Abstract
Metal–organic frameworks (MOFs) are excellent candidates for water harvesting from desert air. MOF-303 (Al(OH)(PZDC), where PZDC is 1-H-pyrazole-3,5-dicarboxylate), a robust and water-stable MOF, is a particularly promising water-harvesting sorbent that can take up water at low relative humidity and release it under mild heating. Accordingly, development of a facile, high-yield synthesis method for its production at scale is highly desirable. Here we report detailed protocols for the green, water-based preparation of MOF-303 on both gram and kilogram scales. Specifically, four synthetic methods (solvothermal, reflux, vessel and microwave), involving different equipment requirements, are presented to guarantee general accessibility. Typically, the solvothermal method takes ~24 h to synthesize MOF-303, while the reflux and vessel methods can reduce the time to 4–8 h. With the microwave-assisted method, the reaction time can be further reduced to just 5 min. In addition, we provide guidance on the characterization of MOF-303, as well as water-harvesting MOFs in general, to ensure high quality of the product in terms of its purity, crystallinity, porosity and water uptake. Furthermore, to address the need for future commercialization of this material, we demonstrate that our protocol can be employed to produce 3.5 kg per batch with a yield of 91%. MOF-303 synthesized at this large scale shows similar crystallinity and water uptake capacity compared to the respective material produced at a small scale. Our synthetic procedure is green and water-based, and can produce the MOF within hours.
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Data availability
The raw data for water vapor sorption and nitrogen sorption are available at https://doi.org/10.6084/m9.figshare.19859002.v3.
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Acknowledgements
We acknowledge financial support from Defense Advanced Research Projects Agency (DARPA) under contract HR0011-21-C-0020. Any opinions, findings and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of DARPA. Helpful comments and suggestions on this work were provided by S. Cohen (DARPA) and D. Moore (GE). We thank E. Neumann from the Yaghi Group for useful suggestions regarding this manuscript. We acknowledge the College of Chemistry Nuclear Magnetic Resonance Facility for resource instruments, which are partially supported by NIH S10OD024998, and staff assistance from H. Celik and A. Lund. Z. Zheng thanks X. Han from the Yaghi Research Group for assisting in setting up the reactor. N.H. is thankful for financial support through a Kavli ENSI Philomathia Graduate Student Fellowship and a Blavatnik Innovation Fellowship.
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Z. Zheng, H.L.N., N.H. and O.M.Y. designed the experiments; Z. Zheng and N.H. performed the syntheses of MOF-303; Z. Zheng and H.L.N. designed the purification of MOF-303 and analyzed the collected data with guidance from O.M.Y.; Z. Zheng, H.L.N., K.K.-Y.L. and Z. Zhou performed the purification of kilogram-scale MOF-303. N.H. collected the water vapor isotherms of MOF-303 samples and interpreted the data; T.M. recorded SEM images for MOF-303 samples. All authors wrote the manuscript.
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O.M.Y. is co-founder of Water Harvesting Inc., aiming at commercializing related technologies.
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Key references using this protocol
Hanikel, N. et al. ACS Cent. Sci. 5, 1699–1706 (2019): https://doi.org/10.1021/acscentsci.9b00745
Hanikel, N. et al. Science 374, 454–459 (2021): https://doi.org/10.1126/science.abj0890
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Zheng, Z., Nguyen, H.L., Hanikel, N. et al. High-yield, green and scalable methods for producing MOF-303 for water harvesting from desert air. Nat Protoc 18, 136–156 (2023). https://doi.org/10.1038/s41596-022-00756-w
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DOI: https://doi.org/10.1038/s41596-022-00756-w
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