GANDALF aims at modifying the surface of positive electrodes (LiFexMn1-xPO4 (LFMP) and LiNi0.5Mn1.5O4 (LNMO)) of Li-ion devices by a novel atomic layer fluorination process, improving their inertness towards their electrolytic environment, augmenting their performances as high-voltage systems, and validating their use as real-life size SAFT prototypes. Through a PhD funded by the RS2E, we could study our novel atomic layer fluorination process, so-called ALF, on TiO2, Li4Ti5O12 (LTO), LiCoO2 (LCO), and Li(Ni0.80Co0.15Al0.05)O2 (NCA). For each system, we demonstrate that ALF-electrodes display improved cyclability, polarization, and cycle life. Electrochemical operando FTIR measurements show that ALF-NCA is relatively inert towards its electrolyte, as compared to pristine NCA. Encouraged by the ANR, we were advised to build this project as PRCE in order to reach the industrial validation.

The emission of NOx - nitrogen monoxide (NO) and nitrogen dioxide (NO2) - by engines in a confined work environment without ventilation and exhaust treatments represents major health and safety issues. In France, almost 800,000 workers are exposed to such highly toxic NOx emissions. The NOA project aims to develop a NOx adsorption process for non-road vehicles using an optimal adsorbent. It will be loaded and transportable by the worker, to be placed at the exhaust gas outlet of vehicles. The adsorption cartridge needs then to be periodically changed since it works on an accumulative mode, by gas-solid adsorption. The regeneration of the process will therefore take place in time and deported from the vehicle. The operation chosen is the gas-solid adsorption which is more effective than the catalysis at low temperature. Technical obstacles exist; the proposed process has to be selective: to trap NOx without adsorbing water and carbon dioxide, and the affinity of the trapping materials with NOx has not to be too high to allow the regeneration. Therefore, a selection of materials (MOF, zeolites,) with properties required will be made thanks to DFT and GCMC calculations. The goal is to identify the best adsorbents with the highest affinity and largest uptake to NOx in the presence of H2O and CO2. The most promising adsorbents will be synthesized with different morphologies and characterized. A first principle model based on momentum, heat and mass balances will be developed in order to accurately predict the NOx concentration profiles over time at the outlet of a column containing the best adsorbents. Finally, calculations and experiments will be carried out to sizing and design of a transportable device. A technology transfer to companies for its development will be performed at the end of the project. These different activities are not time-sequential but fully interwoven throughout the development stages and the validation of the innovative concepts. The work program is divided into seven work packages (WP) over the 48 months, each WP comprising from 1 to 5 tasks. Five French teams are involved in this project: four academics and one private association (coordinator). The consortium is complementary; it combines the advantages of a multidisciplinary research, involving chemistry of materials, thermodynamic and kinetic analyses, multiscale modelling (molecular simulations and process simulations), process and chemical engineering applications with efficient synergies. It should identify the most promising adsorbents for a highly challenging targeted selective adsorption, and intends to develop industrial tools for occupational risk prevention and environmental protection. Technology transfer to companies for the development and commercialisation of the optimised material(s) and selected process will be dealt with by the coordinator. The NOA project contains an important part of experimental/modelling investigations. Therefore, it requires the recruitment of scientists as follows: two PhD students, one post-doc (18 months) and one master2 student (6 months). It requires also the purchase of manometry equipment for corrosive gas to carry out adsorption isotherms. The project has no rental costs. It does not request funding for the costs of acquiring licenses, patents, copyrights, etc. A consortium agreement will be established between the five partners in the first year of the project. The financial support requested for NOA project stands at 535 k€ for four years, and at 131 man-months (permanent staff). The scientific impact of the work will appear at various levels, with the three following objectives: (i) sharing research results with the scientific community (conferences, publications, etc) (ii) ensuring a wide awareness of the project to both potential end-users and to the general audience (technology transfer) and (iii) disseminating knowledge to people outside of the consortium through training activities.

In the context of green chemistry, cascade catalytic reactions appear as ideal solutions for industry. Combining strategies from biocatalysis to chemocatalysis, the Ni(k)AGARA project aims at experimentally demonstrating the concept of cascade catalysis in cristallo on oxidative transformations of alkenes, performed in multi active sites cross-linked artificial enzyme crystals (CLEC). It will consist of an evolution of our mastered CLEC application that will require innovative chemical modifications in NikA protein crystals for the insertion of a second inorganic catalytic site. Our knowledge in high performance of alkenes’ degradation using dioxygen as oxidant will drive us to add downstream transformations in an original cascade of catalytic oxidation reactions, implying carbonation, aldehyde oxidation, or degradation of polyunsaturated biomolecules. Never performed on hybrid solid catalysts, such a catalytic process could eventually reach the requirements for an industrial use. he project is divided into two main objectives: first, the construction of two catalytic sites within a protein, distinguished by their mode of insertion. The first will be based on supramolecular interactions as mastered by the consortium today, while the latter will be covalently linked to the solvent channels of the protein crystal. the method of attachment will be obtained by the mutation of an amino acid of the N-terminal chain with a cysteine; this one will then react with related functions on the ligand of the metal complex to integrate. An alternative will be to perform click chemistry on an unnatural azido amino acid. Catalysis of transformation will be the second objective, a choice resulting from the recent discoveries of the consortium. Oxidative cleavage of alkene has been shown to be catalytic with artificial protein crystals, based on the insertion of iron complexes within the NikA protein. On this basis, the activation of CO2 will be undertaken in the second stage of the cascade reaction: a transformation of epoxides into carbonates or the subsequent oxidation of polyenes are an illustration of this. The interdisciplinary project Ni(k)AGARA deals with the conception of innovative solutions for a sustainable chemistry. It will cover research at the interface of biotechnology and chemistry. Accordingly, the project concerns basic science to develop new catalytic solutions for green chemistry, involving a bio-inspired design of heterogeneous biocatalysts. The outstanding quality of the present project relies into the right combination between sustainability and catalysis, creating new innovative solutions for catalysis while targeting pollutants, or bio-based molecules building blocks. The scientific benefits will be numerous at various levels. Firstly, the consortium will develop new tools to transform chemically crystalline proteins and understand the catalytic mechanisms at molecular level. Secondly, the application for polymer transformation should open new greener routes. Accordingly, it fulfills the requirements of “stimuler le renouveau industriel” and should be evaluated by the CES “chimie moléculaire, chimie durable et procédés associés” since catalysis is associated to eco-efficiency and to the development of new molecules. A second reading level of the project deals with the search of new reactions processes for high value products combining the valorization of CO2 with polymer functionalization, a very active field for polymers with low environmental impacts. Partner 1 and 2 have been involved in collaborative projects since 2008 and their common publications in journals of high impact attest of their efficacy. Partner 3 will afford its knowledge in CO2 activation and polymer science, making the targeted reactions eventually appreciable by the industry world and open a new field of possibilities for this original catalytic approach.

Peptimprint relies on the complementarity and expertise of five teams specialized in the conception of bioactive compounds (Partner 1-IBMM-team amino acids), analytical development (Partner 1-IBMM-team analytical sciences), sol-gel process and hybrid materials (Partner 2-ICG-team CMOS), microfluidics devices (Partner 3-L2C-team POMM) and study of biomolecular interactions by biosensors development (Partner 4-IRCM-team criblage) Objectives The main objective of Peptimprint is to set-up a ground-breaking technology to prepare specific tridimensional and functionalized imprints of peptides and large proteins by sol-gel process, polymerizing original hybrid building blocks mimicking amino acids around the biomolecular template. Unfunctionalized blocks (e.g. tetraethoxysilane, dimethyldichlorosilane) will be used concomitantly to create the network. Once the template biomolecule removed, the hollow cavities will be able to capture these biomolecules with very high selectivity. The second objective of Peptimprint is the preparation of unprecedented imprinted devices for the detection, separation of biomolecules and their extraction and concentration in biological samples. Surface Plasmon Resonance (SPR) and Quartz Crystal Microbalance (QCM) chips as well as polydimethylsiloxane (PDMS) based microfluidics channels will be modified with hybrid biomimetic imprints. Scientific challenges Classical molecular imprinted polymers (MIPs) suffer important limitations. Firstly, the polymerization conditions (organic solvents, non-selectivity vs amino acid side-chains…) affect the structure of the template yielding a non-relevant MIPs. Secondly, the obtainment of a large cavities deprived of functional groups generate non-specific imprints that failed to mimic the diversity of weak interactions found in natural recognitions systems. Peptimprint approach is bringing down such barriers. The sol-gel process takes place at physiological pH, in aqueous conditions and at room temperature preserving the structural and functional integrity of the protein template. Moreover, the original hybrid monomers (amino acid mimics) used in Peptimprint will recapitulate all types of interactions (ionic/hydrogen bonding/hydrophobic/aromatic stacking) involved in real interactions between biomolecules. Proceeding much more slowly than photopolymerization used in classical MIPS, sol-gel approach of Peptimprint favours a self-organization of all the functionalized hybrid blocks around the template. First models and applications Several peptide and proteins templates covering a wide range of size (from 1.5 to 150 kDa) and functions will be used as models for Peptimprint. It includes vancomycin, C-peptide, human kallikrein1, antibody fragments and therapeutic antibody. Hybrid imprints of such proteins will be prepared on the surface of QCM and SPR devices and the interaction will be studied. On the other hand, models will be either adsorbed or covalently grafted on the silicon mold to cast hybrid-PDMS microchannels. The later will be used for electrophoric analyses. Expected impacts Fundamental knowledge on molecular imprinting will be gathered thanks to Peptimprint project including (i) a generic and straightforward sol-gel method and (ii) tailored reagents (hybrid amino acids) for the inorganic polymerization of functionalized imprints. From a technological point of view, if convincing analytical data are obtained using imprinted microfluidics devices or sensors, the development of relevant selective sensors for the detection and the quantification of biomarkers will be envisioned. Indeed, Peptimprint concept can be generalized to any other types of biomolecules (oligosaccharides, oligonucleotides etc.) or even objects (viruses, bacteria) enlarging the scope of biomedical applications. A strategic advisory board will be gathered (month 24) to discuss the technological transfer opportunities and to maximize the dissemination impact.

Solar energy assisted overall water splitting (OWS) has emerged as a low-cost green technology to produce sustainable H2. Current photocatalysts suffer from a lack of viable solar-to-hydrogen (STH) energy conversion efficiency, stability under operation, easy synthesis routes, or inactivity under visible light irradiation. Based on a recent bimetallic Metal–Organic Framework (MOF) we discovered that exhibits a remarkable OWS efficiency under visible light, the project targets an understanding of the OWS mechanism through a combination of advanced experimental and computational efforts, to decipher the key structural and chemical features that govern this outstanding performance and establish a photophysical/structure-activity relationship. The performance and durability of the catalysts using a solar light demonstrator will be equally addressed. This knowledge will guide us to design new generations of MOFs with superior STH efficiency and durability while meeting the cost threshold.