General Synthesis of Amorphous Pd‐Based Nanoparticles Towards Highly Efficient Nitrate‐to‐Ammonia Electrocatalysis
Lei Xu, Chuhao Luan, Mingzi Sun, Weiwei Chen, Xiaozhi Liu, Chen Ma, Long Zheng, Gang Wang, Peng Han, Ping Gu, Xiao Wang, Chenhao Shu, Cheng Lyu, Zhenyu Zhang, Nailiang Yang, Hongyan He, Xiaohong Li, Dong Su, Bolong Huang, Wenjun Zhang, Ye ChenABSTRACT
Electrocatalytic nitrate reduction reaction (NO 3 RR) towards ammonia (NH 3 ) production is a critical process that sustainably converts hazardous nitrate to value‐added chemicals. Amorphous metal‐based nanomaterials are promising NO 3 RR catalysts owing to the abundant surface active sites, but their performance is still unsatisfactory for practical needs. We develop a robust one‐pot strategy to prepare a family of amorphous PdMP ( a ‐PdMP, M = Cu, Ni, Co, Fe, Mn, and Zn) nanoparticles with high yield, high structural stability, uniform morphology, and tunable composition. Impressively, the as‐prepared a ‐PdCoP nanoparticles show excellent electrocatalytic activity (onset potential measured at +0.3 V vs. reversed hydrogen electrode), high NH 3 selectivity, and outstanding long‐term stability (Faradaic efficiency (FE) maintained > ∼98% at 200 mA cm −2 for 200 h) in NO 3 RR. Theoretical calculations demonstrate that alloying in PdM can enhance overall electron exchange/transfer, while phosphization helps to stabilize the metal valence. Particularly, the a ‐PdCoP possesses a moderate d‐band center to avoid intermediate overbinding, meanwhile, it has the lowest work function to accelerate the electron transfer during NO 3 RR. Our work demonstrates that synergistic amorphization and phosphization of Pd alloy nanocatalysts can greatly promote their activity and durability in NO 3 RR. The universal synthesis approach provides guidance to prepare amorphous multielement nanomaterials as highly efficient electrocatalysts.