The electrocatalytic CO2 reduction reaction (CO2RR) powered by renewable energy and promoted by transition metal catalysts, will play an important role in the global decarbonization process of the chemical industry, since represents a sustainable route for the production of value-added chemicals using CO2 as a feedstock. [1]-[2] However, despite the significant progress made in the field, selectivity, durability and intrinsic activity of the catalysts are still key challenges to achieve an efficient CO2RR. For organometallic molecular systems, characterized by a well-defined chemical environment of the active site, a rational tuning of the CO2RR efficiency and selectivity can be precisely controlled through a rational modification of the ligand scaffold. [3]-[5] Moreover, the encapsulation of molecularly defined active units into reticular frameworks was recently shown as an effective strategy to boost the CO2RR performances of molecular catalysts, but also to alter their redox behavior. [6]
In recent years, the synergy between molecules and nanostructured materials has been proposed as a promising approach to design efficient heterogeneous catalysts for CO2 electroreduction. For instance, the presence of organic modifiers on metallic surfaces was found to tune the stability of key reaction intermediates or the local surface microenvironment, thus altering the product selectivity. [7]-[8] In this contribution, we will discuss novel strategies and approaches to form hybrid electrocatalysts based on the utilization of reticular or molecular chemistry as tools to steer the CO2RR selectivity and activity of transition metal-based nanostructured catalysts. The discussion will focus on providing a molecular perspective towards a rational design of heterogeneous catalysts.
