<p>Electro-catalytic reduction of carbon dioxide to value-added fuel conversion is one of the most challenging technologies available for mitigating environmental problems. Here, we report CO₂ reduction on a series of six selected doped and undoped Ti₂O₄ and Zr₂O₄ nanoparticles to explore the activation and reduction of CO₂ to formic acid. To tune the electronic structure and activation process, we doped transition metal (M = Cr, Mo, W) into Ti₂O₄ and Zr₂O₄ nanoparticles. Various parameters like adsorption energy, binding energy, projected density of states (PDOS), Mulliken charges, charge density geometric properties, and molecular dynamics were analyzed using density functional theory (DFT). Highest adsorption is associated with Mo and W-doped systems and the lowest by Cr. Only Mo and W doped nanoparticles are able to activate CO₂. Molecular dynamics studies also revealed that CO₂ is strongly adsorbed on TiMoO₄, TiWO₄, ZrMoO₄, and ZrWO₄ and is retained without migration. These findings are immensely important, providing new ideas for the design of M@Ti₂O₄ and M@Zr₂O₄ cluster catalysts for the conversion of CO₂ into valuable fuels.</p>