Phase engineering of nanomaterials (PEN) has emerged as a new research field by enabling precise control of crystallographic phases at the nanometer scale. The capability of stabilizing unconventional phases unlocks a vast library of physiochemical properties inaccessible to the conventional, thermodynamically stable crystals. This review provides a comprehensive framework to map the past, present, and future of PEN. We first briefly introduce the concept of PEN. Then, we summarize synthetic methodologies, including direct phase-controlled synthesis and phase transition. The discussion also underscores the pivotal role of advanced characterization, particularly the transition from ex situ to in situ and operando techniques, in probing dynamic phase behaviors under realistic conditions. We present key applications in (electro)catalysis, energy conversion and storage, functional devices, and biomedicine to illustrate the PEN's broad impact. Looking ahead, we identify key challenges and future directions, emphasizing robust phase stabilization, architecture control, and artificial intelligence-integrated phase design. The field is ultimately advancing toward the artificial atomically-assembled structures (AAASs), enabling the deterministic assembly of atoms with precisely controlled phase and architecture to achieve targeted functions and applications.
Chen et al. (Tue,) studied this question.