This article presents a mechanistic study of silver nanodecahedra prepared by the method of photoassisted sodium citrate reduction under irradiation of blue light-emitting diodes (LEDs). This synthesis of silver nanodecahedra can be easily reproduced in the absence of silver seeds and can be completed in one-pot. The data suggest a combination of two processes including gradual growth from multiple-twinned particles and subsequent plasmonmediated crystal growth. More than 85% of as-prepared silver nanoparticles are decahedra with edge lengths of 43.5 ± 5.2 nm. In addition, the as-prepared silver colloids exhibit a spectroscopic enhancement in comparison with spherical silver nanoparticle colloids and silver nanoprism colloids in the measurement of surface enhanced Raman spectroscopy (SERS) spectra of Rhodamin 6G, and with the decahedral silver colloids synthesized in the presence of PVP for detecting SERS signal of Rhodamin 6G. Overall, this photoassisted citrate reduction process is simple, and highly reproducible. As-prepared silver nanodecahedra are more stable and provide optimal SERS signal than those synthesized using commonly used plasmon-mediated photochemical methods.

Plasmon-mediated shape conversion of spherical silver nanoparticles (NPs) to nanostructures with other shapes under the irradiation of green LEDs (520 ± 20 nm, 35 mw/cm2) at various temperatures (60, 40, 20, 10, 5, and 0 °C) was performed in this study. It was found that the bath temperature used in the reaction can influence the reaction rates, i.e., the times needed for the shape transformation process were 5, 11.5, 25, 45, 72, and 100 h at 60, 40, 20, 10, 5, and 0 °C, respectively. In addition, the bath temperature can also alter the morphologies of the final products. The major products are silver nanoplates at 60, 40 and 20 °C. However, they became decahedral silver NPs at 5 and 0 °C. The percentages of decahedral silver NPs synthesized at 60, 40, 20, 10, 5, and 0 °C are 0%, 1%, 5%, 45%, 73%, and 89%, respectively. Measuring the surface-enhanced Raman spectroscopy (SERS) spectra of the probe molecule R6G in the presence of KBr showed that both silver nanoplate colloids synthesized at 60 °C and decahedral silver NP colloids synthesized at 0 °C in the absence of PVP had good SERS activities.

Silver nanoparticles can be prepared by using a seed-free photo-assisted citrate reduction method under the irradiation of a sodium lamp. Under the same irradiation intensity, bath temperatures are crucial in influencing the reaction rate, morphologies of final products, and shape evolution of the silver nanostructures. For example, when the bath temperature is 80 °C, the product yields of silver nanoplates, nanorods, and nanodecahedra are 38±6 %, 35±10 %, and 12±8 %, respectively. However, when the bath temperature is 30 °C, the product yields of silver nanoplates, nanorods, and nanodecahedra are 6±3 %, 0 %, and 83±16 %, respectively. Time-dependent UV/Vis spectra and TEM images show that silver nanoplates were formed at the earlier reaction stage and greatly decreased in amount at the later stage when the bath temperatures are less than or equal to 40 °C. This indicates that the silver nanoplates, which can be regarded as intermediates, are kinetically favored products. They are not thermodynamically favored products at these relatively low bath temperatures. The SERS spectra of crystal violet (CV) show that all the silver colloids synthesized at various temperatures exhibit good enhancement factors and that the colloids prepared at lower bath temperatures have a higher enhancement factor.