Towards developing efficient metalloporphyrin-based hybrid photocatalysts for CO₂reduction; anab initiostudy

Abstract

A series of thiophene-based donor-acceptor-donor (D–A–D) oligomer substituted metalloporphyrins (MPors) with different 3d central metal-ions (M=Co, Ni, Cu, and Zn) were systematically investigated to screen efficient hybrid photocatalysts for CO2...

Mechanistic Insights of Photocatalytic CO2 Reduction: Experimental versus Computational Studies

“…One of them is the design of systems with tight electronic interactions between the catalysts and the PS. The strategy of integrating into the same molecule the complexes that [98] Scheme 10. Different mechanisms proposed in the literature based on computational results.…”

“…For the particular case of the mechanisms of catalytic photoreduction reactions from CO 2 to CO using molecular transition metal-based catalysts, the first studies are even more recent (2015) and globally they are not very abundant. All of them use methods based on the density functional theory (DFT) and the most used functionals are the B3LYP, [62,80,96,98] in most cases [46,48,80,92] with the D3 correction for the dispersion proposed by Grimme, [99] and the M06 in some of its variants (M06L, M06-2X, M06-D3). [47,56,62] In general the geometries are optimised in the gas phase with a more modest basis set (they use usually pseudopotential for metals and 6-31G(d) for the rest of the atoms), and the energies are refined including the effect of the solvent with the Polarisable Continuum Model (PCM) or Solvent Model Density (SMD) using somewhat larger bases (the pseudopotential for the metal is maintained and the bases of the rest of the atoms are extended in many cases to 6-311 + G(d)).…”

“…In the same line of development of catalytic systems for CO 2 reduction of unifying photosensitised and catalyst, a work has been published recently [98] in which a series of complexes are studied computationally seeking to displace their absorption bands to the visible zone to achieve a hybrid photocatalyst, being capable of coordinating CO 2 and at the same time absorbing in the visible area and promoting the reduction of the substrate. Based on previous experimental CO 2 photoreduction studies [108,109] this work considers the thiophene-based donor-acceptor-donor (DÀ AÀ D) oligomer substituted metalloporphyrins (15, Figure 13) with different 3d central metal-ions (M = Co, Ni, Cu, and Zn).…”

Magnetically Recyclable Fe3O4@TMU-32 Metal–Organic Framework Photocatalyst for Tetracycline Degradation Under Visible Light

“…Figure a shows the structures of the relaxed TMU-32, Fe 3 O 4 , and Fe 3 O 4 @TMU-32, which contain 7, 216, and 223 atoms, respectively. To include weak van der Waals (vdW) interactions, the long-range vdW dispersion by the method of Grimme was employed to correct the generalized gradient approximation developed by the Perdew–Burke–Ernzerhof method . The core electrons were approximated by Troullier–Martins nonlocal pseudopotentials, and valence electrons were modeled with the double-ζ plus polarization basis set .…”

Highly sensitive and low-power consumption metalloporphyrin-based junctions for COx detection with excellent recovery

“…The C site itself can adopt three different geometrical orientations over the central metal of MPor. 51 In configurations named A and B, CO is horizontally placed along two pyrrole rings of MPor. But in B configuration, CO orients between two pyrrole rings of the MPor.…”