Search

Understanding the early stages of interactions between oxygen and material surfaces—especially at very high spatial resolutions—is highly beneficial for fields ranging from materials degradation, corrosion, geological sciences, forensics, and catalysis. The ability of in situ atom probe tomography (APT) is demonstrated to track the diffusion of oxygen and metal ions at nanoscale spatial resolution during the early stages of oxidation of a model Fe–Cr–Ni alloy. Using 18O isotope tracers in these in situ APT experiments and complementary ex situ multimodal microscopy, spectroscopy, and computational simulations allows to precisely analyze the kinetics of oxidation and determine that outward cation diffusion to oxide/air interface is the primary mechanism for intragranular oxide growth in this alloy at 300 °C. This unique in situ isotopic tracer APT approach and the insights gained can be highly beneficial for studying early stages of gas–surface reactions in a broad array of materials.

Many important chemical processes involve reactivity and dynamics in complex solutions. Gaining a fundamental understanding of these reaction mechanisms is a challenging goal that requires advanced computational and experimental approaches. However, important techniques such as molecular simulation have limitations in terms of scales of time, length, and system complexity. Furthermore, among the currently available solvation models, there are very few designed to describe the interaction between the molecular scale and the mesoscale. To help address this challenge, here, we establish a novel hybrid approach that couples first-principles plane-wave density functional theory with classical density functional theory (cDFT). In this approach, a region of interest described by ab initio molecular dynamics (AIMD) interacts with the surrounding medium described using cDFT to arrive at a self-consistent ground state. cDFT is a robust but efficient mesoscopic approach to accurate thermodynamics of bulk electrolyte solutions over a wide concentration range (up to 2M concentrations). Benchmarking against commonly used continuum models of solvation, such as SMD, as well as experiments, demonstrates that our hybrid AIMD–cDFT method is able to produce reasonable solvation energies for a variety of molecules and ions. With this model, we also examined the solvent effects on a prototype SN2 reaction of the nucleophilic attack of a chloride ion on methyl chloride in the solution. The resulting reaction pathway profile and the solution phase barrier agree well with experiment, showing that our AIMD/cDFT hybrid approach can provide insight into the specific role of the solvent on the reaction coordinate. [ABSTRACT FROM AUTHOR]

Efficient removal of heterocyclic organosulfur compounds from fuels can relieve increasingly serious environmental problems (e.g., gas exhaust contaminants triggering the formation of acid rain that can damage fragile ecological systems). Toward this end, novel metal-organic frameworks (MOFs)-based sorbent materials are designed and synthesized with distinct hard and soft metal building units, specifically {[Yb6Cu12(OH)4(PyC)12(H2O)36]·(NO3)14·xS} n (QUST-81) and {[Yb4O(H2O)4Cu8(OH)8/3(PyC)8(HCOO)4]·(NO3)10/3·xS} n (QUST-82), where H2PyC = 4-Pyrazolecarboxylic acid. Exploiting the hard/soft duality, it is shown that the more stable QUST-82 can preserve desulfurization efficiency in the presence of competing nitrogen-containing contaminate. In addition, thermodynamically controlled single-crystal-to-single-crystal (SC-SC) phase transition is uncovered from QUST-81 to QUST-82, and in turn, mechanistic features are probed via X-ray diffraction, inductively coupled plasma atomic emission spectroscopy, and ab initio molecular dynamics simulations.

Current methods for separating critical materials from feedstock solutions remain chemistry- and energy-intensive. We demonstrate the rapid extraction of a pure magnesium phase from seawater via precipitation with sodium hydroxide in a flow-gel device. Our approach is scalable, suitable for high-throughput extraction, and does not rely on specialty chemicals. [ABSTRACT FROM AUTHOR]

Crystallization by particle attachment (CPA) is a frequently occurring mechanism of colloidal crystallization that results in hierarchical morphologies.sup.1-4. CPA has been exploited to create nanomaterials with unusual properties.sup.4-6 and is implicated in the development of complex mineral textures.sup.1,7. Oriented attachment.sup.7,8--a form of CPA in which particles align along specific crystallographic directions--produces mesocrystals that diffract as single crystals do, although the constituent particles are still discernible.sup.2,9. The conventional view of CPA is that nucleation provides a supply of particles that aggregate via Brownian motion biased by attractive interparticle potentials.sup.1,9-12. However, mesocrystals often exhibit regular morphologies and uniform sizes. Although many crystal systems form mesocrystals.sup.1-9 and individual attachment events have been directly visualized.sup.10, how random attachment events lead to well defined, self-similar morphologies remains unknown, as does the role of surface-bound ligands, which are ubiquitous in nanoparticle systems.sup.3,9,11. Attempts to understand mesocrystal formation are further complicated in many systems by the presence of precursor nanoparticles with a phase distinct from that of the bulk.sup.1,13,14. Some studies propose that such particles convert before attachment.sup.15, whereas others attribute conversion to the attachment process itself.sup.16 and yet others conclude that transformation occurs after the mesocrystals exceed a characteristic size.sup.14,17. Here we investigate mesocrystal formation by iron oxides, which are important colloidal phases in natural environments.sup.18,19 and classic examples of systems forming ubiquitous precursor phases and undergoing CPA accompanied by phase transformations.sup.15,19-21. Combining in situ transmission electron microscopy (TEM) at 80 degrees Celsius with 'freeze-and-look' TEM, we tracked the formation of haematite (Hm) mesocrystals in the presence of oxalate (Ox), which is abundant in soils, where iron oxides are common. We find that isolated Hm particles rarely appear, but once formed, interfacial gradients at the Ox-covered surfaces drive Hm particles to nucleate repeatedly about two nanometres from the surfaces, to which they then attach, thereby generating mesocrystals. Comparison to natural and synthetic systems suggests that interface-driven pathways are widespread. Mesocrystal formation is investigated for haematite in the presence of oxalate, showing that chemical gradients at interfaces cause nucleation near surfaces rather than in the bulk, followed by particle attachment., Author(s): Guomin Zhu [sup.1] [sup.2] , Maria L. Sushko [sup.1] , John S. Loring [sup.1] , Benjamin A. Legg [sup.1] [sup.2] , Miao Song [sup.1] , Jennifer A. Soltis [sup.1] [...]

Two‐dimensional (2D) conductive metal‐organic frameworks (MOF) represent a unique class of electrode materials with high capacity and power density. Understanding molecular mechanisms and pathways for heterogeneous nucleation of 2D π‐conjugated MOFs is highly desirable for controlling the structure and properties of conductive MOFs on solid substrates. Herein, a systematic study of nucleation and growth of 2D π‐conjugated Ni‐catecholate (Ni‐CAT‐1) MOFs on highly oriented pyrolytic graphite (HOPG) and copper substrates is reported. It is discovered that the nucleation density and growth kinetics of the MOF film can be controlled by varying substrate interactions with the organic linker. Specifically, π–π interactions between the linker and the HOPG dictate lower nucleation density, whereas π–metal interactions between the linker and the copper substrate dictate faster nucleation and higher nucleation densities. These studies reveal the key mechanism for Ni‐CAT‐1 nucleation on different surfaces and provide insights into interfacial control over the growth of other 2D π‐conjugated MOF films on solid substrates to inform synthesis of functional materials. [ABSTRACT FROM AUTHOR]

The self-assembled monolayers (SAMs) on the gold surface are analyzed for their structures based on the electrostatic interactions influencing the degree of disorder in carboxyl-terminated SAMs. The findings suggest that the presence of dipole moments influences the structure of the corresponding alkanethiol monolayer.

The adsorption of a number of organic molecules consisting of methyl, benzyl and carboxylic groups on the rutile TiO2 (110) surface is studied by using both ab initio and atomistic simulation techniques. The applicability of a simple embedded cluster model is tested to study the adsorption of small organic molecules at the rutile TiO2 (110) surface and this model is used to develop a classical force field for the interactions of a wide class of organic molecules consisting of these groups with the rutile TiO2 (110) surface.

Understanding the mechanism of particle-based crystallization is a formidable problem due to the complexity of macroscopic and interfacial forces driving particle dynamics. The oriented attachment (OA) pathway presents a particularly challenging phenomenon because it occurs only under select conditions and involves a precise crystallographic alignment of particle faces often from distances of several nanometers. Despite the progress made in recent years in understanding the driving forces for particle face selectivity and alignment, questions about the competition between ion-by-ion crystallization, near-surface nucleation, and OA remain. This study examines hydrothermal conditions leading to apparent OA for hematite using three initial particle morphologies with various exposed faces. All three particle types formed single-crystal or twinned one-dimensional (1D) chain-like structures along the [001] direction driven by the attractive interactions between (001) faces and repulsive interactions between other pairs of hematite faces. Moreover, simulations of the potential of mean force for iron species and scanning transmission electron microscopy (S/TEM) imaging confirm that the formation of 1D chains is a result of the attachment of independently nucleated particles and does not follow the near-surface nucleation or ion-by-ion crystallization pathways. These results highlight that strong face specificity along one crystallographic direction can render OA to be independent of initial particle morphology. [ABSTRACT FROM AUTHOR]

High temperature intergranular oxidation and corrosion of metal alloys is one of the primary causes of materials degradation in nuclear systems. In order to gain insights into grain boundary oxidation processes, a mesoscale metal alloy oxidation model is established by combining quantum Density Functional Theory (DFT) and mesoscopic Poisson-Nernst-Planck/classical DFT with predictions focused on Ni alloyed with either Cr or Al. Analysis of species and fluxes at steady-state conditions indicates that the oxidation process involves vacancy-mediated transport of Ni and the minor alloying element to the oxidation front and the formation of stable metal oxides. The simulations further demonstrate that the mechanism of oxidation for Ni-5Cr and Ni-4Al is qualitatively different. Intergranular oxidation of Ni-5Cr involves the selective oxidation of the minor element and not matrix Ni, due to slower diffusion of Ni relative to Cr in the alloy and due to the significantly smaller energy gain upon the formation of nickel oxide compared to that of Cr2O3. This essentially one-component oxidation process results in continuous oxide formation and a monotonic Cr vacancy distribution ahead of the oxidation front, peaking at alloy/oxide interface. In contrast, Ni and Al are both oxidized in Ni-4Al forming a mixed spinel NiAl2O4. Different diffusivities of Ni and Al give rise to a complex elemental distribution in the vicinity of the oxidation front. Slower diffusing Ni accumulates in the oxide and metal within 3 nm of the interface, while Al penetrates deeper into the oxide phase. Ni and Al are both depleted from the region 3-10 nm ahead of the oxidation front creating voids. The oxide microstructure is also different. Cr2O3 has a plate-like structure with 1.2-1.7 nm wide pores running along the grain boundary, while NiAl2O4 has 1.5 nm wide pores in the direction parallel to the grain boundary and 0.6 nm pores in the perpendicular direction providing an additional pathway for oxygen diffusion through the oxide. The proposed theoretical methodology provides a framework for modeling metal alloy oxidation processes from first principles and on the experimentally relevant length scales. [ABSTRACT FROM AUTHOR]