Buckybowls as adsorbents forCO₂, CH₄, and C₂H₂: Binding and structural insights from computational study

Abstract

Noncovalent functionalization of buckybowls sumanene (S), corannulene (R), and coronene (C) with greenhouse gases (GGs) such as CO2 , CH4 (M), and C2 H2 (A) has been studied using hybrid density functional theory. The propensity and preferences of these small molecules to interact with the concave and convex surfaces of the buckybowls has been quantitatively estimated. The results indicate that curvature plays a significant role in the adsorption of these small molecules on the π surface and it is observed that buckybowls have higher binding energies (BEs) compared with their planar counterpart coronene. The concave surface of the buckybowl is found to be more feasible for adsorption of small molecules. BEs of small molecules towards π systems is CO2 > A > M and the BEs of π systems toward small molecules is S > R > C. Obviously, the binding preference is dictated by the way in which various noncovalent interactions, such as π···π, lone pair···π, and CH···π manifest themselves on carbaneous surfaces. To delineate the intricate details of the interactions, we have employed Bader's quantum theory of atoms in molecule and localized molecular orbital energy decomposition analysis (LMO-EDA). LMO-EDA, which measures the contribution of various components and traces the physical origin of the interactions, indicates that the complexes are stabilized largely by dispersion interactions.

Piperine Encapsulation within Cucurbit[n]uril (n=6,7): A Combined Experimental and Density Functional Study

“…In piperine@CB[7] there was 27 number of BCP's which can be classified into interactions such as,13 C=O⋅⋅⋅H and 13 N⋅⋅⋅H type, and one C⋅⋅⋅O=C type interaction. The heteroatom interactions in these systems were in the range of 0.007 to 0.011 a.u, which are well within those observed for the weak non‐covalent interactions . The Laplacian of electron density ∇ 2 ρ, at all the BCPs are negative, indicating the presence of covalent interaction between the guest and host molecule.…”

“…The measure of electron density (ρ) at the BCP provides the information about the nature and strength of bonding between the molecules in an inclusion complex . The sign of the Laplacian is determined by the energy that dominates in the bonding zone.…”

Performance of density functionals for modeling vapor liquid equilibria of CO2 and SO2

“…Conventional technologies (such as ammonia scrubbing, solvent absorption) to remove these gases have certain disadvantages such as, high energy cost, corrosion, solvent loss, degradation, and byproducts production . The development of new materials, ionic liquids, and modification of industrial processes are an ongoing effort by researchers to efficiently capture these gases . Our ability to model these sorption processes using a first principles approach can have significant impact in speeding up the discovery process.…”

Structure, electronic, inclusion complex formation behavior and spectral properties of pillarplex

“…Thus, it can be suggested that the Au-Pillarplex have more π bond character towards the guest molecules [40]. EDA analysis provides quantitate measurement, which would be useful to understand the nature of interaction in these complexes [41]. The total binding energies are decomposed into ΔE disp , ΔE Pauli , ΔE elstat , and ΔE orb terms.…”