Karoline L. Hebisch, Risha Goel, Kinga Gołą̨bek, Pawel A. Chmielniak* and Carsten Sievers*,
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Synergy between Brønsted Acid Sites and Carbonaceous Deposits during Skeletal 1-Butene Isomerization over Ferrierite
During skeletal 1-butene isomerization over ferrierite carbonaceous deposits block 98% of the micropores within 24 h, rendering them effectively inaccessible to reactants, while the catalytic activity improves continuously for 100 h on stream. Ex-situ pyridine adsorption shows that the concentration of conventional Brønsted acid sites in the 10-R channels decreases below the detection threshold of infrared spectroscopy within 2 h. However, the operando addition of the base triethyl amine to the feed quenches the reaction, showing that mediated acidity is necessary. The larger base 2,2,6,6-tetramethyl piperidine only deactivates catalytic activity after several hours because it cannot directly bind to active sites at the sterically restricted pore mouths. The communication of internal Brønsted acid sites to the external reactants via a concerted mechanism involving protonated monoaromatic deposits trapped in the pore mouths explains the promoting effects of coke species in zeolite-catalyzed skeletal butene isomerization. This work presents a consolidated explanation of the synergy of solid acidity, structural confinement, and carbonaceous deposits in zeolites.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.