The feasibility of the C100 fullerene as a nanocontainer for glycine, alanine, and serine has been investigated using density functional theory (B3LYP-D3), second-order Møller-Plesset perturbation theory, and the domain-based local pair natural orbital-coupled cluster singles doubles and perturbative triples (DLPNO-CCSD(T)) method. The interaction energies for glycine@C100, alanine@C100, and serine@C100 are calculated to be -47.8, -45.5, and -43.8 kcal mol-1, respectively, for their most stable conformers, at the DLPNO-CCSD(T) level, indicating favorable host-guest interactions. Furthermore, encapsulation leads to substantial stabilization of both the intramolecular hydrogen-bonded and nonhydrogen-bonded conformers of the amino acids. Vibrational frequency analysis shows a blueshift for most of the vibrational modes, indicative of restricted motion due to the confined space. However, the OH-stretch mode, especially for the intramolecular hydrogen-bonded conformers, exhibits a large redshift upon encapsulation, suggesting a strengthening of the hydrogen bond due to confinement. The results of the dipole moment calculations reveal a significant reduction in the dipole moment after encapsulation, indicating an effective screening of the dipole by the C100 cage. 1H NMR chemical shift calculations reveal a large downfield shift, consistent with the deshielding effects experienced by the encapsulated molecules due to the unique electronic environment within the fullerene cavity.

Stimulated by recent findings of a beneficial effect of a high-temperature treatment on the activity and selectivity of highly active and selective Ru/TiO2 catalysts in the COx methanation, a detailed study of the dynamic changes in the chemical and structural properties is performed, induced by this treatment and their correlation with the changes in the catalytic performance of the catalyst. These changes are characterized by time-resolved operando X-ray absorption spectroscopy at the Ru and Ti K-edges, together with structural characterization by high-resolution transmission electron microscopy. The observation of differently long times required for the reduction of the oxidic Ru nanoparticles in CO-free CO2/H2 gas mixtures (1000 min) and in trace amounts of CO containing CO/CO2/H2 gas mixtures (100 min) under reaction conditions (190 °C, atmospheric pressure) correlates very well with the different times required for catalyst activation in these reaction gas mixtures.

Herein, a density functional theory based mechanistic and kinetics study of experimentally reported pincer metal complex catalyzed homogenous dehydrogenation of methanol and diamine into diamide is explored. The reaction proceeds through dehydrogenation and hydrogenation reactions for the reversible interconversion between methanol and diamine. The mechanism proceeds via a step-by-step formation of aldehyde, amide, and diamide complexes. The generated formaldehyde reacts with ethylenediamine in the second cycle to make monoamide, which reacts with formaldehyde from the first cycle to produce diamide. The complete diamide formation reaction follows a cross-multicarrousel type mechanism. The turnover-determining transition state is the formation of the first amide bond, where the addition of amine and metal aldehyde takes place. The alternative reaction of metal aldehyde and alcohol via an ester formation reaction is a minor path. The rate equation is derived from the most feasible path. From the dissociation dynamics simulations, the dehydrogenation reaction of metal hydride is found to be favorable, and a strong Mn and H2 interaction is present during the H2 release, which may facilitate the hydrogenation reaction. Diamide dissociation is more challenging than amide dissociation, and a high temperature is required for diamide dissociation dynamics.

Modular synthetic modification to ligand scaffolds of metal complexes provides an approach to rational improvement of existing molecular catalytic systems. A previous report from the Marinescu group has shown that a cobalt phosphino thiolate complex ([Co(triphos)(bdt)]+) has excellent selectivity and activity for electrocatalytic CO2 reduction to formate. Here, a multimetallic analogue, [Co3(triphos)3(tht)]3+, that is conjugated through a trinucleating dithiolene ligand in the form of triphenylene-2,3,6,7,10,11-hexathiolate is investigated. While voltammetric studies indicate enhanced current densities under similar conditions to [Co(triphos)(bdt)]+, electrolysis and ultraviolet-visible spectroscopy results suggest significant catalyst degradation and overall moderate faradaic yields.

Electrochemical fluorination on a nickel anode (Simons process) is an important process for producing fluorinated compounds. Despite its success, the mechanism is still under debate. Here a first-principles study is presented of fluorination of ethene on a model fluorinated (001) NiF surface, which is chosen because it is stabilized under the external potential close to that at which the Simons cell operates and because it has a readily available unit providing fluorine source to aid fluorination reactions. The adsorption of the simplest double bond containing hydrocarbon on this surface is investigated. It is placed on the surface in different orientation, leading to six distinct structural outcomes upon relaxation. These include formation of 1,2-difluoroethane, fluoroethene, and 1,2-difluoroethene, alongside other fluorinated products as well as monocarbon fragments. This is one of the first computational studies of the catalytic Simons-type fluorination and can, despite its simplicity, offers some insight into reaction pathways and surface interactions.

Water is widely recognized as critical to the tunability and electrochemical stability of nonaqueous solvents such as deep eutectic solvents (DESs) and ionic liquids (ILs). Traditionally, the water content of these solvents has been controlled by either drying or adding small amounts of water to control their bulk properties to meet specific application requirements. The total water content by itself, does not provide sufficient information about the chemical reactivity and molecular interactions within DES- and IL-water mixtures. In this concept article, water activity is highlighted as a thermodynamically more rigorous descriptor to quantify the influence of the co-solvent water on DES- and IL-water mixtures. Water activity relates measurable physical properties, such as vapor pressure, density, viscosity, electrochemical stability, and conductivity of DESs and ILs to the underlying molecular interactions between their components. Furthermore, water activity of DESs and ILs correlates with changes in local solvent structures and thermodynamic excess properties, including excess molar volume, enthalpy, and Gibbs energy.

Benzazole derivatives exhibit distinctive photophysical behavior due to excited-state intramolecular proton transfer (ESIPT), making them promising candidates for optoelectronic applications such as organic light-emitting diodes (OLEDs) and fluorescent sensors. Understanding their sublimation energetics, phase behavior, and emissive properties is essential for both fundamental studies and materials design. This article reports an investigation on two benzazole derivatives-2-(2-hydroxyphenyl)benzothiazole and 2-(2-hydroxyphenyl)benzoxazole (HBO)-through studies of thermal analysis, vapor pressure measurements, and fluorescence spectroscopy to establish structure-property relationships. Thermal stability and phase transitions are characterized using simultaneous thermogravimetry-differential scanning calorimetry (TG-DSC) and heat-flux DSC. Vapor pressures are determined using both Knudsen effusion mass loss and mass spectrometry. The derived standard molar enthalpies of sublimation, vaporization, and fusion highlight the presence of heteroatom (S versus O) on intermolecular interactions. Solid-state fluorescence measurements reveal strong emission in both compounds, with a large Stokes shift-consistent with ESIPT-and complex spectra attributed to solid-state molecular packing. This comprehensive experimental strategy delivers benchmark thermodynamic and photophysical data, offering new insights into the interplay between molecular structure, thermal behavior, and fluorescence of benzazole derivatives. Such understanding is relevant for the development of advanced optoelectronic materials.

The construction of efficient Z-scheme heterojunctions is considered as a promising approach to improve the transfer and separation of photogenerated carries in the field of photocatalytic hydrogen evolution from water splitting. Herein, a novel CdS/UiO-66(Ce) with Z-scheme heterostructure is successfully fabricated from metal sulfide CdS and cerium-based UiO-66 metal-organic framework via a hydrothermal method. The Z-scheme CdS/UiO-66(Ce) heterojunctions can provide abundant active centers, broaden the response range to visible-light region, accelerate the transfer of interfacial charges, and suppress the recombination rate of photogenerated electron-hole pairs. As a result, CdS/UiO-66(Ce) (ω(CdS) = 30%) exhibits a hydrogen production rate of 1.975 mmol g-1 h-1, which is 19.1 times higher than that of UiO-66(Ce). Overall, this article may provide a new pathway for the rational design of efficient Z-scheme heterojunctions with photocatalytic hydrogen evolution.

Chalcogen bond (ChB) catalysis is a significant strategy in organocatalysis due to its modifiable polarity, notable directionality, and the flexibility that aids both binding and dissociation. As an important benchmark reaction, the transfer hydrogenation of quinoline (QNL) is widely used to evaluate the catalytic performance and to explore the relationship between the structure and activity of catalysts. In this work, density functional theory calculations are employed to elucidate the mechanism of the ChB-catalyzed transfer hydrogenation of QNL using Hantzsch ester (HEH) as the hydrogen source. Analysis of the transition state properties in the rate-determining step reveals that the σ-hole of ChB catalysts interacts with the nitrogen lone pairs of HEH, accompanied by charge transfer and rearrangement processes occurring throughout the reaction. Energy decomposition analysis (EDA), together with Natural Bond Orbital (NBO) and quantum theory of atoms in molecules (QTAIM) analyses, reveals that polarization effects predominantly stabilize the chalcogen bond (ChB), thereby lowering the reaction energy barriers. This insight provides a foundation for the rational design of new ChB catalysts.

The development of highly efficient and sustainable electrocatalytic technologies offers a significant solution to the growing global demand for energy, as well as to the achievement of carbon neutrality goals, where its success relies on the design and fabrication of electrocatalysts. Currently, carbon-based materials are promising alternative materials due to the tunable electronic structure, high conductivity, excellent stability, and abundant reserves; however, inherent inert structure significantly limits its catalytic activity. Herein, incorporating oxygen functional groups (OFGs) into carbon-based materials has been reviewed as a pivotal strategy to regulate electronic structure, charge transfer processes, and adsorption energy toward reaction intermediates, thereby enhancing electrocatalytic performance. The latest research progress of OFGs in crucial electrocatalytic reaction such as oxygen reduction reaction, CO2 reduction reaction, and oxygen evolution reaction is systematically reviewed, deeply exploring core mechanisms of reaction kinetics regulation, while summarizing the precise structure-function relationships of different OFGs types in multireaction systems. Further, technical challenges and prospective opportunities in precise design and modulation of OFGs are discussed, offering a basis for research focusing on dynamic controllable strategies and optimal design of interfacial microenvironments. Finally, research insights and technical pathways of developing low-cost and high-performance oxygen-functionalized carbon-based materials for electrocatalytic applications are provided.