Multimodal Nanoscale Mapping of Local Structure and CO2 Adsorption in Metal-Organic Frameworks.
Journal Article
Overview
abstract
Diamine functionalization of the metal-organic framework Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) significantly enhances its selectivity for CO2 capture from flue gases and air. The structure and CO2 capacity of such materials are typically assessed using bulk techniques that rely on averaging signal over large ensembles of unit cells, obscuring local heterogeneities, such as variations in CO2 occupancy across individual nanocrystals. To resolve this limitation, we demonstrate a multimodal, nanoscale characterization of Mg2(dobpdc) appended with 1,3-diaminopropane. By employing recently developed characterization techniques at progressively smaller length scales, we uncover insights from correspondingly smaller populations of unit cells. First, we use parallel-beam 3D electron diffraction (3D ED) to identify a prominent expansion in lattice parameters upon desorption of CO2, as observed at the level of single nanocrystals. Second, we use convergent-probe 4D scanning transmission electron microscopy (4D-STEM) to quantify associated differences in lattice strain as a function of gas loading and diamine appending. These measurements sample small subvolumes within individual nanocrystals. Finally, we apply infrared scattering scanning near-field optical microscopy (IR s-SNOM) to confirm variable CO2 chemisorption across adsorption sites at the surface of single nanocrystals. This multimodal, multiscale approach allows us to map heterogeneity within individual nanocrystals. Collectively, these findings emphasize the importance of local, nanoscale characterization of metal-organic frameworks in revealing previously unresolvable features that impact their performance.
