An Overview of Common Infrared Techniques for Detecting CO Intermediates on Metal Surfaces for Hydrocarbon Products

Detection of intermediates during the catalytic process by infrared techniques has been widely implemented for many important reactions. For the reduction of CO2 into hydrocarbons on metal surfaces, CO molecule is one of the most important transient species to be followed due to its involvement in several products’ pathways, and its distinct vibrational features. Herein, basic understandings behind these utilized infrared techniques are illustrated aiming for highlighting the potential of each infrared technique and its advantages over the other ones for detecting CO molecules on metal surfaces.

Acid-Catalyzed Esterification of Betaines: Theoretical Exploration of the Impact of the Carbon Chain Length on the Reaction Mechanism

Betaine derivatives, especially esters, are compounds of interest for the development of a more sustainable fine chemistry, as they are widely available from biomass and currently produced as side-products from various industries (among which, sugar production). In this publication, we studied the impact of carbon chain length on three considered reaction mechanisms for the esterification of (CH3)3N(CH2)nCO2 betaine (n = 1, 2, 3) with glycerol under acid catalysis. DFT calculations show that the mechanism proposed by Bachmann–Frapper et al. may also be active here, but it can interestingly be seen as an avatar of the former proposition by Watson. Conversely, Ingold’s proposition is in this case too energetically prevented. Overall, lower activation barriers and higher reaction exergonicity are reported, suggesting esterification of longer carbon-chain based betaines is more readily achieved.

Surface Coatings and Treatments for Controlled Hydrate Formation: A Mini Review

Gas hydrates (GHs) are known to pose serious flow assurance challenges for the oil and gas industry. Neverthless, over the last few decades, gas hydrates-based technology has been explored for various energy- and environmentally related applications. For both applications, a controlled formation of GHs is desired. Management of hydrate formation by allowing them to form within the pipelines in a controlled form over their complete mitigation is preferred. Moreover, environmental, benign, non-chemical methods to accelerate the rate of hydrate formation are in demand. This review focused on the progress made in the last decade on the use of various surface coatings and treatments to control the hydrate formation at atmospheric pressure and in realistic conditions of high pressure. It can be inferred that both surface chemistry (hydrophobicity/hydrophilicity) and surface morphology play a significant role in deciding the hydrate adhesion on a given surface.

Identification of Adsorbed Species and Surface Chemical State on Ag(111) in the Presence of Ethylene and Oxygen Studied with Infrared and X-ray Spectroscopies

Using a combination of two surface-sensitive spectroscopy techniques, the chemical state of the Ag(111) surface and the nature of the adsorbed species in the presence of ethylene and oxygen gases are identified. In the 10 mbar pressure range and 25–200 °C studied here, Ag(111) remains largely metallic even in O2-rich conditions. The only adsorbed molecular species with a low but discernible coverage is surface carbonate, which forms due to further oxidation of produced CO2, in a similar manner to its formation in ambient air on Ag surfaces. Its formation is also pressure-dependent, for instance, it is not observed when the total pressure is in the 1 mbar pressure range. Production of carbonate, along with carbon dioxide and water vapor as the main gas-phase products, suggests that an unpromoted Ag(111) surface catalyzes mainly the undesired full oxidation reaction.

The Local Structure of the BiS2 Layer in RE(O,F)BiS2 Determined by In-Plane Polarized X-ray Absorption Measurements

We have investigated the local structure of BiS2-based layered materials by Bi L3-edge extended X-ray absorption fine structure (EXAFS) measurements performed on single crystal samples with polarization of the X-ray beam parallel to the BiS2 plane. The results confirm highly instable nature of BiS2 layer, characterized by ferroelectric like distortions. The distortion amplitude, determined by the separation between the two in-plane (Bi-S1) bonds, is found to be highest in LaO0.77F0.23BiS2 with ΔR∼0.26 Å and lowest in NdO0.71F0.29BiS2 with ΔR∼0.13 Å. Among the systems with intrinsic doping, CeOBiS2 shows smaller distortion (ΔR∼0.15 Å) than PrOBiS2 (ΔR∼0.18 Å) while the highest distortion appears for EuFBiS2 revealing ΔR∼0.22 Å. It appears that the distortion amplitude is controlled by the nature of the RE(O,F) spacer layer in the RE(O,F)BiS2 structure. The X-ray absorption near edge structure (XANES) spectra, probing the local geometry, shows a spectral weight transfer that evolves systematically with the distortion amplitude in the BiS2-layer. The results provide a quantitative measurements of the local distortions in the instable BiS2-layer with direct implication on the physical properties of these materials.

Toward Computational Accuracy in Realistic Systems to Aid Understanding of Field-Level Water Quality Issues

Contemplating what will unfold in this new decade and those after, it is not difficult to imagine the increasing importance of conservation and protection of clean water supplies. A worrying but predictable offshoot of humanity’s technological advances is the seemingly ever-increasing chemical load burdening our waterways. In this perspective are presented a few modest areas where computational chemistry modelling could provide benefit to these efforts by harnessing the continually improving computational power available to the field. In the acute event of a chemical spill incident, true quantum-chemistry-based predictions of physicochemical properties and surface-binding behaviors can be used to help decision making in remediating the spill threat. The chronic burdens of microplastics and perfluorinated “forever chemicals” can also be addressed with computational modelling to fill the gap between feasible laboratory experiment timescales and the much-longer material lifetimes. For all of these systems, field-level accuracy models will avail themselves as the model computational systems are able to incorporate more realistic features that are relevant to water quality issues.

A Computational Study of Molecular Mechanism of Chloroquine Resistance by Chloroquine Resistance Transporter Protein of Plasmodium falciparum via Molecular Modeling and Molecular Simulations

The molecular mechanism of chloroquine resistance by the chloroquine resistance transporter protein of Plasmodium sp. is explored using molecular modeling and computational methods. The key mutation, lysine(K)-76 to threonine(T) (LYS76THR) in the transporter protein pertains to increased recognition of the protonated forms of the antimalarial drug. Such enhanced affinity can promote drug efflux from host digestive vacuole, rendering aminoquinoline-based treatment ineffective.

Dislocations as a Tool for Nanostructuring Advanced Materials

Dislocations present unique opportunities for nanostructuring advanced structural and functional materials due to the recent discoveries of linear complexions thermodynamically stable nanoscale features with unique chemistry and structure confined at dislocations. The formation of such features is driven by solute segregation near the dislocation core and results in the stabilization of dislocations, altering mechanical, thermodynamic, and transport properties of the final material. This perspective article gives an overview of the recent discoveries and predictions made by high-resolution experimental characterization techniques, as well as large-scale atomistic simulations in the newly emerging field of linear complexions.

Predicting 1,9-Decadiene−Water Partition Coefficients Using the 3D-RISM-KH Molecular Solvation Theory

The Three-Dimensional Reference Interaction Site Model (3D-RISM) with Kovalenko−Hirata (KH) closure is applied to calculate the 1,9-Decadiene/Water partition coefficients for a diverse class of compounds. The liquid state of 1,9-Decadiene is represented with the united atom TraPPE force field parameters. The 3D-RISM-KH computed partition functions are in good agreement with the experimental results. Our computational scheme can be used for a quantitative structure partitioning prediction for decadiene-water system, which has been used in membrane-mimicking of the egg-lecithin/water permeability experiments.

The Water Polymorphism and the Liquid–Liquid Transition from Transport Data

NMR spectroscopic literature data are used, in a wide temperature-pressure range (180–350 K and 0.1–400 MPa), to study the water polymorphism and the validity of the liquid–liquid transition (LLT) hypothesis. We have considered the self-diffusion coefficient DS and the reorientational correlation time τθ (obtained from spin-lattice T1 relaxation times), measured, respectively, in bulk and emulsion liquid water from the stable to well inside the metastable supercooled region. As an effect of the hydrogen bond (HB) networking, the isobars of both these transport functions evolve with T by changing by several orders of magnitude, whereas their pressure dependence become more and more pronounced at lower temperatures. Both these transport functions were then studied according to the Adam–Gibbs model, typical of glass forming liquids, obtaining the water configurational entropy and the corresponding specific heat contribution. The comparison of the evaluated CP,conf isobars with the experimentally measured water specific heat reveals the full consistency of this analysis. In particular, the observed CP,conf maxima and its diverging behaviors clearly reveals the presence of the LLT and with a reasonable approximation the liquid–liquid critical point (LLCP) locus in the phase diagram.