Continuous flow synthesis of MOF UTSA-16(Zn), mixed-metal and magnetic composites for CO2 capture – toward scalable manufacture

Woodliffe, John Luke; Molinar-Díaz, Jesús; Clowes, Rob; Hussein, Oday H.; Lester, Ed; Ferrari, Rebecca; Ahmed, Ifty; Laybourn, Andrea

Abstract

UTSA-16(Zn) is a zinc and citrate-based metal-organic framework (MOF) which has shown highly promising performance for CO2 capture. However, the transition of this MOF to industrial application has been hindered as a scalable synthesis method has not yet been reported. Herein we report the first scalable continuous flow synthesis of UTSA-16(Zn), demonstrating a production rate of 173 g/h, which is a 77-fold increase compared to previously reported batch methods. Sustainability of the synthesis was maximised using low-cost non-toxic reagents and a low-energy flow reactor operating at atmospheric pressure. Chemical (reactant ratios, Zn/Mg mixed-metal) and process parameters (solvent ratio, flow rate, temperature) were optimised to continuously produce UTSA-16(Zn) which also demonstrated a high CO2 adsorption capacity up to 3.8 mmol/g and conversion yield of up to 66 %. Pristine MOFs are typically thermally insulating, thus thermal regeneration is challenging. To overcome this limitation, magnetic nanoparticles can be embedded within the MOF. This enables fast and energy efficient regeneration through magnetic induction heating. Here, citrate-coated Fe3O4 magnetic nanoparticles (MNP-CA) were successfully incorporated into the flow synthesis process of UTSA-16(Zn) to form UTSA-16(Zn)@MNP-CA magnetic framework composites (MFCs), representing the highest production rate reported of any MFC to date (152 g/h c.f. 13 g/h for MgFe2O4@UiO-66-NH2). UTSA-16(Zn)@MNP-CA MFCs demonstrate rapid heating under a magnetic field (26–150 °C in 60 s). The flow method developed herein is also widely applicable for scalable manufacture of other MOFs and MFCs, enabling their broader transition towards industrial applications.

Citation

Woodliffe, J. L., Molinar-Díaz, J., Clowes, R., Hussein, O. H., Lester, E., Ferrari, R., Ahmed, I., & Laybourn, A. (2024). Continuous flow synthesis of MOF UTSA-16(Zn), mixed-metal and magnetic composites for CO2 capture – toward scalable manufacture. Journal of Environmental Chemical Engineering, 12(6), Article 114167. https://doi.org/10.1016/j.jece.2024.114167

• Journal Article Type: Article
• Acceptance Date: Sep 16, 2024
• Online Publication Date: Sep 28, 2024
• Publication Date: 2024-12
• Deposit Date: Oct 1, 2024
• Publicly Available Date: Sep 29, 2025
• Journal: Journal of Environmental Chemical Engineering
• Print ISSN: 2213-2929
• Electronic ISSN: 2213-3437
• Publisher: Elsevier
• Peer Reviewed: Peer Reviewed
• Volume: 12
• Issue: 6
• Article Number: 114167
• DOI: https://doi.org/10.1016/j.jece.2024.114167
• Keywords: Metal-organic framework; Magnetic framework composite; Magnetic nanoparticles; Induction heating; Carbon capture; Adsorption
• Public URL: https://nottingham-repository.worktribe.com/output/40270455
• Publisher URL: https://www.sciencedirect.com/science/article/pii/S221334372402298X?via%3Dihub