Han Di, Du Gaohui, Wang Yunting, Jia Lina, Chen Shixian, Zhao Wenqi, Su Qingmei, Ding Shukai, Zhang Miao, Xu Bingshe
Materials Institute of Atomic and Molecular Science, Shaanxi University of Science and Technology, Xi'an 710021, China.
Materials Institute of Atomic and Molecular Science, Shaanxi University of Science and Technology, Xi'an 710021, China; Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan 030000, China.
J Colloid Interface Sci. 2023 Dec;651:415-423. doi: 10.1016/j.jcis.2023.08.008. Epub 2023 Aug 3.
Black phosphorus (BP), as a burgeoning two-dimensional material, has shown good electrocatalytic activity due to its unique electronic structure and abundant active sites.However, the presence of lone pair electrons in black phosphorus leads to its poor stability and rapid degradation in an oxygen/water environment, which greatly limits its practical application. Herein, BP-Co heterojunctions were synthesized on carbon nanotube@nitrogen-doped carbon (BP-Co/CNT@NC) by the pyrolysis of ZnCo-zeolitic imidazolate frameworks and subsequent solvothermal treatment. The BP-Co Schottky junction improved the electrocatalytic stability of BP, modulated its electronic structure, improved its conductivity and electron transfer during the electrocatalytic reaction. Density functional theory calculation was used to confirm the electron transfer and redistribution at the interface between BP and Co, which constructed an oppositely charged region and formed a strong built-in field. Energy band configuration analysis revealed a narrowed band gap because of the formation of BP-Co Schottky junction. Consequently, the optimized BP-Co/CNT@NC exhibited a superior oxygen evolution reaction (OER) performance, a low overpotential of 370 mV@100 mA/cm, with a small Tafel slope of 40 mV/dec and good long-term stability. Particularly, the catalyst has an excellent OER performance at the high current density of 100-400 mA/cm. This strategy improves the stability of BP electrocatalysts and strengthens their utilization in electrocatalytic applications.
黑磷（BP）作为一种新兴的二维材料，因其独特的电子结构和丰富的活性位点而表现出良好的电催化活性。然而，黑磷中孤对电子的存在导致其稳定性较差，在氧气/水环境中会迅速降解，这极大地限制了其实际应用。在此，通过热解锌钴沸石咪唑酯骨架并随后进行溶剂热处理，在碳纳米管@氮掺杂碳（BP-Co/CNT@NC）上合成了BP-Co异质结。BP-Co肖特基结提高了BP的电催化稳定性，调节了其电子结构，提高了其导电性以及电催化反应过程中的电子转移。利用密度泛函理论计算证实了BP与Co界面处的电子转移和重新分布，构建了一个带相反电荷的区域并形成了一个强内建电场。能带结构分析表明，由于BP-Co肖特基结的形成，带隙变窄。因此，优化后的BP-Co/CNT@NC表现出优异的析氧反应（OER）性能，在100 mA/cm²时过电位低至370 mV，塔菲尔斜率小至40 mV/dec，并且具有良好的长期稳定性。特别地，该催化剂在100 - 400 mA/cm²的高电流密度下具有优异的OER性能。这种策略提高了BP电催化剂的稳定性，并增强了它们在电催化应用中的利用率。
