Engineering multiphasic MoSe2/NiSe heterostructure interfaces for superior hydrogen production electrocatalysis

Jiang-Yan Xue , Fei-Long Li , Bingbing Chen , Hongbo Geng , Wei Zhang , Wan-Ying Xu , Hongwei Gu , 

Pierre Braunstein , Jian-Ping Lang

Constructing heterojunction nanocomposites with optimized active sites and interface electronic structures is promising for hydrogen evolution reaction (HER). Herein, we present an interface engineering strategy to fabricate two heterostructures, triphase MoSe2/NiSe-1 including 1T-MoSe2, 2H-MoSe2 and hexagonal phase NiSe (H-NiSe), and tetraphase MoSe2/NiSe-2 including 1T-MoSe2, 2H-MoSe2, H-NiSe and rhombohedral phase NiSe (R-NiSe). MoSe2/NiSe-1 exhibited remarkably enhanced HER activity with an overpotential of 30 mV at 10 mA cm−2, and negligible voltage change even when operated for 40 h. The strong electronic synergistic interaction between the different interfaces of mixed MoSe2/NiSe greatly enhanced the HER performance. Density functional theory calculations helped rationalize why the combination of three phases is more active, by increasing the interface electron concentration, facilitating electron transfer and decreasing the free energy ΔGH2O and ΔGH*. This work provides a rational strategy to design and assemble stable and high-performance multiphasic heterojunctioned HER electrocatalysts.

设计多相 MoSe2/NiSe 异质结构界面以实现卓越的制氢电催化

构建具有优化的活性位点和界面电子结构的异质结纳米复合材料有望用于析氢反应（HER）。在此，我们提出了一种界面工程策略来制造两种异质结构，包括 1T-MoSe 2、2H-MoSe 2和六方相 NiSe (H-NiSe) 的三相 MoSe 2 /NiSe-1 和包括 1T 的四相 MoSe 2 /NiSe-2 -MoSe 2、2H-MoSe 2、H-NiSe 和菱面体相 NiSe (R-NiSe)。MoSe 2 /NiSe-1 表现出显着增强的 HER 活性，在 10 mA cm -2时过电位为 30 mV，即使运行 40 小时，电压变化也可忽略不计。混合MoSe 2 /NiSe不同界面之间的强电子协同作用极大地提高了HER性能。密度泛函理论计算通过增加界面电子浓度、促进电子转移和降低自由能 ΔG H2O和 ΔG H*帮助解释了为什么三相的组合更活跃。这项工作为设计和组装稳定和高性能的多相异质结 HER 电催化剂提供了合理的策略。

DOI: 10.1016/j.apcatb.2022.121434