TY - JOUR A1 - Sarhan, Radwan Mohamed A1 - Koopman, Wouter-Willem Adriaan A1 - Schuetz, Roman A1 - Schmid, Thomas A1 - Liebig, Ferenc A1 - Koetz, Joachim A1 - Bargheer, Matias T1 - The importance of plasmonic heating for the plasmondriven photodimerization of 4-nitrothiophenol JF - Scientific Reports N2 - Metal nanoparticles form potent nanoreactors, driven by the optical generation of energetic electrons and nanoscale heat. The relative influence of these two factors on nanoscale chemistry is strongly debated. This article discusses the temperature dependence of the dimerization of 4-nitrothiophenol (4-NTP) into 4,4′-dimercaptoazobenzene (DMAB) adsorbed on gold nanoflowers by Surface-Enhanced Raman Scattering (SERS). Raman thermometry shows a significant optical heating of the particles. The ratio of the Stokes and the anti-Stokes Raman signal moreover demonstrates that the molecular temperature during the reaction rises beyond the average crystal lattice temperature of the plasmonic particles. The product bands have an even higher temperature than reactant bands, which suggests that the reaction proceeds preferentially at thermal hot spots. In addition, kinetic measurements of the reaction during external heating of the reaction environment yield a considerable rise of the reaction rate with temperature. Despite this significant heating effects, a comparison of SERS spectra recorded after heating the sample by an external heater to spectra recorded after prolonged illumination shows that the reaction is strictly photo-driven. While in both cases the temperature increase is comparable, the dimerization occurs only in the presence of light. Intensity dependent measurements at fixed temperatures confirm this finding. KW - enhanced raman-scattering KW - charge-transfer KW - metal KW - nanoparticles KW - catalysis KW - AU KW - 4-nitrobenzenethiol KW - aminothiophenol KW - photocatalysis KW - wavelength Y1 - 2019 U6 - https://doi.org/10.1038/s41598-019-38627-2 SN - 2045-2322 VL - 9 PB - Macmillan Publishers Limited CY - London ER - TY - JOUR A1 - Liebig, Ferenc A1 - Henning, Ricky A1 - Sarhan, Radwan Mohamed A1 - Prietzel, Claudia Christina A1 - Schmitt, Clemens Nikolaus Zeno A1 - Bargheer, Matias A1 - Koetz, Joachim T1 - A simple one-step procedure to synthesise gold nanostars in concentrated aqueous surfactant solutions JF - RSC Advances N2 - Due to the enhanced electromagnetic field at the tips of metal nanoparticles, the spiked structure of gold nanostars (AuNSs) is promising for surface-enhanced Raman scattering (SERS). Therefore, the challenge is the synthesis of well designed particles with sharp tips. The influence of different surfactants, i.e., dioctyl sodium sulfosuccinate (AOT), sodium dodecyl sulfate (SDS), and benzylhexadecyldimethylammonium chloride (BDAC), as well as the combination of surfactant mixtures on the formation of nanostars in the presence of Ag⁺ ions and ascorbic acid was investigated. By varying the amount of BDAC in mixed micelles the core/spike-shell morphology of the resulting AuNSs can be tuned from small cores to large ones with sharp and large spikes. The concomitant red-shift in the absorption toward the NIR region without losing the SERS enhancement enables their use for biological applications and for time-resolved spectroscopic studies of chemical reactions, which require a permanent supply with a fresh and homogeneous solution. HRTEM micrographs and energy-dispersive X-ray (EDX) experiments allow us to verify the mechanism of nanostar formation according to the silver underpotential deposition on the spike surface in combination with micelle adsorption. KW - optical-properties KW - nanoparticles KW - sers KW - ultrafast KW - size KW - nanotriangles KW - nanoflowers KW - wavelength Y1 - 2019 U6 - https://doi.org/10.1039/C9RA02384D SN - 2046-2069 VL - 9 SP - 23633 EP - 23641 PB - RSC Publishing CY - London ER -