Department of Electrical and Computer Engineering, Rice University, Houston, TX, 77005, USA.
Laboratory for Nanophotonics, Rice University, Houston, TX, 77005, USA.
Nat Commun. 2017 Jun 21;8(1):27. doi: 10.1038/s41467-017-00055-z.
The rational combination of plasmonic nanoantennas with active transition metal-based catalysts, known as 'antenna-reactor' nanostructures, holds promise to expand the scope of chemical reactions possible with plasmonic photocatalysis. Here, we report earth-abundant embedded aluminum in cuprous oxide antenna-reactor heterostructures that operate more effectively and selectively for the reverse water-gas shift reaction under milder illumination than in conventional thermal conditions. Through rigorous comparison of the spatial temperature profile, optical absorption, and integrated electric field enhancement of the catalyst, we have been able to distinguish between competing photothermal and hot-carrier driven mechanistic pathways. The antenna-reactor geometry efficiently harnesses the plasmon resonance of aluminum to supply energetic hot-carriers and increases optical absorption in cuprous oxide for selective carbon dioxide conversion to carbon monoxide with visible light. The transition from noble metals to aluminum based antenna-reactor heterostructures in plasmonic photocatalysis provides a sustainable route to high-value chemicals and reaffirms the practical potential of plasmon-mediated chemical transformations.Plasmon-enhanced photocatalysis holds promise for the control of chemical reactions. Here the authors report an Al@CuO heterostructure based on earth abundant materials to transform CO into CO at significantly milder conditions.
等离子体纳米天线与活性过渡金属基催化剂的合理组合，即所谓的“天线-反应器”纳米结构，有望扩大等离子体光催化可能的化学反应范围。在这里，我们报告了在氧化铜天线-反应器异质结构中嵌入丰富的铝，与传统热条件相比，在更温和的光照下，该异质结构更有效地、更有选择性地进行反向水气变换反应。通过对催化剂的空间温度分布、光吸收和集成电场增强的严格比较，我们能够区分竞争的光热和热载流子驱动的机理途径。天线-反应器几何形状有效地利用了铝的等离子体共振，为高能热载流子提供能量，并增加了氧化铜的光吸收，从而在可见光下选择性地将二氧化碳转化为一氧化碳。在等离子体光催化中，从贵金属到基于铝的天线-反应器异质结构的转变为高价值化学品提供了一条可持续的途径，并再次证实了等离子体介导的化学转化的实际潜力。
