The adsorption and reaction properties of heterogeneous zeolite catalysts (e.g. for catalytic cracking of petroleum, partial oxidation of natural gas) depend strongly on the types and distributions of Al heteroatoms in the aluminosilicate frameworks. The origins of these properties have been challenging to discern, owing in part to the structural complexity of aluminosilicate zeolites. Herein, combined solid-state NMR and synchrotron X-ray powder diffraction analyses show the Al atoms locate preferentially in certain framework sites in the zeolite catalyst Al-SSZ-70. Through-covalent-bond 2D Al{ Si} J-correlation NMR spectra allow distinct framework Al sites to be identified and their relative occupancies quantified. The analyses show that 94 % of the Al atoms are located at the surfaces of the large-pore interlayer channels of Al-SSZ-70, while only 6 % are in the sub-nm intralayer channels. The selective siting of Al atoms accounts for the reaction properties of catalysts derived from SSZ-70.
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http://dx.doi.org/10.1002/anie.201813533 | DOI Listing |
J Am Chem Soc
January 2025
Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing 100084, China.
Substituting the molecular metal complexes used in the industrial olefin hydroformylation process is of great significance in fundamental research and practical application. One of the major difficulties in replacing the classic molecular metal catalysts with supported metal catalysts is the low chemoselectivity and regioselectivity of the supported metal catalysts because of the lack of a well-defined coordination environment of the metal active sites. In this work, we have systematically studied the influences of key factors (crystallinity, alkali promoters, etc.
View Article and Find Full Text PDFAdv Sci (Weinh)
January 2025
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, Shaanxi Key Laboratory for Advanced Energy Devices, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi'an, 710119, P. R. China.
Understanding the oxygen evolution reaction (OER) mechanism is pivotal for improving the overall efficiency of water electrolysis. Despite methylammonium lead halide perovskites (MAPbX) have shown promising OER performance due to their soft-lattice nature that allows lattice-oxygen oxidation of active α-PbO layer surface, the role of A-site MA or X-site elements in the electrochemical reconstruction and OER mechanisms has yet to be explored. Here, it is demonstrated that the OER mechanism of perovskite@zeolite composites is intrinsically dominated by the A-site group of lead-halide perovskites, while the type of X-site halogen is crucial for the reconstruction kinetics of the composites.
View Article and Find Full Text PDFChem Sci
December 2024
Department of Applied Chemistry, School of Engineering, University of Toyama Gofuku 3190 Toyama 930-8555 Japan
Direct conversion of CO with renewable H to produce methanol provides a promising way for CO utilization and H storage. Cu/ZnO catalysts are active, but their activities depend on the preparation methods. Here, we reported a facile mechanical grinding method for the fast synthesis of Cu@zeolitic imidazolate framework-8 (ZIF-8) derived Cu/ZnO catalysts applied in CO hydrogenation to methanol.
View Article and Find Full Text PDFChemistry
January 2025
Ningbo University, School of Material Science and Chemical Engineering, Rokkakubashi, Kanagawa-ku, Yokohama-shi, Kanagawa, 221-8686, Japan., 315211, Ningbo, CHINA.
Direct oxidation of methane to methanol utilizing molecular oxygen under mild conditions is an important yet challenging process due to the difficulty in activation of methane under such conditions. In this research, we report zeolitic octahedral metal oxides based on cobalt vanadotungstates, which act as the catalysts for oxidation of methane using molecular oxygen as the oxidant without co-reductants at a low temperature of 90 oC even as low as 60 oC. This catalytic process results in the high-yield production of methanol as the major product.
View Article and Find Full Text PDFInt J Mol Sci
December 2024
Department of Solid State Chemistry, Faculty of Chemical Technology, University of Chemistry and Technology, Technická 5, 16628 Prague, Czech Republic.
The most commonly used homogeneous catalyst for fatty acid esterification is a corrosive sulphuric acid. However, this requires costly investment in non-corrosive equipment, presents a safety risk, is time consuming, and increases effluent generation. In this study, inorganic 3D heteroborane cluster strong acids are employed for the first time as homogeneous catalysts.
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