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. 2026 Mar 12;4(9):1440–1446. doi: 10.1021/prechem.6c00010

Isoreticular Ni8‑Dipyrazolate Frameworks for Reversible Low-Humidity Water Vapor Sorption

Xiang-Jing Kong †, Tao He †,‡,*, Tang-Hao Liu †,‡, Ying-Jie Wang †,‡, You-Tuo Zhang †,‡, Jian-Rong Li †,‡,*
PMCID: PMC13625916  PMID: 42820056

Abstract

Water vapor sorption in metal–organic frameworks (MOFs) is governed by a delicate interplay between framework topology, pore dimension, and distribution of water-binding sites. Isoreticular MOFs provide a powerful platform to disentangle these factors, yet direct comparisons that isolate the role of the metal node remain rare. Herein, we report a systematic study of water vapor adsorption in a family of fcu-type Ni8-dipyrazolate frameworks, BUT-191–BUT-194 (BUT = Beijing University of Technology), constructed from a series of dipyrazolate ligands incorporating various heteroaromatic cores, including pyridyl, pyrimidyl, pyrazinyl, and pyridazinyl. All four Ni8 frameworks exhibit exceptional chemical stability under harsh aqueous conditions. Water vapor sorption measurements at 298 K reveal pronounced S-shaped isotherms with steep uptake below ∼32% relative humidity (RH), with a maximum water uptake of up to 0.59 g g–1. In contrast to previously reported isoreticular Co8-dipyrazolate frameworks, no detectable redox transformation of the metal node is observed in the Ni8 analogues during water sorption, enabling fully reversible adsorption–desorption behavior with excellent cycling stability. Particle size control experiments further reveal that hysteresis can be effectively suppressed without sacrificing the adsorption capacity, highlighting the role of mass transport in tuning water sorption reversibility. These findings provide fundamental insights into metal-node-dependent water sorption mechanisms in robust azolate MOFs, offering practical guidelines for the rational design of recyclable water vapor sorbents.

Keywords: metal−organic framework, reticular chemistry, pyrazolate, water vapor sorption, low-humidity

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graphic file with name pc6c00010_0006.webp

Introduction

Atmospheric water vapor plays a central role in a wide range of energy, chemical and environmental processes, including climate regulation, hydrological cycle, air purification, and corrosion control. − Porous materials capable of capturing water vapor efficiently at low relative humidity (RH) while maintaining long-term structural and chemical stability are therefore of considerable interest. − Among them, metal–organic frameworks (MOFs) have emerged as a versatile platform for water vapor sorption owing to their modular architechtures, tunable pore environments, and well-defined host–guest interactions. − In particular, MOFs featuring S-shaped water sorption isotherms with steep uptake at low RH are highly desirable, as they enable high working capacities within narrow humidity swings. −

Extensive studies have shown that water sorption in MOFs is governed by a subtle interplay between pore geometry, surface chemistry, and framework flexibility. − While early work has focused predominantly on carboxylate-based materials, azolate MOFsespecially those constructed from pyrazolate linkershave attracted increasing attention due to their exceptional framework robustness under hydrothermal, acidic, and alkaline conditions. − The characteristic strong M–N coordination and high-connectivity cluster nodes render them particularly well suited for repeated water adsorption–desorption cycling. Beyond pore chemistry, an emerging theme in water sorbents is the role of framework responsiveness. In some systems, water loading is accompanied by redox evolution or structural rearrangements at the metal nodes, which can alter adsorption thermodynamics, kinetics, and cycling behavior. − In parallel, a contrasting class of materials operates without such framework-level transformations, relying instead on cooperative host–guest interactions within chemically inert pore environments. Disentangling these distinct factors remains challenging, as differences in topology, pore size, or stability often obscure direct comparisons.

Isoreticular MOFs offer powerful platforms to address this challenge by enabling direct evaluation and comparison of adsorption behavior while minimizing structural variables. − Within such platforms, it is possible to distinguish adsorption processes that are coupled to framework or metal-node responses from those governed primarily by pore-wall chemistry and cooperativity. Establishing clear structure–property relationships across these regimes is essential for the rational design of water sorbents tailored to specific humidity ranges and operational requirements. Herein, we present a family of isoreticular fcu-type Ni8-dipyrazolate MOFs that exhibit efficient and reversible low-humidity water vapor adsorption. Unlike their Co8 counterparts with “breathing” nodes, these Ni8 frameworks adsorb water without a change in nickel oxidation state while maintaining high working capacities during cycling experiments (Figure ). This contrast delineates redox-active and redox-inert adsorption behaviors within otherwise isoreticular MOF platforms.

1.

1

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Schematic comparison of water vapor adsorption behavior in isoreticular fcu-type dipyrazolate frameworks based on Ni8 and Co8 clusters: (a) fcu network, (b) dipyrazolate framework, and water vapor adsorption behavior of (c) Co8 and (d) Ni8 dipyrazolate frameworks.

Results and Discussion

To directly interrogate distinct water vapor adsorption pathways within an isoreticular framework platform, we investigated a family of fcu-type dipyrazolate MOFs constructed from closely related linkers bearing different heteroaromatic cores, including 2,5-di­(1H-pyrazol-4-yl)­pyridine (1), 2,5-di­(1H-pyrazol-4-yl)­pyrazine (2), 3,6-di­(1H-pyrazol-4-yl)­pyridazine (3), and 2,5-di­(1H-pyrazol-4-yl)­pyrimidine (4) but with different octanuclear metal clusters. This system enables the isolation of the role of metal-node chemistry in water adsorption while minimizing variations in framework topology and pore geometry. In particular, redox-active Co8-based frameworks and their redox-inert Ni8 analogues provide a well-defined pair for examining adsorption behavior that is either coupled to metal-node oxidation state evolution or occurs within a chemically inert scaffold. Building on these frameworks, we focus here on a series of Ni8-dipyrazolate MOFs, which serve as a redox-inert reference system for low-humidity water vapor adsorption.

The dipyrazolate ligands 1–4 were synthesized following previously reported procedures (Figures S1–S4). A family of isoreticular fcu-type Ni8-dipyrazolate frameworks, BUT-191–BUT-194 (BUT = Beijing University of Technology), was synthesized via solvothermal reactions between dipyrazolate ligands (with various heteroaromatic cores, including pyridine for BUT-191, pyrazine for BUT-192, pyridazine for BUT-193, and pyrimidine for BUT-194) and nickel salts, affording high-quality octahedral single crystals suitable for structural analysis (Figures S5–S8). Single-crystal X-ray diffraction analysis was successfully performed on BUT-194 comprising the pyrimidyl-based ligand, which crystallizes in the cubic crystal system with space group Fm3̃m (Table S1). The structure contains 12-connected octanuclear Ni8-pyrazolate clusters bridged by linear dipyrazolate linkers, giving rise to a fcu topology (Figure a,d,e). This framework features two types of cages characteristic of the fcu net: smaller tetrahedral cages and larger octahedral cages (Figure b,c,f,g). These cages are interconnected through pore windows defined by the pyrazolate linkers, forming a spacious microporous architecture. The octahedral cages have an effective internal diameter of approximately 17.4 Å, while the tetrahedral cages exhibit a smaller cavity size of approximately 8.8 Å (values estimated from crystallographic analysis).

2.

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Design and structure of BUT-191–BUT-194: (a,d) dipyrazolate ligands and 12-connected [Ni8(μ4–OH)4(μ4–OH2)4(pz)12] clusters; (b) structure of BUT-194 with (c) octahedral and (g) tetrahedral cages; assembly between (e) linear linkers and icosahedral nodes forming a (f) fcu network.

Powder X-ray diffraction (PXRD) patterns of four Ni8-dipyrazolate frameworks (BUT-191–BUT-194) are in good agreement with that calculated from the single-crystal structure of BUT-194, confirming their isoreticular structure and phase purity (Figure a). The permanent porosity was evaluated by N2 adsorption–desorption measurements at 77 K. All four materials exhibit typical Type I isotherms, with N2 uptakes of 501, 508, 477, and 495 cm3 g–1 at 1 bar for BUT-191, BUT-192, BUT-193, and BUT-194, respectively (Figures S9–S12), confirming their microporous nature and full gas accessibility after activation. Correspondingly, the BET surface areas were determined to be 1440, 1459, 1362, and 1414 m2 g–1, consistent with the isoreticular fcu structure across the series. Pore size distribution analysis reveals two distinct micropores in each framework, centered at approximately 8.2 and 17.4 Å, which can be assigned to the tetrahedral and octahedral cages characteristic of the fcu network, respectively (Figure S13). These pore sizes also agree well with those estimated from single-crystal structural analysis, indicating that the crystallographically defined dual-cage pore architecture is retained in the activated materials.

3.

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PXRD patterns of (a) as-synthesized BUT-191 to 194 and (b) BUT-194 after different treatments.

In addition, the Ni8-dipyrazolate frameworks demonstrate excellent thermal and chemical stability. Thermogravimetric analysis reveals that the frameworks remain intact up to 623 K (350 °C) under an inert N2 atmosphere (Figures S14–S17). They can also retain their crystallinity after immersion in boiling water, acidic aqueous solution (pH = 3), and concentrated alkaline solution (4 M NaOH), as confirmed by PXRD measurements (Figure b and S18–S20). The preservation of the characteristic diffraction patterns after these treatments indicates framework integrity under harsh aqueous conditions.

Given the excellent structural stability of the Ni8-dipyrazolate frameworks, their water vapor sorption behavior was investigated and compared. Water vapor adsorption–desorption isotherms collected at 298 K reveal that all BUT-191–BUT-194 frameworks exhibit pronounced S-shaped profiles with steep uptake below approximately 32% relative humidity (RH) (Figure a,b and S21–S22). Despite differences in linker identification, the step pressure/inflection humidity of the isotherms (the RH corresponding to the end of the steep uptake region in the adsorption isotherm, determined from the maximum slope (d­(uptake)/dRHmax) of the adsorption branch), is observed at similar humidities across the heteroaromatic series, indicating a comparable onset of cooperative water adsorption. At 32% RH, BUT-191 exhibits a water uptake of 0.50 g g–1, while frameworks constructed from more nitrogen-rich heteroaromatic cores show progressively higher capacities of 0.57, 0.58, and 0.59 g g–1 for the pyrazinyl-(BUT-192), pyridazinyl-(BUT-193), and pyrimidyl-based (BUT-194) materials, respectively (Figure d).

4.

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Water vapor sorption isotherms of (a) BUT-191, (b) BUT-194, and (c) BUT-2 (Ni8–BDP) at 298 K. (d) Comparison of water uptake and step pressure at 298 K between BUT-2 and BUT-191–BUT-194.

To further contextualize this behavior, a benzene-based dipyrazolate Ni8 analogue (BUT-2, Ni8–BDP) was synthesized as a nonpolar reference (Figures S23–S25). In contrast to the heteroaromatic Ni8 frameworks, the benzene-based BUT-2 exhibits a substantially delayed adsorption step, which ends at a higher RH of 60% with a lower water uptake of 0.46 g g–1 (Figure c). These results indicate that the incorporation of heteroaromatic nitrogen-containing cores significantly enhances water affinity and advances the cooperative adsorption regime to lower humidity, while variations among the nitrogen-containing linkers primarily modulate the overall adsorption capacity rather than the inflection humidity.

To probe adsorption reversibility, dynamic water vapor sorption measurements were conducted on the pyrimidyl-based BUT-194 in the low-humidity regime (0–40% RH). Adsorption reaches the maximum uptake within 200 min, while desorption is completed within 213 min, indicating comparable kinetics for loading and release (Figure a). Cycling tests reveal negligible capacity loss over 30 adsorption–desorption cycles, with the maximum water uptake remaining close to 0.59 g g–1 throughout the experiments (Figure b). These results demonstrate excellent framework robustness and operational stability of BUT-194.

5.

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(a) Kinetics curve of BUT-194 for 0–40% RH humidity swing. (b) Water sorption cycling profile of BUT-194 between 0 and 40% RH. Structure of water-loaded BUT-194 showing the location of adsorbed water molecules in (c) octahedral and (d) tetrahedral cages.

The isoreticular Co8-dipyrazolate family was previously reported to exhibit a significant decrease (26%) in adsorption capacity due to air-induced metal oxidation from Co­(II) to Co­(III) and the resultant framework contraction during cycling water vapor sorption measurements. In this work, no evidence of nickel oxidation and framework transformation is observed for the Ni8 analogue BUT-194 during repeated water vapor adsorption–desorption cycling. Its water sorption isotherms remain fully reproducible over multiple cycles, with no detectable shift in the step pressure or loss of crystallinity. This indicates that water sorption proceeds without changes in the framework structure or pore environments. A direct comparison of the water uptake further reveals distinct sorption characteristics between these two systems. While the maximum water uptake of the Ni8 frameworks is slightly lower than that of the corresponding Co8 analogues, the Ni8 compounds demonstrate excellent cycling stability and maintain consistent adsorption capacity over repeated adsorption–desorption cycles. In contrast, the Co8 frameworks exhibit diminished adsorption capacity upon cycling, owing to oxidation-induced structural contraction. This comparison highlights that although redox activity in Co8 frameworks can initially enhance water affinity, the redox-inert Ni8 frameworks provide a steady adsorption capacity that exceeds that of the oxidized Co8 analogues under comparable conditions.

To gain structural insights into the water adsorption behavior, a single-crystal X-ray diffraction analysis was performed on the BUT-194 framework after water loading. The crystal structure remains intact upon water adsorption. The variations in crystallographic parameters upon water loading, including the cubic cell parameter (25.2480(13) to 25.2445(2) Å), unit cell volume (16095(2) to 16087.9(4) Å3), and Ni···Ni distance (2.9847(7) to 2.9723(7) Å) (Tables S1 and S2; Figure S26), all fall within experimental uncertainty. Such trivial differences provide no evidence of framework contraction, breathing behavior, or rearrangement of the Ni8 clusters, confirming that the overall framework architecture is preserved upon water adsorption. Structural analysis reveals that the water molecules reside in the channels and interact mainly with the linker backbones. Short contacts consistent with hydrogen-bonding interactions (with O–H···N and O–H···O distances in the range of 3.25–4.01 Å and 2.51–3.12 Å, respectively) form between water molecules and heteroaromatic nitrogen sites of the dipyrazolate ligands (Figure c,d and S27). No direct coordination between water molecules and the Ni8 clusters is observed. These crystallographic observations provide direct structural evidence that water adsorption in the Ni8 framework occurs predominantly within the pore cavities through host–guest interactions with the organic linkers, rather than through metal binding or framework rearrangement. This also accounts for the difference in water sorption isotherms between the two systems: direct metal binding to the Co8 cluster leads to higher hydrophilicity and thereby higher uptake at low RH, while the number and position of linker nitrogen sites alter the step pressure and adsorption capacity of the Ni8 frameworks.

The impact of particle size on water sorption behavior was further investigated. Powdered crystalline sample of BUT-194 was synthesized under acid-free conditions (Figures S28–S30). Compared to the crystal sample with a larger particle size, the water adsorption–desorption isotherm of the small-particle powder sample shows a markedly reduced hysteresis loop, indicating enhanced adsorption reversibility (Figure S31). In addition, the step pressure of the isotherm is shifted slightly to higher relative humidity, from approximately 32% RH to around 40% RH, while the overall water uptake remains largely unchanged. These observations suggest that reducing particle size alters the kinetics of water adsorption and desorption, affecting the location of hysteresis and the humidity range over which cooperative adsorption occurs without significantly impacting the equilibrium adsorption capacity. Such a particle-size modulation strategy therefore provides a practical approach to tuning water sorption reversibility and dynamics while preserving uptake capacity.

Conclusion

In summary, a family of isoreticular fcu-type Ni8-dipyrazolate frameworks exhibits efficient and reversible low-humidity water vapor sorption, with heteroaromatic linkers tuning the step pressure of water sorption isotherms and enhancing the adsorption capacity. Single-crystal analysis of the water-loaded structure reveals that water molecules are confined within the pore cavities and interact primarily with the hydrophilic organic linkers rather than the metal clusters. Compared to their Co8 analogues, neither metal-node redox transformation nor network breathing is observed in the Ni8 frameworks during water adsorption–desorption cycling, resulting in stable, reproducible water sorption performance. Furthermore, particle-size modulation enables tuning of the adsorption hysteresis and inflection humidity without significantly affecting equilibrium uptake. These results establish Ni8-dipyrazolate frameworks as a structurally and chemically robust platform for predictable water vapor sorption and clarify the metal-independent origins of water sorption behavior in azolate MOFs, providing practical guidelines for the rational design of advanced porous water sorbents.

Supplementary Material

pc6c00010_si_001.pdf (2.1MB, pdf)
pc6c00010_si_002.cif (298.8KB, cif)
pc6c00010_si_003.cif (159.6KB, cif)

Acknowledgments

J.R.L. acknowledges the National Natural Science Foundation of China (22225803) and Beijing Outstanding Young Scientist Program (JWZQ20240102008). T.H. acknowledges the National Natural Science Foundation of China (22401168), the Postdoctoral Fellowship Program of CPSF (GZC20250645), and the China Postdoctoral Science Foundation (2025M780887).

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/prechem.6c00010.

  • Detailed synthesis methods, physical measurements, and instrumentation; additional figures and tables (PDF)

  • X-ray data for BUT-194 (CCDC 2523415) (CIF)

  • X-ray data for BUT-194@H2O (CCDC 2523416) (CIF)

All authors have given approval to the final version of the manuscript.

The authors declare no competing financial interest.

Published as part of Precision Chemistry special issue “Precision Chemistry for MetalOrganic Frameworks (MOFs)”.

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Associated Data

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Supplementary Materials

pc6c00010_si_001.pdf (2.1MB, pdf)
pc6c00010_si_002.cif (298.8KB, cif)
pc6c00010_si_003.cif (159.6KB, cif)

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