This paper describes microcontact printing (muCP) of long-chain alkanethiolates on palladium, followed by solution-phase etching with an iron(III)-based etchant, to make patterned structures. The commonly used soft-lithographic procedure for fabricating microstructures-muCP of SAMs on gold-has three shortcomings: a significant surface density of pinhole defects, substantial edge roughness, and incompatibility with processes used in CMOS fabrication. Microcontact printing on palladium gives fewer defects and smaller edge roughness than on gold, and is compatible with CMOS. The mechanism by which etch-resistant patterns are formed is different for palladium and gold. The Pd/S interfacial layer formed by the reaction of palladium films with sulfur-containing compounds provides good resistance to etches independently of the barrier to access the surface provided by the film of (CH2)n groups in the long-chain SAMs. This barrier is the basis of the etch resistance of SAMs on gold, but only supplements the etch resistance of the sulfur-containing interfacial layer on palladium. Characterization of the SAM formed from hexadecanethiol on palladium is described.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/ja012569l | DOI Listing |
ACS Appl Nano Mater
November 2019
Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Boulevard, Long Beach, California 90840, United States.
Alkanethiolate-capped palladium nanoparticles (PdNPs) have previously been synthesized by using a modified Brust-Schiffrin synthesis (using alkanethiosulfate instead of alkanethiol), in which the nanoparticle core size is established during alkanethiosulfate ligand passivation of the nanoparticle nucleation-growth initiated by borohydride reduction. Because of the dependence of core size on the amount of ligand present, surface ligand density decreases with increasing core size. Herein we present a method in which the core size is established independent of ligand addition, allowing the formation of PdNPs with similar core sizes yet different surface ligand densities.
View Article and Find Full Text PDFCatalysts
October 2018
Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Blvd., Long Beach, CA 90840, USA.
Colloidal Pd nanoparticles capped with octanethiolate ligands have previously shown an excellent selectivity toward the mono-hydrogenation of both isolated and conjugated dienes to internal alkenes. This paper reports an efficient stereoselective mono-hydrogenation of cumulated dienes (allenes) to either Z or E olefinic isomers, depending on the substitution pattern around C=C bonds. Kinetic studies indicate that the reaction progresses through the hydrogenation of less hindered C=C bonds to produce internal Z olefinic isomers.
View Article and Find Full Text PDFNanomaterials (Basel)
May 2018
Department of Chemistry and Biochemistry, California State University Long Beach, 1250 Bellflower Blvd., Long Beach, CA 90840, USA.
Evaluation of metal nanoparticle catalysts functionalized with well-defined thiolate ligands can be potentially important because such systems can provide a spatial control in the reactivity and selectivity of catalysts. A synthetic method utilizing Bunte salts (sodium -alkylthiosulfates) allows the formation of metal nanoparticles (Au, Ag, Pd, Pt, and Ir) capped with alkanethiolate ligands. The catalysis studies on Pd nanoparticles show a strong correlation between the surface ligand structure/composition and the catalytic activity and selectivity for the hydrogenation/isomerization of alkenes, dienes, trienes, and allylic alcohols.
View Article and Find Full Text PDFCatal Sci Technol
October 2017
Department of Chemistry and Biochemistry and Keck Energy Materials Program, California State University, Long Beach, 1250 Bellflower Blvd., Long Beach, California 90840, USA.
Selective hydrogenation of dienes and trienes is an important process in the pharmaceutical and chemical industries. Our group previously reported that the thiosulfate protocol using a sodium -alkylthiosulfate ligand could generate catalytically active Pd nanoparticles (PdNP) capped with a lower density of alkanethio-late ligands. This homogeneously soluble PdNP catalyst offers several advantages such as little contamination Pd leaching and easy separation and recycling.
View Article and Find Full Text PDFLangmuir
January 2018
Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, Pennsylvania 15260, United States.
We report the use of gold nanoparticle surface chemistry as a tool for site-selective noble metal deposition onto colloidal gold nanoparticle substrates. Specifically, we demonstrate that partial passivation of the gold nanoparticle surface using thiolated ligands can induce a transition from linear palladium island deposition to growth of palladium selectively at plasmonic hotspots on the edges or vertices of the underlying particle substrate. Further, we demonstrate the broader applicability of this approach with respect to substrate morphology (e.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!