Controlled synthesis of Ru nanoparticle covalent assemblies and their catalytic application / Yuanyuan Min  

Public ISBD Titre : Controlled synthesis of Ru nanoparticle covalent assemblies and their catalytic application Type de document : texte imprimé Auteurs : Yuanyuan Min, Auteur ; Philippe Serp, Directeur de thèse ; Maria Rosa Axet Marti, Directeur de thèse Langues : Anglais (eng) Tags : RUTHENIUM  NANOPARTICLE  CARBOXYLIC ACIDS  AMINES  POLYMANTANE  TRIPHENYLENE  HYDROGENATION  PHENYLACETYLENE Résumé : "This research work focuses on the preparation of Ru nanoparticle (NP) covalent assemblies stabilized by different functional molecules, and the study of structure/activity relationships for catalytic hydrogenation reactions. Chapter 1 reviews the metal NP covalent assemblies according to the synthesis strategies and their application in catalysis. Chapter 2 described the preparation of three-dimension (3D) Ru NP covalent assemblies characterized by: i) well-defined nanometricsized Ru NP stabilized by functionalized adamantane, bis-adamantane and diamantane ligands, and ii) a tunable interparticle distance. The coordination chemistry with amine and carboxylic acid ligands towards the Ru NP surface was investigated. In the case of carboxylic acid ligands it was shown that Ru species formed during the NP assembly are able to partially decarbonylate carboxylic acid ligands at room temperature. The mechanism of this reaction was elucidated by DFT. Chapter 3 detailed the use of other molecular building blocks for Ru NP assembly formation. We showed that the use of tricarboxylic-hexyloxy triphenylene ligand leads to the formation of twodimensional (2D) Ru NP assemblies with homogeneous interparticle distance and NP size. Additionally, 3D Ru NP assemblies were prepared with 9, 10-dicarboxylic anthracene and a hexaadduct functionalized C60 fullerene. In Chapter 4 we studied the catalytic performances of the Ru NP networks in various reactions. All these materials constitute an interesting set to investigate the structural and electronic effects in heterogeneous catalysis. In the selective hydrogenation of phenyl acetylene, the assemblies are active, reaching good selectivity towards styrene. Especially, we demonstrated that confinement and electronic effects are occurring and that Ru NP interparticle distance affects the catalyst activity, whereas electronic effects mainly govern the catalyst selectivity. The stability of the Ru NP assembly is finally discussed." Document : Thèse de Doctorat Etablissement_delivrance : Institut National Polytechnique de Toulouse - INPT Date_soutenance : 14/02/2020 Ecole_doctorale : Sciences de la Matière (SdM) (Toulouse) Domaine : Chimie Organométallique et de Coordination En ligne : https://theses.hal.science/tel-04163415 Controlled synthesis of Ru nanoparticle covalent assemblies and their catalytic application [texte imprimé] / Yuanyuan Min, Auteur ; Philippe Serp, Directeur de thèse ; Maria Rosa Axet Marti, Directeur de thèse . - [s.d.]. Langues : Anglais (eng) Tags : RUTHENIUM  NANOPARTICLE  CARBOXYLIC ACIDS  AMINES  POLYMANTANE  TRIPHENYLENE  HYDROGENATION  PHENYLACETYLENE Résumé : "This research work focuses on the preparation of Ru nanoparticle (NP) covalent assemblies stabilized by different functional molecules, and the study of structure/activity relationships for catalytic hydrogenation reactions. Chapter 1 reviews the metal NP covalent assemblies according to the synthesis strategies and their application in catalysis. Chapter 2 described the preparation of three-dimension (3D) Ru NP covalent assemblies characterized by: i) well-defined nanometricsized Ru NP stabilized by functionalized adamantane, bis-adamantane and diamantane ligands, and ii) a tunable interparticle distance. The coordination chemistry with amine and carboxylic acid ligands towards the Ru NP surface was investigated. In the case of carboxylic acid ligands it was shown that Ru species formed during the NP assembly are able to partially decarbonylate carboxylic acid ligands at room temperature. The mechanism of this reaction was elucidated by DFT. Chapter 3 detailed the use of other molecular building blocks for Ru NP assembly formation. We showed that the use of tricarboxylic-hexyloxy triphenylene ligand leads to the formation of twodimensional (2D) Ru NP assemblies with homogeneous interparticle distance and NP size. Additionally, 3D Ru NP assemblies were prepared with 9, 10-dicarboxylic anthracene and a hexaadduct functionalized C60 fullerene. In Chapter 4 we studied the catalytic performances of the Ru NP networks in various reactions. All these materials constitute an interesting set to investigate the structural and electronic effects in heterogeneous catalysis. In the selective hydrogenation of phenyl acetylene, the assemblies are active, reaching good selectivity towards styrene. Especially, we demonstrated that confinement and electronic effects are occurring and that Ru NP interparticle distance affects the catalyst activity, whereas electronic effects mainly govern the catalyst selectivity. The stability of the Ru NP assembly is finally discussed." Document : Thèse de Doctorat Etablissement_delivrance : Institut National Polytechnique de Toulouse - INPT Date_soutenance : 14/02/2020 Ecole_doctorale : Sciences de la Matière (SdM) (Toulouse) Domaine : Chimie Organométallique et de Coordination En ligne : https://theses.hal.science/tel-04163415

Rational design of bimetallic nanoparticles based catalysts : application for apgrading biomass / Miquel Cardona Farreny  

Public ISBD Titre : Rational design of bimetallic nanoparticles based catalysts : application for apgrading biomass Titre original : Conception rationnelle de catalyseurs à base de nanoparticules bimétalliques : application à la valorisation de la biomasse Type de document : texte imprimé Auteurs : Miquel Cardona Farreny, Auteur ; Maria Rosa Axet Marti, Directeur de thèse ; Karine Philippot, Directeur de thèse Année de publication : 2023 Langues : Anglais (eng) Tags : CATALYSIS  BIMETALLIC NANOPARTICLES  BIOMASS  FURFURAL Résumé : " An accumulation of social, economic, and energetic crises occurring for decades drives the society to a critical situation. The dependency on fossil fuels for energy and chemicals production is noticeable and needs to be rapidly reduced by replacing those sources with renewable ones. Lignocellulosic biomass appears as a good alternative to the production of sustainable chemicals and fuels. This renewable feedstock is composed of cellulose, hemicelluloses and lignin, and can be vastly found in waste streams, wood, energy crops and agricultural residues. Liquid fuels may be produced from second generation feedstocks of biomass, which are chemically identical to the ones from petroleum, and which can be used in the same combustion engines as those present nowadays. The replacement of fossil by biomass feedstocks for the production of chemicals is of great interest for environmental purposes. This promising feedstock can produce several platform molecules, such as furfural and 5-hydroxymethylfurfural, from which a vast range of value-added compounds can be obtained. For a better performance of these transformations, selective and effective bimetallic nanocatalysts have been developed in this work, containing earth-abundant metals, thinking about their potential incorporation in industrial processes for energy transition. For this purpose, a series of Ru bimetallic materials containing either Ni or Cu as second metal were synthesised. Several stabilisers for the nanoparticles were used such as polyvinylpyrrolidone, diphenyl-2-pyridylphosphine and hexadecylamine. The synthesis of ultra-small (<2nm) RuCu and RuNi bimetallic nanomaterials, as well as their monometallic counterparts, was successful, by controlling the metal ratio between metals. RuNi/PVP nanoparticles showed synergetic effects between metals in both efficient and selective catalytic hydrogenations of furfural and 5-hydroxymethylfurfural. DFT calculations were performed to help us understand the experimental results, by modelling Ru, Ni and RuNi nanoparticles and adsorbing the different species on their surface. The results from theoretical calculations are in the line of the activity and selectivity observed in experimental catalytic experiments. RuCu/PVP nanoparticles, used as catalysts in the same hydrogenation reaction, were less performant than the corresponding monometallic counterparts, as well as the RuNi/PVP nanoparticles. RuNi/PVP and RuNi/PPh2Py nanoparticles were used as catalysts on the selective hydrogenation of quinoline, observing a dependence of the activity on the temperature and the Ru content. By using 1-propanol as solvent, N-alkylation of the substrat occurred, noticeably from 125ºC. Deuterium-labelled molecules, being a stable and safe hydrogen isotope, have received great interest in different scientific domains, especially in pharmaceutical industry for the design of new drugs. Ru/PVP nanoparticles were tested for deuteration reactions of 4-methoxyaniline, 4-trifluoromethylbenzaldehyde, methyl-2,3-O-Isopropylidene-beta-D-ribofuranoside and adenosine. Deuterations were not successful in the two first substrates nor in the third, where, nevertheless, deprotection and epimerisation reactions were observed. In the case of adenosine, the deuteration took place in a selective manner. This work offers the synthesis of new bimetallic nanomaterials with tunable properties. Some of the developed catalysts were tested in the hydrogenation of platform molecules, such as furfural and 5-hydroxymethylfurfural, and the monometallic Ru/PVP nanoparticles were used as catalysts in deuteration reactions." Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse 3 Date_soutenance : 25/01/2023 Ecole_doctorale : Science de la matière (SdM) (Toulouse) Domaine : Chimie organométallique et de coordination Localisation : LCC En ligne : https://theses.hal.science/tel-04552662v1 Rational design of bimetallic nanoparticles based catalysts : application for apgrading biomass = Conception rationnelle de catalyseurs à base de nanoparticules bimétalliques : application à la valorisation de la biomasse [texte imprimé] / Miquel Cardona Farreny, Auteur ; Maria Rosa Axet Marti, Directeur de thèse ; Karine Philippot, Directeur de thèse . - 2023. Langues : Anglais (eng) Tags : CATALYSIS  BIMETALLIC NANOPARTICLES  BIOMASS  FURFURAL Résumé : " An accumulation of social, economic, and energetic crises occurring for decades drives the society to a critical situation. The dependency on fossil fuels for energy and chemicals production is noticeable and needs to be rapidly reduced by replacing those sources with renewable ones. Lignocellulosic biomass appears as a good alternative to the production of sustainable chemicals and fuels. This renewable feedstock is composed of cellulose, hemicelluloses and lignin, and can be vastly found in waste streams, wood, energy crops and agricultural residues. Liquid fuels may be produced from second generation feedstocks of biomass, which are chemically identical to the ones from petroleum, and which can be used in the same combustion engines as those present nowadays. The replacement of fossil by biomass feedstocks for the production of chemicals is of great interest for environmental purposes. This promising feedstock can produce several platform molecules, such as furfural and 5-hydroxymethylfurfural, from which a vast range of value-added compounds can be obtained. For a better performance of these transformations, selective and effective bimetallic nanocatalysts have been developed in this work, containing earth-abundant metals, thinking about their potential incorporation in industrial processes for energy transition. For this purpose, a series of Ru bimetallic materials containing either Ni or Cu as second metal were synthesised. Several stabilisers for the nanoparticles were used such as polyvinylpyrrolidone, diphenyl-2-pyridylphosphine and hexadecylamine. The synthesis of ultra-small (<2nm) RuCu and RuNi bimetallic nanomaterials, as well as their monometallic counterparts, was successful, by controlling the metal ratio between metals. RuNi/PVP nanoparticles showed synergetic effects between metals in both efficient and selective catalytic hydrogenations of furfural and 5-hydroxymethylfurfural. DFT calculations were performed to help us understand the experimental results, by modelling Ru, Ni and RuNi nanoparticles and adsorbing the different species on their surface. The results from theoretical calculations are in the line of the activity and selectivity observed in experimental catalytic experiments. RuCu/PVP nanoparticles, used as catalysts in the same hydrogenation reaction, were less performant than the corresponding monometallic counterparts, as well as the RuNi/PVP nanoparticles. RuNi/PVP and RuNi/PPh2Py nanoparticles were used as catalysts on the selective hydrogenation of quinoline, observing a dependence of the activity on the temperature and the Ru content. By using 1-propanol as solvent, N-alkylation of the substrat occurred, noticeably from 125ºC. Deuterium-labelled molecules, being a stable and safe hydrogen isotope, have received great interest in different scientific domains, especially in pharmaceutical industry for the design of new drugs. Ru/PVP nanoparticles were tested for deuteration reactions of 4-methoxyaniline, 4-trifluoromethylbenzaldehyde, methyl-2,3-O-Isopropylidene-beta-D-ribofuranoside and adenosine. Deuterations were not successful in the two first substrates nor in the third, where, nevertheless, deprotection and epimerisation reactions were observed. In the case of adenosine, the deuteration took place in a selective manner. This work offers the synthesis of new bimetallic nanomaterials with tunable properties. Some of the developed catalysts were tested in the hydrogenation of platform molecules, such as furfural and 5-hydroxymethylfurfural, and the monometallic Ru/PVP nanoparticles were used as catalysts in deuteration reactions." Document : Thèse de Doctorat Etablissement_delivrance : Université de Toulouse 3 Date_soutenance : 25/01/2023 Ecole_doctorale : Science de la matière (SdM) (Toulouse) Domaine : Chimie organométallique et de coordination Localisation : LCC En ligne : https://theses.hal.science/tel-04552662v1

Controlled synthesis and characterization of ru-fullerene nanostructures and their catalytic applications / Faqiang Leng  

Public ISBD Titre : Controlled synthesis and characterization of ru-fullerene nanostructures and their catalytic applications Type de document : texte imprimé Auteurs : Faqiang Leng, Auteur ; Philippe Serp, Directeur de thèse ; Maria Rosa Axet Marti, Directeur de thèse Année de publication : 2016 Langues : Anglais (eng) Tags : RUTHENIUM  NANOPARTICLES  C60  C66(COOH)12  CATALYSIS, HYDROGENATION  NITROBENZENE  CINNAMALDEHYDE Résumé : "The work described in this thesis aims to produce well-ordered nanostructures presenting high catalytic activity, on the bases of the assembly of ruthenium nanoparticles and fullerene/functionalized fullerene. Chapter 1 provides a review on the use of fullerene and fullerene-based materials in heterogeneous catalysis, emphasizing their specific properties such as thermal stability, high capacity for hydrogen adsorption and the ability of various coordination modes. Chapter 2 describes the synthesis and characterization of Ru@C60 nanostructures produced by the decomposition reaction of [Ru(COD)(COT)] in the presence of C60. The effect of the solvent and ratios of Ru/C60 on the course of the reaction have been investigated. Several characterizations of spherical Ru@C60 objects and DFT calculations allow us to propose a pathway for their formation. Chapter 3 presents new nano-assembly preparation based on [Ru(COD)(COT)] and functionalized fullerene using the same method as they are described in chapter 2. First, the synthesis of functionalized fullerene C66(COOH)12 is detailed, and then the synthesis and characterization of Ru@C66(COOH)12 is studied. Chapter 4 describes the use of these nanomaterials in catalysis. We have prepared three Ru@fullerene catalysts, which are Ru@C60 in dichloromethane, T-Ru@C60 in toluene, and Ru@C66(COOH)12. Then, the catalytic activity and selectivity of the prepared catalyst Ru@C60, T-Ru@C60 and Ru@C66(COOH)12 are studied for the hydrogenation of nitrobenzene and cinnamaldehyde. DFT calculations allow to rationalize the results obtained for the selective hydrogenation of nitrobenzene over Ru@C60." Document : Thèse de doctorat Etablissement_delivrance : Institut National Polytechnique de Toulouse - INPT Date_soutenance : 06/10/2016 Ecole_doctorale : École doctorale Sciences de la Matière (Toulouse) Domaine : Chimie organométallique de coordination En ligne : https://oatao.univ-toulouse.fr/16619/ Controlled synthesis and characterization of ru-fullerene nanostructures and their catalytic applications [texte imprimé] / Faqiang Leng, Auteur ; Philippe Serp, Directeur de thèse ; Maria Rosa Axet Marti, Directeur de thèse . - 2016. Langues : Anglais (eng) Tags : RUTHENIUM  NANOPARTICLES  C60  C66(COOH)12  CATALYSIS, HYDROGENATION  NITROBENZENE  CINNAMALDEHYDE Résumé : "The work described in this thesis aims to produce well-ordered nanostructures presenting high catalytic activity, on the bases of the assembly of ruthenium nanoparticles and fullerene/functionalized fullerene. Chapter 1 provides a review on the use of fullerene and fullerene-based materials in heterogeneous catalysis, emphasizing their specific properties such as thermal stability, high capacity for hydrogen adsorption and the ability of various coordination modes. Chapter 2 describes the synthesis and characterization of Ru@C60 nanostructures produced by the decomposition reaction of [Ru(COD)(COT)] in the presence of C60. The effect of the solvent and ratios of Ru/C60 on the course of the reaction have been investigated. Several characterizations of spherical Ru@C60 objects and DFT calculations allow us to propose a pathway for their formation. Chapter 3 presents new nano-assembly preparation based on [Ru(COD)(COT)] and functionalized fullerene using the same method as they are described in chapter 2. First, the synthesis of functionalized fullerene C66(COOH)12 is detailed, and then the synthesis and characterization of Ru@C66(COOH)12 is studied. Chapter 4 describes the use of these nanomaterials in catalysis. We have prepared three Ru@fullerene catalysts, which are Ru@C60 in dichloromethane, T-Ru@C60 in toluene, and Ru@C66(COOH)12. Then, the catalytic activity and selectivity of the prepared catalyst Ru@C60, T-Ru@C60 and Ru@C66(COOH)12 are studied for the hydrogenation of nitrobenzene and cinnamaldehyde. DFT calculations allow to rationalize the results obtained for the selective hydrogenation of nitrobenzene over Ru@C60." Document : Thèse de doctorat Etablissement_delivrance : Institut National Polytechnique de Toulouse - INPT Date_soutenance : 06/10/2016 Ecole_doctorale : École doctorale Sciences de la Matière (Toulouse) Domaine : Chimie organométallique de coordination En ligne : https://oatao.univ-toulouse.fr/16619/

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