MOF非晶相固相转变的见解,Inorganic Chemistry

当前位置： X-MOL 学术 › Inorg. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

MOF非晶相固相转变的见解
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-08-24 , DOI: 10.1021/acs.inorgchem.2c01978
Yuri A Mezenov ₁ , Stephanie Bruyere ₂ , Andrei Krasilin ₃ , Ekaterina Khrapova ₃ , Semyon V Bachinin ₁ , Pavel V Alekseevskiy ₁ , Sergei Shipiloskikh ₁ , Pascal Boulet ₂ , Sebastien Hupont ₂ , Alexandre Nomine ₂ , Brigitte Vigolo ₂ , Alexander S Novikov _{4,

5} , Thierry Belmonte ₂ , Valentin A Milichko _{1,

2}

Affiliation

金属有机框架（MOF）最近被探索为结晶固体，用于转化为非特定的机械、催化和光学特性的无定形相。对这种结构转型及其结果的实时控制仍然是一个挑战。在这里，我们使用具有 0.01 秒时间分辨率的原位高分辨率透射电子显微镜来探索 MOF 单晶的非热（电子诱导）非晶化，然后转化为非晶纳米材料。通过比较一系列M -BTC ( M : Fe ³⁺ , Co ³⁺ , Co ²⁺ , Ni ²⁺ , 和 Cu ²⁺; BTC：1,3,5-苯三甲酸），我们证明母体 MOF 的金属簇的拓扑结构决定了含有完整配体和金属或金属氧化物纳米粒子的所得相的形成速率和化学性质。共焦拉曼和光致发光光谱进一步证实了 BTC 配体的完整性和配位键断裂，而随着时间的推移具有化学和结构分析的高分辨率成像允许跟踪固体到固体转变的动态。初始结构和最终结构之间揭示的关系以及所获得相的稳定性及其随时间的光致发光有助于设计新的基于非晶 MOF 的光学纳米材料。

"点击查看英文标题和摘要"

Insights into Solid-To-Solid Transformation of MOF Amorphous Phases

Metal–organic frameworks (MOFs) have been recently explored as crystalline solids for conversion into amorphous phases demonstrating non-specific mechanical, catalytic, and optical properties. The real-time control of such structural transformations and their outcomes still remain a challenge. Here, we use in situ high-resolution transmission electron microscopy with 0.01 s time resolution to explore non-thermal (electron induced) amorphization of a MOF single crystal, followed by transformation into an amorphous nanomaterial. By comparing a series of M-BTC (M: Fe³⁺, Co³⁺, Co²⁺, Ni²⁺, and Cu²⁺; BTC: 1,3,5-benzentricarboxylic acid), we demonstrate that the topology of a metal cluster of the parent MOFs determines the rate of formation and the chemistry of the resulting phases containing an intact ligand and metal or metal oxide nanoparticles. Confocal Raman and photoluminescence spectroscopies further confirm the integrity of the BTC ligand and coordination bond breaking, while high-resolution imaging with chemical and structural analysis over time allows for tracking the dynamics of solid-to-solid transformations. The revealed relationship between the initial and resulting structures and the stability of the obtained phase and its photoluminescence over time contribute to the design of new amorphous MOF-based optical nanomaterials.

更新日期：2022-08-24

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南