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High-yield, green and scalable methods for producing MOF-303 for water harvesting from desert air

Nature Protocols volume 18, pages 136–156 (2023)Cite this article

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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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Fig. 1: Crystal structure of MOF-303 constructed from infinite [Al(OH)(–CO2)2]n rod SBUs stitched together by PZDC linking units.
Fig. 2: Various methods for the synthesis of MOF-303 along with the reaction time of each.
Fig. 3: Equipment setup for MOF-303 synthesis.
Fig. 4: A 3-kg-scale synthesis of MOF-303 in a 200 L reaction vessel.
Fig. 5: Purification of MOF-303 at 3 kg scale.
Fig. 6: PXRD patterns of MOF-303 synthesized by different methods.
Fig. 7: Solution-state 1H-NMR spectrum of the fully base-hydrolyzed MOF-303.
Fig. 8: TGA profile of MOF-303 synthesized by the vessel method measured under N2 flow.
Fig. 9: N2 sorption isotherms of MOF-303 samples measured at 77 K.
Fig. 10: Water vapor sorption isotherms of MOF-303 samples measured at 25 °C.
Fig. 11: Water vapor sorption isotherms of MOF-303-reflux samples with minor hysteresis and substantial hysteresis measured at 25 °C.
Fig. 12: SEM images of MOF-303.

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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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Authors and Affiliations

  1. Department of Chemistry, University of California, Berkeley, CA, USA

    Zhiling Zheng, Ha L. Nguyen, Nikita Hanikel, Kelvin Kam-Yun Li, Zihui Zhou, Tianqiong Ma & Omar M. Yaghi

  2. Kavli Energy Nanoscience Institute, University of California, Berkeley, CA, USA

    Zhiling Zheng, Ha L. Nguyen, Nikita Hanikel, Kelvin Kam-Yun Li, Zihui Zhou, Tianqiong Ma & Omar M. Yaghi

  3. Bakar Institute of Digital Materials for the Planet, Division of Computing, Data Science, and Society, University of California, Berkeley, CA, USA

    Zhiling Zheng & Omar M. Yaghi

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Contributions

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.

Corresponding author

Correspondence to Omar M. Yaghi.

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Competing interests

O.M.Y. is co-founder of Water Harvesting Inc., aiming at commercializing related technologies.

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Nature Protocols thanks Ruzhu Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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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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