopy

Thermal desorption spectroscopy (TDS) under ultra high vacuum (UHV) condition has been used to investigate the desorption characteristics of Cu/CeO₂/γ-Al₂O₃ thin film catalysts coated onto the microchannel of a microreactor. TDS results demonstrate that surface desorption profiles and chemical properties (acid–base and redox properties) are remarkably influenced by the catalyst composition, i.e. the loading of copper and ceria. The enhanced basicity with the increase of ceria loading and the decrease of copper loading is evident from the shifted desorption maximum of CO₂ in TDS spectra. Three oxygen species, ranging from weakly bound oxygen desorbed at low temperature to the strongly held lattice oxygen desorbed at high temperature, are easily discernible and clearly identified by O₂ TDS spectra, depending on the catalyst compositions. The concomitant thermal desorption of O₂, CO₂, and H₂O at low temperature indicates the unique chemical properties of copper/ceria catalyst with appropriate copper and ceria contents. The observed low-temperature feature is ascribed to the role of porthole of copper/ceria interfacial area for several desorbed species. The weakly bound oxygen species is attributed to the enhanced abundance of copper/ceria interfacial anionic vacancies created by the intimate contact between copper and ceria entities and its impact on steam reforming of methanol (SRM) reaction is tentatively discussed in terms of reverse oxygen spillover.     

Direct formation of H2O2 from H2 and O2 and decomposition/hydrogenation of H2O2 in aqueous acidic reaction medium over halide-containing Pd/SiO2 catalytic system

Formation of H₂O₂ from H₂ and O₂ and decomposition/hydrogenation of H₂O₂ have been studied in aqueous acidic medium over Pd/SiO₂ catalyst in presence of different halide ions (viz. F⁻, Cl⁻ and Br⁻). The halide ions were introduced in the catalytic system via incorporating them in the catalyst or by adding into the reaction medium. The nature of the halide ions present in the catalytic system showed profound influence on the H₂O₂ formation selectivity in the H₂ to H₂O₂ oxidation over the catalyst. The H₂O₂ destruction via catalytic decomposition and by hydrogenation (in presence of hydrogen) was also found to be strongly dependent upon the nature of the halide ions present in the catalytic system. Among the different halides, Br⁻ was found to selectivity promote the conversion of H₂ to H₂O₂ by significantly reducing the H₂O₂ decomposition and hydrogenation over the catalyst. The other halides, on the other hand, showed a negative influence on the H₂O₂ formation by promoting the H₂ combustion to water and/or by increasing the rate of decomposition/hydrogenation of H₂O₂ over the catalyst. An optimum concentration of Br⁻ ions in the reaction medium or in the catalyst was found to be crucial for obtaining the higher H₂O₂ yield in the direct synthesis.     

Improvement of coke resistance of Ni/Al2O3 catalyst in CH4/CO2 reforming by ZrO2 addition

This work investigates the improvement of Ni/Al₂O₃ catalyst stability by ZrO₂ addition for H₂ gas production from CH₄/CO₂ reforming reactions. The initial effect of Ni addition was followed by the effect of increasing operating temperature to 500–700 °C as well as the effect of ZrO₂ loading and the promoted catalyst preparation methods by using a feed gas mixture at a CH₄:CO₂ ratio of 1:1.25. The experimental results showed that a high reaction temperature of 700 °C was favored by an endothermic dry reforming reaction. In this reaction the deactivation of Ni/Al₂O₃ was mainly due to coke deposition. This deactivation was evidently inhibited by ZrO₂, as it enhances dissociation of CO₂ forming oxygen intermediates near the contact between ZrO₂ and nickel where the deposited coke is gasified afterwards. The texture of the catalyst or BET surface area was affected by the catalyst preparation method. The change of the catalyst texture resulted from the formation of ZrO₂–Al₂O₃ composite and the plugging of Al₂O₃ pore by ZrO₂. The 15% Ni/10% ZrO₂/Al₂O₃ co-impregnated catalyst showed a higher BET surface area and catalytic activity than the sequentially impregnated catalyst whereas coke inhibition capability of the promoted catalysts prepared by either method was comparable. Further study on long-term catalyst stability should be made.     

Influence of H4SiW12O40 loading on hydrocracking activity of non-sulfide Ni-H4SiW12O40/SiO2 catalysts

The effect of H₄SiW₁₂O₄₀ loading on the catalytic performance of the reduced Ni-H₄SiW₁₂O₄₀/SiO₂ catalysts for hydrocracking of n-decane with or without the presence of thiophene and pyridine is studied. The catalysts were characterized by BET, XRD, Raman, XPS, H₂-TPR, H₂-TPD, NH₃-TPD and FT-IR of pyridine adsorption. It was found that addition of H₄SiW₁₂O₄₀ to the system increases the catalytic activity and the promoting effect is a function of the H₄SiW₁₂O₄₀ loading. The best result was obtained on 5%Ni-50%H₄SiW₁₂O₄₀/SiO₂ catalyst which shows the highest activity for hydrocracking of n-decane and excellent tolerance to the sulfur and nitrogen compounds in the feedstock. The results showed that a suitable amount of H₄SiW₁₂O₄₀ loading on the 5%Ni/SiO₂ catalyst increases the amount of both hydrogen adsorbed and Brønsted acid and Lewis acid sites on the catalyst. The high catalytic performance of the catalyst can be related to the nature of H₄SiW₁₂O₄₀ and the proper balance between metal and acid functions.     

Parametric study of coiled carbon fibre synthesis on an in situ generated H2S-modified Ni/Al2O3 catalyst

Coiled carbon fibre (CCF) synthesis on an in situ generated H₂S-modified Ni/Al₂O₃ catalyst is investigated using a high-throughput reaction system that allows real time observation of weight changes. The influence of reduction and synthesis temperatures, reduction duration, H₂ addition during synthesis, synthesis duration, C₂H₂ concentration in the synthesis gas and catalyst loading are investigated and products are analysed by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and thermogravimetric analysis. Thermodynamic equilibrium models of various experimental scenarios provide insight into the predominant species present at equilibrium. Reduction temperature and reduction duration affect H₂S concentration, a vital parameter for CCF synthesis, and CCFs form in only a narrow reduction and synthesis temperature range of 650 °C ± 50 °C with greatest coil yields observed at 650 °C and following reduction durations of between 1 and 20 min with greatest coil yields observed after a 10 min reduction. The presence of H₂ during synthesis was found to have a positive effect on CCF formation. The ratio of thick to thin carbon fibres increased with catalyst nickel loading and the greatest ratio of CCFs was produced with a 1:20 wt. Ni:Al₂O₃ catalyst.     

Study of intrinsic sulfidation behavior of Fe2O3 for high temperature H2S removal

Iron-based sorbent was preferable for desulfurization from coal-derived gas due to economic consideration and favorable dynamic property. The intrinsic behavior of Fe-based sorbent should be primarily understood in the sulfidation process for improving its performance. A series of tests were carried out with Fe₂O₃, Fe and other compounds containing-Fe (FO) made from the same precursor FeC₂O₄·2H₂O in H₂S-N₂ mixture in this study. The formation of H₂ was observed with Fe and FO as sorbents. While SO₂ was detected with FO and Fe₂O₃ as sorbents, its concentration in outlet was gradually decreased. The crystal phase and surface chemical state of fresh and sulfided Fe₂O₃ with different reaction times were characterized by XRD and XPS measurements. The result suggested that the intrinsic H₂S removal by Fe₂O₃ would produce multi-phase of sulfides. The possible mechanism of sulfidation reaction was discussed.     

Modeling of H2O2 formation in PEMFCs

A model for H₂O₂ formation, transport, and reaction in PEMFCs is established for the first time. Profiles of oxygen and H₂O₂ concentration inside the fuel cell are simulated using the agglomerate model for the electrode. The predicted concentration of H₂O₂ shows the same trend as experimental data under different conditions, but the level was only of the same magnitude. Low humidity, high temperature, and high oxygen/hydrogen partial pressures were found to increase the concentration of H₂O₂. An increase in membrane thickness or metal ion contaminant level reduces the concentration of H₂O₂ in the membrane. Lowering the oxygen permeability in the ionomer is the most important and effective method to reduce the formation of H₂O₂. The simulation results also show little change in H₂O₂ concentration while operating the fuel cell above 0.6 V. Anodes designed with considerable thickness, high catalyst loadings and active areas can also help to suppress H₂O₂ formation. Finally, recommendations are made to mitigate the effects of H₂O₂ and prolong membrane lifetimes.     

Effects of pore diameter and catalyst loading in hydroliquefaction of coal with CoO/MoO3/Al2O3 catalysts

The effect of catalyst pore size has been studied for the hydroliquefaction of a West Virginia coal in the presence of Co/Mo/Al₂O₃ catalyst. The alumina supports used for catalyst preparation had relatively sharp, unimodal pore size distribution with average pore diameters in the range of 100 Å to almost 1000 Å. Loading of MoO₃ and CoO on the Al₂O₃ supports was in the constant weight ratio of 5:1, but the absolute loading was in direct proportion to the surface area of the support. Two series of catalyst were studied: “High loading”, with 9.7 × 10^?4 g MoO₃/m² Al₂O₃, and “low loading”, with 4.5 × 10^?4 g MoO₃/m² Al₂O₃; both loadings were less than the amount necessary for monolayer distribution of MoO₃ on Al₂O₃. The weight of catalyst charged in each autoclave run was varied so that the same weight of MoO₃ and CoO was present for each experiment.The principal results were: (1) Al₂O₃ alone is not catalytic, even in large amount; (2) conversion of coal increases as catalyst pore diameter increases; from 100 Å to at least 500 Å; (3) the increased conversion with increasing pore size is manifested mainly as increased yield of asphaltenes at 400°C, so the ratio of oil to oil-plus-asphaltenes decreases as pore diameter increases; and (4) catalysts with “low loading” of MoO₃ and CoO on the Al₂O₃ surface give higher liquefactions than their counterparts with “high loading”. Most of the results are consistent with an expected low diffusion rate of large, coal-derived molecules through the catalyst pore system. The higher liquefaction with “low loading” of the Al₂O₃ surface might result from slow desorption of large product molecules (asphaltenes) exhibiting multiple-site adsorption to Mo neighbors on the surface.     

The deposition of coke from methane on a Ni/MgAl2O4 catalyst

Temperature-programmed reaction techniques and Raman spectroscopy were used to characterize coke species deposited on a 5% Ni/MgAl₂O₄ catalyst for dry reforming of methane. The CH₄ temperature-programmed decomposition profiles showed that the ignited decomposition temperatures of CH₄ increased from 273 to 378 °C when MgAl₂O₄ replaced the catalyst support γ-Al₂O₃. The temperature-programmed oxidation, temperature-programmed hydrogenation and temperature-programmed CO₂ reaction profiles showed that there were three carbon species (i.e. C_α, C_β and C_γ) on the catalyst surface. Raman spectroscopy showed that C_γ was graphite-like carbon species, which was responsible for catalyst deactivation. The C_γ species was the most inactive species toward H₂ and O₂, while it was unexpectedly more active toward CO₂. The unique reactivity of CO₂ with different coke specie could be ascribed to the carbonate, bidentate and formate species formation on MgAl₂O₄ surface. These surface species enhanced the oxidation of C_γ species and thus contributed to the high stability of Ni/MgAl₂O₄ catalyst.     

NO reduction with H2 in the presence of excess O2 over Pd/MFI catalyst

The NO SCR (selective catalytic reduction) activity with H₂ in the presence of excess O₂ was investigated over Pd/MFI catalyst prepared by sublimation method. With GHSV=90?000 h⁻¹, a very high steady-state conversion of NO to N₂ (70%) is achieved at 100 °C. Significant reorganizations take place inside the catalyst upon its first contact with all reactants and products at the reaction temperature. Pd⁰, which has a significant role in the NO-H₂-O₂ reaction, is possibly the active site for NO reduction. The formation of Pd-β hydride deactivates the catalyst for NO reduction. Throughout the entire NO-H₂-O₂ reaction, no N₂O or NO₂ is formed; N₂ is the only N-containing product. The presence of O₂ inhibits the formation of undesirable NH₃. The rate of the NO+H₂ reaction is fast or comparable to that of the H₂+O₂ reaction. The oxidation of Pd⁰ and subsequent agglomeration of PdO are responsible for the decreased NO reduction activity at high temperature.     

A Pd/Al2O3/cordierite monolithic catalyst for hydrogenation of 2-ethylanthraquinone

A novel Pd/Al₂O₃/cordierite monolithic catalyst was prepared and investigated in hydrogenation of 2-ethylanthraquinone (eAQ) for H₂O₂ production. It was found that there was an optimal penetrating depth on the monolithic catalyst. By adjusting the loading on the Al₂O₃, the penetrating depth of Pd could be efficiently confined in the Al₂O₃ washcoat. When Pd distribution matched well with Pd content, the higher yields of H₂O₂ could be obtained. As a result, the average yield on monolithic catalyst was 1.3 times of that on pellet catalyst, and the products distribution confirmed the monolithic catalyst was the optimal for H₂O₂ production.     

Ethanol reforming and partial oxidation with Cu/Nb2O5 catalyst

Ethanol reforming and partial oxidation were studied on Cu/Nb₂O₅ and Ni/Al₂O₃ catalysts. Compared to the Ni/Al₂O₃ catalyst, the Cu/Nb₂O₅ catalyst presents conversion as high as Ni/Al₂O₃ catalyst, however, for the same level of formation of hydrogen it occurs at much lower temperature on the Cu/Nb₂O₅ catalyst, 200 °C lower than for the Ni/Al₂O₃ catalyst, with remarkable little formation of CO, which can be attributed to the strong interaction between copper and niobia. Temperature-programmed desorption (TPD-ethanol) and surface reactions (TPSR) of partial oxidation of ethanol showed formation of ethylene, acetaldehyde, ethane and mainly H₂ and CO₂ besides little methane. DRIFTS results are in accordance with TPD analysis and the formation of acetate species at room temperature suggests reactivity of the surface and its oxidative dehydrogenation capacity. The adsorption of ethanol gives rise to ethoxide species, which form acetate and acetaldehyde that can be oxidized to CO₂ via carbonate. A comparison with reported results for Cu/Al₂O₃ this catalyst is promising, yielding high level of H₂ with little CO production during reforming and partial oxidation reaction. The maximum H₂ formation for the partial oxidation of ethanol was 41% at ratio (O₂/Et) 0.8, increasing to 50% at ratio 1.5. The H₂/CO is around 10 for the partial oxidation and 7 for steam reforming, which is excellent, compared to the Ni/Al₂O₃ catalyst with a factor 4–8 lower.     

羟基磷灰石负载钯催化剂用于H2和O2直接合成H2O2的动力学

H₂和O₂直接合成H₂O₂过程绿色环保,反应具有原子经济性,是最有潜力的H₂O₂合成新方法之一。采用等量浸渍法,将Pd负载于羟基磷灰石（HAp）载体上,得到了高分散的Pd/HAp纳米催化剂,Pd平均粒径2.5 nm。运用幂指数模型,研究该催化剂在H₂O₂加氢及H₂和O₂直接合成反应中的动力学,计算得到H₂O₂加氢、H₂O₂和H₂O的生成反应的表观活化能及O₂、H₂表观反应级数。结果表明低温及高O₂分压有利于H₂O₂的生成,而高H₂分压则有利于H₂O的生成。     

Co-production of hydrogen and multi-wall carbon nanotubes from ethanol decomposition over Fe/Al2O3 catalysts

The co-production of hydrogen and carbon nanotubes (CNTs) from the decomposition of ethanol over Fe/Al₂O₃ at different temperatures and feeding rates of ethanol was investigated systematically. The results indicated that Fe/Al₂O₃ was a quite active catalyst for the co-production of hydrogen and CNTs and that its activity and stability depended strongly on the Fe loading. Among all catalysts tested, 10 mol% Fe/Al₂O₃ was the most effective catalyst based on the ratio of hydrogen production, the total H₂ yield, and the quality of the CNTs formed. The efficiency of hydrogen production from ethanol decomposition over 10 mol% Fe/Al₂O₃ reached a maximum of 80% at 800 °C and the yield of CNTs with well-oriented growth and uniform diameter was 141%. In addition, the reaction of hydrogen and CNTs co-produced from ethanol decomposition was proposed.     

Localised visualisation of O2 consumption and H2O2 formation by means of SECM for the characterisation of fuel cell catalyst activity

Catalytic reduction of O₂ at metal catalysts either follows a 2-electron transfer pathway to the formation of H₂O₂ or a 4-electron transfer pathway to the formation of H₂O. The branching ratio of this reaction has a significant impact on the applicability of catalyst materials. The previously introduced oxygen competition mode of SECM, which allows high-resolution imaging of local O₂ consumption, has been extended to a potential-pulse sequence enabling the sequential detection of O₂ reduction followed by the detection of local H₂O₂ formation. Thus, not only the local catalytic activity of a catalyst can be visualised but, additionally, the degree of the branching can be estimated. The selectivity of a catalyst candidate can thereby be visualised sequentially to the elucidation of its activity. First results on the properties of electrodeposited Pt and Au test structures are shown demonstrating the feasibility to clearly distinguish catalyst activity and selectivity under variation of the polarisation potential.     

A crucial role of surface oxygen mobility on nanocrystalline Y2O3 support for oxidative steam reforming of ethanol to hydrogen over Ni/Y2O3 catalysts

Y₂O₃ nanocrystals hydrothermally synthesized at different pH are found to have different morphologies and crystal sizes. These Y₂O₃ nanocrystals have been investigated as supports of Ni-based catalysts in oxidative reforming reaction of ethanol. Result of H₂-chemisorption shows that the particle size and dispersion of nickel on Y₂O₃ nanocrystals are not affected significantly by the crystal size of Y₂O₃. XPS and H₂-TPR results show that no association between nickel and the support-Y₂O₃ has taken place and the reducibility of nickel is not affected by the crystal size of Y₂O₃. However, it is found that the surface oxygen mobility of Y₂O₃ nanocrystal increases with decreasing crystal size. The surface oxygen mobility is believed to play an important role in promoting the H₂ production rate and selectivity of the Ni/Y₂O₃ catalyst over the oxidative steam reforming of ethanol.     

Fe2O3/β-SiC: A new high efficient catalyst for the selective oxidation of H2S into elemental sulfur

Over the last decades, sulfur recovery from the H₂S-containing acid gases (issued from oil refineries or natural gas plants) has become more and more important due to the ever increasing standards of efficiency required by environmental protection pressures. The H₂S-tail gas was directly oxidized by oxygen to yield elemental sulfur. A significant improvement of the H₂S conversion and selectivity has been developed, however, the support which is the core of the process still needs to be improved. Recently, β-SiC has been reported to be an efficient and selective catalyst support for the H₂S-to-S reaction. One expected reason for this superior yield should be due to the high thermal conductivity of the support. The high thermal conductivity of the silicon carbide plays an important role in the maintenance of the high selectivity by avoiding the formation of hot spots on the catalyst surface which could favor secondary reactions. On the other hand, insulator supports such as alumina exhibit a poor selectivity due to catalyst surface temperature runaway.     

Kinetic modeling of storage and reduction with different reducing agents (CO, H2, and C2 H4) on a Pt–Ba/-Al2O3 catalyst in the presence of CO2 and H2O

In this paper a global reaction kinetic model is used to understand and describe the NO_x storage/reduction process in the presence of CO₂ and H₂O. Experiments have been performed in a packed bed reactor with a Pt–Ba/γ-Al₂O₃ powder catalyst (1 wt% Pt and 30 wt% Ba) with different lean/rich cycle timings at different temperatures (200, 250, and ) and using different reductants (H₂, CO, and C₂H₄). Model simulations and experimental results are compared. H₂O inhibits the NO oxidation capability of the catalyst and no NO₂ formation is observed. The rate of NO storage increases with temperature. The reduction of stored NO with H₂ is complete for all investigated temperatures. At temperatures above , the water gas shift (WGS) reaction takes place and H₂ acts as reductant instead of CO. At , CO and C₂H₄ are not able to completely regenerate the catalyst. At the higher temperatures, C₂H₄ is capable of reducing all the stored NO, although C₂H₄ poisons the Pt sites by carbon decomposition at . The model adequately describes the NO breakthrough profile during 100 min lean exposure as well as the subsequent release and reduction of the stored NO. Further, the model is capable of simulating transient reactor experiments with 240 s lean and 60 s rich cycle timings.     

Synthesis of DME from syngas on the bifunctional Cu–ZnO–Al2O3/Zr-modified ferrierite: Effect of Zr content

The catalytic activity on the coprecipitated Cu–ZnO–Al₂O₃/Zr-ferrierite (CZA–ZrFER) with different Zr content from 0 to 5 wt.% was investigated for the direct synthesis of dimethylether (DME) from H₂-deficient and biomass-derived model syngas (H₂/CO molar ratio = 0.93). The catalytic functionalities, such as CO conversion and DME selectivity, showed their maxima on the bifunctional catalyst with 3 wt.% Zr-modified ferrierite. Detailed characterization studies were conducted on the catalysts to measure their properties such as surface area, acidity by temperature-programmed desorption of ammonia (NH₃-TPD), reducibility of Cu oxide by temperature-programmed reduction (TPR), copper surface area measurements by N₂O titration method, electronic states of copper by IR analysis and particle size measurement by XRD and TEM analysis. The number of acid sites measured by NH₃-TPD on the bifunctional catalysts decreased monotonously with the increase of Zr content, meanwhile, the acidic strength is found to be minimal on the catalyst showing best performance. The reducibility of copper oxide and the surface area of metallic copper also exhibited their maximum values at the same Zr composition indicating that these are responsible for the optimum functionality of the bifunctional CZA–ZrFER catalyst. The role of easily reducible copper species with small particle size and the suppressed strong acidic sites is also emphasized in the consecutive reaction from syngas to DME on the bifunctional catalyst. The different behavior of intrinsic rate of the bifunctional catalysts is also well correlated with the metallic surface area of copper and the amount of acidic sites with their acidic strength.     

A crucial role of O2 and O2 on mayenite structure for biomass tar steam reforming over Ni/Ca12Al14O33

Newly synthesized nickel calcium aluminum catalysts (Ni/Ca₁₂Al₁₄O₃₃) were tested in a fixed bed reactor for biomass tar steam reforming, toluene as tar destruction model compound. Four catalysts (Ni/Ca₁₂Al₁₄O₃₃) were prepared with Ni loading amount from 1, 3, 5 to 7 wt%, even 1% loading catalyst also showed excellent performance. Catalysts aged experiments in the absence (60 h on stream) and presence of H₂S were characterized by BET, X-ray diffraction (XRD), and Raman spectra. It was observed that Ni/Ca₁₂Al₁₄O₃₃ showed excellent sustainability against coke formation due to the “free oxygen” in the catalysts. It also exhibited higher H₂S-poisoning resistance property compared to the commercial catalysts Ni/Al₂O₃ (5%) and Ni/CaO_0.5/MgO_0.5. Raman spectra revealed that “free oxygen O₂⁻ and O₂²⁻” in the structure of the catalysts could be substituted by sulfur then protected Ni poisoning on some degree, but reactivation experiments by O₂ flowing showed that the sulfide Ni/Ca₁₂Al₁₄O₃₃ was difficult to completely restore, incorporation of sulfur in the structure only partly regain by O₂. The kinetic model proposes, as generally accepted, a first-order reaction for toluene with activation energy of 82.06 kJ mol⁻¹ was coincident with the literature data. The Ni/Ca₁₂Al₁₄O₃₃ catalyst was effective and relative cheap, which may be lead to reduction in the cost of hot gas cleaning process.