Continuous flow synthesis of ultrasmall gold nanoparticles in a microreactor using trisodium citrate and their SERS performance

• Sub-3 nm gold nanoparticles were synthesized in continuous flow capillary reactors. • Negatively charged capillary-solution interface offered enhanced nucleation rate. • Gold nanoparticles with a weaker capping agent provided higher SERS signal. Ultrasmall gold nanoparticles were synthesized without strong capping agents by using a capillary-based continuous flow system. A mixture of gold(III) chloride trihydrate and trisodium citrate flowed through capillaries at elevated temperature. The effect of capillary material (polytetrafluoroethylene, fluorinated ethylene propylene, polyetheretherketone, fused silica), surface-to-volume ratio (capillary internal diameter 0.3–1 mm), average residence time (1.5–30 min) and temperature (70–100 °C) were investigated. At a flow rate of 0.006 ml/min (residence time 30 min), 100 °C, 275 kPa back pressure, citrate/gold molar ratio 3.15 and using PTFE capillary tubing with an inner diameter of 0.3 mm, very small (1.9 ± 0.2 nm) nanoparticles were obtained. For comparison, experiments were also performed under the same experimental conditions, but in slug flow using octane as segmenting fluid, thus isolating the reactants from the tubing wall. The synthesized particles were 17.4 ± 1.4 nm for segmented flow, demonstrating the important effect of the capillary wall surface. The performance of these citrate-capped gold nanoparticles was tested for Surface-Enhanced Raman Scattering (SERS). The average enhancement factor (AEF) of 2 nm gold nanoparticles capped by citrate from our work (AEF = 1.54 × 10 8 ) was nearly double when compared to 2 nm phosphate-capped commercial gold nanoparticles (AEF = 7.34 × 10 7 ). The adsorption of analyte molecules onto citrate-capped gold surface was easier due to the weaker binding strength of the carboxylate ligand and more hotspots formed with narrower gaps between neighbouring particles, giving rise to improved enhancement. This work has been selected by the Editors as a Featured Cover Article for this issue.