Complex nanomineral formation utilizing kinetic control by PLAL.
We used pulsed-laser ablation in liquids (PLAL) of Cu or Zn foil targets in water or in aqueous Cu or Zn salt solutions. PLAL in neat water generated mixtures of metal and (thermodynamically preferred) metal oxide nanomaterials, whereas the availability of select dissolved anions predictably led to the fabrication of more complex phase-pure nanominerals. PLAL of Cu foil in aqueous CuCl2solution produced nano-paratacamite, Cu2Cl(OH)3, whereas nano-rouaite, Cu2(NO3)(OH)3, was formed in aqueous Cu(NO3)2and NH4OH solution. Likewise, we synthesized simonkolleite, Zn5(OH)8Cl2·H2O, or layered zinc hydroxide nitrate, Zn5(OH)8(NO3)2·2H2O, nanoparticles by PLAL of Zn targets in aqueous ablation liquids with added ZnCl2and NH4OH or Zn(NO3)2, respectively. Bimetallic zincian paratacamite resulted from PLAL of Cu foil in aqueous Cu and Zn chloride solution. Our results show that kinetic control exceeded thermodynamic product formation during nanosecond ultraviolet PLAL.
Beckman Institute and Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.
Christopher W
CW
Roske
College of Natural and Agricultural Sciences, University of California, Riverside, CA 92521, USA.
Jeffery W
JW
Lefler
Beckman Institute and Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA. Electronic address: astridm@caltech.edu.
Astrid M
AM
Müller
Copper nanoparticles; CuO nanoparticles; Kinetic control; Layered zinc hydroxide nitrate; Paratacamite; Pulsed laser ablation in liquids; Simonkolleite; Zinc nanoparticles; Zincian paratacamite; ZnO nanoparticles