Synthesis and characterization of accessible metal surfaces in calixarene-bound gold nanoparticles
Use of organic ligands to partially passivate nanoparticles against sintering yet retain a degree of small molecule accessibility to the metal surface has been a lofty goal in functional materials synthesis, which in principle also enables the design of preferred electronic and steric environments o...
| Veröffentlicht in: | Langmuir : the ACS journal of surfaces and colloids. - 1992. - 25(2009), 18 vom: 15. Sept., Seite 10548-53 |
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| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2009
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| Zugriff auf das übergeordnete Werk: | Langmuir : the ACS journal of surfaces and colloids |
| Schlagworte: | Journal Article |
| Zusammenfassung: | Use of organic ligands to partially passivate nanoparticles against sintering yet retain a degree of small molecule accessibility to the metal surface has been a lofty goal in functional materials synthesis, which in principle also enables the design of preferred electronic and steric environments on a nanoparticle surface. Catalysis using gold in particular requires donor ligands that facilitate an electron-rich metal surface and generalizable strategies for dealing with deactivation due to sintering. Here, synthesis and characterization of gold nanoparticles postsynthetically modified with the chelating ligand cone-5,11,17,23,29,35-hexa(tert-butyl)-37,39,41-tris(diphenylphosphinomethoxy)-38,40,42-trimethoxycalix[6]arene (1) is reported. In solution as well as when supported on the surface of TiO2, nanoparticles modified with tripodal calix[6]arene phosphine ligand 1 demonstrate enhanced protection against sintering relative to unmodified, tetraoctylammonium bromide-surfactant-stabilized gold nanoparticles. In between adsorbed calixarene ligands, there is accessible gold surface area in these nanoparticles, and this is measured quantitatively for the first time for a calixarene-modified nanoparticle, using a newly developed fluorescence methodology involving 2-naphthalenethiol as a relevant chemisorption probe molecule. Ligand steric bulk critically influences amount of accessible surface on the metal nanoparticle since the use of a smaller calix[4]arene ligand (MBC) results in a 7-fold lower accessible surface area relative to using 1 under otherwise similar conditions. In addition, surface coverage of 1 controls accessible surface area in an unintuitive fashion: a 4-fold increase in accessible metal surface area is observed upon increasing the surface coverage of 1 to be 1.5-fold higher than the minimum required for surface saturation. This is presumably the result of a more open ligand packing of 1 at higher surface coverages, which allows greater accessibility to 2-napthalenethiol |
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| Beschreibung: | Date Completed 04.12.2009 Date Revised 08.09.2009 published: Print Citation Status PubMed-not-MEDLINE |
| ISSN: | 1520-5827 |
| DOI: | 10.1021/la9013174 |