南京师范大学刘影研究团队报道了在大电流密度下，Mo迁移诱导的晶体向非晶态转化和RuMo/NiMoO₄非均相纳米阵列的形成。相关研究成果于2024年9月03日发表于国际顶尖学术期刊《德国应用化学》。

调控催化剂的原子结构和定制催化剂-电解质界面处的离解水-氢键网络对于推进碱性析氢反应（HER）和肼氧化反应（HzOR）至关重要，但仍然是一个巨大的挑战。

该文中，通过杂原子注入策略构建了一种先进的a-RuMo/NiMoO₄/NF非均相电催化剂，其中非晶RuMo合金纳米簇锚定在Ni泡沫上的非晶NiMoO₄骨架上。理论计算和原位拉曼测试表明，a-RuMo/NiMoO₄/NF的非晶态和合金化结构不仅诱导了界面H₂O的定向演化，还降低了a-RuMo/NiMo₄/NF的d带中心（从-0.43 eV到-2.22 eV）、氢吸附的吉布斯自由能（ΔGH*，从-1.29 eV到-0.06 eV）和HzOR的能垒（ΔGN2（g）=1.50 eV到ΔGN2*=0.47 eV）。

得益于这些有利因素，a-RuMo/NiMoO₄/NF表现出优异的电催化性能，特别是在大电流密度下，HER的过电势为13和129 mV，达到10和1000 mA cm^-2。而对于HzOR，分别只需要-91和276 mV即可提供10和500 mA cm^-2电流密度。此外，所构建的a-RuMo/NiMoO₄/NF||a-RuMo/NiMoO4/NF电解槽，仅需要7和420 mV即可提供10和500 mA cm^-2的电流密度。

附：英文原文

Title: Mo Migration-Induced Crystalline to Amorphous Conversion and Formation of RuMo/NiMoO4 Heterogeneous Nanoarray for Hydrazine-Assisted Water Splitting at Large Current Density

Author: Yanan Chang, Lingyi Kong, Dongdong Xu, Xuyun Lu, Shasha Wang, Yafei Li, Jianchun Bao, Yu Wang, Ying Liu

Issue&Volume: 03 September 2024

Abstract: Manipulating the atomic structure of the catalyst and tailoring the dissociative water-hydrogen bonding network at the catalyst-electrolyte interface is essential for propelling alkaline hydrogen evolution reactions (HER) and hydrazine oxidation reaction (HzOR), but remains a great challenge. Herein, we constructed an advanced a-RuMo/NiMoO4/NF heterogeneous electrocatalysts with amorphous RuMo alloy nanoclusters anchored to amorphous NiMoO4 skeletons on Ni foam by a heteroatom implantation strategy. Theoretical calculations and in-situ Raman tests show that the amorphous and alloying structure of a-RuMo/NiMoO4/NF not only induces the directional evolution of interfacial H2O, but also lowers the d-band center (from -0.43 to -2.22 eV) of a-RuMo/NiMoO4/NF, the Gibbs free energy of hydrogen adsorption (ΔGH*, from -1.29 to -0.06 eV), and the energy barrier of HzOR (ΔGN2(g) = 1.50 eV to ΔGN2* = 0.47 eV). Profiting from these favorable factors, the a-RuMo/NiMoO4/NF exhibits excellent electrocatalytic performances, especially at large current densities, with an overpotential of 13 and 129 mV to reach 10 and 1000 mA cm-2 for HER. While for HzOR, it needs only -91 and 276 mV to deliver 10 and 500 mA cm-2, respectively. Further, the constructed a-RuMo/NiMoO4/NF||a-RuMo/NiMoO4/NF electrolyzer demands only 7 and 420 mV to afford 10 and 500 mA cm-2.

DOI: 10.1002/anie.202414234

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202414234