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Solid-water interfaces are crucial for clean water, conventional and renewable energy, and effective nuclear waste management. However, reflecting the complexity of reactive interfaces in continuum-scale models is a challenge, leading to oversimplified representations that often fail to predict real-world behavior. This is because these models use fixed parameters derived by averaging across a wide physicochemical range observed at the molecular scale. Recent studies have revealed the stochastic nature of molecular-level surface sites that define a variety of reaction mechanisms, rates, and products even across a single surface. To bridge the molecular knowledge and predictive continuum-scale models, we propose to represent surface properties with probability distributions rather than with discrete constant values derived by averaging across a heterogeneous surface. This conceptual shift in continuum-scale modeling requires exponentially rising computational power. By incorporating our molecular-scale understanding of solid-water interfaces into continuum-scale models we can pave the way for next generation critical technologies and novel environmental solutions.

The utility of UiO-67 Metal–Organic Frameworks (MOFs) for practical applications requires a comprehensive understanding of intermolecular host-guest MOF–analyte interactions. To investigate intermolecular interactions between UiO-67 MOFs and complex molecules, it is useful to evaluate the interactions with simple polar and non-polar analytes. This problem is approached by investigating the interactions of polar (acetone and isopropanol) and non-polar (n-heptane) molecules with functionalized UiO-67 MOFs via temperature programmed desorption mass spectrometry and temperature programmed Fourier transform infrared spectroscopy. We find that isopropanol, acetone, and n-heptane bind reversibly and non-destructively to UiO-67 MOFs, where MOF and analyte functionality influence relative binding strengths (n-heptane ≈ isopropanol > acetone). During heating, all three analytes diffuse into the internal pore environment and directly interact with the μ3-OH groups located within the tetrahedral pores, evidenced by the IR response of ν(μ3-OH). We observe nonlinear changes in the infrared cross sections of the ν(CH) modes of acetone, isopropanol, and n-heptane following diffusion into UiO-67. Similarly, acetone's ν(C=O) infrared cross section increases dramatically when diffused into UiO-67. Ultimately, this in situ investigation provides insights into how individual molecular functional groups interact with UiO MOFs and enables a foundation where MOF interactions with complex molecular systems can be evaluated. [ABSTRACT FROM AUTHOR]

A previous combined experimental and theoretical study found that the position of anchoring groups on a phenanthrene (PHE) backbone played a large role in determining the single‐molecule conductance of the PHE derivative. However, a consistent 0.1 G0 feature was found across all PHE derivatives. To understand this, the previously investigated PHE derivatives were placed flat on a simulated Au substrate with a scanning tunneling microscope (STM) tip over PHE and conductance was calculated using the non‐equilibrium Green's function technique in conjunction with density functional theory (NEGF‐DFT). The location of the tip was varied to find the most conductive and most energetically favorable arrangements, which did not coincide. Furthermore, the variation in conductance found in erect junctions was not present when PHE derivatives were lying flat, with all derivatives calculated to have conductance values around 0.1 G0. [ABSTRACT FROM AUTHOR]

Classical electrochemistry and electrochemical scanning tunneling microscopy (EC-STM) were combined to provide molecular level insight into electrochemical reactions and the molecular adsorption state at the electrolyte-electrode interface. This provides direct, molecular level evidence of the electrochemically 'invisible' species and electrochemical activity of absorbed species is recovered by allowing the oxidized molecule sufficient time to reduce.

Sulfur was impregnated onto activated carbon fibers (ACFs) through [H.sub.2]S oxidation catalyzed by the sorbent surface in a fixed-bed reactor. By changing the temperature and duration of the sulfur impregnation process, ACFs with different sulfur contents were developed. Characterization of ACFs before and after sulfur impregnation was conducted by surface area analysis, energy dispersive X-ray analysis, thermogravimetric analysis, X-ray photoelectron spectroscopy, and temperature programmed desorption. Vapor phase mercury adsorption experiments were carried out in a fixed-bed reactor. Sulfur was impregnated mainly as elemental sulfur and the amount of sulfur deposited on the ACF increased with an increase in impregnation temperature. Higher temperature leads to more uniform sulfur distribution inside the sorbent pores. The impregnation process can be explained by a combination of pore filling and monolayer adsorption, with the former mechanism predominating at low temperatures. In the absence of sulfur, the mercury adsorption capacity can be correlated with surface area and pore volume. DOI: 10.1061/(ASCE)0733-9372(2006)132:3(292) CE Database subject headings: Activated carbon; Sulfur; Mercury; Hydrogen sulfides; Oxidation; Abatement and removal.

The oxygen-containing functional groups, introduced by common purification procedures, on single-walled carbon nanotubes made by both the HiPco and laser-ablation techniques are studied by Fourier Transform Infrared (FTIR) spectroscopy from 90 to 1400 K under vacuum. Effectiveness of the vacuum heating in removing most of the functionalities created in HNO3-treated HiPco samples is revealed.