宏观尺寸单晶多孔材料

Macroscopic Porous Single-crystalline Materials

摘要

多孔材料和单晶材料在现代科学技术中均具有重要应用价值. 若能在宏观尺寸单晶中引入孔隙, 有望获得兼具开放孔结构和连续单晶骨架的新型材料, 即宏观尺寸单晶多孔材料. 其连续单晶骨架保持长程有序晶体结构, 可有效减少晶界对传输过程和结构稳定性的影响, 同时孔隙结构可提供传质通道和可接触内表面. 然而, 传统晶体生长过程通常趋向于致密化, 孔隙往往被视为夹杂或缺陷, 因此在单晶中可控引入孔结构仍面临本征挑战. 本文围绕基于“固-固相变”的晶格重构策略展开综述, 重点讨论高密度单晶母相经特定组分脱除、 晶格重排和相变界面迁移后, 原位转化为低密度目标相单晶骨架并形成孔隙结构的基本机制. 进一步结合二氧化钛和二氧化铈等典型氧化物体系, 分析了母相晶向、 组成、 相对密度变化和热处理条件对晶面取向、 孔隙率、 孔径及表面结构的调控作用. 最后, 以光电化学能源转化为例, 探讨了连续单晶骨架、 三维连通孔道和可调缺陷结构之间的协同效应, 并展望了该类材料在电子-声子输运解耦、 同位素分离等结构敏感型功能过程中的潜在应用前景.

Abstract

Porous materials and single crystals both hold significant application value in modern science and technology. Introducing porosity into macroscopic single crystals offers a promising route to a new class of materials that combine an open porous architecture with a continuous single-crystalline skeleton, namely macroscopic porous single crystal (PSC). In PSC, the continuous single-crystalline skeleton maintains long-range crystallographic order and effectively reduces grain-boundary effects on transport processes and structural stability, while the porous architecture provides mass-transport channels and accessible internal surfaces. However, conventional crystal growth processes generally tend toward densification, and pores are usually regarded as inclusions or defects. Therefore, the controllable introduction of porous structures into single crystals remains a fundamental challenge. This review focuses on lattice reconstruction strategies driven by solid-solid phase transformations. We discuss the basic mechanism by which a high-density single-crystalline mother phase is transformed in situ into a low-density target single-crystalline skeleton through selective component removal, lattice rearrangement, and phase-boundary migration, accompanied by pore formation. Using typical oxide systems such as TiO₂ and CeO₂ as examples, we further analyze how the crystallographic orientation, composition, relative density variation, and heat-treatment conditions of the mother phase regulate the facet orientation, porosity, pore size, and surface structure of the resulting PSC. Finally, with photoelectrochemical energy conversion as a representative application, we discuss the synergistic effects of the continuous single-crystalline skeleton, three-dimensionally interconnected pore channels, and tunable defect structures. We also outline future opportunities for these materials in structure-sensitive functional processes, including electron-phonon transport decoupling and isotope separation.

关键词

单晶-多孔材料 / 单晶结构 / 多孔结构 / 固-固相变

Key words

Porous single-crystalline material / Single-crystalline structure / Porous architecture / Solid-solid phase transformation

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基金资助

国家自然科学基金(22325506)