Plasmonic Switching of the Reaction Pathway: Visible-Light Irradiation Varies the Reactant Concentration at the Solid-Solution Interface of a Gold-Cobalt Catalyst.
Plasmonic Switching of the Reaction Pathway: Visible-Light Irradiation Varies the Reactant Concentration at the Solid-Solution Interface of a Gold-Cobalt Catalyst.
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DOI：
10.1002/anie.201904452
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发表时间：
2019-06
影响因子：
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通讯作者：
Erandi Peiris;Sarina Sarina-Sarina;E. Waclawik;G. Ayoko;Pengfei Han;Jianfeng Jia;Huaiyong Zhu
中科院分区：
文献类型：
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作者：
Erandi Peiris;Sarina Sarina-Sarina;E. Waclawik;G. Ayoko;Pengfei Han;Jianfeng Jia;Huaiyong Zhu
催化Au 2 Co合金纳米颗粒（NPs）上的炔氢胺化的产物选择性可以通过光开/光关过程进行切换，在可见光照射下产生亚胺（苯胺和炔的交叉偶联产物），但在黑暗中产生1，4-二苯基丁二炔。低通量光照射使苯胺集中在催化剂上，即使在非常低的总苯胺浓度（1.0×10-3 mol L-1）下也能使催化交叉偶联加速几个数量级。一个初步的机制是Au 2 Co纳米颗粒吸收光，产生强烈的边缘电磁场和热电子。尖锐的场梯度（等离子体激元光学力）可以选择性地增强光极化苯胺分子在催化剂上的吸附。因此，光照射改变了NP表面的苯胺/炔比，从而切换产物选择性。这代表了通过光来改变催化过程的新范例。
Product selectivity of alkyne hydroamination over catalytic Au2 Co alloy nanoparticles (NPs) can be made switchable by a light-on/light-off process, yielding imine (cross-coupling product of aniline and alkyne) under visible-light irradiation, but 1,4-diphenylbutadiyne in the dark. The low-flux light irradiation concentrates aniline on the catalyst, accelerating the catalytic cross-coupling by several orders of magnitude even at a very low overall aniline concentrations (1.0×10-3 mol L-1 ). A tentative mechanism is that Au2 Co NPs absorb light, generating an intense fringing electromagnetic field and hot electrons. The sharp field-gradient (plasmonic optical force) can selectively enhance adsorption of light-polarizable aniline molecules on the catalyst. The light irradiation thereby alters the aniline/alkyne ratio at the NPs surface, switching product selectivity. This represents a new paradigm to modify a catalysis process by light.