title: In situ immobilization of palladium nanoparticles in microfluidic reactors and assessment of their catalytic activity.
abstract: We report on the synthesis and characterization of catalytic palladium nanoparticles (Pd NPs) and their immobilization in microfluidic reactors fabricated from polydimethylsiloxane (PDMS). The Pd NPs were stabilized with D-biotin or 3-aminopropyltrimethoxysilane (APTMS) to promote immobilization inside the microfluidic reactors. The NPs were homogeneous with narrow size distributions between 2 and 4 nm, and were characterized by transmission electron microscopy (TEM), selected-area electron diffraction (SAED), and x-ray diffraction (XRD). Biotinylated Pd NPs were immobilized on APTMS-modified PDMS and glass surfaces through the formation of covalent amide bonds between activated biotin and surface amino groups. By contrast, APTMS-stabilized Pd NPs were immobilized directly onto PDMS and glass surfaces rich in hydroxyl groups. Fourier transform infrared spectroscopy (FT-IR) and x-ray photoelectron spectroscopy (XPS) results showed successful attachment of both types of Pd NPs on glass and PDMS surfaces. Both types of Pd NPs were then immobilized in situ in sealed PDMS microfluidic reactors after similar surface modification. The effectiveness of immobilization in the microfluidic reactors was evaluated by hydrogenation of 6-bromo-1-hexene at room temperature and one atmosphere of hydrogen pressure. An average first-run conversion of 85% and selectivity of 100% were achieved in approximately 18 min of reaction time. Control experiments showed that no hydrogenation occurred in the absence of the nanocatalysts. This system has the potential to provide a reliable tool for efficient and high throughput evaluation of catalytic NPs, along with assessment of intrinsic kinetics.
authors.affiliation: Department of Chemical Engineering and Materials Science, Michigan State University, East Lansing, MI 48824, USA.
authors.forename: Rui
authors.initials: R
authors.lastname: Lin
authors.forename: Ruel G
authors.initials: RG
authors.lastname: Freemantle
authors.forename: Nicholas M
authors.initials: NM
authors.lastname: Kelly
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Fielitz
authors.forename: Sherine O
authors.initials: SO
authors.lastname: Obare
authors.forename: Robert Y
authors.initials: RY
authors.lastname: Ofoli