Hot-Carrier Organic Synthesis via the Near-Perfect Absorption of Light,ACS Catalysis

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Hot-Carrier Organic Synthesis via the Near-Perfect Absorption of Light
ACS Catalysis ( IF 11.3 ) Pub Date : 2018-09-26 00:00:00 , DOI: 10.1021/acscatal.8b03486
Qi Xiao ₁ , Timothy U. Connell ₂ , Jasper J. Cadusch ₃ , Ann Roberts ₄ , Anthony S. R. Chesman _{1,

5} , Daniel E. Gómez _{2,

5}

Affiliation

Photocatalysis enables the synthesis of valuable organic compounds by exploiting photons as a chemical reagent. Although light absorption is an intrinsic step, existing approaches rely on poorly absorbing catalysts that require high illumination intensities to afford enhanced efficiencies. Here, we demonstrate that a plasmonic metamaterial capable of near-perfect light absorption (94%) readily catalyzes a model organic reaction with a 29-fold enhancement in conversion relative to controls. The oxidation of benzylamine proceeds via a reactive iminium intermediate with high selectivity at ambient temperature and pressure, using only low-intensity visible irradiation. Control experiments demonstrated that only hot charge carriers produced following photoexcitation facilitate the formation of superoxide radicals, which, in turn, leads to iminium formation. Modeling shows that hot holes with energies that overlap with the highest-occupied molecular orbital (HOMO) of the reactant can participate and initiate the photocatalytic conversion. These results have important implications for hot-carrier photocatalysis and plasmon-hot-carrier extraction.

中文翻译：

通过近乎完美的光吸收进行热载体有机合成

通过利用光子作为化学试剂，光催化能够合成有价值的有机化合物。尽管光吸收是必不可少的步骤，但是现有方法依赖于吸收不良的催化剂，这些催化剂需要较高的照明强度才能提供更高的效率。在这里，我们证明，能够实现近乎完美的光吸收（94％）的等离子体超材料可以催化模型有机反应，相对于对照，转化率提高29倍。苄胺的氧化仅在低强度的可见光照射下，通过在环境温度和压力下具有高选择性的反应性亚胺中间体进行。对照实验表明，只有在光激发后产生的热电荷载流子才能促进超氧化物自由基的形成，而超氧化物自由基又反过来，导致形成亚胺基。建模显示，能量与反应物的最高占据分子轨道（HOMO）重叠的热空穴可以参与并引发光催化转化。这些结果对热载流子的光催化和等离激元热载流子的提取具有重要意义。

更新日期：2018-09-26

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