V. Van Speybroeck
Covalent organic frameworks (COFs), as highly porous crystalline structures, are newly emerging materials designed with tuneable features. They have a high potential to be a host to immobilize metal catalysts. The unique property of these materials, such as their high surface area, oriented channels, and heteroatom enrichment, make them promising materials to improve some disadvantages of heterogeneous metal catalysts. In this review, the fabrication and application of Pd anchored COFs as one of the most critical transition-metal catalysts that play a crucial role in a wide range of reactions is summarized.
An important aspect within zeolite synthesis is to make fully tunable framework materials with controlled aluminium distribution. A major challenge in characterising these zeolites at operating conditions is the presence of water. In this work, we investigate the effect of hydration on the 27 Al NMR parameters of the ultracrystalline K,Na-compensated aluminosilicate JBW zeolite using experimental and computational techniques. The JBW framework, with Si/Al ratio of 1, is an ideal benchmark system as a stepping stone towards more complicated zeolites. The presence and mobility of water and extraframework species directly affect NMR fingerprints. Excellent agreement between theoretical and experimental spectra is obtained provided dynamic methods are employed with hydrated structural models. This work shows how NMR is instrumental in characterising aluminium distributions in zeolites at operating conditions.
In the stride toward the production of low-carbon-footprint commodity chemicals, the development of a complete wood biorefinery plays a pivotal role. The lignin fraction of wood can be depolymerized and demethoxylated mainly into 4-alkylphenols. These phenolic compounds can further catalytically be C-dealkylated within the H-ZSM-5 zeolite at relatively high temperatures and in the presence of steam, producing phenol and olefins. Experimentally, the dealkylation reaction was found to have two striking features: first, different reactants possess very different reactivity. 4-Ethylphenol (4-EP) is somehow less reactive than 4-n-propylphenol (4-n-PP), which is in turn much less reactive than 4-isopropylphenol (4-iso-PP). Second, cofeeding of steam in the reaction mixture was necessary to prevent rapid and reversible catalyst deactivation. Herein, a combination of static and dynamic density functional theory (DFT) simulations is used to unravel the molecular and mechanistic origin of these observations. Free-energy profiles obtained from static calculations confirm the experimentally observed reactivity sequence, where our computations show that the secondary nature of the alkyl carbon involved in 4-iso-PP dealkylation strongly stabilizes the respective transition states. To investigate the effect of water on the mobility of the reactive species and their interaction with the active site, we investigated the diffusion of phenol along the H-ZSM-5 straight channel in the presence of water loadings from 0 to 3 molecules per zeolite unit cell. We show that water has a strongly beneficial effect in promoting desorption and diffusion of phenol away from the Brønsted acid site through competitive adsorption and by the formation of hydrogen bond chains with the diffusing phenol. This effect could lead to a shorter residence time inside the zeolite, preventing active site poisoning and condensation to bulkier biphenylether moieties.