The article reported an efficientvisible-light-driven deuteration of organic halides using plasmonic Au/CdS asphotocatalyst and green D2O as deuterium donor. The highphotocatalytic activity is a result of plasmon-generated hot electrons andenhanced charge separation/transfer on the Au/CdS nanocomposites. Thedeuteration mechanism is proved to be a radical pathway in which C−X bonds areactivated by the photoinduced electron transfer to generate active arylradicals, and the aryl radicals are trapped by the D2O to give thedeuterated products. This work provides an efficient approach forvisible-light-driven deuteration under mild conditions and sheds light on theinteraction between plasmonic NPs and semiconductor, which is very helpful forrational design of photocatalyst.
This article reported on the combination of plasmonic Au NPs and semiconductors for plasmon-promoted electrocatalytic water splitting. By using SERS, we find a strong spontaneous interfacial charge transfer between Au and NiCo LDH. Through selective blocking of the metal surface with a thiol molecular monolayer, it is found that the plasmon-promoted OER occurs on LDH semiconductor but HER are mainly located on Au NP surface. This work demonstrates the critical role of interfacial charge transfer in hot electron-driven water splitting and paves the way for rational design of high-performance plasmonic electrocatalysts.
The authors synthesized a bifunctional gold-nickel composite nanostructure by self-assembly method (many small-particle nickel nanoparticles were assembled on the surface of large-particle gold nanoparticles). Compared with the previous complicated method for preparing bifunctional nanoparticles, this strategy has three advantages: firstly, the method is simple, and the synthesis is one step; the second is that the yield is close to 100%; the third is high-dose synthesis. Subsequently, the authors characterized the in situ SERS to characterize the C-C coupling reaction of mercaptobenzene on the surface of nickel nanoparticles to form mercaptobiphenyl.Surprisingly, by in situ SERS, the authors found that the CC coupling reaction, which was originally thought to be Ullmann self-coupling, was actually achieved by dehalogenation of thiol bromide to phenylthiol, which was then cross coupling with thiol bromide. In situ SERS detection played a key role in this work, and the authors found a new class of heterogeneous C-C coupled photocatalysts.
An argument has lasted for several decadesin studying the mechanism of Pd nanoparticles-catazyzed Suzuki-Miyaura couplingreactions, heterogeneous or homogeneous catalysis. By using in-situsurface-enhanced Raman spectroscopy (SERS) with high specificity andselectivity, the real catalytically-active sites of Pd nanoparticles for Suzukicoupling reactions are investigated and heterogeneous catalysis is concluded. Theresearch provides new opportunity in mechanistic study of interfacial reactionsby using SERS which will benefit the rational design of high-performance Pdcatalysts.