Unraveling Spatially Dependent Hydrophilicity and Reactivity of Confined Carbocation Intermediates during Methanol Conversion over ZSM-5 Zeolite.

Carbocations play a pivotal role as reactive intermediates in zeolite-catalyzed methanol-to-hydrocarbon (MTH) transformations. However, the interaction between carbocations and water vapor and its subsequent effects on catalytic performance remain poorly understood. Using micro-magnetic resonance imaging (µMRI) and solid-state NMR techniques, this work investigates the hydrophilic behavior of cyclopentenyl cations within ZSM-5 pores under vapor conditions. We show that the polar cationic center of cyclopentenyl cations readily initiates water nucleus formation through water molecule capture. This leads to an inhomogeneous water adsorption gradient along the axial positions of zeolite, correlating with the spatial distribution of carbocation concentrations. The adsorbed water promotes deprotonation and aromatization of cyclopentenyl cations, significantly enhancing the aromatic product selectivity in MTH catalysis. These results reveal the important influence of adsorbed water in modulating the carbocation reactivity within confined zeolite pores.

Revealing the BroÌ·nsted Acidic Nature of Penta-Coordinated Aluminum Species in Dealuminated Zeolite Y with Solid-State NMR Spectroscopy.

The inevitable dealumination process of zeolite Y is closely related to ultrastabilization, enhanced BroÌ·nsted acidity, and deactivation throughout its life cycle, producing complex aluminum and acidic hydroxyl species. Most investigations on dehydrated zeolites have focused on the BroÌ·nsted acidity of tetra-coordinated Al (Al(IV)) and Lewis acidity associated with tricoordinated Al (Al(III)) sites, which has left the penta-coordinated Al (Al(V)) in dealuminated zeolites scarcely discussed. This is largely due to the oversimplified view of detectable Al(V) as an exclusively extra-framework species with Lewis acidity. Here we report the formation of BroÌ·nsted acidic penta-coordinated Al species (Al(V)-BAS) in the dealumination process. Two-dimensional (2D) through-bond and multiquantum 1H-{27Al} correlation solid-state NMR experiments demonstrate the presence of a bridging Si-OH-Al(V) structure in dealuminated Y zeolites. Different from the conventional belief that water attack leads to the breaking of zeolite framework Al-O bonds in the initial stage of zeolite dealumination, the observed Al(V) as a dealumination intermediate is directly correlated with a BAS pair because of the direct dissociation of water on the framework tetrahedral aluminum (Al(IV)), thus bypassing the cleavage of Al-O bonds. 1H double-quantum solid-state NMR experiments and theoretical calculations provide further evidence for this mechanism, whereas pyridine adsorption experiments confirm stronger acidity of Al(V)-BASs than the traditional bridging hydroxyl groups associated with Al(IV). We were also able to detect the Al(V)-BAS site from dealuminated SSZ-13 zeolite with CHA topology, suggesting that its creation is not specific to the framework structure of zeolites.

Through-space 11 B-27 Al correlation: Influence of the recoupling channel.

Through-space heteronuclear correlation (D-HETCOR) experiments based on heteronuclear multiple-quantum correlation (D-HMQC) and refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT) sequences have been proven to be useful approaches for the detection of the spatial proximity between half-integer quadrupolar nuclei in solids under magic-angle spinning (MAS) conditions. The corresponding pulse sequences employ coherence transfers mediated by heteronuclear dipolar interactions, which are reintroduced under MAS by radiofrequency irradiation of only one of the two correlated nuclei. We investigate herein using numerical simulations of spin dynamics and solid-state NMR experiments on magnesium aluminoborate glass how the choice of the channel to which the heteronuclear dipolar recoupling is applied affects the transfer efficiency of D-HMQC and D-RINEPT sequences between 11 B and 27 Al nuclei. Experimental results show that maximum transfer efficiency is achieved when the recoupling scheme is applied to the channel, for which the spin magnetization is parallel to the B0 axis in average.

Advanced solid-state NMR spectroscopy and its applications in zeolite chemistry.

Solid-state NMR spectroscopy (ssNMR) can provide details about the structure, host-guest/guest-guest interactions and dynamic behavior of materials at atomic length scales. A crucial use of ssNMR is for the characterization of zeolite catalysts that are extensively employed in industrial catalytic processes. This review aims to spotlight the recent advancements in ssNMR spectroscopy and its application to zeolite chemistry. We first review the current ssNMR methods and techniques that are relevant to characterize zeolite catalysts, including advanced multinuclear and multidimensional experiments, in situ NMR techniques and hyperpolarization methods. Of these, the methodology development on half-integer quadrupolar nuclei is emphasized, which represent about two-thirds of stable NMR-active nuclei and are widely present in catalytic materials. Subsequently, we introduce the recent progress in understanding zeolite chemistry with the aid of these ssNMR methods and techniques, with a specific focus on the investigation of zeolite framework structures, zeolite crystallization mechanisms, surface active/acidic sites, host-guest/guest-guest interactions, and catalytic reaction mechanisms.