title: Beneficial effects of microwave-assisted heating versus conventional heating in noble metal nanoparticle synthesis.
abstract: An extensive comparative study of the effects of microwave versus conventional heating on the nucleation and growth of near-monodisperse Rh, Pd, and Pt nanoparticles has revealed distinct and preferential effects of the microwave heating method. A one-pot synthetic method has been investigated, which combines nucleation and growth in a single reaction via precise control over the precursor addition rate. Using this method, microwave-assisted heating enables the convenient preparation of polymer-capped nanoparticles with improved monodispersity, morphological control, and higher crystallinity, compared with samples heated conventionally under otherwise identical conditions. Extensive studies of Rh nanoparticle formation reveal fundamental differences during the nucleation phase that is directly dependent on the heating method; microwave irradiation was found to provide more uniform seeds for the subsequent growth of larger nanostructures of desired size and surface structure. Nanoparticle growth kinetics are also markedly different under microwave heating. While conventional heating generally yields particles with mixed morphologies, microwave synthesis consistently provides a majority of tetrahedral particles at intermediate sizes (5-7 nm) or larger cubes (8+ nm) upon further growth. High-resolution transmission electron microscopy indicates that Rh seeds and larger nanoparticles obtained from microwave-assisted synthesis are more highly crystalline and faceted versus their conventionally prepared counterparts. Microwave-prepared Rh nanoparticles also show approximately twice the catalytic activity of similar-sized conventionally prepared particles, as demonstrated in the vapor-phase hydrogenation of cyclohexene. Ligand exchange reactions to replace polymer capping agents with molecular stabilizing agents are also easily facilitated under microwave heating, due to the excitation of polar organic moieties; the ligand exchange proceeds with excellent retention of nanoparticle size and structure.
authors.affiliation: Department of Chemistry and Biochemistry, The University of Texas at Austin, 1 University Station A5300, Austin, Texas 78712-0165, United States.
authors.forename: Naween
authors.initials: N
authors.lastname: Dahal
authors.forename: Stephany
authors.initials: S
authors.lastname: García
authors.forename: Jiping
authors.initials: J
authors.lastname: Zhou
authors.forename: Simon M
authors.initials: SM
authors.lastname: Humphrey
mesh_terms: D003460:Crystallization / Q000379:methods*; D006361:Heating / Q000379:methods*; D046911:Macromolecular Substances / Q000737:chemistry / Q000528:radiation effects; D008422:Materials Testing; D053768:Metal Nanoparticles / Q000737:chemistry* / Q000528:radiation effects* / Q000648:ultrastructure; D008872:Microwaves; D008968:Molecular Conformation / Q000528:radiation effects; D010316:Particle Size; D011829:Radiation Dosage; D013499:Surface Properties / Q000528:radiation effects
chemical_list: D046911:Macromolecular Substances