Research Projects

The electrocatalytic conversion of CO₂ into valuable chemicals and fuels has emerged as a clean and sustainable technology to mitigate the increasing levels of CO₂ emissions while reducing dependence on non-renewable resources such as fossil fuels. The electrocatalyst plays a pivotal role in determining the performance of electrocatalytic carbon dioxide reduction reaction (ECO₂RR). Over the past decade, a wide range of homogeneous and heterogeneous catalysts have been extensively investigated for ECO₂RR. However, these systems often encounter several limitations such as poor stability, low selectivity, high activation energies and overpotentials. Very recently, bimetallic covalent-organic frameworks (BMCOFs) based electrocatalysts appeared as a compelling alternative for CO₂RR. The integration of two metal species within the COF structure gives rise to a synergistic effect, leading to significantly enhanced catalytic activity when compared to monometallic counterparts. The unique electronic and geometric characteristics of the two metal species within BMCOFs offer exciting opportunities for optimized electronic structures, adjustable redox potentials and an increased number of active sites, rendering BMCOFs as efficient catalysts for CO₂RR. Although BMCOF-based electrocatalysts hold great promise, they still encounter several key challenges, such as limited electrical conductivity, insufficient insight into the interaction mechanism of bimetallic sites and selectivity of catalysts toward high-value ECO₂RR products, highlighting the need for further structural and compositional innovations. Cobalt bis(dicarbollide) anion tethered metal porphyrin or phthalocyanine based bimetallic mixed-valence COFs as efficient electrocatalysts for the CO₂RR can bridge these gaps. Integrating cobalt bis(dicarbollide) anions into the metal porphyrin or phthalocyanine based COFs is expected to not only enhances structural stability but also promotes the formation of mixed valence states (M³⁺/M²⁺), which can facilitate intervalence charge transfer (IVCT), enabling rapid and efficient electron hopping between metal centers, thereby improving the overall conductivity. Additionally, the presence of multiple accessible oxidation states can support dynamic redox cycling, which is essential for effective CO₂ reduction, favoring the formation of other high value hydrocarbons over the more commonly observed CO production by most of the COF-based electrocatalysts. A further advantage lies in the coexistence of both high- and low-spin states within the same COFs (except Zn²⁺), which is anticipated to play a pivotal role in reactant adsorption, intermediate formation and electron transfer, ultimately influencing the selectivity and lowering the energy barrier for C–C coupling in electrochemical CO₂RR.