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Mechanistic aspects of water adsorption-desorption in porphyrin containing MOFs
Microporous and Mesoporous Materials 290 (2019) 109649
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Mechanistic aspects of water adsorption-desorption in porphyrin containing MOFs
T
Marek Wiśniewskia, Adam Bienieka, Paulina Boliboka, Stanisław Koterb, Paweł Brykc, ⁎ Piotr Kowalczykd, Artur P. Terzyka, a
Faculty of Chemistry, Physicochemistry of Carbon Materials Research Group, Nicolaus Copernicus University in Toruń, Gagarin Street 7, 87-100, Toruń, Poland Faculty of Chemistry, Department of Physical Chemistry, Nicolaus Copernicus University in Toruń, Gagarin Street 7, 87-100, Toruń, Poland c Department for the Modelling of Physico-Chemical Processes, Maria Curie-Skłodowska University, 20-031, Lublin, Poland d School of Engineering and Information Technology, Murdoch University, Murdoch, WA 6150, Australia b
ARTICLE INFO
ABSTRACT
Keywords: Adsorption MOF DRIFT SAFT VR
Although porphyrin containing metal organic frameworks (PCMOFs) have found applications in different important fields, for example catalysis, phototherapy, adsorption etc. the mechanism of water adsorption on these materials remains unknown. In this study we analyze adsorption-desorption data on three PCMOFs. It is shown that hysteresis on adsorption-desorption isotherms is caused probably by the structural deformations. The application of SAFT-VR model to describe the experimental data is in agreement with the in - situ DRIFT insight of the process showing that the affinity between water and studied MOFS decreases as follows: CaTCPP > MgTCPP > ZnTCPP > TCPP. Application of the in-situ DRIFT method leads to important information about the nature of water material interactions showing for example the creation of aqua complexes and hydrogen bonds.
1. Introduction Porphyrin Containing Metal Organic Frameworks (PCMOFs) and their composites [1,2] have found applications in different important fields. For example due to excellent thermal stability, some 0D and 3D PCMOFs have been applied in catalysis [3], their photocytotoxic activity have found application in photodynamic therapy [4,5] and they have also been applied in photovoltaic systems [6,7] and for photoelectron transfer [8]. In some photocatalytic processes they are used for reduction of nitroaromatic compounds [9] or photocatalytic hydrogen production [10]. In catalysis they have found application for oxygen reduction [11], for alkylbenzenes [12], catechol [13] or water oxidation [14–16], for oxidation and/or catalytic epoxidation of styrene [17] and/or alkenes [18]. They also have found application as catalysts for cyanosilylation of aldehydes and Knoevenagel condensation reactions [19], for cycloaddition of CO2 to epoxides [20], in catalytic conversion of CO2 [21], electrochemical reduction of CO2 to CO [22,23], dehydratation of heterocycles [24], selective photooxygenation of phenol and sulfides [25] and photooxidation of a mustard gas [26]. Catalysis by a Zn-PCMOFs was reviewed by Roy at al [27]. and the application of PCMOFs as catalysts in oxidation reactions by Pereira et al. [28]. PCMOFS are also applied as DNA [29], Cu(II) [30], or telomerase activity sensors [31], and as the sensors for detection of nitroaromatic ⁎
compounds [32]. Among other fascinating properties and applications of PCMOFs one can mention interesting features of Mn(III) containing 1-D MOFs possessing right-handed helicity and opticity [33] or PCMOFs application as pH responsive drug carriers [34]. The review on the synthesis methods of PCMOFs was provided by Goldberg [35], the strategies for design by Zha et al. [36], and the stability and porosity of Fe PCMOFs were discussed by Fateeva et al. [37]. Moreover, Gao et al. [38] presented a review emphasising versatile functionalities of a metal-metalloporhyrin networks. PCMOFs have found also application in the field of adsorption and gas storage [39–41]. For example Fe(III), Co(III) and Ni(II) containing 2D porous PCMOFs, were successfully applied for H2 storage, CO2/N2 mixture separation [42] and Mn(II/III) microporous PCMOF for the separation of C2H2/CH4 [43], for the capture and sequestration of CO2 [44], for selective CO2 adsorption [45] and for selective adsorption of other gases [46]. Although some adsorption mechanisms are known (like for example the mechanism of dioxygen binding with cobaltous porphyrin site [47]), the interactions between adsorbed molecules and MOF structure can be complex [48]. Generally, very little is known about water adsorption-desorption in the structure of PCMOFs and up to our knowledge, there are no reports discussing the mechanisms of this process. It is surprising, because water adsorption is very important especially taking into account MOFs stability and bearing in mind that
Corresponding author. E-mail address: [email protected] (A.P. Terzyk).
https://doi.org/10.1016/j.micromeso.2019.109649 Received 30 April 2019; Received in revised form 23 July 2019; Accepted 13 August 2019 Available online 13 August 2019 1387-1811/ © 2019 Elsevier Inc. All rights reserved.
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water is usually present in the atmosphere affecting mentioned above applications of PCMOFs. In this study we present for the first time, the insight into the mechanisms of water adsorption-desorption on a series of PCMOFs. One of the studied MOFs is known however, two remaining are new and, up to our knowledge, have not been fabricated and studied yet.
2.4. In-situ DRIFT investigations Water adsorption was performed under isobaric conditions (p = 4 kPa by flowing He gas through H2O scrubber at 25 °C) changing the temperature of the process up and down from 25 °C to 250 °C, with a period of 0.5 h at each temperature (period of 25 °C) in order to assure that the equilibrium was achieved. A Praying Mantis in situ cell from Harrick Scientific Corporation was used as reactor for the infrared (IR) spectroscopic DRIFT studies. The construction of this cell enables the thermal treatment of the powdered sample up to 600 °C in any controlled atmosphere or in a vacuum. The IR spectra for the samples were recorded (using Nicollet S10) at adsorption temperature, i.e. without cooling down to the room temperature. Spectral changes accompanying H2O adsorption were established by comparing IR spectra of the same sample recorded in a vacuum and those recorded under a defined adsorption temperature. The respective gas phase was the background for each spectrum. This simple operation enables observation of spectral changes of surface, without perturbation from the gas phase. Once the equilibrium was reached, the band at 5235 cm−1 was integrated (I). Experimental results were presented as I/Imax, where Imax is the band of maximum intensity taken at the lowest temperature. Thus the I/Imax value represents the experimental value of relative adsorption.
2. Experimental 2.1. MOFs synthesis 2.1.1. ZnTCPP The synthesis of ZnTCPP was performed using similar procedure to described in Ref. [49]. Zn(NO3)2 6H2O (POCh, 0.089 g) and TCPP (tetrakis (4-carboxyphenyl)porphyrin, TCI chemicals, 0.079 g) in a solvent mixture of DEF (N,N-Diethylformamide, ACROS Organics™)/ EtOH (POCh) 99.8% (15 ml/5 ml) were placed in a 30 ml screw-capped glass vial and mixed by about 15 min. Then the vial was placed into oven at 80 °C for 24 h. Purple with glitter precipitate was then obtained by filtration on nylon membrane filters (pore size 0.8 μm). The product was washed with 5 ml mixture of DEF and EtOH (3:1), and 3 times with 10 ml EtOH 96%. The solid was then evacuated at 50 °C and in vacuum for 24 h to yield activated sample.
3. Results and discussion
2.1.2. MgTCPP Mg(NO3)2 6H2O (POCh, 0.076 g) and TCPP (0.079 g) in a solvent mixture of DEF/EtOH 99.8% (15ml/5 ml) were placed in a 30 ml screwcapped glass vial and mixed about 15 min. Then the vial was placed into oven at 80 °C for 24 h. Burgundy precipitate was then obtained by a filtration on nylon membrane filters (pore size 0.8 μm). The product was washed with 5 ml mixture of DEF and EtOH (3:1), and 3 times with 10 ml EtOH 96%. The solid was then evacuated at 50 °C in vacuum for 24 h to yield activated sample.
3.1. Materials composition and characterisation Thermogravimetric analysis data (Fig. 1) show that the free TCPP decomposed completely during the heating up to 800 °C. First step of loss in weight of 27% appeared at 340 °C and additional step of weight loss of 71% was observed at 420 °C, and this is in good accordance with the data reported in literature [50]. ZnTCPP and CaTCPP decompose at ca. 400 °C (this is related to the TCPP decomposition) which means that both compounds are more stable than the free TCPP. Also good correlation with literature data for ZnTCPP is observed [51,52]. On the other
2.1.3. CaTCPP Ca(NO3)2 4H2O (POCh, 0.079 g) and TCPP (0.264 g) in a solvent mixture of DMF/EtOH 99.8% (22.5ml/7.5 ml) were placed in a 30 ml screw-capped glass vial and mixed about 15 min. Next stage was to pour solution from the vial into Teflon vial from the Parr bomb. Parr bomb with a mixture was placed into oven already heated up to 80 °C and temperature was set/raised to 200 °C (2 °C/min) (the bomb was stored at this temperature for 24 h). Burgundy precipitate was next obtained by a filtration on nylon membrane filters (pore size 0.8 μm). The product was washed with 5 ml mixture of DMF and EtOH (3:1) and 3 times with 10 ml EtOH (96%). The solid was then evacuated at 50 °C and stored in a vacuum for 24 h to yield activated sample. 2.2. Materials characterisation The elemental analysis was performed using a Vario MACRO CHN apparatus from ELEMENTAR Analysensysteme GmbH. Thermogravimetric measurements were performed in air atmosphere using a simultaneous TGA-DTA (TA Instruments, type SDT 2960) thermal analyzer with the heating rate equal to 10 °C min−1. The materials were also characterized with scanning electron microscopy (SEM), using a Quanta 3D FEG (EHT = 30 kV) instrument. The powdered samples were placed onto carbon tabs attached to aluminum SEM stubs and covered with Au. 2.3. Water adsorption-desorption measurements Water adsorption-desorption measurements were performed at the temperature of 24 °C using a typical gravimetric adsorption apparatus equipped with the Baratron pressure transducers (MKS Instruments, Germany). Each sample was thermally desorbed before the measurements under high vacuum until a constant mass was obtained (usually after 3 days).
Fig. 1. Thermal analysis data (air atmosphere): ZnTCPP (black triangles), CaTCPP (red squares), MgTCPP (blue circles) and TCPP (green rhombs). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.) 2
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exhibiting cavities). Fig. S1 in the Supplementary Material shows the SEM image of the TCPP for comparison. The obtained SEM images of ZnTCPP are consistent with the results presented in the literature [53] and correspond to a 2D chemical structure. The PXRD spectra (Supplementary Material Fig. S2) of ZnTCPP are also the same as published in Ref. [53]; thus the structure is known: Zn2(ZnTCPP) 3H2O. It is additionally confirmed by our results of the PXRD, elemental, thermal and FTIR analysis data. The application of these methods for the two remaining materials leads to the following possible composition: Ca3C48H24N4O8 4H2O and C48H28N4O8(Mg) 3H2O. However, these structures need further confirmation, and the results will be reported in future. 3.2. Adsorption - desorption isotherms and theoretical description Fig. 3 collects water adsorption-desorption isotherms (T = 24 °C) on studied PCMOFs. It can be seen that water adsorption values, the shapes of adsorption-desorption isotherms as well as the value of hysteresis depend on the type of studied MOF. Thus, generally the progressive changes in the shapes of isotherms is observed from type IV for ZnTCPP to type II/I for Mg and CaTCPP, respectively. Simultaneously adsorption values increase, thus the largest adsorption is observed for CaTCPP. To estimate the difference between adsorption and desorption the surface areas below the both branches of isotherms (Sads and Sdes, respectively) were calculated and subtracted. Those differences increase with the atomic radius of cations in a PCMOF structure (Fig. 3 B) and depend also on the values of the first (DC = 0.965) and second ionization potentials (IP) of metal atoms however, the correlation with the second IP is slightly better (DC = 0.983) (in fact it should be noted that for the studied metals atomic radii are correlated with the IP values). However, taking into account the progressive changes in the shapes of adsorption isotherms (confirmed by the changes in the surface area values reported below), as well as the in-situ DRIFT results, it can be concluded that the structural changes of studied solids are the most probable reason causing the appearance of adsorption - desorption hysteresis. On the other hand, the correlation between (Sdes - Sads) and the IP can suggests that there is a relation between the IP and the MOF deformation tendencies. This subject needs further studies, and the results will be reported.
Fig. 2. SEM images of ZnTCPP (A) CaTCPP (B) and MgTCPP (C).
hand, the MgTCPP degradation temperature is similar to that of free TCPP i.e. 350 °C. First step of weight loss for the ZnTCPP (around 130 °C) is related to ethanol and water release. In contrast, for the CaTCPP the first step can be assigned to water release (30–190 °C) and the second step to the DMF desorption (190–295 °C). Weight losses for ZnTCPP in rage 400–488 °C are correlated with the TCPP degradation. Thus, above 488 °C only ZnO remains in the sample. Weight losses at 450–520 °C and 520–660 °C for CaTCPP were assigned to the degradation of TCPP and CaCO3 respectively, leading to CaO as the final product. In the case of MgTCPP, water is bonded up to 135 °C and DEF in the range 135–285 °C. In the range 557–800 °C only MgO remains in the sample. The results from the SEM structure determination are presented in Fig. 2. Based on the SEM analysis it can be concluded that ZnTCPP (Fig. 2A) and MgTCPP (Fig. 2C) are built of wafers/layers while the CaTCPP (B) is built of rods (500 nm oriented in 3D cuboids/squares
Fig. 3. A) Experimental water adsorption (open symbols) - desorption (closed symbols) data at T = 24 °C on ZnTCPP (triangles), CaTCPP (squares) and MgTCPP (circles). B) The correlation between the difference in surface areas below desorption and adsorption branches of isotherms and atomic radii and ionization potentials of metal atoms (black squares first IP, violet triangles - second IP). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.) 3
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Fig. 4. A) The influence of pressure range on the quality of the SAFT-VR model fitting to experimental water adsorption data (symbols - T = 24 °C) on ZnTCPP in the range up to: 0.524 (dashed red line), 0.617 (solid black line), 0.916 (dashed blue line). B) The influence of the energy of water - wall interactions (εw) on the shapes of adsorption isotherms (the arrow shows the rise in εw from 1 εw up to 1.3 εw kJ). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
Fig. 5. The influence of the heat treatment temperature (25, 50, 100, 150, 200, 250 °C) in He atmosphere on OH stretching region.
To obtain more detailed information about the mechanism of the process, water adsorption isotherms were described by using different models proposed for water adsorption on porous solids. It should be pointed out that only the SAFT-VR model proposed by Martinez et al.
[54,55] led to satisfactory description of experimental data. This model is based on the statistical thermodynamics forming the partition function of adsorbed gas. Next, Statistical Associating Fluid Theory for Potential of Variable Range (SAFT-VR) is applied for a two dimensional 4
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Where p is the water vapour pressure, a is the water adsorption [mmol/ g], NA is Avogadro number, Aspec – specific surface area in [m2/g]. To fit the SAFT-VR model to experimental data the following values of the parameters were applied: water saturated vapour pressure (pnas) was taken at the measurement temperature as equal to 3.169 × 103 Pa, σ = 0.3 10−9 m, λw = 0.2453 and particle-particle SW range λ, as equal to 1.5 [54]. Surface area of PCMOFs was fitted. To obtain the model parameters (εw, ε, and bads - related to Aspec by Equation (6a) - a specific surface area calculated for a MOF from fitting water adsorption data by the SAFT-VR model) Equations (1)–(6) were fit to the experimental data by minimizing the sum of squares of the residuals using the Mathematica® function NonlinearModelFit. Since no satisfactory results were obtained for the whole measured adsorption range, smaller ranges of fit were tested. Fig. 4A shows the fit for ZnTCPP and Table S1 the sets of parameters obtained for all three ranges of fitting. The data collected in Tabs. S1 and S2. show that for the studied case energy of water interaction with the MOF structure is larger than the energy of water-water interactions (the same situation is observed for the two remaining samples) and the applied fitting range strongly influences the values of obtained specific surface areas. Thus, the larger is the range applied for fitting the smaller Aspec is. For the comparative purposes, we have taken into account only low ranges of adsorption isotherms for all three studied MOFs (ca. 0.6). To check how the changes in the parameters of the model change the shapes of adsorption isotherms we performed some model numerical calculations, by changing the values of respective parameters by ± 2% (see Fig. S3 for details). One can observe that at constant λw, and λ, the energy-related parameters have the most important influence on the adsorption isotherm shape. Thus a rise in εw as well as the rise in ε lead to the rise in adsorption. This is clearly shown in Fig. 4B where we changed the value of εw optimized for ZnTCPP. It can be seen that the isotherm changes its shape and this is in quiet good agreement with the experimental shapes reported in Fig. 3A. This is accompanied by the increase in the values of surface areas of studied PCMOFs. Thus obtained surface areas can be arranged in the following order: ZnTCPP (Aspec = 1703 m2/g) < MgTCPP (and 1911 m2/g) ≪ CaTCPP (Aspec = 3277 m2/g) (see Table S2). To check the reality of these values the molecular package Chemicalize by ChemAxon Ltd. [https:// chemicalize.com/] was applied. Calculated using this package maximum projection area of a single porphyrin molecule is equal to 105.8 Å2. The areas calculated from Aspec values are in the range 106.2–190.7 Å2, thus obtained Aspec values are quiet reliable since it is reasonable to assume that water interacts not only with porphyrin but also with the potential energy field of structure exerted by metal cations. In fact, this is confirmed below by the analysis of the in-situ DRIFT results.
Fig. 6. The influence of H2O adsorption (at 25 °C) on OH stretching region for studied materials. Black spectra - sample before, while red - after H2O adsorption. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
(2D) fluid. It is assumed that this fluid is formed by N molecules each composed of m spherical segments of diameter σ. Next, the equations describing the Helmholtz free energy of a gas (A3D) and adsorbed molecules (Aads) are derived, given by:
A3D = ln( NkT
3)
b
1+
Aads A2D = NkT NkT
ln(
w
A2D = ln( NkT
2)
1+
ads
AHS + a13D + NkT
/ )
1
2a 3D 2
(2)
w
AHD + a12D + NkT
(1)
2a 2D 2
3.3. In-situ DRIFT results Fig. 5 and S4 show spectral changes observed during the thermal treatment in He atmosphere for 0.5 h at the desired temperature i.e. from 25 °C up to 250 °C. For the TCPP - highly hydrophobic structure no spectral changes were observed in the whole tested temperature range. Meaning that water molecules present in the air do not interact strongly with the porphyrin structure and the ligand possess high thermal stability, at least up to 250 °C. In contrast, for metal-containing MOF-structures some differences during the heat treatment were observed. These spectral changes (in the range of –OH stretching region - Fig. 5) are connected with removal of adsorbed water. The most interesting results were obtained for CaTCPP. Purging the sample in He for 0.5 h causes that the most of physically adsorbed H2O was removed while strongly adsorbed molecules in the form of aquacomplexes are still present in the spectrum. Isolation of H2O molecules causes lack of hydrogen bonding visible here as a doublet of OH asymmetric and symmetric stretching vibration. Rise in the temperature diminish its intensity up to ca. 200 °C where it almost completely disappears. For ZnTCPP and MgTCPP physically adsorbed H2O was
(3)
where: ρb is the density of a bulk, σ - adsorbed particle diameter, Λ - is the de Broglie thermal wavelength, AHD, AHS are Helmholtz free energies of a hard-disk fluid, hard sphere fluid, respectively, k - Boltzmann constant, T - temperature (β = 1/kT), a13D and a23D are perturbation expansion terms, λwσ - is the range of the attractive potential, and εw is the potential energy of fluid-wall interactions.Finally, in equilibrium:
Aads A3D = NkT NkT
(4)
The above equation binds two variables, η and γ (they are hidden in the parameters of Equations (1)–(3)), which are related to measurable quantities by: η = ρb π σ2/6 = (p/kT) π σ2/6 2
γ = ρads π (σ/2) = bads a 2
−3
bads = π (σ/2) 10
NA/Aspec
(5) (6) (6a) 5
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Fig. 7. The influence of heat treatment temperature (25, 50, 100, 150, 200, 250 °C) in H2O/He atmosphere on OH stretching region.
removed at lower temperatures i.e. ca. 150 °C. This is in good agreement with the thermal analysis data reported in Fig. 1. These observations led us to decision to look closer to the phenomena accompanying how tested structures behave in H2O atmosphere. Fig. 6 (and S5) present the effect of H2O adsorption at 25 °C on tested materials. H2O adsorption on TCPP causes only little spectral changes observed due to appearance of the bands characteristic for Hbond formation at 3600 and 1275 cm−1 (Fig. 6 and S5). Note that COOH bands of the ligands did not change the position nor intensity. The observed phenomena proved that H2O molecules almost do not interact with the TCPP molecules. Contrary, for metal-containing samples H2O adsorption at 25 °C causes huge spectral changes. In the –OH stretching region (Fig. 6) intense and mutually overlapped bands at ca. 3600 and 3400 cm−1 appear, proving hydrogen bonding of adsorbed H2O molecules. Interestingly, stretching vibrations of CH- and NH-containing ligand fragments are blocked due to the presence of H2O inside the structures. The analysis of fingerprint region (1800 - 600 cm−1 Fig. S5) reveal that adsorbed H2O molecules interact mostly with metal nodes. It is visible as red-shifting of the C]O bands (ca. 40 cm−1) as well as ca. 10 cm−1 of the asymmetric and symmetric stretching vibrations of COO− groups. Heating the samples in the H2O/He atmosphere (Fig. 7 and S6) does not causes spectral changes for the TCCP. However for other tested materials progressive removal of adsorbed H2O occurs, causing first of all, a rise in the intensity of the stretching CH and NH region. Parallel red-shift of the skeletal vibration (Fig. S6) in the fingerprint region, means that water strongly interact with the whole structure, and adsorption does not limit to the metal node. This is in accordance with the calculated form the application of the SAFT-VR model specific surface areas. Moreover some differences between used cation are also visible. For MgTCPP strongly adsorbed H2O molecules form thermally stable hydroxide nodes. For CaTCPP, as it was mentioned above, H2O exist rather as aqua-complexes, without any hydrogen bonding - doublet of the 3668 and 3554 cm−1. The presence of metallic nodes comprising of Ca
(H2O) structures have been recently reported [56]. Such strong adsorption (and fact that this is an equilibrium process) causes the presence of these bands even at 250 °C. Interestingly however, in the case of ZnTCPP water is adsorbed only physically. It is desorbed almost completely already at 150 °C as the interaction of H2O molecules with the structure are the weakest. The differences in adsorption isotherms (see Fig. 4) originated from the differences in interaction energies between H2O and the structures. In order to look closer to the mechanism, performing the isobar spectral analysis seems to be valuable. Nevertheless, due to the presence of NHand CH- stretching vibration of porphyrins structures as well as OH from carboxyl groups disable the simple quantitative analysis. Thus, the near infrared region 4800 - 5600 cm−1 was harvested to analysis of H2O isobars. Their analysis led to the conclusion that interaction energy between H2O molecules and materials’ surface differ depending on the metal node used (Fig. 8). The strongest effect, visible as presence of H2O IR bands at higher temperature range, was observed for CaTCPP while the weakest for ZnTCPP material. This stays in excellent agreement with the results obtained independently from H2O adsorption isotherm analysis. 4. Conclusions Interaction between water and three PCMOFs was studied. It is shown that hysteresis is present on water adsorption - desorption isotherms, and the value of this hysteresis depends on the atomic radius of a metal cation. However, basing on the detailed analysis of isotherms shape as well as on the results of the SAVT - VR model applied for adsorption data description it is concluded that hysteresis is probably caused by structural deformations of a material. Thermal analysis, SAVTVR data as well the results of in - situ DRIFT analysis are in full agreement. Namely the interaction strength sequence between water and tested materials is as follow: CaTCPP > MgTCPP > ZnTCPP > TCPP. In the same sequence decreases the values of studied materials surface 6
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Fig. 8. The influence heat treatment temperature (25–250 °C) in H2O/He atmosphere on NIR region of H2O overtones with calculated adsorption isobars. Note that there is no adsorption hysteresis for all tested samples.
areas. It is proved that H2O molecules interact mainly (but not only) with metallic nodes: for example for CaTCPP strong bands of aqua-complexes exists but also NH- and CH- stretching vibrations rise in intensities while concentration of H2O inside the structures diminish. The effect is also visible as red-shift of skeletal bands of porphyrin structure. Obtained results shade a new light into the mechanistic aspects of water adsorption in MOF structures.
Appendix A. Supplementary data Supplementary data to this article can be found online at https:// doi.org/10.1016/j.micromeso.2019.109649. References [1] J.S. Aguirre-Araque, J.M. Gonçalves, M. Nakamura, P.O. Rossini, L. Angnes, K. Araki, H.E. Toma, GO composite encompassing a tetraruthenated cobalt porphyrin-Ni coordination polymer and its behavior as isoniazid BIA sensor, Electrochim. Acta 300 (2019) 113–122. [2] E.C. Escudero-Adan, A. Bauza, L.P. Hernandez-Eguia, F. Wurthner, P. Ballestera, A. Frontera, Solid-state inclusion of C60 and C70 in a co-polymer induced by metalligand coordination of a Zn-porphyrin cage with a bispyridyl perylene derivative, CrystEngComm 19 (2017) 4911–4919. [3] E. Amayuelas, A. Fidalgo-Marijuan, B. Bazan, M.K. Urtiaga, G. Barandika, M.I. Arriortua, Highly thermally stable heterogeneous catalysts: study of 0D and 3D porphyrinic MOFs, CrystEngComm 19 (2017) 7244–7252.
Acknowledgement The authors gratefully acknowledge financial support by the Polish National Science Centre (NCN) grant OPUS 9 no. 2015/17/B/ST5/ 01446.
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Mechanistic aspects of water adsorption-desorption in porphyrin containing MOFs
T
Marek Wiśniewskia, Adam Bienieka, Paulina Boliboka, Stanisław Koterb, Paweł Brykc, ⁎ Piotr Kowalczykd, Artur P. Terzyka, a
Faculty of Chemistry, Physicochemistry of Carbon Materials Research Group, Nicolaus Copernicus University in Toruń, Gagarin Street 7, 87-100, Toruń, Poland Faculty of Chemistry, Department of Physical Chemistry, Nicolaus Copernicus University in Toruń, Gagarin Street 7, 87-100, Toruń, Poland c Department for the Modelling of Physico-Chemical Processes, Maria Curie-Skłodowska University, 20-031, Lublin, Poland d School of Engineering and Information Technology, Murdoch University, Murdoch, WA 6150, Australia b
ARTICLE INFO
ABSTRACT
Keywords: Adsorption MOF DRIFT SAFT VR
Although porphyrin containing metal organic frameworks (PCMOFs) have found applications in different important fields, for example catalysis, phototherapy, adsorption etc. the mechanism of water adsorption on these materials remains unknown. In this study we analyze adsorption-desorption data on three PCMOFs. It is shown that hysteresis on adsorption-desorption isotherms is caused probably by the structural deformations. The application of SAFT-VR model to describe the experimental data is in agreement with the in - situ DRIFT insight of the process showing that the affinity between water and studied MOFS decreases as follows: CaTCPP > MgTCPP > ZnTCPP > TCPP. Application of the in-situ DRIFT method leads to important information about the nature of water material interactions showing for example the creation of aqua complexes and hydrogen bonds.
1. Introduction Porphyrin Containing Metal Organic Frameworks (PCMOFs) and their composites [1,2] have found applications in different important fields. For example due to excellent thermal stability, some 0D and 3D PCMOFs have been applied in catalysis [3], their photocytotoxic activity have found application in photodynamic therapy [4,5] and they have also been applied in photovoltaic systems [6,7] and for photoelectron transfer [8]. In some photocatalytic processes they are used for reduction of nitroaromatic compounds [9] or photocatalytic hydrogen production [10]. In catalysis they have found application for oxygen reduction [11], for alkylbenzenes [12], catechol [13] or water oxidation [14–16], for oxidation and/or catalytic epoxidation of styrene [17] and/or alkenes [18]. They also have found application as catalysts for cyanosilylation of aldehydes and Knoevenagel condensation reactions [19], for cycloaddition of CO2 to epoxides [20], in catalytic conversion of CO2 [21], electrochemical reduction of CO2 to CO [22,23], dehydratation of heterocycles [24], selective photooxygenation of phenol and sulfides [25] and photooxidation of a mustard gas [26]. Catalysis by a Zn-PCMOFs was reviewed by Roy at al [27]. and the application of PCMOFs as catalysts in oxidation reactions by Pereira et al. [28]. PCMOFS are also applied as DNA [29], Cu(II) [30], or telomerase activity sensors [31], and as the sensors for detection of nitroaromatic ⁎
compounds [32]. Among other fascinating properties and applications of PCMOFs one can mention interesting features of Mn(III) containing 1-D MOFs possessing right-handed helicity and opticity [33] or PCMOFs application as pH responsive drug carriers [34]. The review on the synthesis methods of PCMOFs was provided by Goldberg [35], the strategies for design by Zha et al. [36], and the stability and porosity of Fe PCMOFs were discussed by Fateeva et al. [37]. Moreover, Gao et al. [38] presented a review emphasising versatile functionalities of a metal-metalloporhyrin networks. PCMOFs have found also application in the field of adsorption and gas storage [39–41]. For example Fe(III), Co(III) and Ni(II) containing 2D porous PCMOFs, were successfully applied for H2 storage, CO2/N2 mixture separation [42] and Mn(II/III) microporous PCMOF for the separation of C2H2/CH4 [43], for the capture and sequestration of CO2 [44], for selective CO2 adsorption [45] and for selective adsorption of other gases [46]. Although some adsorption mechanisms are known (like for example the mechanism of dioxygen binding with cobaltous porphyrin site [47]), the interactions between adsorbed molecules and MOF structure can be complex [48]. Generally, very little is known about water adsorption-desorption in the structure of PCMOFs and up to our knowledge, there are no reports discussing the mechanisms of this process. It is surprising, because water adsorption is very important especially taking into account MOFs stability and bearing in mind that
Corresponding author. E-mail address: [email protected] (A.P. Terzyk).
https://doi.org/10.1016/j.micromeso.2019.109649 Received 30 April 2019; Received in revised form 23 July 2019; Accepted 13 August 2019 Available online 13 August 2019 1387-1811/ © 2019 Elsevier Inc. All rights reserved.
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water is usually present in the atmosphere affecting mentioned above applications of PCMOFs. In this study we present for the first time, the insight into the mechanisms of water adsorption-desorption on a series of PCMOFs. One of the studied MOFs is known however, two remaining are new and, up to our knowledge, have not been fabricated and studied yet.
2.4. In-situ DRIFT investigations Water adsorption was performed under isobaric conditions (p = 4 kPa by flowing He gas through H2O scrubber at 25 °C) changing the temperature of the process up and down from 25 °C to 250 °C, with a period of 0.5 h at each temperature (period of 25 °C) in order to assure that the equilibrium was achieved. A Praying Mantis in situ cell from Harrick Scientific Corporation was used as reactor for the infrared (IR) spectroscopic DRIFT studies. The construction of this cell enables the thermal treatment of the powdered sample up to 600 °C in any controlled atmosphere or in a vacuum. The IR spectra for the samples were recorded (using Nicollet S10) at adsorption temperature, i.e. without cooling down to the room temperature. Spectral changes accompanying H2O adsorption were established by comparing IR spectra of the same sample recorded in a vacuum and those recorded under a defined adsorption temperature. The respective gas phase was the background for each spectrum. This simple operation enables observation of spectral changes of surface, without perturbation from the gas phase. Once the equilibrium was reached, the band at 5235 cm−1 was integrated (I). Experimental results were presented as I/Imax, where Imax is the band of maximum intensity taken at the lowest temperature. Thus the I/Imax value represents the experimental value of relative adsorption.
2. Experimental 2.1. MOFs synthesis 2.1.1. ZnTCPP The synthesis of ZnTCPP was performed using similar procedure to described in Ref. [49]. Zn(NO3)2 6H2O (POCh, 0.089 g) and TCPP (tetrakis (4-carboxyphenyl)porphyrin, TCI chemicals, 0.079 g) in a solvent mixture of DEF (N,N-Diethylformamide, ACROS Organics™)/ EtOH (POCh) 99.8% (15 ml/5 ml) were placed in a 30 ml screw-capped glass vial and mixed by about 15 min. Then the vial was placed into oven at 80 °C for 24 h. Purple with glitter precipitate was then obtained by filtration on nylon membrane filters (pore size 0.8 μm). The product was washed with 5 ml mixture of DEF and EtOH (3:1), and 3 times with 10 ml EtOH 96%. The solid was then evacuated at 50 °C and in vacuum for 24 h to yield activated sample.
3. Results and discussion
2.1.2. MgTCPP Mg(NO3)2 6H2O (POCh, 0.076 g) and TCPP (0.079 g) in a solvent mixture of DEF/EtOH 99.8% (15ml/5 ml) were placed in a 30 ml screwcapped glass vial and mixed about 15 min. Then the vial was placed into oven at 80 °C for 24 h. Burgundy precipitate was then obtained by a filtration on nylon membrane filters (pore size 0.8 μm). The product was washed with 5 ml mixture of DEF and EtOH (3:1), and 3 times with 10 ml EtOH 96%. The solid was then evacuated at 50 °C in vacuum for 24 h to yield activated sample.
3.1. Materials composition and characterisation Thermogravimetric analysis data (Fig. 1) show that the free TCPP decomposed completely during the heating up to 800 °C. First step of loss in weight of 27% appeared at 340 °C and additional step of weight loss of 71% was observed at 420 °C, and this is in good accordance with the data reported in literature [50]. ZnTCPP and CaTCPP decompose at ca. 400 °C (this is related to the TCPP decomposition) which means that both compounds are more stable than the free TCPP. Also good correlation with literature data for ZnTCPP is observed [51,52]. On the other
2.1.3. CaTCPP Ca(NO3)2 4H2O (POCh, 0.079 g) and TCPP (0.264 g) in a solvent mixture of DMF/EtOH 99.8% (22.5ml/7.5 ml) were placed in a 30 ml screw-capped glass vial and mixed about 15 min. Next stage was to pour solution from the vial into Teflon vial from the Parr bomb. Parr bomb with a mixture was placed into oven already heated up to 80 °C and temperature was set/raised to 200 °C (2 °C/min) (the bomb was stored at this temperature for 24 h). Burgundy precipitate was next obtained by a filtration on nylon membrane filters (pore size 0.8 μm). The product was washed with 5 ml mixture of DMF and EtOH (3:1) and 3 times with 10 ml EtOH (96%). The solid was then evacuated at 50 °C and stored in a vacuum for 24 h to yield activated sample. 2.2. Materials characterisation The elemental analysis was performed using a Vario MACRO CHN apparatus from ELEMENTAR Analysensysteme GmbH. Thermogravimetric measurements were performed in air atmosphere using a simultaneous TGA-DTA (TA Instruments, type SDT 2960) thermal analyzer with the heating rate equal to 10 °C min−1. The materials were also characterized with scanning electron microscopy (SEM), using a Quanta 3D FEG (EHT = 30 kV) instrument. The powdered samples were placed onto carbon tabs attached to aluminum SEM stubs and covered with Au. 2.3. Water adsorption-desorption measurements Water adsorption-desorption measurements were performed at the temperature of 24 °C using a typical gravimetric adsorption apparatus equipped with the Baratron pressure transducers (MKS Instruments, Germany). Each sample was thermally desorbed before the measurements under high vacuum until a constant mass was obtained (usually after 3 days).
Fig. 1. Thermal analysis data (air atmosphere): ZnTCPP (black triangles), CaTCPP (red squares), MgTCPP (blue circles) and TCPP (green rhombs). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.) 2
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exhibiting cavities). Fig. S1 in the Supplementary Material shows the SEM image of the TCPP for comparison. The obtained SEM images of ZnTCPP are consistent with the results presented in the literature [53] and correspond to a 2D chemical structure. The PXRD spectra (Supplementary Material Fig. S2) of ZnTCPP are also the same as published in Ref. [53]; thus the structure is known: Zn2(ZnTCPP) 3H2O. It is additionally confirmed by our results of the PXRD, elemental, thermal and FTIR analysis data. The application of these methods for the two remaining materials leads to the following possible composition: Ca3C48H24N4O8 4H2O and C48H28N4O8(Mg) 3H2O. However, these structures need further confirmation, and the results will be reported in future. 3.2. Adsorption - desorption isotherms and theoretical description Fig. 3 collects water adsorption-desorption isotherms (T = 24 °C) on studied PCMOFs. It can be seen that water adsorption values, the shapes of adsorption-desorption isotherms as well as the value of hysteresis depend on the type of studied MOF. Thus, generally the progressive changes in the shapes of isotherms is observed from type IV for ZnTCPP to type II/I for Mg and CaTCPP, respectively. Simultaneously adsorption values increase, thus the largest adsorption is observed for CaTCPP. To estimate the difference between adsorption and desorption the surface areas below the both branches of isotherms (Sads and Sdes, respectively) were calculated and subtracted. Those differences increase with the atomic radius of cations in a PCMOF structure (Fig. 3 B) and depend also on the values of the first (DC = 0.965) and second ionization potentials (IP) of metal atoms however, the correlation with the second IP is slightly better (DC = 0.983) (in fact it should be noted that for the studied metals atomic radii are correlated with the IP values). However, taking into account the progressive changes in the shapes of adsorption isotherms (confirmed by the changes in the surface area values reported below), as well as the in-situ DRIFT results, it can be concluded that the structural changes of studied solids are the most probable reason causing the appearance of adsorption - desorption hysteresis. On the other hand, the correlation between (Sdes - Sads) and the IP can suggests that there is a relation between the IP and the MOF deformation tendencies. This subject needs further studies, and the results will be reported.
Fig. 2. SEM images of ZnTCPP (A) CaTCPP (B) and MgTCPP (C).
hand, the MgTCPP degradation temperature is similar to that of free TCPP i.e. 350 °C. First step of weight loss for the ZnTCPP (around 130 °C) is related to ethanol and water release. In contrast, for the CaTCPP the first step can be assigned to water release (30–190 °C) and the second step to the DMF desorption (190–295 °C). Weight losses for ZnTCPP in rage 400–488 °C are correlated with the TCPP degradation. Thus, above 488 °C only ZnO remains in the sample. Weight losses at 450–520 °C and 520–660 °C for CaTCPP were assigned to the degradation of TCPP and CaCO3 respectively, leading to CaO as the final product. In the case of MgTCPP, water is bonded up to 135 °C and DEF in the range 135–285 °C. In the range 557–800 °C only MgO remains in the sample. The results from the SEM structure determination are presented in Fig. 2. Based on the SEM analysis it can be concluded that ZnTCPP (Fig. 2A) and MgTCPP (Fig. 2C) are built of wafers/layers while the CaTCPP (B) is built of rods (500 nm oriented in 3D cuboids/squares
Fig. 3. A) Experimental water adsorption (open symbols) - desorption (closed symbols) data at T = 24 °C on ZnTCPP (triangles), CaTCPP (squares) and MgTCPP (circles). B) The correlation between the difference in surface areas below desorption and adsorption branches of isotherms and atomic radii and ionization potentials of metal atoms (black squares first IP, violet triangles - second IP). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.) 3
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Fig. 4. A) The influence of pressure range on the quality of the SAFT-VR model fitting to experimental water adsorption data (symbols - T = 24 °C) on ZnTCPP in the range up to: 0.524 (dashed red line), 0.617 (solid black line), 0.916 (dashed blue line). B) The influence of the energy of water - wall interactions (εw) on the shapes of adsorption isotherms (the arrow shows the rise in εw from 1 εw up to 1.3 εw kJ). (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
Fig. 5. The influence of the heat treatment temperature (25, 50, 100, 150, 200, 250 °C) in He atmosphere on OH stretching region.
To obtain more detailed information about the mechanism of the process, water adsorption isotherms were described by using different models proposed for water adsorption on porous solids. It should be pointed out that only the SAFT-VR model proposed by Martinez et al.
[54,55] led to satisfactory description of experimental data. This model is based on the statistical thermodynamics forming the partition function of adsorbed gas. Next, Statistical Associating Fluid Theory for Potential of Variable Range (SAFT-VR) is applied for a two dimensional 4
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Where p is the water vapour pressure, a is the water adsorption [mmol/ g], NA is Avogadro number, Aspec – specific surface area in [m2/g]. To fit the SAFT-VR model to experimental data the following values of the parameters were applied: water saturated vapour pressure (pnas) was taken at the measurement temperature as equal to 3.169 × 103 Pa, σ = 0.3 10−9 m, λw = 0.2453 and particle-particle SW range λ, as equal to 1.5 [54]. Surface area of PCMOFs was fitted. To obtain the model parameters (εw, ε, and bads - related to Aspec by Equation (6a) - a specific surface area calculated for a MOF from fitting water adsorption data by the SAFT-VR model) Equations (1)–(6) were fit to the experimental data by minimizing the sum of squares of the residuals using the Mathematica® function NonlinearModelFit. Since no satisfactory results were obtained for the whole measured adsorption range, smaller ranges of fit were tested. Fig. 4A shows the fit for ZnTCPP and Table S1 the sets of parameters obtained for all three ranges of fitting. The data collected in Tabs. S1 and S2. show that for the studied case energy of water interaction with the MOF structure is larger than the energy of water-water interactions (the same situation is observed for the two remaining samples) and the applied fitting range strongly influences the values of obtained specific surface areas. Thus, the larger is the range applied for fitting the smaller Aspec is. For the comparative purposes, we have taken into account only low ranges of adsorption isotherms for all three studied MOFs (ca. 0.6). To check how the changes in the parameters of the model change the shapes of adsorption isotherms we performed some model numerical calculations, by changing the values of respective parameters by ± 2% (see Fig. S3 for details). One can observe that at constant λw, and λ, the energy-related parameters have the most important influence on the adsorption isotherm shape. Thus a rise in εw as well as the rise in ε lead to the rise in adsorption. This is clearly shown in Fig. 4B where we changed the value of εw optimized for ZnTCPP. It can be seen that the isotherm changes its shape and this is in quiet good agreement with the experimental shapes reported in Fig. 3A. This is accompanied by the increase in the values of surface areas of studied PCMOFs. Thus obtained surface areas can be arranged in the following order: ZnTCPP (Aspec = 1703 m2/g) < MgTCPP (and 1911 m2/g) ≪ CaTCPP (Aspec = 3277 m2/g) (see Table S2). To check the reality of these values the molecular package Chemicalize by ChemAxon Ltd. [https:// chemicalize.com/] was applied. Calculated using this package maximum projection area of a single porphyrin molecule is equal to 105.8 Å2. The areas calculated from Aspec values are in the range 106.2–190.7 Å2, thus obtained Aspec values are quiet reliable since it is reasonable to assume that water interacts not only with porphyrin but also with the potential energy field of structure exerted by metal cations. In fact, this is confirmed below by the analysis of the in-situ DRIFT results.
Fig. 6. The influence of H2O adsorption (at 25 °C) on OH stretching region for studied materials. Black spectra - sample before, while red - after H2O adsorption. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)
(2D) fluid. It is assumed that this fluid is formed by N molecules each composed of m spherical segments of diameter σ. Next, the equations describing the Helmholtz free energy of a gas (A3D) and adsorbed molecules (Aads) are derived, given by:
A3D = ln( NkT
3)
b
1+
Aads A2D = NkT NkT
ln(
w
A2D = ln( NkT
2)
1+
ads
AHS + a13D + NkT
/ )
1
2a 3D 2
(2)
w
AHD + a12D + NkT
(1)
2a 2D 2
3.3. In-situ DRIFT results Fig. 5 and S4 show spectral changes observed during the thermal treatment in He atmosphere for 0.5 h at the desired temperature i.e. from 25 °C up to 250 °C. For the TCPP - highly hydrophobic structure no spectral changes were observed in the whole tested temperature range. Meaning that water molecules present in the air do not interact strongly with the porphyrin structure and the ligand possess high thermal stability, at least up to 250 °C. In contrast, for metal-containing MOF-structures some differences during the heat treatment were observed. These spectral changes (in the range of –OH stretching region - Fig. 5) are connected with removal of adsorbed water. The most interesting results were obtained for CaTCPP. Purging the sample in He for 0.5 h causes that the most of physically adsorbed H2O was removed while strongly adsorbed molecules in the form of aquacomplexes are still present in the spectrum. Isolation of H2O molecules causes lack of hydrogen bonding visible here as a doublet of OH asymmetric and symmetric stretching vibration. Rise in the temperature diminish its intensity up to ca. 200 °C where it almost completely disappears. For ZnTCPP and MgTCPP physically adsorbed H2O was
(3)
where: ρb is the density of a bulk, σ - adsorbed particle diameter, Λ - is the de Broglie thermal wavelength, AHD, AHS are Helmholtz free energies of a hard-disk fluid, hard sphere fluid, respectively, k - Boltzmann constant, T - temperature (β = 1/kT), a13D and a23D are perturbation expansion terms, λwσ - is the range of the attractive potential, and εw is the potential energy of fluid-wall interactions.Finally, in equilibrium:
Aads A3D = NkT NkT
(4)
The above equation binds two variables, η and γ (they are hidden in the parameters of Equations (1)–(3)), which are related to measurable quantities by: η = ρb π σ2/6 = (p/kT) π σ2/6 2
γ = ρads π (σ/2) = bads a 2
−3
bads = π (σ/2) 10
NA/Aspec
(5) (6) (6a) 5
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Fig. 7. The influence of heat treatment temperature (25, 50, 100, 150, 200, 250 °C) in H2O/He atmosphere on OH stretching region.
removed at lower temperatures i.e. ca. 150 °C. This is in good agreement with the thermal analysis data reported in Fig. 1. These observations led us to decision to look closer to the phenomena accompanying how tested structures behave in H2O atmosphere. Fig. 6 (and S5) present the effect of H2O adsorption at 25 °C on tested materials. H2O adsorption on TCPP causes only little spectral changes observed due to appearance of the bands characteristic for Hbond formation at 3600 and 1275 cm−1 (Fig. 6 and S5). Note that COOH bands of the ligands did not change the position nor intensity. The observed phenomena proved that H2O molecules almost do not interact with the TCPP molecules. Contrary, for metal-containing samples H2O adsorption at 25 °C causes huge spectral changes. In the –OH stretching region (Fig. 6) intense and mutually overlapped bands at ca. 3600 and 3400 cm−1 appear, proving hydrogen bonding of adsorbed H2O molecules. Interestingly, stretching vibrations of CH- and NH-containing ligand fragments are blocked due to the presence of H2O inside the structures. The analysis of fingerprint region (1800 - 600 cm−1 Fig. S5) reveal that adsorbed H2O molecules interact mostly with metal nodes. It is visible as red-shifting of the C]O bands (ca. 40 cm−1) as well as ca. 10 cm−1 of the asymmetric and symmetric stretching vibrations of COO− groups. Heating the samples in the H2O/He atmosphere (Fig. 7 and S6) does not causes spectral changes for the TCCP. However for other tested materials progressive removal of adsorbed H2O occurs, causing first of all, a rise in the intensity of the stretching CH and NH region. Parallel red-shift of the skeletal vibration (Fig. S6) in the fingerprint region, means that water strongly interact with the whole structure, and adsorption does not limit to the metal node. This is in accordance with the calculated form the application of the SAFT-VR model specific surface areas. Moreover some differences between used cation are also visible. For MgTCPP strongly adsorbed H2O molecules form thermally stable hydroxide nodes. For CaTCPP, as it was mentioned above, H2O exist rather as aqua-complexes, without any hydrogen bonding - doublet of the 3668 and 3554 cm−1. The presence of metallic nodes comprising of Ca
(H2O) structures have been recently reported [56]. Such strong adsorption (and fact that this is an equilibrium process) causes the presence of these bands even at 250 °C. Interestingly however, in the case of ZnTCPP water is adsorbed only physically. It is desorbed almost completely already at 150 °C as the interaction of H2O molecules with the structure are the weakest. The differences in adsorption isotherms (see Fig. 4) originated from the differences in interaction energies between H2O and the structures. In order to look closer to the mechanism, performing the isobar spectral analysis seems to be valuable. Nevertheless, due to the presence of NHand CH- stretching vibration of porphyrins structures as well as OH from carboxyl groups disable the simple quantitative analysis. Thus, the near infrared region 4800 - 5600 cm−1 was harvested to analysis of H2O isobars. Their analysis led to the conclusion that interaction energy between H2O molecules and materials’ surface differ depending on the metal node used (Fig. 8). The strongest effect, visible as presence of H2O IR bands at higher temperature range, was observed for CaTCPP while the weakest for ZnTCPP material. This stays in excellent agreement with the results obtained independently from H2O adsorption isotherm analysis. 4. Conclusions Interaction between water and three PCMOFs was studied. It is shown that hysteresis is present on water adsorption - desorption isotherms, and the value of this hysteresis depends on the atomic radius of a metal cation. However, basing on the detailed analysis of isotherms shape as well as on the results of the SAVT - VR model applied for adsorption data description it is concluded that hysteresis is probably caused by structural deformations of a material. Thermal analysis, SAVTVR data as well the results of in - situ DRIFT analysis are in full agreement. Namely the interaction strength sequence between water and tested materials is as follow: CaTCPP > MgTCPP > ZnTCPP > TCPP. In the same sequence decreases the values of studied materials surface 6
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Fig. 8. The influence heat treatment temperature (25–250 °C) in H2O/He atmosphere on NIR region of H2O overtones with calculated adsorption isobars. Note that there is no adsorption hysteresis for all tested samples.
areas. It is proved that H2O molecules interact mainly (but not only) with metallic nodes: for example for CaTCPP strong bands of aqua-complexes exists but also NH- and CH- stretching vibrations rise in intensities while concentration of H2O inside the structures diminish. The effect is also visible as red-shift of skeletal bands of porphyrin structure. Obtained results shade a new light into the mechanistic aspects of water adsorption in MOF structures.
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Acknowledgement The authors gratefully acknowledge financial support by the Polish National Science Centre (NCN) grant OPUS 9 no. 2015/17/B/ST5/ 01446.
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