High-Performance Ligand-Protected Metal Nanocluster Catalysts for CO₂ Conversion through the Exposure of Undercoordinated Sites

Previous experimental breakthroughs reveal the potential to create novel heterogeneous catalysts for the electroreduction of CO2 to a high-value product CO using ligand-protected Au-based nanoclusters. Since the chemical composition and geometric structures have been precisely defined, it is possible to adopt robust design guidelines for the development of practical catalysts and to fundamentally elucidate the underlying reaction mechanism. In this short review, the computational progress made to understand the experimentally observed reduction process on the following subset of materials—Au25(SR)18−, Au24Pd(SR)18, Au23(SR)16− and Au21Cd2(SR)16−—is described. A significant finding from our first-principles mechanistic studies is that CO2 conversion on the fully ligand protected nanoclusters is thermodynamically unfavorable due to the very weak binding of intermediates on the surface region. However, the reaction becomes feasible when either Au or S sites are exposed through the removal of a ligand. The results particularly point to the role of undercoordinated S sites in the creation of highly functional heterogeneous catalysts that are both active and selective for the CO2 conversion process. The incorporation of dopants could significantly influence the catalytic reactivity of the nanoclusters. As demonstrated in the case of the monopalladium substitution in Au25(SR)18−, the presence of the foreign atom leads to an enhancement of CO production selectivity due to the greater stabilization of the intermediates. With the Cd substitution doping of Au23(SR)16−, the improvement in performance is also attributed to the enhanced binding strength of the intermediates on the geometrically modified surface of the nanocluster