Zhang Zhipu, Lu Shanshan, Zhu Moshuqi, Wang Fuli, Yang Kaiwen, Dong Bin, Yao Qiaofeng, Hu Wenping
State Key Laboratory of Advanced Materials for Intelligent Sensing & Key Laboratory of Organic Integrated Circuits, Ministry of Education & Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, China.
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China.
J Am Chem Soc. 2025 Jul 2;147(26):22806-22817. doi: 10.1021/jacs.5c04572. Epub 2025 Jun 16.
Heteroatom doping is an effective strategy for tuning the electronic structure and stability of non-noble transition metal (e.g., Fe, Co, and Ni) oxides for cost-efficient oxygen evolution reactions (OERs), but conventional doping methods usually give rise to unpredictable and uneven doping sites or even phase separation. Here, we develop an interfacial diffusion strategy for atomically precise doping of less electronegative heteroatoms to the lattices of 3 transition metal (Fe, Co, Ni) oxides, leveraging on the simple yet effective lattice-match principle. Taking FeO as a model, Cr can be uniformly doped and arranged in the alternating cation layers against Fe. As-prepared FeCrO lowers the overpotential from 438 mV of FeO to 258 mV at 10 mA cm in 1.0 M KOH and can operate for at least 1100 h with almost no performance attenuation at 250 mA cm. Multiple characterizations reveal that the ordered arrangement of Cr around Fe sites induces an electron flux from Cr to Fe, stabilizing active Fe species and accelerating the Fe/Fe/Fe redox cycle, thereby promoting water activation and *OH dehydrogenation. Besides, ordered Cr doping improves the OER stability of FeCrO by preserving surface basicity through Lewis acidic Cr and stabilizing the Fe-O bond to shift the reaction mechanism from lattice oxygen oxidation (LOM) to adsorbate evolution (AEM). This atomically precise doping strategy is easily scaled-up for kilogram production of FeCrO, and it is readily extendable to other transition metal oxides (e.g., NiO and CoO). Our work underscores the importance of atomically precise surface engineering in the manufacture of catalysts.
杂原子掺杂是一种调整非贵金属过渡金属（如铁、钴和镍）氧化物的电子结构和稳定性以实现具有成本效益的析氧反应（OER）的有效策略，但传统的掺杂方法通常会导致不可预测且不均匀的掺杂位点，甚至相分离。在此，我们开发了一种界面扩散策略，用于将电负性较小的杂原子精确地掺杂到三种过渡金属（铁、钴、镍）氧化物的晶格中，利用的是简单而有效的晶格匹配原理。以FeO为例，Cr可以均匀地掺杂并排列在与Fe交替的阳离子层中。制备的FeCrO在1.0 M KOH中，在10 mA cm下将过电位从FeO的438 mV降低到258 mV，并且在250 mA cm下可以运行至少1100小时，几乎没有性能衰减。多种表征表明，Fe位点周围Cr的有序排列诱导了从Cr到Fe的电子通量，稳定了活性Fe物种并加速了Fe/Fe/Fe氧化还原循环，从而促进了水的活化和*OH脱氢。此外，有序的Cr掺杂通过Lewis酸性的Cr保持表面碱性并稳定Fe-O键，将反应机理从晶格氧氧化（LOM）转变为吸附质析出（AEM），从而提高了FeCrO的OER稳定性。这种原子精确掺杂策略易于扩大规模以实现FeCrO的千克级生产，并且很容易扩展到其他过渡金属氧化物（如NiO和CoO）。我们的工作强调了原子精确表面工程在催化剂制造中的重要性。
