Plasmonic enhancement of molecular hydrogen dissociation on metallic magnesium nanoclusters.
Plasmonic enhancement of molecular hydrogen dissociation on metallic magnesium nanoclusters.
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DOI：
10.1039/d1nr02033a
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发表时间：
2021-03
期刊：
影响因子：
6.7
通讯作者：
O. A. Douglas-Gallardo;C. Box;R. Maurer
中科院分区：
文献类型：
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作者：
O. A. Douglas-Gallardo;C. Box;R. Maurer
光驱动等离子体增强金属催化剂上的化学反应是实现高选择性和高效率化学转化的一种很有前途的策略。等离子体催化剂材料的研究传统上主要集中在金、银、铜等后过渡金属上。近年来，人们对镁等一系列富含地球的元素的等离子体性质越来越感兴趣，它们在氢化化学中表现出有趣的性质，在氢气存储方面具有潜在的应用前景。本工作采用含时密度泛函紧束缚和密度泛函理论计算方法，研究了含2057个原子的金属镁纳米团簇的光学、电子和催化性质。结果表明，镁纳米团簇能够产生能量高达4 eV的高能超热电子。通过电子结构分析，我们发现这些超热电子与物理吸附的分子氢的电子态能量成正比，超热电子占据这些电子态可以促进氢的解离反应。我们还发现，金属镁上的反向反应，即放氢，可能会被热电子促进，但遵循不同的机制。因此，从理论上讲，镁纳米团簇在光促进氢的储存和释放方面表现出非常有前途的行为。
Light-driven plasmonic enhancement of chemical reactions on metal catalysts is a promising strategy to achieve highly selective and efficient chemical transformations. The study of plasmonic catalyst materials has traditionally focused on late transition metals such as Au, Ag, and Cu. In recent years, there has been increasing interest in the plasmonic properties of a set of earth-abundant elements such as Mg, which exhibit interesting hydrogenation chemistry with potential applications in hydrogen storage. This work explores the optical, electronic, and catalytic properties of a set of metallic Mg nanoclusters with up to 2057 atoms using time-dependent density functional tight-binding and density functional theory calculations. Our results show that Mg nanoclusters are able to produce highly energetic hot electrons with energies of up to 4 eV. By electronic structure analysis, we find that these hot electrons energetically align with electronic states of physisorbed molecular hydrogen, occupation of which by hot electrons can promote the hydrogen dissociation reaction. We also find that the reverse reaction, hydrogen evolution on metallic Mg, can potentially be promoted by hot electrons, but following a different mechanism. Thus, from a theoretical perspective, Mg nanoclusters display very promising behaviour for their use in light promoted storage and release of hydrogen.