Photon illumination of metal nanoparticle catalysts can promote reaction rate and selectivity through transient charge transfer to adsorbed species. Here we demonstrate that illumination of 2 nm diameter Pt nanoparticle catalysts with pulsed visible light enhances time-averaged rates of H₂ production via methanol decomposition compared with static illumination. Based on CO temperature-programmed desorption, in-situ FTIR, and kinetic measurements, we propose that pulsed illumination promotes reaction rates compared to static illumination by oscillating the binding energy of surface intermediates at frequencies that are in resonance with reaction kinetics. We also show that the impact of light is chemically specific, influencing some elementary step energetics more than others. Our results suggest that using light pulses to dynamically control the energetics of elementary steps on catalytic surfaces may enable higher activity or selectivity than is possible with static illumination or dictated by linear free energy scaling relations.

中文翻译：

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通过脉冲照明动态控制基本阶跃能量，增强了对金属纳米粒子的光催化作用

金属纳米粒子催化剂的光子照射可以通过将电荷瞬时转移到吸附的物质上来提高反应速度和选择性。在这里，我们证明了用脉冲可见光照射直径为2 nm的Pt纳米颗粒催化剂可以提高H _2的时间平均速率与静态照明相比，通过甲醇分解生产。基于CO温度编程的解吸，原位FTIR和动力学测量，我们建议与静态光照相比，脉冲照明通过在与反应动力学共振的频率上振荡表面中间体的结合能来提高反应速率。我们还表明，光的影响是化学特异的，对某些基本步骤的能量学影响更大。我们的结果表明，使用光脉冲动态控制催化表面上基本步骤的能量可能比采用静态照明或线性自由能比例关系规定的活性或选择性更高。