Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials (Ministry of Education), School of Materials Science and Engineering, Shandong University, Jingshi Road 17923, Jinan 250061, P.R. China.
Nanoscale. 2018 Sep 20;10(36):17070-17079. doi: 10.1039/c8nr04741c.
Pt-based nanomaterials have been widely investigated as efficient electrocatalysts for energy conversion reactions such as small organic molecule oxidation and hydrogen evolution, but are mainly limited to alloys of Pt with transition metals. Herein, a new PtGa electrocatalyst with unique nanoporous architecture and a self-supported feature (np-PtGa) was fabricated via a liquid Ga-assisted dealloying strategy. Owing to the unique nanoporous structure and alloying effect by the introduction of Ga, the np-PtGa alloy exhibits excellent electrocatalytic activities towards the electrooxidation of methanol, ethanol, ethylene glycol, glycerol, and formic acid, which are three orders of magnitude higher than those of the benchmark Pt foil. Moreover, our np-PtGa alloy displays extraordinary catalytic activities towards the hydrogen evolution reaction in both acidic and alkaline environments. Impressively, the overpotential of np-PtGa is as low as 50 mV at 10 mA cm-2 with a Tafel slope of 55 mV dec-1 in 1 M KOH, outperforming most of the recently reported electrocatalysts. Density functional theory calculations demonstrate that the downshift of the d-band center caused by the Ga 4p/Pt 5d orbital hybridization and compressive stress could weaken the adsorption of intermediate species and well rationalize the enhanced electrocatalytic performance of np-PtGa.
基于铂的纳米材料已被广泛研究为用于能量转换反应的高效电催化剂,例如小分子氧化和析氢反应,但主要限于铂与过渡金属的合金。在此,通过液体 Ga 辅助脱合金化策略制备了具有独特纳米多孔结构和自支撑特征的新型 PtGa 电催化剂(np-PtGa)。由于独特的纳米多孔结构和 Ga 的引入的合金化效应,np-PtGa 合金对甲醇、乙醇、乙二醇、甘油和甲酸的电氧化表现出优异的电催化活性,比基准 Pt 箔高三个数量级。此外,我们的 np-PtGa 合金在酸性和碱性环境中对析氢反应表现出非凡的催化活性。令人印象深刻的是,np-PtGa 的过电势在 1 M KOH 中低至 50 mV,在 10 mA cm-2 时的塔菲尔斜率为 55 mV dec-1,优于大多数最近报道的电催化剂。密度泛函理论计算表明,Ga 4p/Pt 5d 轨道杂化和压缩应力引起的 d 带中心下移可以削弱中间物种的吸附,很好地解释了 np-PtGa 增强的电催化性能。