New low-cost and compact experimental system for characterization of porous materials by quasi-equilibrated thermodesorption of nonane or water

doi:10.21203/rs.3.rs-5037512/v1

Download PDF

Research Article

New low-cost and compact experimental system for characterization of porous materials by quasi-equilibrated thermodesorption of nonane or water

https://doi.org/10.21203/rs.3.rs-5037512/v1

This work is licensed under a CC BY 4.0 License

You are reading this latest preprint version

The new low-cost, simple and compact experimental system for characterization of porous materials by quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA) based on the miniature microprocessor-controlled thermal conductivity sensor Sensirion STC31 has been described in detail. The performance of the new system has been tested in QE-TPDA measurements of nonane for high silica zeolites Y and ZSM-5, as well as for a series of ordered mesoporous silicas SBA-15. Although very good qualitative agreement of the QE-TPDA profiles measured in the new system with those observed in a standard one was found, slightly lower saturation sorption capacities based on the new profiles were obtained. The pores size distributions (PSDs) calculated from the new nonane QE-TPDA profiles for SBA-15 silicas showed very good agreement with those obtained from N₂ adsorption isotherms using the NLDFT method. An excellent correlation between the pore size values based on both sets of PSDs was found. The new system was also applied in the QE-TPDA of water for selected metal-organic frameworks (MOFs). The QE-TPDA profiles of water observed for two fumarate containing MOFs Al-fum (aka Basolite A520) and MIL-88A were consistent with the adsorption-desorption isotherms obtained in a standard manometric apparatus. Hydrothermal stability tests of these MOFs, based on prolonged water QE-TPDA measurements, revealed the onset of structure degradation of Al-fum at 350°C and at 250°C for MIL-88A.

adsorption

thermodesorption

quasi-equilibrated temperature-programmed desorption and adsorption

nonane

water

zeolite

mesoporous silica

metal-organic framework

The standard method for characterization of the porosity of solids is based on low-temperature measurements of nitrogen adsorption and desorption isotherms. Discrimination between microporous, mesoporous, and nonporous or macroporous materials is based on differences in the shape of the isotherms. Numerous methods for quantitative analysis of adsorption isotherms have been developed that allow the determination of the parameters and characteristics describing porosity, including the BET method routinely used for the evaluation of the surface area, the α_s-plot and t-plot methods often employed to find micropore and mesopore volumes as well as the external and mesopore surface area, and the BJH and NLDFT methods used for calculating the pore size distribution. For some specific applications, other adsorbates are preferred in isothermal adsorption-desorption measurements: CO₂ (at 273 or 297 K) for a fast assessment of micropores in activated carbons, Ar (at 87 K) for determining the pore size distribution in zeolites, or Kr (at 77 K) for characterization of low surface area materials [1].

The low-temperature adsorption-desorption measurements have some drawbacks, including prolonged experiments (often exceeding 24 h), relatively large samples required, and limited availability of expensive automatic equipment. These issues served as a motivation to develop another method aimed at characterization of microporous and mesoporous materials, quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA) of n-alkanes, which was proposed by W. Makowski in 2007 [2]. Since then, the QE-TPDA method has been successfully applied to the characterization of zeolites [3–8], mesoporous silicas [4, 9–11], their carbon replicas [10] and metal-organic frameworks (MOFs) [12, 13].

The QE-TPDA measurements may be performed in a flow system equipped with a chromatographic thermal conductivity detector (TCD), by cyclic heating and cooling the sample, through which the carrier gas flows (He, containing about 0.5%v/v of the adsorptive). The QE-TPDA profiles contain desorption maxima observed during heating the sample and adsorption minima recorded during its cooling. The idea of the QE-TPDA experiments is illustrated in Fig. 1.

The QE-TPDA profiles of hexane and heptane on zeolites and other microporous materials are observed in the temperature range 25–400°C. Usually (especially for one-dimensional pore systems [14]) they comprise a single desorption maximum and adsorption minimum. However, for some 3D micropore systems complex QE-TPDA profiles of n-alkanes were observed, attributed to various phase transitions induced by adsorption [6, 7, 13]. As these profiles are characteristic for particular frameworks, they may be used for their identification. The micropore volumes determined from the hexane adsorption capacity for several zeolites were found to be close to those determined by N₂ adsorption [8].

In the case of nonane, its typical concentration in the carrier gas used in the QE-TPDA measurements is close to the saturation level (e.g. 0.6%v/v at 25°C). For this reason additional low temperature maxima, resulting from desorption of the molecules filling the mesopores, may appear below 100°C in the QE-TPDA profiles of nonane. Mesopore size distributions calculated from such profiles according to the modified BJH scheme [9] show very good correlation with the NLDFT PSDs obtained from N₂ desorption isotherms [15].

In principle, any moderately volatile liquid may be used as an adsorbate in the QE-TPDA experiments. A special dosing system based on diffusion control allowed the use of a wide range of n-alkanes, from pentane to decane [6, 7, 13]. In addition to n-alkanes, QE-TPDA measurements of branched alkanes [13, 16], aromatic hydrocarbons [13], alcohols [11, 12] and water [12] were used in studies of various porous materials. In the latter case, prolonged QE-TPDA experiments, comprising many desorption and adsorption cycles combined with high-temperature treatment with carrier gas saturated with water vapor, were found to be an effective tool for probing the hydrothermal stability of MOFs [12].

This work reports recent advances in QE-TPDA instrumentation, based on the utilization of miniature microprocessor-controlled thermal conductivity sensor Sensirion STC31 [17], implemented as an easy-to-use electronic module by SparkFun [18], which comprised also an independent temperature and relative humidity sensor SHTC3. The new QE-TPDA system was constructed and extensively tested in thermodesorption of nonane for high silica zeolites ZSM-5 and Y, as well as for a series of ordered mesoporous silicas SBA-15. Furthermore, the QE-TPDA of water was used to characterize adsorptive properties and hydrothermal stability of two fumarate-based metal-organic frameworks: aluminum fumarate /aka Al-fum, Basolite A520(Al) or MIL-53(Al)-FA [19]/ and MIL-88A(Fe) [20].

2.1. Materials

Commercial high silica zeolites HY (Si/Al > 100, Degussa) and HZSM-5 (Si/Al = 140 and Si/Al = 500, Zeolyst) were already used as reference microporous materials in nonane QE-TPDA [4].

SBA-15 silicas (denoted A, B, C and D), used in the QE-TPDA of nonane as the reference mesoporous materials differing in the pore size, were synthesized earlier [15] according to the published procedure [21]. The mixture of Pluronic P123, H₂O, HCl (37%) and tetraethylorthosilicate (TEOS, Merck), corresponding to the molar ratio of 1 SiO₂ : 0.017 P123 : 2 HCl : 80 H₂O was aged for 24 h at 55°C. Then it was hydrothermally treated for the next 24 h at 40°C (A), 100°C (B) or 150°C (C). Silica (D) was obtained in a similar way as (C), only the hydrothermal treatment was extended to 72 h. The as-prepared products were dried at 80°C and calcined in air at 550°C for 8 h.

The metal organic frameworks Al-fum and MIL-88A(Fe) were synthesized according to the previously published procedures [22, 23]. Al-fum: Al₂(SO₄)₃⋅18H₂O (70.0 g, 0.105 mol) was dissolved in 300 mL of water at 60°C. Separately, a solution of fumaric acid (24.3 g, 0.209 mol) and NaOH (25,2 g; 0,63 mol) in 360 mL of H₂O. After heating to 60°C, this solution was added dropwise to the solution of aluminum sulfate. After 2 h stirring, the resulting precipitate was separated by centrifugation, washed with water and dried in air at 150°C. MIL-88A(Fe): FeCl₃·6H₂O (1.352 g) and fumaric acid (0.580 g) were dissolved in water. The solution was transferred to the PTFE reaction vessel, which was placed in the autoclave and heated at 65°C for 4 h. The solid product was separated by centrifugation, washed four times with water and dried in air at 60°C.

2.2 The QE-TPDA systems

Standard QE-TPDA systems, described earlier [2–5, 8–10, 12–14], were based on a dual channel thermal conductivity detector (MicroVolume TCD2, VICI Valco), with helium being used as a carrier gas. In addition to the TCD, such a system comprised two electronic mass flow controllers and a 4-port switching valve, allowing easy selection of one of two carrier gas streams to flow through the sample, either pure He or He containing small admixture of an adsorptive, added by means of a simple diffuser/saturator, operating at room temperature. The sample studied (approximately 2–10 mg) was placed in a quartz tube, located in a small electric furnace, controlled by an advanced programmable temperature controller.

The new QE-TPDA system, described in detail in the Supplementary Information, is based on the Sensirion STC31 thermal conductivity sensor. Due to its specification, only nitrogen could be used as the carrier gas. For the sake of simplicity and low cost, the new system was constructed as a single channel device, equipped with a saturator which can be bypassed. Compared to the standard one, the new system has some new features, including precise temperature control of the saturator and the sample chamber, as well as easier programming of complex sample temperature profiles with the use of Arduino IDE.

The same simple calibration was used for both systems. Changes in the signal were assumed to be proportional to changes in the partial pressure of the adsorptive. The values of the inlet partial pressure of the adsorptive in the carrier gas were calculated based on the measurements of its flowrate (using the Restek ProFLOW 6000 electronic flowmeter) and a decrease of the mass of the adsorbate in a vial, which is a part of the diffuser/saturator, in a given length of time.

2.3. Other equipment

The low temperature adsorption-desorption isotherms of nitrogen for SBA-15 silicas were measured by means of the Quantachrome Nova 2000 apparatus. Prior to the measurements the samples were outgassed in vacuum for 18 h at 200°C. Autosorb iQ MP (Quantachrome/Anton Paar) was used for measurements of the adsorption-desorption isotherms of water vapor for the MOFs studied. Before the measurements, the samples were evacuated for 6 h at 150°C. The crystallinity of the synthesized MOFs was verified with XRD using the Rigaku MiniFlex 600 diffractometer.

The QE-TPDA profiles of nonane, observed for high-silica zeolites ZSM-5 and Y using the new system, are close to those recorded with the standard one [4] (Fig. 2). The high-temperature desorption maxima and adsorption minima correspond to emptying and filling of the structural micropores in both zeolitic frameworks, respectively. The low-temperature maxima result from desorption from the external surface and interparticle mesopores. The fact that the new profiles are shifted to higher temperatures should be explained in terms of Le Chatelier's principle, taking into account the higher saturator temperature and, consequently, the higher partial pressure of nonane in the carrier gas.

The adsorption isobars, calculated by averaging of the integral adsorption and desorption curves, calculated from the new profiles exhibit similar behavior as those calculated from the old profiles. However, the saturation sorption capacities based on the new isobars are underestimated by about 20%. The reason for this systematic discrepancy is not clear; for both series of experiments (i.e., performed in the old and new QE-TPDA systems), quantitative interpretation was based on the calibration procedure described earlier. However, these problems may be overcome by the application of well-defined microporous materials (e.g. the commercial zeolites) as standard reference materials.

The QE-TPDA profiles of nonane recorded for the selected ordered mesoporous silicas SBA-15 are shown in Fig. 4. They consist of single adsorption minima, resulting from capillary condensation in the mesopores, and desorption maxima corresponding to emptying of the mesopores. As these effects are very intensive and appear in the low temperature range, which is quite narrow (20–80°C). For this reason only low heating/cooling rates may be used in the QE-TPDA measurements for mesoporous materials (e.g. 2°C/min – much lower than 10°C/min usually used in the case of zeolites). Both the new and the old ones conform to the rule ‘the smaller the pores, the higher the desorption temperature’, since for SBA-15 silicas the increase in the hydrothermal treatment results in a larger pore size.

In addition to the qualitative interpretation of the QE-TPDA profiles of nonane, related to the pore sizes, a quantitative method of the pore size analysis is available. The pore size distributions, calculated according to the modified BJH scheme [9] from the desorption parts of the new QE-TPDA profiles of nonane nonane obtained for the studied SBA-15 silicas, are shown in Fig. 5, together with the PSDs calculated from desorption branches of the low-temperature sorption isotherms (shown in Fig. S5), reported earlier [15]. Good agreement of the corresponding PSDs may be noticed. Although QE-TPDA-based pore sizes (determined as positions of the PSDs’ maxima) are systematically underestimated by about 10%, they show a very good correlation with the N₂ desorption-based values (with the R² value above 0.99). This is consistent with previous findings concerning a good correlation of the pore sizes obtained from the QE-TPDA profiles of nonane, measured using the standard system, with those based on N₂ sorption data [15].

The new QE-TPDA system was also used to characterize sorption of water vapor in selected MOFs. The framework of Al-fumarate MOF (Al-fum) is similar to that of MIL-53(Al), containing terephthalate anions as linkers. The framework of Al-fum forms 1D system of micropores with 0.57 × 0.60 nm² openings [19]. Unlike MIL-53 (Al), Al-fum does not exhibit “breathing” behavior upon dehydration and rehydration [19]. The structure of Al-fum synthesized in this study was verified by means of XRD (Fig. S6) and its adsorption properties toward water – in measurements of the adsorption-desorption isotherms, with the use of the standard manometric system (Fig. 6). The QE-TPDA profiles of water observed for Al-fum are consistent with the adsorption isotherms. The main desorption maximum observed in the temperature range 48–70°C (for the heating rate of 2°C/min) corresponds to the first step in the desorption isotherm, observed in the relative pressure range of 0.2–0.3, and should be attributed to the emptying of the structural micropores. The fact that the main desorption peaks present in the QE-TPDA profiles recorded for different heating rates partially overlap may indicate occurring of a sorption driven phase transition, in which partial pressure is the only intensive parameter. Such transitions, similar to capillary condensation and evaporation, have been reported to take place in the microporous carbons [24]. The low-temperature desorption peak clearly corresponds to the second step in the desorption isotherm (p/p_s -0.6-0.9) and should be attributed to adsorption on the external surface and/or in the interparticle mesopores, if they are present.

It should be mentioned that the QE-TPDA profiles in Fig. 7 were actually obtained from the relative humidity signal, originating from the SHTC3 sensor. It has been found that the profiles of partial pressure in the carrier gas, calculated from both signals of the detector (either the RH signal or the thermal conductivity signal from STC31), are practically the same (Fig. S8). Since the RH signal exhibited a better signal-to-noise ratio, it was chosen as a source of data in the QE-TPDA of water.

The new system was also used in modified water QE-TPDA experiments aimed at characterizing the hydrothermal stability of the MOFs studied. The sample temperature consisted of numerous cycles, comprising slow heating in the temperature range of 30–80°C (during which ‘diagnostic’ thermodesorption maxima were recorded), isothermal heating equivalent to hydrothermal treatment, and prolonged cooling to the ambient temperature (when readsorption occurred). After each 3-cycle sequence, the temperature of the hydrothermal treatment was increased by 25°C, starting from 200°C (Fig. S9). The entire hydrothermal test consisted of 31 cycles and lasted 5 days.

The results of the hydrothermal stability test of Al-fum are shown in Fig. 8. Only small changes in the intensity of the low-temperature desorption peak were observed up to 325°C: small increases in the range of 200–275°C and gradual decreases in the range of 275-325C. These changes may be attributed to the degradation of the surface features that contribute to the high external surface. The onset of a decrease in the intensity of the high-temperature desorption peak, indicating damage of the structural micropores, was noticed at 350°C, but only after the treatment at 400°C the micropore volume was considerably decreased.

Another MOF investigated in this study was MIL-88A. Its framework, based on trimers of Fe(III) octahedra connected by fumarate linkers, forms a 3D system of interconnected channels and cages with sizes of 0.5–0.7 nm [26]. The XRD pattern obtained for MIL-88A synthesized in this study (shown in Fig S7) contains all main reflexes of the literature patterns [27, 28], thus confirming the presence of this framework. The low intensity of the XRD data may result from the low crystallinity of the material (Fig. S9). Additional reflexes at 2θ = 9 and 11 ° can indicate the presence of another phase, which could not be identified.

Both the isotherms (Fig. 9) and QE-TPDA profiles (Fig. 10) reveal complex patterns of adsorption and desorption of water, with four distinct steps and substantial hysteresis. This behavior is different from that reported by Luo et al. [29], who observed a three-step adsorption isotherm, with a considerably lower saturation sorption capacity of 340 mg/g. Although MIL-88A has been known since 2005, we could not find any other reports on water sorption in this material. Although the origin of the multistep adsorption and desorption is not clear, the shape of the QE-TPDA profiles recorded at different heating and cooling rates, which practically do not contain any overlapping fragments, suggests a pore filling mechanism.

The results of the hydrothermal stability test of MIL-88A are shown in Fig. 11. It was performed in similar way as in the case of Al-fum, only the initial temperature of the hydrothermal treatment was much lower (125°C). The first notable change appeared after heating at 175°C, when the smallest high temperature peak (visible at 60–70°C) disappeared. This may be related to the presence of another phase indicated by the XRD results. The material retained most of its adsorptive properties after the hydrothermal treatment at 200 and 225°C. Some minor symptoms of hydrothermal damage could be observed after heating at 250°C, but further increase of the temperature to 275°C resulted in a complete loss of the adsorption properties due to structure degradation.

In this work a new low-cost, simple, and compact experimental system for quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA) measurements based on the miniature microprocessor-controlled thermal conductivity sensor Sensirion STC31 has been presented for the first time. It has been demonstrated that using this system, the QE-TPDA profiles, obtained earlier for selected zeolites and mesoporous silicas, could be reproduced with good accuracy. The new system has also been shown to be useful in studying sorption of water in metal-organic frameworks and in characterization of their hydrothermal stability.

In the case of the new QE-TPDA system, its low costs and simplicity may be added to a list of its advantages found earlier, including relatively short time of experiments (typically 2–3 h), cyclic measurements allowing to assess stability of the adsorbent, small samples required (2–10 mg) and possibility of using numerous volatile compounds as probe molecules. The cost of the hardware (about 2 kEUR, excluding VAT), much lower than the cost of the TCD detector used in the standard setup (about 13 kEUR), makes QE-TPDA more affordable and better suited as a method for screening of the porous adsorbents.

Funding

This study was partially funded by the National Science Centre Poland with the project 2018/29/B/ST4/00328. Construction of the new QE-TPDA system was partially funded by the Centre for Technology Transfer CITTRU, Jagiellonian University in Kraków.

Author Contribution

Study conception and design was performed by WM. The new experimental system was constructed and tested by WM and NY. Synthesis and structural characterization of MOFs were performed by PG and NY. Thermodesorption data collection and analysis were performed by WM, PG and NY. Isothermal sorption data collection and analysis were performed by AK, MCG and DM. The manuscript was written by WM, with all authors commenting on and approving the manuscript.

Data Availability

Experimental profiles of quasi-equilibrated temperature-programmed desorption and adsorption of nonane and water, as well as low temperature N2 adsorption-desorption isotherms and XRD patterns recorded for the studied materials are openly available in the Jagiellonian University Repository (https://doi.org/10.57903/UJ/IDRI9P, accessed on September 5, 2024).

M. Thommes, Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report), Chemistry International 38 (2016) 25–25. https://doi.org/10.1515/ci-2016-0119
W. Makowski, Quasi-equilibrated temperature programmed desorption and adsorption: A new method for determination of the isosteric adsorption heat. Thermochim Acta. 454, 26–32 (2007). https://doi.org/10.1016/j.tca.2006.12.015
K. Mlekodaj, K. Tarach, J. Datka, K. Góra-Marek, W. Makowski, Porosity and accessibility of acid sites in desilicated ZSM-5 zeolites studied using adsorption of probe molecules. Microporous Mesoporous Mater. 183, 54–61 (2014). https://doi.org/10.1016/j.micromeso.2013.08.051
W. Makowski, P. Kuśtrowski, Probing pore structure of microporous and mesoporous molecular sieves by quasi-equilibrated temperature programmed desorption and adsorption of n-nonane. Microporous Mesoporous Mater. 102, 283–289 (2007). https://doi.org/10.1016/j.micromeso.2007.01.009
W. Makowski, B. Gil, D. Majda, Characterization of Acidity and Porosity of Zeolite Catalysts by the Equilibrated Thermodesorption of n-Hexane and n-Nonane. Catal. Lett. 120, 154–160 (2008). https://doi.org/10.1007/s10562-007-9268-5
A. Sławek, J.M. Vicent-Luna, B. Marszałek, S.R.G. Balestra, W. Makowski, S. Calero, Adsorption of n -Alkanes in MFI and MEL: Quasi-Equilibrated Thermodesorption Combined with Molecular Simulations. J. Phys. Chem. C 120, 25338–25350 (2016). https://doi.org/10.1021/acs.jpcc.6b06957
A. Sławek, J.M. Vicent-Luna, K. Ogorzały, S. Valencia, F. Rey, W. Makowski, S. Calero, Adsorption of Alkanes in Zeolites LTA and FAU: Quasi-Equilibrated Thermodesorption Supported by Molecular Simulations. J. Phys. Chem. C 123, 29665–29678 (2019). https://doi.org/10.1021/acs.jpcc.9b07907
W. Makowski, Ł. Ogorzałek, Determination of the adsorption heat of n-hexane and n-heptane on zeolites beta, L, 5A, 13X, Y and ZSM-5 by means of quasi-equilibrated temperature-programmed desorption and adsorption (QE-TPDA). Thermochim Acta. 465, 30–39 (2007). https://doi.org/10.1016/j.tca.2007.09.002
W. Makowski, L. Chmielarz, P. Kuśtrowski, Determination of the pore size distribution of mesoporous silicas by means of quasi-equilibrated thermodesorption of n-nonane. Microporous Mesoporous Mater. 120, 257–262 (2009). https://doi.org/10.1016/j.micromeso.2008.11.014
W. Makowski, M. Leżańska, M. Mańko, J. Włoch, Porosity and surface properties of mesoporous silicas and their carbon replicas investigated with quasi-equlibrated thermodesorption of n-hexane and n-nonane. J. Porous Mater. 17, 737–745 (2010). https://doi.org/10.1007/s10934-009-9345-9
M. Mańko, B. Gil, R. Janus, P. Kuśtrowski, W. Makowski, Characterization of the porosity and surface chemistry of mesoporous silicas by quasi-equilibrated thermodesorption of 1-butanol and n-nonane. Thermochim Acta. 511, 82–88 (2010). https://doi.org/10.1016/j.tca.2010.07.028
A. Sławek, J.M. Vicent-Luna, B. Marszałek, B. Gil, R.E. Morris, W. Makowski, S. Calero, Gate-Opening Mechanism of Hydrophilic–Hydrophobic Metal–Organic Frameworks: Molecular Simulations and Quasi-Equilibrated Desorption. Chem. Mater. 30, 5116–5127 (2018). https://doi.org/10.1021/acs.chemmater.8b01603
W. Makowski, M. Mańko, P. Zabierowski, K. Mlekodaj, D. Majda, J. Szklarzewicz, W. Łasocha, Unusual adsorption behavior of volatile hydrocarbons on MOF-5 studied using thermodesorption methods. Thermochim Acta. 587, 1–10 (2014). https://doi.org/10.1016/j.tca.2014.04.016
A. Sławek, J.M. Vicent-Luna, B. Marszałek, W. Makowski, S. Calero, Ordering of n -Alkanes Adsorbed in the Micropores of AlPO ₄ -5: A Combined Molecular Simulations and Quasi-Equilibrated Thermodesorption Study. J. Phys. Chem. C 121, 25292–25302 (2017). https://doi.org/10.1021/acs.jpcc.7b08927
D. Majda, A. Korzeniowska, W. Makowski, A. Michalik-Zym, B.D. Napruszewska, M. Zimowska, E.M. Serwicka, Thermoporosimetry of n-alkanes for characterization of mesoporous SBA-15 silicas – Refinement of methodology. Microporous Mesoporous Mater. 222, 33–43 (2016). https://doi.org/10.1016/j.micromeso.2015.10.002
A. Sławek, J.M. Vicent-Luna, B. Marszałek, W. Makowski, S. Calero, Quasi-Equilibrated Thermodesorption Combined with Molecular Simulation for Adsorption and Separation of Hexane Isomers in Zeolites MFI and MEL. J. Phys. Chem. C 121 (2017). https://doi.org/10.1021/acs.jpcc.7b05347
STC31 Sensor, (n.d.). https://sensirion.com/products/catalog/STC31 (accessed July 12, 2024)
CO₂ Sensor - STC31, (Qwiic), (n.d.). https://www.sparkfun.com/products/18385 (accessed July 12, 2024)
E. Alvarez, N. Guillou, C. Martineau, B. Bueken, B. Van de Voorde, C. Le Guillouzer, P. Fabry, F. Nouar, F. Taulelle, D. de Vos, J. Chang, K.H. Cho, N. Ramsahye, T. Devic, M. Daturi, G. Maurin, C. Serre, The Structure of the Aluminum Fumarate Metal–Organic Framework A520. Angew. Chem. Int. Ed. 54, 3664–3668 (2015). https://doi.org/10.1002/anie.201410459
C. Serre, F. Millange, S. Surblé, G. Férey, A Route to the Synthesis of Trivalent Transition-Metal Porous Carboxylates with Trimeric Secondary Building Units. Angew. Chem. Int. Ed. 43, 6285–6289 (2004). https://doi.org/10.1002/anie.200454250
D. Zhao, J. Feng, Q. Huo, N. Melosh, G.H. Fredrickson, B.F. Chmelka, G.D. Stucky, Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores, Science (1979) 279 (1998) 548–552. https://doi.org/10.1126/science.279.5350.548
R. Rojas-Luna, J. Amaro-Gahete, D.G. Gil-Gavilán, M. Castillo-Rodríguez, C. Jiménez-Sanchidrián, J.R. Ruiz, D. Esquivel, F.J. Romero-Salguero, Visible-light-harvesting basolite-A520 metal organic framework for photocatalytic hydrogen evolution. Microporous Mesoporous Mater. 355, 112565 (2023). https://doi.org/10.1016/j.micromeso.2023.112565
X. Liao, F. Wang, F. Wang, Y. Cai, Y. Yao, B.-T. Teng, Q. Hao, L. Shuxiang, Synthesis of (100) surface oriented MIL-88A-Fe with rod-like structure and its enhanced fenton-like performance for phenol removal. Appl. Catal. B 259, 118064 (2019). https://doi.org/10.1016/j.apcatb.2019.118064
L. Liu, Y. Zeng, S.J. Tan, H. Xu, D.D. Do, D. Nicholson, J. Liu, On the mechanism of water adsorption in carbon micropores – A molecular simulation study. Chem. Eng. J. 357, 358–366 (2019). https://doi.org/10.1016/j.cej.2018.09.160
S. Cui, M. Qin, A. Marandi, V. Steggles, S. Wang, X. Feng, F. Nouar, C. Serre, Metal-Organic Frameworks as advanced moisture sorbents for energy-efficient high temperature cooling. Sci. Rep. 8, 15284 (2018). https://doi.org/10.1038/s41598-018-33704-4
T. Chalati, P. Horcajada, R. Gref, P. Couvreur, C. Serre, Optimisation of the synthesis of MOF nanoparticles made of flexible porous iron fumarate MIL-88A. J. Mater. Chem. 21, 2220–2227 (2011). https://doi.org/10.1039/C0JM03563G
L. Wang, Y. Zhang, X. Li, Y. Xie, J. He, J. Yu, Y. Song, The MIL-88A-Derived Fe3O4-Carbon Hierarchical Nanocomposites for Electrochemical Sensing. Sci. Rep. 5, 14341 (2015). https://doi.org/10.1038/srep14341
A. Galarda, J. Goscianska, Biocompatible Fe-Based Metal-Organic Frameworks as Diclofenac Sodium Delivery Systems for Migraine Treatment. Appl. Sci. 13, 12960 (2023). https://doi.org/10.3390/app132312960
F. Luo, X. Liang, W. Chen, S. Wang, X. Gao, Z. Zhang, Y. Fang, Bimetallic MOF-Derived Solar‐Triggered Monolithic Adsorbent for Enhanced Atmospheric Water Harvesting. Small. 19 (2023). https://doi.org/10.1002/smll.202304477

No competing interests reported.

supplementarymaterialJPM.docx

Download PDF

Reviews received at journal
09 Oct, 2024
Reviews received at journal
27 Sep, 2024
Reviewers agreed at journal
10 Sep, 2024
Reviewers agreed at journal
10 Sep, 2024
Reviewers agreed at journal
09 Sep, 2024
Reviewers agreed at journal
09 Sep, 2024
Reviewers agreed at journal
08 Sep, 2024
Reviewers agreed at journal
08 Sep, 2024
Reviewers invited by journal
07 Sep, 2024
Editor assigned by journal
06 Sep, 2024
Submission checks completed at journal
06 Sep, 2024
First submitted to journal
05 Sep, 2024

You are reading this latest preprint version

New low-cost and compact experimental system for characterization of porous materials by quasi-equilibrated thermodesorption of nonane or water

Status:

Version 1

Abstract

Figures

1. Introduction

2. Experimental

2.1. Materials

2.2 The QE-TPDA systems

2.3. Other equipment

3. Results and discussion

4. Conclusions

Declarations

Funding

Author Contribution

Data Availability

References

Additional Declarations

Supplementary Files

Status:

Version 1