Understanding classical and nonclassical mechanisms of crystal nucleation and growth at the atomic scale is of great interest to scientists in many disciplines. However, fulfilling direct atomic‐scale observation still poses a significant challenge. Here, by taking a thin amorphous bismuth (Bi) metal nanosheet as a model system, direct atomic resolution of the crystal nucleation and growth initiated from an amorphous state of Bi metal under electron beam inside an aberration‐corrected transmission electron microscope is provided. It is shown that the crystal nucleation and growth in the phase transformation of Bi metal from amorphous to crystalline structure takes place via the particle‐mediated nonclassical mechanism instead of the classical atom‐mediated mechanism. The dimension of the smaller particles in two contacted nanoparticles and their mutual orientation relationship are critical to governing several coalescence pathways: total rearrangement pathway, grain boundary migration‐dominated pathway, and surface migration‐dominated pathway. Sequential strain analyses imply that migration of the grain boundary is driven by the strain difference in two Bi nanocrystals and the coalescence of nanocrystals is a defect reduction process. The findings may provide useful information to clarify the nanocrystal growth mechanisms of other materials on the atomic scale.

The chemistry of high-performance magnetic resonance imaging contrast agents remains an active area of research. In this work, we demonstrate that the potassium permanganate-based oxidative chemical procedures used to synthesize graphite oxide or graphene nanoparticles leads to the confinement (intercalation) of trace amounts of Mn2+ ions between the graphene sheets, and that these manganese intercalated graphitic and graphene structures show disparate structural, chemical and magnetic properties, and high relaxivity (up to 2 order) and distinctly different nuclear magnetic resonance dispersion profiles compared to paramagnetic chelate compounds. The results taken together with other published reports on confinement of paramagnetic metal ions within single-walled carbon nanotubes (a rolled up graphene sheet) show that confinement (encapsulation or intercalation) of paramagnetic metal ions within graphene sheets, and not the size, shape or architecture of the graphitic carbon particles is the key determinant for increasing relaxivity, and thus, identifies nano confinement of paramagnetic ions as novel general strategy to develop paramagnetic metal-ion graphitic-carbon complexes as high relaxivity MRI contrast agents.

Capping ligand bonding and the thermal and colloidal stability of Cs 2 AgBiBr 6 nanocrystals were studied. Oleylamine and oleic acid bonding to Cs 2 AgBiBr 6 nanocrystals was studied with 1 H nuclear magnetic resonance and nuclear Overhauser effect spectroscopy. Both molecules are present in the ionic metathesis synthesis reaction, but only oleylamine remains bound to the nanocrystals after purification. Oleic acid is not a capping ligand; however, the synthesis requires it, and its concentration determines the yield of the reaction while oleylamine primarily affects the uniformity of the sample. Substitution of oleic acid in the reaction with diisooctylphosphinic acid still yielded nanocrystals with similar size, cuboidal shape, uniformity, cubic double-perovskite crystal structure, and optical properties. Nanocrystals were assembled into superlattices and heated in air. Grazing incidence smallangle and wide-angle X-ray scattering showed that the nanocrystals sinter at 250 °C, but the crystal structure and preferred crystal orientation on the substrate does not change. When nanocrystals were dispersed in hexane and exposed to light, they precipitated within 24 h. Scanning electron microscopy showed that the aggregated nanocrystals still retained their initial size and shape and had not coalesced.

The packing of spheres is a subject that has drawn the attention of mathematicians and philosophers for centuries, and that currently attracts the interest of the scientific community in several fields. At the nanoscale, the packing of atoms affect the chemical and structural properties of the material, and hence, its potential applications. This report describes the experimental formation of five-fold nanostructures by the packing of interpenetrated icosahedral and decahedral units. These nanowires, formed by the reaction of a mixture of metal salts (Au and Ag) in the presence of oleylamine, are obtained when the chemical composition is specifically Ag/Au=3/1. The experimental images of the icosahedral nanowires have a high likelihood with simulated electron micrographs of structures formed by two or three Boerdijk-Coxeter-Bernal helices roped on a single structure, whereas for the decahedral wires, simulations using a model of adjacent decahedra match the experimental structures. To our knowledge, this is the first report of the synthesis of nanowires formed by the packing of structures with five-fold symmetry. These icosahedral nanowire structures remind those of quasicrystals that can only be formed if at least two atomic species are present and in which icosahedral and decahedral packing has been found for bulk crystals.

Nucleation and growth are critical steps in crystallization, which plays an important role in determining crystal structure, size, morphology, and purity. Therefore, understanding the mechanisms of nucleation and growth is crucial to realize the controllable fabrication of crystalline products with desired and reproducible properties. Based on classical models, the initial crystal nucleus is formed by the spontaneous aggregation of ions, atoms, or molecules, and crystal growth is dependent on the monomer’s diffusion and the surface reaction. Recently, numerous in situ investigations on crystallization dynamics have uncovered the existence of nonclassical mechanisms. This review provides a summary and highlights the in situ studies of crystal nucleation and growth, with a particular emphasis on the state-of-the-art research progress since the year 2016, and includes technological advances, atomic-scale observations, substrate- and temperature-dependent nucleation and growth, and the progress achieved in the various materials: metals, alloys, metallic compounds, colloids, and proteins. Finally, the forthcoming opportunities and challenges in this fascinating field are discussed.