Blanc SIMI 8 - Blanc - SIMI 8 - Chimie du solide, colloïdes, physicochimie

Thermally Activated Reactivity in the micropores of zeolite films Given by controlled Energy Deposition – TAR-G-ED

Thermally Activated Reactivity in the micropores of zeolite films Given by controlled Energy Deposition

The project TAR-G-ED is concerned with the plasmonic assisted photothermal activation of chemical reactions in molecules confined in the micropores of zeolite thin films containing metallic nanoparticles (NPs). The project focuses more specifically on the reactivity of guests molecules of interest for environmental and green fuel chemistry.<br />

Main issues raised & general objectives: investigating the interactions and photoinduced energy transfers between metal nanoparticles and target guest molecules confined in the zeolite framework.

The core-goal of the project is to investigate the interactions and photoinduced energy transfers between metal nanoparticles and target guest molecules confined in the micropores in order to characterize unusual effects resulting from the extremely small-size of the metal in combination with the confinement in the zeolite framework. It is particularly important to distinguish the role of the different types of couplings between the hot electrons, the vibronic molecular states, the metal phonons, and the zeolite framework, and to determine their respective influence on the reactivity of the hosted molecules.<br />Objectives :<br />Characterize a new approach for the activation of thermochemical reactions in microporous media based on the photoexcitation of metal nanoparticles. <br />Benchmark the efficiency of this photothermal activation approach in the case of dissociation of CO, NO, H2O, CH3OH, and CH3CH2OH in copper-zeolite films. <br />Evaluate the potential use of metal nanoparticles doped zeolite films as photoactivatable nano-reactors compatible with applications to environment chemistry and solar energy conversion.<br />For this aim, the project is based on a multidisciplinary approach combining the skills and expertise of the Laboratoire de Spectrochimie Infrarouge et Raman (LASIR), Laboratoire Catalyse et Spectrochimie (LCS), and Equipe Matériaux Avancés pour la Catalyse et la Santé (MACC) in the following fields: <br />– Porous nanomaterials science and engineering (nanozeolites and thin films)<br />– In situ and operando molecular spectroscopy: EPR, NMR, FTIR<br />– Theoretical modelling approaches in chemistry<br />– Femtochemistry and transient UV-vis and IR spectroscopy

The project is based on specific skills of LASIR (ultrafast electronic and vibrational spectroscopies, pulsed and operando EPR, FT-IR spectroscopy), of LCS (synthesis, assembly and functionalization of microporous materials, colloïdal and thin film zeolites, opando and in situ FT-IR and NMR) and of MACS (modelling of meso-microporous systems, molecular dynamics and surface reactivity). It includes 3 tasks:
(i) Preparing and characterizing zeolite films functionalized by metallic copper NPs : synthesis will be optimized to obtain highly dispersed Cu NPs with homogeneous sizes limited by the zeolite pores diameter. Confined Cu NPs will be characterized by FT-IR and EPR, and experimental analyses will be compared to structural quantum calculations.
(ii) Studying the ultrafast photothermal dynamics: femtosecond transient UV-vis absorption spectroscopy will be used to determine the optical response of confined Cu NPs for various types and concentrations of target molecules and to understand the different relaxation routes. The transient signal will be modeled by quantum calculation to determine the evolution of the electronic states and the energy distribution of the NPs during the process. The energy transfer dynamics towards guest molecules will be followed by femtosecond IR spectroscopy. Complementary molecular modelling of the vibrational dynamics of confined molecules and of the energy transfer from the metal.
(iii) Determining reaction intermediates and products: the photothermally activated reactivity in the presence of H2O, CO or NO will be characterized by in situ and operando FT-IR, EPR, and NMR under light irradiation. Final products formation yields, interactions with the zeolite active sites, and NPs modifications will be drawn from these data.

Main key results obtained thus far:
1. Preparation of stable Cu NPs in zeolite suspensions.
2. Introduction of Cu in the framework position of LTL zeolite instead of Al.
3. Preparation of Cu-LTL films with high activity toward CO, NO, H2O.
4. Theoretical computation predicts that completely reduced copper clusters can be formed only under hydration.
5. For the first time, UV-Vis transient absorption measurements in zeolite films under controlled atmosphere have been performed.

Tasks progresses are in line with the initial forecasts.
Current and near futur investigations first focus on the elaboration of Cu NPs with higher Cu concentration for improved femtosecond transient absorption measurements. On the other hand, the photothermal intrazeolite dissociation of CO, CO2, H2O, CH3OH, and C2H5OH under light excitation of the Cu NPs, will be carried out.

published articles
1. Photoreduction of Ag+ by diethylaniline in colloidal zeolite nanocrystals, F. Luchez, Z. Tahri, V. De Waele, I. Yordanov, S. Mintova, A. Moissette, M. Mostafavi, O. Poizat, Microporous Mesoporous Materials, 194, 183-189 (2014).
2. Metal loaded zeolite films with bi-modal porosity for selective detection of carbon monoxide, L. Lakiss, S. Thomas, P. Bazin, V. de Waele, S. Mintova, Mesoporous Materials, 200, 326-333 (2014).
3. Luminescent Silver Clusters Stabilized in EMT Zeolite Suspensions, B. Dong, R. Retoux, V. de Waele, . G. Chiodo, T. Mineva, J. Cardin, S. Mintova, J. Phys. Chem. Submitted (2015)
4. Application of vibrational correlation formalism to internal conversion rate: case study of Cun (n=3, 6 and 9) and H2/Cu3, S.G. Chiodo and T. Mineva, J. Chem. Phys. 2015, 142, 114311.

The project TAR-G-ED is concerned with the photothermal metal-guest interactions and reactivity in confined space as a potential approach to drive thermally activated reactions in the micropores of zeolite films by selective energy deposition. More specifically, TAR-G-ED focuses on the photothermal chemistry of guests molecules (CO, NO, H2O, CH3OH, CH3CH2OH) of interest for environmental and green fuel chemistry, confined in the vicinity of sub-nm copper clusters stabilized within nanosized zeolites (EMT, FAU, LTL) assembled in films. Here, the term “photothermal” refers to the formation of a hot electron distribution in the metal following the absorption of photons in resonance with the metal plasmon band. The excess of energy, several electron-volts, initially concentrated in the electrons inside the conduction band is dissipated in the picosecond time scale via electron-phonon coupling and phonon-phonon coupling into the metal lattice and its surrounding media. The core-goal of the project is to investigate unusual effects resulting from the extremely small-size of the metal in combination with the confinement in the zeolite framework. It is notably important to distinguish the role of the direct coupling between the hot electrons and the vibronic molecular states, from the role of the energy exchange via the metal lattice – molecule interaction and determine the consequences on the reactivity of the hosted molecules. Toward this end, the objective of the project are: (i) the preparation and the exhaustive characterization of Cu-containing zeolite films with controlled porosity, morphology and metal dispersion, (ii) the elucidation of the ultrafast metal-guest reactivity, including the role of the zeolite framework and topology, and finally (iii) to benchmark the efficiency of the photothermally induced dissociation of CO, NO, H2O, CH3OH, and CH3CH2OH on copper-zeolite films. Ultimately, TAR-G-ED will provide the first evaluation of using the metal-containing zeolite films as efficient, selective and eco-friendly light-driven reactor compatible with solar energy application.

Project coordination

Olivier POIZAT (Laboratoire de Spectrochimie Infrarouge et Raman - Université Lille1 - CNRS)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

MACS Institute Charle Gerhardt Montpellier, Equipe Materiaux Avance pour la Catalyse et la Sante
LCS Laboratoire Catalyse & Spectrochimie (LCS) ENSICAEN - Université de Caen - CNRS
LASIR Laboratoire de Spectrochimie Infrarouge et Raman - Université Lille1 - CNRS

Help of the ANR 362,000 euros
Beginning and duration of the scientific project: December 2013 - 42 Months

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