Characterisation by TPR, XRD and NOx Storage Capacity Measurements of the Ageing by Thermal Treatment and SO2 Poisoning of a Pt/Ba/Al NOx-Trap Model Catalyst

The deactivation of a Pt/Ba/Al₂O₃ NO _x -trap model catalyst submitted to SO₂ treatment and/or thermal ageing at 800 °C was studied by H₂ temperature programmed reduction (TPR), X-ray diffraction (XRD) and NO _x storage capacity measurements.The X-ray diffractogram of the fresh sample exhibits peaks characteristic for barium carbonate. Thermal ageing leads to the decomposition of barium carbonate and to the formation of BaAl₂O₄. The TPR profile of the sulphated sample shows the presence of (i) surface aluminium sulphates, (ii) surface barium sulphates, (iii) bulk barium sulphates. The exposure to SO₂ after ageing leads to a small decrease of the surface barium-based sulphates, expected mainly as aluminate barium sulphates. This evolution can be attributed to a sintering of the storage material. TPR experiments also show that thermal treatment at 800 °C after the exposure to SO₂ involves the decomposition of aluminium surface sulphates to give mainly bulk barium sulphates, also pointed out by XRD. Thus, the thermal treatment at 800 °C leads to a stabilization of the sulphates.These results are in accordance with the NO _x storage capacity measurements. On non-sulphated catalysts, the treatment at 800 °C induces to a decrease of the NO _x storage capacity, showing that barium aluminate presents a lower NO _x storage capacity than barium carbonate. Sulphation strongly decreases the NO _x storage capacity of catalysts, whatever the initial thermal treatment, showing that barium sulphates inhibit the NO₂ adsorption. Moreover, the platinum activity for the NO to NO₂ oxidation is lowered by thermal treatments.     

Carbon monoxide oxidation and nitrous oxide reduction on Rh/Pt(1 1 1) electrodes

Rhodium adlayers on Pt(1 1 1) substrates have been prepared by electrodeposition from dilute Rh³⁺ acidic solutions. Resulting deposition rates are lower than 0.03 ML min⁻¹. Pseudomorphic growth of the first monolayer has been confirmed by scanning tunneling microscopy (STM) as well as the formation of small compact islands in the submonolayer range. Carbon monoxide oxidation and nitrous oxide reduction have been studied on Rh/Pt(1 1 1) electrodes. The oxidation of carbon monoxide is catalyzed by the presence of very low coverages of rhodium as demonstrated by the negative shift of the CO oxidation profile. Results are compatible with a bifunctional mechanism for catalysis including CO diffusion in the Pt domains toward the edges of the islands (splitting of the voltammetric oxidation profile). The reduction of nitrous oxide occurs at different potential and with different rates on Pt domains, at the center of the Rh islands and at their edges, being the latter sites especially active. In any case, the adsorptive and catalytic activity of the adlayers differ from those of the bulk Pt(1 1 1) and Rh(1 1 1) electrodes. The existence of strain in the film together with a diminution in the coordination number for adatoms at the edges of the islands are considered to be at the origin of the observed behavior.     

XPS study of irreversibly adsorbed arsenic on a Pt(1 1 1) electrode

The chemical composition of an irreversibly adsorbed layer of arsenic on Pt(1 1 1) in sulfuric acid solution has been studied by X-ray photoelectron spectroscopy (XPS). From the chemical shift of the As 3d level, a change in the valence state from As(0) to As(III) with positive-going electrode potential is deduced, the total amount of As on the surface remaining constant. The As coverage derived from XPS is around 0.33 ML, which is in agreement with the charge under the current peak in the cyclic voltammogram. From the coadsorption of anions, accompanying the valence transition of As, As(III) is assumed to exist as As(OH)₃ on the surface.     

Effect of Ionic Liquids on Surface and Aggregation Properties of Non-ionic Surfactant Triton™ X-100 in Aqueous Media

The effect of the hydrophilic ionic liquids (ILs) 1-butyl-2,3-dimethylimidazolium bromide [bdmim][Br] and 1-hexyl-2,3-dimethylimidazolium bromide [hdmim][Br] on the aggregation and surface active behaviour of the non-ionic surfactant Triton? X-100 (TX-100) was studied in aqueous media. Several aggregation properties of TX-100 + IL/water systems, such as critical micelle concentration (CMC), surface active parameters, aggregation number (N _agg) and aggregate size, were determined by surface tension, fluorescence and dynamic light scattering (DLS) techniques. It was found that the average micellar size and aggregation number decrease, whereas the CMC increases with increasing concentration of ILs. Interestingly, the CMC value of TX-100 is reduced slightly below 0.5 wt% of both the ILs in the medium. At higher wt% of IL in the system the CMC increases. It was demonstrated that ILs [bdmim][Br] and [hdmim][Br] can be judiciously used at different wt% for modifying the physico-chemical properties of TX-100.     

Hydrogenation of nitro compounds with supported platinum catalyst in supercritical carbon dioxide

Hydrogenation of a series of substituted nitro compounds such as 2-,3-,4-nitroanisole, 2-,3-,4-nitrotoluene, 2,4-dinitrobenzene and 2,4-dinitrotoluene has been studied in supercritical carbon dioxide, scCO₂ (two phases), and ethanol (three phases) with a 5 wt.% carbon supported platinum catalyst. The solubility of these compounds in scCO₂ has also been examined in the presence and absence of hydrogen. The solubility of those nitro compounds increases with increasing CO₂ pressure but decreases with the presence of hydrogen. The solubility is in the order of nitrotoluene > nitroanisole > dinitrotoluene, dinitrobenzene. Although the total conversion obtained with hydrogenation in scCO₂ is similar to that in ethanol, the selectivity to amino products is higher in the former reaction medium, indicating that scCO₂ is an ideal medium for the production of amino compounds with hydrogenation of nitro substrates using conventional supported metal catalysts.     

Pt/TiO_2光催化制氢的初步研究

对无氧条件下Pt/TiO_2光催化重整甲醇制氢的基本步骤进行简化,在同一体系中进行了光催化剂的合成和光催化制氢的两步反应。基于正交设计法对该复杂体系进行了分析,得到Pt载量、甲醇/水体积、灯距、前反应时间这4种影响因素的3个不同水平对放氢速率的影响。确定了最佳实验条件为Pt载量0.5％(mol)、甲醇/水体积比5:1、灯距12 cm、前反应时间3h。分析结果表明,Pt载量对放氢速率的影响最大。实验获得的最高放氢速率为5.84 ml·h~(-1)·g~(-1)。     

Effect of Preparation Conditions of Pt/C Catalysts on Oxygen Electrode Performance in Proton Exchange Membrane Fuel Cells

Supported Pt/C catalyst with 3.2 nm platinum crystallites was prepared by the impregnation—reduction method. The various preparation conditions, such as the reaction temperature, the concentration of precursor H₂PtCl₆ solution and the different reducing agents, and the relationship between the preparation conditions and the catalyst performance were studied. The carbon black support after heat treatment in N₂ showed improved platinum dispersion. The particle size and the degree of dispersion of Pt on the carbon black support were observed by transmission electron microscopy (TEM). The crystal phase composition of Pt in the catalyst was determined by X-ray diffraction (XRD). The surface characteristics of the carbon black support and the Pt/C catalyst were studied by X-ray photoelectron spectroscopy (XPS). The electrochemical characteristics of the Pt/C catalysts were evaluated from current—voltage curves of the membrane electrode assembly (MEA) in a proton exchange membrane fuel cell.     

Quantified mass transfer and superior antiflooding performance of ordered macro‐mesoporous electrocatalysts

For oxygen reduction reaction (ORR), constructing porous catalysts are highly important for mass transfer inside. However, the various porous structures usually possess significantly different water buffer efficiency, that is, the antiflooding capability, for which one is still difficult to give a quantitative evaluation. In this work, we designed a special “rattle‐drum” like working electrode, by which an exactly quantitative assessment on the mass transfer efficiencies can be conducted. Particularly, ordered macro‐mesoporous Pt/C shows quantified mass transfer and antiflooding efficiency to be four times high as that of the commercial one. This observation should be attributed to their different pore characteristics, as the dual‐porosity Pt/C has 3.4 times the pore volume of the commercial one, together with regular pore arrangement. Simultaneously, it also demonstrated excellent durability, indicating that the macro‐mesoporous Pt/C indeed owns high stability in both antiflooding and durability. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2881–2889, 2018     

载铂二氧化钛对3B艳红染料溶液光催化降解性能的研究

本文以载铂TiO2为催化剂,光催化降解可溶性染料;对引起染料3B艳 红脱色的作用机理进行了分析并探讨了铂的担载量、催化剂的重复使用性、染料水溶液的pH值、光源波长、H2O2的添加等因素对催化降解效果的影响。结果表明,TiO2表面担载适宜量的金属铂后,对染料降解的催化活性有了明显提高;酸性溶液和添加适量的H2O2均有利于催化降解。     

A FIXED BED BARRIER REACTOR WITH SEPARATE FEED OF REACTANTS

A new type of gas-solid reactor was developed and characterised in the series of reactor configurations with separate Teed of reactants studied by our group. The novelty in the proposed design lies in the use of a fixed bed of small catalytic particles instead of a porous catalytic membrane. The major advantages of this concept, as opposed to the catalytic membrane reactor, are: (i) the barrier activity and pore structure are more homogeneous (good properties for modelling purposes); (ii) an easier integration of the catalyst bed into the reactor is obtained (the fixed bed can be sealed more easily into metallic modules than a catalytic membrane).

A Pt catalyst supported on La-stabilised alumina pellets (d_p = 5 - 50 μm) was used and the catalytic oxidation of carbon monoxide was studied as a model reaction to characterise the reactor. A mathematical model based on the Dusty Gas Model approach was conceived and a good agreement between calculations and experiments was obtained. This fixed bed barrier reactor may thus represent a quicker and easier opportunity, compared to membrane reactors, to check the concept of the separate-feed of reactants with new reactions and catalysts.