title: Prodigious Effects of Concentration Intensification on Nanoparticle Synthesis: A High-Quality, Scalable Approach.
abstract: Realizing the promise of nanoparticle-based technologies demands more efficient, robust synthesis methods (i.e., process intensification) that consistently produce large quantities of high-quality nanoparticles (NPs). We explored NP synthesis via the heat-up method in a regime of previously unexplored high concentrations near the solubility limit of the precursors. We discovered that in this highly concentrated and viscous regime the NP synthesis parameters are less sensitive to experimental variability and thereby provide a robust, scalable, and size-focusing NP synthesis. Specifically, we synthesize high-quality metal sulfide NPs (<7% relative standard deviation for Cu2-xS and CdS), and demonstrate a 10-1000-fold increase in Cu2-xS NP production (>200 g) relative to the current field of large-scale (0.1-5 g yields) and laboratory-scale (<0.1 g) efforts. Compared to conventional synthesis methods (hot injection with dilute precursor concentration) characterized by rapid growth and low yield, our highly concentrated NP system supplies remarkably controlled growth rates and a 10-fold increase in NP volumetric production capacity (86 g/L). The controlled growth, high yield, and robust nature of highly concentrated solutions can facilitate large-scale nanomanufacturing of NPs by relaxing the synthesis requirements to achieve monodisperse products. Mechanistically, our investigation of the thermal and rheological properties and growth rates reveals that this high concentration regime has reduced mass diffusion (a 5-fold increase in solution viscosity), is stable to thermal perturbations (∼64% increase in heat capacity), and is resistant to Ostwald ripening.
authors.affiliation: School of Chemical and Biomolecular Engineering and ‡Department of Materials Science and Engineering, Cornell University , Ithaca, New York 14853, United States.
authors.forename: Curtis B
authors.initials: CB
authors.lastname: Williamson
authors.affiliation: School of Chemical and Biomolecular Engineering and ‡Department of Materials Science and Engineering, Cornell University , Ithaca, New York 14853, United States.
authors.forename: Douglas R
authors.initials: DR
authors.lastname: Nevers
authors.affiliation: School of Chemical and Biomolecular Engineering and ‡Department of Materials Science and Engineering, Cornell University , Ithaca, New York 14853, United States.
authors.forename: Tobias
authors.initials: T
authors.lastname: Hanrath
authors.affiliation: School of Chemical and Biomolecular Engineering and ‡Department of Materials Science and Engineering, Cornell University , Ithaca, New York 14853, United States.
authors.forename: Richard D
authors.initials: RD
authors.lastname: Robinson