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Dehydrogenation catalyzed by plasmonic nanocatalysts based on 3d transition metals




Duration: NanoX master Internship (8 months part-time in-lab immersion)

Latest starting date: 01/10/2023

Team : Systèmes Métalliques Appliqués en Catalyse (SyMAC)
Contact: Université Toulouse III - Paul Sabatier
Bâtiment 2R1, 2ème étage, bureau 2032
118 Route de Narbonne, 31062 Toulouse Cedex 9
Phones: +33561557738, +33561556803

Montserrat Gómez, Prof.
Daniel Pla, Dr

This research master's degree project could be followed by a PhD

Work package:
In recent years, plasmonic nanocatalysts on semiconductors, have enabled new modes of activation either by their intense visible/near infrared response or efficient charge separation redox pathways, giving high activity and selectivity under mild conditions, attractive from environmental and economic viewpoints.1 This M2R project focuses on the study of catalyzed dehydrogenation reactions of alcohols and amines under UV-visible irradiation, leading to both the formation of H2 (fuel) and aldehydes and nitriles (intermediates of industrial interest, see Scheme 1), requiring the rational design of nanocatalytic composites containing metal nanoparticles of 3d metals that facilitate the migration of plasmonically induced hot electrons from metal nanoparticles to the semiconductor.2 Based on the know-how acquired by the team in the synthesis of metal-based nanoparticles immobilized on inorganic supports (MWCNTs, halloysites, hydrochars, MgAl2O4, TiO2…),3 particularly from the first row transition metal series,3b,3c composite nanocatalysts based on Cu or Co will be prepared by decomposition of organometallic precursors in the presence of stabilizers [alkaloids (quinidine) or polymers (PVP, chitosan)] and the semiconductor support. To tune the generation of electron-hole pairs in the support under light, semiconductor supports with different band gaps will be used, such as TiO2 (ca. 3.2 eV)4 or α-Bi2O3 (2.1-2.8 eV).5 The prepared materials will be fully characterized: UV-vis, IR, PXRD, ICP, (HR)TEM, FTIR, and magnetism (for Co systems). The photocatalytic reactivity profiles of the as-prepared catalysts will then be evaluated in terms of H2 production under UV-visible light irradiation of the substrates with particular emphasis on mechanistic studies.

Photodehydrogenation strategies catalyzed by plasmonic nanocomposites.

1. Cortés, E., Science 2018, 362, 28. 2. a) Wang, L.; Ge, J.; Wang, A.; Deng, M. et al., Angew. Chem. Int. Ed. 2014, 53, 5107; b) Lu, Z.; Wu, X.; Chen, N.; Cao, M. et al., ACS Energy Lett. 2021, 6, 3473. 3. a) Duarte, T. A. G.; Favier, I.; Pradel, C.; Martins, L. M. D. R. S. et al., ChemCatChem 2020, 12, 2295 ; b) Pérez Alonso, A.; Mauriés, S.; Ledeuil, J.-B.; Madec, L. et al., ChemCatChem 2022, 14, e2022007; c) Serrano-Maldonado, A.; Bendounan, A.; Silly, M. G.; Pla, D. et al., ACS Appl. Nano Mater. 2023; d) Mamontova, E.; Trabbia, C.; Favier, I.; Serrano-Maldonado, A. et al., Nanomaterials 2023, 13, 1435; e) Castillejos, E.; Jahjah, M.; Favier, I.; Orejon, A. et al., ChemCatChem 2012, 4, 118. 4. Janczarek, M.; Kowalska, E., Catalysts 2017, 7, 317. 5. Meng, X.; Zhang, Z., J. Mol. Catal. A: Chem. 2016, 423, 533.

Areas of expertise:
First row transition metals, nanoparticles, plasmonic catalysis, photodehydrogenation

Required skills for the internship:
A bachelor degree in Chemistry is required. This proposal provides an excellent framework to acquire solid competences in the synthesis and characterization of catalytic nanomaterials in the frame of development of sustainable processes. In addition, the use of conventional techniques (IR, GC, MS, HPLC, NMR) for the evaluation of the catalytic reactions will provide the trainee hands on experience in these analytical tools, as well as the characterization of organic compounds.