中国科学技术大学路军岭团队的一项最新研究揭示了单原子催化中的金属支持前沿轨道相互作用。2025年4月2日，国际知名学术期刊《自然》发表了这一成果。

在这里，课题组研究人员报告了钯（Pd₁） SACs的活性与氧化物载体的最低未占据分子轨道（LUMO）的位置呈线性缩放关系。通过将支持颗粒尺寸减小到几纳米来提高LUMO位置，可以在乙炔半氢化过程中提高创纪录的高活性以及优异的稳定性。研究结果表明，载体的LUMO升高减少了其与Pd₁原子的最高已占据分子轨道（HOMO）的能隙，从而促进了Pd₁ -载体轨道杂化以获得高稳定性，并进一步修正了锚定Pd₁原子的LUMO，以增强Pd₁ -吸附物的高活性相互作用。这些发现与前沿分子轨道理论一致，为合理选择具有可预测活性的金属支撑对提供了一般性描述。

研究人员表示，具有最大金属主题和离散能级的单原子催化剂（SACs）在多相催化、能量转换、环境科学和生物医学等领域有着广阔的应用前景。SACs的活性和稳定性是由金属-吸附物和金属-载体对相互作用决定的。然而，理解这些相互作用与它们在自然界的催化性能是具有挑战性的。金属原子的电荷态与活度的相关性经常得出有争议的结论。

附：英文原文

Title: Metal–support frontier orbital interactions in single-atom catalysis

Author: Shi, Xianxian, Wen, Zhilin, Gu, Qingqing, Jiao, Long, Jiang, Hai-Long, Lv, Haifeng, Wang, Hengwei, Ding, Jiani, Lyons, Mason P., Chang, Alvin, Feng, Zhenxing, Chen, Si, Lin, Yue, Xu, Xiaoyan, Du, Pengfei, Xu, Wenlong, Sun, Mei, Li, Yin, Yang, Bing, Zhang, Tao, Wu, Xiaojun, Lu, Junling

Issue&Volume: 2025-04-02

Abstract: Single-atom catalysts (SACs) with maximized metal use and discrete energy levels hold promise for broad applications in heterogeneous catalysis, energy conversion, environmental science and biomedicine1,2,3,4,5,6,7. The activity and stability of SACs are governed by the pair of metal–adsorbate and metal–support interactions8,9,10. However, the understanding of these interactions with their catalytic performance in nature is challenging. Correlations of activity with the charge state of metal atoms have frequently reached controversial conclusions11,12,13,14,15. Here we report that the activity of palladium (Pd1) SACs exhibits a linear scaling relationship with the positions of the lowest unoccupied molecular orbital (LUMO) of oxide supports across 14 types of semiconductor. Elevation of the LUMO position by reducing the support particle size to a few nanometres boosts a record high activity along with excellent stability in the semi-hydrogenation of acetylene. We show that the elevated LUMO of support reduces its energy gap with the highest occupied molecular orbital (HOMO) of Pd1 atoms, which promotes Pd1–support orbital hybridizations for high stability and further amends the LUMO of anchored Pd1 atoms to enhance Pd1–adsorbate interactions for high activity. These findings are consistent with the frontier molecular orbital theory and provide a general descriptor for the rational selection of metal–support pairs with predictable activity.

DOI: 10.1038/s41586-025-08747-z

Source: https://www.nature.com/articles/s41586-025-08747-z