Selective water sorbents for multiple applications, 1. CaCl2 confined in mesopores of silica gel: Sorption properties

This paper presents sorption properties of a selective water sorbent based on mesoporous KSKG silica gel as a host matrix and calcium chloride as a hygroscopic salt. Sorption isobars, isochores and isotherms at T=20–150°C and vapor partial pressures of 8–133 mbar clearly showed two types of water sorption: 1) the formation of solid crystal hydrates at low amounts N of sorbed water, and 2) vapor absorption mainly by the salt solution at higher N. Sorption properties of CaCl₂ crystal hydrates were found to change strongly due to their impregnation into mesoporous silica gel, whereas the solution confinement to the mesopores did not change its water sorption properties with respect to the bulk solution. Isosteric sorption heat was measured to depend on water sorption and to change from 62.5 kJ/mol for solid hydrates to 42.2–45.6 kJ/mol for solution.     

Sorption equilibrium of methanol on new composite sorbents “CaCl<Subscript>2</Subscript>/silica gel”

This paper presents experimental data on methanol sorption on new composite sorbents which consist of mesoporous silica gels and calcium chloride confined to their pores. Sorption isobars and XRD analysis showed the formation of a solid crystalline solvate CaCl₂⋅2MeOH at low methanol uptake, while at higher uptake the formation of the CaCl₂–methanol solution occurred. The solution confined to the silica pores showed the sorption properties similar to those of the CaCl₂–methanol bulk solution. Calorimetric and isosteric analyses showed that the heat of methanol sorption depends on the methanol uptake, ranging from 38±2 kJ/mol for the solution to 81±4 kJ/mol for the solid crystalline phase CaCl₂⋅2MeOH. The above mentioned characterizations allowed the evaluation of the methanol sorption and the energy storage capacities, clearly showing that the optimal applications of these new composite sorbents are the methanol removal from gaseous mixtures, heat storage and sorption cooling driven by low temperature heat.     

1H NMR in CaCl2·xH2O nanocrystals and water sorption isobars in a CaCl2-silica gel system

Mobility of water molecules in nanocrystals and other phases of CaCl₂·xH₂O (x=0–12) formed in the nanopores of silica gel during sorption of water vapor is studied by¹H NMR. The sorption properties of calcium chloride impregnated in the pores of micro- and mesoporous silica gels were measured. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. G. K. Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 2, pp. 261–266, March–April, 1998. This work was supported by RFFR grants No. 96-03-33069 and 97-03-33533 and NATO grant HTECH LG N 970330.     

Selective Water Sorbents for Multiple Applications. 11. CaCl2 Confined to Expanded Vermiculite

This paper presents the water sorption properties of a new selective water sorbent based on expanded vermiculite as a host matrix and calcium chloride as a hygroscopic salt. Sorption isobars, isosters and isotherms at T = 30–150°C and vapor partial pressure 8.2–42.0 mbar clearly show that at low water contents crystalline hydrates with 0.33, 1 and 2 molecules of water per 1 molecule of CaCl₂ are formed in the pores. These hydrates are stable over a temperature change of 20–30°C and exhibit kinetically slow transformations. At higher water uptake, the vapor absorption leads to the formation of a CaCl₂ aqueous solution inside the pores, which properties are close to those in the bulk. Isosteric sorption heat was found to depend on water sorption and change from 76.3 kJ/mol for solid hydrates to 39.1–46.6 kJ/mol.     

Structural and sorption characteristics of the products from zeolitization of sba-15 in the presence of tetraalkylammonium hydroxides

Micro–mesoporous materials combining the structural and sorption characteristics of a mesoporous molecular sieve (MMS) and zeolite BEA were obtained by the “dry gel conversion” method – partial zeolitization of silica MMS SBA-15 in the presence of tetraethylammonium hydroxide. The volume of the mesopores reaches 0.65 cm³/g, while that of the micropores is in the region of 0.1 cm³/g. The acidity of the obtained zeolitized materials differs from that of BEA; the total concentration of medium-strength acid centers (maximum thermal desorption of ammonia at ~315 °C) amounts to 0.15 mmol/g.     

Composite Water Sorbents of the Salt in Silica Gel Pores Type: The Effect of the Interaction between the Salt and the Silica Gel Surface on the Chemical and Phase Compositions and Sorption Properties

The influence of the inorganic salt-silica gel surface interaction on the chemical and phase compositions and sorption properties of composites of the salt in silica gel pores type is studied. Two possible interaction mechanisms are considered: (1) the ion-exchange adsorption of metal cations on the silica gel surface from a solution of a salt (CaCl₂, CuSO₄, MgSO₄, Na₂SO₄, and LiBr) and (2) the solid-phase spreading of a salt (CaCl₂) over the silica gel surface. The adsorption of metal cations on the silica gel surface in the impregnation step affords ≡Si-OM ⁿ⁺¹ surface complexes in the composites. As a result, two salt phases are formed in silica gel pores at the composite drying stage, namely, an amorphous phase on the surface and a crystalline phase in the bulk. The sorption equilibrium between the CaCl₂/SiO₂ system and water vapor depends on the ratio of the crystalline phase to the amorphous phase in the composite.     

Selective water sorbents for multiple applications, 4. CaCl2 confined in silica gel pores: Sorption/desorption kinetics

This paper presents experimental data on water sorption/desorption kinetics on composite SWS-1L and SWS-1S materials, bulk aqueous CaCl₂ solutions and pure KSKG silica gel. Desorption kinetic curves are measured in the temperature range of 328–363 K at different vapor pressures. First order kinetics is found for both SWS materials and the bulk aqueous solution with the apparent activation energies of the water desorption equal to 23.5 kJ/mol and 48.6 kJ/mol, respectively. The difference in the kinetic behavior of the bulk and disperse systems is discussed.     

Water sorption by the calcium chloride/silica gel composite: The accelerating effect of the salt solution present in the pores

The kinetics of isothermal water sorption by the CaCl₂/silica gel composite initiated by a small stepwise pressure rise over the sample has been investigated at a constant underlying plate temperature of 35°C. The initial portion of the kinetic curves is consistent with Fick’s diffusion model: the amount of sorbed water increases in proportion to the square root of the sorption time. This makes it possible to determine the effective diffusivity of water (D _eff). At small amounts of sorbed water (w < 0.19 g/g), D _eff changes slightly. The diffusivity of water in the composite pores (D) calculated for the same conditions is close to the Knudsen diffusivity of water vapor in mesopores. The D _eff value grows with an increasing water content of the composite; that is, sorbed water accelerates water transport in the pores. This is likely due to the appearance of an extra diffusion channel, namely, diffusion through the aqueous solution of the salt, whose formation begins on the silica gel surface at w > 0.1 g/g. The contribution from this channel increases markedly when the amount of adsorbed water is above 0.25 g/g. This can be explained by the formation of the “connected” phase of the solution in the pores.     

Dynamics and isotherms of water vapor sorption on mesoporous silica gels modified by different salts

The mesoporous silica gels impregnated with different metal salts were prepared and studied. The pore structure and specific surface area of adsorbents were evaluated using nitrogen adsorption. Then, the sorption isotherms and dynamics of water vapor were carried out at 303 K and different relative humidity (RH). The temperature programmed desorption experiments were conducted to estimate the activation energy (E _d) of water desorption on the silica gels. The results showed that the sorption capacity for water decreased with the increase of the ionic radius (except the calcium ion) and that CaCl₂ and LiCl were particularly suitable for use in modification of the mesoporous silica gel to improve their sorption rates and capacities for water vapor at the lower and medium RH (RH < 80%). The larger the average pore diameter and pore volume of the initial silica gels, higher the accrual rates of the water vapor sorption rate and capacity were after modification with hygroscopic salts. The activation energy of the water desorption on the mesoporous silica gel modified by CaCl₂ were much higher than that on the silica gel modified by LiCl, because the polarizability of the Ca²⁺ was higher than that of Li⁺.     

Selective water sorbents for multiple applications, 8. sorption properties of CaCl2?SiO2 sol-gel composites

This paper presents sorption properties of CaCl₂/SiO₂ composites synthesized by a sol-gel approach. Desorption isobars measured at T=30–140°C and vapor pressure 12.8–81.0 mbar clearly show a correlation between the sorbents pore structure and their sorption properties. The sample adsorptivities are found to exceed 1.2 kg H₂O/kg adsorbent (or 20–25 mol H₂O/mol of the salt). That is markedly higher than any reported before for silica-based materials. This results in a high energy storage capacity reaching 3,400 kJ/kg of dry sorbent, as confirmed by direct calorimetric measurements. The isosteric desorption heat is found to decrease from 67±5 kJ/mol to 46±5 kJ/mol with increase in the surface coverage.     

Experimental and numerical study on water sorption over modified mesoporous silica

–SO₃H modified mesoporous silica adsorbent with water sorption capacity and fast desorption kinetics for water sorption was synthesized and studied via a combined experimental and numerical approach. Mesoporous silica was synthesized using sol–gel method in H₂SO₄ medium. The water adsorption isotherms and kinetics over the silica were evaluated by a dynamic water vapor sorption analyzer. Mesoporous silica was modeled using annealing simulation with CVFF forcefield. –SO₃H modified mesoporous silica was modeled by the attachment of –SO₃H to the surface hydroxyl groups and validated. Simulation results show water sorption capacity at low relative humidity (RH) increases with –SO₃H loading on mesoporous silica. Energy distribution of intermolecular interaction and micro-view of water sorption over –SO₃H modified mesoporous silica reveal that although strong interaction (intermolecular interaction of ?40 to ?20 kcal/mol) between hydrophilic groups (–SO₃H) with water can increase water sorption capacity at low RH, weak H₂O–H₂O interaction (intermolecular interaction of ?20 to ?10 kcal/mol) dominated water sorption capacity at both low and high RH.     

Improvement of water vapor adsorption ability of natural mesoporous material by impregnating with chloride salts for development of a new desiccant filter

The aim of this study is the development of a new adsorbent for the desiccant material which can be regenerated by the domestic exhaust heat by using natural mesoporous material, Wakkanai siliceous shale. To improve this shale’s performance to adsorb/desorb the water vapor, lithium chloride, calcium chloride or sodium chloride was supported into the mesopores by impregnating with each chloride solution. Especially sodium chloride was effective to increase the water vapor adsorption amount 5–7 times of that of natural shale in the relative humidity range from 50 to 70%. Moreover, the appropriate impregnating concentrations were determined as 5wt% from the relationship between the maximum water vapor adsorption amount and the mesopore volume. Based on these results, a new desiccant filter has been developed by impregnated original paper with lithium chloride and sodium chloride. This paper contained shale powder in the synthetic fibers. The dehumidification performance of this filter was evaluated under the simulated summer condition in Tokyo. From the cyclic adsorption/regeneration test, this shale and chlorides filter could adsorb and desorb 60 g/h water vapor repeatedly at the regeneration temperature of 40°C. On the other hand, a silica gel filter and a zeolite filter adsorbed and desorbed only 10 g/h and 25 g/h, respectively. These results suggested that the shale impregnated with the chlorides has the best dehumidification ability as a new desiccant material. Further, the desiccant filter made from the shale will achieve the effective use of the low temperature exhaust heat.     

Synthesis and physicochemical study of ZSM-5 high-silica zeolite from natural raw materials

ZSM-5 high-silica zeolite was obtained from metakaolinite, Dzhenranchel’sk volcanic ash, and silica gel at T = 150–220°C, pH 9–13, and τ = 48–240 h with the use of an organic structure-forming additive, butanediol-1,4, in an alkaline solution. Optimum conditions for the synthesis of ZSM-5 zeolite were found (T = 200°C, pH 10, τ = 144 h). The catalytic properties of its H-form in vapor-phase esterification of acetic acid (I) with ethanol (II) were studied at 140–180°C and a I: II molar ratio from 1 to 2. Synthesized HZSM-5 showed high activity and selectivity in this reaction.     

Sol–gel synthesis and crystallization behaviour of β-spodumene

Lithium aluminum silicate powders in the form of β-spodumene were synthesized through sol–gel technique by mixing boehmite sol, silica sol and lithium salt. The gel and oxide powders were characterized by thermogravimetry, differential thermal analysis (DTA), X-ray diffraction (XRD), Fourier transformed infrared (FTIR) spectroscopy and scanning electron microscopy. DTA, XRD and FTIR results confirmed that crystallization of β-spodumene took place at about 800 °C. The tiny crystallites with average size less than 1 μm appeared when the gel powders were sintered at 800 °C. A substantial increase of the crystal grain size was observed with increasing sintering temperatures.     

Efficient Solar‐Driven Water Harvesting from Arid Air with Metal–Organic Frameworks Modified by Hygroscopic Salt

Freshwater scarcity is a global challenge threatening human survival, especially for people living in arid regions. Sorption‐based atmospheric water harvesting (AWH) is an appealing way to solve this problem. However, the state‐of‐the‐art AWH technologies have poor water harvesting performance in arid climates owing to the low water sorption capacity of common sorbents under low humidity conditions. We report a high‐performance composite sorbent for efficient water harvesting from arid air by confining hygroscopic salt in a metal–organic framework matrix (LiCl@MIL‐101(Cr)). The composite sorbent shows 0.77 g g^?1 water sorption capacity at 1.2 kPa vapor pressure (30 % relative humidity at 30 °C) by integrating the multi‐step sorption processes of salt chemisorption, deliquescence, and solution absorption. A highly efficient AWH prototype is demonstrated with LiCl@MIL‐101(Cr) that can enable the harvesting of 0.45–0.7 kg water per kilogram of material under laboratory and outdoor ambient conditions powered by natural sunlight without optical concentration and additional energy input.     

Polydimethylsiloxane/silica/titania composites prepared by solvent-free sol–gel technique

Composites based on polydimethylsiloxane incorporating silica and titania were prepared by mixing polydimethylsiloxane with proper oxides precursors, tetraethyl-orthosilicate and tetrabutyl-orthotitanate. In the presence of environmental humidity and in acid catalysis, hydrolysis/condensation processes take place with formation of oxides and concomitantly polymer crosslinking. Partial replacement of SiO₂ in a polydimethylsiloxane/silica composite with titania (both generated in situ by sol–gel process) affects surface hydrophilicity (evaluated by dynamic contact angle), water vapor sorption ability (determined by dynamic vapor sorption) and thermal stability. The dielectric properties are also controlled by composition.     

Nano silver coated patterned silica thin film by sol–gel based soft lithography technique

We report the fabrication of nano silver coated patterned silica thin film by sol–gel based soft lithography technique. Initially, silica gel film on soda lime silica glass was prepared by dipping technique from a silica sol of moderate silica concentration. A PolydimethylSiloxane elastomeric stamp containing the negative replica of the patterns of commercially available compact disc was used for embossing the film and the embossed film was cured up to 450 °C in pure oxygen atmosphere for oxide film. Finally, a precursor solution of AgNO₃ in water containing polyvinyl alcohol as an organic binder was made and used for coating on the patterned silica film by dipping technique and cured the sample up to 450 °C in reducing gas atmosphere to obtain nano silver layer. The formation of only cubic silver (~4.0 nm) and both cubic silver (~5.2 nm) and silver oxide (~3.6 nm) crystallites at 350 and 450 °C film curing temperatures respectively were confirmed by XRD measurements. The % of nano silver metal and silver oxide were 75.4 and 24.6 respectively. The nano-structured surface feature was visualized by FESEM whereas AFM revealed the high fidelity grating structure of the films. Presence of both spherical and rectangular structure (aspect ratio, 2.37) of nano silver/silver oxide was confirmed by TEM. The films were also characterized by UV–Vis spectral study. The patterned film may find application in chemical sensor devices.     

The interaction of the theophylline metastable phase with water vapor

The conditions of hydration of the stable and metastable theophylline phases were determined. Two-phase metastable phase/monohydrate and stable phase/monohydrate equilibrium pressures were measured at 25, 30, and 35°C. The metastable phase began to react with water vapor at lower relative humidities than the stable phase. Processes that occurred with the metastable and stable theophylline phases over various water pressure ranges were considered. The metastable phase exhibited an unusual behavior at 25°C and relative humidity 47%. At constant water vapor pressure and temperature, theophylline was initially hydrated and then lost water and again became anhydrous. Two consecutive processes occurred in the system, the formation of theophylline monohydrate from the metastable phase and its decomposition to the stable phase. The ratio between the rates of these processes determined the content of the monohydrate at the given time moment.     

Aerosol-assisted synthesis of mesoporous titania nanoparticles with high surface area and controllable phase composition

Mesoporous titania nanoparticles (denoted as MTN) with high surface area (e.g., 252 m² g⁻¹) were prepared using tetrapropyl orthotitanate (TPOT) as a titania precursor and 10–20 nm or 20–30 nm silica colloids as templates. Co-assembly of TPOT and silica colloids in an aerosol-assisted process and immediate calcination at 450 °C resulted in anatase/silica composite nanoparticles. Subsequent removal of the silica colloids from the composite by NaOH solution created mesopores in the TiO₂ nanoparticles with pore size corresponding to that of silica colloids. Effects of silica colloids’ contents on MTN porosity and crystallites’ growth at a higher calcination temperature (e.g., 1000 °C) were investigated. Silica colloids suppressed the growth of TiO₂ crystallites during calcination at a higher calcination temperature and controllable contents of the silica colloids in precursor solution resulted in various atomic ratios of anatase to rutile in the calcinated materials. The mesostructure and crystalline structure of these titania materials were characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), differential thermal analysis (DTA)-thermo-gravimetric analysis (TGA), and N₂ sorption.     

Response of semiconducting metal oxides to water vapor as a result of water molecules chemical transformations on catalytically active surfaces

The sensitivity (response) of six semiconducting metal oxide (SMO) structures on the basis of SnO₂ to water vapor was studied in dry and humid air over the H₂O vapor concentration range 0–2.9 vol % (0–100% RH) as the temperature of the samples changed from 200 to 600°C. The temperature dependence of the conductivity and response of SMOs to H₂O vapor had extrema at 300–400 and 250–400°C, respectively, and the sensitivity to water vapor did not decrease below 1.7–1.9 up to 600°C. Data on changes in the conductivity of SMOs and the number of OH⁻ groups in the oxygen-hydroxyl layer on the surface of SMOs depending on temperature and air humidity were obtained. A sharp change in conductivity as air humidity increased from 0 to 10% RH could be related to either a sharp change in the number of OH⁻ groups in the oxygen-hydroxyl layer because of the high polarity of water molecules or a decrease in the intergrain energy barrier. The phenomena observed and the behavior of SMO conductivity in dry and humid air were interpreted. The experimental data were used to suggest a mechanism of the formation of hydroxyl groups on the surface of SMOs. The paper contains practical recommendations concerning the temperature conditions under which the influence of humidity on changes in the conductivity of SMOs is weakest.