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At least 199 records · Page 11

Impact of Annealing on the Chemical and Superconducting Properties of Ta Thin Films

Tantalum thin films are annealed to dissolve the surface oxide. The effect of annealing is studied using material characterization tools, XPS and TOF-SIMS, and electrical transport measurements of the annealed films are taken using standard PPMS methods to correlate with the surface chemistry. Annealing dissociates the surface oxide, and the oxygen produced diffuses into the thin film. The introduction of oxygen reduces the quality of the thin film, as shown by the suppression of Tc and a reduction in RRR.

Shinde, Maithilee [IIT, Chicago]↗

Validated Reactive Force Field Quantifies MXene Interfacial Properties, Mechanics, and Thermal Transport

MXenes combine rich surface chemistry, mechanical strength, and high conductivity for a multitude of emerging applications. Predictive modeling supports accelerated materials designs and has been limited by the absence of validated and transferable force fields. Here, we introduce an interpretable, reactive INTERFACE force field (IFF and IFF-R) for Ti 3 C 2 T x MXenes that is trained based on chemical knowledge and achieves quantitative agreement with experiments across lattice parameters (<0.5%), density (<0.2%), liquid contact angles, Raman spectra, and the in-plane elastic modulus (∼320 GPa). The models cover surface terminations from hydroxyl (−OH) to fluorine (−F) groups and are extensible to other chemistries. We introduce pH-resolved surface chemistry and identify dopamine adsorption mechanisms at MXene–aqueous interfaces supported by QCM-D and UV–Vis experiments. The data reveal coplanar and perpendicular binding modes and concentration-dependent multilayer assembly. We predict previously inaccessible properties, including termination-dependent cleavage energies, interlayer shear moduli and dynamic shear failure, nanoindentation and brittle fracture, anisotropic in-plane and out-of-plane thermal conductivities, including the role of defects. Agreement with available experimental data is consistently close and exceeds DFT accuracy across the benchmark properties examined. The IFF/IFF-R model is compatible with CHARMM, AMBER, OPLS, and CVFF force fields for simulations of MXenes with diverse surface terminations, electrolyte interfaces, biointerfaces, and polymer composites without additional parameters. Parameter sets, 3D models, and analysis scripts are provided for community use. The validated, reactive, and transferable IFF framework facilitates predictive design of MXene-based films, membranes, sensing interfaces, and composites.

MXene↗

Nonthermal Plasma-Stimulated C–N Coupling from CH 4 and N 2 Depends on the Presence of Surface CH x and Plasma-Phase CN Species

Formation of C–N containing compounds from plasma-catalytic coupling of CH 4 and N 2 over various transition metals (Ni, Pd, Cu, Ag, and Au) is investigated using a multimodal spectroscopic approach, combining polarization-modulation infrared reflection–absorption spectroscopy (PM-IRAS) and optical emission spectroscopy (OES). Through sequential experiments utilizing CH 4 and N 2 nonthermal plasmas, we minimize plasma-phase reactions and identify key intermediates for C–N coupling on metal surfaces. Results show that simultaneous CH 4 and N 2 exposure with plasma stimulation produces surface C–N species. However, N 2 –CH 4 sequential exposure does not lead to C–N species formation, while CH 4 –N 2 sequential exposure reveals the presence of CH x surface species and CN radical species as key precursors to C–N species formation. From further analysis using X-ray photoelectron spectroscopy and liquid chromatography–mass spectrometry, the influence of exposure conditions on the degree of nitrogen incorporation and the nature of C–N species formed were revealed. The work highlights the importance of surface chemistry and exposure conditions in surface C–N coupling with plasma stimulation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Machine Learning in Environmental Chemistry: Application to Surface Complexation Modeling

Environmental chemistry – or biogeochemistry – is the scientific discipline typically invoked when examining and quantifying groundwater or surface water contamination, and nutrient cycling in the environment. Over the last three decades, there have been significant advances in mechanistic model development to describe and predict these complex biogeochemical processes. In particular, surface complexation models (SCMs) have been developed to describe the rock/soil surface reactions of metals and radionuclides, and their partitioning between various mobile species in the aqueous phase or immobile species sorbed on solid surfaces. Often represented by a simplified linear isotherm constant – Kd – in reactive transport models, these reactions play a critical role in many environmental science applications; particularly in contamination risk assessments and nuclear waste disposal performance assessments. In the past several decades, efforts by various institutions across the world have focused on developing SCMs based on datasets from laboratory measurements, including the identification of key parameters such as equilibrium constants.

54 ENVIRONMENTAL SCIENCES↗

Cryogenic Carbon Monoxide Oxidation on Cuprous Oxide

Performing oxidation reactions at low temperatures using earth-abundant materials is crucial for advancing solutions for sustainable chemistry. CO oxidation serves as a benchmark reaction to characterize oxidation and to advance fundamental concepts in surface chemistry. While there are several examples of CO oxidation occurring on metal oxides at low temperatures, from 300 K to ∼200 K, reactivity in the cryogenic temperature regime typically requires a metal nanoparticle on a metal oxide. Here, we show oxygen atoms on the (111) facet of Cu 2 O react with CO to form CO 2 at temperatures below 100 K. Combining spectroscopic experimental evidence with calculations, we propose a low barrier path for CO oxidation at reconstructed surface sites on Cu 2 O(111). This finding is a rare example of an earth-abundant metal oxide, in this case copper, that can provide highly reactive multifunctional sites, enabling both adsorption and reaction fundamental steps toward the efficient heterogeneous oxidation of chemicals.

36 MATERIALS SCIENCE↗

Pistia stratiotes L. Biochar for Sorptive Removal of Aqueous Inorganic Nitrogen

Biochar has proven effective in the remediation of excess nitrogen from soil and water. Excess nitrogen from agricultural fields ends up in aquatic systems and leads to reduced water quality and the proliferation of invasive species. This study aimed to assess the efficiency of chemically surface-modified biochar produced from invasive Pistia stratiotes L. for the adsorption of inorganic nitrogen (NH4+ and NO3−). Biochar structure was investigated using scanning electron microscopy, energy-dispersive X-ray analysis, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, and inductively coupled plasma mass spectrometry. The results from adsorption experiments indicate that NH4+ removal was optimal (0.8–1.3 mg N g−1) at near-neutral pH levels (6.0–7.5), while NO3− removal was optimal (0.4–0.8 mg N g−1) under acidic pH conditions (4.8–6.5) using the modified biochar. These findings highlight the significance of solution pH, biochar morphology, and surface chemistry in influencing the adsorption of NH4+ and NO3−. However, further studies are necessary to assess the potential oxidative transformation of NH4+ to NO3− by biochar, which might have contributed to the reduction in NH4+ in the aqueous phase.

36 MATERIALS SCIENCE↗

Thermal Chemistry of Nickel Diketonate Atomic Layer Deposition (ALD) Precursors on Tantalum and Silicon Oxide Surfaces

The mechanism of the thermal conversion of both bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel(II) (Ni(TMHD) 2 ) and the protonated ligand (TMHD-H) adsorbed on TaO x and SiO 2 /TaO x surfaces was characterized under ultrahigh vacuum (UHV) by a combination of temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) experiments. In this work, A stepwise decomposition was observed with Ni(TMHD) 2 encompassing at least four different stages: (1) a ligand loss, to release TMHD-H; (2) a surprising ligand fractioning via the scission of an inner C–C bond within the central β-diketonate moiety to produce an aldehyde (pivaldehyde) and a ketone (pinacolone); (3) further ligand splitting following a more extensive cracking to yield an olefin (from dehydrogenation of the terminal tert-butyl group), carbon monoxide, and adsorbed methylene groups; and finally, (4) the loss of one oxygen atom from the remaining ligands to produce the corresponding enone. As these conversions take place, the Ni ion is reduced, first to a partially oxidized intermediate, as the first ligand is removed, and then to its metallic state as the remaining organic fragments migrate to the surface. A similar sequence was seen on both surfaces, but with the transitions taking place at higher temperatures on SiO 2 . The implications of these results to the surface chemistry of other ALD precursors and to the design of ALD processes are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Data for Rod et al., "Alternating salt and freshwater floods of coastal soils impact soil structure, hydraulic properties, and oxygen dynamics"

This dataset includes laboratory experiment data on soil structure, hydraulic properties, and oxygen dynamics associated with Rod et al. 2026 https://doi.org/10.1002/vzj2.70073. There are six data files from a lab-based flood simulation of either freshwater (FW) or alternating brackish saltwater (SW) and FW using soil cores from a coastal forest at the Smithsonian Environmental Research Center. For soil information please see the Location section of the metadata. Files include: CO2, surface chemistry, water retention, dissolved oxygen, and soil specific surface area. Each file is in CSV format and can be opened/read with any plain text tabular file reader (Microsoft Excel, R, etc.). Purpose of Experiment: To investigate how hydrologic intensification affects soil structure and oxygen dynamics, we conducted a series of laboratory-based flood simulations. After three SW-FW floods (6 floods total) there were significant changes in pore size distribution, significant redistribution of colloids, and the A-horizon became sodic. We concluded that a small number of SW flooding events can induce a measurable change in soil physical properties that directly impacts the biogeochemical dynamics.

54 ENVIRONMENTAL SCIENCES↗

Fundamental Studies of Soiling and Cementation of PV Cover Glass Materials: Addressing Reliability with Advanced X-ray Scattering/Spectroscopy and First Principles Modeling (Final Technical Report)

Accumulation of soils and other particulate matter on the front cover glass of solar photovoltaic (PV) modules results in transmission losses that detrimentally affect the power output of PV installations. The conventional solution to this problem is manual abrasive scrubbing of modules, which entails significant water usage and manpower. To further combat this issue, there is a concerted effort within the PV industry to develop anti-soiling (AS) coatings to mitigate power losses due to soiling of PV modules, which can exceed 35% in some cases. However, relatively little is known about the fundamental physical and chemical mechanisms that enable anti-soiling behavior. In this project, a combination of advanced X-ray analysis tools and first principles computational modeling has employed to understand the physical and chemical interactions between environmental soils and PV cover glass materials. The specific objectives were: 1) investigate soiling interactions and cementation behavior of relevant PV materials, including bare glass, conventional antireflective (AR) coatings, and a commercial AS coating, using a library of representative particulate soils, and 2) utilize first principles computational spectroscopy modeling to interpret the experimental X-ray spectroscopy measurements and determine the detailed surface chemistry changes that occur on these surfaces in the presence of soiling and cementation.

14 SOLAR ENERGY↗

Impacts of Biologically Induced Degradation on Surface Energy, Wettability, and Cohesion of Corn Stover

The impacts of biological degradation on surface area, surface energy, wettability, and cohesion of anatomically fractionated (i.e., leaf, stalk, and cob) and bulk corn stover are presented in this study. The physical, thermal and chemical properties of corn stover are critical material attributes that not only influence the mechanical processing and chemical conversion of corn stover, but also the bulk solids handling and transport. The measured surface areas were observed to be dependent on the degree of biological degradation (mild vs. moderate vs. severe) and on the anatomical fraction. The surface area of the bulk corn stover samples increased with the degree of biological degradation. The leaf fraction was the most sensitive to biological degradation, resulting in an increase in surface area from 0.5 m 2 /g (mildly degraded) to 1.2 m 2 /g (severely degraded). In contrast, the surface area of the cob fraction remained relatively unaffected by the degree of biological degradation (i.e., mildly degraded–0.55 m 2 /g, severely degraded–0.40 m 2 /g. All biologically degraded samples resulted in significant changes to the surface chemistry (evidenced by an increase in surface energy. As a general trend, the surface energy of bulk corn stover increased with the degree of biological degradation—the same trend was observed for the leaf and stalk anatomical fractions; however, the surface energy for the cob fraction remained unchanged. Wettability, calculated from surface energy, for bulk corn stover samples did not reveal any discernable trend with the degree of biological degradation. However, trends in wettability were observed for the anatomical fractions, with wettability increasing for the stalk and leaf fractions, and decreasing for the cob fraction. Excluding the cob fraction, the work of cohesion increased with the degree of biological degradation. Understanding the impacts of biological degradation on the physical, chemical and thermal properties of corn stover offers insights to improve the overall operational reliability, efficiency and economics of integrated biorefineries.

09 BIOMASS FUELS↗

Uranium particle age dating, aggregation, and model age best estimators

We present important aspects of uranium particle age dating by Large-Geometry Secondary Ion Mass Spectrometry (LG-SIMS) that can introduce bias and increase model age uncertainties, especially for small, young, and/or low-enriched particles. This metrology is important for applications related to International Nuclear Safeguards. We explore influential factors related to model age estimation, including the effects of evolving surface chemistry on inter-element measurements of particles (e.g., Th and U), detector background, and aggregation methods using simulated and actual particle samples. We introduce a new model age estimator, called “mid68”, that supplements 95% confidence intervals, providing a “best estimate” and uncertainty about the most likely age. The mid68 estimator can be calculated using the Feldman and Cousins method or Bayesian methods and provides a value with a symmetric uncertainty that can be used for calculations and approximate aggregation of processed model age values when the raw data and correction factors are not available. For particles yielding low 230 Th counts amidst nonzero detector background, their underlying model age probability distributions are asymmetric, so the mid68 estimator provides additional robust information regarding the underlying model age likelihood. This study provides a comprehensive and timely examination of critical aspects of uranium particle age dating as more laboratories establish particle chronometry capabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recrystallization suppression through dispersion-strengthening of tungsten

Tungsten is the material of choice for the divertor region of future nuclear fusion reactors, an environment that will expose plasma-facing components (e.g. divertor, etc...) to high temperatures and transient high heat flux events. Under these conditions, recrystallization and grain growth of tungsten can occur, leading to undesirable microstructural and mechanical property changes. Therefore, there is a need to raise the recrystallization temperature of tungsten and limit the kinetics of the recrystallization and grain growth processes. In this work, we examine the effect of different types (TiC vs. TaC vs. ZrC) and different concentrations (1.1 vs. 5 vs. 10 wt.%) of dispersed second phase particles in a tungsten matrix on the high temperature performance. Additionally, the addition of second-phase particles effectively increases the temperature of and time for recrystallization and slow grain growth; however, the addition of a high weight fraction of particles alters the surface chemistry, which may impact subsequent plasma-surface interactions. These results show that the addition of small concentrations of dispersed particles can be effectively employed in tungsten to raise the upper operating temperature limit for tungsten in a fusion reactor.

36 MATERIALS SCIENCE↗

Exploring New Diamond Surfaces with Precision Chemistry and Quantum Spectroscopy

Point defects in diamond known as color centers are a promising platform for quantum sensing. As atom-like systems, they can exhibit excellent spin coherence and can be manipulated with light. As solid-state defects, they can be produced at high densities and be incorporated into scalable devices. Diamond is a uniquely excellent host; it has a large band gap, can be synthesized with sub-ppb impurity concentrations, and can be isotopically purified to eliminate magnetic noise from nuclear spins. Specifically, the nitrogen vacancy (NV) center has been demonstrated to be a highly sensitive, non-invasive magnetic probe capable of resolving the magnetic field of a single electron spin with nanometer spatial resolution. However, the development of NV centers and other color centers in diamond as a quantum platform crucially relies on developing methods to functionalize and process diamond surfaces. Diamond is the hardest material, making polishing and processing challenging, and diamond surfaces are inert and sterically hindered, making them notoriously difficult to chemically terminate and functionalize. Our approach is to discover new surface chemistries for diamond by combining multimodal surface spectroscopy with NV-based quantum spectroscopy to carefully characterize the diamond surface. We have developed a suite of techniques for characterizing the diamond surface using rapid tools for reaction screening and detailed surface spectroscopy tools for definitive identification of the surface bonding.

36 MATERIALS SCIENCE↗

Dimolybdenum Paddlewheel Complexes with Cation Binding Sites as Electrolyte Additives to Manipulate the Solid-Electrolyte Interphase at Lithium Metal Anodes

The use of electrolyte additives at millimolar loadings to control the surface chemistry of lithium metal anodes (LMAs) is a leading strategy to improve lithium metal batteries and promote electrosynthetic reactions. Whereas previous studies employed either inorganic or organic additives, in this study, we report the first organometallic additive, Mo 2 (mea) 4 [1, mea = 2-(2-methoxyethoxy)acetate], a dimolybdenum paddlewheel complex that is stable under Li plating conditions and features cation binding sites in the second coordination sphere that promote reversible Li + coordination. Binding of Li + ions to 1 induces immobilization of cationically charged aggregates (or products thereof) into the solid electrolyte interphase (SEI), imparting multiple beneficial functions. The modified SEI was found to protect the LMA against parasitic side reactions, produce modest but measurable improvements to Li plating properties (e.g., overpotential, surface structure, and Coulombic efficiency), and improve interfacial charge transport properties. Furthermore, the most notable benefit to battery cycling performance appears in calendar aging tests, which show that the presence of the additive protects the LMA from parasitic side reactions that would otherwise decrease overall cell cycling efficiency over time. Collectively, these data disclose a tactic for designing electrolyte additives using principles of organometallic synthesis.

Additives↗

Molecular Origin of Wettability Alteration of Subsurface Porous Media upon Gas Pressure Variations

Upon extraction/injection of a large quantity of gas from/into a subsurface system in shale gas production or carbon sequestration, the gas pressure varies remarkably, which may significantly change the wettability of porous media involved. Mechanistic understanding of such changes is critical for designing and optimizing a related subsurface engineering process. Using molecular dynamics simulations, in this work we have calculated the contact angle of a water droplet on various solid surfaces (kerogen, pyrophyllite, calcite, gibbsite, and montmorillonite) as a function of CO 2 or CH 4 gas pressure up to 200 atm at a temperature of 300 K. The calculation reveals a complex behavior of surface wettability alteration by gas pressure variation depending on surface chemistry and structure, and molecular interactions of fluid molecules with surfaces. As the CO 2 gas pressure increases, a partially hydrophilic kerogen surface becomes highly hydrophobic, while a calcite surface becomes more hydrophilic. Considering kerogen and calcite being the major components of a shale formation, we postulate that the wettability alteration of a solid surface induced by a gas pressure change may play an important role in fluid flows in shale gas production and geological carbon sequestration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Supramolecular Effects of Alkyl Sulfonates in Silver Nanocrystal Synthesis

While cationic surfactants such as hexadecyltrimethylammonium bromide (CTAB) are ubiquitous in the synthesis of noble metal nanocrystals, anionic surfactants are rarely used. This work explores the addition of sodium alkyl sulfonates with chain lengths ranging from one to eight carbons to a silver nanoplatelet reaction. Short-chain sulfonates comprised of one to four carbons show little effect on the nanocrystal synthesis, but alkyl sulfonates comprised of five or more carbons at concentrations above 1 mM have a pronounced effect on the absorbance of the nanocrystals, causing a blueshift in the wavelength of maximum absorbance (λ max ) from approximately 800 to 400 nm as the sulfonate concentration is increased to 7 mM. Higher concentrations of sulfonate result in a subsequent red-shift of the peak. Investigation into the possible formation mechanisms responsible for this synthetic control revealed the absence of sulfonate micelles under the reaction conditions. Instead, we hypothesize that sulfonate bilayers are nucleated around the silver nanocrystals at concentrations below the critical micelle concentration and interact with either the citrate ligands or the silver surface to influence nanocrystal morphology, and thus absorbance. Strikingly, the addition of long-chain alkyl sulfonates to already-synthesized nanocrystals results in similar changes to the nanocrystal absorbance that occur within seconds, providing further support for the proposal that these effects are related to the surface chemistry of the nanocrystals, which appear to be highly dynamic.

alkyls↗

Ligand Locking on Quantum Dot Surfaces via a Mild Reactive Surface Treatment

At the outermost surface of colloidal QDs are organic surface ligands which dynamically bind and release in solution to control the growth kinetics, control the size/shape of the crystals, passivate surface states, and provide colloidal stability through favorable interactions with the solvent. However, the dynamicity comes at the expense of the stability of the QD suspension. Here, we show that ligands can be permanently locked on the QD surface by a thin layer of an inert metal oxide which forms within the ligand shell, over the headgroup. By interrogating the surface chemistry with different spectroscopic methods, we prove the ligand locking on the QD surface. As a result, an exceptional stability of the coated QD inks is achieved in a wide concentration range, even in the presence of chemically competing surface ligands in solution. We anticipate that this critical breakthrough will benefit different areas related to colloidal QDs, spanning from single-particle studies to displays and solar cells and biological applications. Furthermore, the same chemistry could be easily translated to surface treatments of bulk materials and thin films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗