Zhang Jinyang, Zhang Yujing, Zhou Jiayi, Guo Haoran, Qi Limin
Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China.
Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, Xiangtan, Hunan, 411105, China.
Small Methods. 2025 Mar;9(3):e2401139. doi: 10.1002/smtd.202401139. Epub 2024 Sep 5.
The development of bifunctional, non-noble metal-based electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) through morphology and electronic engineering is highly attractive for efficient water splitting. Herein, hierarchical nanoarrays consisting of crystalline cobalt phosphide nanorods covered by amorphous Fe-doped cobalt phosphide nanocuboids (CoP/FeCoP) are constructed as bifunctional catalysts for both HER and OER. Experimental results and theoretical calculations reveal that the catalysts exhibit balanced dual-catalytic properties due to simultaneous introduction of Fe doping and phosphorus vacancies, leading to an optimized electronic structure of the CoP/FeCoP. Furthermore, the hierarchical nanoarrays made of crystalline/amorphous heterostructures significantly enhance the performance of the electrocatalysts. As a result, the CoP/FeCoP catalyst demonstrates remarkable performance in both HER and OER, with overpotentials of 74 and 237 mV at 10 mA cm in 1 m KOH, respectively, as well as a low cell voltage of 1.53 V at 10 mA cm for alkaline overall water splitting. This work integrates the morphology engineering involving design of hierarchical crystalline/amorphous nanoarrays and the electronic engineering through Fe doping and phosphorus vacancies for efficient water electrolysis. It may open a new route toward rational design and feasible fabrication of high-performance, multifunctional, non-noble metal-based electrocatalysts for energy conversion.
通过形貌和电子工程开发用于析氢反应（HER）和析氧反应（OER）的双功能、非贵金属基电催化剂，对于高效水分解极具吸引力。在此，构建了由非晶态铁掺杂磷化钴纳米立方体覆盖的结晶磷化钴纳米棒组成的分级纳米阵列，作为用于HER和OER的双功能催化剂。实验结果和理论计算表明，由于同时引入铁掺杂和磷空位，催化剂表现出平衡的双催化性能，从而导致CoP/FeCoP的电子结构得到优化。此外，由结晶/非晶异质结构制成的分级纳米阵列显著提高了电催化剂的性能。结果，CoP/FeCoP催化剂在HER和OER中均表现出卓越性能，在1 M KOH中10 mA cm时的过电位分别为74和237 mV，在10 mA cm时碱性全水分解的电池电压低至1.53 V。这项工作将涉及分级结晶/非晶纳米阵列设计的形貌工程与通过铁掺杂和磷空位的电子工程相结合，用于高效水电解。它可能为合理设计和可行制备用于能量转换的高性能、多功能、非贵金属基电催化剂开辟一条新途径。
