Mesoporous phosphates are a group of nanostructured materials with promising applications, particularly in biomedicine and catalysis. However, their controlled synthesis via conventional template-based routes presents a number of challenges and limitations. Here, we show how to synthesize a mesoporous magnesium phosphate with a high surface area and a well-defined pore structure through thermal decomposition of a crystalline struvite (MgNH₄PO₄·6H₂O) precursor. In a first step, struvite crystals with various morphologies and sizes, ranging from a few micrometers to several millimeters, had been synthesized from supersaturated aqueous solutions (saturation index (SI) between 0.5 and 4) at ambient pressure and temperature conditions. Afterwards, the crystals were thermally treated at 70–250 °C leading to the release of structurally bound water (H₂O) and ammonia (NH₃). By combining thermogravimetric analyses (TGA), scanning and transmission electron microscopy (SEM, TEM), N₂ sorption analyses and small- and wide-angle X-ray scattering (SAXS/WAXS) we show that this decomposition process results in a pseudomorphic transformation of the original struvite into an amorphous Mg-phosphate. Of particular importance is the fact that the final material is characterized by a very uniform mesoporous structure with 2–5 nm wide pore channels, a large specific surface area of up to 300 m² g⁻¹ and a total pore volume of up to 0.28 cm³ g⁻¹. Our struvite decomposition method is well controllable and reproducible and can be easily extended to the synthesis of other mesoporous phosphates. In addition, the so produced mesoporous material is a prime candidate for use in biomedical applications considering that magnesium phosphate is a widely used, non-toxic substance that has already shown excellent biocompatibility and biodegradability.

Clays are crucial mineral phases in Earth’s weathering engine, but we do not know how they form in surface environments under (near-)ambient pressures and temperatures. Most synthesis routes, attempting to give insights into the plausible mechanisms, rely on hydrothermal conditions, yet many geological studies showed that clays may actually form at moderate temperatures (< 100 °C) in most terrestrial settings. Here, we combined high-energy X-ray diffraction, infrared spectroscopy and transmission electron microscopy to derive the mechanistic pathways of the low-temperature (25-95 °C) crystallization of a synthetic Mg-clay, saponite. Our results reveal that saponite crystallizes via a two-stage process: 1) a rapid (several minutes) co-precipitation where ~20 % of the available magnesium becomes incorporated into an aluminosilicate network followed by 2) a much slower crystallization mechanism (several hours to days) where the remaining magnesium becomes gradually incorporated into the growing saponite sheet structure.

Adsorption and subsequent precipitation of dissolved phosphates on iron oxides, such as hematite and goethite, is of considerable importance in predicting the bioavailability of phosphates. We used in situ atomic force microscopy (AFM) to image the kinetic processes of phosphate-bearing solutions interacting with hematite or goethite surfaces. The nucleation of nanoparticles (1.0–4.0 nm in height) of iron phosphate (Fe(III)-P) phases, possibly an amorphous phase at the initial stages, was observed during the dissolution of both hematite and goethite at the earliest crystallization stages. This was followed by a subsequent aggregation stage where larger particles and layered precipitates are formed under different pH values, ionic strengths, and organic additives. Kinetic analysis of the surface nucleation of Fe-P phases in 50 mM NH₄H₂PO₄ at pH 4.5 showed the nucleation rate was greater on goethite than hematite. Enhanced goethite and hematite dissolution in the presence of 10 mM AlCl₃ resulted in a rapid increase in Fe-P nucleation rates. A low concentration of citrate promoted the nucleation, whereas nucleation was inhibited at higher concentrations of citrate. By modeling using PHREEQC, calculated saturation indices (SI) showed that the three Fe(III)-P phases of cacoxenite, tinticite, and strengite may be supersaturated in the reacted solutions. Cacoxenite is predicted to be more thermodynamically favorable in all the phosphate solutions if equilibrium is reached with respect to hematite or goethite, although possibly only amorphous precipitates were observed at the earliest stages. These direct observations at the nanoscale may improve our understanding of phosphate immobilization in iron oxide-rich acid soils.