Zhang Weichuang, Xiao Qi, Wen Jin
State Key Laboratory of Advanced Fiber Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China.
J Phys Chem Lett. 2025 Jun 19;16(24):6073-6080. doi: 10.1021/acs.jpclett.5c01072. Epub 2025 Jun 9.
The solvent-free metal-catalyzed synthesis of benzaldehyde from benzyl alcohol requires high temperatures or pressures to achieve high reaction efficiencies, which can reduce the stability of the catalyst. To address this issue, utilizing solar energy to facilitate the photocatalytic conversion of benzyl alcohol into benzaldehyde via the plasmonic effects of metal nanoparticles under ambient conditions has emerged as a promising approach. However, the microscopic mechanism underlying the plasmon-induced photocatalytic conversion of benzyl alcohol remains unclear. In this work, we employ time-dependent density functional theory to investigate the ultrafast carrier dynamics during the plasmon-driven photocatalysis mediated by PdAu nanoparticles, revealing the electron transfer process at the atomic scale during the photochemical reactions. Our findings indicate that the reaction is governed by multiple charge transfer mechanisms, with indirect charge transfer driven by hot carriers within the metal being predominant. Direct charge transfer between the metal and the adsorbed molecule, as well as within the adsorbed molecule, plays secondary roles. This study provides a detailed pathway for understanding the plasmon-driven photocatalytic conversion of benzyl alcohol to benzaldehyde and offers valuable insights into the design of catalysts for various organic syntheses under ambient conditions using light.
由苯甲醇无溶剂金属催化合成苯甲醛需要高温或高压才能实现高反应效率，这会降低催化剂的稳定性。为了解决这个问题，利用太阳能在环境条件下通过金属纳米颗粒的等离子体效应促进苯甲醇光催化转化为苯甲醛已成为一种有前景的方法。然而，等离子体诱导苯甲醇光催化转化的微观机制仍不清楚。在这项工作中，我们采用含时密度泛函理论来研究由钯金纳米颗粒介导的等离子体驱动光催化过程中的超快载流子动力学，揭示光化学反应过程中原子尺度上的电子转移过程。我们的研究结果表明，该反应由多种电荷转移机制控制，其中金属内热载流子驱动的间接电荷转移占主导。金属与吸附分子之间以及吸附分子内部的直接电荷转移起次要作用。这项研究为理解等离子体驱动的苯甲醇光催化转化为苯甲醛提供了详细途径，并为在环境条件下利用光进行各种有机合成的催化剂设计提供了有价值的见解。
