title: Mechanistic study of the hydrothermal reduction of palladium on the Tobacco mosaic virus.
abstract: The fundamental mechanisms governing reduction and growth of palladium on the genetically engineered Tobacco mosaic virus in the absence of an external reducer have been elucidated via in situ X-ray absorption spectroscopy. In recent years, many virus-inorganic materials have been synthesized as a means to produce high quality nanomaterials. However, the underlying mechanisms involved in virus coating have not been sufficiently studied to allow for directed synthesis. We combined XAS, via XANES and EXAFS analysis, with TEM to confirm an autocatalytic reduction mechanism mediated by the TMV1Cys surface. This reduction interestingly proceeds via two first order regimes which result in two linear growth regimes as spherical palladium nanoparticles are formed. By combining this result with particle growth data, it was discovered that the first regime describes growth of palladium nanoparticles on the virion while the second regime describes a second layer of larger particles which grew sporadically on the first palladium nanoparticle layer. Subsequent aggregation of free solution based spherical particles and metallized nanorods characterize a third and final regime. At the end of the second reduction regime, the average particle diameter of particles tethered to the TMV1Cys surface are approximately 4.5 nm. The use of XAS to simultaneously monitor the kinetics of biotemplated reactions along with growth of metal nanoparticles will provide insight into the pertinent reduction and growth mechanisms so that nanorod properties can be controlled through their populating nanoparticles.
authors: School of Chemical Engineering, Purdue University, 480 Stadium Drive, Forney Hall, IN 47907, United States. Electronic address: oadigun@purdue.edu.
authors: Oluwamayowa O
authors: OO
authors: Adigun
authors: School of Chemical Engineering, Purdue University, 480 Stadium Drive, Forney Hall, IN 47907, United States. Electronic address: afreer@purdue.edu.
authors: Alexander S
authors: AS
authors: Freer
authors: School of Chemical Engineering, Purdue University, 480 Stadium Drive, Forney Hall, IN 47907, United States. Electronic address: jeffrey-t-miller@purdue.edu.
authors: Jeffrey T
authors: JT
authors: Miller
authors: Department of Botany and Plant Pathology, Purdue University, West Lafayette, IN 47907, United States. Electronic address: loeschfr@purdue.edu.
authors: L Sue
authors: LS
authors: Loesch-Fries
authors: Department of Botany and Plant Pathology, Purdue University, West Lafayette, IN 47907, United States. Electronic address: kim1@purdue.edu.
authors: Bong Suk
authors: BS
authors: Kim
authors: School of Chemical Engineering, Purdue University, 480 Stadium Drive, Forney Hall, IN 47907, United States. Electronic address: mtharris@purdue.edu.
authors: Michael T
authors: MT
authors: Harris
mesh_terms: D003545:Cysteine / Q000737:chemistry; D053768:Metal Nanoparticles / Q000737:chemistry*; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D014027:Tobacco Mosaic Virus / Q000737:chemistry*; D014771:Virion / Q000737:chemistry*
chemical_list: D010165:Palladium; D003545:Cysteine
keywords: Hydrothermal synthesis; In situ; Mineralization; Reduction; Tobacco mosaic virus; X-ray Absorption Spectroscopy (XAS)