The refinery of the future.

Fossil fuels-coal, oil and gas-supply most of the world's energy and also form the basis of many products essential for everyday life. Their use is the largest contributor to the carbon dioxide emissions that drive global climate change, prompting joint efforts to find renewable alternatives that might enable a carbon-neutral society by as early as 2050. There are clear paths for renewable electricity to replace fossil-fuel-based energy, but the transport fuels and chemicals produced in oil refineries will still be needed. We can attempt to close the carbon cycle associated with their use by electrifying refinery processes and by changing the raw materials that go into a refinery from fossils fuels to carbon dioxide for making hydrocarbon fuels and to agricultural and municipal waste for making chemicals and polymers. We argue that, with sufficient long-term commitment and support, the science and technology for such a completely fossil-free refinery, delivering the products required after 2050 (less fuels, more chemicals), could be developed. This future refinery will require substantially larger areas and greater mineral resources than is the case at present and critically depends on the capacity to generate large amounts of renewable energy for hydrogen production and carbon dioxide capture.

Molecular Accessibility and Diffusion of Resorufin in Zeolite Crystals.

Invited for the cover of this issue is the group of Professor Bert Weckhuysen at Utrecht University. The image depicts the change in fluorescence color of a resorufin dye molecule when it is protonated and confined inside the micropores of zeolite-ß. Read the full text of the article at 10.1002/chem.202302553.

Molecular Accessibility and Diffusion of Resorufin in Zeolite Crystals.

We have used confocal laser scanning microscopy on the small, fluorescent resorufin dye molecule to visualize molecular accessibility and diffusion in the hierarchical, anisotropic pore structure of large (~10 µm-sized) zeolite-ß crystals. The resorufin dye is widely used in life and materials science, but only in its deprotonated form because the protonated molecule is barely fluorescent in aqueous solution. In this work, we show that protonated resorufin is in fact strongly fluorescent when confined within zeolite micropores, thus enabling fluorescence microimaging experiments. We find that J-aggregation guest-guest interactions lead to a decrease in the measured fluorescence intensity that can be prevented by using non-fluorescent spacer molecules. We characterized the pore space by introducing resorufin from the outside solution and following its diffusion into zeolite-ß crystals. The eventual homogeneous distribution of resorufin molecules throughout the zeolite indicates a fully accessible pore network. This enables the quantification of the diffusion coefficient in the straight pores of zeolite-ß without the need for complex analysis, and we found a value of 3×10-15  m2  s-1 . Furthermore, we saw that diffusion through the straight pores of zeolite-ß is impeded when crossing the boundaries between zeolite subunits.

Correction: Propane to olefins tandem catalysis: a selective route towards light olefins production.

Correction for 'Propane to olefins tandem catalysis: a selective route towards light olefins production' by Matteo Monai et al., Chem. Soc. Rev., 2021, 50, 11503-11529, https://doi.org/10.1039/D1CS00357G.

Visualizing the Structure, Composition and Activity of Single Catalyst Particles for Olefin Polymerization and Polyolefin Decomposition.

The structural and morphological characterization of individual catalyst particles for olefin polymerization, as well as for the reverse process of polyolefin decomposition, can provide an improved understanding for how these catalyst materials operate under relevant reaction conditions. In this review, we discuss an emerging analytical toolbox of 2D and 3D chemical imaging techniques that is suitable for investigating the chemistry and reactivity of related catalyst systems. While synchrotron-based X-ray microscopy still provides unparalleled spatial resolutions in 2D and 3D, a number of laboratory-based techniques, most notably focused ion beam-scanning electron microscopy, confocal fluorescence microscopy, infrared photoinduced force microscopy and laboratory-based X-ray nano-computed tomography, have helped to significantly expand the arsenal of analytical tools available to scientists in heterogeneous catalysis and polymer science. In terms of future research, the review outlines the role and impact of in situ and operando (spectro-)microscopy experiments, involving sophisticated reactors as well as online reactant and product analysis, to obtain real-time information on the formation, decomposition, and mobility of polymer phases within single catalyst particles. Furthermore, the potential of fluorescence microscopy, X-ray microscopy and optical microscopy is highlighted for the high-throughput characterization of olefin polymerization and polyolefin decomposition catalysts. By combining these chemical imaging techniques with, for example, chemical staining methodologies, selective probe molecules as well as particle sorting approaches, representative structure-activity relationships can be derived at the level of single catalyst particles.

Fluorescent-Probe Characterization for Pore-Space Mapping with Single-Particle Tracking.

Porous solids often contain complex pore networks with pores of various sizes. Tracking individual fluorescent probes as they diffuse through porous materials can be used to characterize pore networks at tens of nanometers resolution. However, understanding the motion behavior of fluorescent probes in confinement is crucial to reliably derive pore network properties. Here, we introduce well-defined lithography-made model pores developed to study probe behavior in confinement. We investigated the influence of probe-host interactions on diffusion and trapping of confined single-emitter quantum-dot probes. Using the pH-responsiveness of the probes, we were able to largely suppress trapping at the pore walls. This enabled us to define experimental conditions for mapping of the accessible pore space of a one-dimensional pore array as well as a real-life polymerization-catalyst-support particle.

Elucidating the Structure and Composition of Individual Bimetallic Nanoparticles in Supported Catalysts by Atom Probe Tomography.

Understanding and controlling the structure and composition of nanoparticles in supported metal catalysts are crucial to improve chemical processes. For this, atom probe tomography (APT) is a unique tool, as it allows for spatially resolved three-dimensional chemical imaging of materials with sub-nanometer resolution. However, thus far APT has not been applied for mesoporous oxide-supported metal catalyst materials, due to the size and number of pores resulting in sample fracture during experiments. To overcome these issues, we developed a high-pressure resin impregnation strategy and showcased the applicability to high-porous supported Pd-Ni-based catalyst materials, which are active in CO2 hydrogenation. Within the reconstructed volume of 3 × 105 nm3, we identified over 400 Pd-Ni clusters, with compositions ranging from 0 to 16 atom % Pd and a size distribution of 2.6 ± 1.6 nm. These results illustrate that APT is capable of quantitatively assessing the size, composition, and metal distribution for a large number of nanoparticles at the sub-nm scale in industrial catalysts. Furthermore, we showcase that metal segregation occurred predominately between nanoparticles, shedding light on the mechanism of metal segregation. We envision that the presented methodology expands the capabilities of APT to investigate porous functional nanomaterials, including but not limited to solid catalysts.

Tandem catalysis with double-shelled hollow spheres.

Metal-zeolite composites with metal (oxide) and acid sites are promising catalysts for integrating multiple reactions in tandem to produce a wide variety of wanted products without separating or purifying the intermediates. However, the conventional design of such materials often leads to uncontrolled and non-ideal spatial distributions of the metal inside/on the zeolites, limiting their catalytic performance. Here we demonstrate a simple strategy for synthesizing double-shelled, contiguous metal oxide@zeolite hollow spheres (denoted as MO@ZEO DSHSs) with controllable structural parameters and chemical compositions. This involves the self-assembly of zeolite nanocrystals onto the surface of metal ion-containing carbon spheres followed by calcination and zeolite growth steps. The step-by-step formation mechanism of the material is revealed using mainly in situ Raman spectroscopy and X-ray diffraction and ex situ electron microscopy. We demonstrate that it is due to this structure that an Fe2O3@H-ZSM-5 DSHSs-showcase catalyst exhibits superior performance compared with various conventionally structured Fe2O3-H-ZSM-5 catalysts in gasoline production by the Fischer-Tropsch synthesis. This work is expected to advance the rational synthesis and research of hierarchically hollow, core-shell, multifunctional catalyst materials.

Understanding the Reactivity of Supported Late Transition Metals on a Bare Anatase (101) Surface: A Periodic Conceptual DFT Investigation.

The rapidly growing interest for new heterogeneous catalytic systems providing high atomic efficiency along with high stability and reactivity triggered an impressive progress in the field of single-atom catalysis. Nevertheless, unravelling the factors governing the interaction strength between the support and the adsorbed metal atoms remains a major challenge. Based on periodic density functional theory (DFT) calculations, this paper provides insight into the adsorption of single late transition metals on a defect-free anatase surface. The obtained adsorption energies fluctuate, with the exception of Pd, between -3.11 and -3.80 eV and are indicative of a strong interaction. Depending on the considered transition metal, we could attribute the strength of this interaction with the support to i) an electron transfer towards anatase (Ru, Rh, Ni), ii) s-d orbital hybridisation effects (Pt), or iii) a synergistic effect between both factors (Fe, Co, Os, Ir). The driving forces behind the adsorption were also found to be strongly related to Klechkowsky's rule for orbital filling. In contrast, the deviating behaviour of Pd is most likely associated with the lower dissociation enthalpy of the Pd-O bond. Additionally, the reactivity of these systems was evaluated using the Fermi weighted density of states approach. The resulting softness values can be clearly related to the electron configuration of the catalytic systems as well as with the net charge on the transition metal. Finally, these indices were used to construct a model that predicts the adsorption strength of CO on these anatase-supported d-metal atoms. The values obtained from this regression model show, within a 95 % probability interval, a correlation of 84 % with the explicitly calculated CO adsorption energies.

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.

Carbon Deposit Analysis in Catalyst Deactivation, Regeneration, and Rejuvenation.

Hydrocarbon conversion catalysts suffer from deactivation by deposition or formation of carbon deposits. Carbon deposit formation is thermodynamically favored above 350 °C, even in some hydrogen-rich environments. We discuss four basic mechanisms: a carbenium-ion based mechanism taking place on acid sites of zeolites or bifunctional catalysts, a metal-induced formation of soft coke (i.e., oligomers of small olefins) on bifunctional catalysts, a radical-mediated mechanism in higher-temperature processes, and fast-growing carbon filament formation. Catalysts deactivate because carbon deposits block pores at different length scales, or directly block active sites. Some deactivated catalysts can be re-used, others can be regenerated or have to be discarded. Catalyst and process design can mitigate the effects of deactivation. New analytical tools allow for the direct observation (in some cases even under in situ or operando conditions) of the 3D-distribution of coke-type species as a function of catalyst structure and lifetime.

Advancing the Compositional Analysis of Olefin Polymerization Catalysts with High-Throughput Fluorescence Microscopy.

To optimize the performance of supported olefin polymerization catalysts, novel methodologies are required to evaluate the composition, structure, and morphology of both pristine and prepolymerized samples in a resource-efficient, high-throughput manner. Here, we report on a unique combination of laboratory-based confocal fluorescence microscopy and advanced image processing that allowed us to quantitatively assess support fragmentation in a large number of autofluorescent metallocene-based catalyst particles. Using this approach, significant inter- and intraparticle heterogeneities were detected and quantified in a representative number of prepolymerized catalyst particles (2D: ≥135, 3D: 40). The heterogeneity that was observed over several stages of slurry-phase ethylene polymerization (10 bar) is primarily attributed to the catalyst particles' diverse support structures and to the inhomogeneities in the metallocene distribution. From a mechanistic point of view, the 2D and 3D analyses revealed extensive contributions from a layer-by-layer fragmentation mechanism in synergy with a less pronounced sectioning mechanism. A significant number of catalyst particles were also found to display limited support fragmentation at the onset of the reaction (i.e., at lower polymer yields). This delay in activity or "dormancy" is believed to contribute to a broadening of the particle size distribution during the early stages of polymerization. 2D and 3D catalyst screening via confocal fluorescence microscopy represents an accessible and fast approach to characterize the structure of heterogeneous catalysts and assess the distribution of their fluorescent components and reaction products. The automation of both image segmentation and postprocessing with machine learning can yield a powerful diagnostic tool for future research as well as quality control on industrial catalysts.

Probing the Dynamics of Low-Overpotential CO2-to-CO Activation on Copper Electrodes with Time-Resolved Raman Spectroscopy.

Oxide-derived copper electrodes have displayed a boost in activity and selectivity toward valuable base chemicals in the electrochemical carbon dioxide reduction reaction (CO2RR), but the exact interplay between the dynamic restructuring of copper oxide electrodes and their activity and selectivity is not fully understood. In this work, we have utilized time-resolved surface-enhanced Raman spectroscopy (TR-SERS) to study the dynamic restructuring of the copper (oxide) electrode surface and the adsorption of reaction intermediates during cyclic voltammetry (CV) and pulsed electrolysis (PE). By coupling the electrochemical data to the spectral features in TR-SERS, we study the dynamic activation of and reactions on the electrode surface and find that CO2 is already activated to carbon monoxide (CO) during PE (10% Faradaic efficiency, 1% under static applied potential) at low overpotentials (-0.35 VRHE). PE at varying cathodic bias on different timescales revealed that stochastic CO is dominant directly after the cathodic bias onset, whereas no CO intermediates were observed after prolonged application of low overpotentials. An increase in cathodic bias (-0.55 VRHE) resulted in the formation of static adsorbed CO intermediates, while the overall contribution of stochastic CO decreased. We attribute the low-overpotential CO2-to-CO activation to a combination of selective Cu(111) facet exposure, partially oxidized surfaces during PE, and the formation of copper-carbonate-hydroxide complex intermediates during the anodic pulses. This work sheds light on the restructuring of oxide-derived copper electrodes and low-overpotential CO formation and highlights the power of the combination of electrochemistry and time-resolved vibrational spectroscopy to elucidate CO2RR mechanisms.

Understanding the Effects of Binders in Gas Sorption and Acidity of Aluminium Fumarate Extrudates.

Understanding the impact of shaping processes on solid adsorbents is critical for the implementation of MOFs in industrial separation processes or as catalytic materials. Production of MOF-containing shaped particles is typically associated with loss of porosity and modification of acid sites, two phenomena that affect their performance. Herein, we report a detailed study on how extrusion affects the crystallinity, porosity, and acidity of the aluminium fumarate MOF with clays or SiO2 gel binders. Thorough characterization showed that the clay binders confer the extrudates a good mechanical robustness at the expense of porosity, while silica gel shows an opposite trend. The CO2 selectivity towards CH4 , of interest for natural gas separation processes, is maintained upon the extrusion process. Moreover, probe FTIR spectroscopy revealed no major changes in the types of acid sites. This study highlights that these abundant and inexpensive clay materials may be used for scaling MOFs as active adsorbents.

Propane to olefins tandem catalysis: a selective route towards light olefins production.

On-purpose synthetic routes for propylene production have emerged in the last couple of decades in response to the increasing demand for plastics and a shift to shale gas feedstocks for ethylene production. Propane dehydrogenation (PDH), an efficient and selective route to produce propylene, saw booming investments to fill the so-called propylene gap. In the coming years, however, a fluctuating light olefins market will call for flexibility in end-product of PDH plants. This can be achieved by combining PDH with propylene metathesis in a single step, propane to olefins (PTO), which allows production of mixtures of propylene, ethylene and butenes, which are important chemical building blocks for a.o. thermoplastics. The metathesis technology introduced by Phillips in the 1960s and mostly operated in reverse to produce propylene, is thus undergoing a renaissance of scientific and technological interest in the context of the PTO reaction. In this review, we will describe the state-of-the-art of PDH, propylene metathesis and PTO reactions, highlighting the open challenges and opportunities in the field. While the separate PDH and metathesis reactions have been extensively studied in the literature, understanding the whole PTO tandem-catalysis system will require new efforts in theoretical modelling and operando spectroscopy experiments, to gain mechanistic insights into the combined reactions and finally improve catalytic selectivity and stability for on-purpose olefins production.

Operando Laboratory-Based Multi-Edge X-Ray Absorption Near-Edge Spectroscopy of Solid Catalysts.

Laboratory-based X-ray absorption spectroscopy (XAS) and especially X-ray absorption near-edge structure (XANES) offers new opportunities in catalyst characterization and presents not only an alternative, but also a complementary approach to precious beamtime at synchrotron facilities. We successfully designed a laboratory-based setup for performing operando, quasi-simultaneous XANES analysis at multiple K-edges, more specifically, operando XANES of mono-, bi-, and trimetallic CO2 hydrogenation catalysts containing Ni, Fe, and Cu. Detailed operando XANES studies of the multielement solid catalysts revealed metal-dependent differences in the reducibility and re-oxidation behavior and their influence on the catalytic performance in CO2 hydrogenation. The applicability of operando laboratory-based XANES at multiple K-edges paves the way for advanced multielement catalyst characterization complementing detailed studies at synchrotron facilities.

Bifunctional Europium for Operando Catalyst Thermometry in an Exothermic Chemical Reaction.

Often the reactor or the reaction medium temperature is reported in the field of heterogeneous catalysis, even though it could vary significantly from the reactive catalyst temperature. The influence of the catalyst temperature on the catalytic performance and vice versa is therefore not always accurately known. We here apply EuOCl as both solid catalyst and thermometer, allowing for operando temperature determination. The interplay between reaction conditions and the catalyst temperature dynamics is studied. A maximum temperature difference between the catalyst and oven of +16 °C was observed due to the exothermicity of the methane oxychlorination reaction. Heat dissipation by radiation appears dominating compared to convection in this set-up, explaining the observed uniform catalyst bed temperature. Application of operando catalyst thermometry could provide a deeper mechanistic understanding of catalyst performances and allow for safer process operation in chemical industries.

Unravelling Channel Structure-Diffusivity Relationships in Zeolite ZSM-5 at the Single-Molecule Level.

The development of improved zeolite materials for applications in separation and catalysis requires understanding of mass transport. Herein, diffusion of single molecules is tracked in the straight and sinusoidal channels of the industrially relevant ZSM-5 zeolites using a combination of single-molecule localization microscopy and uniformly oriented zeolite thin films. Distinct motion behaviors are observed in zeolite channels with the same geometry, suggesting heterogeneous guest-host interactions. Quantification of the diffusion heterogeneities in the sinusoidal and straight channels suggests that the geometry of zeolite channels dictates the mobility and motion behavior of the guest molecules, resulting in diffusion anisotropy. The study of hierarchical zeolites shows that the addition of secondary pore networks primarily enhances the diffusivity of sinusoidal zeolite channels, and thus alleviating the diffusion limitations of microporous zeolites.

Finned zeolite catalysts.

There is growing evidence for the advantages of synthesizing nanosized zeolites with markedly reduced internal diffusion limitations for enhanced performances in catalysis and adsorption. Producing zeolite crystals with sizes less than 100 nm, however, is non-trivial, often requires the use of complex organics and typically results in a small product yield. Here we present an alternative, facile approach to enhance the mass-transport properties of zeolites by the epitaxial growth of fin-like protrusions on seed crystals. We validate this generalizable methodology on two common zeolites and confirm that fins are in crystallographic registry with the underlying seeds, and that secondary growth does not impede access to the micropores. Molecular modelling and time-resolved titration experiments of finned zeolites probe internal diffusion and reveal substantial improvements in mass transport, consistent with catalytic tests of a model reaction, which show that these structures behave as pseudo-nanocrystals with sizes commensurate to that of the fin. This approach could be extended to the rational synthesis of other zeolite and aluminosilicate materials.

Influence of Pore Structure and Metal-Node Geometry on the Polymerization of Ethylene over Cr-Based Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) have received increasing interest as solid single-site catalysts, owing to their tunable pore architecture and metal node geometry. The ability to exploit these modulators makes them prominent candidates for producing polyethylene (PE) materials with narrow dispersity index (Ð) values. Here a study is presented in which the ethylene polymerization properties, with Et2 AlCl as activator, of three renowned Cr-based MOFs, MIL-101(Cr)-NDC (NDC=2,6-dicarboxynapthalene), MIL-53(Cr) and HKUST-1(Cr), are systematically investigated. Ethylene polymerization reactions revealed varying catalytic activities, with MIL-101(Cr)-NDC and MIL-53(Cr) being significantly more active than HKUST-1(Cr). Analysis of the PE products revealed large Ð values, demonstrating that polymerization occurs over a multitude of active Cr centers rather than a singular type of Cr site. Spectroscopic experiments, in the form of powder X-ray diffraction (pXRD), UV/Vis-NIR diffuse reflectance spectroscopy (DRS) and CO probe molecule Fourier transform infrared (FTIR) spectroscopy corroborated these findings, indicating that indeed for each MOF unique active sites are generated, however without alteration of the original oxidation state. Furthermore, the pXRD experiments indicated that one major prerequisite for catalytic activity was the degree of MOF activation by the Et2 AlCl co-catalyst, with the more active materials portraying a larger degree of activation.