Anion Exchange Membrane Water Electrolysis (AEMWE) is a very promising technology for producing clean H2 at a target cost of 2 $/kg. Like Proton Exchange Membrane Water Electrolysis (PEMWE), this membrane-based technology has the advantages of an “all solid” system (coupling with intermittent energy sources, high energy efficiency, high purity of H2). In addition it allows the use of earth abundant transition metals as electrocatalysts for both the evolution of O2 at the anode (OER) and of H2 at the cathode (HER), as opposed to PEMWE, where these catalysts rely exclusively on rare and expensive Platinum-Group Metals (PGM). However several challenges remain for AEMWE to reach as high and stable performance as PEMWE and be spread on the market. To achieve the increase of performance in AEMWE, essential components of the MEA must be optimized, with a specific emphasis on HER catalysts. Indeed, while being very fast in acidic conditions, the HER kinetics in alkaline medium are slow because they imply the adsorption of a water molecule, generally considered as the rate-determining step. In order to improve the rate of this first step, the new concept of heterofunctional catalysts has recently emerged. It consists in the tight interfacing of two or more active components so as to create a synergy between them, thus favoring water dissociation. In particular, bifunctional catalysts combining (i) one material with good water dissociation properties and (ii) another one with appropriate hydrogen adsorption energies, have displayed a 7-fold increase in alkaline HER rate. In the HYKALIN project we propose to significantly improve the performances of AEMWE so they can compete favorably with PEMWE. To do so, we intend to cover some untouched aspects in this field, through an integrative approach dealing with both fundamental and more applied aspects. In particular, we aim at: 1) Developing a new class of transition-metal-based heterofunctional catalysts being highly active for the HER in alkaline medium. Ni, Co, Cu and Mo are selected because they are already known to be very active for this reaction. We target composite catalysts associating a metal with either an oxide or a sulfide. They will be obtained by a 2-step process to achieve a maximum number of interfaces and catalytic sites. In the first step, we will synthesize MM’ alloys where the two metals are distributed at the nanoscale, using either polyol or spray-drying processes. In a second step, these alloys will be converted in M@M’Ox and M@M’Sx by thermal treatment or solution route. We will focus on producing specific porous morphologies which are crucial to induce good gas and water transport inside the MEA in order to improve the performances. 2) Deeply characterizing their electrochemical properties as well as their structure by operando X-ray spectroscopy to understand and improve their activity. Chemical nature, stoichiometry and morphology of the catalysts will be investigated in order to understand the behavior of the materials in the catalytic layer under functioning conditions. Ab initio and DFT calculations will also be crucial in this section to complement the interpretation of the experimental results. This should allow us to propose a comprehensive mechanism for alkaline HER. 3) Finally the best catalysts will be processed into membrane electrode assemblies and tested in situ in AEMWE. We will optimize MEA preparation and investigate the best operation conditions for the 5 cm2 electrolysis cell in order to achieve performances better than Pt/C. In a second step, we will perform degradation studies and get information on the mechanism of performance decrease. This fundamental and applied approach will significantly improve knowledge in the still emerging field of alkaline electrolyzers and should allow, in the mid-term, major breakthroughs in the domain of advanced water electrolysis and carbon-free hydrogen production.

The hydroxyl radical (HO•) is a highly reactive oxidant, produced via autoxidation in biological systems, in advanced oxidation processes, or in electrocatalysis. If it is leverage for photodegradation, harmful HO• content must be tempered in many devices (energy conversion materials, biomedical implants, nanotechnologies…) to improve their durability. Probing HO• in situ at the earliest stage is key to understand and control the chemical reaction responsible for its formation. Because of HO• short lifetime, one needs diagnosing its production at the nanoscale, or equivalently at single nanoparticle level (NP). In this context, the PIRaNa project will be devoted to the development of a correlative opto-electrochemical multi-microscopies platform allowing to image HO• formation both at individual and within a set of NPs. It will allow breaking the limit of operando detection and quantification of HO• at the ultimate scales using firstly model chemical systems, such as i) Pt NPs, still key elements in fuel cells and ii) TiO2 NPs, used in many applications, from photocatalysis to biomedicine. The project lies on two complementary sensing methodologies: i) local electrochemical probe microscopies (SECPMs), herein the scanning electrochemical microscopy (SECM, allowing to characterize interfacial reactivity in solution using a micro/nanoelectrode) and the scanning electrochemical cell microscopy (SECCM, allowing to confine, by a nanopipette, single NPs within an electrolytic nanodroplet cell) ii) high resolution interferometric optical microscopy (IOM). The operating range of both SECM and IOM will be delved in WP1 and WP2 respectively, while a synergistic combination of SECPMs (SECM, SECCM) and IOM in WP3 and WP4 will highlight the deleterious effect of HO• (i.e. the material nanocorrosion) and the importance of cross-talk in autocatalytic processes. WP1 will achieve the sensing and imaging of local HO• production based on its chemical reaction with a redox probe next to a micro/nanoelectrode tip of a SECM. The electrochemical (EC) current fluctuations caused by this reaction, amplified by the feedback loop provided by the geometrical confinement, allows a highly sensitive, operando, probing of HO• flux generated at Pt or TiO2 NPs (from ensemble to single entities). WP2 is dedicated to HO• sensing by the highly sensitive IOM. The approach is based on the optical monitoring of gaz nanobubbles growth from the degradation of a chemical probe by HO•. The IOM will image and quantify, at high throughput, the HO• production at the single NP level, allowing for the first time to establish a structure/HO• production relationship through computerized data treatment and statistical analyses. In a second step, and thanks to the new implementation of SECCM in the laboratory, the SECPMs, will be combined to IOM. WP3 will use such correlative opto-SECPM microscopies as an incomparable methodology to visualize and apprehend operando NPs nano-corrosion induced by HO•. WP4 will extend the methodology to decipher autocatalytic mechanisms, at the origin of a drastic increase of [HO•], believed to be triggered by NPs cross talk. It will bring an overview of such processes for which the parameters conditioning their activation will be investigated at multiscale ranging from arrays to individual NPs. The PIRaNa project brings together young researchers having complementary skills and scientific interests (SECPMs, IOM, NPs synthesis, etc.) ensuring the development of a unique platform in France, and only mastered by few prestigious groups worldwide. The completion of this project will lead to a multidisciplinary operational methodology adaptable to many environment (various temperature condition and electrolytic media) making it relevant for many other field of research.

Parkinson's disease (PD) is one of the major degenerative diseases for which there is no cure. There is therefore a pressing need to identify mechanisms implicated in PD pathogenesis that can be targeted for therapy. In this context, LRRK2, one of the major genetic determinants of sporadic and familial forms of MP, has emerged as a promising therapeutic target. Specifically, the importance of LRRK2 phosphorylation for its physiological and pathological functioning has recently become clear. Here, we will study the targeting of LRRK2 phosphorylation in PD models in drosophila, rodent neurons, rodent brains and in human cells. The validation of LRRK2 phosphorylation as a potential therapeutic target will open perspectives to develop modulators of phosphoregulators as candidate therapeutics for PD.

Despite considerable efforts, the transformation of biomass products into valuable nitrogen-containing chemicals still represents an important challenge today. Yet, their demand is dramatically increasing worldwide, since amines are sought for their unique properties as corrosion inhibitors, paints and coatings, as well as in cosmetic, detergence and food industries. The GLYNANO project aims to provide a one-pot efficient and selective catalytic route upgrading glycerol into valuable bio-based amines through its direct amination with ammonia or primary amines. We target in this project the amination of the central hydroxyl group of glycerol. Keeping the two terminal-hydroxyl groups free will facilitate further chemical modifications and will confer hydrophilicity to the resulting surfactant when using a fatty amine as an aminating agent. Since the central hydroxyl of glycerol is often less reactive than the two terminal ones (statistically and sterically), the amination of glycerol at its central position is highly challenging and chemoselective catalysts are required. We will use magnetically recyclable and unsupported ligand-decorated Co-based metal nanoparticles with controlled sizes and shapes that have already shown excellent activity, chemoselectivity and recyclability for the acceptorless alcohol dehydrogenation (the first step of the direct amination of alcohols). Their catalytic performances will be adjusted through the fine control of their composition (alloying Co with Ru or Cu), size, shape and surface ligand decoration. To obtain a better understanding of the structure/selectivity relationships and to further improve our catalysts, computational investigations (e.g. adsorption of the substrate through the ligand layer, reaction mechanism) will be carried out. Based on this integrated approach combining expertise in the fields of materials chemistry, reactivity and theoretical chemistry, this project is expected to lead not only to a better understanding on the influence of the surface ligands used to stabilize metal NPs on the catalytic amination of glycerol but also to the emergence of novel catalysts and eco-efficient processes to produce selectively modified bio-sourced amines.

Reconciling human development and environment preservation is one of the most difficult problem researchers will face in the coming years. This will be all the more difficult with the need to shift from fossil fuel use to renewable energies such as solar energy, find alternatives for rare elements and manage resources in a more sustainable way. In this project, we propose to explore the photocatalytic properties of low price and environmental-friendly alumino-silicate nanotubes, i.e. imogolites, to trigger unfavorable redox reactions on both sides of the hybrid imogolite wall, taking advantage of confinement inside the cavity and of the polarization of the wall. A specificity, and the originality, of this project is that under confinement in a nanoreactor, the majority of the molecules are under the influence of structurally controlled interactions that can modify chemical reactions in a way inaccessible in the bulk phase. The project will in particular try to evaluate the role of the curvature-induced polarization for the separation of charge through the wall of imogolites and to control interfaces and interactions at the nanometer scale to obtain original properties. To meet these objectives and fully exploit the remarkable properties of these still little-known materials, several challenges will be faced in the BENALOR project. First, it is necessary to prepare and characterize organic/inorganic hybrid imogolites able to host, organize and transform the desired organic reactants in their internal cavity by tuning the size, the functionalization groups in the cavity as well as the wall composition. The synthesis will be optimized both at the laboratory and at larger scale. This will be the aim of the first work package (WP1). Secondly, the encapsulation efficiency, the related thermodynamics in correlation with the internal arrangement of the organic substrates have to be finely understood (WP2) to fully optimize the targeted catalytic properties. Finally, to assess the dual reactivity specific to imogolite-based tubular nanoreactors, the synergetic integration of an oxidation reaction (decomposition of an organic pollutant) inside the tube will be coupled to a reduction reaction at the outer surface (WP3). Several reactions have been selected with increasing challenge: light-induced reduction of metal ions at the external surface, water and carbon dioxide reduction. To tackle these challenges, the project joins the efforts of 3 academic partners (i.e. NIMBE, ITODYS and ICGM) with highly recognized and complementary expertise in material, surface and interface science as well as reactivity. NIMBE laboratory, which has already been the investigator of different projects on imogolites and has installed a facility for large scale synthesis of these materials, will coordinate the project (WP 0). One PhD student, one post-doc and six Master students will also contribute to this study, and the 48 months project will gather nearly 20 permanent and non- permanent researchers. Coupling hydrophilic/hydrophobic redox reactions in a nanoreactor is very unique and the development of the hybrid materials presented may open an avenue of new possible photoinduced reactions. The realization of this project is expected to have a very strong impact not only on the understanding of reactivity in confined systems, as well as in the field of photocatalysis for environmental and energy applications.