Ab-initio simulation studies of chromium solvation in molten fluoride salts

Understanding molten salt chemistry is essential in ongoing research of the molten salt nuclear reactor (MSR). In this context, detailed understanding of the mechanisms underlying selective oxidation of metal species, such as Cr, is required to guide the design of effective corrosion mitigation strategies in molten salts. An important starting point for such mechanistic understanding is knowledge of the solvation structure and its role in controlling metal speciation. In this work, we use ab initio molecular dynamics simulations to study the short-range (on the scale of the nearest-neighbor bond lengths) and medium-range (over length scales of several neighbor spacings) structure in three different fluoride melts with and without Cr addition; namely, 2KF-NaF, 2LiF-BeF2, and 3LiF-AlF3. We find that Cr-0, Cr2+, Cr3+ can each be coordinated by different numbers of F-, with the variance in coordination number decreasing as oxidation state increases, and that these coordination geometries are largely independent of solvent. The manner by which Cr changes the medium-range structure, however, is found to be solvent-dependent. While 2KF-NaF melts show short and medium range order that is highly dynamic, 2LiF-BeF2 and 3LiF - AlF3 are characterized by molecular associates that are relatively long-lived that organize into oligomer structures on larger length scales. Rather than being solvated by F- ions alone, we find that Cr can incorporate into and be solvated within this oligomer structure. Fluoroacidity, alone, may therefore prove too simple a metric for assessing the corrosivity of molten fluorides. As our work suggests, the ability of Cr to solvate must be understood in the context of the short- and medium-range structure of the solvent. (C) 2021 The Authors. Published by Elsevier B.V.

Automated summary

Understanding the solvation behavior of Cr in molten salts and its effect on coordination geometry, as well as the medium-range structure changes, is crucial for assessing the corrosivity of molten fluorides. The presence of Cr and its solvation within oligomer structures in different fluoride melts suggests that fluoroacidity alone may not be a sufficient metric for evaluating corrosion. The solvent-dependent manner in which Cr alters the medium-range structure highlights the importance of considering the short- and medium-range structure of the solvent in understanding its solvation behavior.