Crystal Nucleation and Growth of Inorganic Ionic Materials from Aqueous Solution: Selected Recent Developments, and Implications

Abstract

In this review article, selected, latest theoretical, and experimental developments in the field of nucleation and crystal growth of inorganic materials from aqueous solution are highlighted, with a focus on literature after 2015 and on non‐classical pathways. A key point is to emphasize the so far underappreciated role of water and solvent entropy in crystallization at all stages from solution speciation through to the final crystal. While drawing on examples from current inorganic materials where non‐classical behavior has been proposed, the potential of these approaches to be adapted to a wide‐range of systems is also discussed, while considering the broader implications of the current re‐assessment of pathways for crystallization. Various techniques that are suitable for the exploration of crystallization pathways in aqueous solution, from nucleation to crystal growth are summarized, and a flow chart for the assignment of specific theories based on experimental observations is proposed.

Matrix-Directed Mineralization for Bulk Structural Materials

“…It has been reported that, by adding the soluble proteins extracted from the prismatic layer (calcite) or the nacreous layer (aragonite) of red abalone shell into the mineralization system, the polymorph of the precipitated CaCO 3 can switch from calcite to aragonite back and forth . The mineral morphologies can be changed via the kinetic stabilization of soluble additives to specific crystal phases. − The bioinspired pathways developed to precisely control mineralization have been summarized in previous reviews. ,,,− However, as the precursory phases, which have been widely found in biomineralization process, are promising in the fast and scalable fabrication of MBSMs, it is worth detailed discussions of their potentials in making MBSMs.…”

Molecular Mechanism of Organic Crystal Nucleation: A Perspective of Solution Chemistry and Polymorphism

“…Myerson et al and Vekilov [20] reviewed the evidence of the two-step nucleation mechanism where Vekilov detailed a two-step sequence scenario in which structure order is preceded by the separation of a dense, disordered liquid phase in protein systems. Gebauer and Cölfen differentiated the nature of clusters at different nucleation stages and reviewed the evidence of pre-nucleation clusters in inorganic systems [21,22]. Anwar et al [23] and Michaelides et al [24] reviewed computational approaches used to elucidate the molecular nature of nucleation and pointed to challenges in the simulation accuracy of interatomic potentials and enhanced sampling methods.…”

New insights into the nucleation of magnesium hydroxide and the influence of poly(acrylic acid) during the early stages of Mg(OH)2 crystallisation

“…Over the past ten years, our understanding of the mechanisms underlying the crystallisation of inorganic minerals from aqueous solutions has advanced significantly thanks to a large number of pioneering, and sometimes controversial, studies. [1][2][3][4][5] While many of the key discoveries were made for prominent mineral systems such as calcium carbonate, [6][7][8] calcium phosphate, [9][10][11] or iron (oxy)(hydr) oxides, [12][13][14] other inorganic compounds have received much less attention. In this context, one rather neglected example is magnesium hydroxide.…”