Water motifs in zirconium metal-organic frameworks induced by nanoconfinement and hydrophilic adsorption sites.

The intricate hydrogen-bonded network of water gives rise to various structures with anomalous properties at different thermodynamic conditions. Nanoconfinement can further modify the water structure and properties, and induce specific water motifs, which are instrumental for technological applications such as atmospheric water harvesting. However, so far, a causal relationship between nanoconfinement and the presence of specific hydrophilic adsorption sites is lacking, hampering the further design of nanostructured materials for water templating.

The Operando Nature of Isobutene Adsorbed in Zeolite H-SSZ-13 Unraveled by Machine Learning Potentials Beyond DFT Accuracy.

Unraveling the nature of adsorbed olefins in zeolites is crucial to understand numerous zeolite-catalyzed processes. A well-grounded theoretical description critically depends on both an accurate determination of the potential energy surface (PES) and a reliable account of entropic effects at operating conditions. Herein, we propose a transfer learning approach to perform random phase approximation (RPA) quality enhanced sampling molecular dynamics simulations, thereby approaching chemical accuracy on both the determination and exploration of the PES.

Investigation of the Octahedral Network Structure in Formamidinium Lead Bromide Nanocrystals by Low-Dose Scanning Transmission Electron Microscopy.

Metal halide perovskites (MHP) are highly promising semiconductors. In this study, we focus on FAPbBr nanocrystals, which are of great interest for green light-emitting diodes. Structural parameters significantly impact the properties of MHPs and are linked to phase instability, which hampers long-term applications.

Reaching Quantum Accuracy in Predicting Adsorption Properties for Ethane/Ethene in Zeolitic Imidazolate Framework-8 at Low Pressure Regime.

Nanoporous materials in the form of metal-organic frameworks such as zeolitic imidazolate framework-8 (ZIF-8) are promising membrane materials for the separation of hydrocarbon mixtures. To compute the adsorption isotherms in such adsorbents, grand canonical Monte Carlo simulations have proven to be very useful. The quality of these isotherms depends on the accuracy of adsorbate-adsorbent interactions, which are mostly described using force fields owing to their low computational cost.

Gas adsorption and framework flexibility of CALF-20 explored via experiments and simulations.

In 2021, Svante, in collaboration with BASF, reported successful scale up of CALF-20 production, a stable MOF with high capacity for post-combustion CO capture which exhibits remarkable stability towards water. CALF-20's success story in the MOF commercialisation space provides new thinking about appropriate structural and adsorptive metrics important for CO capture. Here, we combine atomistic-level simulations with experiments to study adsorptive properties of CALF-20 and shed light on its flexible crystal structure.

Computational Protocol for the Spectral Assignment of NMR Resonances in Covalent Organic Frameworks.

Solid-state nuclear magnetic resonance spectroscopy is routinely used in the field of covalent organic frameworks to elucidate or confirm the structure of the synthesized samples and to understand dynamic phenomena. Typically this involves the interpretation and simulation of the spectra through the assumption of symmetry elements of the building units, hinging on the correct assignment of each line shape. To avoid misinterpretation resulting from library-based assignment without a theoretical basis incorporating the impact of the framework, this work proposes a first-principles computational protocol for the assignment of experimental spectra, which exploits the symmetry of the underlying building blocks for computational feasibility.

The Application of Porous Organic Polymers as Metal Free Photocatalysts in Organic Synthesis.

Concerns about increasing greenhouse gas emissions and their effect on our environment highlight the urgent need for new sustainable technologies. Visible light photocatalysis allows the clean and selective generation of reactive intermediates under mild conditions. The more widespread adoption of the current generation of photocatalysts, particularly those using precious metals, is hampered by drawbacks such as their cost, toxicity, difficult separation, and limited recyclability.

Transitioning from Methanol to Olefins (MTO) toward a Tandem CO Hydrogenation Process: On the Role and Fate of Heteroatoms (Mg, Si) in MAPO-18 Zeotypes.

The tandem CO hydrogenation to hydrocarbons over mixed metal oxide/zeolite catalysts (OXZEO) is an efficient way of producing value-added hydrocarbons (platform chemicals and fuels) directly from CO methanol intermediate in a single reactor. In this contribution, two MAPO-18 zeotypes (M = Mg, Si) were tested and their performance was compared under methanol-to-olefins (MTO) conditions (350 °C, = 0.04 bar, 6.

A Critical Assessment on Calculating Vibrational Spectra in Nanostructured Materials.

Vibrational spectroscopy is an omnipresent spectroscopic technique to characterize functional nanostructured materials such as zeolites, metal-organic frameworks (MOFs), and metal-halide perovskites (MHPs). The resulting experimental spectra are usually complex, with both low-frequency framework modes and high-frequency functional group vibrations. Therefore, theoretically calculated spectra are often an essential element to elucidate the vibrational fingerprint.

OGRe: Optimal Grid Refinement Protocol for Accurate Free Energy Surfaces and Its Application in Proton Hopping in Zeolites and 2D COF Stacking.

While free energy surfaces are the crux of our understanding of many chemical and biological processes, their accuracy is generally unknown. Moreover, many developments to improve their accuracy are often complicated, limiting their general use. Luckily, several tools and guidelines are already in place to identify these shortcomings, but they are typically lacking in flexibility or fail to systematically determine how to improve the accuracy of the free energy calculation.

Super-Oxidizing Covalent Triazine Framework Electrocatalyst for Two-Electron Water Oxidation to H O.

Electrochemical two-electron water oxidation (2e WOR) is gaining surging research traction for sustainable hydrogen peroxide production. However, the strong oxidizing environment and thermodynamically competitive side-reaction (4e WOR) posit as thresholds for the 2e WOR. We herein report a custom-crafted covalent triazine network possessing strong oxidizing properties as a proof-of-concept metal-free functional organic network electrocatalyst for catalyzing 2e WOR.

On the Prediction of Spectroscopic Fingerprints of Co Complexes Relevant for the ZIF Nucleation Process.

The nucleation process of zeolitic imidazolate frameworks (ZIFs) is to date not completely understood. Recently, it has been found that, during the formation of Co-ZIF-67, after mixing imidazole-type ligands with octahedral precursors containing oxygen-coordinated ligands, a metal-organic pool with a diversity of transition metal complexes (TMCs) is formed showing fingerprints of octahedral and tetrahedral Co complexes with both types of ligands [Filez, M. 2021, 2, 100680].

The electrophilic aromatic bromination of benzenes: mechanistic and regioselective insights from density functional theory.

The HBr-assisted electrophilic aromatic bromination of benzene, anisole and nitrobenzene was investigated using static DFT calculations in gas phase and implicit apolar (CCl4) and polar (acetonitrile) solvent models at the ωB97X-D/cc-pVTZ level of theory. The reaction profiles corresponding to either a direct substitution reaction or an addition-elimination process were constructed and insight into the preferred regioselectivity was provided using a combination of conceptual DFT reactivity indices, aromaticity indices, Wiberg bond indices and the non-covalent interaction index. Our results show that under the considered reaction conditions the bromination reaction preferentially occurs through an addition-elimination mechanism and without formation of a stable charged Wheland intermediate.

Operando Modeling of Zeolite-Catalyzed Reactions Using First-Principles Molecular Dynamics Simulations.

Within this Perspective, we critically reflect on the role of first-principles molecular dynamics (MD) simulations in unraveling the catalytic function within zeolites under operating conditions. First-principles MD simulations refer to methods where the dynamics of the nuclei is followed in time by integrating the Newtonian equations of motion on a potential energy surface that is determined by solving the quantum-mechanical many-body problem for the electrons. Catalytic solids used in industrial applications show an intriguing high degree of complexity, with phenomena taking place at a broad range of length and time scales.

DFT-Quality Adsorption Simulations in Metal-Organic Frameworks Enabled by Machine Learning Potentials.

Nanoporous materials such as metal-organic frameworks (MOFs) have been extensively studied for their potential for adsorption and separation applications. In this respect, grand canonical Monte Carlo (GCMC) simulations have become a well-established tool for computational screenings of the adsorption properties of large sets of MOFs. However, their reliance on empirical force field potentials has limited the accuracy with which this tool can be applied to MOFs with challenging chemical environments such as open-metal sites.

Exploring the Charge Storage Dynamics in Donor-Acceptor Covalent Organic Frameworks Based Supercapacitors by Employing Ionic Liquid Electrolyte.

Two donor-acceptor type tetrathiafulvalene (TTF)-based covalent organic frameworks (COFs) are investigated as electrodes for symmetric supercapacitors in different electrolytes, to understand the charge storage and dynamics in 2D COFs. Till-date, most COFs are investigated as Faradic redox pseudocapacitors in aqueous electrolytes. For the first time, it is tried to enhance the electrochemical performance and stability of pristine COF-based supercapacitors by operating them in the non-Faradaic electrochemically double layer capacitance region.

Engineering of Phenylpyridine- and Bipyridine-Based Covalent Organic Frameworks for Photocatalytic Tandem Aerobic Oxidation/Povarov Cyclization.

Covalent organic frameworks (COFs) are emerging as a new class of photoactive organic semiconductors, which possess crystalline ordered structures and high surface areas. COFs can be tailor-made toward specific (photocatalytic) applications, and the size and position of their band gaps can be tuned by the choice of building blocks and linkages. However, many types of building blocks are still unexplored as photocatalytic moieties and the scope of reactions photocatalyzed by COFs remains quite limited.

Challenges in modelling dynamic processes in realistic nanostructured materials at operating conditions.

The question is addressed in how far current modelling strategies are capable of modelling dynamic phenomena in realistic nanostructured materials at operating conditions. Nanostructured materials used in applications are far from perfect; they possess a broad range of heterogeneities in space and time extending over several orders of magnitude. Spatial heterogeneities from the subnanometre to the micrometre scale in crystal particles with a finite size and specific morphology, impact the material's dynamics.

Simulations in the era of exascale computing.

Exascale computers - supercomputers that can perform 10 floating point operations per second - started coming online in 2022: in the United States, Frontier launched as the first public exascale supercomputer and Aurora is due to open soon; OceanLight and Tianhe-3 are operational in China; and JUPITER is due to launch in 2023 in Europe. Supercomputers offer unprecedented opportunities for modelling complex materials. In this Viewpoint, five researchers working on different types of materials discuss the most promising directions in computational materials science.

Pyrene-Based Covalent Organic Frameworks for Photocatalytic Hydrogen Peroxide Production.

Four highly porous covalent organic frameworks (COFs) containing pyrene units were prepared and explored for photocatalytic H O production. The experimental studies are complemented by density functional theory calculations, proving that the pyrene unit is more active for H O production than the bipyridine and (diarylamino)benzene units reported previously. H O decomposition experiments verified that the distribution of pyrene units over a large surface area of COFs plays an important role in catalytic performance.

Nuclear quantum effects on zeolite proton hopping kinetics explored with machine learning potentials and path integral molecular dynamics.

Proton hopping is a key reactive process within zeolite catalysis. However, the accurate determination of its kinetics poses major challenges both for theoreticians and experimentalists. Nuclear quantum effects (NQEs) are known to influence the structure and dynamics of protons, but their rigorous inclusion through the path integral molecular dynamics (PIMD) formalism was so far beyond reach for zeolite catalyzed processes due to the excessive computational cost of evaluating all forces and energies at the Density Functional Theory (DFT) level.