Enhancing CO electroreduction with decamethylcucurbit[5]uril-alkaline earth metal modified Pd nanoparticles

The electrochemical CO 2 reduction reaction (CO 2 RR) offers a promising pathway to convert CO 2 into value-added chemicals, with CO production being a primary target. While the conversion of CO 2 to CO hinges on the delicate balance of *COOH and *CO binding energies, this study introduces a series of Pd-based hybrid catalysts, Me 10 CB[5]-M/Pd (M = Sr, Ca, and Cd), to address this challenge. The catalysts were synthesized via thermal treatment of supramolecular precursors formed by Me 10 CB[5], M 2+ , and [PdCl 4 ] 2− ions. Notably, Me 10 CB[5]-Sr/Pd exhibited exceptional CO selectivity (91.3% FE CO at −0.7 V vs. RHE) and long-term stability. The incorporation of Me 10 CB[5]-Sr into the Pd catalyst system enhanced CO 2 adsorption, modulated the electronic structure of Pd, and optimized the adsorption/desorption energies of critical intermediates, ultimately leading to superior CO 2 RR performance. This work underscores the potential of supramolecular engineering in designing high-performance electrocatalysts for CO 2 conversion. Pd NP modification with Me 10 CB[5]-M capsules boosted CO 2 RR by enhancing CO 2 adsorption, tuning Pd's electronic structure, and optimizing *COOH/*CO binding.