Document Type
Article
Original Publication Date
2017
Journal/Book/Conference Title
The Journal of Physical Chemistry A
Volume
121
First Page
6742
Last Page
6754
DOI of Original Publication
10.1021/acs.jpca.7b05370
Date of Submission
August 2019
Abstract
Free electrons and H2O2 formed in an optical breakdown plasma are found to directly control the kinetics of [AuCl4]− reduction to form Au nanoparticles (AuNPs) during femtosecond laser-assisted synthesis of AuNPs. The formation rates of both free electrons and H2O2 strongly depend on the energy and duration of the 800 nm laser pulses over the ranges of 10−2400 μJ and 30−1500 fs. By monitoring the conversion of [AuCl4]− to AuNPs using in situ UV−vis spectroscopy during laser irradiation, the first- and second-order rate constants in the autocatalytic rate law, k1 and k2, were extracted and compared to the computed free electron densities and experimentally measured H2O2 formation rates. For laser pulse energies of 600 μJ and lower at all pulse durations, the first-order rate constant, k1, was found to be directly proportional to the theoretically calculated plasma volume, in which the electron density exceeds the threshold value of 1.8 × 1020 cm−3. The second-order rate constant, k2, was found to correlate with the measured H2O2 formation rate at all pulse energies and durations, resulting in the empirical relationship k2 ≈ H2O20.5. We have demonstrated that the relative composition of free electrons and H2O2 in the optical breakdown plasma may be controlled by changing the pulse energy and duration, which may make it possible to tune the size and dispersity of AuNPs and other metal nanoparticle products synthesized with femtosecond laser-based methods.
Is Part Of
VCU Chemistry Publications
Comments
The accepted manuscript is attached. The published version is available here: https://doi.org/10.1021/acs.jpca.7b05370