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 CuCl₂ solution produced nano-paratacamite, Cu₂Cl(OH)₃, whereas nano-rouaite, Cu₂(NO₃)(OH)₃, was formed in aqueous Cu(NO₃)₂ and 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 ZnCl₂ and 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.