Qiao Liang, Fu Zheng, Zhao Wenxia, Cui Yan, Xing Xin, Xie Yin, Li Ji, Gao Guanhui, Xuan Zhengxi, Liu Yang, Lee Chaeeon, Han Yimo, Cheng Yingwen, He Shengbao, Jones Matthew R, Swihart Mark T
Department of Chemical and Biological Engineering, University at Buffalo (SUNY) Buffalo NY 14260 USA
Division of Fundamental Research, Petrochemical Research Institute, PetroChina Beijing 102206 China
Chem Sci. 2022 Dec 26;14(5):1205-1217. doi: 10.1039/d2sc05077c. eCollection 2023 Feb 1.
Branching phenomena are ubiquitous in both natural and artificial crystallization processes. The branched nanostructures' emergent properties depend upon their structures, but their structural tunability is limited by an inadequate understanding of their formation mechanisms. Here we developed an ensemble of Nickel-Based nano-Composites (NBCs) to investigate branching phenomena in solution-phase synthesis with precision and in depth. NBCs of 24 morphologies, including dots, core@shell dots, hollow shells, clusters, polyhedra, platelets, dendrites, urchins, and dandelions, were synthesized through systematic adjustment of multiple synthesis parameters. Relationships between the synthesis parameters and the resultant morphologies were analyzed. Classical or non-classical models of nucleation, nascent growth, 1D growth, 2D growth, 3D reconstruction, aggregation, and carburization were defined individually and then integrated to provide a holistic view of the formation mechanism of branched NBCs. Finally, guidelines were extracted and verified to guide the rational solution-phase syntheses of branched nanomaterials with emergent biological, chemical, and physical properties for potential applications in immunology, catalysis, energy storage, and optics. Demonstrating a systematic approach for deconvoluting the formation mechanism and enhancing the synthesis tunability, this work is intended to benefit the conception, development, and improvement of analogous artificial branched nanostructures. Moreover, the progress on this front of synthesis science would, hopefully, deepen our understanding of branching phenomena in nature.
分支现象在自然和人工结晶过程中普遍存在。分支纳米结构的新兴特性取决于其结构,但其结构可调性受到对其形成机制理解不足的限制。在此,我们开发了一组镍基纳米复合材料(NBCs),以精确、深入地研究溶液相合成中的分支现象。通过系统调整多个合成参数,合成了包括点、核壳点、空心壳、簇、多面体、血小板、树枝状、海胆状和蒲公英状等24种形态的NBCs。分析了合成参数与所得形态之间的关系。分别定义了成核、初生生长、一维生长、二维生长、三维重构、聚集和渗碳的经典或非经典模型,然后将它们整合起来,以全面了解分支NBCs的形成机制。最后,提取并验证了指导方针,以指导具有新兴生物、化学和物理特性的分支纳米材料的合理溶液相合成,用于免疫学、催化、能量存储和光学等潜在应用。这项工作展示了一种系统的方法来解析形成机制并提高合成可调性,旨在有益于类似人工分支纳米结构的构思、开发和改进。此外,合成科学这一前沿领域的进展有望加深我们对自然中分支现象的理解。