Tunable 2D Conjugated Porous Organic Polymer Films for Precise Molecular Nanofiltration and Optoelectronics

Kristen Miller; Jessica M Gayle; Soumyabrata Roy; Mohamed H Abdellah; Rifan Hardian; Levente Cseri; Pedro G Demingos; Hema Rajesh Nadella; Frank Lee; Manoj Tripathi; Sashikant Gupta; Galio Guo; Sohini Bhattacharyya; Xu Wang; Alan B Dalton; Ashish Garg; Chandra Veer Singh; Robert Vajtai; Gyorgy Szekely; Pulickel Ajayan

doi:10.1002/smll.202401269

Tunable 2D Conjugated Porous Organic Polymer Films for Precise Molecular Nanofiltration and Optoelectronics

Small. 2024 Apr 30:e2401269. doi: 10.1002/smll.202401269. Online ahead of print.

Authors

Kristen Miller¹, Jessica M Gayle¹, Soumyabrata Roy¹, Mohamed H Abdellah², Rifan Hardian², Levente Cseri^{3

4}, Pedro G Demingos⁵, Hema Rajesh Nadella⁵, Frank Lee⁶, Manoj Tripathi⁶, Sashikant Gupta⁷, Galio Guo¹, Sohini Bhattacharyya¹, Xu Wang⁸, Alan B Dalton⁶, Ashish Garg⁹, Chandra Veer Singh⁵, Robert Vajtai¹, Gyorgy Szekely^{2

10}, Pulickel Ajayan¹

Affiliations

¹ Department of Materials Science and NanoEngineering, Rice University, Houston, Texas, 77005, USA.
² Advanced Membranes and Porous Materials Center, Physical Science and Engineering Division, King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.
³ Department of Chemical Engineering & Analytical Science, School of Engineering, The University of Manchester, The Mill, Sackville Street, Manchester, M1 3BB, UK.
⁴ Department of Chemistry, Femtonics Ltd., Tuzolto u. 58, Budapest, 1094, Hungary.
⁵ Department of Material Science and Engineering, University of Toronto, Ontario, ON M5S 1A1, Canada.
⁶ Department of Physics and Astronomy, University of Sussex, Brighton, BN1 9RH, UK.
⁷ Department of Materials Science and Engineering, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016, India.
⁸ Shared Equipment Authority, Rice University, Houston, Texas, 77005, USA.
⁹ Department of Sustainable Energy Engineering, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016, India.
¹⁰ Chemical Engineering Program, Physical Science and Engineering Division (PSE), King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.

PMID: 38687141
DOI: 10.1002/smll.202401269

Abstract

Structural design of 2D conjugated porous organic polymer films (2D CPOPs), by tuning linkage chemistries and pore sizes, provides great adaptability for various applications, including membrane separation. Here, four free-standing 2D CPOP films of imine- or hydrazone-linked polymers (ILP/HLP) in combination with benzene (B-ILP/HLP) and triphenylbenzene (TPB-ILP/HLP) aromatic cores are synthesized. The anisotropic disordered films, composed of polymeric layered structures, can be exfoliated into ultrathin 2D-nanosheets with layer-dependent electrical properties. The bulk CPOP films exhibit structure-dependent optical properties, triboelectric nanogenerator output, and robust mechanical properties, rivaling previously reported 2D polymers and porous materials. The exfoliation energies of the 2D CPOPs and their mechanical behavior at the molecular level are investigated using density function theory (DFT) and molecular dynamics (MD) simulations, respectively. Exploiting the structural tunability, the comparative organic solvent nanofiltration (OSN) performance of six membranes having different pore sizes and linkages to yield valuable trends in molecular weight selectivity is investigated. Interestingly, the OSN performances follow the predicted transport modeling values based on theoretical pore size calculations, signifying the existence of permanent porosity in these materials. The membranes exhibit excellent stability in organic solvents at high pressures devoid of any structural deformations, revealing their potential in practical OSN applications.

Keywords: 2D conjugated porous polymers; 2D nanosheets; optoelectronic; organic solvent nanofiltration; porous organic polymer thin films.