Zoran Ristanović

High‐Resolution Single‐Molecule Fluorescence Imaging of Zeolite Aggregates within Real‐Life Fluid Catalytic Cracking Particles

Fluid catalytic cracking (FCC) is a major process in oil refineries to produce gasoline and base chemicals from crude oil fractions. The spatial distribution and acidity of zeolite aggregates embedded within the 50–150 μm-sized FCC spheres heavily influence their catalytic performance. Single-molecule fluorescence-based imaging methods, namely nanometer accuracy by stochastic chemical reactions (NASCA) and super-resolution optical fluctuation imaging (SOFI) were used to study the catalytic activity of sub-micrometer zeolite ZSM-5 domains within real-life FCC catalyst particles. The formation of fluorescent product molecules taking place at Brønsted acid sites was monitored with single turnover sensitivity and high spatiotemporal resolution, providing detailed insight in dispersion and catalytic activity of zeolite ZSM-5 aggregates. The results point towards substantial differences in turnover frequencies between the zeolite aggregates, revealing significant intraparticle heterogeneities in Brønsted reactivity.

Determining the location and nearest neighbours of aluminium in zeolites with atom probe tomography

Zeolite catalysis is determined by a combination of pore architecture and Brønsted acidity. As Brønsted acid sites are formed by the substitution of AlO4 for SiO4 tetrahedra, it is of utmost importance to have information on the number as well as the location and neighbouring sites of framework aluminium. Unfortunately, such detailed information has not yet been obtained, mainly due to the lack of suitable characterization methods. Here we report, using the powerful atomic-scale analysis technique known as atom probe tomography, the quantitative spatial distribution of individual aluminium atoms, including their three-dimensional extent of segregation. Using a nearest-neighbour statistical analysis, we precisely determine the short-range distribution of aluminium over the different T-sites and determine the most probable Al–Al neighbouring distance within parent and steamed ZSM-5 crystals, as well as assess the long-range redistribution of aluminium upon zeolite steaming.

Quantitative 3D Fluorescence Imaging of Single Catalytic Turnovers Reveals Spatiotemporal Gradients in Reactivity of Zeolite H-ZSM-5 Crystals upon Steaming

Optimizing the number, distribution, and accessibility of Brønsted acid sites in zeolite-based catalysts is of a paramount importance to further improve their catalytic performance. However, it remains challenging to measure real-time changes in reactivity of single zeolite catalyst particles by ensemble-averaging characterization methods. In this work, a detailed 3D single molecule, single turnover sensitive fluorescence microscopy study is presented to quantify the reactivity of Brønsted acid sites in zeolite H-ZSM-5 crystals upon steaming. This approach, in combination with the oligomerization of furfuryl alcohol as a probe reaction, allowed the stochastic behavior of single catalytic turnovers and temporally resolved turnover frequencies of zeolite domains smaller than the diffraction limited resolution to be investigated with great precision. It was found that the single turnover kinetics of the parent zeolite crystal proceeds with significant spatial differences in turnover frequencies on the nanoscale and noncorrelated temporal fluctuations. Mild steaming of zeolite H-ZSM-5 crystals at 500 °C led to an enhanced surface reactivity, with up to 4 times higher local turnover rates than those of the parent H-ZSM-5 crystals, and revealed remarkable heterogeneities in surface reactivity. In strong contrast, severe steaming at 700 °C significantly dealuminated the zeolite H-ZSM-5 material, leading to a 460 times lower turnover rate. The differences in measured turnover activities are explained by changes in the 3D aluminum distribution due to migration of extraframework Al-species and their subsequent effect on pore accessibility, as corroborated by time-of-flight secondary ion mass spectrometry (TOF-SIMS) sputter depth profiling data.

Intergrowth structure and aluminium zoning of a zeolite ZSM-5 crystal as resolved by synchrotron-based micro-X-ray diffraction imaging

Zeolites represent an important group of heterogeneous catalysts and are heavily used in the petrochemical and refining industries.[1] Since their discovery, zeolites with MFI topology, namely ZSM-5, have been utilized in a number of large-scale industrial applications. The unique combination of acidic properties and pore architecture[2] enabled their use as solid acid catalysts in the alkylation of arenes,[3] the oligomerization of light olefins,[4] and the methanol-to-hydrocarbon reaction.[5] The internal crystallographic architecture, microand mesoporosity, as well as the 3D distribution of Bronsted acid sites play a crucial role in the catalytic performance of zeolites.

Single Molecule Nanospectroscopy Visualizes Proton-Transfer Processes within a Zeolite Crystal

Visualizing proton-transfer processes at the nanoscale is essential for understanding the reactivity of zeolite-based catalyst materials. In this work, the Brønsted-acid-catalyzed oligomerization of styrene derivatives was used for the first time as a single molecule probe reaction to study the reactivity of individual zeolite H-ZSM-5 crystals in different zeolite framework, reactant and solvent environments. This was accomplished via the formation of distinct dimeric and trimeric fluorescent carbocations, characterized by their different photostability, as detected by single molecule fluorescence microscopy. The oligomerization kinetics turned out to be very sensitive to the reaction conditions and the presence of the local structural defects in zeolite H-ZSM-5 crystals. The remarkably photostable trimeric carbocations were found to be formed predominantly near defect-rich crystalline regions. This spectroscopic marker offers clear prospects for nanoscale quality control of zeolite-based materials. Interestingly, replacing n-heptane with 1-butanol as a solvent led to a reactivity decrease of several orders and shorter survival times of fluorescent products due to the strong chemisorption of 1-butanol onto the Brønsted acid sites. A similar effect was achieved by changing the electrophilic character of the para-substituent of the styrene moiety. Based on the measured turnover rates we have established a quantitative, single turnover approach to evaluate substituent and solvent effects on the reactivity of individual zeolite H-ZSM-5 crystals.

Large Ferrierite Crystals as Models for Catalyst Deactivation during Skeletal Isomerisation of Oleic Acid : Evidence for Pore Mouth Catalysis

Large zeolite crystals of ferrierite have been used to study the deactivation, at the single particle level, of the alkyl isomerisation catalysis of oleic acid and elaidic acid by a combination of visible micro-spectroscopy and fluorescence microscopy (both polarised wide-field and confocal modes). The large crystals did show the desired activity, albeit only traces of the isomerisation product were obtained and low conversions were achieved compared to commercial ferrierite powders. This limited activity is in line with their lower external non-basal surface area, supporting the hypothesis of pore mouth catalysis. Further evidence for the latter comes from visible micro-spectroscopy, which shows that the accumulation of aromatic species is limited to the crystal edges, while fluorescence microscopy strongly suggests the presence of polyenylic carbocations. Light polarisation associated with the spatial resolution of fluorescence microscopy reveals that these carbonaceous deposits are aligned only in the larger 10-MR channels of ferrierite at all crystal edges. The reaction is hence further limited to these specific pore mouths.

Single-Molecule Fluorescence Microscopy Reveals Local Diffusion Coefficients in the Pore Network of an Individual Catalyst Particle

We used single-molecule fluorescence microscopy to study self-diffusion of a feedstock-like probe molecule with nanometer accuracy in the macropores of a micrometer-sized, real-life fluid catalytic cracking (FCC) particle. Movies of single fluorescent molecules allowed their movement through the pore network to be reconstructed. The observed tracks were classified into three different states by machine learning and all found to be distributed homogeneously over the particle. Most probe molecules (88%) were immobile, with the molecule most likely being physisorbed or trapped; the remainder was either mobile (8%), with the molecule moving inside the macropores, or showed hybrid behavior (4%). Mobile tracks had an average diffusion coefficient of D = 8 × 10–14 ± 1 × 10–13 m2 s–1, with the standard deviation thought to be related to the large range of pore sizes found in FCC particles. The developed methodology can be used to evaluate, quantify and map heterogeneities in diffusional properties within complex hierarchically porous materials.

X-ray Excited Optical Fluorescence and Diffraction Imaging of Reactivity and Crystallinity in a Zeolite Crystal : Crystallography and Molecular Spectroscopy in One

Abstract Structure–activity relationships in heterogeneous catalysis are challenging to be measured on a single‐particle level. For the first time, one X‐ray beam is used to determine the crystallographic structure and reactivity of a single zeolite crystal. The method generates μm‐resolved X‐ray diffraction (μ‐XRD) and X‐ray excited optical fluorescence (μ‐XEOF) maps of the crystallinity and Brønsted reactivity of a zeolite crystal previously reacted with a styrene probe molecule. The local gradients in chemical reactivity (derived from μ‐XEOF) were correlated with local crystallinity and framework Al content, determined by μ‐XRD. Two distinctly different types of fluorescent species formed selectively, depending on the local zeolite crystallinity. The results illustrate the potential of this approach to resolve the crystallographic structure of a porous material and its reactivity in one experiment via X‐ray induced fluorescence of organic molecules formed at the reactive centers.

Breakthroughs in Hard X-ray Diffraction: Towards a Multiscale Science Approach in Heterogeneous Catalysis†

Diffraction at hard work: Modern heterogeneous catalysis would benefit from a multiscale science approach bridging the molecular world with the macroscopic world. Because of recent breakthroughs in X‐ray diffraction methods, including the surface X‐ray diffraction of atomically flat model catalysts, X‐ray diffraction tomography of catalyst bodies, and X‐ray profiling of an active catalyst in a chemical reactor, such an approach is now within reach.WILEY-VCH

Integrated Transmission Electron and Single Molecule Fluorescence Microscopy Correlates Reactivity with Ultrastructure in a Single Catalyst Particle

Abstract Establishing structure–activity relationships in complex, hierarchically structured nanomaterials, such as fluid catalytic cracking (FCC) catalysts, requires characterization with complementary, correlated analysis techniques. An integrated setup has been developed to perform transmission electron microscopy (TEM) and single‐molecule fluorescence (SMF) microscopy on such nanostructured samples. Correlated structure–reactivity information was obtained for 100 nm thin, microtomed sections of a single FCC catalyst particle using this novel SMF‐TEM high‐resolution combination. High reactivity in a thiophene oligomerization probe reaction correlated well with TEM‐derived zeolite locations, while matrix components, such as clay and amorphous binder material, were found not to display activity. Differences in fluorescence intensity were also observed within and between distinct zeolite aggregate domains, indicating that not all zeolite domains are equally active.