title: Precise localization of metal nanoparticles in dendrimer nanosnakes or inner periphery and consequences in catalysis.
abstract: Understanding the relationship between the location of nanoparticles (NPs) in an organic matrix and their catalytic performances is essential for catalyst design. Here we show that catalytic activities of Au, Ag and CuNPs stabilized by dendrimers using coordination to intradendritic triazoles, galvanic replacement or stabilization outside dendrimers strongly depends on their location. AgNPs are found at the inner click dendrimer periphery, whereas CuNPs and AuNPs are encapsulated in click dendrimer nanosnakes. AuNPs and AgNPs formed by galvanic replacement are larger than precursors and only partly encapsulated. AuNPs are all the better 4-nitrophenol reduction catalysts as they are less sterically inhibited by the dendrimer interior, whereas on the contrary CuNPs are all the better alkyne azide cycloaddition catalysts as they are better protected from aerobic oxidation inside dendrimers. This work highlights the role of the location in macromolecules on the catalytic efficiency of metal nanoparticles and rationalizes optimization in catalyst engineering.
authors.affiliation: ISM, UMR CNRS N°5255, Univ. Bordeaux, 33405 Talence, France.|UMR 6226, Institut des Sciences Chimiques de Rennes, CNRS-Université de Rennes 1, Campus de Beaulieu, 35042 Rennes, France.
authors.forename: Xiang
authors.initials: X
authors.lastname: Liu
authors.affiliation: CIC biomaGUNE, Unidad Biosuperficies, Paseo Miramon No. 182, Edif 'C', 20009 Donostia-San Sebastian, Spain.
authors.forename: Danijela
authors.identifier: 0000-0002-3316-8008
authors.initials: D
authors.lastname: Gregurec
authors.affiliation: CIC biomaGUNE, Unidad Biosuperficies, Paseo Miramon No. 182, Edif 'C', 20009 Donostia-San Sebastian, Spain.
authors.forename: Joseba
authors.initials: J
authors.lastname: Irigoyen
authors.affiliation: CIC biomaGUNE, Unidad Biosuperficies, Paseo Miramon No. 182, Edif 'C', 20009 Donostia-San Sebastian, Spain.
authors.forename: Angel
authors.initials: A
authors.lastname: Martinez
authors.affiliation: CIC biomaGUNE, Unidad Biosuperficies, Paseo Miramon No. 182, Edif 'C', 20009 Donostia-San Sebastian, Spain.
authors.forename: Sergio
authors.initials: S
authors.lastname: Moya
authors.affiliation: ISM, UMR CNRS N°5255, Univ. Bordeaux, 33405 Talence, France.|Chemistry Department of San Sebastian, Basque Country University, Apdo. 1072, 20080 San Sebastian, Spain.
authors.forename: Roberto
authors.initials: R
authors.lastname: Ciganda
authors.affiliation: ISM, UMR CNRS N°5255, Univ. Bordeaux, 33405 Talence, France.
authors.forename: Philippe
authors.initials: P
authors.lastname: Hermange
authors.affiliation: ISM, UMR CNRS N°5255, Univ. Bordeaux, 33405 Talence, France.
authors.forename: Jaime
authors.initials: J
authors.lastname: Ruiz
authors.affiliation: ISM, UMR CNRS N°5255, Univ. Bordeaux, 33405 Talence, France.
authors.forename: Didier
authors.initials: D
authors.lastname: Astruc