Ultrafine Nanoporous Ordered High-Entropy Intermetallics with Isolated Multisites toward Electrocatalytic Aldehyde Hydrogenation

Developing high-efficiency alloy catalysts toward electrocatalytic hydrogenation is crucial for large-scale sustainable chemical transformations, but traditional single-principal-element alloys usually suffer from insufficient activity and stability due to randomly dispersed active sites and limited electron-donating ability. Here, we report a Zn-assisted electrochemical phase transformation (Zn-EPT) strategy to synthesize ultrafine nanoporous (∼2 nm) high-entropy intermetallics (np-HEIs) featuring spatially isolated multisites under mild conditions, utilizing the low melting point and mixing enthalpy of Zn as a sacrificial element to incorporate disparate metals into a nanoporous body-centered framework. Among all candidates, the nanoporous (Pd 0.25 Cu 0.25 Ag 0.25 Ir 0.25 )Zn (np-PCAIZ) achieves exceptional electrocatalytic furfural hydrogenation performance with 93.8% conversion, 92.4% FE, and 100% selectivity at −0.2 V vs RHE and demonstrates outstanding stability over 120 h at 100 mA cm –2 in a membrane electrode assembly for gram-scale production of furfuryl alcohol. Theoretical calculations combined with experimental results reveal that the ordered high-entropy structure and isolated multisites of np-PCAIZ optimize the η 2 -(C, O)-aldehyde adsorption configuration for C═O bond activation and facilitate a highly interconnected two-coordinated hydrogen-bonded network for directional H* transfer and suppressing the competitive hydrogen evolution reaction (HER). The presented Zn-EPT strategy for synthesizing ultrafine np-HEIs offers a general blueprint for designing high-efficiency electrocatalysts for electrocatalytic hydrogenation and other related applications.