Elaboration de bioélectrodes à base de nanotubes de carbone pour la réalisation de biopiles enzymatiques Glucose/02

This work focuses on the optimization of the electrical wiring of glucose oxidizing and dioxygen reducing enzymes on carbon nanotube (CNT) matrixes for glucose biofuel cells.In the first part, glucose oxidase (GOx) mediated electron transfer (MET) is optimized in nanostructured CNTs matrixes by mechanical compression of a CNTs/GOx composite containing 1,4-naphtoquinone as redox mediator. This bioanode was then combined with MCOs (laccase and tyrosinase) based biocathodes. The GOx-NQ/Lac biofuel cell was able to deliver a maximum power density of 1.5 mW.cm-2. The use of this biofuel cell in short/long time discharge and in storage has also been studied. The second part presents the preparation of another bioanode based on the indirect wiring of a NAD+-dependant glucose dehydrogenase (GDH-NAD+) as an alternative for glucose oxidation. The GDH-NAD+ has been combined with an NADH oxidation catalyst by two different techniques. The first one involves the encapsulation of the protein in the metallopolymer redox film, whereas the second one relies on the supramolecular modification of the CNTs by the molecular catalyst and the enzyme. Both bioanodes showed good catalytic properties toward glucose oxidation in presence of NAD+ with respectively 1.04 mA cm-2 and 6 mA cm-2. The latter has been combined with a BOD based biocathode to form a biofuel cell exhibiting maximum power densities of 140 µW cm-2. The last part of this work focuses on the design of a bienzymatic biocathode for O2 reduction. The DET of horseradish peroxidase (HRP) was first investigated and optimized by modification of the CNTs with pyrenes derivatives. The combination of the HRP with the GOx on the same electrode enables an efficient reduction of O2 in a 2-step process. The biocathode could exhibit maximum currents densities of 200 µA cm-2. This cathode along with the previous GDH bioanode formed a biofuel cell functional in physiological conditions and 10 mM NAD+ showing maximum power densities of 57 µW cm-2.Ce mémoire est consacré à l'optimisation de la connexion enzymatique d'enzymes pour l'oxydation du glucose et la réduction de O2 sur matrices de nanotube de carbone (CNT) dans les biopiles à glucose.Premièrement, le transfert électronique indirect de la glucose oxydase (GOx) est optimisé dans une matrice nanostructurée de CNT contenant la 1,4-naphtoquinone comme médiateur rédox. Cette bioanode a ensuite été combinée avec des biocathodes similaires à bases d'enzymes à cuivre (laccase et tyrosinase). La biopile GOx-NQ/Lac a permis d'obtenir des puissances maximales de l'ordre de 1,5 mW.cm-2. Les utilisations de cette pile en décharge courte, longue et sa stabilité dans le temps ont également été étudiées. La seconde partie présente la préparation d'une autre anode basée sur la connexion indirecte d'une glucose déshydrogènase NAD+-dépendante (GDH-NAD+) comme alternative pour l'oxydation du glucose. La GDH-NAD+ a été combinée avec un catalyseur d'oxydation de NADH par différentes méthodes. Tout d'abord, elle a été encapsulée au sein du métallopolymère rédox, puis, la modification supramoléculaire a dans un second temps permis d'immobiliser le catalyseur moléculaire et l'enzyme à la surface des CNTs. Ces deux bioanodes ont permis respectivement l'obtention de courants catalytiques d'oxydation du glucose de 1,04 et 6 mA.cm-2. La seconde bioanode a été combinée avec une biocathode à base de BOD et a permis l'obtention de densités de courants maximales de l'ordre de 140 µW.cm-2 La dernière partie concerne l'élaboration d'une biocathode bienzymatique pour la réduction de O2. Le DET de la HRP sur CNTs a dans un premier temps été optimisé par modification de la surface par différents dérivés pyrène. Ensuite, la combinaison de la GOx et de la HRP sur la même électrode a permis de réduire efficacement O2 en 2 étapes. La biocathode est capable de délivrer une densité de courant maximale de l'ordre de 200 µA.cm-2. Cette dernière, combinée avec la bioanode GDH présentée précédemment a permis d'obtenir une biopile opérationnelle en conditions physiologiques et 10 mM de NAD+, en étant capable de débiter une densité de puissance maximale de l'ordre de 57 µW.cm-2

Electro- and Solar-Driven Fuel Synthesis with First Row Transition Metal Complexes.

The synthesis of renewable fuels from abundant water or the greenhouse gas CO2 is a major step toward creating sustainable and scalable energy storage technologies. In the last few decades, much attention has focused on the development of nonprecious metal-based catalysts and, in more recent years, their integration in solid-state support materials and devices that operate in water. This review surveys the literature on 3d metal-based molecular catalysts and focuses on their immobilization on heterogeneous solid-state supports for electro-, photo-, and photoelectrocatalytic synthesis of fuels in aqueous media. The first sections highlight benchmark homogeneous systems using proton and CO2 reducing 3d transition metal catalysts as well as commonly employed methods for catalyst immobilization, including a discussion of supporting materials and anchoring groups. The subsequent sections elaborate on productive associations between molecular catalysts and a wide range of substrates based on carbon, quantum dots, metal oxide surfaces, and semiconductors. The molecule-material hybrid systems are organized as "dark" cathodes, colloidal photocatalysts, and photocathodes, and their figures of merit are discussed alongside system stability and catalyst integrity. The final section extends the scope of this review to prospects and challenges in targeting catalysis beyond "classical" H2 evolution and CO2 reduction to C1 products, by summarizing cases for higher-value products from N2 reduction, C x>1 products from CO2 utilization, and other reductive organic transformations.Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and National Foundation for Research, Technology and Development), the OMV Group, the Woolf Fisher Trust (New Zealand), the Cambridge Trust (University of Cambridge), the EPSRC (IAA Follow on Fund), the ERC Consolidator Grant “MatEnSAP” (GAN 682833) and a Blavatnik Fellowshi

Carbon nanotube-based bioelectrodes for Glucose/O2 biofuel cells

Ce mémoire est consacré à l'optimisation de la connexion enzymatique d'enzymes pour l'oxydation du glucose et la réduction de O2 sur matrices de nanotube de carbone (CNT) dans les biopiles à glucose.Premièrement, le transfert électronique indirect de la glucose oxydase (GOx) est optimisé dans une matrice nanostructurée de CNT contenant la 1,4-naphtoquinone comme médiateur rédox. Cette bioanode a ensuite été combinée avec des biocathodes similaires à bases d'enzymes à cuivre (laccase et tyrosinase). La biopile GOx-NQ/Lac a permis d'obtenir des puissances maximales de l'ordre de 1,5 mW.cm-2. Les utilisations de cette pile en décharge courte, longue et sa stabilité dans le temps ont également été étudiées. La seconde partie présente la préparation d'une autre anode basée sur la connexion indirecte d'une glucose déshydrogènase NAD+-dépendante (GDH-NAD+) comme alternative pour l'oxydation du glucose. La GDH-NAD+ a été combinée avec un catalyseur d'oxydation de NADH par différentes méthodes. Tout d'abord, elle a été encapsulée au sein du métallopolymère rédox, puis, la modification supramoléculaire a dans un second temps permis d'immobiliser le catalyseur moléculaire et l'enzyme à la surface des CNTs. Ces deux bioanodes ont permis respectivement l'obtention de courants catalytiques d'oxydation du glucose de 1,04 et 6 mA.cm-2. La seconde bioanode a été combinée avec une biocathode à base de BOD et a permis l'obtention de densités de courants maximales de l'ordre de 140 µW.cm-2 La dernière partie concerne l'élaboration d'une biocathode bienzymatique pour la réduction de O2. Le DET de la HRP sur CNTs a dans un premier temps été optimisé par modification de la surface par différents dérivés pyrène. Ensuite, la combinaison de la GOx et de la HRP sur la même électrode a permis de réduire efficacement O2 en 2 étapes. La biocathode est capable de délivrer une densité de courant maximale de l'ordre de 200 µA.cm-2. Cette dernière, combinée avec la bioanode GDH présentée précédemment a permis d'obtenir une biopile opérationnelle en conditions physiologiques et 10 mM de NAD+, en étant capable de débiter une densité de puissance maximale de l'ordre de 57 µW.cm-2.This work focuses on the optimization of the electrical wiring of glucose oxidizing and dioxygen reducing enzymes on carbon nanotube (CNT) matrixes for glucose biofuel cells.In the first part, glucose oxidase (GOx) mediated electron transfer (MET) is optimized in nanostructured CNTs matrixes by mechanical compression of a CNTs/GOx composite containing 1,4-naphtoquinone as redox mediator. This bioanode was then combined with MCOs (laccase and tyrosinase) based biocathodes. The GOx-NQ/Lac biofuel cell was able to deliver a maximum power density of 1.5 mW.cm-2. The use of this biofuel cell in short/long time discharge and in storage has also been studied. The second part presents the preparation of another bioanode based on the indirect wiring of a NAD+-dependant glucose dehydrogenase (GDH-NAD+) as an alternative for glucose oxidation. The GDH-NAD+ has been combined with an NADH oxidation catalyst by two different techniques. The first one involves the encapsulation of the protein in the metallopolymer redox film, whereas the second one relies on the supramolecular modification of the CNTs by the molecular catalyst and the enzyme. Both bioanodes showed good catalytic properties toward glucose oxidation in presence of NAD+ with respectively 1.04 mA cm-2 and 6 mA cm-2. The latter has been combined with a BOD based biocathode to form a biofuel cell exhibiting maximum power densities of 140 µW cm-2. The last part of this work focuses on the design of a bienzymatic biocathode for O2 reduction. The DET of horseradish peroxidase (HRP) was first investigated and optimized by modification of the CNTs with pyrenes derivatives. The combination of the HRP with the GOx on the same electrode enables an efficient reduction of O2 in a 2-step process. The biocathode could exhibit maximum currents densities of 200 µA cm-2. This cathode along with the previous GDH bioanode formed a biofuel cell functional in physiological conditions and 10 mM NAD+ showing maximum power densities of 57 µW cm-2

Deciphering Reversible Homogeneous Catalysis of the Electrochemical H2 Evolution and Oxidation: Role of Proton Relays and Local Concentration Effects

Nickel bisdiphosphine complexes bearing pendant amines form a unique series of catalysts (so-called DuBois' catalysts) capable of bidirectional/reversible electrocatalytic oxidation and production of dihydrogen. This unique behaviour is directly linked to the presence of proton relays installed close to the metal center. We report here for the arginine derivative [Ni((P2N2Arg)-N-Cy)(2)](6+) on a mechanistic model and its kinetic treatment that may apply to all DuBois' catalysts and show that it allows for a good fit of experimental data measured at different pH values, catalyst concentrations and partial hydrogen pressures. The bidirectionality of catalysis results from balanced equilibria related to hydrogen uptake/evolution on one side and (metal)-hydride installation/capture on the other side, both controlled by concentration effects resulting from the presence of proton relays and connected by two square schemes corresponding to proton-coupled electron transfer processes. We show that the catalytic bias is controlled by the kinetic of the H-2 uptake/evolution step. Reversibility does not require that the energy landscape be flat, with redox transitions occurring at potentials up to 250 mV away for the equilibrium potential, although such large deviations from a flat energy landscape can negatively impacts the rate of catalysis when coupled with slow interfacial electron transfer kinetics

Bias-free solar syngas production by integrating a molecular cobalt catalyst with perovskite-BiVO4 tandems.

The photoelectrochemical (PEC) production of syngas from water and CO2 represents an attractive technology towards a circular carbon economy. However, the high overpotential, low selectivity and cost of commonly employed catalysts pose challenges for this sustainable energy-conversion process. Here we demonstrate highly tunable PEC syngas production by integrating a cobalt porphyrin catalyst immobilized on carbon nanotubes with triple-cation mixed halide perovskite and BiVO4 photoabsorbers. Empirical data analysis is used to clarify the optimal electrode selectivity at low catalyst loadings. The perovskite photocathodes maintain selective aqueous CO2 reduction for one day at light intensities as low as 0.1 sun, which provides pathways to maximize daylight utilization by operating even under low solar irradiance. Under 1 sun irradiation, the perovskite-BiVO4 PEC tandems sustain bias-free syngas production coupled to water oxidation for three days. The devices present solar-to-H2 and solar-to-CO conversion efficiencies of 0.06 and 0.02%, respectively, and are able to operate as standalone artificial leaves in neutral pH solution.Christian Doppler Research Association (Austrian Federal Ministry for Digital and Economic Affairs and the National Foundation for Research, Technology and Development), the OMV Group, Cambridge Trusts (Vice-Chancellor’s Award), the Winton Programme for the Physics of Sustainability, BBSR

Bias-free solar syngas production by integrating a molecular cobalt catalyst with perovskite-BiVO4 tandems.

The photoelectrochemical (PEC) production of syngas from water and CO2 represents an attractive technology towards a circular carbon economy. However, the high overpotential, low selectivity and cost of commonly employed catalysts pose challenges for this sustainable energy-conversion process. Here we demonstrate highly tunable PEC syngas production by integrating a cobalt porphyrin catalyst immobilized on carbon nanotubes with triple-cation mixed halide perovskite and BiVO4 photoabsorbers. Empirical data analysis is used to clarify the optimal electrode selectivity at low catalyst loadings. The perovskite photocathodes maintain selective aqueous CO2 reduction for one day at light intensities as low as 0.1 sun, which provides pathways to maximize daylight utilization by operating even under low solar irradiance. Under 1 sun irradiation, the perovskite-BiVO4 PEC tandems sustain bias-free syngas production coupled to water oxidation for three days. The devices present solar-to-H2 and solar-to-CO conversion efficiencies of 0.06 and 0.02%, respectively, and are able to operate as standalone artificial leaves in neutral pH solution.Christian Doppler Research Association (Austrian Federal Ministry for Digital and Economic Affairs and the National Foundation for Research, Technology and Development), the OMV Group, Cambridge Trusts (Vice-Chancellor’s Award), the Winton Programme for the Physics of Sustainability, BBSR

Deciphering Reversible Homogeneous Catalysis of the Electrochemical H2 Evolution and Oxidation: Role of Proton Relays and Local Concentration Effects

Nickel bisdiphosphine complexes bearing pendant amines form a unique series of catalysts (so-called DuBois catalysts) capable of bidirectional or even reversible electrocatalytic oxidation and production of dihydrogen. While this unique behaviour is directly linked to the presence of proton relays installed within the molecular structure, close to its metal center, quantitative activity descriptors are still lacking to guide the rational design of molecular catalysts with enhanced activity. We report here for the arginine derivative [Ni(P2CyN2Arg)2]6+ on a detailed kinetic treatment based on a mechanistic model that applies to the whole DuBois catalyst series and show that, with a unique set of parameters, it allows, for a good fit of the experimental data measured in a wide range of pH values, catalyst concentrations and partial hydrogen pressures. The bidirectionality of catalysis results from the balanced equilibrium constant of the kinetically critical hydrogen uptake and evolution chemical step and the corresponding rate constants being large enough in both directions, as well as a very fast intramolecular proton transfer, both being likely due to concentration effects resulting from the presence of proton relays at the immediate vicinity of the catalysts. In that specific case, we show that hydrogen oxidation, kinetically limited by H2 insertion, has a larger turnover frequency than hydrogen evolution that is kinetically limited by H2 release. The reversibility of catalysis appears also to result from a subtle balance between the characteristics of two sequential proton-coupled electron transfer square schemes and the equilibrium constants as well as the kinetic constants of both chemical steps. We illustrate experimentally that reversibility does not required that the energy landscape be flat, with in the present case redox transitions occurring at potentials ~250 mV away for the equilibrium potential. Still, large deviations from a flat energy landscape requires interfacial electron transfers to occur far from their equilibrium potential, which impacts their kinetics and the overall rate of catalysis. At that point, the rate of catalysis may be limited by the efficiency of deprotonation/reprotonation of the relays, a concern that also holds for the design of improved monodirectional electrocatalysts

Noble metal free molecular based anode for H2-O2 fuel cell

Selected conferences on abstractInternational audienc

Noble metal free molecular based anode for H2-O2 fuel cell

Selected conferences on abstractInternational audienc