PhD offer (CSOB group) – Gas-phase study of the metal-CO2 interaction for an improved efficiency of catalyzed CO2 reduction

The CSOB, in collaboration with the group of Dr Kacper Błaziak (Warsaw University), is looking for a candidate for a PhD scholarship on the topic:

Gas-phase study of the metal-CO2 interaction for an improved efficiency of catalyzed CO2 reduction

Project overview :  

Download PhD offer

The goal of this PhD project is to explore – in a systematic way – the metal-CO2 interaction along the periodic table in order to provide experimental quantitative knowledge on how metal atoms interact with CO2 molecule and –CO2− moieties incorporated within diverse organic structures.

Investigation of the chemical interactions between the metal-organic (M-R) compounds and the CO2 molecules that lead to the formation of appropriate carboxylates will bring a valuable information about the catalytic abilities of the metal atoms in the CO2-capturing prospective technologies. Furthermore, description of the formation reaction of metal-carboxylate complexes and their fragmentation mechanisms will organize the knowledge about the stability of the CO2-accumulation molecular architecture. Finally, the description of the kinetic properties of metal-carboxylate and metal-CO2 reaction will give a useful tool for electrochemical and technological design processes. Taking above, it is intended to recognize and describe the subtle relationships between electronic structures, molecular size and reaction energy requirements of the key moieties within the chemical molecules. In this way, we want join our efforts, share our unique and state-of-art experimental techniques and theoretical experience to obtain key insights into the physical factors across molecular systems that govern CO2 reduction catalyzed by metal atoms at the most fundamental level.

Scientific approach

Both partners involved in the project has developed a long-time expertise in experimental gas-phase chemistry, in particular in the measurement of thermochemical quantities on the French side4a, b, c and in ion-molecule reactions on the Polish one.3a, 5 Gas-phase studies are particularly relevant in the context of this project because most of the CO2 reduction reactions occur – at leastpartly – in the gas phase and this phase is also the most suited to evaluate intrinsic properties of molecules. The most appropriate dedicated tool in this context is mass spectrometry as it is known to be one of the rare experimental techniques able to provide either accurate thermochemical data6 or to give access to a fine elucidation of reaction mechanisms through the identification of elusive and “short-living” intermediates. 7a, b

Taking advantage of the complementary profiles and skills of the two supervision teams, the PhD candidate will have access to state-to-the-art instruments in Paris and Warsaw to:

  1. Provide for the first time a complete description of the metal-CO2 reactivity, including the effect of the metal along the periodic table, using a designed state-of-the-art instrument implemented in Warsaw University.

This extensive study will provide an extensive overview of the RCO2 reactivity towards a large range of metals in order to rationalize the differences that are observed in CO2 reduction reactions by means of efficiency or selectivity, depending on the metal catalyst used and organic ligand size.

  1. Quantify the interaction between the metal and the CO2 moiety using a methodology developed within the Sorbonne University group which includes mass-spectrometry based experiments and kinetic modelling.

The French team has developed a strong expertise in the MS-based measurements of thermochemical quantities of ion dissociation in the gas phase for several years now. This includes the use of well-documented threshold-CID8a, b or BIRD4b methods but also the development of new approaches such as the use of multi-collisional regime4a, c, 9 or of low-energy CID in a linear ion trap,10 both providing high accuracy results. The PhD candidate will thus have access to various mass spectrometers and approaches to evaluate the metal-CO2 bond strength with the highest accuracy.

  1. Support experimental results through an extensive theoretical work, involving bond-dissociation energy calculations and electronic structure calculations of the reaction mechanism.

The PhD candidate will be trained to state-of-the-art quantum chemistry modelization in order to support the experimental results by calculating reaction rates, equilibrium and transition state structures as well as bond-dissociation energies (BDEs). This theoretical study will help to benchmark theoretical methods which will be useful as predictive tools for new catalytic systems.

Profiles : 

– Master degree in Physical Chemistry, Chemical Physics or Chemistry;
– Very good communication and writing skills;
– First experience in mass spectrometry will be positively considered.

Duration:

36 months from October 2024

Application:

– Send a cover letter
– a detailed CV
– with the name or addresses of minimum 1 referee

Références

  1. European Commission, Directorate-General for Climate Action, Going Climate-Neutral by 2050 – a Strategic Long-Term Vision for a Prosperous, Modern, Competitive and Climate-Neutral Eu Economy, Publications Office, 2019. https://data.europa.eu/doi/10.2834/02074.
  2. (a) Caner, J., et al. Transition-Metal-Catalyzed C-H Carboxylation. Wiley-VCH, Weinheim, 2020; (b) Crawford, J. M., et al. J. Chem. Technol. Biotechnol. 2020, 95, 102; (c) Fu, X., et al. Chem. Commun. 2020, 56, 2791; (d) Hachem, M., et al. Eur. J. Org. Chem. 2020, 2052; (e) Pei, C., et al. Org. Lett., 2020, 22, 6897; (f) Perry, G. J. P., et al. Eur. J. Org. Chem. 2017, 3517.
  3. (a) Blaziak, K., et al. Phys. Chem. Chem. Phys. 2018, 20, 25495; (b) Nguyen, T. N., et al. ACS Catal. 2020, 10, 10068; (c) Sun, J.-F., et al. Environ. Chem. Lett. 2020, 18, 1593; (d) Xu, H., et al. Catalysis Science & Technology 2017, 7, 5860.
  4. (a) Bourehil, L., et al. Inorg. Chem. 2023, 62, 13304; (b) Gatineau, D., et al. Int. J. Mass Spectrom. 2021, 463, 116545; (c) Gatineau, D., et al. Dalton Trans. 2018, 47, 15497.
  5. Błaziak, K., et al. Eur. J. Org. Chem. 2017, 2017, 4272.
  6. Armentrout, P. B. Int. J. Mass spectrom. 2015, 377, 54.
  7. (a) Böhme, D. K., et al. Angew. Chem. Int. Ed. 2005, 44, 2336; (b) O’Hair, R. A. J. Chem. Commun. 2006, 1469.
  8. (a) Bourgoin-Voillard, S., et al. J. Am. Soc. Mass Spectrom. 2013, 24, 365; (b) Gatineau, D., et al. Int. J. Mass Spectrom. 2017, 417, 69.
  9. Bayat, P., et al. J. Mass Spectrom. 2022, 57, e4879.
  10. Bayat, P., et al. J. Mass Spectrom. 2019, 54, 437.