Energetic Performances of âZIF-71âAqueous Solutionâ Systems: A

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Energetic Performances of “ZIF-71–Aqueous Solution” Systems: A Perfect Shock-Absorber With Water Guillaume Ortiz, Habiba Nouali, Claire Marichal, Gérald Chaplais, and Joël Patarin J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/jp505484x • Publication Date (Web): 21 Aug 2014 Downloaded from http://pubs.acs.org on August 27, 2014

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The Journal of Physical Chemistry

Energetic performances of “ZIF-71–aqueous solution” systems: A perfect shock-absorber with water

Guillaume Ortiz, Habiba Nouali, Claire Marichal, Gérald Chaplais*, Joël Patarin*

Univ de Haute Alsace (UHA), CNRS, Équipe Matériaux à Porosité Contrôlée (MPC), Institut de Science des Matériaux de Mulhouse (IS2M), UMR 7361, 3 rue Alfred Werner, 68093 Mulhouse Cedex, France

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Abstract Intrusion-extrusion experiments of water as well as electrolyte solutions (KCl 1 and 4 M) under high pressure were performed in metal-organic framework ZIF-71 (RHO-type structure) in order to study the performances of this system in energy absorption and storage. The experimental results reveal that “ZIF-71–water” system displays a perfect shock-absorber behavior, reproducible over several cycles. With this new studied system, the stored energy (25.5 J g-1) is almost doubled compared to that measured recently for “ZIF-8–water” system (13.3 J g-1) (SOD-type structure). When water is replaced by KCl aqueous solutions, a gain of intrusion pressure (74 and 96 MPa with KCl 1 M and 4 M, respectively) is observed. However, for the highest salt concentration, the system evolves to a bumper behavior, and as confirmed by XRD analysis, the RHO-type structure collapses.


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Introduction Recently the development of new routes for clean and renewable alternative energy solutions with the possibility to store and restore the unused energy is stimulated by the actual economic and environmental context.1, 2 Since the pioneering works of Eroshenko in 1996,3, 4 there has been an exponential growth of interest in the field of energy storage thanks to intrusion-extrusion of a non-wetting liquid into a lyophobic porous material. In our group, this process was applied to strongly hydrophobic zeolites (so called zeosils) using water, a non-polluting and very accessible liquid at low cost, as a non-wetting liquid. This opened a new domain of applications for this type of porous solids.5,

6

Indeed, the mechanical energy used for the intrusion of liquid is

transformed into interfacial energy.7 The corresponding work (W) can be expressed as V

W=∫ -PdV where P is the pressure, and V is the intruded volume. Since then, the energetic 0

performances of numerous “zeosil-water” systems have been widely studied.8-13 Depending on zeosil, such systems are able to restore, dissipate or absorb the supplied mechanical energy during the compression step (intrusion), and hence acts as a spring, shock-absorber or bumper, respectively when the pressure is released (extrusion). In the same time, in order to increase the stored energy, other hydrophobic materials with a higher porosity than zeolites were studied like modified mesoporous materials.14,

15

Experiments were also performed on zeosils by creating additional micro-, meso- and macropores using porogen or templating agents.16 However, the formation of few additional micropores led only to a slight increase of the stored energy; the presence of meso- and macropores having no real contribution. Due to a larger porosity than zeolites, Metal-Organic Frameworks (MOFs)17-20 and especially a subclass of MOFs, namely the Zeolitic imidazolate frameworks (ZIFs),21-23 3 ACS Paragon Plus Environment


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appears promising to increase the stored energy. These porous materials are formed via coordination between metal centers and organic imidazolate linkers. ZIFs are known to generally possess permanent porosity and to display a high chemical and thermal stability when compared to most of MOFs materials.24,

25

However, the water intrusion-extrusion

process requires hydrophobic Zeolitic Imidazolate Frameworks. Two ZIFs are well-known for their very low adsorption capacities of water indicating their hydrophobic character: ZIF-826, 27

and ZIF-71.27, 28 ZIF-8 [Zn(meIm)2, where meIm = 2-methylimidazolate] presents a SOD-

type topology (cubic symmetry, a ≈ 17.0 Å, space group 11.6 Å21,

22

and a 3.3-3.4 Å24,

26, 29-31

I 43m ), with a cage diameter of

cage aperture delimited by 6 membered-rings (MR).

Furthermore, this material possesses a large microporous volume of around 0.6 cm3 g-1,26, 31, 32 and is stable in water,24, 25, 30, 33 even if this is still a matter of debate in the literature.34 ZIF-71 [Zn(dcIm)2, where dcIm = 4,5-dichloroimidazolate] exhibits a RHO-type topology. It crystallizes in a cubic symmetry (space group

Pm 3m ) with a lattice constant a ≈ 28.5 Å.21

The framework is built from large α-cages (16.5-16.8 Å21,

22, 35

of diameter) connected by

double eight-membered ring units (D8R) leading to 8 MR cage windows of 4.2-4.8 Å.21, 22, 28, 35

In a previous work, promising results were obtained with the “ZIF-8–water” system. This system displays a shock-absorber behavior at a rather low pressure (around 27 MPa) with a stored energy (13 J g-1) close to that observed for the best “zeosil–water” systems.36 However, despite a large pore volume, the stored energy is still rather low. An alternative route to enhance the stored energy consists in increasing the intrusion pressure. This aim can be reached by substituting aqueous electrolyte solutions to pure water. Several groups have demonstrated the strong impact of the electrolytes addition in water on the intrusion pressure,37-42 the latter growing with the electrolyte solution concentration. One of the hypotheses advanced by Liu et al.39 and Zhao et al.41 to explain such a result is the increase of 4 ACS Paragon Plus Environment

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the effective liquid-vapor interfacial tension and/or an electrostatic repulsion which contribute to a higher transport resistant force. The increase of the applied pressure observed in the presence of aqueous electrolyte solutions might also be explained by the additional force required to break the solvation bonds of the solvated cations.42 Recently, the effect of the nature of aqueous electrolyte solutions on the intrusion pressure in Silicalite-1, a pure-silica zeolite was highlighted.40 Compared to the water-containing system, the intrusion pressure is higher and the stored energy can be tripled as, for instance, for the “Silicalite-1–LiCl3H2O” system.40, 43 A similar trend was observed for the “ZIF-8–aqueous electrolyte solutions” systems.44 Notably, the intrusion pressures increase and the stored energies are almost doubled when LiCl, NaCl or KCl 4 M solutions are used instead of water (23.6-26.0 vs 13.3 J g-1). In this paper, we describe the remarkable energetic performances of the “ZIF-71–water” system and compare them to the “ZIF-8–water” system. The influence of additives such as KCl at variable concentrations (1 and 4 M) on the intrusion-extrusion pressure in ZIF-71 is also investigated. The samples, before and after intrusion-extrusion experiments, were fully characterized by XRD, SEM, TG and N2 adsorption-desorption measurements.



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Experimental section Reagents Zinc acetate (99%), 4,5-dichloroimidazole (HdcIm, 98%) and methanol (99.9%) were purchased from Acros, Alfa Aesar and Aldrich, respectively. All reagents were used without further purification. Synthesis of ZIF-71 ZIF-71 was synthesized from the recipe described by Lively et al.28 Briefly, a solution of zinc acetate (0.440 g, 2.39 mmol) in methanol (70 g, 2.18 mol) and a solution of 4,5dichloroimidazole (1.314 g, 9.59 mmol) in methanol (70 g, 2.18 mol) were poured in a glass vial and mixed, then left without stirring at room temperature for 24 h. The methanol was then removed and replaced by chloroform (222 g). Immediately after, the resulting suspension was centrifuged for 5 min at 8000 rpm and the soaking-centrifugation process was repeated two more times with 22 g of chloroform each times. After drying under vacuum at 80 °C for 12 h, a white crystalline powder was obtained (0.807 g, yield based on metal: 98 %). Intrusion-Extrusion Experiments 1 M and 4 M KCl solutions were prepared by dissolving the corresponding amount of salts in distilled water. The intrusion-extrusion of water experiments under high pressure in the ZIF-71 samples were carried out at room temperature using a modified mercury porosimeter (Micromeritics Model Autopore IV) as described in our previous works.44 The value of the intrusion (Pint) and extrusion (Pext) pressures correspond to that of the half volume total variation. Pressure is expressed in MPa, and volume variation in mL per gram of sample.


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Powder X-ray Diffraction X-ray diffraction patterns of the different samples were recorded in a Debye-Scherrer geometry, on STOE STADI-P diffractometer equipped with a curved germanium (111), primary monochromator and a linear position sensitive detector (6° 2θ) using Cu Kα1 radiation (λ = 0.15406 nm). Measurements were achieved for 2θ angle values in the 3-45 range and step of 0.04° 2θ. Thermogravimetric Analyses The TG measurements were performed under air until 800 °C (rate of 2 °C min-1) using a METTLER-TOLEDO TG/DSC1 STARe System apparatus. Scanning Electron Microscopy The size and the shape of ZIF-71 particles were determined using a Philips XL 30 FEG microscope. Nitrogen Adsorption-Desorption Measurements Nitrogen adsorption isotherms were carried out using a Micromeritics ASAP 2420 apparatus. Prior to the measurements, the samples were outgassed at 80 °C overnight under vacuum. Langmuir and Brunauer–Emmett–Teller surface areas denoted as SL and SBET respectively, were calculated in the 0.004 ≤ p/p° ≤ 0.07 range according to the criteria given in the literature.45, 46 The microporous volumes (Vµ ) were determined using the t-plot method.



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Results and Discussion Intrusion-Extrusion experiments The intrusion-extrusion process is performed from three different solutions, firstly with pure water and secondly with 1 and 4 M potassium chloride solutions. The latter concentration is slightly lower than that of the saturated solution. All the results were compared to those obtained with “ZIF-8–water” and “ZIF-8–KCl aqueous solution” systems.36,

44

The pressure-volume diagrams for the “ZIF-71–water” and “ZIF-71–KCl

aqueous solutions” systems after the first, second and third intrusion-extrusion cycles are reported in Figure 1. The detailed data are listed in Table 1. Moreover, the low pressure range (P < 10 MPa) on the pressure-volume diagrams is not reported since this domain corresponds to the compression of the powder and to the filling of the interparticular porosity.36 “ZIF-71–water” system For the “ZIF-71–water” system, the three intrusion-extrusion cycles exhibit one step with an intrusion pressure close to 71 MPa (Pint). The intruded volume (Vint) is around 0.36 cm3 g-1 and close to the microporous volume obtained from nitrogen adsorption-desorption isotherms (i.e., 0.39 cm3 g-1).28 The water intrusion-extrusion process is completely reversible with a prominent hysteresis since the extrusion of water occurs at a much lower pressure than the one observed for the intrusion (Pext ≈ 30 MPa). The high similarity between the three intrusion-extrusion cycles indicates both the excellent reliability and reversibility of the phenomenon. The “ZIF-71–water” system exhibits a strong shock-absorber behavior with a stored energy close to 26 J g-1. Indeed, compared to the “ZIF-8–water” system, the energy is almost doubled36 and the gap between the intrusion and the extrusion pressures is much higher in the case of ZIF-71 (i.e. 41 vs 5 MPa) (see Table 2 and Figure 2). This difference is mainly due to the intrusion pressure which is two and a half times higher for the RHO-type structure.


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Such a result is quite surprising since the largest cage aperture is delimited by 8 metal centers against 6 for the SOD-type structure and according to the Laplace-Washburn relation,47 an opposite result would have been expected. However, the cage windows are estimated close to 4.2 or 4.8 Å21,

22, 28, 35

for ZIF-71 and evolving from 3.4 Å to about 7 Å for ZIF-8, which

enable the accommodation of para-xylene but exclude that of ortho-xylene, with a kinetic diameter of 6.7 and 7.4 Å, respectively.48 The higher flexibility of the SOD-type structure due to the highest capability of meIm linkers to twist compared to dcIm moieties, is therefore probably responsible of the lower intrusion pressure observed for the ZIF-8 material.49-52 “ZIF-71–KCl aqueous solutions” system In the case of the “ZIF-71–KCl aqueous solutions” system, as a general observation and in agreement with the results published by Han and co-workers on Y zeolite,37 the intrusion pressure increases with the salt concentration; this consequently leads to an increase of the stored energy. These results are illustrated in Figure 1. A similar behavior was also observed in the case of ZIF-8.44 The intrusion curve of cycle 1 (arrow A, Figure 1) exhibits one main steep step around 74 MPa (Pint) for KCl 1 M and 96 MPa for KCl 4 M. In both cases, the intruded volume is around 0.36 mL g-1. After the extrusion step of the first cycle (arrow C, Figure 1), whatever the concentration, the extruded volume is lower. A part of the liquid (0.12 cm3/g for KCl 1 M and 0.31 cm3/g for KCl 4 M) is still present in the porous solid. Consequently, the intruded volume for the next cycles is lower. Thus, for the second cycle, this volume is close to 0.24 cm3/g for KCl 1 M (Table 1) but surprisingly, for the second and third cycles the intrusionextrusion process is reversible (arrows B and C, Figure 1). The extruded volumes being close to the intruded ones a shock-absorber behavior is also observed when KCl 1 M is used as solution. However, the shape of the second and third intrusion curves is clearly less steep. In the case of KCl 4 M, for the second and third cycles, no real intrusion is observed. Therefore, 9 ACS Paragon Plus Environment


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the “ZIF-71–KCl 4 M” system behaves mainly as a bumper. Such a behavior, as it will be seen below from XRD analysis (see XRD characterizations), can be explained by the collapse of ZIF-71 framework. It is interesting to note that for this highest salt concentration, the “ZIF8–KCl solution” system displays, whatever the number of intrusion-extrusion cycles, a shockabsorber behavior (see Figure 3) and no collapse of the framework is observed. However, the intrusion pressure is much lower (53 instead of 96 MPa).44 Finally, even if the “ZIF-71–KCl 4 M” system is highlighted mainly with the first cycle it is worthy to underline that this bumper enables to absorb a large amount of energy close to 35 j g-1

Pint (MPa)

Pext (MPa)

Vint (cm3 g-1)

Vext (cm3 g-1)

Es (J g-1)

Er (J g-1)

cycle 1

~ 71

~ 30

0.36

0.36

25.5

10.8

cycle 2

~ 71

~ 30

0.36

0.36

25.5

10.7

cycle 3

~ 71

~ 30

0.36

0.36

25.4

10.7

cycle 1

~ 74

~ 32

0.36

0.24

26.6

7.7

cycle 2

~ 65

~ 32

0.24

0.20

15.6

6.4

cycle 3

~ 61

~ 32

0.20

0.20

12.2

6.4

cycle 1

~ 96

~ 36

0.36

0.05

34.6

1.8

cycle 2

~ 62

~ 36

0.05

0.05

3.1

1.8

cycle 3

~ 62

~ 36

0.05

0.05

3.1

1.8

Solution

Water

KCl 1 M

KCl 4 M

Table 1 Characteristics of the ZIF-71 samples, Intrusion (Pint) and Extrusion (Pext) Pressures, Intruded (Vint) and Extruded (Vext) Volumes, Stored (Es) and Restored (Er) Energies after water and KCl aqueous solution intrusion-extrusion experiments at two different salt concentrations (1 and 4 M). Es,r is quantified as the result of Pint,ext*Vint,ext


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Figure 1 Pressure-volume diagrams of the “ZIF-71–water”, “ZIF-71–KCl 1 M” and “ZIF-71–KCl 4 M” systems. For clarity, the diagrams for each aqueous solution are shifted by 0.8 mL g-1.

Figure 2 Pressure-volume diagrams of the “ZIF-71–water” and “ZIF-8–water” systems. For clarity the diagrams for each aqueous solution are shifted by 0.9 mL g-1.



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Figure 3 Pressure-volume diagrams of the “ZIF-71–KCl 4 M aqueous solution” and “ZIF-8–KCl 4 M aqueous solution” systems. For clarity the diagrams for each aqueous solution are shifted by 0.8 mL g-1. Materia l

Topolo Pore gy aperture (Å)

Pint (MPa)

Vint (mL g-1)

Pext (MPa)

Vext (mL g-1)

Es (J g1 )

Er (J g1 )

Energy yield (%)

ZIF-8

SOD

3.4-≈ 7

27

0.50

22

0.50

13.3

11.2

84

ZIF-71

RHO

4.8

71

0.36

30

0.36

25.5

10.8

42

Referen ce 36

This work

Table 2 Characteristics of the “ZIF-8–water and ZIF-71–water” systems, Intrusion (Pint) and Extrusion (Pext) Pressures, Intruded (Vint) and Extruded (Vext) Volumes and Stored (Es) and restored (Er) Energies. Es,r is quantified as the result of Pint,ext*Vint,ext XRD characterizations The ZIF-71 samples before and after intrusion-extrusion experiments were characterized by XRD analysis and the XRD patterns are reported in Figure 4. After intrusion-extrusion of water, the structure of ZIF-71 is preserved. It is not the case in the presence of KCl since the intensity of the XRD peaks decreases (KCl 1 M) and for the highest KCl concentration (4 M), a complete collapse of the framework occurs.


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Figure 4 XRD patterns of ZIF-71 samples before (a), after three intrusionextrusion cycles with water (b) and with KCl solutions at 1 M (c) and 4 M (d). * denote traces of KCl. SEM characterizations A typical scanning electron micrograph of the ZIF-71 sample after water intrusion is given in Figure 5. Crystals display preferentially rhombic dodecahedron shape with a size ranging from 1 to 3 µm. After such a treatment, some crystals are broken and small particles are clearly visible. However, no real significant changes on the morphology are observed whatever the non-wetting liquid (water or KCl solutions).

Figure 5 SEM image of ZIF-71 after intrusion-extrusion of water.



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Thermal analysis The thermogravimetric analyses carried out under air are depicted in Figure 6. The curves of the non-intruded and water intruded-extruded samples are similar. The total weight loss (86 % exp. vs 75 % calc., from 400 to 700 °C) corresponds to the collapse of the ZIF structure which leads to the formation of ZnO. This result seems to be in agreement with the work of Fei et al.53 According to Lively et al.,28 the difference between the theoretical and experimental mass losses could be explained by the presence of 4,5-dichloroimidazolate groups coordinated to the terminal zinc atoms at the surface of the crystal. For Schweinefuß et al.,54 this difference is related to the escape of volatile Zn species at high temperatures above 700 °C in addition to the dcim moiety. Anyway, it is worth noting that no mass loss was observed between 30 and 200 °C ruling out the presence of liquid in the porosity even after three water intrusion-extrusion cycles in agreement with the intruded (Vint) and extruded (Vext) volumes (Table 1).

Figure 6 TG curves under air of ZIF-71 before (a) and after (b) three water intrusion-extrusion cycles.


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N2 Adsorption-Desorption isotherms at 77 K Figure 7 illustrates the N2 adsorption-desorption isotherms of the ZIF-71 samples before and after three intrusion-extrusion cycles with water and KCl 4 M solution. The corresponding textural characteristics (BET and Langmuir surface areas as well as microporous volumes) are reported in Table 3 . Before intrusion-extrusion experiments, the isotherm of ZIF-71 adopts a type I profile with a microporous volume of 0.39 cm3/g as previously measured.28 It is striking to note that despite a more porous topology, the RHO-type structure (ZIF-71) possesses a lower microporous volume (expressed in cm3/g) than SOD-type structure (ZIF-8) (i.e. 0.66 cm3/g). It can be explained by the nature of ligands since dcim linkers (ZIF-71) are heavier than 2methylimidazolate due to the presence of two chlorine atoms vs CH3 group. Furthermore, the SOD-type structure involving the dcim linkers has been prepared recently.54 As expected, its microporous volume is lower than that of ZIF-71 (0.23 vs 0.39 cm3/g) After intrusion-extrusion of water, the isotherms are mainly of type I. However, compared to those of the non-intruded sample, a slight decrease of the microporous volume is observed (15 %). Since from both intrusion-extrusion experiments and TG analysis, it has been evidenced that all the water is expelled from the solid, such a decrease might be due to a partial degradation of the ZIF-71 structure even if, at the long range order, the framework is preserved according to the XRD pattern. For KCl 4 M aqueous solution, the microporous volume is very low (0.05 cm3/g), traducing the collapse of the RHO structure after the intrusion-extrusion experiments as already observed by XRD. For the intruded samples the presence of mesoporosity, revealed by an increase of the adsorbed volume at p/p° =0.9 and the hysteresis is also evidenced. This latter is attributed to an interparticular porosity resulting of the deterioration of some crystals.



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Figure 7 N2 adsorption-desorption isotherms of ZIF-71 samples at 77 K before (a) and after three intrusion-extrusion cycles with water (b) and KCl 4 M (c). Adsorption branch (filled circles), desorption branch (open circles).

ZIF-71

Vµ (cm3 g-1)

SBET (m2 g-1)

SL (m2 g-1)

before intrusion-extrusion experiment

0.39

1050

1140

after water intrusion-extrusion experiments

0.33

890

940

after KCl 4 M solution intrusion-extrusion experiments

0.05

150

160

Table 3 N2 Adsorption Data (Microporous Volume (Vµ), BET surface (SBET) and Langmuir surface (SL) of the ZIF-71 samples before and after three intrusionextrusion cycles with water or with KCl 4 M solution.


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Conclusion The energetic performances of ZIF-71 (RHO-type structure) were investigated by nonwetting liquid intrusion-extrusion experiments and compared to ZIF-8 (SOD-type structure). The “ZIF-71–water” system behaves as a perfect shock-absorber with a large gap between the intrusion and the extrusion pressure (∆P ≈ 41 MPa). It is worthy to note that both the intrusion pressure (71 MPa) and the stored energy (close to 26 J.g-1) are considerably higher than the ones measured for ZIF-8 (27 MPa and 13 J.g-1). It seems that the flexibility of the structure, which could be related to the twist of the imidazolate linkers, is an important parameter governing the intrusion pressure and thus the stored energy. Moreover, an increase of the intrusion pressure and therefore to an increase of the stored energy are also observed with KCl electrolyte aqueous solutions. At low KCl concentration (1 M), as for the “ZIF-71–water” system, a shock-absorber behavior is observed, even if after the first cycle, a part of the liquid is not completely expelled from the solid. A different behavior is observed at high KCl concentration (4 M). The “ZIF-71–KCl 4 M aqueous solution” system exhibits a bumper behavior associated with the collapse of the ZIF-71 framework. Nevertheless, this single-use bumper is capable to adsorb an energy close to 35 J.g-1. In comparison, whatever the KCl concentration, the “ZIF-8–KCl systems” behave as a weaker shock-absorber. Studies involving ZIFs are under progress in order to enhance again the stored energy and also shed the light on the key parameters governing the intrusion pressure and the global behavior of the “ZIFs–aqueous solutions” systems (bumper, shock-absorber or spring). Acknowledgment The authors acknowledge funding from the Agence Nationale de la Recherche under the project ‘‘SOFT-CRYSTAB’’ (ANR-2010-BLAN-0822).



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Figure 1 Pressure-volume diagrams of the “ZIF-71–water”, “ZIF-71–KCl 1 M” and “ZIF-71–KCl 4 M” systems. For clarity, the diagrams for each aqueous solution are shifted by 0.8 mL g-1. 82x82mm (300 x 300 DPI)

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Figure 2 Pressure-volume diagrams of the “ZIF-71–water” and “ZIF-8–water” systems. For clarity the diagrams for each aqueous solution are shifted by 0.9 mL g-1. 82x82mm (300 x 300 DPI)


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Figure 3 Pressure-volume diagrams of the “ZIF-71–KCl 4 M aqueous solution” and “ZIF-8–KCl 4 M aqueous solution” systems. For clarity the diagrams for each aqueous solution are shifted by 0.8 mL g-1. 82x82mm (300 x 300 DPI)



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Figure 4 XRD patterns of ZIF-71 samples before (a), after three intrusion-extrusion cycles with water (b) and with KCl solutions at 1 M (c) and 4 M (d). * denote traces of KCl. 82x82mm (300 x 300 DPI)


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SEM image of ZIF-71 after intrusion-extrusion of water 20x13mm (300 x 300 DPI)



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Figure 6 TG curves under air of ZIF-71 before (a) and after (b) three water intrusion-extrusion cycles. 82x82mm (300 x 300 DPI)


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Figure 7 N2 adsorption-desorption isotherms of ZIF-71 samples at 77 K before (a) and after three intrusionextrusion cycles with water (b) and KCl 4 M (c). Adsorption branch (filled circles), desorption branch (open circles). 82x82mm (300 x 300 DPI)



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50x50mm (300 x 300 DPI)


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Energetic Performances of âZIF-71âAqueous Solutionâ Systems: A

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