南开大学杜亚平团队报道了Pt修饰的高熵稀土氧化物在pH通用环境下高效析氢。相关研究成果于2024年3月22日发表在国际顶尖学术期刊《美国化学会杂志》。

开发高效稳定的宽pH范围电解水制氢催化剂对缓解能源危机具有重要意义。

该文首次制备了锚定在高熵稀土氧化物（HEREOs）空位上的Pt纳米粒子（NPs），用于水电解高效制氢。所制备的Pt-（LaCeSmYErGdYb）O具有优异的电化学性能，在0.5 M H₂SO₄、1.0 M KOH和1.0 M PBS环境中分别仅需12、57和77 mV即可实现100 mA cm^–2的电流密度。

此外，Pt-（LaCeSmYErGdYb）O在0.5 M H₂SO₄中成功地在60°C下400 mA cm^–2下工作了100小时，呈现出37.7 A mg^–1Pt的高质量活性和12 mV下38.2 s^–1的转换频率（TOF）值，这远远优于最近报道的析氢反应（HER）催化剂。密度泛函理论（DFT）计算表明，Pt和HEREO之间的相互作用优化了电子转移的电子结构和中间体的结合强度。这进一步导致优化的质子结合和水解离，调高不同环境中高效和稳健的HER性能。

该项工作为高效稀土基电催化剂的设计提供了新的思路。

附：英文原文

Title: Pt-Modified High Entropy Rare Earth Oxide for Efficient Hydrogen Evolution in pH-Universal Environments

Author: Yong Jiang, Zhong Liang, Hao Fu, Mingzi Sun, Siyuan Wang, Bolong Huang, Yaping Du

Issue&Volume: March 22, 2024

Abstract: The development of efficient and stable catalysts for hydrogen production from electrolytic water in a wide pH range is of great significance in alleviating the energy crisis. Herein, Pt nanoparticles (NPs) anchored on the vacancy of high entropy rare earth oxides (HEREOs) were prepared for the first time for highly efficient hydrogen production by water electrolysis. The prepared Pt-(LaCeSmYErGdYb)O showed excellent electrochemical performances, which require only 12, 57, and 77 mV to achieve a current density of 100 mA cm–2 in 0.5 M H2SO4, 1.0 M KOH, and 1.0 M PBS environments, respectively. In addition, Pt-(LaCeSmYErGdYb)O has successfully worked at 400 mA cm–2 @ 60 °C for 100 h in 0.5 M H2SO4, presenting the high mass activity of 37.7 A mg–1Pt and turnover frequency (TOF) value of 38.2 s–1 @ 12 mV, which is far superior to the recently reported hydrogen evolution reaction (HER) catalysts. Density functional theory (DFT) calculations have revealed that the interactions between Pt and HEREO have optimized the electronic structures for electron transfer and the binding strength of intermediates. This further leads to  optimized proton binding and water dissociation, supporting the highly efficient and robust HER performances in different environments. This work provides a new idea for the design of efficient RE-based electrocatalysts.

DOI: 10.1021/jacs.3c13367

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.3c13367