Understanding of economically and industrially important reactions, such as hydrocarbon transformation, CO oxidation and carbon dioxide reduction at atomistic level is challenging for designing nano-catalysts with high activity and selectivity toward desirable products. To clearly envision the reaction mechanism, state-of-the-art electronic structure theory is able to offer an excellent and practical tool that provides insight to structure and reaction mechanism complementing experiments or in certain cases, suggest and offer an important findings that is not possible by experimental investigations. Computational methods are powerful tools to study reaction mechanism and perform a high-throughput screening of the catalysts with a reasonable cost.

We investigated industrially important reactions on nano-reactors, i.e. zeolites, metal organic frameworks (MOFs), graphenes, and transition metal carbides. Charge transfers played an important role on the activity of the catalyst by governing the bond breaking and forming of molecules. In case of zeolites, long range interaction from the framework structures also contributed to assist and select the preferable transition structures in the confined spaces.

We investigate the reaction mechanism of the CO oxidation on Zn⁺ ion in ZSM-5 zeolite and alkoxide functionalized MOF-5 by means of density functional theory (DFT). Unlike ionic ion-exchanged zeolites, metal-covalent character between Zn site and organic linker plays a key role in controlling the charge transfer to and from Zn site and in turn controls the reaction activity. In our study, organic-linker of the MOF system is modified with respect to its electron donating and withdrawing capabilities and the effect of electronic structure on the activity is evaluated. We establish the relationship to obtain activity descriptors which are useful for the molecular design and engineering process. By systematically modifying the linkers, we propose that MOFs with controllable activity are a promising platform for uniform and highly loaded metal-catalyst.

Capture and conversion of carbon dioxide (CO₂) into valuable chemicals is a critical challenge in the development of environmentally friendly, economic, and renewable energy technologies. We establish the electronic structure based model to predict efficient catalysts based on tungsten carbide with a sub-monolayer metal ad-atoms. We employ the model to tune the oxophilicity and carbophilicity of the surface and exploit to tailor catalysts with desirable product selectivity and optimized activation potential by tuning. Our approach can be used to predict site preference and binding energy trends for complex catalyst surfaces.

Intermediate adsorption governs CO₂ electroreduction on metal coated Tungsten Carbides (WC).