Bimetallic PdFe 3 Nano‐Alloy with Tunable Electron Configuration for Boosting Electrochemical Nitrogen Fixation

作者：Jianjia Mu, Zhiwei Zhao, Xuan‐Wen Gao, Zhao-Meng Liu, Wen Luo, Zhenhua Sun, Qinfen Gu, Feng Li · 发表于：Advanced Energy Materials · 年份：2023 · DOI：10.1002/aenm.202303558 · 被引用次数：48 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Advanced Photocatalysis Techniques、Nanomaterials for catalytic reactions

Abstract Electrocatalyst plays animportant role in electrochemical ammonia synthesis by determining the nitrogen reduction reaction pathway. Featuring the inherent half‐filled 3d orbitals, ion‐based alloy electrocatalysts have been attracting much more attention owing to the controllable driving force to adsorb and activate N≡N bonds. Besides supplying unoccupied d ‐orbital to accommodate lone‐pair electrons to facilitate nitrogen adsorption, donating d ‐orbital electrons to nitrogen antibonding orbitals to dissociate N≡N bond is demandedas well. By palladium (Pd) to synthesize PdFe 3 nano‐alloy, numerous Fe 3d orbitals can be reconstructed via charge polarization between Fe and Pd, simultaneously lowering corresponding work functions. Meanwhile, the positively charged Fesites in PdFe 3 can strengthen suppress the proton adsorption by electrostatic repulsion. A considerably optimized ammonia production rate of 29.07 µg h −1 mg cat. −1 and Faradic efficiency of 22.8% are accomplished at a low overpotential of −0.2 V vs. RHE. Density functional theory combined with in‐situ ATR‐FTIR results confirmthe electrocatalytic nitrogen reduction follows the associative distalmechanism and the electron‐deficient Fe induced through Pd facilitates significantly lowering the first‐step‐protonation energy barrier of only 0.07 eV ( * N 2 + * H → * NNH).