@article {46413,
	title = {Covalent self-assembly in two dimensions: connecting covalent organic framework nanospheres into crystalline and porous thin films},
	journal = {Journal of the American Chemical Society},
	volume = {141},
	year = {2019},
	month = {DEC },
	pages = {20379},
	type = {Article},
	chapter = {20371},
	abstract = {<p>Insolubility of covalent organic frameworks (COFs) in organic solvents is one of the major obstacles for the potential application of these extended networks such as drug delivery, sensing, optoelectronics, and semiconductor device fabrication. The present work proposes a unique way to make uniform, solution-processable, crystalline, and porous COF nanospheres directly from the homogeneous solution of amine and aldehyde via spatial and temporal control of the nucleation and growth. This strategy of direct nucleation simultaneously showcases the caliber to tune the size of the COF nanospheres from 25 to 570 nm. We have also demonstrated the concept of mesoscale covalent self-assembly of those solution-processable COF nanospheres in the liquid-liquid interface (DCM-water bilayer) for the very first time, transmuting them into self-standing COF thin films with long-range ordered arrangements in two dimensions. The crystalline and porous (with TpAzo showing highest S-BET of 1932 m(2) g(-1)) free-standing COF thin films could be fabricated in a wide range of thicknesses from as low as 21 nm to as high as 630 nm. Both beta-ketoenamine (TpAzo, TpDPP) and imine (TpOMeAzo, TpOMeDPP) linked COF thin films have been synthesized via mesoscale covalent self-assembly of the solution-processable COF nanospheres illustrating the generality of this eloquent methodology. Further, the solution processability has been tested and utilized to cast COF thin films uniformly in the inner and outer surface of an alumina hollow fiber membrane. The COF thin film-alumina hollow fiber membrane composites have showcased promising selective molecular separation of He and O-2, He and CO2, and He and N-2.</p>
},
	issn = {0002-7863},
	doi = {10.1021/jacs.9b10788},
	author = {Sasmal, Himadri Sekhar and Halder, Arjun and Kunjattu, Shebeeb and Dey, Kaushik and Nadol, Athulya and Ajithkumar, Thalasseril G. and Bedadur, Prachiti Ravindra and Banerjee, Rahul}
}
@article {46867,
	title = {Connecting microscopic structures, mesoscale assemblies, and macroscopic architectures in 3D-printed hierarchical porous covalent organic framework foams},
	journal = {Journal of the American Chemical Society},
	volume = {142},
	year = {2020},
	month = {MAY },
	pages = {8252-8261},
	type = {Article},
	abstract = {<p>The induction of macro and mesopores into two-dimensional porous covalent organic frameworks (COFs) could enhance the exposure of the intrinsic micropores toward the pollutant environment, thereby, improving the performance. However, the challenge is to build a continuous hierarchically porous macro-architecture of crystalline organic materials in the bulk scale. In this regard, we have strategized a novel synthetic method to create hierarchically porous COF foams consisting of ordered micropores (2-2.2 nm) and disordered meso and macropores (50 nm to 200 mu m) as well as ordered macropores (1.5 mm to 2 cm). Herein, graphene oxide was used for creating disordered macro and mesopores in COF-GO foams. Considering the rheological features of the precursor hydrogel, we could integrate crystalline and porous COF-GO foams into self-supported three-dimensional (3D)-printed objects with the desired shapes and sizes. Therefore, we have engineered the 3D macro-architecture of COF-GO foams into complex geometries keeping their structural order and continuous porosity intact over a range of more than a million (10(-9) m to 10(-3) m). The interconnected 3D openings in these COF-GO foams further enhance the rapid and efficient uptake of organic and inorganic pollutants from water (\&gt;95\% removal within 30 s). The abundant distribution of interconnected macroporous volume (55\%) throughout the COF-GO foam matrix enhances the flow of water (1.13 x 10(-3) m.s(-1)) which results in efficient mass transport and adsorption.</p>
},
	issn = {0002-7863},
	doi = {10.1021/jacs.0c00555},
	author = {Mohammed, Abdul Khayum and Usgaonkar, Saurabh and Kanheerampockil, Fayis and Karak, Suvendu and Halder, Arjun and Tharkar, Minakshi and Addicoat, Matthew and Ajithkumar, Thalasseril G. and Banerjee, Rahul}
}
