Electronic structure and oxygen reduction on tunable [Ti(IV)Pc]2+and Ti(II)Pc titanyl-phthalocyanines: A quantum chemical prediction

TL;DR

This study uses quantum chemical calculations to explore non-precious metal phthalocyanine complexes as potential catalysts for oxygen reduction in fuel cells, highlighting the effects of ligand substitution on catalytic activity.

Contribution

It provides a theoretical prediction of how ligand modifications in Ti(IV) and Ti(II) phthalocyanines enhance oxygen reduction, proposing new catalyst candidates for PEMFCs.

Findings

Ti(II)Pc triplet complexes can spontaneously reduce peroxide.

Fluorine substitution lowers energy barriers for reduction.

Chlorine substitution enables spontaneous peroxide reduction.

Abstract

The high cost of platinum-based catalysts has hampered the commercialization of polymer electrolyte membrane fuel cells (PEMFCs). Hence, the electronic structure and oxygen reduction ability of [Ti(IV)Pc]2+, Ti(II)Pc titanyl-phthalocyanines, and their tailored peripheral and axial ligand complexes were theoretically investigated to determine non-precious cathode catalysts. Our results revealed that the peripherally substituted and unsubstituted Ti(II)Pc triplet complexes can spontaneously reduce peroxide. The singlet [Ti(IV)Pc]2+ parent complex has a 6.45 eV barrier. However, fluorine substitution at peripheral positions reduced the energy barrier up to 0.45 eV. In addition, chlorine substitution has shown spontaneous peroxide reduction as in the case of triplets. The high catalytic activity of Ti(II)Pc complexes and singlet chlorine substituted complex is attributed to the optimal charge transfer between dioxygen molecule and the novel catalyst complexes. As a result, Ti(II)Pcs and chlorine substituted singlet complexes are considered as potential substitutions for the noble Pt-based catalyst for the PEMFCs.