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Article

High-Pressure Intrusion of Saline Solutions in Hydrophobic STT-Type Zeosil

by
Yacine-Malik Chaib-Draa
1,2,
Amir Astafan
1,2,
Gérald Chaplais
1,2,
Habiba Nouali
1,2,
Séverinne Rigolet
1,2 and
Andrey Ryzhikov
1,2,*
1
Axe Matériaux à Porosité Contrôlée (MPC), UMR 7361 CNRS, Institut de Science des Matériaux de Mulhouse (IS2M), Université de Haute-Alsace, F-68100 Mulhouse, France
2
Université de Strasbourg, F-67000 Strasbourg, France
*
Author to whom correspondence should be addressed.
Inorganics 2025, 13(11), 371; https://doi.org/10.3390/inorganics13110371
Submission received: 17 September 2025 / Revised: 26 October 2025 / Accepted: 3 November 2025 / Published: 6 November 2025
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Abstract

High-pressure intrusion of water and LiCl aqueous solutions at different concentrations in hydrophobic STT-type zeosil was studied for possible applications in absorption and storage of mechanical energy. The water is intruded at a pressure of 35 MPa and remains trapped in the pores after pressure release, which corresponds to bumper behavior with total energy absorption. The use of LiCl solution leads to a change in system behavior, regardless of the concentration investigated (10, 15, or 20 M). Its intrusion is mainly reversible, but a small part of the intruded liquid remains in the pores after the first intrusion–extrusion cycle, which corresponds to a mixed behavior of bumper and shock absorber. The intrusion pressure rises strongly with an increase in salt concentration and reaches 227 MPa for a LiCl 20 M solution; the stored energy of 27 J/g can be achieved. The characterization of STT-type zeosil before and after intrusion–extrusion tests by structural and physicochemical methods shows that silanol defects are formed both under the intrusion of water and LiCl solutions. The relationship between zeosil structure and intrusion–extrusion characteristics is discussed by comparing the results obtained with those of other structural types of zeosils.

1. Introduction

Intrusion of non-wetting liquids into porous solids occurs at a pressure higher than the capillary pressure. This process can be used for absorption and storage of mechanical energy, which was demonstrated in the works of Ukrainian physicist V. Eroshenko for the first time in the 1980s [1,2]. During the intrusion, the liquid is transformed into molecular clusters and chains inside the pores, and the supplied mechanical energy is converted to the breaking of liquid intermolecular bonds and to the energy of the solid–liquid interface. Upon release of the applied pressure, an expulsion of the liquid from the pores (extrusion) may occur or not; thus, the mechanical energy is either restored or absorbed, respectively. Depending on the nature of the porous solid and non-wetting liquid, the system “porous solid—non-wetting liquid” is able to restore, dissipate, or absorb supplied mechanical energy, which corresponds to a spring, shock absorber, or bumper behavior, respectively [3,4].
Firstly, the intrusion of liquid metals into the porous silica was used; later, water was found as an environmentally friendly, light, and cheap non-wetting liquid for intrusion–extrusion into hydrophobic porous solids. Since then, high-pressure intrusion of water has been studied in various hydrophobic meso- and microporous solids such as functionalized mesoporous silicas [5,6,7,8,9,10,11,12], high and pure silica zeolites [13,14,15,16,17,18,19,20,21], and Zeolitic Imidazolate Frameworks (ZIFs) [22,23,24,25,26], where a pressure of up to 210 MPa was achieved. Later, it was found that the use of aqueous salt solutions allows for a considerable increase in intrusion pressure. This effect is strongly pronounced for pure silica zeolites (zeosils), highly hydrophobic crystalline microporous solids with a framework built from tetrahedra SiO4. The intrusion of salt solutions into several zeosils of different structures has been studied [27,28,29,30,31,32,33,34,35,36,37,38]. It was found that the intrusion rises with salt concentration, and the amplitude of this increase varies for the zeosils of different structures. The pressure rise is higher for the zeosils with small pore openings. The highest increase by 7.4 times compared to the intrusion of water, was observed for LTA-type zeosil with small eight-member-ring (8 MR) pore openings [31], whereas for large pore zeolites with 12 or 14 MR pore openings it is less pronounced, the pressures rises generally by 2–3 times [34,38]. The impact of silanol defects on intrusion pressure and its dependence on electrolyte concentration has also been observed [38]. Moreover, in the case of several zeosils showing irreversible water intrusion, the intrusion becomes reversible when lithium chloride concentrated aqueous solutions are intruded. This phenomenon is not entirely understood, but it is related to a lower formation of hydrophilic silanol defects compared to water intrusion [30,31] or with weaker interactions of intruded hydrated ions with silanol groups already present in the framework [33,34]. In spite of previous results, more pure silica zeolites of different structure should be studied in order to better understand the influence of framework parameters on intrusion–extrusion characteristics of “zeosil—aqueous salt solution” systems. STT-type zeosil (SSZ-23) has a bidimensional porous system consisting of cages connected by unusual 7 and 9 MR pore openings with dimensions of 2.4 × 3.5 Å and 3.7 × 5.3 Å, respectively. This zeosil has been previously studied for water intrusion [39], but never before for electrolyte solutions. In this work, we present experimental results regarding high-pressure intrusion of LiCl solutions in STT-type zeosil.

2. Results and Discussion

2.1. Intrusion–Extrusion Experiments

Intrusion–extrusion experiments in STT-type zeosil have been performed with water and LiCl aqueous solutions of different concentrations up to the saturated one (10, 15, and 20 M). The intrusion–extrusion curves (P–V diagrams) are presented in Figure 1, where the intrusion–extrusion curves are shifted along the Y axis for better visibility (by 0.1 cm3/g for H2O, then 0.3, 0.6, and 0.9 cm3/g for LiCl solutions of different concentrations). The corresponding intrusion–extrusion characteristics are reported in Table 1. The intrusion of water occurs at a pressure of 35 MPa. The process is irreversible; no extrusion is observed under pressure decrease. Thus, the water remains trapped in the pores, which corresponds to bumper behavior. This result is different from the previous study on water intrusion in these materials [39], where the intrusion was reversible, but the pressure remains similar (34–40 MPa). The intruded volume is 0.10 cm3/g. The intrusion becomes mostly reversible with salt solutions, and a strong increase in intrusion pressure is also observed. The pressure rises to 154 MPa with a LiCl 10 M solution in the first intrusion–extrusion cycle, with the intruded volume of 0.09 cm3/g. Most of the liquid (0.08 cm3/g) is extruded at 95 MPa, whereas a smaller part (~0.01 cm3/g) remains in the pores. In the following cycles, the intrusion pressure decreases to 112 MPa, and the curves become more spread. The difference between the first and the following intrusions might be related to the formation of silanol defects or to the intruded ions remaining in the pores, which impact the interactions with solution species. A similar trend is observed with the use of solutions of 15 and 20 M. The intrusion pressure in the first cycle increases to 191 (15 M) and 227 MPa (20 M). In the following cycles, the intrusion becomes very broad, continuous, with no pronounced slope. The average values of intrusion pressure are 131 and 166 MPa, for 15 and 20 M LiCl solutions, respectively. A small volume of solution (~0.02 cm3/g) remains in the pores after the first intrusion, but the intrusion is entirely reversible in the following cycles. The extrusion curves are also very broad with the corresponding pressures of 114 and 136 MPa, for 15 and 20 M solutions, respectively. The intrusion volume increases for the most concentrated solution (20 M) up to 0.14 cm3/g; this effect has already been observed previously [38]. It can be related to better filling of the zeolite porosity by LiCl solution species in comparison with water, or their more compact organization inside the pores. The extruded volume follows the same trend. Thus, demonstrating bumper behavior for H2O, the systems using LiCl solutions show a combination of shock-absorber and bumper behavior in the first cycle and shock-absorber behavior in the following cycles.
Such a difference in the behavior between water and aqueous salt solutions was previously observed for several other zeolites. A similar increase in intrusion reversibility with highly concentrated LiCl solutions has been observed for *BEA- [30], BEC- [36], ITH- [37] and LTA-type zeosils [31], and in less pronounced form for the CHA- [33] and STF-type [35] ones. Two main phenomena can explain this effect. Firstly, lower formation of silanol defects under the intrusion of concentrated electrolyte solutions in comparison with water is observed for some zeosils [30,31]. This can be related to the absence of free water molecules, all of which are included in solvation shells of salt ions, which decreases their reactivity towards the zeosil framework. Secondly, the interactions of intruded hydrated ions with silanol defects in the framework are probably weaker than those of free water molecules; thus, the intruded species do not remain inside the pores when the pressure decreases [33,35,36,37].
For a LiCl 20 M solution, the pressure rises from 35 (water) to 227 MPa (LiCl 20 M). The rise in intrusion pressure should be mainly caused by osmotic phenomena related to desolvation of hydrated ions. It should be noted that the issue of the intruded species’ nature for aqueous salt solutions is not sufficiently understood. The intruded species can be water molecules or hydrated salt ions. In the first case, energy is required to liberate water molecules from the ions’ hydration shells and intrude them into the micropores; in the second case, the ions are distorted or partially dehydrated. A simulation of aqueous solutions’ intrusion into hydrophobic micropores by MD and MC shows that the ions do not enter hydrophobic micropores of zeosils and ZIFs [40]. Nevertheless, a number of experimental studies demonstrate that, at least in certain cases, particularly for highly concentrated solutions, the intruded species are not water molecules, but hydrated ions. For example, in situ high-pressure XRD demonstrated that the intruded species in CHA-, FER-, and LTA-type zeosils are partially dehydrated ions [41]. A change in behavior when using salt solutions compared to water observed in many works, including this one, is also a sign that the intruded liquid is not only water molecules, but also hydrated ions [30,31,38].
The pressure rises by 6.5 times compared to water (from 35 to 227 MPa). This relative rise is one of the highest among all the zeosils studied [38]; however, it is quite typical for the zeosils with cage-type pores and narrow pore openings. The rise is close to the ones obtained for CHA- (5.6 times), DDR- (6.0), and LTA-type (7.4) zeosils having similar porosity (cages with 8 MR pore openings) [38]. STT-type zeosil also has a cage pore system with 7 and 9 MR openings. Thus, it can be supposed that a smaller pore sizes require higher pressure to intrude hydrated ions into the pores, which corresponds to a higher pressure increase. For the most concentrated solution (20 M), the stored energy (Es = Pint × Vint) of the intrusion in STT-type zeosil attains ~32 J per gram of zeolite. It should be noted that this value is one of the highest among all zeolites studied.
In order to study the stability of STT-type zeosil under intrusion–extrusion experiments and the formation of silanol groups, the samples were investigated by structural, textural, and physicochemical characterization techniques.

2.2. Characterization

The patterns of X-ray diffraction of samples before and after intrusion–extrusion experiments performed over three cycles until 400 MPa are shown in Figure 2. They confirm the presence of STT-type zeolite phase with no impurity before and after intrusion–extrusion tests, and that there is no significant variation in crystalline structure after intrusion–extrusion experiments.
Nitrogen adsorption–desorption isotherms of the samples as-synthesized and after intrusion–extrusion tests are depicted in Figure 3. The corresponding values of the BET specific surface (SBET) area and microporous volumes (Vmicro) are reported in Table 2. All the isotherms are of type I characteristic of microporous solids. STT-type-zeosil before intrusion shows the BET surface area of 536 m2/g and microporous volume of 0.21 cm3/g. After intrusion of water, the textural properties of post-intruded material decrease slightly, to 533 m2/g and 0.20 cm3/g. The intrusion–extrusion of LiCl aqueous solutions leads to a considerable decrease in specific surface area (253–355 m2/g) and microporous volume (0.10–0.15 cm3/g). No significant difference in structural properties was observed after intrusion–extrusion tests. Consequently, it can be supposed that this decrease is related to the presence of LiCl species remaining inside the pores and to the formation of silanol defects.
The intruded volume of water and LiCl aqueous solutions (0.09–0.14 cm3/g) is considerably lower than the pore volume of STT-type zeosil. However, this is consistent with previous results obtained on different zeosils and with the simulations of Desbiens et al. [42] and Bushuev et al. [43], where a lower density of intruded water was demonstrated.
The results of thermogravimetric (TG) analysis of STT-type zeosil samples before and after intrusion–extrusion experiments are shown in Figure 4. The total weight loss is 0.8 wt. % for the nonintruded sample between 30° and 800 °C which confirms hydrophobic nature of STT-type zeosil. It increases slightly for the intruded sample, up to 1.0 wt. %, then the increase continues with LiCl concentration—1.2, 1.3, and 1.8 wt. % for the ones with 10, 15, and 20 M solutions, respectively.
Two main weight loss steps are observed. The first one at low temperature (<150 °C) is related to the desorption of weakly adsorbed water molecules, and the second one, in the range of 300–500 °C, can be ascribed to the dehydroxylation reactions of silanol groups. The main difference between the TG curves is observed in the first weight loss, but there is no significant difference at higher temperatures. This can be related to additional water adsorption on the LiCl species that remained after intrusion.
The samples of STT-type zeosil before and after intrusion–extrusion of water and LiCl 20 M solution were also characterized by 29Si MAS NMR. The corresponding spectra are presented in Figure 5. They exhibit ten visible resonances situated between −116.4 and −118.2 ppm corresponding to Q4 groups (Si-(OSi)4), which can be assigned to sixteen non-equivalent crystallographic sites of STT-zeosil framework [44]. The resonances become larger for the intruded samples, which shows a small structure deformation after intrusion–extrusion tests. A small broad resonance with two pronounced peaks in the case of intruded samples is also detected between −98 and −104 ppm and can be attributed to Q3 groups (HO-Si-(OSi)3 or -O-Si-(OSi)3). It corresponds to ~3% of the total 29Si signal for the non-intruded sample and to ~9% for both intruded ones. The increase in Q3 groups’ content indicates the creation of defect sites after the intrusion of water and LiCl 20 M solution—approximately from 2 to 6 OH groups per unit cell. Nevertheless, this cannot explain the difference between the reversibility of intrusion with water and LiCl 20 M solution since both samples demonstrate the same content of silanol defects.
Thus, taking into account a similar number of silanol groups after the intrusion of water and LiCl aqueous solutions, it can be supposed that the higher reversibility of LiCl solutions intrusion is explained by weaker interactions of intruded species with silanol defects of the framework. Since the behavior is different for water and LiCl aqueous solutions, it can be supposed that the nature of intruded species is not the same—water molecules in the first case and hydrated ions, despite simulation works showing impossibility of ions intrusion [40]. Such a change in system behavior observed in many experimental works is difficult to explain in any other way [30,31,35,36,37,38]. Moreover, the penetration of solvated ions in the pores after partial dehydration was demonstrated by in situ high-pressure X-ray powder diffraction (HP XRPD) studies on several “zeosil–salt aqueous solution” systems [41]. It can be supposed that the hydrated ions are intruded into the pores of STT-type zeosil and that their interactions with zeosil framework and silanol defects are weaker than those of free water molecules. Thus, the intruded species are expelled more easily from the pores than in the case of pure water when the pressure is released.

3. Materials and Methods

STT-type zeosil was synthesized using fluoride ion as mineralizing agent (F− medium) according to the procedure published by Camblor et al. [44] using trimethyladamantammonium hydroxide (TMAdaOH) as structure-directing agent (SDA). The molar composition of the synthesis gel was as follows: 1 SiO2:0.5 TMAdaOH:0.5 HF:10 H2O. Tetraethylorthosilicate (Sigma-Aldrich, Burlington, MA, USA), used as a silica source, was added to aqueous TMAdaOH solution (Sachem, Austin, TX, USA). After completing TEOS hydrolysis and complete evaporation of formed ethanol and water excess over 24 h under stirring under open air, hydrofluoric acid (HF ≥ 40 wt.%, Sigma-Aldrich) was added to the gel. The mixture was then stirred, introduced into a Teflon-lined stainless-steel autoclave, and heated at 150 °C for 15 days. After the synthesis, the product was filtered, washed with distilled water and ethanol, then dried in an oven at 70 °C overnight and calcined at 500 °C in air for 6 h to remove the organic SDA.
The intrusion–extrusion of water and LiCl aqueous solutions of high concentration (10, 15, and 20 M—the saturated one) in STT-type zeosil was performed at ambient temperature using a Micromeritics mercury porosimeter (Model Autopore IV), as described in a previous work [32].
X-ray diffraction patterns were collected on a PANalytical MPD X’Pert Pro diffractometer (Malvern Panalytical, Alvelo, The Netherlands) operating with Cu Kα radiation equipped with an X’Celerator detector at ambient temperature.
Nitrogen adsorption−desorption isotherms were performed at 77 K using a Micromeritics ASAP 2420 apparatus (Micromeritics, Norcross, GA, USA). Before the measurements, the samples were outgassed at 90 °C overnight to eliminate physisorbed water, but not to impact the presence of silanol groups. The specific surface area and microporous volume were calculated using the BET and t-plot methods, respectively.
Thermogravimetric (TG) analyses were performed using a Mettler Toledo STARe apparatus (Mettler Toledo, Greifensee, Switzerland), under airflow, at a heating rate of 5 °C/min in the range from 30 to 700 °C.
1H decoupled 29Si MAS NMR spectra (Magic Angle Spinning) were recorded at room temperature with a double-channel 7 mm Bruker MAS probe on a Bruker Avance NEO 300 WB spectrometer (Bruker, Billerica, MA, USA) (B0 = 9.4 T) operating at B0 = 7.1 T giving Larmor frequencies of 59.61 MHz for 29Si and 300.08 MHz for 1H, with a silicon π/6-pulse duration of 1.87 μs, a recycle delay of 80 s and a 1H high-power decoupling at 67 kHz. The spinning frequency was set at 4 kHz, and 29Si chemical shifts were reported relative to external tetramethylsilane (TMS).

4. Conclusions

High-pressure intrusion–extrusion of water and LiCl aqueous solutions (10, 15, and 20 M) has been studied for STT-type zeosil, which has a bidimensional pore system consisting of cages connected by seven- and nine-member-ring (MR) pore openings. Such a structure has not been studied yet for salt solutions intrusion under high pressure. A change in the behavior of STT-type zeosil-based systems, using LiCl solutions instead of water, has been observed. The intrusion of water in the zeosil is irreversible; the liquid remains in the pores, which corresponds to bumper behavior, whereas “STT-type zeosil—LiCl solution” systems demonstrate a combination of bumper and shock-absorber behavior with mostly reversible intrusion. Nevertheless, the characterization of zeosil samples before and after intrusion–extrusion experiments with water and LiCl solutions has not shown a significant difference in the formation of silanol defects in the zeosil framework between water and LiCl solutions. Thus, the change in behavior can be explained by weaker interactions of intruded hydrated ions with silanol groups in comparison with water molecules. A strong rise in intrusion pressure with salt concentration has been found—from 35 to 227 MPa for water and LiCl 20 M solution, respectively. This increase in intrusion pressure by 6.5 times is one of the highest among all the zeosils studied, which is quite typical for the zeosils with small pore openings. “STT-type zeosil—LiCl 20 M solution” system attains the stored energy value of 32 J/g.

Author Contributions

Conceptualization, A.R., G.C. and H.N.; Methodology, A.R., G.C. and H.N.; Investigation, Y.-M.C.-D., A.A. and S.R.; Data Curation, Y.-M.C.-D., A.A. and S.R.; Writing—Original Draft Preparation, A.R.; Writing—Review and Editing, A.R., G.C., S.R. and H.N.; Supervision, A.R. and G.C.; Project Administration, A.R.; Funding Acquisition, A.R. All authors have read and agreed to the published version of the manuscript.

Funding

The authors thank the French National Research Agency (ANR) for its financial support of the MESAMM project (ANR-19-CE05-0031).

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The original contributions presented in this study are included in the article. Further inquiries can be directed to the corresponding author.

Conflicts of Interest

The authors declare no conflicts of interest.

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Inorganics 13 00371 g001
Figure 1. The first and the second intrusion–extrusion cycles of water and LiCl aqueous solutions (10, 15, and 20 M) in STT-type zeosil. For clarity, the intrusion–extrusion isotherms are shifted along the Y axis.
Figure 1. The first and the second intrusion–extrusion cycles of water and LiCl aqueous solutions (10, 15, and 20 M) in STT-type zeosil. For clarity, the intrusion–extrusion isotherms are shifted along the Y axis.
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Inorganics 13 00371 g002
Figure 2. XRD patterns of STT-type zeosil samples before and after intrusion–extrusion tests with water, LiCl 10, 15, and 20 M aqueous solutions.
Figure 2. XRD patterns of STT-type zeosil samples before and after intrusion–extrusion tests with water, LiCl 10, 15, and 20 M aqueous solutions.
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Inorganics 13 00371 g003
Figure 3. N2 adsorption–desorption isotherms at 77 K of STT-type zeosil samples before and after intrusion–extrusion tests with water and LiCl solutions.
Figure 3. N2 adsorption–desorption isotherms at 77 K of STT-type zeosil samples before and after intrusion–extrusion tests with water and LiCl solutions.
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Inorganics 13 00371 g004
Figure 4. TG curves of STT-type zeosil samples before and after intrusion–extrusion tests with water and LiCl solutions.
Figure 4. TG curves of STT-type zeosil samples before and after intrusion–extrusion tests with water and LiCl solutions.
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Inorganics 13 00371 g005
Figure 5. 29Si-MAS NMR spectra of STT-type zeosil samples before and after intrusion–extrusion tests with water and LiCl 20 M solution.
Figure 5. 29Si-MAS NMR spectra of STT-type zeosil samples before and after intrusion–extrusion tests with water and LiCl 20 M solution.
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Table 1. Characteristics of intrusion–extrusion of water and LiCl solutions in STT-type zeosil: Intrusion (Pint) and Extrusion (Pext) Pressure, Intruded (Vint), Extruded (Vext) Volume, and System behavior.
Table 1. Characteristics of intrusion–extrusion of water and LiCl solutions in STT-type zeosil: Intrusion (Pint) and Extrusion (Pext) Pressure, Intruded (Vint), Extruded (Vext) Volume, and System behavior.
System STT+Pint (MPa)Pext (MPa)Vint (mL/g)Vext (mL/g)Behavior
H2O35-0.10-B
10 M LiCl154 a/112 b95 a/95 b0.09 a/0.08 b0.08SA+B a/S b
15 M LiCl191 a/131 b114 a/114 b0.10 a/0.08 b0.09SA+B a/S b
20 M LiCl227 a/166 b136 a/133 b0.14 a/0.12 b0.12SA+B a/A b
a First intrusion–extrusion cycle, b Second and third intrusion–extrusion cycles.
Table 2. Textural characteristics of STT-type zeosil samples before and after intrusion–extrusion tests: micropore volume (Vmicro) and specific surface area (SBET).
Table 2. Textural characteristics of STT-type zeosil samples before and after intrusion–extrusion tests: micropore volume (Vmicro) and specific surface area (SBET).
SampleVmicro (cm3/g)SBET (m2/g)
STT before intrusion0.21536
STT H2O (0 M)0.20533
STT—LiCl 10 M0.15355
STT—LiCl 15 M0.13317
STT—LiCl 20 M0.10253
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MDPI and ACS Style

Chaib-Draa, Y.-M.; Astafan, A.; Chaplais, G.; Nouali, H.; Rigolet, S.; Ryzhikov, A. High-Pressure Intrusion of Saline Solutions in Hydrophobic STT-Type Zeosil. Inorganics 2025, 13, 371. https://doi.org/10.3390/inorganics13110371

AMA Style

Chaib-Draa Y-M, Astafan A, Chaplais G, Nouali H, Rigolet S, Ryzhikov A. High-Pressure Intrusion of Saline Solutions in Hydrophobic STT-Type Zeosil. Inorganics. 2025; 13(11):371. https://doi.org/10.3390/inorganics13110371

Chicago/Turabian Style

Chaib-Draa, Yacine-Malik, Amir Astafan, Gérald Chaplais, Habiba Nouali, Séverinne Rigolet, and Andrey Ryzhikov. 2025. "High-Pressure Intrusion of Saline Solutions in Hydrophobic STT-Type Zeosil" Inorganics 13, no. 11: 371. https://doi.org/10.3390/inorganics13110371

APA Style

Chaib-Draa, Y.-M., Astafan, A., Chaplais, G., Nouali, H., Rigolet, S., & Ryzhikov, A. (2025). High-Pressure Intrusion of Saline Solutions in Hydrophobic STT-Type Zeosil. Inorganics, 13(11), 371. https://doi.org/10.3390/inorganics13110371

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