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Electron microscopy touches on nearly every aspect of modern life, underpinning materials development for quantum computing, energy and medicine. We discuss the open, highly integrated and data-driven microscopy architecture needed to realize transformative discoveries in the coming decade.

Crystals grow in a number a ways, including pathways involving the assembly of other particles and multi-ion complexes. De Yoreo et al. review the mounting evidence for these nonclassical pathways from new observational and computational techniques, and the thermodynamic basis for these growth mechanisms. Developing predictive models for these crystal growth and nucleation pathways will improve materials synthesis strategies. These approaches will also improve fundamental understanding of natural processes such as biomineralization and trace element cycling in aquatic ecosystems. Science , this issue 10.1126/science.aaa6760 Materials nucleate and grow by the assembly of small particles and multi-ion complexes. Field and laboratory observations show that crystals commonly form by the addition and attachment of particles that range from multi-ion complexes to fully formed nanoparticles. The particles involved in these nonclassical pathways to crystallization are diverse, in contrast to classical models that consider only the addition of monomeric chemical species. We review progress toward understanding crystal growth by particle-attachment processes and show that multiple pathways result from the interplay of free-energy landscapes and reaction dynamics. Much remains unknown about the fundamental aspects, particularly the relationships between solution structure, interfacial forces, and particle motion. Developing a predictive description that connects molecular details to ensemble behavior will require revisiting long-standing interpretations of crystal formation in synthetic systems, biominerals, and patterns of mineralization in natural environments.

Minerals are more complex than previously thought because of the discovery that their chemical properties vary as a function of particle size when smaller, in at least one dimension, than a few nanometers, to perhaps as much as several tens of nanometers. These variations are most likely due, at least in part, to differences in surface and near-surface atomic structure, as well as crystal shape and surface topography as a function of size in this smallest of size regimes. It has now been established that these variations may make a difference in important geochemical and biogeochemical reactions and kinetics. This recognition is broadening and enriching our view of how minerals influence the hydrosphere, pedosphere, biosphere, and atmosphere.

Shaped zeolite nanocrystals and larger zeolite particles with three-dimensionally ordered mesoporous (3DOm) features hold exciting technological implications for manufacturing thin, oriented molecular sieve films and realizing new selective, molecularly accessible and robust catalysts. A recognized means for controlled synthesis of such nanoparticulate and imprinted materials revolves around templating approaches, yet identification of an appropriately versatile template has remained elusive. Because of their highly interconnected pore space, ordered mesoporous carbon replicas serve as conceptually attractive materials for carrying out confined synthesis of zeolite crystals. Here, we demonstrate how a wide range of crystal morphologies can be realized through such confined growth within 3DOm carbon, synthesized by replication of colloidal crystals composed of size-tunable (about 10–40 nm) silica nanoparticles. Confined crystal growth within these templates leads to size-tunable, uniformly shaped silicalite-1 nanocrystals as well as 3DOm-imprinted single-crystal zeolite particles. In addition, novel crystal morphologies, consisting of faceted crystal outgrowths from primary crystalline particles have been discovered, providing new insight into constricted crystal growth mechanisms underlying confined synthesis. Zeolite nanocrystals with three-dimensionally ordered mesoporous structures are important for designing molecularly accessible and selective catalysts. With a single zeolite synthesis procedure, uniform nanocrystals and crystal zeolites with ordered imprinted mesoporosity can now be obtained.

Crystals are generally considered to grow by attachment of ions to inorganic surfaces or organic templates. High-resolution transmission electron microscopy of biomineralization products of iron-oxidizing bacteria revealed an alternative coarsening mechanism in which adjacent 2- to 3-nanometer particles aggregate and rotate so their structures adopt parallel orientations in three dimensions. Crystal growth is accomplished by eliminating water molecules at interfaces and forming iron-oxygen bonds. Self-assembly occurs at multiple sites, leading to a coarser, polycrystalline material. Point defects (from surface-adsorbed impurities), dislocations, and slabs of structurally distinct material are created as a consequence of this growth mechanism and can dramatically impact subsequent reactivity.

The iron (oxyhydr)oxides hematite (α-Fe2O3) and goethite (α-FeOOH) are natural and reactive minerals common in soils and sediments, and their adsorption of Fe(II) produces reactive surface sites that facilitate reduction of oxidized environmental pollutants. Single-exposure experiments with 4-chloronitrobenzene showed that hematite is more reactive than goethite, when normalized by surface area loading. Interestingly, the product of Fe(II) oxidation is a mixture of goethite and hematite, and the goethite to hematite ratio depends on the distribution of Fe(II) activated surface sites, which is a function of aqueous Fe(II) concentration, surface area loading, and pH. More goethite is produced under conditions of higher Fe(II), lower surface area loading, and higher pH. Recurrent-exposure experiments showed a substantial decrease in reaction rate after one to three exposures, a trend suggestive of reaction contributions from the increasing goethite surface area over time. Using known atomic surface geometry for goethite and hematite, the hematite {012} facet is proposed as the site of primary mineral growth with goethite {021} at the interface between the two minerals. These results have implications in contaminant fate modeling, where the mineral phases present in the environment, the minerals likely to form, and the surrounding aqueous conditions all have an impact on contaminant reaction rate.

Dislocations are common defects in solids, yet all crystals begin as dislocation-free nuclei. The mechanisms by which dislocations form during early growth are poorly understood. When nanocrystalline materials grow by oriented attachment at crystallographically specific surfaces and there is a small misorientation at the interface, dislocations result. Spiral growth at two or more closely spaced screw dislocations provides a mechanism for generating complex polytypic and polymorphic structures. These results are of fundamental importance to understanding crystal growth.

Precursor nanoparticles that form spontaneously on hydrolysis of tetraethylorthosilicate in aqueous solutions of tetrapropylammonium (TPA) hydroxide evolve to TPA-silicalite-1, a molecular-sieve crystal that serves as a model for the self-assembly of porous inorganic materials in the presence of organic structure-directing agents. The structure and role of these nanoparticles are of practical significance for the fabrication of hierarchically ordered porous materials and molecular-sieve films, but still remain elusive. Here we show experimental findings of nanoparticle and crystal evolution during room-temperature ageing of the aqueous suspensions that suggest growth by aggregation of nanoparticles. A kinetic mechanism suggests that the precursor nanoparticle population is distributed, and that the 5-nm building units contributing most to aggregation only exist as an intermediate small fraction. The proposed oriented-aggregation mechanism should lead to strategies for isolating or enhancing the concentration of crystal-like nanoparticles.

Ferrihydrite is an important iron oxyhydroxide for earth and environmental sciences, biology, and technology. Nevertheless, its mineral structure remains a matter of debate. The stumbling block is whether a significant amount of tetrahedrally coordinated iron is present. Here we present the first X‐ray magnetic circular dichroïsm (XMCD) measurements performed on a well characterized synthetic sample of 6‐line ferrihydrite, at both K and L2,3energy edges of iron. XMCD results demonstrate unambiguously the presence of tetrahedrally coordinated Fe(III) in the mineral structure, in quantities compatible with the latest extended X‐ray absorption fine structure (EXAFS) analyses suggesting a concentration of 20–30%. Moreover, we find an antiferromagnetic coupling between tetrahedral and octahedral sublattices, with the octahedral sublattice parallel to the external magnetic field. Key Points Significant tetrahedral Fe(III) in the structure of ferrihydrite shown by XMCD

Porous metals represent a class of materials where the interplay of ligament length, width, node structure, and local geometry/curvature offers a rich parameter space for the study of critical length scales on mechanical behavior. Colloidal crystal templating of three-dimensionally ordered macroporous (3DOM, i.e., inverse opal) tungsten provides a unique structure to investigate the mechanical behavior at small length scales across the brittle–ductile transition. Micropillar compression tests show failure at 50 MPa contact pressure at 30 °C, implying a ligament yield strength of approximately 6.1 GPa for a structure with 5% relative density. In situ SEM frustum indentation tests with in-plane strain maps perpendicular to loading indicate local compressive strains of approximately 2% at failure at 30 °C. Increased sustained contact pressure is observed at 225 °C, although large (20%) nonlocal strains appear at 125 °C. The elevated-temperature mechanical performance is limited by cracks that initiate on planes of greatest shear under the indenter.