Selective formation of metastable polymorphs in solid-state synthesis.
Sci Adv
; 10(3): eadj5431, 2024 Jan 19.
Article
in En
| MEDLINE
| ID: mdl-38232170
ABSTRACT
Metastable polymorphs often result from the interplay between thermodynamics and kinetics. Despite advances in predictive synthesis for solution-based techniques, there remains a lack of methods to design solid-state reactions targeting metastable materials. Here, we introduce a theoretical framework to predict and control polymorph selectivity in solid-state reactions. This framework presents reaction energy as a rarely used handle for polymorph selection, which influences the role of surface energy in promoting the nucleation of metastable phases. Through in situ characterization and density functional theory calculations on two distinct synthesis pathways targeting LiTiOPO4, we demonstrate how precursor selection and its effect on reaction energy can effectively be used to control which polymorph is obtained from solid-state synthesis. A general approach is outlined to quantify the conditions under which metastable polymorphs are experimentally accessible. With comparison to historical data, this approach suggests that using appropriate precursors could enable targeted materials synthesis across diverse chemistries through selective polymorph nucleation.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Type of study:
Prognostic_studies
Language:
En
Journal:
Sci Adv
Year:
2024
Document type:
Article
Affiliation country:
United States
Country of publication:
United States