A novel green process for the preparation of high MOF loading paper membrane
Résumé
Metal-Organic Frameworks (MOFs) have shown great potential reaching the industrialization stage. However, MOFs are obtained in loose powder form requiring a shaping method for their practical use. The ideal shaping of a material should involve a simple, fast and environmentally friendly process using low toxicity precursors and lead to a final functional product with the highest possible MOF content without changing the initial properties of the powder applicable to a wide range of MOFs. Porous membranes such as Mixed Matrix Membranes (MMMs) have gained attention due to their easy production by simply combining MOF particles into a polymeric matrix as well as their excellent mass transfer properties. Reaching a high MOF loading (>70wt%) to get higher efficiency (i.e. high permeability and selectivity) while maintaining sufficient mechanical stability remains very challenging. Polymer generally used (poly(vinylidene fluoride), poly(ethylene-co-vinyl acetate)) have drawbacks because they are oil-derived, poorly processable in water/alcohols and/or quite expensive [1]. Cellulose is alternatively proposed to replace these polymers to form a paper membrane. In the paper structure, the strength of the paper is highly dependent on inter-fibre interactions and therefore decreases with increasing filler content hindering the development of high-loading composites. To overcome this issue, we combined two cellulosic products with different dimensions and aspect ratio (Softwood bleached kraft pulp fibres (SBKP) and nano-fibrillated cellulose (NFC)) to prepare through a sustainable one-pot route high loading (>70wt%) MOF paper membranes with preserved adsorption properties while keeping good mechanical stability [2,3]. This process involves a rapid mixture, at room temperature in water, of the fibrous materials and the MOF, followed by a rapid filtering and drying step. This process was first demonstrated with the well-known MIL-100(Fe), an iron trimesate mesoporous MOF and optimized by playing with the particle size, the ratio between the fibres and the pH of the solution. It was then applied to other porous solids such as hydrophobic MOF, activated carbon and zeolite. This simple, scalable and versatile method enables to produce paper membranes applicable to a wide range of potential applications in thermochemical energy, water purification, gas separation and biomedicine among others.
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