Enhancing CO2 electroreduction with decamethylcucurbit[5]uril-alkaline earth metal modified Pd nanoparticles

Abstract

The electrochemical CO₂ reduction reaction (CO₂RR) offers a promising pathway to convert CO₂ into value-added chemicals, with CO production being a primary target. While the conversion of CO₂ to CO hinges on the delicate balance of *COOH and *CO binding energies, this study introduces a series of Pd-based hybrid catalysts, Me₁₀CB[5]–M/Pd (M = Sr, Ca, and Cd), to address this challenge. The catalysts were synthesized via thermal treatment of supramolecular precursors formed by Me₁₀CB[5], M²⁺, and [PdCl₄]²⁻ ions. Notably, Me₁₀CB[5]–Sr/Pd exhibited exceptional CO selectivity (91.3% FE_CO at −0.7 V vs. RHE) and long-term stability. The incorporation of Me₁₀CB[5]–Sr into the Pd catalyst system enhanced CO₂ adsorption, modulated the electronic structure of Pd, and optimized the adsorption/desorption energies of critical intermediates, ultimately leading to superior CO₂RR performance. This work underscores the potential of supramolecular engineering in designing high-performance electrocatalysts for CO₂ conversion.