Preparation of Ru-Based Systems Through Metal Carbonyl Cluster Decomposition for the Base-Free 5-Hydroxymethylfurfural (HMF) Oxidation

Metal carbonyl clusters, which can be seen as monodispersed and atomically defined nanoparticles stabilized by CO ligands, were used to prepare Ru-based catalysts with tuned basic properties to conduct the 5-hydroxymethylfurfural (HMF) aerobic oxidation to produce 2,5-furandicarboxylic acid (FDCA) i...

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Main Authors: Francesca Liuzzi, Francesco Di Renzo, Cristiana Cesari, Alice Mammi, Lorenzo Monti, Alessandro Allegri, Stefano Zacchini, Giuseppe Fornasari, Nikolaos Dimitratos, Stefania Albonetti
Format: Article
Language:English
Published: MDPI AG 2025-05-01
Series:Molecules
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Online Access:https://www.mdpi.com/1420-3049/30/10/2120
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author Francesca Liuzzi
Francesco Di Renzo
Cristiana Cesari
Alice Mammi
Lorenzo Monti
Alessandro Allegri
Stefano Zacchini
Giuseppe Fornasari
Nikolaos Dimitratos
Stefania Albonetti
author_facet Francesca Liuzzi
Francesco Di Renzo
Cristiana Cesari
Alice Mammi
Lorenzo Monti
Alessandro Allegri
Stefano Zacchini
Giuseppe Fornasari
Nikolaos Dimitratos
Stefania Albonetti
author_sort Francesca Liuzzi
collection DOAJ
description Metal carbonyl clusters, which can be seen as monodispersed and atomically defined nanoparticles stabilized by CO ligands, were used to prepare Ru-based catalysts with tuned basic properties to conduct the 5-hydroxymethylfurfural (HMF) aerobic oxidation to produce 2,5-furandicarboxylic acid (FDCA) in base-free conditions. The controlled decomposition of the carbonyl cluster [HRu<sub>3</sub>(CO)<sub>11</sub>]<sup>−</sup>, a methodology not yet applied to Ru catalysts for this reaction, on different supports focusing on controlling and tuning the basic properties of support allowed the formation of small Ru nanoparticles with a mean diameter of around 1 nm. The catalytic systems obtained resulted in more activity in the HMF oxidation than those prepared through a more common salt-impregnation technique, and the deposition of Ru nanoparticles on materials with basic functionalities has allowed avoiding the use of basic solutions in the reaction. The characterization by CO<sub>2</sub>-TPD of Mg(Al)O catalysts obtained from decomposition of layered double hydroxide hydrotalcites with different composition and activation has allowed disclosure of an important correlation between the selectivity of FDCA and the fraction of weak basic sites, which is decreased by the calcination treatment at increased temperature.
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spelling doaj-art-e2d1da2b56d14254aa3f51f3dc84977a2025-08-20T02:33:58ZengMDPI AGMolecules1420-30492025-05-013010212010.3390/molecules30102120Preparation of Ru-Based Systems Through Metal Carbonyl Cluster Decomposition for the Base-Free 5-Hydroxymethylfurfural (HMF) OxidationFrancesca Liuzzi0Francesco Di Renzo1Cristiana Cesari2Alice Mammi3Lorenzo Monti4Alessandro Allegri5Stefano Zacchini6Giuseppe Fornasari7Nikolaos Dimitratos8Stefania Albonetti9Department of Industrial Chemistry, C3-Centre for Chemical Catalysis, Alma Mater Studiorum—University of Bologna, 40129 Bologna, ItalyICGM, Université de Montpellier-CNRS-ENSCM, 34293 Montpellier, FranceDepartment of Industrial Chemistry, C3-Centre for Chemical Catalysis, Alma Mater Studiorum—University of Bologna, 40129 Bologna, ItalyDepartment of Industrial Chemistry, C3-Centre for Chemical Catalysis, Alma Mater Studiorum—University of Bologna, 40129 Bologna, ItalyDepartment of Industrial Chemistry, C3-Centre for Chemical Catalysis, Alma Mater Studiorum—University of Bologna, 40129 Bologna, ItalyDepartment of Industrial Chemistry, C3-Centre for Chemical Catalysis, Alma Mater Studiorum—University of Bologna, 40129 Bologna, ItalyDepartment of Industrial Chemistry, C3-Centre for Chemical Catalysis, Alma Mater Studiorum—University of Bologna, 40129 Bologna, ItalyDepartment of Industrial Chemistry, C3-Centre for Chemical Catalysis, Alma Mater Studiorum—University of Bologna, 40129 Bologna, ItalyDepartment of Industrial Chemistry, C3-Centre for Chemical Catalysis, Alma Mater Studiorum—University of Bologna, 40129 Bologna, ItalyDepartment of Industrial Chemistry, C3-Centre for Chemical Catalysis, Alma Mater Studiorum—University of Bologna, 40129 Bologna, ItalyMetal carbonyl clusters, which can be seen as monodispersed and atomically defined nanoparticles stabilized by CO ligands, were used to prepare Ru-based catalysts with tuned basic properties to conduct the 5-hydroxymethylfurfural (HMF) aerobic oxidation to produce 2,5-furandicarboxylic acid (FDCA) in base-free conditions. The controlled decomposition of the carbonyl cluster [HRu<sub>3</sub>(CO)<sub>11</sub>]<sup>−</sup>, a methodology not yet applied to Ru catalysts for this reaction, on different supports focusing on controlling and tuning the basic properties of support allowed the formation of small Ru nanoparticles with a mean diameter of around 1 nm. The catalytic systems obtained resulted in more activity in the HMF oxidation than those prepared through a more common salt-impregnation technique, and the deposition of Ru nanoparticles on materials with basic functionalities has allowed avoiding the use of basic solutions in the reaction. The characterization by CO<sub>2</sub>-TPD of Mg(Al)O catalysts obtained from decomposition of layered double hydroxide hydrotalcites with different composition and activation has allowed disclosure of an important correlation between the selectivity of FDCA and the fraction of weak basic sites, which is decreased by the calcination treatment at increased temperature.https://www.mdpi.com/1420-3049/30/10/2120biomass valorizationmetal carbonyl clustersheterogeneous catalysisnanoparticles-based catalysts
spellingShingle Francesca Liuzzi
Francesco Di Renzo
Cristiana Cesari
Alice Mammi
Lorenzo Monti
Alessandro Allegri
Stefano Zacchini
Giuseppe Fornasari
Nikolaos Dimitratos
Stefania Albonetti
Preparation of Ru-Based Systems Through Metal Carbonyl Cluster Decomposition for the Base-Free 5-Hydroxymethylfurfural (HMF) Oxidation
Molecules
biomass valorization
metal carbonyl clusters
heterogeneous catalysis
nanoparticles-based catalysts
title Preparation of Ru-Based Systems Through Metal Carbonyl Cluster Decomposition for the Base-Free 5-Hydroxymethylfurfural (HMF) Oxidation
title_full Preparation of Ru-Based Systems Through Metal Carbonyl Cluster Decomposition for the Base-Free 5-Hydroxymethylfurfural (HMF) Oxidation
title_fullStr Preparation of Ru-Based Systems Through Metal Carbonyl Cluster Decomposition for the Base-Free 5-Hydroxymethylfurfural (HMF) Oxidation
title_full_unstemmed Preparation of Ru-Based Systems Through Metal Carbonyl Cluster Decomposition for the Base-Free 5-Hydroxymethylfurfural (HMF) Oxidation
title_short Preparation of Ru-Based Systems Through Metal Carbonyl Cluster Decomposition for the Base-Free 5-Hydroxymethylfurfural (HMF) Oxidation
title_sort preparation of ru based systems through metal carbonyl cluster decomposition for the base free 5 hydroxymethylfurfural hmf oxidation
topic biomass valorization
metal carbonyl clusters
heterogeneous catalysis
nanoparticles-based catalysts
url https://www.mdpi.com/1420-3049/30/10/2120
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