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Microporous water with high gas solubilities

Abstract

Liquids with permanent microporosity can absorb larger quantities of gas molecules than conventional solvents1, providing new opportunities for liquid-phase gas storage, transport and reactivity. Current approaches to designing porous liquids rely on sterically bulky solvent molecules or surface ligands and, thus, are not amenable to many important solvents, including water2,3,4. Here we report a generalizable thermodynamic strategy to preserve permanent microporosity and impart high gas solubilities to liquid water. Specifically, we show how the external and internal surface chemistry of microporous zeolite and metal–organic framework (MOF) nanocrystals can be tailored to promote the formation of stable dispersions in water while maintaining dry networks of micropores that are accessible to gas molecules. As a result of their permanent microporosity, these aqueous fluids can concentrate gases, including oxygen (O2) and carbon dioxide (CO2), to much higher densities than are found in typical aqueous environments. When these fluids are oxygenated, record-high capacities of O2 can be delivered to hypoxic red blood cells, highlighting one potential application of this new class of microporous liquids for physiological gas transport.

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Fig. 1: Creating aqueous fluids with permanent microporosity.
Fig. 2: Density measurements to evaluate the porosity of aqueous solutions.
Fig. 3: Equilibrium gas sorption isotherms and MD simulations.
Fig. 4: O2 release measurements in water and blood.

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Data availability

The main data supporting the findings of this study are available in the paper and its Supplementary Information. Further data are available from the corresponding author on request. Source data are provided with this paper.

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Acknowledgements

We thank A. Slavney for helpful discussions. This work was partially supported by the Arnold and Mabel Beckman Foundation through a Beckman Young Investigator grant (J.A.M.), by a DoD National Defense Science and Engineering Graduate (NDSEG) Fellowship (D.P.E.) and by a Department of Energy Computational Science Graduate Fellowship under grant DE-FG02-97ER25308 (M.B.W.). MOF synthesis and functionalization efforts were supported by the Office of Naval Research under award N00014-19-1-2148. Gas absorption and release experiments were supported under a Multidisciplinary University Research Initiative, sponsored by the Department of the Navy, Office of Naval Research, under grant N00014-20-1-2418. F.J.-A., B.Q. and M.O.d.l.C. thank the support of the Department of Energy, Office of Basic Energy Sciences under the contract DE-FG02-08ER46539 and the Sherman Fairchild Foundation. This work was performed in part at the Harvard University Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Coordinated Infrastructure Network (NNCI), which is supported by the National Science Foundation under NSF award no. ECCS-2025158.

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Authors and Affiliations

Authors

Contributions

D.P.E., M.B.W., J.C. and J.A.M. formulated the project. D.P.E., J.C., C.D., M.V.W. and R.S. synthesized the compounds. D.P.E. collected all electron microscopy images and D.P.E., J.C. and C.D. analysed all electron microscopy images. D.P.E. and M.V.W. collected the viscosity data. M.B.W. performed all density measurements. M.B.W. and J.C. collected and analysed all sorption data. D.P.E., M.B.W., J.C. and C.D. performed all oxygen-release experiments in water. D.P.E., Y.P. and B.D.P. performed all oxygen-release experiments in donated human blood. F.J.-A., B.Q. and M.O.d.l.C. designed, performed and analysed the MD simulations. D.P.E., M.B.W., J.C., C.D. and J.A.M. wrote the paper and all authors contributed to revising the paper.

Corresponding author

Correspondence to Jarad A. Mason.

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D.P.E., M.B.W., J.C., C.D. and J.A.M. are inventors on a patent application related to this work held and submitted by Harvard University.

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Extended data figures and tables

Extended Data Fig. 1 Density measurements.

Solution density (black circles) as a function of concentration and temperature for colloidal solutions of 90-nm silicalite-1 nanocrystals in water (ac), a colloidal solution of 90-nm silicalite-1 nanocrystals with 5 wt% dextrose in water (df), colloidal solutions of 90-nm silicalite-1 nanocrystals in ethanol (gi), colloidal solutions of zeolite LTL nanocrystals in water (jl), colloidal solutions of (mPEG)ZIF-8 nanocrystals in water (mo), a colloidal solution of (mPEG)ZIF-8 with 5 wt% dextrose in water (pr) and colloidal solutions of ZSM-5 nanocrystals (Si/Al = 64) in water (su). A gradient shows the possible range of theoretical densities for different degrees of pore filling, from air-filled (grey) to solvent-filled (blue or purple) micropores. Note that the maximum pore-filling density corresponds to the bulk solvent density, but the density of nanoconfined solvent is often lower than the bulk solvent density24.

Extended Data Fig. 2 Zeolite viscosity data.

Viscosity as a function of concentration for colloidal solutions of 193-nm ZSM-5 (Si to Al / ratio, SAR = 64) nanocrystals (a) and 90-nm silicalite-1 nanocrystals in water (b) using an electromagnetically spinning viscometer at a magnetic motor rotation speed of 1,000 rpm. The measurements were taken at 25 °C.

Extended Data Fig. 3 Surface area and pore-volume measurements.

a, N2 adsorption (closed circles) and desorption (open circles) isotherms at 77 K on a linear scale for as-synthesized ZIF-67, ZIF-8, zeolite LTL and silicalite-1. Calculated BET surface areas and pore volumes are listed in Supplementary Table 4. b, N2 adsorption (closed circles) and desorption (open circles) isotherms at 77 K on a logarithmic scale for as-synthesized ZIF-67, ZIF-8, zeolite LTL and silicalite-1. c, N2 adsorption (closed circles) and desorption (open circles) isotherms at 77 K on a linear scale for ZIF-8 nanocrystals before and after functionalization with mPEG, showing that covalent functionalization has minimal impact on the accessible surface area. d, N2 adsorption (closed circles) and desorption (open circles) isotherms at 77 K on a logarithmic scale for ZIF-8 nanocrystals before and after functionalization with mPEG, showing that covalent functionalization has minimal impact on the accessible surface area. e, N2 adsorption isotherms at 77 K for 60-nm silicalite-1 and ZSM-5 nanocrystals before dispersion in water. The micropore volume of 60-nm silicalite-1 calculated by the t-plot method (fit range 3.5–9.8 Å) is 0.16 ml g−1, which is consistent with the micropore volume of 90-nm silicalite-1 (Supplementary Table 4). The micropore volume calculated by the t-plot method (fit range 4.7–13 Å) of ZSM-5 is 0.17 ml g−1.

Extended Data Fig. 4 Solid-state isotherms.

O2 adsorption isotherms at 25 °C (a,b) and 37 °C (c,d) in the solid state are plotted on a gravimetric and volumetric basis. Volumetric values are calculated from gravimetric values using the crystallographic density. Consistent with the accessible surface area, covalent functionalization of ZIF-8 has a negligible impact on adsorption of O2, as demonstrated by comparing the isotherms for ZIF-8 and (mPEG)ZIF-8.

Extended Data Fig. 5 External surface area in the solid state.

Analysis of external surface area by the t-plot method using the Harkins and Jura thickness curve for 90-nm silicalite-1 nanocrystals (a), ZIF-8 nanocrystals (b), (mPEG)ZIF-8 (c) and ZIF-67 (d). Solid-state adsorption isotherms for 90-nm silicalite-1 nanocrystals before and after calcination, demonstrating the lack of accessible microporosity in non-calcined samples and the contribution of external surface area to adsorption in calcined silicalite-1. e, t-Plot analysis indicating that the total surface area of non-calcined silicalite-1 is consistent with the external surface area of calcined silicalite-1. Adsorption isotherms for O2 (f) and CO2 (g) are compared for calcined and non-calcined silicalite-1 nanocrystals at 25 °C.

Extended Data Fig. 6 Oxygen adsorption kinetics.

Oxygen adsorption kinetics of colloidal solutions of 13 vol% silicalite-1 (navy blue) (a), 1.5 vol% silicalite-1 (navy blue) (b), 3.8 vol% (mPEG)ZIF-8 (dark yellow) (c) and 3.8 vol% BSA/ZIF-67 (purple) (d) nanocrystals in water at 20 °C are monitored under 1 bar of flowing O2. Blank runs with pure water (blue) are included for comparison.

Extended Data Fig. 7 Silicalite-1 and ZIF-67 atomistic MD simulations.

The H2O (a) and O2 (b) densities inside a silicalite-1 nanocrystal filled with 2,270 mmol l−1 H2O molecules at t = 0. Note that, after addition of an initial 3,500 H2O molecules, the system was thermalized for 1 ns before beginning the production run shown above. This initial loading of 3,500 H2O molecules inside the nanocrystal corresponds to a starting H2O concentration of 8,600 mmol l−1. The thermodynamic driving force for water expulsion is so large that about 74% of the H2O molecules leave before starting the production run. The residual water at the end of the simulation represents less than 2% of the total micropore volume. Atomistic simulation of O2 adsorption inside ZIF-67 surrounded by liquid water is depicted in c, with snapshots of the simulation shown at 0 ns and 600 ns. ZIF-67 is coloured in black, O2 in red and OH in green. ZIF-67 hydrogen atoms are omitted for clarity. The simulation box is indicated by solid black lines. The equilibrium concentration profiles of O2 and water are shown in d, with the shadows representing the standard deviations from four blocks of 100-ns simulations. The relative densities in the gas phase, in the water phase and inside ZIF-67 support that the adsorption of water molecules by ZIF-67 is energetically unfavoured, whereas O2 adsorption is favoured. A simulation of the protein BSA adsorbing on the surface of ZIF-67 is illustrated in e. Water is represented as a semi-transparent volume in light blue. f, Calculation of the interaction energy between the protein and ZIF-67. The Coulomb and Lennard-Jones components of the interaction between ZIF-67 and BSA show that the Coulomb interactions dominate.

Extended Data Fig. 8 Colloidal stability.

DLS measurements of colloidal solutions of silicalite-1 (a), ZSM-5 (b), (mPEG)ZIF-8 (c) and BSA/ZIF-67 (d) nanocrystals in water before and after 1 week of stability testing. The starting solutions contained 11.5 vol% silicalite-1, 34.4 vol% ZSM-5, 8.3 vol% (mPEG)ZIF-8 and 3.4 vol% BSA/ZIF-67. The samples were diluted 70-fold (for silicalite-1), 230-fold (for ZSM-5) and tenfold (for (mPEG)ZIF-8) to obtain accurate DLS data. PXRD patterns before and after dispersion in H2O are shown for 98-nm silicalite-1 nanocrystals (11.5 vol%) (e), ZSM-5 (34.4 vol%) (f), (mPEG)ZIF-8 nanocrystals (8.3 vol%) (g) and BSA/ZIF-67 (3.4 vol%) (h). All samples were dispersed for 1 week before PXRD characterization apart from (mPEG)ZIF-8, which was taken after 2 weeks of dispersion.

Extended Data Fig. 9 SEM images.

Representative SEM images of nanocrystals used to form colloidal solutions in water: silicalite-1 (average diameter = 90 ± 16 nm) (a), silicalite-1 (average diameter = 59 ± 8 nm) (b), ZSM-5 (average diameter = 193 ± 32 nm) (c), zeolite LTL (d), (mPEG)ZIF-8 nanocrystals (average diameter = 113 ± 10 nm) (e), BSA/ZIF-67 nanocrystals (average diameter = 1,010 ± 185 nm) (f) and PEG/ZIF-67 (g). All samples were sputter coated with a 10-nm layer of 80:20 Pt:Pd except for b and d, which were sputter coated with a 5-nm layer.

Extended Data Table 1 Summary of O2-carrying capacities

Supplementary information

Supplementary Information

This file contains Supplementary Text, Supplementary Figs. 1–55, Supplementary Tables 1–56 and Supplementary References.

Supplementary Video 1

MD simulation of O2 adsorption and spontaneous dewetting of water-filled silicalite-1 nanocrystal immersed in a bulk water phase. The nanocrystal has roughly 3,500 H2O molecules inserted initially, 95% of which are ejected within 50 ns of the simulation. The pore architecture of the nanocrystal is shown by a red wireframe outline, and the bulk water phase is represented as a semi-transparent blue volume. Red spheres represent O atoms from O2 molecules and H3O+ ions, whereas white spheres represent H atoms from H3O+ ions.

Supplementary Video 2

MD simulation of a single BSA molecule binding to the surface of ZIF-67 from the bulk water phase. The ZIF-67 crystal is located at the bottom of the simulation box. The backbone of BSA is shown using a ribbon representation in purple. Red spheres denote oxygen atoms from O2 molecules and OH ions, whereas white spheres represent H atoms from OH ions. The bulk water phase is represented as a semi-transparent blue volume.

Supplementary Video 3

All-atom explicit solvent MD simulation (600 ns) of O2 adsorption into ZIF-67 surrounded by a bulk water phase. The ZIF-67 structure (represented by the black outline denoting the pore architecture) is surrounded by liquid water (represented by the semi-transparent grey phase). Red circles denote O2 molecules, whereas blue circles denote H2O molecules inside ZIF-67. Black solid lines denote the boundary of the simulation box.

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Erdosy, D.P., Wenny, M.B., Cho, J. et al. Microporous water with high gas solubilities. Nature 608, 712–718 (2022). https://doi.org/10.1038/s41586-022-05029-w

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