The structural transformation of materials, which involves the evolution of different structural features, including phase, composition, morphology, etc., under external conditions, represents an important fundamental phenomenon and has drawn substantial research interest. Recently, materials with unconventional phases that are different from their thermodynamically stable ones have been demonstrated to possess distinct properties and compelling functions and can further serve as starting materials for structural transformation studies. The identification and mechanism study of the structural transformation process of unconventional-phase starting materials can not only provide deep insights into their thermodynamic stability in potential applications but also offer effective approaches for the synthesis of other unconventional structures. Here, we briefly summarize the recent research progress on the structural transformation of some typical starting materials with various unconventional phases, including the metastable crystalline phase, amorphous phase, and heterophase, induced by different approaches. The importance of unconventional-phase starting materials in the structural modulation of resultant intermediates and products will be highlighted. The employment of diverse in situ/operando characterization techniques and theoretical simulations in studying the mechanism of the structural transformation process will also be introduced. Finally, we discuss the existing challenges in this emerging research field and provide some future research directions.
Keywords: phase engineering; structural transformation; thermodynamic stability; unconventional phase.