Probing the Interaction of Poly(vinylpyrrolidone) with Platinum Nanocrystals by UV−Raman and FTIR

The vibrational spectra of platinum nanoparticles (2.4-9 nm) capped with poly(N-vinylpyrrolidone) (PVP) were investigated by deep UV-Raman and FTIR spectroscopy and compared with those of pure PVP. Raman spectra of PVP/Pt show selective enhancement of C=O, C-N, and CH2 vibrational modes attributed to the pyrrolidone ring. Selective enhancement of ring vibrations is attributed both to the resonance Raman effect and SERS chemical enhancement. A red shift of the PVP carbonyl frequency on the order of 60 cm-1 indicates the formation of strong >C=O-Pt bonds. It is concluded that PVP adheres to the nanoparticles through a charge-transfer interaction between the pyrrolidone rings and surface Pt atoms. Heating the Pt nanoparticles under reducing conditions initiates the decomposition of the capping agent, PVP, at a temperature 100 degrees C below that of pure PVP. Under oxidizing conditions, both PVP/Pt and PVP degrade to form amorphous carbon.