Nucleation and growth of gold nanoparticles initiated by nanosecond and femtosecond laser irradiation of aqueous [AuCl4]-

Irradiation of aqueous [AuCl4]with 532 nm nanosecond (ns) laser pulses produces monodisperse (PDI = 0.04) 5 nm Au nanoparticles (AuNPs) without any additives or capping agents via a plasmon- enhanced photothermal autocatalytic mechanism. Compared with 800 nm femtosecond (fs) laser pulses, the AuNP growth kinetics under ns laser irradiation follow the same autocatalytic rate law, but with a significantly lower sensitivity to laser pulse energy. The results are explained using a simple model for simulating heat transfer in liquid water and at the interface with AuNPs. While the extent of water superheating with the ns laser is smaller compared to the fs laser, its significantly longer duration can provide sufficient energy to dissociate a small fraction of the [AuCl4]present, resulting in the formation of AuNPs by coalescence of the resulting Au atoms. Irradiation of initially formed AuNPs at 532 nm results in plasmon-enhanced superheating of water, which greatly accelerates the rate of thermal dissociation of [AuCl4]and accounts for the observed autocatalytic kinetics. The plasmon-enhanced heating under ns laser irradiation fragments the AuNPs and results in nearly uniform 5 nm particles, while the lack of particles’ heating under fs laser irradiation results in the growth of the particles as large as 40 nm

LASER SYNTHESIS OF NANOMATERIALS INCORPORATED WITHIN HIGH SURFACE AREA MATERIALS: APPLICATIONS FOR HETEROGENEOUS CATALYSIS, WATER TREATMENT, AND PHOTOTHERMAL ENERGY CONVERSION

Chemical methods are generally used for the synthesis of active nanoparticles (metals, semi-metals, metal oxides, and etc) supported on high surface area materials. Chemical methods involve using strong solvents, harmful gases (H2 & CO), and high temperature techniques such as high boiling solvents, calcination and pyrolysis. The main drawbacks of using this approach, is the prevalence of chemical agents on nanomaterials which tends to negate its applications. Alternatively, photochemical and photothermal methods are widely being considered for the synthesis and design of nanomaterials. For these studies, the active nanomaterials incorporated within high surface area materials were prepared by the laser vaporization-controlled condensation (LVCC) technique or by the laser irradiation in solution (LIS) technique. The LVCC technique involves the irradiation of a solid target at the focal point of a laser beam (532 nm, 30 Hz) by the Nd: YAG laser inside a chamber that is sandwiched between two steel plates in the presence of high purity He. Whereas, the LIS technique involves the laser irradiation of chemical precursors in aqueous solvents using an unfocused beam. The LVCC technique was used for the preparation of carbonaceous and N-doped carbonaceous TiO2 support materials from MIL-125(Ti) and NH2-MIL-125(Ti) metal organic frameworks, Ge and GeO2 nanostructures, GeOx/PRGO nanocomposite, and the Fe3O4/PRGO nanocomposite. On the other hand, Pd supported on MIL-125(Ti) and NH2-MIL-125(Ti) nanocatalysts, GeO2/RGO, and the poly(ethylene glycol methacrylate-co-bisacrylamide) hydrogels were all prepared by the LIS technique