David Farrusseng - Academia.edu (original) (raw)
Papers by David Farrusseng
Applied Catalysis B-environmental, 2017
Inorganic Chemistry Frontiers
The multiscale porosity of hierarchical zeolite materials is analyzed through advanced adsorption... more The multiscale porosity of hierarchical zeolite materials is analyzed through advanced adsorption-based characterization in conjunction with additional techniques including electron tomography.
Il a été financé par la Région Rhône-Alpes au travers du Cluster de Recherche Transport, Territoi... more Il a été financé par la Région Rhône-Alpes au travers du Cluster de Recherche Transport, Territoires et Société que je remercie. Je tiens à remercier M. Michel Lacroix, Directeur de l'IRCELYON, qui m'a accueilli dans son laboratoire et qui a mis à ma disposition les services (scientifiques et administratifs) nécessaires à ce travail. Mme Mintova et M. Méthivier ont droit à toute ma gratitude pour avoir accepté de juger mon travail et de participer au jury de ma thèse. J'adresse mes sincères remerciements à David Farrusseng, Chargé de Recherche à l'IRCELYON, pour ne pas m'avoir signé de chèque en bois. Bien malgré lui, il a assumé la direction de ce travail et a su me conseiller avec tout le recul nécessaire. Ma profonde reconnaissance va à l'encontre de M. Marc Pera-Titus, Chargé de Recherche à l'IRCELYON, pour avoir encadré ce travail. Ces quelques lignes sont bien peu de choses face à tout ce que j'ai appris en côtoyant Marc. Ses conseils aussi bien théoriques que pratiques m'ont permis de mener à bien ce projet. Mais c'est son dynamisme, sa disponibilité, sa culture et son humour (parfois malgré lui) qui ont sûrement le plus contribué au bon déroulement de ces 3 années de doctorat. Je remercie M. Jean-Pierre Roumegoux, Directeur de Recherche au LTE, pour son expertise, ses conseils et sa gentillesse. Au delà de tous les remerciements j'ai une pensée particulière pour M. Sylvain Miachon, Chargé de Recherche à l'IRCELYON, qui nous a malheureusement quitté au commencement de cette aventure. Instigateur de ce projet ambitieux, Sylvain m'a accordé sa confiance dès le début de mon stage de Master et je lui en suis infiniment reconnaissant. Plus encore que son goût pour la recherche, c'est le courage dont il a fait preuve que je tiens à saluer. Ce travail est définitivement marqué de son empreinte.
Studies in Surface Science and Catalysis, 2007
HAL is a multidisciplinary open access archive for the deposit and dissemination of scientific re... more HAL is a multidisciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.
Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the p... more Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1] Amongst the catalytic applications, photochemical CO2 reduction is of tremendous importance as routes to renewable energy sources. Here we present series of heterogeneous photocatalysts based on MOFs and microporous polymers used as macroligands ...
Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the p... more Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks (MOF) and purely organic microporous polymers are promising candidates. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1] Here we present series of heterogeneous catalysts based on MOFs and microporous polymers used as macroligands for heterogenized organometallic comple...
Mixed ionic-electronic oxygen conducting (MIEC) ma-terials are an important class of materials wh... more Mixed ionic-electronic oxygen conducting (MIEC) ma-terials are an important class of materials which found applications in high temperature catalysis and separation such as cathode for SOFCs and oxygen separation mem-branes. Among MIEC ceramic membranes, perovskites and related structures are conductors which exhibit highest oxygen semi-permeability. The mechanism of ionic oxygen diffusion originates from oxygen vacancies which are pre-sent in the structure (d) and relatively low energetic diffu-sion barrier for oxygen mobility. Under a concentration gradient, anionic oxygen can diffuse from the highest (PO2) to lowest compartment (PO2). Although the diffusion is well understood at molecular level, the quantitative prediction of oxygen permeability of a dense MIEC membrane is a remaining scientific challenge. This lack of understanding arises partly from grain boundaries in which the diffusion constants can be hardly determined. More importantly, the vacancy gradient across the me...
Journal of Catalysis, 2021
The direct synthesis of Dimethyl carbonate (DMC) from methanol and CO 2 is a green process which ... more The direct synthesis of Dimethyl carbonate (DMC) from methanol and CO 2 is a green process which allows CO 2 valorization. Among efficient catalysts, ceria, zirconia and cerium-zirconium mixed oxides are often reported as the most active catalysts. In a recent report, we discovered that ceriumzirconium mixed oxides prepared by Flame Spray Pyrolysis (FSP) show greater catalytic activities than those prepared by precipitation, although both exhibit very similar surface area and bulk features. The objective of this study was to find out the origins of the superior catalytic activities obtained by flame spray pyrolysis synthesis method by a deeper analysis of bulk and surface properties. We have opted to focus on mixed ceria-zirconia of equimolar composition (Ce 0.5 Zr 0.5 O 2) as it exhibits maximum catalytic activity for both synthesis methods. Combining bulk and surface characterization as well as surface adsorption measurements using probe molecules, we propose that flame spray pyrolysis enables a surface enrichment in cerium oxide still in interaction with zirconium oxide that leads to a high concentration of adsorbed methanol at the surface, which might explain the greater activity of the catalysts prepared using this method. Beyond the application of DMC synthesis, we can anticipate that Flame Spray Pyrolysis synthesis should generate relative high surface area mixed oxides with different catalytic performances with respect to mixed oxides prepared at lower temperature owing their metastable nature.
Studies in Surface Science and Catalysis, 2004
The oxidative dehydrogenation of ethane to ethylene (ODHE) has been studied in a catalytic membra... more The oxidative dehydrogenation of ethane to ethylene (ODHE) has been studied in a catalytic membrane reactor (CMR) using a dense mixed ionic oxygen and electronic conducting perovskite membrane Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-&. At 1080K, an ethylene yield of 66% was obtained with the bare membrane. After Pd cluster deposition, the ethylene yield reached 76% at 1050K. Ni cluster deposition led to a decrease of ethane conversion compared to the bare membrane without changing ethylene selectivity.
Faraday Discussions, 2021
This paper describes the cost-efficient and scalable synthesis and shaping processes of Al(OH)-fu... more This paper describes the cost-efficient and scalable synthesis and shaping processes of Al(OH)-fumarate beads of various sizes appropriate for use in water Adsorption Heat-Pumps (AHPs).
Catalysts, 2021
A simple kinetic model based on the zeolite acid strength, the number of Brønsted acid sites, and... more A simple kinetic model based on the zeolite acid strength, the number of Brønsted acid sites, and the catalyst efficiency was developed for the cracking of n-hexane. A series of HY zeolites with a mesopore volume from 0.04 to 0.32 cm3/g was synthesized and characterized by various physical-chemical methods and tested for n-hexane cracking. The generation of mesoporosity influenced several other important parameters, such as acidity and extra-framework aluminum. Zero-length column diffusion measurements for mesitylene showed a large decrease in the characteristic diffusion time upon the introduction of mesoporosity, which changed only slightly with a further increase in mesoporosity. Similar n-hexane physisorption enthalpies were measured for all samples. The highest initial activity for n-hexane cracking per catalyst volume was observed for the sample with an intermediate mesopore volume of 0.15 cm3/g. The three mesoporous H-USY zeolites showed the same value of the intrinsic rate c...
Faraday Discussions, 2021
New Journal of Chemistry, 2020
The direct synthesis of dimethyl carbonate from methanol and CO2 is particularly attractive as it... more The direct synthesis of dimethyl carbonate from methanol and CO2 is particularly attractive as it provides a green alternative to other routes while allowing CO2 conversion.
Microporous and Mesoporous Materials, 2018
Air purification of ammonia, a toxic industrial chemicals (TICs), by adsorption process on Metal-... more Air purification of ammonia, a toxic industrial chemicals (TICs), by adsorption process on Metal-Organic Framework solids is attracting high scientific and commercial interests. While active carbon based adsorbents required high level of relative humidity for achieving proper performance ammonia capture, zeolite performance degrades in presence of humidity. For MOFs, the presence of humidity has been shown to be MOF dependent, either beneficial or detrimental. It appears that the role of humidity is of key importance and that different ammonia adsorption mechanisms co-exist depending on the material's physico-chemical features. Based on a screening of various microporous adsorbents including carbons, zeolites and MOFs, we show that in the presence of humidity, the ammonia uptake
ChemCatChem, 2020
The synthesis of 19 carefully selected Pt/γ-Al2O3-Cl formulations was followed by high-throughput... more The synthesis of 19 carefully selected Pt/γ-Al2O3-Cl formulations was followed by high-throughput catalytic testing in order to unravel the effect of an active phase formulation change on n-heptane reforming performances. Pt/γ-Al2O3-Cl catalysts were prepared with different Pt (0.3-1%wt) and Cl (0.1-1.4%wt) contents and using two γ-Al2O3 supports so that both sites concentrations and sites locations at the crystallite surface vary among the catalyst pool. Catalytic tests were conducted in mild conditions for a comparison of catalysts in kinetic regime. Results show that Pt and Cl concentrations control the competition between hydroisomerisation, hydrogenolysis and hydrocracking pathways. Aromatisation, on the contrary, is poorly affected by formulation changes. Nonmonotonous trends linking Pt/Cl ratio to isomerisation selectivity are found for both γ-Al2O3 supports. This study provides new insights for the description of bi-functional transformations in catalytic naphtha reforming.
ChemCatChem, 2018
Here we report the synthesis of two bipyridine-based porous polymers and their use as platform fo... more Here we report the synthesis of two bipyridine-based porous polymers and their use as platform for the heterogenization of Cp*Rh catalytic species. These highly stable heterogeneous catalysts demonstrate their efficiency in the transfer hydrogenation of α-aryl ketones. Moreover, we show that their catalytic activity is similar to that of homogeneous analogues, highlighting the absence of diffusion limitation in the solids. We rationalize the differences in the measured activities using the Hammett parameter as descriptor of the electronic environment of the catalytic site in both homogeneous and heterogeneous systems.
Catalysts, 2019
Silver nanoparticles are currently one of the most studied nanostructured nanomaterials. Because ... more Silver nanoparticles are currently one of the most studied nanostructured nanomaterials. Because nanoparticle size and dispersion act together in determining a material’s physical and chemical properties, there is a continuous quest to develop size-controlled synthesis methods. Nonetheless, the instability of the nanometer-sized particles, which is caused by their tendency to aggregate irreversibly into larger particles, remains a recurrent problem. The use of confining scaffolds, such as the regular system of cages in a crystalline zeolite-type material, is often reported in the literature as an efficient solution to overcome particle migration at the surface. Silver nanoparticles encapsulated in ZSM-5 (Ag@ZSM-5) represent a new generation of adsorbent for Xe enrichment from the atmosphere that is currently being developed at the pilot scale in a Temperature Swing Adsorption (TSA) process. In this study, we have found that the presence of Cl-containing compounds in the air (VOCs) l...
Applied Catalysis B-environmental, 2017
Inorganic Chemistry Frontiers
The multiscale porosity of hierarchical zeolite materials is analyzed through advanced adsorption... more The multiscale porosity of hierarchical zeolite materials is analyzed through advanced adsorption-based characterization in conjunction with additional techniques including electron tomography.
Il a été financé par la Région Rhône-Alpes au travers du Cluster de Recherche Transport, Territoi... more Il a été financé par la Région Rhône-Alpes au travers du Cluster de Recherche Transport, Territoires et Société que je remercie. Je tiens à remercier M. Michel Lacroix, Directeur de l'IRCELYON, qui m'a accueilli dans son laboratoire et qui a mis à ma disposition les services (scientifiques et administratifs) nécessaires à ce travail. Mme Mintova et M. Méthivier ont droit à toute ma gratitude pour avoir accepté de juger mon travail et de participer au jury de ma thèse. J'adresse mes sincères remerciements à David Farrusseng, Chargé de Recherche à l'IRCELYON, pour ne pas m'avoir signé de chèque en bois. Bien malgré lui, il a assumé la direction de ce travail et a su me conseiller avec tout le recul nécessaire. Ma profonde reconnaissance va à l'encontre de M. Marc Pera-Titus, Chargé de Recherche à l'IRCELYON, pour avoir encadré ce travail. Ces quelques lignes sont bien peu de choses face à tout ce que j'ai appris en côtoyant Marc. Ses conseils aussi bien théoriques que pratiques m'ont permis de mener à bien ce projet. Mais c'est son dynamisme, sa disponibilité, sa culture et son humour (parfois malgré lui) qui ont sûrement le plus contribué au bon déroulement de ces 3 années de doctorat. Je remercie M. Jean-Pierre Roumegoux, Directeur de Recherche au LTE, pour son expertise, ses conseils et sa gentillesse. Au delà de tous les remerciements j'ai une pensée particulière pour M. Sylvain Miachon, Chargé de Recherche à l'IRCELYON, qui nous a malheureusement quitté au commencement de cette aventure. Instigateur de ce projet ambitieux, Sylvain m'a accordé sa confiance dès le début de mon stage de Master et je lui en suis infiniment reconnaissant. Plus encore que son goût pour la recherche, c'est le courage dont il a fait preuve que je tiens à saluer. Ce travail est définitivement marqué de son empreinte.
Studies in Surface Science and Catalysis, 2007
HAL is a multidisciplinary open access archive for the deposit and dissemination of scientific re... more HAL is a multidisciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.
Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the p... more Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1] Amongst the catalytic applications, photochemical CO2 reduction is of tremendous importance as routes to renewable energy sources. Here we present series of heterogeneous photocatalysts based on MOFs and microporous polymers used as macroligands ...
Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the p... more Heterogeneous catalysis allows to circumvent the problem of separation of the catalyst from the products and to simplify its recyclability. The integration of the catalytically active centers into a solid support without loss of performance compared to the homogeneous analog is still a major challenge. In this context, a molecularly defined support as macroligand, i.e. a solid acting like the ligand in the corresponding molecular complex, can be considered as a key to bridge the gap between molecular and heterogeneous catalysis. Metal-Organic Frameworks (MOF) and purely organic microporous polymers are promising candidates. In particular, porous frameworks made by the repetition of a coordinating motif, like the bipyridine motif are of a high interest as far as bipyridines are widely used as chelating ligand for molecular catalysts.[1] Here we present series of heterogeneous catalysts based on MOFs and microporous polymers used as macroligands for heterogenized organometallic comple...
Mixed ionic-electronic oxygen conducting (MIEC) ma-terials are an important class of materials wh... more Mixed ionic-electronic oxygen conducting (MIEC) ma-terials are an important class of materials which found applications in high temperature catalysis and separation such as cathode for SOFCs and oxygen separation mem-branes. Among MIEC ceramic membranes, perovskites and related structures are conductors which exhibit highest oxygen semi-permeability. The mechanism of ionic oxygen diffusion originates from oxygen vacancies which are pre-sent in the structure (d) and relatively low energetic diffu-sion barrier for oxygen mobility. Under a concentration gradient, anionic oxygen can diffuse from the highest (PO2) to lowest compartment (PO2). Although the diffusion is well understood at molecular level, the quantitative prediction of oxygen permeability of a dense MIEC membrane is a remaining scientific challenge. This lack of understanding arises partly from grain boundaries in which the diffusion constants can be hardly determined. More importantly, the vacancy gradient across the me...
Journal of Catalysis, 2021
The direct synthesis of Dimethyl carbonate (DMC) from methanol and CO 2 is a green process which ... more The direct synthesis of Dimethyl carbonate (DMC) from methanol and CO 2 is a green process which allows CO 2 valorization. Among efficient catalysts, ceria, zirconia and cerium-zirconium mixed oxides are often reported as the most active catalysts. In a recent report, we discovered that ceriumzirconium mixed oxides prepared by Flame Spray Pyrolysis (FSP) show greater catalytic activities than those prepared by precipitation, although both exhibit very similar surface area and bulk features. The objective of this study was to find out the origins of the superior catalytic activities obtained by flame spray pyrolysis synthesis method by a deeper analysis of bulk and surface properties. We have opted to focus on mixed ceria-zirconia of equimolar composition (Ce 0.5 Zr 0.5 O 2) as it exhibits maximum catalytic activity for both synthesis methods. Combining bulk and surface characterization as well as surface adsorption measurements using probe molecules, we propose that flame spray pyrolysis enables a surface enrichment in cerium oxide still in interaction with zirconium oxide that leads to a high concentration of adsorbed methanol at the surface, which might explain the greater activity of the catalysts prepared using this method. Beyond the application of DMC synthesis, we can anticipate that Flame Spray Pyrolysis synthesis should generate relative high surface area mixed oxides with different catalytic performances with respect to mixed oxides prepared at lower temperature owing their metastable nature.
Studies in Surface Science and Catalysis, 2004
The oxidative dehydrogenation of ethane to ethylene (ODHE) has been studied in a catalytic membra... more The oxidative dehydrogenation of ethane to ethylene (ODHE) has been studied in a catalytic membrane reactor (CMR) using a dense mixed ionic oxygen and electronic conducting perovskite membrane Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-&. At 1080K, an ethylene yield of 66% was obtained with the bare membrane. After Pd cluster deposition, the ethylene yield reached 76% at 1050K. Ni cluster deposition led to a decrease of ethane conversion compared to the bare membrane without changing ethylene selectivity.
Faraday Discussions, 2021
This paper describes the cost-efficient and scalable synthesis and shaping processes of Al(OH)-fu... more This paper describes the cost-efficient and scalable synthesis and shaping processes of Al(OH)-fumarate beads of various sizes appropriate for use in water Adsorption Heat-Pumps (AHPs).
Catalysts, 2021
A simple kinetic model based on the zeolite acid strength, the number of Brønsted acid sites, and... more A simple kinetic model based on the zeolite acid strength, the number of Brønsted acid sites, and the catalyst efficiency was developed for the cracking of n-hexane. A series of HY zeolites with a mesopore volume from 0.04 to 0.32 cm3/g was synthesized and characterized by various physical-chemical methods and tested for n-hexane cracking. The generation of mesoporosity influenced several other important parameters, such as acidity and extra-framework aluminum. Zero-length column diffusion measurements for mesitylene showed a large decrease in the characteristic diffusion time upon the introduction of mesoporosity, which changed only slightly with a further increase in mesoporosity. Similar n-hexane physisorption enthalpies were measured for all samples. The highest initial activity for n-hexane cracking per catalyst volume was observed for the sample with an intermediate mesopore volume of 0.15 cm3/g. The three mesoporous H-USY zeolites showed the same value of the intrinsic rate c...
Faraday Discussions, 2021
New Journal of Chemistry, 2020
The direct synthesis of dimethyl carbonate from methanol and CO2 is particularly attractive as it... more The direct synthesis of dimethyl carbonate from methanol and CO2 is particularly attractive as it provides a green alternative to other routes while allowing CO2 conversion.
Microporous and Mesoporous Materials, 2018
Air purification of ammonia, a toxic industrial chemicals (TICs), by adsorption process on Metal-... more Air purification of ammonia, a toxic industrial chemicals (TICs), by adsorption process on Metal-Organic Framework solids is attracting high scientific and commercial interests. While active carbon based adsorbents required high level of relative humidity for achieving proper performance ammonia capture, zeolite performance degrades in presence of humidity. For MOFs, the presence of humidity has been shown to be MOF dependent, either beneficial or detrimental. It appears that the role of humidity is of key importance and that different ammonia adsorption mechanisms co-exist depending on the material's physico-chemical features. Based on a screening of various microporous adsorbents including carbons, zeolites and MOFs, we show that in the presence of humidity, the ammonia uptake
ChemCatChem, 2020
The synthesis of 19 carefully selected Pt/γ-Al2O3-Cl formulations was followed by high-throughput... more The synthesis of 19 carefully selected Pt/γ-Al2O3-Cl formulations was followed by high-throughput catalytic testing in order to unravel the effect of an active phase formulation change on n-heptane reforming performances. Pt/γ-Al2O3-Cl catalysts were prepared with different Pt (0.3-1%wt) and Cl (0.1-1.4%wt) contents and using two γ-Al2O3 supports so that both sites concentrations and sites locations at the crystallite surface vary among the catalyst pool. Catalytic tests were conducted in mild conditions for a comparison of catalysts in kinetic regime. Results show that Pt and Cl concentrations control the competition between hydroisomerisation, hydrogenolysis and hydrocracking pathways. Aromatisation, on the contrary, is poorly affected by formulation changes. Nonmonotonous trends linking Pt/Cl ratio to isomerisation selectivity are found for both γ-Al2O3 supports. This study provides new insights for the description of bi-functional transformations in catalytic naphtha reforming.
ChemCatChem, 2018
Here we report the synthesis of two bipyridine-based porous polymers and their use as platform fo... more Here we report the synthesis of two bipyridine-based porous polymers and their use as platform for the heterogenization of Cp*Rh catalytic species. These highly stable heterogeneous catalysts demonstrate their efficiency in the transfer hydrogenation of α-aryl ketones. Moreover, we show that their catalytic activity is similar to that of homogeneous analogues, highlighting the absence of diffusion limitation in the solids. We rationalize the differences in the measured activities using the Hammett parameter as descriptor of the electronic environment of the catalytic site in both homogeneous and heterogeneous systems.
Catalysts, 2019
Silver nanoparticles are currently one of the most studied nanostructured nanomaterials. Because ... more Silver nanoparticles are currently one of the most studied nanostructured nanomaterials. Because nanoparticle size and dispersion act together in determining a material’s physical and chemical properties, there is a continuous quest to develop size-controlled synthesis methods. Nonetheless, the instability of the nanometer-sized particles, which is caused by their tendency to aggregate irreversibly into larger particles, remains a recurrent problem. The use of confining scaffolds, such as the regular system of cages in a crystalline zeolite-type material, is often reported in the literature as an efficient solution to overcome particle migration at the surface. Silver nanoparticles encapsulated in ZSM-5 (Ag@ZSM-5) represent a new generation of adsorbent for Xe enrichment from the atmosphere that is currently being developed at the pilot scale in a Temperature Swing Adsorption (TSA) process. In this study, we have found that the presence of Cl-containing compounds in the air (VOCs) l...