DS03 - Stimuler le renouveau industriel

Metallic nanoclusters embedded in Nitride Nanolaminates for efficient gas separation membranes – MeNiNA

Metallic nanoclusters embedded in Nitride Nanolaminates for efficient gas separation membranes

Hydrogen represents a serious alternative clean energy carrier in the future. The separation and purification of H2 applying membrane processes is of great importance and new strategies for developing stable and selective membranes are required. This project proposes to develop novel nanocomposite membranes by atomic layer deposition, that combine both the stability of a nitride ceramic matrix and the selectivity of metals. This project therefore directly faces the environmental challenge.

Preparation of novel nanocomposite membranes that combine both the stability of a nitride ceramic matrix and the selectivity of metals used as nanofillers, using the atomic layer deposition technology

Over the next decades, the world population is expected to increase even more, resulting in a greater demand for (preferably clean) energy. A mix of both green fuels and efficient technologies will be required to meet this growing energy demand, while supporting the transition to a lower-carbon economy. Hydrogen has attracted a lot of attention in the recent years, as it represents a serious alternative clean energy carrier in the future. The separation and purification of H2 applying membrane processes is of great importance for the development of hydrogen technologies, and new strategies for developing stable and selective membranes are urgently required to provide an efficient alternative to classical palladium-based membrane systems (limited by high cost raw materials and surface poisoning issues).<br />This project proposes to develop an original approach for the preparation of novel nanocomposite membranes that combine both the stability of a nitride ceramic matrix and the selectivity of metals used as nanofillers. Atomic layer deposition (ALD), a scalable vapor phase deposition technology, will be used for the deposition of nitrides thin films and metal nanoclusters within ceramic membrane supports, ensuring a fine control over both film thickness and metal clusters sizes. Rapid Thermal Processing (RTP) will then be employed in order to stabilize and tune the properties of the prepared materials. The performance of all the synthesized membrane series will be investigated. This screening phase will permit the selection and development of the best membrane technology applicable to H2 separation and purification. Finally, the possibility to up-scale and industrialize the newly developed nanocomposites membranes will be assessed.

Atomic layer deposition (ALD) is a vapor phase deposition technique enabling the synthesis of ultrathin films of inorganic materials, with a subnanometer thickness control. ALD can be used to coat 3D substrates with a conformal and uniform layer of a high quality material; this is a unique capability amongst thin film deposition techniques. ALD is based on self-limiting reactions taking place at the surface of the substrate in a cycle-wise fashion. A typical ALD cycle consists of alternate pulses of a precursor and co-reactant gases in the reactor chamber, separated by purge steps. The properties of the synthetized nanostructures can be tuned by adjusting the process conditions – e.g. chemistry of the precursor(s) and co-reactants, deposition temperature, number of cycles, or nature of the substrate.
Herein, we propose an original strategy able to ensure both the deposition of ultra-thin nitride films on a porous ceramic support, and the loading of nitride films with Pd-based clusters in order to activate the membrane efficiency for H2 purification and/or hydrogenation reaction purposes. The embedded Pd clusters within high temperature resistant materials such as nitrides deposited on highly porous supports is expected to form the desired temperature resistant H2-selective membranes.
Rapid Thermal Processing (RTP) will be used to apply a fast and high temperature treatment to the prepared nanomaterials in order to either stabilize or adjust/modify their properties while minimizing the diffusivity issues of solid species. The high temperature treatment is expected to enhance the crystallinity of the deposited nitride matrix and metal clusters.

The first objectives of the project were to develop ALD processes for the synthesis of nitride films and palladium clusters with controllable properties. At IEM, a boron nitride process has been developed. This ALD process was based on the use of BBr3 and NH3 as precursors in order to synthesize BN thin films. The deposited films were smooth, presented a turbostratic microstructure and very low contamination level. The scalable synthesis of boron nitride nanotubes with tunable dimensions has been achieved using this novel process, and the assessment of their sorption properties showed that they absorb up to 110 times their own weight in oils while repelling water, which opens prospects for water purification. This proof-of-concept work led to a publication (Weber et al, Advanced Materials Interfaces 5 (16), 1800056 (2018)). At CiNaM, a process allowing for the synthesis of controlled TiN thin films has been developed as well. The preparation of palladium nanoparticles with tunable dimensions has been ensured as well, using Pd(hfac)2 as precursor and formalin as coreactant, and the process has been used to prepare Pd nanoparticles on BN surfaces. The physico-chemical characterization of the nanomaterials has been carried out, and annealing studies revealed that the Pd nanoparticles were coalescing at high temperature. This work has been done in collaboration between partner 1 (IEM) and 2 (CiNAM), and led to a publication (Weber et al., Nanomaterials 8, 10, 849 (2018)).
Rapid thermal annealing processing experiments (RTP) have been performed as well on multiple samples, using the set-up and facilities of Annealsys (partner 3). Samples from both partners 1 and 2 (IEM and CiNAM) have been thermally treated by partner 3 (Annealsys).

The focus will be on the physicochemical characterization of these membranes, coupled with a study of their performance for gas mixture separations, which will allow both understanding and mastering the formation mechanisms of optimized membranes applicable to H2 separation. In a broader context, the membranes could also be applied for other gaseous compounds separations (rare gases). The future prospects is to obtain membranes yielding high selectivities and permeabilities in the temperature range (50-600°C) and that could work up to 1000°C. Our objective is to separate H2 from other gases with flow rate >1 L/cm²·min–1. The permeated H2 should be very pure with a stream concentration at least 1000 times higher than that of other gases. Finally, an extension of this strategy to different nitrides and other metals (i.e. Ni, Co, bimetallic systems) will also be considered in order to find an alternative to the high cost and limited resource of Pd on earth. While the project aims to demonstrate the proof of concept of such original nanocomposite membranes, the feasibility of industrialization and the technology upscaling will be also evaluated.

Weber et al, Advanced Materials Interfaces 5 (16), 1800056 (2018)
Weber et al, ACS Applied materials & interfaces 10 (40), 34765-34773 (2018)
Weber et al, Chemistry of Materials 30 (21), 7368-7390 (2018)
Weber et al, Journal of Material Chemistry A, 7, 8107-8116 (2019)
Weber et al, Pure and Applied Chemistry, Accepted (2019). DOI: 10.1515/pac-2019-0109.

Weber et al, Journal of Applied Physics,126, 041101 (2019)
Weber et al, Applied Catalysis B: Environmental, just accepted

Over the next decades, the world population is expected to multiply more rapidly than ever before, resulting in greater demand for (preferably clean) energy. A mix of both green fuels and efficient technologies will be required to meet this growing energy demand, while supporting the transition to a lower-carbon economy.
Hydrogen has attracted a lot of attention in the recent years, as it represents a serious alternative clean energy carrier in the future. The separation and purification of H2 applying membrane processes is of great importance for the development of hydrogen technologies, and new strategies for developing stable and selective membranes are urgently required to provide an efficient alternative to classical palladium-based membrane systems (limited by high cost raw materials and surface poisoning issues).
This project proposes to develop an original approach for the preparation of novel nanocomposite membranes that combine both the stability of a nitride ceramic matrix and the selectivity of metals used as nanofillers. Atomic layer deposition (ALD), a scalable vapor phase deposition technology, will be used for the deposition of nitrides thin films and metal nanoclusters within ceramic membrane supports, ensuring a fine control over both film thickness and metal clusters sizes. Rapid Thermal Processing (RTP) will then be employed in order to stabilize and tune the properties of the prepared materials.
The performance of all the synthesized membrane series will be investigated. This screening phase will permit the selection and development of the best membrane technology applicable to H2 separation and purification. Finally, the possibility to up-scale and industrialize the newly developed nanocomposites membranes will be assessed.
This project, aiming to develop novel membranes for hydrogen technology, is therefore directly facing the environmental challenge, meanwhile helping establishing an industrial and sustainable competitiveness.

Project coordination

mikhael Bechelany (Institut Européen des Membranes)

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

CNRS DR12_CINAM Centre National de la Recherche Scientifique délégation Provence et Corse _ Centre Interdisciplinaire de Nanoscience de Marseille
ANNEALSYS
CNRS - IEMM Institut Européen des Membranes

Help of the ANR 440,456 euros
Beginning and duration of the scientific project: January 2018 - 48 Months

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