Unveiling the Electrocatalytic Activity of Metallophthalocyanine Based Metal–Organic Frameworks toward CO ₂ Reduction Reactions

The exploration of innovative materials possessing significant efficiency and durability has become a focal point in electrochemical energy conversion, driven by escalating energy demands. While the pathways leading to C2+ products are often complex, the wide scope of their application has motivated the ongoing search for suitable electrocatalysts. Transition metal macrocyclic metallophthalocyanine (MPc) based catalysts, characterized by their unique 2D structure, have gathered attention due to their potential for highly tailorable structures and molecular functionalities, thus expanding their utility as electrocatalytic materials for energy conversion. Here, we have explored the potential of CuPc–Cu–O MOF (in short CuPc), to achieve fuels with more than one carbon atom, such as ethylene and ethanol in addition to methane by computationally designing a 2D monolayer slab structure of the CuPc. The equilibrium geometry, structural and electronic properties of the CuPc were examined by using the periodic hybrid density functional theory with the addition of Grimme’s dispersion corrected (i.e., B3LYP-D3) method. The study revealed its semiconducting nature, with a very low electronic bandgap of 0.64 eV, indicating good electrical conductivity and efficient charge transfer. The exploration of the reaction mechanism shows that the CuPc favors the generation of C2H5OH over C2H4, with a more favorable relative adsorption energy (ΔEads) of −2.76 eV compared to 2.11 eV for C2H4 formation. This MPc-based MOF also demonstrates a remarkable electrocatalytic activity for CO2 reduction to CH4, with a ΔEads value of −2.28 eV. Thus, CuPc underscores its promise for the rational development of efficient electrocatalysts and holds significance in elucidating the electrocatalytic CO2 reduction mechanism.