Multimetallic alloys (MMAs) with various compositions enrich the materials library with increasing diversity and have received much attention in catalysis applications. However, precisely shaping MMAs in mesoporous nanostructures and mapping the distributions of multiple elements remain big challenge due to the different reduction kinetics of various metal precursors and the complexity of crystal growth. Here we design a one-pot wet-chemical reduction approach to synthesize core–shell motif PtPdRhRuCu mesoporous nanospheres (PtPdRhRuCu MMNs) using a diblock copolymer as the soft template. The PtPdRhRuCu MMNs feature adjustable compositions and exposed porous structures rich in highly entropic alloy sites. The formation processes of the mesoporous structures and the reduction and growth kinetics of different metal precursors of PtPdRhRuCu MMNs are revealed. The PtPdRhRuCu MMNs exhibit robust electrocatalytic hydrogen evolution reaction (HER) activities and low overpotentials of 10, 13, and 28 mV at a current density of 10 mA cm⁻² in alkaline (1.0 M KOH), acidic (0.5 M H₂SO₄), and neutral (1.0 M phosphate buffer solution (PBS)) electrolytes, respectively. The accelerated kinetics of the HER in PtPdRhRuCu MMNs are derived from multiple compositions with synergistic interactions among various metal sites and mesoporous structures with excellent mass/electron transportation characteristics.

具有各种成分的多金属合金（MMA）丰富了材料库，其多样性不断增加，并在催化应用中受到广泛关注。然而，由于各种金属前驱体的还原动力学不同以及晶体生长的复杂性，在介孔纳米结构中精确成型MMA并绘制多种元素的分布仍然是巨大的挑战。在这里，我们设计了一种一锅湿化学还原方法，使用二嵌段共聚物作为软模板合成核壳图案 PtPdRhRuCu 介孔纳米球（PtPdRhRuCu MMN）。PtPdRhRuCu MMN 具有可调节的成分和富含高熵合金位点的暴露多孔结构。揭示了 PtPdRhRuCu MMN 介孔结构的形成过程以及不同金属前体的还原和生长动力学。PtPdRhRuCu MMNs在碱性(1.0 M KOH)、酸性(0.5 MH ₂ SO ₄ )中在10 mA cm ^-2的电流密度下表现出强大的电催化析氢反应(HER)活性和10、13和28 mV的低过电位和中性（1.0 M 磷酸盐缓冲溶液 (PBS)）电解质。PtPdRhRuCu MMN 中 HER 的加速动力学源自多种成分，这些成分具有各种金属位点和具有优异质量/电子传输特性的介孔结构之间的协同相互作用。