Nucleation and Crystallization of Ferrous Phosphate Hydrate via an Amorphous Intermediate.

The fundamental processes of nucleation and crystallization are widely observed in systems relevant to material synthesis and biomineralization; yet most often, their mechanism remains unclear. In this study, we unravel the discrete stages of nucleation and crystallization of Fe3(PO4)2·8H2O (vivianite). We experimentally monitored the formation and transformation from ions to solid products by employing correlated, time-resolved in situ and ex situ approaches. We show that vivianite crystallization occurs in distinct stages via a transient amorphous precursor phase. The metastable amorphous ferrous phosphate (AFEP) intermediate could be isolated and stabilized. We resolved the differences in bonding environments, structure, and symmetric changes of the Fe site during the transformation of AFEP to crystalline vivianite through synchrotron X-ray absorption spectroscopy at the Fe K-edge. This intermediate AFEP phase has a lower water content and less distorted local symmetry, compared to the crystalline end product vivianite. Our combined results indicate that a nonclassical, hydration-induced nucleation and transformation driven by the incorporation and rearrangement of water molecules and ions (Fe2+ and PO43-) within the AFEP is the dominating mechanism of vivianite formation at moderately high to low vivianite supersaturations (saturation index ≤ 10.19). We offer fundamental insights into the aqueous, amorphous-to-crystalline transformations in the Fe2+-PO4 system and highlight the different attributes of the AFEP, compared to its crystalline counterpart.

Mechanism and Control of Saponite Synthesis from a Self-Assembling Nanocrystalline Precursor.

Saponite is a clay mineral of the smectite group that finds applications in the chemical industry as a catalyst or catalyst precursor as well as in nanocomposites used for structural or catalytic applications. Saponite of controlled composition, crystallinity, particle size, and morphology would be highly beneficial to industry; however, such materials are not found in a sufficiently pure form in nature. Synthetic methods to produce saponite with specific properties are currently lacking as the understanding of the mechanisms controlling its formation, crystalline properties and particle morphology, is limited. Understanding the saponite formation mechanism is crucial for the development of a highly tuned and controlled synthesis leading to materials with specific properties. Here, we report a new chemical reaction mechanism explaining the nucleation and kinetics of saponite growth at different pHs, at 95-100 °C, and under the influence of pH-modifying additives explored via a combination of X-ray scattering methods and infrared spectroscopy. Our results show that the main factor affecting the nucleation and growth kinetics of saponite is the pH, which has a particularly significant impact on the rate of initial nucleation. Non-uniform reactivity of the aluminosilicate gel also significantly affects saponite growth kinetics and causes a change in the rate-determining step as seen in graphical abstract. The most crystalline saponite is obtained when the nucleation is suppressed by a low initial pH (<7), but the reaction is performed at a higher pH of about 9. The stacking of the saponite sheets can be further improved by a separate postsynthesis treatment with an alkali (NaOH) solution. A simple, ambient pressure method for synthesizing a highly crystalline saponite is proposed that could be easily upscaled for industrial purposes.

Nanomagnetic properties of the meteorite cloudy zone.

Meteorites contain a record of their thermal and magnetic history, written in the intergrowths of iron-rich and nickel-rich phases that formed during slow cooling. Of intense interest from a magnetic perspective is the "cloudy zone," a nanoscale intergrowth containing tetrataenite-a naturally occurring hard ferromagnetic mineral that has potential applications as a sustainable alternative to rare-earth permanent magnets. Here we use a combination of high-resolution electron diffraction, electron tomography, atom probe tomography (APT), and micromagnetic simulations to reveal the 3D architecture of the cloudy zone with subnanometer spatial resolution and model the mechanism of remanence acquisition during slow cooling on the meteorite parent body. Isolated islands of tetrataenite are embedded in a matrix of an ordered superstructure. The islands are arranged in clusters of three crystallographic variants, which control how magnetic information is encoded into the nanostructure. The cloudy zone acquires paleomagnetic remanence via a sequence of magnetic domain state transformations (vortex to two domain to single domain), driven by Fe-Ni ordering at 320 °C. Rather than remanence being recorded at different times at different positions throughout the cloudy zone, each subregion of the cloudy zone records a coherent snapshot of the magnetic field that was present at 320 °C. Only the coarse and intermediate regions of the cloudy zone are found to be suitable for paleomagnetic applications. The fine regions, on the other hand, have properties similar to those of rare-earth permanent magnets, providing potential routes to synthetic tetrataenite-based magnetic materials.

A high spatial resolution synchrotron Mössbauer study of the Tazewell IIICD and Esquel pallasite meteorites.

Metallic phases in the Tazewell IIICD iron and Esquel pallasite meteorites were examined using 57Fe synchrotron Mössbauer spectroscopy. Spatial resolution of ~10-20 µm was achieved, together with high throughput, enabling individual spectra to be recorded in less than 1 h. Spectra were recorded every 5-10 µm, allowing phase fractions and hyperfine parameters to be traced along transects of key microstructural features. The main focus of the study was the transitional region between kamacite and plessite, known as the "cloudy zone." Results confirm the presence of tetrataenite and antitaenite in the cloudy zone as its only components. However, both phases were also found in plessite, indicating that antitaenite is not restricted exclusively to the cloudy zone, as previously thought. The confirmation of paramagnetic antitaenite as the matrix phase of the cloudy zone contrasts with recent observations of a ferromagnetic matrix phase using X-ray photoemission electron spectroscopy. Possible explanations for the different results seen using these techniques are proposed.

Impact of organic phosphates on the structure and composition of short-range ordered iron nanophases.

Organic phosphates (OP) are important nutrient components for living cells in natural environments, where they readily interact with ubiquitous iron phases such as hydrous ferric oxide, ferrihydrite (FHY). FHY partakes in many key bio(geo)chemical reactions including iron-mediated carbon storage in soils, or iron-storage in living organisms. However, it is still unknown how OP affects the formation, structure and properties of FHY. Here, we document how ß-glycerophosphate (GP), a model OP ligand, affects the structure and properties of GP-FHY nanoparticles synthesized by coprecipitation at variable nominal molar P/Fe ratios (0.01 to 0.5). All GP-FHY precipitates were characterized by a maximum solid P/Fe ratio of 0.22, irrespective of the nominal P/Fe ratio. With increasing nominal P/Fe ratio, the specific surface area of the GP-FHY precipitates decreased sharply from 290 to 3 m2 g-1, accompanied by the collapse of their pore structure. The Fe-P local bonding environment gradually transitioned from a bidentate binuclear geometry at low P/Fe ratios to monodentate mononuclear geometry at high P/Fe ratios. This transition was accompanied by a decrease in coordination number of edge-sharing Fe polyhedra, and the loss of the corner-sharing Fe polyhedra. We show that Fe(iii) polymerization is impeded by GP, and that the GP-FHY structure is highly dependent on the P/Fe ratio. We discuss the role that natural OP-bearing Fe(iii) nanophases have in biogeochemical reactions between Fe-P and C species in aquatic systems.

Goethite Mineral Dissolution to Probe the Chemistry of Radiolytic Water in Liquid-Phase Transmission Electron Microscopy.

Liquid-Phase Transmission Electron Microscopy (LP-TEM) enables in situ observations of the dynamic behavior of materials in liquids at high spatial and temporal resolution. During LP-TEM, incident electrons decompose water molecules into highly reactive species. Consequently, the chemistry of the irradiated aqueous solution is strongly altered, impacting the reactions to be observed. However, the short lifetime of these reactive species prevent their direct study. Here, the morphological changes of goethite during its dissolution are used as a marker system to evaluate the influence of radiation on the changes in solution chemistry. At low electron flux density, the morphological changes are equivalent to those observed under bulk acidic conditions, but the rate of dissolution is higher. On the contrary, at higher electron fluxes, the morphological evolution does not correspond to a unique acidic dissolution process. Combined with kinetic simulations of the steady state concentrations of generated reactive species in the aqueous medium, the results provide a unique insight into the redox and acidity interplay during radiation induced chemical changes in LP-TEM. The results not only reveal beam-induced radiation chemistry via a nanoparticle indicator, but also open up new perspectives in the study of the dissolution process in industrial or natural settings.

Tailoring the Acidity of Liquid Media with Ionizing Radiation: Rethinking the Acid-Base Correlation beyond pH.

Advanced in situ techniques based on electrons and X-rays are increasingly used to gain insights into fundamental processes in liquids. However, probing liquid samples with ionizing radiation changes the solution chemistry under observation. In this work, we show that a radiation-induced decrease in pH does not necessarily correlate to an increase in acidity of aqueous solutions. Thus, pH does not capture the acidity under irradiation. Using kinetic modeling of radiation chemistry, we introduce alternative measures of acidity (radiolytic acidity π* and radiolytic ion product KW*), that account for radiation-induced alterations of both H+ and OH- concentration. Moreover, we demonstrate that adding pH-neutral solutes such as LiCl, LiBr, or LiNO3 can trigger a significant change in π*. This provides a huge parameter space to tailor the acidity for in situ experiments involving ionizing radiation, as present in synchrotron facilities or during liquid-phase electron microscopy.