Weathering influences the ice nucleation activity of microplastics.

Microplastics are being increasingly detected in the atmosphere at altitudes relevant to mixed-phase cloud formation. However, the extent to which microplastics, along with their dynamic surface properties resulting from environmental weathering, could influence atmospheric microphysical processes remains largely unexplored. Here, through a series of ice nucleation experiments and droplet freezing assays, we highlight the capability of model polyethylene microplastics to induce heterogeneous ice nucleation via immersion freezing under atmospherically relevant conditions.

Flow-gel approach enables rapid extraction of pure magnesium phase from seawater.

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 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.

A molecular view of peptoid-induced acceleration of calcite growth.

The extensive deposits of calcium carbonate (CaCO) generated by marine organisms constitute the largest and oldest carbon dioxide (CO) reservoir. These organisms utilize macromolecules like peptides and proteins to facilitate the nucleation and growth of carbonate minerals, serving as an effective method for CO sequestration. However, the precise mechanisms behind this process remain elusive.

Ion Correlations Decrease Particle Aggregation Rate by Increasing Hydration Forces at Interfaces.

The connection between solution structure, particle forces, and emergent phenomena at solid-liquid interfaces remains ambiguous. In this case study on boehmite aggregation, we established a connection between interfacial solution structure, emerging hydration forces between two approaching particles, and the resulting structure and kinetics of particle aggregation. In contrast to expectations from continuum-based theories, we observed a nonmonotonic dependence of the aggregation rate on the concentration of sodium chloride, nitrate, or nitrite, decreasing by 15-fold in 4 molal compared to 1 molal solutions.

Effect of Solvent Composition on Non-DLVO Forces and Oriented Attachment of Zinc Oxide Nanoparticles.

Oriented attachment (OA) occurs when nanoparticles in solution align their crystallographic axes prior to colliding and subsequently fuse into single crystals. Traditional colloidal theories such as DLVO provide a framework for evaluating OA but fail to capture key particle interactions due to the atomistic details of both the crystal structure and the interfacial solution structure. Using zinc oxide as a model system, we investigated the effect of the solvent on short-ranged and long-ranged particle interactions and the resulting OA mechanism.

Molecular Mechanisms of Sorbed Ion Effects during Boehmite Particle Aggregation.

Classical theories of particle aggregation, such as Derjaguin-Landau-Verwey-Overbeek (DLVO), do not explain recent observations of ion-specific effects or the complex concentration dependence for aggregation. Thus, here, we probe the molecular mechanisms by which selected alkali nitrate ions (Na, K, and NO) influence aggregation of the mineral boehmite (γ-AlOOH) nanoparticles. Nanoparticle aggregation was analyzed using classical molecular dynamics (CMD) simulations coupled with the metadynamics rare event approach for stoichiometric surface terminations of two boehmite crystal faces.

Effects of particle shape and surface roughness on van der Waals interactions and coupling to dynamics in nanocrystals.

The van der Waals interaction between colloids and nanoparticles is one of the key components to understanding particle aggregation, attachment, and assembly. While the ubiquity of anisotropic particle shapes and surface roughness is well-recognized in nanocrystalline materials, the effects of both on van der Waals forces and torques have not been adequately investigated. In this study, we develop a numerical scheme to determine the van der Waals forces and torques between cubic particles with multiple configurations and relative orientations.

Predicting Outcomes of Nanoparticle Attachment by Connecting Atomistic, Interfacial, Particle, and Aggregate Scales.

Predicting nanoparticle aggregation and attachment phenomena requires a rigorous understanding of the interplay among crystal structure, particle morphology, surface chemistry, solution conditions, and interparticle forces, yet no comprehensive picture exists. We used an integrated suite of experimental, theoretical, and simulation methods to resolve the effect of solution pH on the aggregation of boehmite nanoplatelets, a case study with important implications for the environmental management of legacy nuclear waste. Real-time observations showed that the particles attach preferentially along the (010) planes at pH 8.

Understanding the mechanisms of anisotropic dissolution in metal oxides by applying radiolysis simulations to liquid-phase TEM.

Iron-based redox-active minerals are ubiquitous in soils, sediments, and aquatic systems. Their dissolution is of great importance for microbial impacts on carbon cycling and the biogeochemistry of the lithosphere and hydrosphere. Despite its widespread significance and extensive prior study, the atomic-to-nanoscale mechanisms of dissolution remain poorly understood, particularly the interplay between acidic and reductive processes.

Discrete Orientations of Interfacial Waters Direct Crystallization of Mica-Binding Proteins.

Understanding the basis of templated molecular assembly on a solid surface requires a fundamental comprehension of both short- and long-range aqueous response to the surface under a variety of solution conditions. Herein we provide a detailed picture of how the molecular-scale response to different mica surfaces yields distinct solvent orientations that produce quasi-static directional potentials onto which macromolecules can adsorb. We connect this directionality to observed (a)symmetric epitaxial alignment of designed proteins onto these surfaces, corroborate our findings with 3D atomic force microscopy experiments, and identify slight differences in surface structure as the origin of this effect.

Spiers Memorial Lecture: Assembly-based pathways of crystallization.

Solution crystallization of materials ranging from simple salts to complex supramolecular assemblies has long been viewed through the lens of classical nucleation and growth theories in which monomeric building blocks assemble into ordered structures through inherent thermal fluctuations that overcome a free energy barrier and continue to grow by the addition of such units to atomic steps. However, recent observations have revealed a rich set of hierarchical pathways during both nucleation and growth involving species of a higher order than monomers. While many studies have investigated and deduced the mechanisms underlying hierarchical nucleation pathways, much less research has been directed towards the development of a mechanistic picture of growth by the assembly of more complex units.

In situ imaging of amorphous intermediates during brucite carbonation in supercritical CO.

Progress in understanding crystallization pathways depends on the ability to unravel relationships between intermediates and final crystalline products at the nanoscale, which is a particular challenge at elevated pressure and temperature. Here we exploit a high-pressure atomic force microscope to directly visualize brucite carbonation in water-bearing supercritical carbon dioxide (scCO) at 90 bar and 50 °C. On introduction of water-saturated scCO, in situ visualization revealed initial dissolution followed by nanoparticle nucleation consistent with amorphous magnesium carbonate (AMC) on the surface.

Visualizing Solution Structure at Solid-Liquid Interfaces using Three-Dimensional Fast Force Mapping.

Amongst the challenges for a variety of research fields are the visualization of solid-liquid interfaces and understanding how they are affected by the solution conditions such as ion concentrations, pH, ligands, and trace additives, as well as the underlying crystallography and chemistry. In this context, three-dimensional fast force mapping (3D FFM) has emerged as a promising tool for investigating solution structure at interfaces. This capability is based on atomic force microscopy (AFM) and allows the direct visualization of interfacial regions in three spatial dimensions with sub-nanometer resolution.

Using Atom Dynamics to Map the Defect Structure Around an Impurity in Nano-Hematite.

The bulk behavior of materials is often controlled by minor impurities that create nonperiodic localized defect structures due to ionic size, symmetry, and charge balance mismatches. Here, we used transmission electron microscopy (TEM) of atom-resolved dynamics to directly map the topology of Fe vacancy clusters surrounding structurally incorporated U in nanohematite (α-FeO). Ab initio molecular dynamic simulations provided additional independent constraints on coupled U, Fe, and vacancy mobility in the solid.

Correlating inter-particle forces and particle shape to shear-induced aggregation/fragmentation and rheology for dilute anisotropic particle suspensions: A complementary study via capillary rheometry and in-situ small and ultra-small angle X-ray scattering.

Hypothesis: Understanding the stability and rheological behavior of suspensions composed of anisotropic particles is challenging due to the complex interplay of hydrodynamic and colloidal forces. We propose that orientationally-dependent interactions resulting from the anisotropic nature of non-spherical sub-units strongly influences shear-induced particle aggregation/fragmentation and suspension rheological behavior.

Experiments: Wide-, small-, and ultra-small-angle X-ray scattering experiments were used to simultaneously monitor changes in size and fractal dimensions of boehmite aggregates from 6 to 10,000 Å as the sample was recirculated through an in-situ capillary rheometer.

Connecting energetics to dynamics in particle growth by oriented attachment using real-time observations.

The interplay between crystal and solvent structure, interparticle forces and ensemble particle response dynamics governs the process of crystallization by oriented attachment (OA), yet a quantitative understanding is lacking. Using ZnO as a model system, we combine in situ TEM observations of single particle and ensemble assembly dynamics with simulations of interparticle forces and responses to relate experimentally derived interparticle potentials to the underlying interactions. We show that OA is driven by forces and torques due to a combination of electrostatic ion-solvent correlations and dipolar interactions that act at separations well beyond 5 nm.

Oriented attachment induces fivefold twins by forming and decomposing high-energy grain boundaries.

Natural and synthetic nanoparticles composed of fivefold twinned crystal domains have distinct properties. The formation mechanism of these fivefold twinned nanoparticles is poorly understood. We used in situ high-resolution transmission electron microscopy combined with molecular dynamics simulations to demonstrate that fivefold twinning occurs through repeated oriented attachment of ~3-nanometer gold, platinum, and palladium nanoparticles.

Revisiting the Growth Mechanism of Hierarchical Semiconductor Nanostructures: The Role of Secondary Nucleation in Branch Formation.

Although there have been advances in synthesizing hierarchical semiconductor materials,  few studies have investigated the fundamental nucleation mechanisms to explain the origins of such complex structures. Resolving these nucleation and growth pathways is technically challenging but  critical for developing predictive synthetic capabilities for the synthesis and application of new materials. In this Letter, we use state-of-the-art liquid phase scanning electron microscopy (SEM) and high-resolution transmission electron microscopy in a combination with classical density functional theory (cDFT) to study the nucleation of highly branched wurtzite ZnO nanostructures via a facile, room-temperature aqueous synthesis route.

Connecting wettability, topography, and chemistry in a simple lipid-montmorillonite system.

Hypothesis: While soil water repellency causes a variety of undesirable environmental effects, the underlying mechanism is unknown. We investigate the coupled effects of chemical characteristics and surface topology in a simple model system of two lipids, DSPE (1,2-distearoyl-sn-glycero-3-phosphoethanolamine) and DOPE (1,2-dioleoyl-sn-glycero-3-phosphoethanolamine), and a clay substrate. These closely-related lipids allowed the study of how a small change in chemical structure influences the surface hydrophobicity.

Interplay between Short- and Long-Ranged Forces Leading to the Formation of Ag Nanoparticle Superlattice.

Nanoparticle (NP) superlattices have attracted increasing attention due to their unique physicochemical properties. However, key questions persist regarding the correlation between short- and long-range driving forces for nanoparticle assembly and resultant capability to predict the transient and final superlattice structure. Here the self-assembly of Ag NPs in aqueous solutions is investigated by employing in situ liquid cell transmission electron microscopy, combined with atomic force microscopy-based force measurements, and theoretical calculations.

Mechanistic Understanding of the Growth Kinetics and Dynamics of Nanoparticle Superlattices by Coupling Interparticle Forces from Real-Time Measurements.

Superlattice structures formed by nanoparticle (NP) self-assembly have attracted increasing attention due to their potential as a class of nanomaterials with enhanced physicochemical properties tailored by the assembly structure. However, many key questions remain regarding the correlation between the dynamics of individual NPs and emerging superlattice patterns. Here we investigated the self-assembly of gold NPs by employing in situ transmission electron microscopy equipped with direct detection camera capabilities, which enabled us to track the rapid motion of individual nanoparticles in real time.

Impact of Solution Chemistry and Particle Anisotropy on the Collective Dynamics of Oriented Aggregation.

Although oriented aggregation of particles is a widely recognized mechanism of crystal growth, the impact of many fundamental parameters, such as crystallographically distinct interfacial structures, solution composition, and nanoparticle morphology, on the governing mechanisms and assembly kinetics are largely unexplored. Thus, the collective dynamics of systems exhibiting OA has not been predicted. In this context, we investigated the structure and dynamics of boehmite aggregation as a function of solution pH and ionic strength.

Near surface nucleation and particle mediated growth of colloidal Au nanocrystals.

During non-classical growth of nanostructures via assembly of primary nuclei, nucleation and assembly are assumed to be distinct processes: nanoparticles nucleate randomly and aggregate to form extended structures through Brownian motion in the presence of long-range attractive interactions. Here we investigate the relationship between these two processes by using in situ AFM, in situ, ex situ and cryo TEM and UV-Vis spectroscopy to observe growth of colloidal gold and simulations to develop a mechanistic model of the process. Our results reveal an inexorable link between nucleation and assembly with nuclei forming almost exclusively within a ∼1 nm interfacial region of existing particles.

Polyelectrolyte complex films influence the formation of polycrystalline micro-structures.

Silica-carbonate biomorphs are inorganic materials composed of thousands of crystalline nanorods that assemble complex morphologies such as helices, vessels, and sheets. We investigate the effect on biomorph crystallization of polyelectrolyte complex films that are prepared using the layer-by-layer deposition technique and post-processed to obtain three stable, chemically distinct films. Biomorph growth on poly(diallyldimethylammonium)-dominated substrates (cationic) shows polycrystalline helical and sheet structures bounded by large witherite prisms.

Biomimetic mineral self-organization from silica-rich spring waters.

Purely inorganic reactions of silica, metal carbonates, and metal hydroxides can produce self-organized complex structures that mimic the texture of biominerals, the morphology of primitive organisms, and that catalyze prebiotic reactions. To date, these fascinating structures have only been synthesized using model solutions. We report that mineral self-assembly can be also obtained from natural alkaline silica-rich water deriving from serpentinization.