Zhang Luyao, Wang Kun, Zhao Xin, Yang Guoping, Jiang Yulong, Yang Feng
Department of Chemistry, Southern University of Science and Technology Shenzhen Guangdong 518055 China
Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, Jiangxi Province Key Laboratory of Synthetic Chemistry, East China University of Technology Nanchang 330013 China.
Chem Sci. 2024 Aug 27;15(38):15737-44. doi: 10.1039/d4sc03415e.
Understanding the atomic structures and dynamic evolution of uranium oxides is crucial for the reliable operation of fission reactors. Among them, UO-as an important intermediate in the oxidation of UO to UO -plays an important role in the nucleation and conversion of uranium oxides. Herein, we realize the confined assembly of uranyl within SWCNTs in liquid phase and reveal the directional growth and reconstruction of UO nanorods in nanochannels, enabled by scanning transmission electron microscopy (STEM) e-beam stimulation. The nucleation and crystallization of UO nanorods in nanochannels obey the "non-classical nucleation" mechanism and exhibit remarkably higher growth rate compared to those grown outside. The rapid growth process is found to be accompanied by the formation and elimination of U atom vacancies and strain, aiming to achieve the minimum interfacial energy. Eventually, the segments of UO nanorods in SWCNTs merge into single-crystal UO nanorods structural reconstruction at the interfaces, and 79% of them exhibit anisotropic growth along the specific 〈11̄0〉 direction. These findings pave the way for tailoring the atomic structures and interfaces of uranium oxides during the synthesis process to help improve the mechanical properties and stability of fission reactors.
了解铀氧化物的原子结构和动态演化对于裂变反应堆的可靠运行至关重要。其中,UO作为UO氧化为UO过程中的重要中间体,在铀氧化物的成核和转化中起着重要作用。在此,我们在液相中实现了铀酰在单壁碳纳米管内的受限组装,并通过扫描透射电子显微镜(STEM)电子束刺激揭示了纳米通道中UO纳米棒的定向生长和重构。纳米通道中UO纳米棒的成核和结晶遵循“非经典成核”机制,并且与在外部生长的相比,其生长速率显著更高。发现快速生长过程伴随着U原子空位和应变的形成与消除,目的是实现最小界面能。最终,单壁碳纳米管中UO纳米棒的片段合并为单晶UO纳米棒,在界面处进行结构重构,其中79%沿特定〈11̄0〉方向呈现各向异性生长。这些发现为在合成过程中定制铀氧化物的原子结构和界面铺平了道路,有助于提高裂变反应堆的机械性能和稳定性。