Understanding bottom-up continuous hydrothermal synthesis of nanoparticles using empirical measurement and computational simulation

Continuous hydrothermal synthesis was highlighted in a recent review as an enabling technology for the production of nanoparticles. In recent years, it has been shown to be a suitable reaction medium for the synthesis of a wide range of nanomaterials. Many single and complex nanomaterials such as metals, metal oxides, doped oxides, carbonates, sulfides, hydroxides, phosphates, and metal organic frameworks can be formed using continuous hydrothermal synthesis techniques. This work presents a methodology to characterize continuous hydrothermal flow systems both experimentally and numerically, and to determine the scalability of a counter current supercritical water reactor for the large scale production (>1,000 T·year–1) of nanomaterials. Experiments were performed using a purpose-built continuous flow rig, featuring an injection loop on a metal salt feed line, which allowed the injection of a chromophoric tracer. At the system outlet, the tracer was detected using UV/Vis absorption, which could be used to measure the residence time distribution within the reactor volume. Computational fluid dynamics (CFD) calculations were also conducted using a modeled geometry to represent the experimental apparatus. The performance of the CFD model was tested against experimental data, verifying that the CFD model accurately predicted the nucleation and growth of the nanomaterials inside the reactor

Rapid continuous microwave-assisted synthesis of silver nanoparticles to achieve very high productivity and full yield: from mechanistic study to optimal fabrication strategy

Systematic studies of silver nanoparticle synthesis in a continuous-flow single-mode microwave reactor using polyol process were performed, revealing that the synthesis is exceptionally effective to give very small metal particles at full reaction yield and very high productivity. Inlet concentration of silver nitrate or silver acetate, applied as metal precursors, varied between 10 and 50 mM, and flow rates ranged from 0.635 to 2.5 dm3/h, to give 3–24 s reaction time. Owing to its much higher reactivity, silver acetate was shown to be far superior substrate for the synthesis of small (10–20 nm) spherical silver nanoparticles within a few seconds. Its restricted solubility in ethylene glycol, applied as the solvent and reducing agent, appeared to be vital for effective separation of the stage of particle growth from its nucleation to enable rapid synthesis of small particles in a highly loaded system. This was not possible to obtain using silver nitrate. All the observations could perfectly be explained by a classical LaMer–Dinegar model of NPs’ formation, but taking into account also nonisothermal character of the continuous-flow process and acetate dissolution in the reaction system. The performed studies indicate an optimal strategy for the high-yield fabrication of metal particles using polyol method