Balanced NO₃⁻ reduction and NH₃ synthesis enabled by PdCuSnCoNi high-entropy metallene aerogels.

Major Contributions
 

1.A universal seed-mediated synthesis strategy was developed to overcome multi-metallic nucleation and growth disparities, enabling the first successful fabrication of structurally uniform high-entropy metallene aerogels (HEMAs), including PdCuSnCoNi and other quinary/senary compositions. 

2.PdCuSnCoNi HEMAs exhibit exceptional NO₃RR performance, achieving a maximum NH₃ Faradaic efficiency of 99.5% and an ultrahigh NH₃ yield rate of 4117.8 µg h⁻¹ mgcat ⁻¹, significantly surpassing conventional Pd metallene aerogels while maintaining excellent operational stability. 

3.Combined in situ ATR-IRAS, online DEMS, and DFT calculations reveal that electronic modulation within the multi-metallic framework optimizes Pd d-band center alignment, tunes *NO₂/*NO adsorption energies, and kinetically balances *H production and consumption—promoting efficient *NO₃ → *NO₂ → *NH₃ conversion and enabling superior NO₃RR activity.

主要貢獻
 

1.晶種介導合成策略：開發了一種通用的晶種介導（seed-mediated）合成策略，克服了多金屬成核與生長的差異，首次成功製備出結構均勻的高熵金屬烯氣凝膠（HEMAs），包括 PdCuSnCoNi 及其他五元/六元組分。

2.卓越的氨合成性能：PdCuSnCoNi HEMAs 展現出卓越的硝酸鹽還原反應（NO₃RR）性能。其氨（NH3）法拉第效率高達 99.5%，且產率達到超高的 4117.8 µg h⁻¹ mgcat ⁻¹。此性能顯著超越傳統 Pd 金屬烯氣凝膠，同時保持優異的操作穩定性。

3.機制揭示：電子調控與動力學平衡：結合原位 ATR-IRAS、線上 DEMS 與 DFT 計算揭示：多金屬骨架內的電子調控優化了 Pd d-帶中心（d-band center）的排列，調節了 *NO2/*NO 的吸附能，並在動力學上平衡了活性氫（*H）的生成與消耗。這促進了高效的 *NO₃ → *NO₂ → *NH₃轉化路徑，從而實現NO₃RR優異的活性。