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Abstract: Resonant inelastic X-ray scattering (RIXS) was applied to investigate whether the iron–oxygen species created upon reaction of Fe-ZSM-5 with N2O have a (partial) 3d4 configuration, i.e. oxidation state Fe(IV). Fe-ZSM-5 samples with low iron loading were pre-treated at high temperatures before reaction with N2O. Then Fe K-edge XANES spectra were recorded either by selecting the fluorescence of the main Kβ1,3 line or the satellite Kβ′ line in the Kβ emission spectrum. The experiments were performed in situ and imitated the experiments performed in the laboratory reactor. The absence of a pre-edge in the Kβ′ line spectrum proves that the configuration of the active iron–oxygen species is purely 3d5. The result was confirmed for several differently treated Fe-ZSM-5 catalysts. The high reactivity of Fe-ZSM-5 is therefore not due to the formation of high oxidation states of iron, but must be ascribed to the particular oxygen species that is created by the reaction of N2O with the catalyst. [Copyright &y& Elsevier]

Abstract: The mechanism of N2O decomposition was studied on a series of Fe-ZSM-5 catalysts prepared by ion exchange (IE) and chemical vapor deposition (CVD). N2O decomposition activity depends strongly on the extent of autoreduction of the catalyst during the pretreatment in He at high temperatures. The extent of autoreduction is significantly lower for catalysts prepared by CVD compared with that for catalysts prepared by aqueous ion exchange. As a result, the global turnover frequencies of the ion-exchanged catalysts are significantly higher. If the activity is normalized by the concentration of Fe2+ sites, however, then the CVD catalyst is the most active sample. This is attributed to the fact that high iron loading favors the surface migration and recombination of surface oxygen atoms to O2, which is the rate-limiting step of the reaction. O2 formation by slow recombination of two surface oxygen atoms is the dominating mechanism even for IE samples with very low iron loadings. [Copyright &y& Elsevier]

Abstract: The hydrothermal stability of WIE-based Fe-ZSM-5 and Fe-BEA for N2O decomposition in the presence of NO, H2O and O2 was studied at 723K. Catalysts were characterized with UV–vis, IR and Al-XANES. The N2O conversion remains at a constant level with Fe–H-BEA even in the presence of large amounts of H2O. Deactivation was, however, observed with Fe–H-ZSM-5 already in the presence of 0.5vol.% water. The analysis of deactivated samples indicated that steam-dealumination and clustering of iron occurred during the reaction with Fe-ZSM-5. Replacement of protons for sodium in Fe-ZSM-5 slowed down the rate of catalyst deactivation significantly. Steam-dealumination is likely to precede the clustering of iron in Fe–H-ZSM-5. The excellent hydrothermal stability of WIE-based Fe–H-BEA relates to the high initial degree of dealumination in the as-received BEA. [Copyright &y& Elsevier]

Abstract: Fe-FER is an active catalyst for the abatement of N2O in the tail gas of nitric acid plants. The activity of Fe-FER can be increased if Ru is added as a second active component. This is a surprising finding, because noble metals are usually strongly inhibited by NO, which is always present in tail gas. Yet the bimetallic FeRu-FER catalyst is more active than the sum of the components, Fe-FER and Ru-FER. A synergy between Fe and Ru can explain this phenomenon. This work discusses the role of Fe and Ru in the reaction mechanism as well as the interplay of these two components. In situ IR measurements show that the preferential adsorption of NO and its reaction products on Fe in the bimetallic catalyst reduces the inhibiting effect of NO on the Ru component; this effect largely contributes to the synergy between Fe and Ru. Moreover, in situ X-ray absorption data are presented, which allow for tracing the average oxidation state of the two active components Fe and Ru under reaction conditions. [Copyright &y& Elsevier]

Abstract: NO-assisted N2O decomposition over four different Fe-ZSM-5 samples prepared by wet ion exchange (WIE) or chemical vapor deposition (CVD) of FeCl3 was investigated by steady-state kinetics, in situ infrared (IR) spectroscopy, and transient response methods. Despite their lower iron loading, the samples prepared by WIE had the highest activity for N2O decomposition in the presence of NO. The in situ IR experiments showed that the most active sample was characterized by a high concentration of adsorbed NO, as well as adsorbed NO2 under reaction conditions. Step response experiments proved that NO2 is an intermediate of the catalytic cycle and functions as intermediate oxygen storage. IR and transient kinetic experiments showed that WIE catalysts behave qualitatively different in NO-assisted N2O decomposition than CVD catalysts. These differences are discussed in terms of the different structure of the iron species in the two types of samples. [Copyright &y& Elsevier]

Abstract: The mechanism of decomposition of N2O on Fe-ZSM-5 prepared by chemical vapor deposition was studied by step and pulse response experiments and by isotope labeling. The results show that only a very small fraction of the iron sites is taking part in the catalytic cycle. N2O deposits its oxygen atoms on these sites, the deposited oxygen atoms migrate over the iron cluster, exchange with other oxygen atoms and then desorb by recombination to O2. On strongly dehydroxylated iron sites also a direct recombination of two oxygen atoms, which were deposited from N2O, is possible. The concentration of these sites increases after treatment of the samples at high temperatures in inert gas. The relation between the sites involved in N2O decomposition and the α-sites, which were first described by the group of Panov, is discussed. We can conclude that the deposition of N2O on Fe-ZSM-5 CVD catalysts creates active oxygen species on the catalyst surface (in particular, after pretreatments at high temperature), but their properties are different from those of α-oxygen. [Copyright &y& Elsevier]

The effect of pretreatment conditions on the N2O-decomposition activity of Fe-ZSM-5 prepared by chemical vapor deposition (CVD) was studied by steady-state kinetics and step-response experiments. Pretreatment at 873 K in H2 or He significantly increased the N2O-decomposition activity of Fe-ZSM-5 CVD. In addition to the increased steady-state activity, the catalyst exhibited a very high initial activity in the step-response experiments, which slowly decayed to steady state. This “transient” activity was particularly high after pretreatment of the samples in He, whereas it vanished completely after pretreatment in O2 or exposure to water vapor. This led to the conclusion that the transient activity is related to strongly dehydroxylated Fe2+ sites created by autoreduction at high temperatures. On the basis of isotope-labeling data a mechanism for N2O decomposition is proposed. The first step is the reaction of Fe2+ with N2O to give a Fe3+O- species, which quickly transforms into a Fe2+–peroxo complex. Desorption of O2 occurs upon reaction of the complex with another N2O molecule (mainly during the transient) or via the recombination of two peroxo species after their migration over the iron oxide cluster (mainly during steady state). [Copyright &y& Elsevier]

Iron-containing zeolites were prepared by aqueous ion exchange, sublimation of FeCl3, or hydrothermal synthesis and were modified by steaming at 873 K. The samples contained different kinds of iron species ranging from isolated iron atoms to small clusters that contain a few atoms and somewhat larger oligomers. Yet, the dynamic behavior of all samples in N2O decomposition was qualitatively similar. Pulse experiments showed that a slow and fast pathway of O2 formation, which is the rate-limiting step of the reaction, exists. Both contributed to the overall activity. The fast pathway dominated on isolated iron sites, whereas the contribution of the slow pathway increased on catalysts with high iron loadings. Steaming led to an agglomeration of the iron clusters and increased the activity (with one exception). The steamed samples had a peculiar time-on-stream behavior. They exhibited a very high initial activity and then slowly decayed to steady state. This indicates that steaming did not merely agglomerate the iron clusters, but qualitatively changed the nature of the active sites. [Copyright &y& Elsevier]

The nitration of toluene and 2-nitrotoluene was investigated using different batches of zeolite BEA. In the nitration of toluene, notable differences in the product composition were obtained depending on the batch of BEA used. In the nitration of 2-nitrotoluene, all the catalysts displayed a good selectivity, but different conversions. Steaming improved the performance of the catalysts, but strong dealumination with oxalic acid had a negative effect. The positive effect of steaming was attributed to the enhanced transport of the reaction products out of the pores. Lewis acidity did not seem to play a role in the nitration reaction. A high concentration of Brønsted sites was detrimental, because it slowed down the diffusion of the products, but a small concentration of Brønsted sites was required to catalyze the heterogeneous reaction. [Copyright &y& Elsevier]

The reaction of Fe-zeolites prepared by sublimation of FeCl3 with N2O was studied by step- and pulse-response experiments. Steps from 0 to 5000 ppm N2O were performed at 673 K, after pretreatment of the catalyst in H2, He, or O2. When the catalysts were prereduced in H2, N2O was first consumed for the reoxidation of the catalyst, before steady-state N2O decomposition started. Also pretreatment in He reduced the catalyst. This autoreduction was not spontaneous, but caused by a small amount of hydrocarbons adsorbed on the catalyst. Prereduced catalysts had a higher steady-state activity, indicating that the incorporation of oxygen from N2O changed the structure of the active sites. Pulse responses proved that O2 desorption is the rate-limiting step of N2O decomposition. O2 desorption was relatively fast from a small fraction of sites, while a second oxygen pool desorbed only slowly from the catalyst. Only the former is responsible for catalytic activity. [Copyright &y& Elsevier]

The nitration of toluene and 2-nitrotoluene with acetyl nitrate was investigated using several solid acid catalysts. In the nitration of toluene, enhanced para-selectivity was observed only with zeolite BEA. For the nitration of 2-nitrotoluene, all the catalysts displayed good para-selectivity, but only BEA led to high yields. The superior performance of BEA was due to the fact that only with this zeolite did the heterogeneously catalyzed reaction compete successfully with the homogeneous nitration in the liquid phase. Geometrical considerations showed that the high para-selectivity of BEA was not caused by classical transition-state selectivity but was induced by the reaction of the arene with a surface-bound acetyl nitrate complex. The existence of this complex was supported by NMR measurements, which showed that its formation is a specific property of zeolite BEA. [Copyright &y& Elsevier]

[Display omitted] • Co promotion do not alter metal-support interactions compared to non-promoted systems. • Co promotion is not surface-dependent but contingent to the formation of MoS 2. • Highest catalytic activity for metal-support interactions of intermediate strength. The current environmental and industrial contexts require constant revision and improvement of hydrotreating processes for obtaining cleaner (bio)fuels through the development of supported transition metal sulfide (TMS) catalysts. The present work proposes a surface-science approach to describe the surface-dependent genesis of the cobalt-promoted active phase (CoMoS) supported on α-Al 2 O 3 single crystals used as surrogates of the industrial γ-Al 2 O 3 support. Co-Mo precursor solutions are deposited by aqueous-phase impregnation onto four α-Al 2 O 3 single crystals of C(0001), A (11 2 ¯ 0) , M (10 1 ¯ 0) , and R (1 1 ¯ 02) orientations, which display specific OH sorption sites. The model catalysts are characterized in the oxide and sulfide states by XPS, AFM, and TEM revealing a surface dependent sulfidation and dispersion as a result of metal-support interactions of diverse nature. The surfaces can be ranked following metal-support interactions of increasing strength C(0001) < A (11 2 ¯ 0) , M (10 1 ¯ 0) < R (1 1 ¯ 02) in good agreement with model non-promoted catalysts. However, AFM and TEM imaging also reveal that cobalt incorporation leads to an increase in the stacking of CoMoS particles with respect to non-promoted catalysts. The activity of the model catalysts in thiophene hydrodesulfurization cannot be simply related to the common features of the active phase (sulfidation, dispersion, promotion extent) but a volcano-shape curve is obtained when plotting the activity as a function of metal-support interactions. These results suggest that high activity is obtained on surfaces with intermediate metal-support interactions that lead to an optimal metal-sulfur bond energy in agreement with the Sabatier principle. Transposing these results to the traditional γ-Al 2 O 3 support suggests an enhanced activity of the (1 0 0) facet, which can lead to the development of improved supports for hydrotreating catalysts. [ABSTRACT FROM AUTHOR]

Abstract: The N2O decomposition activity of the Fe-ZSM-5 catalysts, prepared by chemical vapor deposition (CVD) and aqueous ion exchange (IE), was studied after steaming and high temperature treatment at 1218K (HT) and compared with the activity of the corresponding non-steamed catalysts after pretreatment at 873K. FTIR spectra showed that dehydroxylation and/or dealumination took place during steaming and high temperature treatment of the catalysts, which leads to the formation of oxygen vacancies (i.e. lattice defect). These lattice defects leads to a change in electronic properties of the iron sites, which are associated with electron withdrawing Al Lewis centers. The iron sites in close proximity of defects are responsible for the initial higher N2O decomposition (transient activity) of the steamed and HT catalysts. The increase in steady-state activity over steamed and HT catalysts can be mainly attributed to an increase in the number of active sites created by autoreduction of the iron centers during steaming and high temperature treatment. The above-mentioned trends are valid for both CVD and IE samples. [Copyright &y& Elsevier]

In order to meet the demand for cleaner fuels, it is necessary to develop high performing hydrotreating catalysts. Although organic additives are often used to improve the performances of hydrotreating catalysts, bio-polymer additives have not yet been thoroughly investigated. We recently showed that dopamine, a neurotransmitter molecule, which is also frequently found in adhesive bio-polymers, efficiently coats the surface of an alumina carrier material and modifies the interaction with active components of hydrotreating catalysts, i.e . cobalt and molybdenum. The catalytic performance of the CoMoS/Al 2 O 3 catalysts could, thus, be improved. In the present paper we extend the strategy to other carrier materials (silica and titania). The catalysts prepared on (poly)dopamine (Pdop) coated silica showed enhanced activity for the hydrogenation of toluene reaction and the selective HDS of FCC gasoline model feed. Pdop coating lowers the MoS 2 nanocrystallites' stacking on silica, thereby improving the accessibility of active edge sites. The origin of this increase in catalytic activity may be found in the higher capacity of Pdop's functional groups to interact with metallic precursors leading to a better dispersion of the active phase. On the contrary, when the interaction between the dopamine and the support is too strong (as observed for TiO 2 ), the functional groups of Pdop are not available for interaction with Co and Mo species, resulting in decreased catalytic activity. [ABSTRACT FROM AUTHOR]

A detailed kinetic study of the hydrodenitrogenation (HDN) network of quinoline was carried out over Ni-promoted MoS 2 catalysts supported either on γ-Al 2 O 3 or on amorphous silica alumina (ASA), the objective is to identify the role of the support acidity in HDN reactions. The kinetic data obtained from catalytic tests in a batch reactor were analyzed by a model including the liquid-vapor mass transfer. The adsorption constants of all intermediates and the kinetic constants of all elementary steps were estimated. We found that the NiMo(P)/ASA exhibited a higher rate constant in the hydrogenation of tetrahydroquinoline, which was the rate determining step of the main reaction pathway, and in exocyclic carbon-nitrogen bond cleavage reactions, than the NiMo(P)/Al 2 O 3 . Characterization data by Infra-Red spectroscopy of CO suggested that this result might be related to the modification of the electronic properties of promoted NiMoS phase due to higher acidity of ASA. However, the stronger self-inhibiting effect due to stronger adsorption of nitrogen compounds over NiMo(P)/ASA and its lower content of NiMoS phase decreased its global catalytic activity. [ABSTRACT FROM AUTHOR]

The constant improvement of hydrotreating (HDT) catalysts, driven by industrial and environmental needs, requires a better understanding of the interactions between the oxide support (mostly alumina) and the MoS 2 active phase. Hence, this work addresses the support-dependent genesis of MoS 2 on four planar single-crystal α-Al 2 O 3 surfaces with different crystal orientations (C (0 0 0 1), R ( 1 1 ¯ 0 2 ) , M ( 1 0 1 ¯ 0 ) , and A ( 1 1 2 ¯ 0 ) ). In contrast to classical surface science techniques, which often rely on UHV-type deposition methods, Mo is introduced by impregnation from an aqueous solution in order to mimic standard incipient wetness impregnation. Comparison between different preparation routes, impregnation vs. equilibrium adsorption (selective adsorption), is also considered. Atomic force microscopy, X-ray absorption spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy show that the α-Al 2 O 3 orientation has a clear impact on the strength of metal–support interactions in the oxide state with consequences for the sulfidation, size, stacking, and orientation of MoS 2 slabs. Aggregation of molybdenum oxide particles is observed on the C (0 0 0 1) plane, suggesting weak metal–support interactions leading to a high sulfidation degree with large slabs. Conversely, the presence of well-dispersed individual oxide particles on the R ( 1 1 ¯ 0 2 ) plane implies stronger metal–support interactions, leading to a low sulfidation degree and shorter MoS 2 slabs. Both A ( 1 1 2 ¯ 0 ) and M ( 1 0 1 ¯ 0 ) facets, of similar crystallographic structure, display intermediate behavior in terms of sulfidation rate and MoS 2 size, in line with intermediate metal–support interactions. Polarization-dependent grazing-incidence-EXAFS experiments, as well as high-angle annular dark-field (HAADF) scanning transmission electron microscopy analysis, allow us to demonstrate a surface-dependent orientation of MoS 2 slabs. Predominant basal bonding is suggested on the C (0 0 0 1) plane, in agreement with the existence of weak metal–support interactions. Conversely, a random orientation (edge and basal bonding) is observed for the other planes. Generalization of these conclusions to industrial catalysts is proposed, based on comparison of the surface structure of the various model α-Al 2 O 3 orientations used in this work and the predominantly exposed γ-Al 2 O 3 surfaces ((1 1 0), (1 0 0), and (1 1 1)). [ABSTRACT FROM AUTHOR]