The light induced hot-electron on plasmonic nanostructures has been recognized as a breakthrough discovery for photovoltaic and photocatalytic applications. With mass spectrometry, we demonstrate the dynamics of hot electron transfers of anaerobic oxidization reactions on Au decorated TiO₂ plasmonic nanoparticles, which were coated on the inner surface of a flask. Those nanoparticles were covered by continuously renewed liquid droplets of solvent and reactants that were transported through a Venturi jet mixer with auto-spray. In addition to intensive mass transfer in such droplet-based nanoreactors, as well as strong adsorption of reactants and rapid desorption of products on materials surfaces, the localized surface plasmon resonance (LSPR) excitation upon visible light illumination, by which accumulated energies of plasmons are transferred to electrons in the conduction band of the material, attributes to the efficient photocatalytic transformation. Mass spectrometric detection of intermediate radical anions and negative ions with stable isotope labeling unambiguously identifies that highly energetic hot electrons can escape from the plasmonic nanostructures, be collected by adsorbed molecules, and initiate bond cleavages. It was demonstrated that losses of two H atoms result in the anaerobic oxidization of each benzyl alcohol molecule to a benzyl aldehyde molecule in the absence of molecular oxygen with more than 90 % yields. The well recyclable plasmonic nanoreactors implicate the injection of transferred electrons eventually back to electronically depleted Au⁺ positive ions. Bridged by adsorbed molecules, electrons were repeatedly circulated back and forth in plasmonic nanoreactors, where the collected light was eventually converted into chemical energy.

等离子体纳米结构上的光诱导热电子已被认为是光伏和光催化应用的突破性发现。通过质谱分析，我们展示了涂在烧瓶内表面的金修饰的 TiO _{2等离子体纳米颗粒上厌氧氧化反应的热电子转移动力学。}这些纳米颗粒被不断更新的溶剂和反应物液滴覆盖，这些液滴通过具有自动喷雾功能的文丘里喷射混合器输送。除了这种基于液滴的纳米反应器中的密集传质，以及反应物的强烈吸附和产物在材料表面的快速解吸之外，可见光照射下的局域表面等离子体共振（LSPR）激发，通过这种方式积累的等离子体激元能量转移到材料导带中的电子，归因于有效的光催化转化。通过稳定同位素标记对中间自由基阴离子和负离子进行质谱检测，明确地识别出高能热电子可以从等离子体纳米结构中逸出，被吸附的分子收集，并引发键断裂。结果表明，在没有分子氧存在的情况下，失去两个 H 原子会导致每个苯甲醇分子无氧氧化为苯甲醛分子，产率超过 90%。可良好回收的等离子体纳米反应器意味着转移电子的注入最终回到电子耗尽的Au ⁺正离子。通过吸附分子桥接，电子在等离子体纳米反应器中反复来回循环，收集到的光最终转化为化学能。