Xi Wenguang, Yan Gang, Lang Zhongling, Ma Yuanyuan, Tan Huaqiao, Zhu Haotian, Wang Yonghui, Li Yangguang
Key Laboratory of Polyoxometalate Science of the Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, 130024, China.
College of Material Science and Engineering, Jilin Jianzhu University, Changchun, 130118, China.
Small. 2018 Oct;14(42):e1802204. doi: 10.1002/smll.201802204. Epub 2018 Sep 21.
A rationally designed oxygen evolution reaction (OER) catalyst with advanced structural and compositional superiority is highly desirable to optimize electrocatalytic performance. Prussian blue analogues (PBAs) with adjustable element compositions and accessible porous structures represent a promising precursor for the preparation of OER catalysts. Herein, oxygen-doped nickel iron phosphide nanocube arrays (Ni P/(NiFe) P(O) NAs) grown on Ni foam is rationally designed and fabricated from PBAs. The porous structure and the synergistic effect of Ni and Fe enable superior electrocatalytic performance and stability toward the OER in alkaline electrolytes. Density functional theory calculations reveal that Fe-incorporated Ni P can generate new active sites on the Fe atoms, and the energy barriers of the intermediates and products are decreased efficiently in the presence of surface doped oxygen, both processes are crucial factors for enhanced catalytic performances. In 1 m KOH, the Ni P/(NiFe) P(O) NAs afford current densities of 10 and 800 mA cm at overpotentials of 150 and 530 mV, respectively, which outperform the commercial noble metal IrO . Ni P/(NiFe) P(O) NAs also have long-term stability over 100 h at a high current density. The present approach may provide a new avenue for the controlled assembly of nanoarrays for energy storage and conversion applications.
为了优化电催化性能，迫切需要一种具有先进结构和成分优势的合理设计的析氧反应（OER）催化剂。具有可调节元素组成和可及多孔结构的普鲁士蓝类似物（PBAs）是制备OER催化剂的有前途的前驱体。在此，通过PBAs合理设计并制备了生长在泡沫镍上的氧掺杂镍铁磷化物纳米立方阵列（NiP/(NiFe)P(O)NAs）。多孔结构以及Ni和Fe的协同效应使其在碱性电解质中对OER具有优异的电催化性能和稳定性。密度泛函理论计算表明，掺入Fe的NiP可以在Fe原子上产生新的活性位点，并且在表面掺杂氧的情况下，中间体和产物的能垒会有效降低，这两个过程都是提高催化性能的关键因素。在1 m KOH中，NiP/(NiFe)P(O)NAs在过电位分别为150和530 mV时，提供的电流密度分别为10和800 mA cm，优于商业贵金属IrO。NiP/(NiFe)P(O)NAs在高电流密度下也具有超过100 h的长期稳定性。本方法可为储能和转换应用中纳米阵列的可控组装提供一条新途径。
