David Rutherford

Continuous In-Flight Synthesis for On-Demand Delivery of Ligand-Free Colloidal Gold Nanoparticles

We demonstrate an entirely new method of nanoparticle chemical synthesis based on liquid droplet irradiation with ultralow (<0.1 eV) energy electrons. While nanoparticle formation via high energy radiolysis or transmission electron microscopy-based electron bombardment is well-understood, we have developed a source of electrons with energies close to thermal which leads to a number of important and unique benefits. The charged species, including the growing nanoparticles, are held in an ultrathin surface reaction zone which enables extremely rapid precursor reduction. In a proof-of-principle demonstration, we obtain small-diameter Au nanoparticles (∼4 nm) with tight control of polydispersity, in under 150 μs. The precursor was almost completely reduced in this period, and the resultant nanoparticles were water-soluble and free of surfactant or additional ligand chemistry. Nanoparticle synthesis rates within the droplets were many orders of magnitude greater than equivalent rates reported for radiolysis, electron beam irradiation, or colloidal chemical synthesis where reaction times vary from seconds to hours. In our device, a stream of precursor loaded microdroplets, ∼15 μm in diameter, were transported rapidly through a cold atmospheric pressure plasma with a high charge concentration. A high electron flux, electron and nanoparticle confinement at the surface of the droplet, and the picoliter reactor volume are thought to be responsible for the remarkable enhancement in nanoparticle synthesis rates. While this approach exhibits considerable potential for scale-up of synthesis rates, it also offers the more immediate prospect of continuous on-demand delivery of high-quality nanomaterials directly to their point of use by avoiding the necessity of collection, recovery, and purification. A range of new applications can be envisaged, from theranostics and biomedical imaging in tissue to inline catalyst production for pollution remediation in automobiles.

Controlled microdroplet transport in an atmospheric pressure microplasma

We report the controlled injection of near-isolated micron-sized liquid droplets into a low temperature He-Ne steady-state rf plasma at atmospheric pressure. The H2O droplet stream is constrained within a 2 mm diameter quartz tube. Imaging at the tube exit indicates a log-normal droplet size distribution with an initial count mean diameter of 15 μm falling to 13 μm with plasma exposure. The radial velocity profile is approximately parabolic indicating near laminar flow conditions with the majority of droplets travelling at >75% of the local gas speed and having a plasma transit time of <100 μs. The maximum gas temperature, determined from nitrogen spectral lines, was below 400 K and the observed droplet size reduction implies additional factors beyond standard evaporation, including charge and surface chemistry effects. The demonstration of controlled microdroplet streams opens up possibilities for gas-phase microreactors and remote delivery of active species for plasma medicine.