Abstract
Although tailored porosity is a defining feature of layered, two-dimensional (2D) polymers known as 2D covalent organic frameworks (COFs), understanding the interplanar stacking of 2D COFs and their resulting three-dimensional (3D) pore structure remains challenging. Here, we use scanning transmission electron microscopy and ptychography, an emerging 3D angstrom-scale imaging method, to study single-crystalline particles of the imine-linked 2D COF TAPB-DMPDA. Previously assumed to adopt an average-eclipsed structure with only angstrom-level stacking disorder, we find the crystals contain widespread stacking disorder of larger magnitudes, including interplanar shifts up to a half unit cell and nanoscale inhomogeneities in stacking and tilt. 3D visualizations show pore channels are distorted by this stacking disorder. The extensive stacking disorder found in even high-quality 2D COFs has profound implications for envisioned applications and should motivate the development of design strategies to control their 3D structures.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 11821-11828 |
| Number of pages | 8 |
| Journal | Journal of the American Chemical Society |
| Volume | 147 |
| Issue number | 14 |
| DOIs | |
| State | Published - Apr 9 2025 |
Funding
This work was supported primarily by a Packard Foundation fellowship, with additional support from NSF CAREER award DMR-1846206 and the Army Research Office under Grant Number W911NF-23-1-0306. This work was carried out in part in the Materials Research Laboratory Central Facilities at the University of Illinois, where electron microscopy and deposition facilities were supported by C.Q. Chen. This work utilized facilities provided by the NSF-MRSEC award number DMR-2309037. This work made use of the Illinois Campus Cluster, a computing resource that is operated by the Illinois Campus Cluster Program (ICCP) in conjunction with the National Center for Supercomputing Applications (NCSA) and which is supported by funds from the University of Illinois at Urbana-Champaign. Data processing was carried out using the cSAXS ptychography MATLAB package developed by the Science IT and the coherent X-ray scattering (CXS) groups, Paul Scherrer Institut, Switzerland. This work was supported primarily by a Packard Foundation fellowship, with additional support from NSF CAREER award DMR-1846206 and the Army Research Office under Grant Number W911NF-23-1-0306. This work was carried out in part in the Materials Research Laboratory Central Facilities at the University of Illinois, where electron microscopy and deposition facilities were supported by C.Q. Chen. This work utilized facilities provided by the NSF-MRSEC award number DMR-2309037. This work made use of the Illinois Campus Cluster, a computing resource that is operated by the Illinois Campus Cluster Program (ICCP) in conjunction with the National Center for Supercomputing Applications (NCSA) and which is supported by funds from the University of Illinois at Urbana\u2013Champaign. Data processing was carried out using the cSAXS ptychography MATLAB package developed by the Science IT and the coherent X-ray scattering (CXS) groups, Paul Scherrer Institut, Switzerland.
ASJC Scopus subject areas
- Catalysis
- General Chemistry
- Biochemistry
- Colloid and Surface Chemistry