Surface Enhanced Raman Spectroscopy Studies on the “Hot Spot” Localized Area from Free Collision Behavior of Gold Nanoparticle-Gold Single Crystal Microplate

doi:10.6023/A23120527

Abstract

The investigation on the free motion of nanoparticles and their interaction with other media has become an attractive field for extending the practical application. However, the real-time monitoring of dynamic behaviors still exists significant challenge. In this paper, based on surface enhanced Raman spectroscopy (SERS) and the formation of “hot spots” during collision between Au nanoparticles and Au single crystal microplate under Brownian motion, the real-time monitoring of free motion behaviors of Au nanoparticles during collision and the dynamic SERS study were realized accordingly by using thiophenol (TP) as the probe molecule. The nature and influencing factors of microscopic motion of nanoparticles were investigated by statistical analysis of the “spikes” in the SERS trajectories, including “single spikes” and “cluster spikes”. The results reveal that the “spike” is mainly attributed to the “hot spots” formed by reversible collision of nanoparticle and plane. “Single spikes” correspond to the rapid departure of Au nanoparticles from the surface of the Au microplate after collision with the microplate, and “cluster spikes” correspond to the process of Au nanoparticles staying on the surface of the Au microplate for a short time after colliding with the plane and then leaving or possibly multiple nanoparticles colliding continuously. Increasing the concentration of nanoparticles is beneficial to the formation of “cluster spike”. The intensity distribution of the corresponding SERS characteristic peaks is concentrated in 5.2 cps and 8.7 cps, respectively. The relative intensities of SERS peaks of TP in the “spikes” are critically depended on the vibrational modes. It demonstrates that the probability of stretching vibrational modes is higher, and it is mainly due to the different orientations of molecules in the localized area during the dynamic collision processes. The realization of dynamic collision is beneficial to deeply understand the nature of microscopic motion of nanoparticles. It provides the basis for the investigation of dynamic interfacial chemical reactions in localized area.

Key words: surface enhanced Raman spectroscopy, collision, thiophenol, “hot spot”, concentration

Cite this article

Qing Yang, Xiaoyu Liu, Chen Wang, Minmin Xu, Jianlin Yao. Surface Enhanced Raman Spectroscopy Studies on the “Hot Spot” Localized Area from Free Collision Behavior of Gold Nanoparticle-Gold Single Crystal Microplate[J]. Acta Chimica Sinica, 2024, 82(3): 281-286.

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Fig. & Tab. 6

Figure 1. (a) The time-dependent SERS trajectories of band intensity at 1572 cm?1 before and after adding Au nanoparticles. (b) The time-dependent SERS image of TP from 2920 s to 3120 s with Au nanoparticles and the corresponding SERS trajectories of band intensity at 1572 cm?1

Figure 2. (a) SERS spectra extracted from a “spike” of Figure 1a from 3083 s to 3092 s. (b) The statistical analysis of the occurrence probability of four vibrational modes of TP in 6000 s

Figure 3. The shape of “single spike” (a) and schematic diagram of collision model (b). The shape of “cluster spike” (c) and schematic diagram of collision model (d)

Figure 4. Statistical diagram of SERS intensity distribution of “single spike” (a) and “cluster spike” (b) detected after the addition of Au nanoparticles in Figure 1a

Figure 5. (a) The time-dependent SERS trajectories of TP at 1572 cm?1 from different concentrations of Au nanoparticles (i) 0, (ii) 5.7×10?14 mol?dm?3, (iii) 1.14×10?13 mol?dm?3, (iv) 5.7×10?13 mol?dm?3, (v) 1.14×10?12 mol?dm?3, respectively. (b) Characteristic SERS spectra corresponding to different concentrations of Au nanoparticles

Figure 6. The statistical results of the number of “single spike” and “cluster spike” in the time-dependent SERS trajectories of TP at 1572 cm?1 in the solution of Au nanoparticles with different concentrations

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