CO₂ Reduction by an Iron(I) Porphyrinate System: Effect of Hydrogen Bonding on the Second Coordination Sphere

Abstract

Transforming CO 2 into valuable materials is an important reaction in catalysis, especially because CO 2 concentrations in the atmosphere have been growing steadily due to extensive fossil fuel usage. From an environmental perspective, reduction of CO 2 to valuable materials should be catalyzed by an environmentally benign catalyst and avoid the use of heavy transition-metal ions. In this work, we present a computational study into a novel iron(I) porphyrin catalyst for CO 2 reduction, namely, with a tetraphenylporphyrin ligand and analogues. In particular, we investigated iron(I) tetraphenylporphyrin with one of the meso-phenyl groups substituted with o-urea, purea, or o-2-amide groups. These substituents can provide hydrogen-bonding interactions in the second coordination sphere with bound ligands and assist with proton relay. Furthermore, our studies investigated bicarbonate and phenol as stabilizers and proton donors in the reaction mechanism. Potential energy landscapes for double protonation of iron(I) porphyrinate with bound CO 2 are reported. The work shows that the bicarbonate bridges the urea/amide groups to the CO 2 and iron center and provides a tight bonding pattern with strong hydrogen-bonding interactions that facilitates easy proton delivery and reduction of CO 2 . Specifically, bicarbonate provides a low-energy proton shuttle mechanism to form CO and water efficiently. Furthermore, the o-urea group locks bicarbonate and CO 2 in a tight orientation and helps with ideal proton transfer, while there is more mobility and lesser stability with an o-amide group in that position instead. Our calculations show that the o-urea group leads to reduction in proton-transfer barriers, in line with experimental observation. We then applied electric-fieldeffect calculations to estimate the environmental effects on the two proton-transfer steps in the reaction. These calculations describe the perturbations that enhance the driving forces for the proton-transfer steps and have been used to make predictions about how the catalysts can be further engineered for more enhanced CO 2 reduction processes.

Interface properties of hydroxyapatite in ternary composites cathodes for electromethanogenesis

“…Several studies have reported that the presence of groups able to provide hydrogen-bonding interactions is beneficial for electroreduction processes, since it facilitates easy proton transfer and stabilize key intermediates. 77–82…”