Li Zhijuan, Hou Minghao, Yao Baoye, Ma Chuhan, Zhang Shitong, An Honglei, Liu Yichen, Duan Haibao, Li Tongfei, Tang Yawen
School of Environmental Science, Nanjing Xiaozhuang University, Nanjing 211171, China.
School of Environmental Science, Nanjing Xiaozhuang University, Nanjing 211171, China.
J Colloid Interface Sci. 2025 Sep 14;702(Pt 2):139029. doi: 10.1016/j.jcis.2025.139029.
The development of high-entropy alloy (HEA) nanocatalysts with ultrasmall size and hollow structures is vital yet challenging for efficient hydrogen evolution reaction (HER) across all pH conditions. Herein, we present a mild and facile hydrothermal strategy for synthesizing hollow PtRuRhCoCu HEA nanospheres (NSs) via self-assembly of sub-3 nm alloy nanoparticles directed by N, N'-methylenebisacrylamide (MBAA). The resulting PtRuRhCoCu HEA features a multielement composition, interconnected hollow architecture, and well-dispersed ultrafine particles, providing abundant active sites and strong synergistic electronic interactions. As a result, the PtRuRhCoCu HEA catalyst achieves remarkable HER activity with low overpotentials of 10 mV (1 M KOH), 15 mV (0.5 M HSO) and 30 mV (1 M phosphate-buffered saline, PBS) at 10 mA cm, outperforming commercial Pt black. Moreover, this catalyst also exhibits outstanding long-term stability across a broad pH range, operating continuously for 80 h under alkaline conditions at various current densities without noticeable degradation. The density functional theory (DFT) calculations confirm that this HEA exhibits optimized hydrogen adsorption energy and electronic structure. When integrated into a full electrolyzer, it delivers a cell voltage of 1.48 V at 10 mA cm, demonstrating great potential for water splitting. This work presents an effective design strategy for next-generation HEA electrocatalysts toward green hydrogen production.
开发具有超小尺寸和中空结构的高熵合金（HEA）纳米催化剂对于在所有pH条件下高效析氢反应（HER）至关重要，但也具有挑战性。在此，我们提出了一种温和且简便的水热策略，通过由N，N'-亚甲基双丙烯酰胺（MBAA）引导的亚3纳米合金纳米颗粒的自组装来合成中空PtRuRhCoCu HEA纳米球（NSs）。所得的PtRuRhCoCu HEA具有多元素组成、相互连接的中空结构和分散良好的超细颗粒，提供了丰富的活性位点和强大的协同电子相互作用。因此，PtRuRhCoCu HEA催化剂在10 mA cm时实现了显著的HER活性，在1 M KOH中过电位低至10 mV，在0.5 M HSO中为15 mV，在1 M磷酸盐缓冲盐水（PBS）中为30 mV，性能优于商业Pt黑。此外，该催化剂在广泛的pH范围内还表现出出色的长期稳定性，在碱性条件下以各种电流密度连续运行80小时而无明显降解。密度泛函理论（DFT）计算证实，这种HEA表现出优化的氢吸附能量和电子结构。当集成到全电解槽中时，它在10 mA cm时的电池电压为1.48 V，展现出巨大的水分解潜力。这项工作为下一代用于绿色制氢的HEA电催化剂提出了一种有效的设计策略。
