As the efficient approaches for obtaining clean H₂ energy, methanol oxidation (MOR) and water over slitting reactions have been increasingly essential. A series of novel semiconductive CoNi bimetal–organic framework (Co_xNi_3-x(HAB)₂ MOF) have been prepared using hexaaminobenzene (HAB) as an organic linker. The obtained series of Co_xNi_3-x(HAB)₂ MOFs were then explored as efficient multifunctional electrocatalysts for the non-Pt MOR and overall water splitting in alkaline medium. The basic characterizations of Co_xNi_3-x(HAB)₂ MOFs revealed that they comprised multiple metal valence states (Co⁰/Co²⁺/Co³⁺ and Ni²⁺/Ni³⁺) and graphene-like nanostructures embedded with abundant CoNi alloy nanoparticles. Compared with the sole-metal MOFs (Co₃(HAB)₂ MOF and Ni₃(HAB)₂ MOF), the Co_xNi_3-x(HAB)₂ MOF with a mass ratio of Co:Ni = 1:3 (Co_xNi_3-x(HAB)₂ MOF-2) exhibited superior electrocatalytic performance for MOR. It gave a high current density of 92.8 mA cm⁻² at 1.6 V vs. reversible hydrogen electrode (RHE) for MOR, along with the low overpotentials at the current density of 10 mV cm⁻² (η₁₀) and Tafel slopes toward hydrogen evolution reaction (η₁₀ = 119 mV, Tafel slope = 46 mV dec^-1) and oxygen evolution reaction (η₁₀ = 1.35 V, Tafel slope = 26 mV dec⁻¹). The analysis on the catalysis mechanism of MOR and water splitting in alkaline medium was also proposed. The voltages applied to the three- and two-electrode systems based on the bifunctional Co_xNi_3-x(HAB)₂ MOF-2 catalyst for overall water splitting are 1.52 V vs. RHE and 1.45 V vs. silver/silver chloride (Ag/AgCl), respectively. This work provides a novel strategy for investigating the applications of promising two-dimensional semiconductive MOF as multifunctional electrocatalysts with boosted electrocatalytic activities in energy fields.

作为获得清洁的H ₂能量的有效方法，在分馏反应中甲醇氧化（MOR）和水已变得越来越重要。使用六氨基苯（HAB）作为有机连接基，制备了一系列新颖的CoNi双金属-有机骨架（Co _x Ni _3-x（HAB）₂ MOF）。然后，研究了所得的Co _x Ni _3-x（HAB）₂ MOF系列作为有效的多功能电催化剂，用于非Pt MOR和碱性介质中的总水分解。Co _x Ni _3-x（HAB）₂的基本特征MOFs显示它们包含多个金属化合价态（Co ⁰ / Co ²⁺ / Co ³⁺和Ni ²⁺ / Ni ³⁺）以及嵌有丰富CoNi合金纳米粒子的石墨烯状纳米结构。与单一金属MOF（Co ₃（HAB）₂ MOF和Ni ₃（HAB）₂ MOF）相比，Co _x Ni _3-x（HAB）₂ MOF的质量比为Co：Ni = 1：3（ Co _x Ni _3-x（HAB）₂ MOF-2）对MOR具有优异的电催化性能。它提供了92.8 mA cm ^-2的高电流密度在：1.6 V VS。可逆氢电极（RHE）对MOR，与以10毫伏厘米的电流密度低的超电势沿着^-2（η ₁₀）和朝向塔菲尔析氢反应的斜坡（η ₁₀  = 119毫伏，塔菲尔斜率= 46毫伏癸^-1）和析氧反应（η ₁₀  = 1.35 V，塔菲尔斜率= 26毫伏癸^-1）。提出了在碱性介质中MOR和水分解的催化机理的分析。基于双功能Co _x Ni _3-x（HAB）₂ MOF-2催化剂的三电极和两电极系统的总水分解电压为1.52 V vs。RHE和1.45 V分别相对于银/氯化银（Ag / AgCl）。这项工作提供了一种新颖的策略，用于研究前景广阔的二维半导体MOF作为具有增强的电催化活性的多功能电催化剂在能源领域中的应用。