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Abstract Plasmonic metal nanostructures are essential for plasmon‐mediated chemical reactions (PMCRs) and surface‐enhanced Raman spectroscopy (SERS). The nanostructures are commonly made from the coinage metals gold and silver. Copper (Cu) is less used mainly due to the difficulties in fabricating stable nanostructures. However, Cu is an attractive option with its strong plasmonic properties, high catalytic activities, and relatively cheap price. Herein, we fabricated tunable, reliable, and efficient Cu nanoelectrodes (CuNEs). Using time‐resolved electrochemical SERS, we have comprehensively studied the reversible chemical transformations between aromatic amine and nitro groups modified on the CuNE surface. Their PMCRs are well‐controlled by changing the surface roughness, the oxidation states of Cu, and the applied electrode potential. We thus demonstrate that the Cu nanostructures enable better investigations in the interplays between PMCR, electrochemistry, and Cu catalysis.
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Nanopipette‐based electrochemical SERS platforms: Using electrodeposition to produce versatile and adaptable plasmonic substrates
Abstract A method for fabricating localized EC‐SERS probes based on nanopipettes and electrodeposition is described. Gold particles of fractal geometry with excellent SERS performance are produced, reliably and at low cost. By adapting the electrodeposition procedure, nanostructures of different sizes can be obtained, allowing the SERS platform to be tailored to many experimental configurations. In particular, by producing unique SERS platforms of dimensions comparable to the laser spot, quantitative comparison with electrochemical current is possible. By analyzing hundreds of samples, we thoroughly characterize the resulting geometry of the structures and their ability to enhance Raman signal, providing guidelines for the fabrication of optimized platforms. Control over the probes' surface potential also allows convenient modulation of surface‐analyte affinity and enable chemically unstable materials, such as Cu, to be reliably used. These are demonstrated by showing that Cu particles exposed to air can be easily re‐reduced, with no detriment in SERS performance.
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- Award ID(s):
- 1807278
- PAR ID:
- 10452343
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Journal of Raman Spectroscopy
- Volume:
- 52
- Issue:
- 2
- ISSN:
- 0377-0486
- Format(s):
- Medium: X Size: p. 339-347
- Size(s):
- p. 339-347
- Sponsoring Org:
- National Science Foundation
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