Han, Bo , Ng, Mai Sheng , Chakraborty, Anutosh
2025-10-01 CHEMICAL ENGINEERING JOURNAL 2025 521(卷), null(期), (null页)
Water scarcity poses an urgent global challenge, particularly in arid and semi-arid regions, necessitating innovative and sustainable water-sourcing technologies. Adsorption-based atmospheric water harvesting (AWH) using metal-organic frameworks (MOFs) has garnered growing attention due to their high-water uptake, tunable hydrophilicity, and structural versatility. However, the vast chemical space of MOFs complicates the selection of optimal materials. To address this, we first performed a comprehensive literature screening of over 100 MOFs based on two key criteria-low isosteric heat of adsorption (Qst) and fast water sorption kinetics-to identify promising candidates with high cycling efficiency and low energy demand. This screening guided the selection of seven representative pristine MOFs: MIL-53 (Al), MIL-101 (Cr), MIL-125 (Ti), MOF-199 (Cu), MOF-801 (Zr), UiO-66 (Zr), and aluminum fumarate (Al-Fum). These MOFs, with diverse metal centers and structural motifs, were systematically compared based on their intrinsic water adsorption behaviors. To enhance their performance, we applied five rational design strategies-functionalization, ligand extension, protonation, hybridization, and ion doping-resulting in over thirty modified derivatives with tailored pore chemistry, hydrophilicity, and kinetic profiles. A distinguishing feature of this work is the detailed analysis of water sorption kinetics, a crucial yet often neglected factor in realistic AWH deployment. Furthermore, a thermodynamic model was developed to assess material feasibility under varying climatic conditions. Finally, case studies across arid, semi-arid, and humid regions demonstrate how environmental humidity can inform material choice and system optimization. This work delivers a unified framework for the design, evaluation, and deployment of MOFs for water harvesting, offering both fundamental insights and practical pathways to mitigate water scarcity.