Porous two-dimensional monolayers have gained interest both in theoretical and experimental research because of their controlled pore size and evenly distributed holes within the basal plane. Herein, we have investigated the efficient trapping of three pollutants (HF, HCN, and H2S) on the recently synthesized porous two-dimensional nitrogeneted holey carbon (C2N-h2D) monolayer using periodic density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The differential binding positions/orientations of HF, HCN, and H2S in the cavity of C2N depend on their adsorption energy and charge transfer efficiency. H2S serves as a charge donor while HF and HCN act as charge acceptors. Our AIMD simulations demonstrate that the C2N monolayer is thermally stable at room temperature. Adsorption occurs through physisorption, and no chemical bond is formed between the molecule and the C2N surface irrespective of the site of interaction. Electrostatic interactions and hydrogen bonding facilitate strong noncovalent interactions between the polar pollutants and C2N. I-V characteristics of the C2N monolayer in the presence of the adsorbed molecules show an increase in current for H2S at a bias of 1.0 V. However, for acceptor molecules, it shows a decrease (HF, bias = 3.0 V and HCN, bias = 2.5 V). Such unique sensitivity of C2N toward donor/acceptor molecules advocates its application for gas sensing applications.
Bibliographical noteFunding Information:
K.B. gratefully acknowledges IACS for financial assistance in the form of doctoral fellowships. S.M.P. thanks IACS for awarding Research Associate Fellowships. A.D. thanks DST, BRNS, and INSA for partial funding. We thank the CRAY supercomputer and IBM P7 cluster for computational facilities.
© 2018 American Chemical Society.