Functionalized Rutile TiO₂(110) as a Sorbent To Capture CO₂ through Noncovalent Interactions: A Computational Investigation

Abstract

The present study evaluates the CO2 adsorption capacity of functionalized rutile TiO2(110), using the density functional theory and ab initio molecular dynamics simulations. The defect-free TiO2 surface is functionalized (f-TiO2) with alkanolamines (AKAs), namely, monoethanolamine (MEA), 3-aminopropanol (3AP), and amino acids (AAs) glycine (GLY) and β-alanine (β-ALA). These functionalized adsorbents attain stability through bifunctional/bidentate binding of weakly acidic OH/COOH groups to TiO2 surface. The AKAs bind parallel to the surface, whereas the AAs bind perpendicular to the TiO2 surface, exhibiting several binding sites favorable for multiple, cooperative noncovalent interactions with CO2. The nature and strength of these interactions are evaluated in terms of binding energies, vibrational frequencies, quantum theory of atoms in molecules (QTAIM) approach, and charge-transfer analysis. The subtle yet substantial interactions of CO2 with f-TiO2 will lead to physisorption and diffusion through pores/channels of f-TiO2-based solid adsorbents, which consequently reduce the energy required for the regeneration process. Among all of the configurations of CO2 binding with f-TiO2, GLY-TiO2···CO2 displays the highest binding energy of −46 kJ/mol, and the trend is follows as: GLY > 3AP > MEA > β-ALA. Finally, this study examines the possibility of f-TiO2-based solid adsorbents as promising materials for CO2 capture at reduced cost in view of their preference toward physisorption of CO2 gas molecules.

Role of Functional Groups in an Ionic Liquid Decorated Au(111) Surface for CO2 Capture and Activation: A First Principle Approach

“…Our studies are well correlated with the recent reports on the non-covalent interaction of CO 2 at amino acid-functionalized TiO 2 surface by DFT methods. 19 In the present work, we achieved better activation compared with previous work. 19 The details about the charge delocalization of CO 2 at the interfacial are discussed in the next section.…”

“…18 This is because CO 2 has strongly bounded with the metal surfaces leads to large energy consumption for the adsorbent (CO 2 ) regeneration. This problem can be avoided by the amino acids, 19 alkali metal cations, 20 and ionic liquids 21 incorporated to the metal surfaces. 22,23 The electrocatalytic incorporation of above mentioned functionalized cocatalyst (ILs) with solid adsorbents (i.e., Au, Ag, Cu, and graphene, etc) [24][25][26][27][28][29] can effectively activate and convert CO 2 molecules.…”

Brookite TiO2 Nanoparticles Decorated with Ag/MnOx Dual Cocatalysts for Remarkably Boosted Photocatalytic Performance of the CO2 Reduction Reaction

“…In the last few decades, titania (TiO 2 ) has been the most popularly used photocatalyst in the field of solar-driven energy conversion. Among the three naturally existing crystal phases (anatase, rutile, and brookite), brookite has been relatively rarely studied owing to the difficulty in fabricating a pure phase via the traditional solution preparation process. − In 2012, high-quality brookite titania single-crystalline nanosheets with specific facets exposed were synthesized through a hydrothermal process . Compared with other morphologies, it has better photodegradation activity for organic contaminants.…”

NaNO3-Promoted MgO-Based Adsorbents Prepared from Bischofite for CO2 Capture: Experimental and Density Functional Theory Study

“…All simulations were conducted on the basis of density functional theory using the CASTEP code of Material Studio software. Perdew–Burke–Ernzerhof exchange–correlation functional and generalized gradient approximation are used to perform geometric optimization of the simulation. − The energy cutoff was set to 370 eV. The Brillouin zone was sampled using the Monkhorst–Pack grid of 4 × 4 × 1 for simulation calculations.…”