Stability is the key property of functional materials. In this work we investigate computationally the degradative potential of a model Mn-BTC (BTC = benzene-1,3,5-tricarboxylate) metal–organic framework (MOF) building block in aqueous solutions under oxidative conditions. Model density functional theory calculations have shown that the direct hydrolysis of the Mn-containing moieties is more difficult than their decomposition via oxidation-induced paths. While the interaction with H2O2 species is of non-covalent nature and requires O–O-bond breaking to initiate Mn-center oxidation, open-shell O2 species readily oxidize radical Mn-centers and form bonds of σ-, π-, or δ-symmetry with the metal. The oxidative transformations of di-Mn paddle-wheel carboxylate structure-forming units are accompanied with substantial distortions of the coordination polyhedra that, together with the increased Lewis acidity of the oxidized metal centers, facilitates the hydrolysis leading to the degradation of the structure at a larger scale. Whereas such a mechanism is expected to hamper the catalytic applications of such Mn-MOFs, the associated structural response to oxidizing and radical species can create a basis for the construction of Mn-MOF-based drug delivery systems with increased bio-compatibility.@en

Linear energy scaling laws connect the kinetic and thermodynamic parameters of key elementary steps for heterogeneously catalyzed reactions over defined active sites on open surfaces. Such scaling laws provide a framework for a rapid computational activity screening of families of catalysts, but they also effectively impose a fundamental limit on the theoretically attainable activity. Understanding the limits of applicability of the linear scaling laws is therefore crucial for the development of predictive models in catalysis. In this work, we computationally investigate the role of secondary effects of the active site environment on the reactivity of defined Fe complexes in ZSM-5 zeolite toward methane oxofunctionalization. The computed C-H activation barriers over Fe-sites at different locations inside the zeolite pores generally follow the associated reaction enthalpies and the hydrogen affinities of the active site, reflecting the O-H bond strength. Nevertheless, despite the close similarity of the geometries and intrinsic reactivities of the considered active complexes, substantial deviations from these linear scaling relations are apparent from the DFT calculations. We identify three major factors behind these deviations, namely, (1) confinement effects due to the zeolite micropores, (2) coordinative flexibility, and (3) multifunctionality of the active site. The latter two phenomena impact the mechanism of the catalytic reaction by providing a cooperative reaction channel for the substrate activation or by enabling the stabilization of the intrazeolite complex along the reaction path. These computational findings point to the need for the formulation of multidimensional property-Activity relationships accounting for both the intrinsic chemistry of the reactive ensembles and secondary effects due to their environmental and dynamic characteristics.@en

Metal-modified zeolites are versatile catalytic materials with a wide range of industrial applications. Their catalytic behaviour is determined by the nature of externally introduced cationic species, i.e., its geometry, chemical composition, and location within the zeolite pores. Superior catalyst designs can be unlocked by understanding the confinement effect and spatial limitations of the zeolite framework and its influence on the geometry and location of such cationic active sites. In this study, we employ the genetic algorithm (GA) global optimization method to investigate extraframework aluminum species and their structural variations in different zeolite matrices. We focus on extraframework aluminum (EFAl) as a model system because it greatly influences the product selectivity and catalytic stability in several zeolite catalyzed processes. Specifically, the GA was used to investigate the configurational possibilities of EFAl within the mordenite (MOR) and ZSM-5 frameworks. The xTB semi-empirical method within the GA was employed for an automated sampling of the EFAl-zeolite space. Furthermore, geometry refinement at the density functional theory (DFT) level of theory allowed us to improve the most stable configurations obtained from the GA and elaborate on the limitations of the xTB method. A subsequent ab initio thermodynamics analysis (aiTA) was chosen to predict the most favourable EFAl structure(s) under the catalytically relevant operando conditions.@en

Extraframework cations define the chemical versatility of zeolite catalysts. Addressing their structural complexity and dynamic behavior represents one of the main fundamental challenges in the field. Herein, we present a computational approach for the identification and analysis of the accessible pool of intrazeolite extraframework complexes with a Cu/MOR catalyst as an industrially important model system. We employ ab initio molecular dynamics for capturing the ensemble of reactive isomers with the [Cu3O3]2+ stoichiometry confined in the mordenite channels. The high structural diversity of the generated isomers was ensured by concentrating the kinetic energy along the low-curvature directions of the potential energy surface (PES). Geometrically distinct [Cu3O3]2+ complexes were identified via a series of clustering procedures ensuring that one structure of each local minima is retained. The proposed procedure has resulted in a set of previously unknown peroxo-complexes, which are >50 kJ/mol more stable than the recently hypothesized chair-shaped structure. Our analysis demonstrates that the most stable peroxo-containing clusters can be formed under operando conditions from molecular oxygen and the Cu3O unit, similar to that in methane monooxygenase (MMO) enzymes. @en

Copper-oxo clusters exchanged in zeolite mordenite are active in the stoichiometric conversion of methane to methanol at low temperatures. Here, we show an unprecedented methanol yield per Cu of 0.6, with a 90–95 % selectivity, on a MOR solely containing [Cu3(μ-O)3]2+ active sites. DFT calculations, spectroscopic characterization and kinetic analysis show that increasing the chemical potential of methane enables the utilization of two μ-oxo bridge oxygen out of the three available in the tricopper-oxo cluster structure. Methanol and methoxy groups are stabilized in parallel, leading to methanol desorption in the presence of water.@en

The production of valuable aromatics and the rapid catalyst deactivation due to coking are intimately related in the zeolite-catalyzed aromatization reactions. Here, we demonstrate that these two processes can be decoupled by promoting the Ga/HZSM-5 aromatization catalyst with Ca. The resulting bimetallic catalysts combine high selectivity to light aromatics with extended catalyst lifetime in the methanol-to-aromatics process. Evaluation of the catalytic performance combined with detailed catalyst characterization suggests that the added Ca interacts with the Ga-LAS, with a strong effect on the aromatization processes. A genetic algorithm approach complemented by ab initio thermodynamic analysis is used to elucidate the possible structures of bimetallic extraframework species formed under reaction conditions. The promotion effect of minute amounts of Ca is attributed to the stabilization of the intra-zeolite extraframework gallium oxide clusters with moderated dehydrogenation activity. @en

Here we report the methodology for nanocomposite fabrication based on the inkjet printing technique. Doped TiO2 nanoparticles with Sc contents up to 10 wt.% were synthesized and adapted towards a facile fabrication of microscale structures and thin film printing. Implementation of the state-of-the-art low-temperature synthesis allowed to us successfully incorporate high concentrations of Sc3+ ions into the TiO2 lattice and improve the light absorption characteristics of the resulting materials. Without affecting the anatase structure substantially, Sc doping gave rise to an intensified absorbance capacity and provided the means for the efficient fabrication of Sc-TiO2 microarchitectures via the inkjet printing technique. The changes in the spectral and structural characteristics of the Sc-TiO2 composites were observed by Energy Dispersive X-Ray spectroscopy (EDX), X-ray diffraction (XRD), and UV-vis methods. The rheological parameters of the colloidal suspension based on the synthesized Sc-TiO2 nanoparticles were adapted for inkjet printing in terms of the optimal viscosity, morphology, and surface tension. The developed individual ink characteristics allowed us to produce a close coherence between the enhanced optical properties of the Sc-TiO2 prepared the sol-gel method and the inkjet-printed films. The introduced methodology features the possibility to inkjet-print doped and pure TiO2 robust films for potential large-scale fabrication.@en

A highly selective adsorbent for multivalent cationic species based on a sitinakite-type titanosilicate was prepared from a leucoxene ore enrichment waste. The synthesized material was used as for the selective removal of alkali-earth strontium (II) and barium (II) cations as well as for the cationic species based on the natural isotopes of uranium, radium, and thorium from aqueous solutions. The influence of such parameters as the pH, the initial concentration of the ions, the presence of other electrolytes on the sorption parameters was investigated. The sorption capacity of the synthesized material at ambient conditions is 80 and 110 mg/g for Sr2+ and Ba2+, respectively, and it rises with increasing temperature. Furthermore, the material shows a high selectivity towards radionuclides of radium, uranium, and thorium. By using the current titanosilicate materials, the extracting degree of over 99% could be achieved when extracting these species from their respective standard aqueous solutions. The origin of the high adsorption selectivity for cationic complexes of thorium and uranium is rationalized based on periodic density functional theory calculations. The obtained results indicate that the described materials could be promising and inexpensive sorbents for the selective extraction of radioactive isotopes and particularly those of Sr, Ba and U, Th, Ra.@en

This is a response to a comment on the interpretation of the origin of the nonlinear changes of optical properties of van der Waals' metal–organic frameworks (MOFs). The concerns are addressed by clarifying potential pitfalls in density functional theory (DFT) simulations, careful analysis of prior literature, and additionally discussing the previous experimental results to emphasize the applicability of the excitonic concept in molecular crystals, such as MOFs.@en

The stoichiometric conversion of methane to methanol by Cu-exchanged zeolites can be brought to highest yields by the presence of extraframework Al and high CH4 chemical potentials. Combining theory and experiments, the differences in chemical reactivity of monometallic Cu-oxo and bimetallic Cu-Al-oxo nanoclusters stabilized in zeolite mordenite (MOR) are investigated. Cu-L3 edge X-ray absorption near-edge structure (XANES), infrared (IR), and ultraviolet-visible (UV-vis) spectroscopies, in combination with CH4 oxidation activity tests, support the presence of two types of active clusters in MOR and allow quantification of the relative proportions of each type in dependence of the Cu concentration. Ab initio molecular dynamics (MD) calculations and thermodynamic analyses indicate that the superior performance of materials enriched in Cu-Al-oxo clusters is related to the activity of two μ-oxo bridges in the cluster. Replacing H2O with ethanol in the product extraction step led to the formation of ethyl methyl ether, expanding this way the applicability of these materials for the activation and functionalization of CH4. We show that competition between different ion-exchanged metal-oxo structures during the synthesis of Cu-exchanged zeolites determines the formation of active species, and this provides guidelines for the synthesis of highly active materials for CH4 activation and functionalization.@en

In this thesis, we have presented and investigated the possible strategies for modelling complex heterogeneous catalytic systems in operando regimes. By introducing modern computational approaches to sample the potential energy surface of the catalytic active site, we have attempted to account for the reactive conditions, solvent presence, additives inclusion, and structural dynamics of the active site. There is growing spectroscopic and theoretical evidence of the critical role of the active site dynamics for the catalytic performance, advocating for the active site representation as an ensemble of possible isomers. Challenged by the complexity of the reactive environment and common heterogeneous catalysts, we strongly believe that addressing these factors and incorporating them explicitly into the model description will contribute to a more realistic representation of the catalytic system.@en

The electrocatalytic CO2 reduction reaction (CO2RR) is one of the key technologies of the clean energy economy. Molecular-level understanding of the CO2RR process is instrumental for the better design of electrodes operable at low overpotentials with high current density. The catalytic mechanism underlying the turnover and selectivity of the CO2RR is modulated by the nature of the electrocatalyst, as well as the electrolyte liquid, and its ionic components that form the electrical double layer (EDL). Herein we demonstrate the critical non-innocent role of the EDL for the activation and conversion of CO2 at a high cathodic bias for electrocatalytic conversion over a silver surface as a representative low-cost model cathode. By using a multiscale modeling approach we demonstrate that under such conditions a dense EDL is formed, which hinders the diffusion of CO2 towards the Ag111 electrocatalyst surface. By combining DFT calculations and ab initio molecular dynamics simulations we identify favorable pathways for CO2 reduction directly over the EDL without the need for adsorption to the catalyst surface. The dense EDL promotes homogeneous phase reduction of CO2via electron transfer from the surface to the electrolyte. Such an outer-sphere mechanism favors the formation of formate as the CO2RR product. The formate can undergo dehydration to CO via a transition state stabilized by solvated alkali cations in the EDL.@en