Superior Performance and Catalytic Mechanism of an Icosahedral Quasicrystal Al‐Cu‐Fe in CO ₂ Reduction to CO

Dissimilar to long-range periodic crystals, quasicrystals feature long-range aperiodic order and noncrystallographic rotational symmetry. These structural peculiarities and complexities endow it with unique properties and untold research values, together with significant challenges in decoding the structure-property relationship. Herein, the application of icosahedral quasicrystal (iQC) Al₆₃Cu₂₅Fe₁₂ as a high-performance catalyst is investigated for reducing CO₂ to CO, known as the reverse water-gas shift reaction, which is a key reaction for producing useful chemicals. Compared with the samples with similar compositions but different structures, it shows superior CO₂ conversion rate and CO selectivity. Combined with density functional theory calculations, the origin of the high catalytic activity of iQC Al₆₃Cu₂₅Fe₁₂ has been deciphered. It is found that for the approximant crystal of the quasicrystal, the reaction tends to occur near the icosahedral cluster. Compared to other control groups, it exhibits much lower reaction barriers during CO₂ reduction to CO. This demonstrates that the high catalytic performance of iQC Al₆₃Cu₂₅Fe₁₂ stems from its internally rich icosahedral cluster content. The research exemplifies the potential of quasicrystals in the field of catalysis and sheds light on the structure-property relationship of complex structures.