反应性气体调变金属纳米结构的核数并提升催化活性

doi:10.1016/S1872-2067(26)65004-8

摘要/Abstract

摘要： 本文描述了在低压低温的温和条件下, 采用反应活性气体(CO, NO, H₂, H₂O和O₂)来调节金属纳米粒子表面的动态性能. 量子化学模拟、实验方法和机器学习揭示了明显的影响: NO促进纳米粒子碎裂成高活性的单原子物种; H₂,H₂O和O₂诱导的纳米粒子生长; CO稳定了它们的结构. 这种反应性气体调制(RGM)效应能够灵活控制纳米粒子的尺寸和分布, 有利于纳米级金属的有效控制. 在实际应用中, NO气体增强了Pd/C催化剂的性能, 促进了温和条件(35 °C)下Suzuki-Miyaura交叉偶联反应的高效进行. 将该方法用于其他金属(Ni, Fe, Co, Cu, Au, Pt, Ru, Ir, Rh)的评估, 也取得相应的效果, 证明了控制纳米级形貌的多种可能性. 该研究结果突出了一种基于RGM效应的灵活控制金属核度的工具, 用于优化精细有机合成的催化体系, 通过纳米级精度为催化和材料科学的进步开辟了道路.
综上, 本文采用理论和实验等多层次研究, 开发了一种快速、节能和易于推广的方法来合成克级单原子催化剂.

关键词: 单原子中心, 金属纳米颗粒, 动态表面现象, 金属核性调控, 催化剂活化, 多相催化

Abstract: This study describes the dynamic behavior of metal nanoparticles on surfaces modulated by reactive gases (CO, NO, H₂, H₂O, and O₂) under soft conditions at low pressure and temperature. Quantum chemical simulations, experimental methods, and machine learning revealed distinct effects: NO promoted nanoparticle fragmentation into highly active single-atom species; H₂, H₂O, and O₂induced nanoparticle growth; and CO stabilized their structure. This reactive gas modulation (RGM) effect enables flexible control over nanoparticle size and distribution, advancing nanoscale metal tuning. In practical applications, NO gas enhanced the performance of the Pd/C catalyst, facilitating Suzuki-Miyaura cross-coupling under mild conditions (35 °C) with superior efficiency. The developed approach was evaluated for other metals and corresponding effects were studied (Ni, Fe, Co, Cu, Au, Pt, Ru, Ir, Rh), demonstrating versatile possibilities to control nanoscale morphology. The results highlight a flexible metal nuclearity control tool based on the RGM effect in the optimization of catalytic systems for fine organic synthesis, opening the way for advances in catalysis and materials science through nanoscale precision. Through a multilevel study using theoretical and experimental approaches, a methodology for a rapid, energy-efficient and easily scalable approach to synthesize single-atom catalyst at the gram-scale was developed.

Key words: Single-atomic centers, Metal nanoparticles, Dynamic surface phenomena, Metal nuclearity control, Catalyst activation, Heterogeneous catalysis

Alexey S. Galushko, Ilya V. Chepkasov, Ruslan R. Shaydullin, Daniil A. Boiko, Alexander G. Kvashnin, Artem M. Abakumov, Valentine P. Ananikov. 反应性气体调变金属纳米结构的核数并提升催化活性[J]. 催化学报, DOI: 10.1016/S1872-2067(26)65004-8.

Alexey S. Galushko, Ilya V. Chepkasov, Ruslan R. Shaydullin, Daniil A. Boiko, Alexander G. Kvashnin, Artem M. Abakumov, Valentine P. Ananikov. Reactive gas modulation alters metal nanostructures nuclearity and boosts catalytic activity[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)65004-8.

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