Structural, electronic, and mechanical properties of transition metal porphyrin-like graphenes, and their application in hydroxylation of methane

This study employs density functional theory to investigate the structural, electronic, and mechanical properties of Co, Fe, and Ni Porphyrin-Like Graphene (N4-G) structures. The study reveals a preference for in-plane configurations of metal atoms on N-doped graphene. Analysis of Bulk modulus, band structure, density of states, and magnetization highlights the distinctive electronic behaviors of Fe-N4-G and Ni-N4-G, showcasing semiconductor characteristics with narrow indirect band gaps, while Co-N4-G exhibits metallic behavior. Notably, Ni-N4-G lacks magnetic properties, distinguishing it from the magnetic behavior observed in the other structures. The investigation extends to the potential application of these structures as novel and promising catalysts for methane hydroxylation, a process critical for clean-burning fuel production. The results indicate moderate energy barriers for Co-N4-G and Ni-N4-G, with Fe-N4-G displaying the highest barrier, approximately five times larger. These valuable findings suggest that Co-N4-G and Ni-N4-G would be a promising candidate catalyst for methane hydroxylation, offering effective and stable catalytic capabilities. Overall, these findings present these metal-N4-G structures as appealing options for environmentally friendly and cost-effective oxidation processes.