Electrochemically roughened silver surface versus fractal leaf-shaped silver crystals for surface-enhanced Raman scattering investigation of polypyrrole

Guerraf, A. El; Aouzal, Z.; Bouabdallaoui, M.; Jadi, S. Ben; Jaouhari, Abdelhadi El; Wang, R.; Bazzaoui, M.; Bazzaoui, E.A.

doi:10.1007/s10008-019-04288-4

Cited by 12 publications

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“…27,28 In contrast, both the ring-stretching and CC bond peaks in the SERS spectra of PPy on Ag electrodes are blue-shifted. 29 Even though the same metal (Ag) was utilized for the SERS of PPy, the ring-stretching SERS peak shifted in opposite directions. However, an exact reason why this SERS peak shift occurs has not yet been studied.…”

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“…PPy, a polymerized form of pyrrole, is a conducting polymer and a well-known SERS-active material. In the SERS spectra of PPy with silver (Ag) nanoparticles (NPs), the ring-stretching peak is red-shifted, while the CC bond peak is blue-shifted. , In contrast, both the ring-stretching and CC bond peaks in the SERS spectra of PPy on Ag electrodes are blue-shifted . Even though the same metal (Ag) was utilized for the SERS of PPy, the ring-stretching SERS peak shifted in opposite directions.…”

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“…As previously mentioned, it was reported that the SERS peak of ring stretching in PPy nanomaterials shows opposite red or blue shifts depending on the kind of coordinated Ag that is present (i.e., Ag NPs or a Ag electrode). However, the SERS peak of the CC bond in the spectra of both PPy nanomaterials shows only a blue shift. − It can be assumed that bulky (electrode, film) or nanostructured (NPs) Ag materials result in the opposite SERS peak shift in PPy. To verify the opposite SERS peak shift in PPy with different Ag materials, PPy materials with both Ag NP (nanostructured Ag) and Ag dendrite film (bulky Ag) coordination were prepared as illustrated in Figure , which shows the reported tendency of SERS peak shifts in the insets.…”

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“…As shown in Table , the ring-stretching peaks in the SERS spectra are either red-shifted or blue-shifted depending on the type of Ag material present. El Guerraf et al reported that the SERS ring-stretching peak in the spectrum of PPy with a bulky Ag electrode (PPy-Ag electrode) is blue-shifted (1328 cm –1 to 1363 cm –1 ) compared to that of PPy without the SERS effect (PPy-Pt electrode), where the SERS effect of platinum is known to be lower or nonexistent . In contrast, Gan et al reported that the SERS peak of ring stretching in PPy with nanostructured Ag (PPy-Ag nanostructures) is red-shifted (1387 cm –1 to 1384 cm –1 ) .…”

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“…Gniadek et al reported that the SERS peak of ring stretching in PPy is more red-shifted (1326 cm –1 to 1322 cm –1 ) when more Ag NPs attached to PPy structures (assumed by the higher metal content per mass) . However, it was reported that SERS peaks of CC stretching in both bulky and nanostructured Ag are blue-shifted (1581 cm –1 to 1610 cm –1 , 1573 cm –1 to 1575 cm –1 , and 1590 cm –1 to 1598 cm –1 , ref ). By comparison with previous reports, it is assumed that the Ag NPs and Ag dendrite films used in this study can be regarded as nanostructured and bulky Ag systems, respectively, due to the SERS shifts of the ring-stretching peaks.…”

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Opposite Raman Shift of Ring Stretching Dependent on the Coordinated Silver Volume in Surface-Enhanced Raman Spectroscopy of Polypyrrole

Jeon

Lee

Jang

2022

J. Phys. Chem. Lett.

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Surface-enhanced Raman spectroscopy (SERS) can sense some molecules in a nondestructive manner. Using SERS, we investigate the shifts in the Raman peaks of polypyrrole (PPy) with two different coordinated silver (Ag) structures, Ag nanoparticles (NPs) and Ag dendrite film. The SERS spectrum of PPy with Ag NPs presents a ring-stretching peak that is red-shifted compared to the ring-stretching peak in the Raman spectrum of PPy. In contrast, the spectrum of the PPy with the Ag dendrite film exhibits a blue-shifted ring stretching peak. The various coordinated Ag nanostructures result in opposite Raman shifts of the ring stretching peak; this phenomenon has been investigated and confirmed by density functional theory (DFT) calculations of the Raman shift of the pyrrole (Py) molecule with a Ag layer (SERS of PPy with Ag NPs) and that of a charge-transferred Py molecule (SERS of PPy with Ag dendrite films). This result demonstrates that DFT calculations can be an effective tool to scrutinize Raman shifts in SERS.

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