Silicalite-1 Layer Secures the Bifunctional Nature of a CO2 Hydrogenation Catalyst.

Close proximity usually shortens the travel distance of reaction intermediates, thus able to promote the catalytic performance of CO2 hydrogenation by a bifunctional catalyst, such as the widely reported In2O3/H-ZSM-5. However, nanoscale proximity (e.g., powder mixing, PM) more likely causes the fast deactivation of the catalyst, probably due to the migration of metals (e.g., In) that not only neutralizes the acid sites of zeolites but also leads to the reconstruction of the In2O3 surface, thus resulting in catalyst deactivation. Additionally, zeolite coking is another potential deactivation factor when dealing with this methanol-mediated CO2 hydrogenation process. Herein, we reported a facile approach to overcome these three challenges by coating a layer of silicalite-1 (S-1) shell outside a zeolite H-ZSM-5 crystal for the In2O3/H-ZSM-5-catalyzed CO2 hydrogenation. More specifically, the S-1 layer (1) restrains the migration of indium that preserved the acidity of H-ZSM-5 and at the same time (2) prevents the over-reduction of the In2O3 phase and (3) improves the catalyst lifetime by suppressing the aromatic cycle in a methanol-to-hydrocarbon conversion step. As such, the activity for the synthesis of C2 + hydrocarbons under nanoscale proximity (PM) was successfully obtained. Moreover, an enhanced performance was observed for the S-1-coated catalyst under microscale proximity (e.g., granule mixing, GM) in comparison to the S-1-coating-free counterpart. This work highlights an effective shielding strategy to secure the bifunctional nature of a CO2 hydrogenation catalyst.

Micro- and Nanoscale Heterogeneities in Zeolite Beta as Measured by Atom Probe Tomography and Confocal Fluorescence Microscopy.

Micro- and nanoscale information on the activating and deactivating coking behaviour of zeolite catalyst materials increases our current understanding of many industrially applied processes, such as the methanol-to-hydrocarbon (MTH) reaction. Atom probe tomography (APT) was used to reveal the link between framework and coke elemental distributions in 3D with sub-nanometre resolution. APT revealed 10-20 nanometre-sized Al-rich regions and short-range ordering (within nanometres) between Al atoms. With confocal fluorescence microscopy, it was found that the morphology of the zeolite crystal as well as the secondary mesoporous structures have a great effect on the microscale coke distribution throughout individual zeolite crystals over time. Additionally, a nanoscale heterogeneous distribution of carbon as residue from the MTH reaction was determined with carbon-rich areas of tens of nanometres within the zeolite crystals. Lastly, a short length-scale affinity between C and Al atoms, as revealed by APT, indicates the formation of carbon-containing molecules next to the acidic sites in the zeolite.

Detecting Cage Crossing and Filling Clusters of Magnesium and Carbon Atoms in Zeolite SSZ-13 with Atom Probe Tomography.

The conversion of methanol to valuable hydrocarbon molecules is of great commercial interest, as the process serves as a sustainable alternative for the production of, for instance, the base chemicals for plastics. The reaction is catalyzed by zeolite materials. By the introduction of magnesium as a cationic metal, the properties of the zeolite, and thereby the catalytic performance, are changed. With atom probe tomography (APT), nanoscale relations within zeolite materials can be revealed: i.e., crucial information for a fundamental mechanistic understanding. We show that magnesium forms clusters within the cages of zeolite SSZ-13, while the framework elements are homogeneously distributed. These clusters of just a few nanometers were analyzed and visualized in 3-D. Magnesium atoms seem to initially be directed to the aluminum sites, after which they aggregate and fill one or two cages in the zeolite SSZ-13 structure. The presence of magnesium in zeolite SSZ-13 increases the lifetime as well as the propylene selectivity. By using operando UV-vis spectroscopy and X-ray diffraction techniques, we are able to show that these findings are related to the suppression of aromatic intermediate products, while maintaining the formation of polyaromatic compounds. Further nanoscale analysis of the spent catalysts showed indications of magnesium redistribution after catalysis. Unlike zeolite H-SSZ-13, for which only a homogeneous distribution of carbon was found, carbon can be either homogeneously or heterogeneously distributed within zeolite Mg-SSZ-13 crystals as the magnesium decreases the coking rate. Carbon clusters were isolated, visualized, and analyzed and were assumed to be polyaromatic compounds. Small one-cage-filling polyaromatic compounds were identified; furthermore, large-cage-crossing aromatic molecules were found by isolating large coke clusters, demonstrating the unique coking mechanism in zeolite SSZ-13. Short-length-scale evidence for the formation of polyaromatic compounds at acid sites is discovered, as clear nanoscale relations between aluminum and carbon atoms exist.

Probing coke formation during the methanol-to-hydrocarbon reaction on zeolite ZSM-5 catalyst at the nanoscale using tip-enhanced fluorescence microscopy.

The deactivation mechanism of the widely used zeolite ZSM-5 catalysts remains unclear to date due to the lack of analytical techniques with sufficient sensitivity and/or spatial resolution. Herein, a combination of hyperspectral confocal fluorescence microscopy (CFM) and tip-enhanced fluorescence (TEFL) microscopy is used to study the formation of different coke (precursor) species involved in the deactivation of zeolite ZSM-5 during the methanol-to-hydrocarbon (MTH) reaction. CFM submicron-scale imaging shows a preferential formation of graphite-like coke species at the edges of zeolite ZSM-5 crystals within 10 min of the MTH reaction (i.e., working catalyst), whilst the amount of graphite-like coke species uniformly increased over the entire zeolite ZSM-5 surface after 90 min (i.e., deactivated catalyst). Furthermore, TEFL nanoscale imaging with ∼35 nm spatial resolution revealed that formation of coke species on the zeolite ZSM-5 surface is non-uniform and a relatively larger amount of coke is formed at the crystal steps, indicating a higher initial catalytic activity.

Emerging analytical methods to characterize zeolite-based materials.

Zeolites and zeolitic materials are, through their use in numerous conventional and sustainable applications, very important to our daily lives, including to foster the necessary transition to a more circular society. The characterization of zeolite-based materials has a tremendous history and a great number of applications and properties of these materials have been discovered in the past decades. This review focuses on recently developed novel as well as more conventional techniques applied with the aim of better understanding zeolite-based materials. Recently explored analytical methods, e.g. atom probe tomography, scanning transmission X-ray microscopy, confocal fluorescence microscopy and photo-induced force microscopy, are discussed on their important contributions to the better understanding of zeolites as they mainly focus on the micro- to nanoscale chemical imaging and the revelation of structure-composition-performance relationships. Some other techniques have a long and established history, e.g. nuclear magnetic resonance, infrared, neutron scattering, electron microscopy and X-ray diffraction techniques, and have gone through increasing developments allowing the techniques to discover new and important features in zeolite-based materials. Additional to the increasing application of these methods, multiple techniques are nowadays used to study zeolites under working conditions (i.e. the in situ/operando mode of analysis) providing new insights in reaction and deactivation mechanisms.

Biodegradable Microparticles for Simultaneous Detection of Counterfeit and Deteriorated Edible Products.

In an era of globalized trade relations where food and pharmaceutical products cross borders effortlessly, consumers face counterfeit and deteriorated products at elevated rates. This paper presents multifunctional, biodegradable hydrogel microparticles that can provide information on the authenticity and the potential deterioration of the tagged food or pharmaceutical formulations. These microparticles integrate spatially patterned authenticity code with two sensors-the first one detects possible presence of pathogenic microbes through monitoring pH while the second one identifies products stored above optimal temperatures via optical monitoring of the microparticle degradation. Particles are synthesized from a biocompatible polymer and a photoinitiator, dextran modified with 2-hydroxyethylmethacrylate and riboflavin, respectively, using a continuous, high throughput method stop-flow lithography. The proposed synthesis approach also enables crosslinking with visible light bringing about additional flexibility to flow lithography. Model liquid and solid food and pharmaceutical products are successfully labeled with microparticles and the functionality of the sensors in aqueous solutions is demonstrated.