Crystal‐Phase‐Engineered High‐Entropy Alloy Aerogels for Enhanced Ethylamine Electrosynthesis from Acetonitrile

Abstract Crystal‐phase engineering that promotes the rearrangement of active atoms to form new structural frameworks achieves excellent result in the field of electrocatalysis and optimizes the performance of various electrochemical reactions. Herein, for the first time, it is found that the different components in metallic aerogels will affect the crystal‐phase transformation, especially in high‐entropy alloy aerogels (HEAAs), whose crystal‐phase transformation during annealing is more difficult than medium‐entropy alloy aerogels (MEAAs), but they still show better electrochemical performance. Specifically, PdPtCuCoNi HEAAs with the parent phase of face‐centered cubic (FCC) PdCu possess excellent 89.24% of selectivity, 746.82 mmol h⁻¹ g⁻¹_cat. of yield rate, and 90.75% of Faraday efficiency for ethylamine during acetonitrile reduction reaction (ARR); while, maintaining stability under 50 h of long‐term testing and ten consecutive electrolysis cycles. The structure–activity relationship indicates that crystal‐phase regulation from amorphous state to FCC phase promotes the atomic rearrangement in HEAAs, thereby optimizing the electronic structure and enhancing the adsorption strength of reaction intermediates, improving the catalytic performance. This study provides a new paradigm for developing novel ARR electrocatalysts and also expands the potential of crystal‐phase engineering in other application areas.