The PhD project will aim at synthesizing heterogeneous catalysts based on abundant metals, whose key parameters will be optimized: (i) textural properties of the supports, and in particular the stabilization of a hierarchical porosity, (ii) oxophilicity / acidity of the surface, (iii) and fine characteristics of the metals (dispersion, localization and composition). Thus, silica supports with hierarchical porosities will be synthesized, modified by the introduction of different oxide phases (ZrOx, TiOx, AlOx, ZnO), and then the metal phases (Ni, Fe, Co and Cu) will be dispersed in a controlled manner on the surface of the pores to obtain single atome to clustered supported catalysts. These catalysts will be studied for the HDO of model oxygenated molecules (m-cresol, anisole and guaiacol) under moderate hydrogen pressures (2-4 MPa) before being tested on real lignin in a reaction micropilot (IC2MP partner). The properties of the catalysts (activity, aromatic yield, and stability) will be rationalized by DFT studies conducted on the adsorption of model oxygenated molecules, taking into account the effect of H2O, CO and CO2 inhibitors (LPCT partner). All these results will allow the description of the reaction pathway and the obtaining of key kinetic data in real conditions of reaction conducted over lignin (at LRGP partner).
Proposal summary: The transformation of lignocellulosic biomass into fuels or reaction
synthons of interest for fine chemistry is an essential issue for reducing the environmental
impact associated with the use of fossil resources. Contrary to cellulose and hemicellulose,
lignin is a resource that is still not very well valorized, although it is abundantly produced by
the pulp and paper industry and will be an abundant by-product of next generation cellulosic
biorefineries. Different technologies exist for lignin liquefaction, but fast pyrolysis has
undeniable advantages. It can convert 60-75% of lignocellulosic biomass into crude bio-oil, and
it operates continuously, in an inert environment, and without solvent consumption. However,
the bio-oil must be upgraded to be valorized. Containing up to 55% of phenolic compounds, it
is a source of simple aromatic hydrocarbons (BTX). Catalytic hydrodeoxygenation (HDO) is
the most suitable catalytic process to transform phenolic monomers into BTX. The catalyst, by
selectively activating the C-O bonds, will allow the deoxygenation of phenolic compounds
while avoiding their hydrogenation. These two processes are therefore essential to ensure the
economic viability of biorefineries through a better valorization of the lignocellulosic fraction.
The project aims developing original catalysts for the deoxygenation of lignin pyrolysis vapors,
with the goal to improve the yield of aromatic hydrocarbons. In order to gather skils in materials
chemistry, molecular modelling, heterogeneous catalysis and process engineering, the project
team associates 5 laboratories, labelled by CNRS: UCCS (Univ. Lille), IC2MP (Univ. Poitiers),
and L2CM, LPCT, and LRGP (all three from Univ. Lorraine). The skills thus gathered allow
the development of a multi-scale approach, from ab initio modeling at the molecular scale of
surfaces to the study of catalyst performance on lignin pyrolysis vapors from a continuous
Starting date: Flexible, until march 2022
Application: CV + motivation letter by email to the supervisors
Sebastien Royer, Professor Université de Lille, France (firstname.lastname@example.org) & Nadia Canilho, MCF Université de Lorraine, France (email@example.com)
French partner: http://uccs.univ-lille1.fr/index.php/en/heterogeneous-catalysis/matcat
Approx. 1600 euros net/month
This thesis position will be dedicated to 1) the multistep organic synthesis of fluorescent dyes with aggregation induced emission properties and bearing a functionality to attach them to polymeric carrier, 2) the preparation of polymers with tailored properties (amphiphilicity, stimuli-responsiveness) and side-chain or end-chain functionality to attach the AIEgen-dye, 3) the evaluation of self-assembly properties and characterization of the formed nanoparticles at nanoscale, 4) the evaluation of photophysical properties of dyes, dye-polymer conjugates and dyes nanoparticles, 4) the exploration of properties toward in vivo applications (photothermal production efficiency, photoacoustic response). In the framework of this project, competences in organic synthesis, polymer synthesis, photophysics and physical-chemistry and associated characterization techniques will be developed. The project is focusing on a multidisciplinary research area of great interest in academia and truly represents an opportunity for highly motivated graduate students. The selected candidate will also have the opportunity to interact proactively with a network of collaborators and will have the opportunity to use modern synthesis and characterization tools.
One of the main projects of our laboratory (L2CM, Nancy, France) aims at the design of photoactive organic molecules and metal complexes or applications in photomedicine or photovoltaics. In this context, applications are opened for a postdoctoral fellowship position funded by the European FEDER project entitled “FireLight: Photoactive molecules and nanoparticles” to investigate the ultrafast excited state dynamics of these photoactive systems. More specifically, the research program will focus on (1) the investigation of ultrafast photochemical processes behind Z/E photoisomerization of bioinspired molecular photoswitches and (2) the determination of the excited state properties of photoactive metal complexes.