Inorganic molecular sieves: Preparation, modification and industrial application in catalytic processes

[EN] The increasing environmental concern and promotion of “green processes” are forcing the substitution of traditional acid and base homogeneous catalysts by solid ones. Among these heterogeneous catalysts, zeolites and zeotypes can be considered as real “green” catalysts, due to their benign nature from an environmental point of view. The importance of these inorganic molecular sieves within the field of heterogeneous catalysis relies not only on their microporous structure and the related shape selectivity, but also on the flexibility of their chemical composition. Modification of the zeolite framework composition results in materials with acidic, basic or redox properties, whereas multifunctional catalysts can be obtained by introducing metals by ion exchange or impregnation procedures, that can catalyze hydrogenation–dehydrogenation reactions, and the number of commercial applications of zeolite based catalysts is continuously expanding. In this review we discuss determinant issues for the development of zeolite based catalysts, going from zeolite catalyst preparation up to their industrial application. Concerning the synthesis of microporous materials we present some of the new trends moving into larger pore structures or into organic free synthesis media procedures, thanks to the incorporation of novel organic templates or alternative framework elements, and to the use of high-throughput synthesis methods. Post-synthesis zeolite modification and final catalyst conformation for industrial use are briefly discussed. In a last section we give a thorough overview on the application of zeolites in industrial processes. Some of them are well established mature technologies, such as fluid catalytic cracking, hydrocracking or aromatics alkylation. Although the number of zeolite structures commercially used as heterogeneous catalysts in these fields is limited, the development of new catalysts is a continuous challenge due to the need for processing heavier feeds or for increasing the quality of the products. The application of zeolite based catalysts in the production of chemicals and fine chemicals is an emerging field, and will greatly depend on the discovery of new or known structures by alternative, lower cost, synthesis routes, and the fine tuning of their textural properties. Finally, biomass conversion and selective catalytic reduction for conversion of NOx are two active research fields, highlighting the interest in these potential industrial applications.The authors acknowledge financial support from Ministerio de Ciencia e Innovacion (project Consolider-Ingenio 2010 MULTICAT).Martínez Sánchez, MC.; Corma Canós, A. (2011). Inorganic molecular sieves: Preparation, modification and industrial application in catalytic processes. Coordination Chemistry Reviews. 255(13-14):1558-1580. doi:10.1016/j.ccr.2011.03.014S1558158025513-1

Monitoring early zeolite formation via in situ electrochemical impedance spectroscopy

Hitherto zeolite formation is not fully understood. Although electrochemical impedance spectroscopy has proven to be a versatile tool for characterizing ionic solutions, it was never used for monitoring zeolite growth. We show here that EIS can quantitatively monitor zeolite formation, especially during crucial early steps where other methods fall short.crosscheck: This document is CrossCheck deposited related_data: Supplementary Information identifier: E. Breynaert (ORCID) copyright_licence: The Royal Society of Chemistry has an exclusive publication licence for this journal copyright_licence: This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0) history: Received 3 February 2016; Accepted 19 March 2016; Accepted Manuscript published 21 March 2016; Advance Article published 29 March 2016; Version of Record published 7 April 2016status: publishe

Mechanistic and Kinetic Analysis of Complete Methane Oxidation on a Practical PtPd/Al2O3 Catalyst

A PtPd/Al2O3 catalyst developed for the complete oxidation of methane from the ventilation air of underground coal mines is compared against a model PdO/Al2O3 catalyst. Although the PtPd/Al2O3 catalyst is substantially more active and stable than the model catalyst, the nature of active sites between the two catalysts is deemed to be fundamentally the same based on their response to different feed gas compositions and the evolution of surface CO adsorption complexes during time-resolved CO adsorption DRIFTS experiment. For both catalysts, coordinatively unsaturated Pd sites are considered the active centers for methane activation and the subsequent oxidation reaction. H2O competes with CH4 for the same active sites, resulting in severe inhibition. Additionally, the CH4 oxidation reaction also causes self-inhibition. Taking both inhibition effects into consideration, a relatively simple kinetic model is developed. The model provides a good fit of the 72 sets of kinetic data collected on the PtPd/Al2O3 catalyst under practically relevant reaction conditions with CH4 concentration in the range of 0.05–0.4%, H2O concentration of 1.0–5.0%, and reaction temperatures of 450–700 °C. Kinetic parameters based on the model suggest that the CH4 activation energy on the PtPd/Al2O3 catalyst is 96.7 kJ/mol, and the H2O adsorption energy is −31.0 kJ/mol. Both values are consistent with the parameters reported in the literature. The model can be used to develop catalyst sizing guidelines and be incorporated into the control algorithm of the catalytic system

Spontaneous Formation of Silica Nanoparticles in Basic Solutions of Small Tetraalkylammonium Cations

We have found that the spontaneous formation of silica nanoparticles is a general phenomenon in basic solutions of small tetraalkylammonium (TAA) cations. The nanoparticle formation and structure have been investigated using conductivity, pH, and small-angle scattering methods. The particles have a core−shell structure with silica at the core and the TAA cations at the shell. The particle core size is nearly independent of the size of the TAA cation but decreases with pH, suggesting electrostatic forces are a key element controlling their size and stability. The nanoparticle formation is a reversible process at low temperatures, in several ways similar to surfactant aggregation into micelles. These silica nanparticles may be a connection between the synthesis of zeolites and ordered mesoporous silicas such as MCM-41