Selectivity of Cobalt Corrole for CO vs. O2 and N2 in Indoor Pollution

Abstract

Coal combustion causes indoor pollution of CO. In this work, DFT calculations on cobalt corrole (Co(Cor)) with three most common indoor gas molecules (N2, O2 and CO) were performed. The Mulliken spin densities show that the ground states of Co(N2)(Cor), Co(CO)(Cor) and Co(OC)(Cor) have an anti-ferromagnetic coupling fashion of the electrons on the Co 3d z 2 orbital and the π orbital of the corrole ring. However, Co(O2)(Cor) has a triplet ground state. With the spin contamination corrections, the Co(N2)(Cor) binding energy was obtained at −50.6 kcal mol−1 (B3LYP-D3). While CO can interact with Co(Cor) in two different ways, and their binding energies were −22.8 and −10.9 kcal mol−1 (B3LYP-D3) for Co(CO)(Cor) and Co(OC)(Cor), respectively. The natural bond orbital charges on the axial ligands (NO, CO, OC) are increased upon the chemical bond formation. These are the cause of the shorten metal-ligand bond and the increase of the wavenumber of the metal-ligand bond vibrational transitions. While the charges for O2 are decreased, leading to bond elongation as well as the decrease of the wavenumber upon complexation. Overall, O2 was found to be hardly coordinated with Co(Cor). This study provides a detailed molecular understanding of interactions between a gas sensor and gaseous indoor air-pollutants.

Revealing the Superior Electrocatalytic Performance of 2D Monolayer WSe2 Transition Metal Dichalcogenide for Efficient H2 Evolution Reaction

“…[36][37][38][39][40][41] This B3LYP-D3 DFT method suffers less (or no) spin contaminations effect compared to the other post-Hartree-Fock (HF) methods which helps to provide an excellent calculations for geometry, energy and electron density. [24,35,[42][43][44][45][46] Semi-empirical Grimme's 3 rd order dispersion correction (Grimme's-D3) is taken account to encounter the non-bonding weak van del Waals (vdW) interactions among different layers and atoms to achieve a fine equilibrium geometry. [47][48][49][50] Triple-ζ valence polarization (TZVP) quality Gaussian types of basis set with Gaussian types of atomic orbitals (GTO) has been used for the Se atoms and Gaussian basis sets of W_cora_1996 has been used for the W atoms in the present computations.…”

Porous organic polymers based on cobalt corroles for carbon monoxide binding

“…Cobalt metallocorroles are a class of molecules belonging to the porphyrinoid family that are able to coordinate CO at the cobalt(III) center with no interference with O 2 and N 2 since no coordination of these gas occurs on the metal. [33][34][35] Therefore, the introduction of such molecular complexes in a porous solid should confer the same properties to the material. In our recent investigations, cobalt corroles based materials have demonstrated high affinity for CO binding and promising results have been obtained by our group and others [33][34][35] for the elaboration of design CO sensors associated with a sensible technology transduction process.…”

“…[33][34][35] Therefore, the introduction of such molecular complexes in a porous solid should confer the same properties to the material. In our recent investigations, cobalt corroles based materials have demonstrated high affinity for CO binding and promising results have been obtained by our group and others [33][34][35] for the elaboration of design CO sensors associated with a sensible technology transduction process. 36 However, more convincing results have to be obtained in virtue of the relative instability of cobalt corrole in its tetracoordinated active state, that means without axial donor ligands.…”

Magnetite–Corrole Hybrid Nanoparticles

“…Recent developments on chemical functionalization approaches of corroles have given new impetus to the application of these compounds in several areas [1][2][3][4][5][6]. For example, they are used in the therapeutic field as inactivation agents for bacteria, viruses, and fungi; contrast agents for biomedical imaging; photosensitizers for photodynamic therapy to fight cancer [7][8][9][10][11][12][13][14][15][16]; and also as catalysts [5] and sensors [4].…”