Hot-Electron-Induced Photothermal Catalysis for Energy-Dependent Molecular Oxygen Activation
Hot-Electron-Induced Photothermal Catalysis for Energy-Dependent Molecular Oxygen Activation
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热电子诱导光热催化能量依赖性分子氧活化
DOI：
10.1002/anie.202012306
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Jiuhui Qu
中科院分区：
文献类型：
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作者：
Wei Zhang;Yu Chen;Gong Zhang;Xiao Tan;Qinghua Ji;Zhaowu Wang;Huijuan Liu;Jiuhui Qu
热电子通过给电子来激活反应物并降低反应的活化能垒(EA)。然而，对这种电子捐赠效应的内在驱动力缺乏全面的了解，更不用说对电子捐赠过程的精确操纵了。本文以分子氧活化(MOA)为模型反应，阐明了热电子能量在给电子效应中的本质和促进作用。通过为传统的光热转换系统提供可用的电子源，超热电子携带的高能被释放出来，极大地增强了对O2的LUMO(π*)轨道的电子贡献。能量也被转移到O2上，提高了MOA的势能面(PES)，这反映在超氧阴离子的促进形成上。正如预测的那样，MOA的Ea值降低了45.1 %，并表现出很大的光依赖性，表明由于光子能量的开发和转化，MOA变得更节能。
Hot electrons activate reactants and reduce the activation energy barrier (Ea) of a reaction through electron donation. However, a comprehensive understanding of the intrinsic driving force of this electron‐donating effect is lacking, let alone the precise manipulation of electron donation processes. Herein, the essential and promotional role of hot electron energy on the electron‐donating effect was elucidated using molecular oxygen activation (MOA) as a model reaction. Through providing an available electron source to the conventional photo‐thermal conversion system, the high energy carried by hot electrons was liberated and greatly enhanced the electron donation towards the LUMO (π*) orbit of O2. The energy was also transferred to O2and elevated the potential energy surface (PES) of MOA, which was reflected by the enhanced formation of superoxide oxygen anions. As predicted, theEaof MOA decreased by 45.1 % and exhibited a substantial light dependence, demonstrating that MOA became energy‐efficient due to improved exploitation and conversion of photon energies.