Imaging and analysis of covalent organic framework crystallites on a carbon surface: a nanocrystalline scaly COF/nanotube hybrid


Synthesis of covalent organic frameworks (COFs) is well-advanced but understanding their nanoscale structure and interaction with other materials remains a significant challenge. Here, we have developed a methodology for the detailed imaging and analysis of COF crystallites using carbon nanotube substrates for COF characterisation. Detailed investigation using powder X-ray diffraction, infrared spectroscopy, mass spectrometry and scanning electron microscopy in conjunction with a local probe method, transmission electron microscopy (TEM), revealed details of COF growth and nucleation at the nanoscale. A boronate ester COF undergoes preferential growth in the a-b crystallographic plane under solvothermal conditions. Carbon nanotubes were found to not impact the mode of COF growth, but the crystallites on nanotubes were smaller than COF crystallites not on supports. COF crystalline regions with sizes of tens of nanometres exhibited preferred orientation on nanotube surfaces, where the c-axis is oriented between 50 and 90 degrees relative to the carbon surface. The COF/nanotube hybrid structure was found to be more complex than the previously suggested concentric core-shell model and can be better described as a nanocrystalline scaly COF/nanotube hybrid.




Chemistry, Multidisciplinary; Nanoscience & Nanotechnology; Materials Science, Multidisciplinary; Physics, Applied


Weare, BL; Lodge, RW; Zyk, N; Weilhard, A; Housley, CL; Strutynski, K; Melle-Franco, M; Mateo-Alonso, A; Khlobystov, AN

nossos autores


The authors would like to acknowledge the EPSRC, Royal Society and the University of Nottingham, and Nanoscale and Microscale Research Centre (nmRC) at the University of Nottingham for access to TEM and SEM facilities. Additional support was through the project IF/00894/2015 and within the scope of the project CICECO-Aveiro Insitutie of Materials, UIDB/50011/2020 and UIDP/50011/2020, financed by the national funds through the Portuguese Foundation for Science and Technology/MCTES, UIDB/50011/2020, UIDP/50011/2020 & IF/00894/2015, is gratefully acknowledged. This work was carried out with support from the Basque Science Foundation for Science (Ikerbasque), POLYMAT, the University of the Basque Country (Grupo de Investigacion GIU17/054), Gobierno de Espana (Ministerio de Ciencia e Innovacion, Plan Estatal de Investigacion Cientifica y Tecnica y de Innovacion), Gobierno Vasco (PIBA and BERC programmes) and acknowledge technical and human support provided by SGIker of UPV/EHU and European funding (ERDF and ESF). This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement no. 722951). This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreements no. 899895 and 664878.

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