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Microporous cavities and channels of zeolites frameworks have been used for decades for the encapsulation of cations, complexes and metals. In the particular case of metals, nanoparticles are usually formed after post-synthesis modifications such as ion-exchange or wetness impregnation. Tough encapsulation can provide a strict control of the nanoparticle size as well as a limitation of aggregation at high temperature; encapsulated nanoparticles are often hardly accessible due to diffusion limitations of reactants in sub-nanometric micropores. Recent developments in zeolite synthesis have offered a new class of materials with hierarchical structures or unusual morphologies in which the mean diffusion path is considerably reduced. Those zeolites with inter-crystalline and/or intra-crystalline mesopore systems are particularly adapted for supporting nanoparticles both in microporous cavities of the framework and in mesoporous channels. More sophisticated architectures such as yolk/core–shell materials, in which nanoparticles are protected against poisoning or sintering by a thin zeolite shell, are particularly attractive. In contrast to nanometric intrinsic cavities of zeolite frameworks, a large internal void is available for chemical reactions and such catalysts can be considered as nanoreactors in which the reaction is essentially governed by the permeability of the shell. This review focuses on the most recent progress as well as perspectives in the design of zeolite-containing metal nanoparticles, which differ from traditional materials by the originality of the synthesis method or the morphology of the support. [ABSTRACT FROM AUTHOR]

The conversion of methane or natural gas into turquoise H2 and carbon represents a promising pathway towards decarbonised energy. The pyrolysis of biogas (mainly a mixture of methane and CO2) is considered to be a negative carbon-emission technology, as the carbon source comes from biomass and the carbon is captured in solid form. In addition, the presence of CO2 in the gas mixture enables the dry reforming of methane into syngas. In this study, we show that direct biogas conversion in a fluidised catalytic reactor can produce a syngas whose composition meets the requirements for methanol synthesis or for liquid hydrocarbon production via the Fischer-Tropsch process. Confirmed by thermodynamic analysis, we show that the reaction proceeds at temperatures above 900 1C to produce carbon materials, whereas at lower temperatures the carbon is converted to CO by the Boudouard reaction. At 950 1C, very high methane and CO2 conversions are achieved (490% and 99%, respectively), accompanied by high hydrogen yield (490%) and the sequestration of carbon into a turbostratic structure. We believe that the direct catalytic reforming of biogas in a fluidised bed, when combined in series with an FTS process, could allow the production of liquid fuels with no need for costly gas separation units, in particular those implemented for CO2 capture. [ABSTRACT FROM AUTHOR]

The direct synthesis of dimethyl carbonate from methanol and CO2 is particularly attractive as it provides a green alternative to other routes while allowing CO2 conversion. Although the evaluation of catalyst formulations figures prominently in the literature, one can hardly identify which formulations are the most active. One of the reasons is that there is no standard testing protocol. Initial water content in the reactive mixture is critical as it can drag down thermodynamic equilibrium. This study aims to rank catalyst activities and to identify the most active catalysts using a systematic protocol for the measurement of the true catalytic activity. Based on an assessment of critical parameters, a protocol for the measurement of the activity in the liquid phase, taking care to the limitation induced by thermodynamic equilibrium, was developed. Special attention was paid to the quantitative assessment of critical experimental parameters. Following the protocol, a screening of various pure and mixed oxides of about 60 different solids was carried out. Finally, an optimization study was carried out on Zr–Ce mixed oxides produced by different synthesis methods, leading to the discovery of the catalyst which, to the best of our knowledge, is the most active reported so far. [ABSTRACT FROM AUTHOR]

The characterization of acid sites on solid catalysts is a key to understanding reaction mechanisms at the molecular level. This is generally done indirectly using a model probe molecule able to coordinate or be protonated on surface acid sites. For instance, Temperature Programmed Desorption (TPD) of the pyridine probe molecule followed by IR spectroscopy has become a standard method for the quantification and identification of Brønsted and Lewis acid sites found in zeolites. On the other hand, there is a lack of molecules able to be protonated on very weak Brønsted acid sites. In this work 2,6-ditert- butylpyridine is shown to be a suitable probe for characterizing weak Brønsted acidity. The proof of concept is performed on a series of Pt catalysts supported on a chlorinated alumina support (Pt--γ-Al2O3--Cl) generally used in the reforming process. In particular, we show that the area of the 1617 cm-1 vibration band is correlated to the concentration of Cl introduced into the catalyst. We also underline the relative insensitivity of pyridine as an IR probe molecule and the inadequacy of NH3 TPD for the characterization of acid sites of reforming catalysts, making 2,6-di-tert-butylpyridine a particularly important and specific probe molecule. [ABSTRACT FROM AUTHOR]

Several major refining catalytic processes show a strong dependence of overall performances upon catalyst formulations and their structure. This observation is particularly true in naphtha catalytic reforming for which the product distribution is sensitive to slight changes in active phase formulations. This review presents different issues encountered in naphtha reforming that are related to active phase formulation changes. Two research and development approaches are usually proposed. (i) Rationalise the development of new catalytic formulations in order to increase selectivity towads valuable products. (ii) Design simulators that would guide operation in order to maintain process performances. Current limitations to a faster process development come from the disjunction between kinetic modelling and catalyst optimisation. This critical review is not an extensive analysis of existing naphtha reforming kinetic modelling methodologies or advances in catalytic behaviour elucidation. Rather, it proposes an original and pragmatic process development approach aimed at merging catalyst development with kinetic modelling through the identification of "effective" and "measurable" catalytic descriptors. The specificities of the structure–property relationships of naphtha reforming catalysts are reviewed and taken into account in order to list potential catalytic descriptors for this process. A focus is made on a current bottleneck faced in the description of the active phase which lies in understanding the role of the proximity and the interaction between acid and metallic sites in the balance between different bi-functional pathways. A variety of experimental approaches that can be used to measure these naphtha reforming active phase catalytic descriptors are presented and compared. [ABSTRACT FROM AUTHOR]

A set of 15 metal–organic frameworks (MIL-53, MIL-68, MIL-125, UiO-66, ZIF) exhibiting different pore size, morphology, and surface chemistry is used to unravel the numerous behaviors of water adsorption at room temperature in this class of materials. Outstanding “S”-shaped (type V) adsorption isotherms are observed for MIL-68 type solids. We show that the underlying mechanism of water adsorption can be rationalized using a simple set of three parameters: the Henry constant (i.e. the slope of the adsorption pressure in the low pressure range), the pressure at which pore filling occurs, and the maximum water adsorption capacity. While the Henry constant and pore filling pressure mostly depend on the affinity of water for the surface chemistry and on pore size, respectively, these two parameters are correlated as they both reflect different aspects of the hydrophobicity–hydrophilicity of the material. For a given type of porous structure, the functionalization of the material by hydrophilic moieties such as hydrogen bonding groups (amine or aldehyde) systematically leads to an increase in the Henry constant concomitantly with a decrease in the pore filling pressure. As for the adsorption mechanism, we show that, for a given temperature, there is a critical diameter (Dc∼ 20 Å for water at room temperature) above which pore filling occurs through irreversible capillary condensation accompanied by capillary hysteresis loops. Below this critical diameter, pore filling is continuous and reversible unless the material exhibits some adsorption-induced flexibility. [ABSTRACT FROM AUTHOR]

A key to address advanced MOF materials suitable for more sophisticated applications is to add functionalities of greater complexity in a controlled manner. We report a generic and original post-synthetic modification method starting from amino derived MOFs. The first step consists in converting the amino group into azide (N3). Without isolation nor purification, the desired functionalized material is obtained by grafting the corresponding alkyne using “Click Chemistry”. This work reports for the first time the synthesis of a two-dimensional combinatorial library of 24 functionalized MOFs. We also show that the grafting yield can be controlled from 10 to 100%. Finally, we compare the effect of the grafting yield on the porous volume of (1D) and (3D)MOF porous structures. [ABSTRACT FROM AUTHOR]

The zinc benzimidazolate coordination polymer (ZIF-7) shows a reversible gate-opening effect upon variation of partial pressure of CO2or temperature. This phenomenon, which is unique for a MOF with sodalite topology, arises from a phase-to-phase transformation upon guest adsorption–desorption. [ABSTRACT FROM AUTHOR]