Hydrogels consisting of poly(acrylic acid) (PAA) and calcium ions are a promising class of materials with shapeable, stretchable and self-healing behaviour originating from the reversible and dynamic nature of the...

Hematite (α‐Fe2O3) is thermodynamically stable under ambient conditions, of vast geological importance, and widely used in applications, for example, as corrosion protection and as a pigment. It forms at elevated temperatures, whereas room‐temperature reactions typically yield metastable akaganéite or ferrihydrite. The mechanistic key changes underlying this observation were explored in the present study. The entropic contribution to the prenucleation hydrolysis reaction categorically implies the presence of prenucleation clusters (PNCs) as fundamental precursors. The formation of hematite is then due to a change in the reaction mechanism above approximately 50 °C, whereby the reaction limitation towards oxolation in phase‐separated clusters is overcome. A model that rationalizes the occurrence of hematite, akaganéite, and ferrihydrite based on the chemistry of olation PNCs is proposed. Supersaturation and the temperature dependence of olation and oxolation rates from monomeric precursors are irrelevant in this nonclassical mechanism.

Analytical ultracentrifugation (AUC) is a powerful technique to observe colloidal nanocrystals (NCs) directly in solution and obtain critical information about their physical-chemical properties. Nevertheless, a more comprehensive implementation of AUC for the characterisation of such a class of crystalline colloids has been traditionally impaired by the requirement of having a priori knowledge of the complex, multilayered structure formed by NC in solution. This includes the nature (density and mass) of the surface ligands (SLs) that provide NC colloidal stability and the shell of solvent molecules formed on it. Herein, we propose a methodology to determine the NCs size by using SLs with a density equal to that of the solvent. Thereby, the buoyancy force of the SL shell is neutral, and the density of the NCs is sufficient a priori knowledge to calculate their related mass and size distributions. The simplicity and reliability of the method are evaluated with cetyltrimethylammonium bromide (CTAB) stabilized spherical gold NCs (AuNCs) of dimensions ranging from 1 to 17 nm. The proposed method has great potential to be transferred to any non-crystalline and crystalline colloids of different nature and composition, which have a density that is equal to the bulk and can be stabilized by SLs having a density that matches that of the solvent.