Cao Wen, Wu Jie, Zhou Chunyan, Gao Xuehui, Hu Enlai, Zhang Jing, Chen Zhongwei
Department of Chemistry, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University, Jinhua, 321004, P. R. China.
Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, N2L 3G1, Canada.
Small. 2024 Jun;20(24):e2309769. doi: 10.1002/smll.202309769. Epub 2023 Dec 29.
Complicated oxygen evolution reaction (OER) poses the bottleneck in improving the efficiency of hydrogen production through water electrolysis. Herein, an integrated strategy to modulate the electronic structure of NiFe layered double hydroxide (NiFe-LDH) is reported by constructing Ag-incorporated NiCo-PBA@NiFe-LDH heterojunction with a hierarchical hollow structure. This "double heterojunction" facilitates local charge polarization at the interface, thereby promoting electron transfer and reducing the adsorption energy of intermediates, ultimately enhancing the intrinsic activity of the catalyst. It is noteworthy that an exchange bias field is observed between NiCo-PBA and NiFe-LDH, which will be conducive to regulating the electron spin states of metals and facilitating the production of triplet oxygen. Additionally, the unique hierarchical nanoboxes provide a large specific surface area that ensures adequate exposure to adsorption sites and active sites. Profiting from the synergistic advantages, the overpotential is as low as 190 mV at a current density of 10 mA cm, with a low Tafel slope of 21 mV dec. Moreover, density functional theory (DFT) calculation further substantiated that the incorporation of Ag in the heterojunction can effectively reduce the adsorption energy of reactant intermediates and enhance the conductivity.
复杂的析氧反应(OER)是提高水电解制氢效率的瓶颈。在此,通过构建具有分级中空结构的Ag掺入的NiCo-PBA@NiFe-LDH异质结,报道了一种调节NiFe层状双氢氧化物(NiFe-LDH)电子结构的集成策略。这种“双异质结”促进了界面处的局部电荷极化,从而促进了电子转移并降低了中间体的吸附能,最终提高了催化剂的本征活性。值得注意的是,在NiCo-PBA和NiFe-LDH之间观察到交换偏置场,这将有利于调节金属的电子自旋态并促进三线态氧的产生。此外,独特的分级纳米盒提供了大的比表面积,确保了吸附位点和活性位点的充分暴露。得益于协同优势,在电流密度为10 mA cm时过电位低至190 mV,塔菲尔斜率低至21 mV dec。此外,密度泛函理论(DFT)计算进一步证实,异质结中Ag的掺入可以有效降低反应物中间体的吸附能并提高电导率。