In situ study of Au nanoparticle formation in a mechanochemical-aging-based method.

As we strive to perform chemical transformations in a more sustainable fashion, enabling solid-state reactions through mechanochemistry has emerged as a highly successful approach. Due to the wide-ranging applications of gold nanoparticles (AuNPs), mechanochemical strategies have already been employed for their synthesis. However, the underlying processes surrounding gold salt reduction, nucleation and growth of AuNPs in the solid state are yet to be understood. Here, we present a mechanically activated aging synthesis of AuNPs, through a solid-state Turkevich reaction. Solid reactants are only briefly exposed to input of mechanical energy before being aged statically over a period of six weeks at different temperatures. This system offers an excellent opportunity for an in situ analysis of both reduction and nanoparticle formation processes. During the aging period, the reaction was monitored using a combination of X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, powder X-ray diffraction and transmission electron microscopy, to gain meaningful insights into the mechanisms of solid-state formation of gold nanoparticles. The acquired data allowed for the establishment of the first kinetic model for solid-state nanoparticle formation.

Direct observation by high resolution transmission electron microscopy of gold(III) particle transformation during aging reduction reaction.

We use a gold nanoparticle synthesis as a model system to study the morphological and compositional changes in gold(III) precursor particles, while reduction is taking place during aging after mechanical activation. Scanning transmission electron microscopy coupled with a high-angle annular dark field detector revealed the nanoscale changes in particle morphology, while electron energy loss spectroscopy mapped the changes in the chemical landscape during the reduction process. Tracking a specific region of interest on the sample grid allowed for comparisons to be made of the same particles across a two day monitoring period. High-angle annular dark field images permitted the visualization of particle size reduction of the gold salt while electron energy loss spectroscopy captured the surprising mobility of the lighter chlorine and sodium ions in a solid matrix during the reduction process. This system offers unique insight into precursor particle reactivity in the solid phase, which is relevant for many mechanochemical and aging-based reactions.

Mechanochemical bottom-up synthesis of phosphorus-linked, heptazine-based carbon nitrides using sodium phosphide.

Herein, we present the bottom-up, mechanochemical synthesis of phosphorus-bridged heptazine-based carbon nitrides (g-h-PCN). The structure of these materials was determined through a combination of powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), 31P magic angle spinning nuclear magnetic resonance (MAS NMR), density functional theory (DFT) and electron energy loss spectroscopy (EELS). Compared to traditional furnace-based techniques, the presented method utilizes milder conditions, as well as shorter reaction times. Both samples of g-h-PCN directly after milling and aging and after an hour of annealing at 300 °C (g-h-PCN300) show a reduction in photoluminescent recombination, as well as a nearly two-time increase in photocurrent under broad spectrum irradiation, which are appealing properties for photocatalysis.

Mechanochemical methods for the transfer of electrons and exchange of ions: inorganic reactivity from nanoparticles to organometallics.

Mechanochemistry by milling, grinding, extrusion or other types of shear and mechanical agitation has shown novel reactivity for a wide range of reactions, not seen in traditional solution-based environments. While the area has been extensively investigated and reviewed in the context of organic and solid-state supramolecular chemistry, less attention has been given to the recent advances in the context of inorganic transformations. Here we provide a perspective of inorganic mechanochemical reactions, focusing on transformations that are based on transfer of charged species: exchange of ions and electrons (redox reactions). These types of mechanochemical transformations typically lead to the formation of new nanoparticles and organometallic complexes. Herein, we provide an overview of mechanochemical reactivity that complements the recent developments in organic synthesis and catalysis.