Tip-Enhanced Raman Analysis of Plasmonic and Photocatalytic Properties of Copper Nanomaterials.

Theoretical predictions suggest that, in addition to gold (Au) and silver (Ag), several other metals such as copper (Cu) and aluminum (Al) can be used as plasmonic materials. However, their plasmonic and photocatalytic properties remain poorly understood. In this contribution, we employed tip-enhanced Raman spectroscopy to examine photocatalytic properties of Cu nanowires and nanocubes (CuNWs and CuNCs). Our results show that both CuNWs and CuNCs demonstrate a far more efficient photocatalytic dimerization of 4-nitrobenzenethiol to 4,4'-dimercaptoazobenzene than Au nano and microplates. We also found that CuNWs and CuNCs can neither reduce 4-mercaptobenzoic acid (4-MBA) to the corresponding aromatic alcohol nor dearboxylate it forming benzenethiol. We infer that this is due to a unique coordination of 4-MBA on Cu surfaces that was only rarely observed on Au and Ag nanomaterials. Finally, we found that Cu nanostructures can oxidize 4-mercapto-phenyl-methanol to 4-MBA, which was previously only observed on gold-platinum nanoplates.