Swellable Organically Modified Silica Research Articles

Animated organic-inorganic hybrid materials and their use as catalyst scaffolds

For the past two decades, organic-inorganic hybrids (OIHs) have been researched extensively and tailored in a facile manner to suit a wide variety of applications due to their highly functional and tunable nature. The molecular scale mixing of the organic and inorganic components imparts unique properties to these materials. Stimuli-responsiveness or animated nature is one such property, resulting from the non-covalent interactions of the organic groups present in close proximity with the inorganic (-Si-O-Si-) framework. In this article, we provide a comprehensive review of the animated silica-based OIHs synthesized by sol-gel technique. The earlier sections of the review focus on the development and synthesis of animated materials derived from bis-[3-(trimethoxysilyl)propyl] ethylenediamine (enTMOS) and bis-trimethoxysilylethyl benzene (BTEB). Their response to stimuli and the principles governing their animated nature along with the effect of synthesis parameters on their properties have been discussed. The latter portion of the article offers a detailed overview of the application of swellable organically modified silica (SOMS) supported Pd catalysts for aqueous phase hydrodechlorination of the toxic organic contaminant, trichloroethylene, which is commonly found in groundwater. The affinity of SOMS to organics and its ability to swell and adsorb organics from aqueous solutions impacted the accessibility of the active Pd sites and imparted resistance to deactivation against anionic species encountered in groundwater. Finally, other catalytic applications of SOMS and an outlook on the future research avenues and applications of SOMS have been presented.

Aqueous phase hydrodechlorination of trichloroethylene using Pd supported on swellable organically modified silica (SOMS): Effect of support derivatization

Herein, the role of swellability and hydrophobicity of swellable organically modified silica (SOMS) in shielding Pd against deactivation due to HCl produced during hydrodechlorination (HDC) of trichloroethylene (TCE) is investigated. The extent of surface derivatization during sol gel synthesis of SOMS was found to directly impact the extent of hydrophobicity, swellability and surface area, as confirmed by infrared spectroscopy and N2 physisorption, respectively. Furthermore, after Pd impregnation, the resultant particle size, location, and atomic environment of Pd were also dictated by the extent of support derivatization such that the least derivatized material provided lowest protection to Pd from HCl. Post HCl-treatment, the batch activity rate constants decreased by 66% for the least derivatized sample and 17% for the most derivatized one, suggesting that hydrophobicity and swellability are essential for obtaining high resistance to HCl which could potentially impact the economic viability of HDC of TCE process.

On the dual role of the reactant during aqueous phase hydrodechlorination of trichloroethylene (HDC of TCE) using Pd supported on swellable organically modified silica (SOMS)

Herein, the dual role of trichloroethylene (TCE) in liquid-phase hydrodechlorination with Pd catalysts supported on swellable organically modified silica (SOMS), is investigated. Batch experiments with TCE-soaked Pd/SOMS showed 45% higher conversion after 4 h than dry Pd/SOMS, suggesting that TCE acts as a reactant and as a swelling-agent. Flow experiments performed with and without ethanol (external swelling-agent) exhibited similar steady-state activities, confirming that TCE itself can cause swelling. Moreover, flow experiments, regardless of whether the SOMS-supported Pd catalysts were pre-reduced or not, yielded similar steady-state conversions, suggesting that Pd(2+) is rapidly reduced by H2 dissolved in water during approach to steady-state. In-situ characterization performed under reaction conditions using time-resolved X-ray absorption spectroscopy confirmed the reduction of Pd(2+) species to Pd(0) by dissolved H2. Overall, this study shows economic viability of hydrodechlorination of TCE using Pd/SOMS by eliminating the need for an external swelling-agent as well as a catalyst pre-reduction step.

Elucidating the role of ethanol in aqueous phase hydrodechlorination of trichloroethylene over Pd catalysts supported on swellable organically modified silica (SOMS)

In this study, effect of ethanol on the performance of Pd supported on swellable organically modified silica (SOMS) for hydrodechlorination (HDC) of trichloroethylene (TCE) is investigated. SOMS is a hydrophobic material that swells to 3–4 times its original volume when contacted with organic solvents. Catalytic HDC of TCE suffers from inhibition due to HCl which is worsened by the slow removal of HCl from the hydrophobic pores of SOMS. Addition of ethanol resulted in swelling of SOMS matrix causing expansion of pores, thereby facilitating the removal of HCl. The inhibitory effect of HCl was alleviated by ethanol, without altering the HDC reaction pathway. Characterization using near-ambient pressure X-ray photoelectron spectroscopy and extended X-ray absorption fine structure showed the effect of ethanol on swellability and HCl removal, respectively. Lastly, a mechanism has been proposed for the uninhibited reaction, which exhibited first order kinetics with respect to TCE.

Modeling and measuring the absorption-induced expansion of swellable organically modified silica

We present a theoretical framework that describes the force generated by the expansion of swellable organically modified silica (SOMS) upon exposure to organic solvent. The total swelling force, produced from the differential contributions of localized swelling domains, is related logarithmically to the amount of material confined to a rigid space. The model is further parameterized according to the physical dimensions of that space and the intrinsic swellability of SOMS. This mathematical representation is validated experimentally using a piston force sensor apparatus, which shows that the solvent-induced force and pressure exerted by SOMS increase logarithmically with the amount of material that is present. Comparison with theory implies that the commercially available varieties of SOMS CyclaSorbTM and OsorbTM have Young’s expansion moduli YC ∼ 0.8 MPa and YO ∼ 0.7 MPa, respectively, which succinctly quantifies their relative behavior. The theoretical model and experimental technique should be widely applicable to other swellable and stimuli-responsive materials.

Effect of High Temperature on Swellable Organically Modified Silica (SOMS) and Its Application for Preferential CO Oxidation in H2 Rich Environment

AbstractTransition metal oxide catalysts tend to deactivate in the presence of moisture during hydrogen purification using preferential oxidation (PROX) of carbon monoxide (CO) . Thus, novel water‐tolerant catalysts need to be developed. Herein, the evolution of heat treated swellable organically‐modified silica (SOMS), a hydrophobic organic‐inorganic hybrid material, has been characterized and applied as a catalyst support for PROX under moisture‐rich conditions. While the SOMS‐supported cobalt manganese oxide was found to be inactive, drastic improvement in CO conversion was observed for heat treated SOMS (HSOMS) supported catalysts. From thermogravimetric analysis and NMR spectroscopy it was found that SOMS retains its structural properties and hydrophobicity up to 400 °C. The performance of these catalysts was improved upon using toluene as the impregnation solvent, which enhanced the support wettability and improved active site deposition. The catalyst supported on HSOMS‐400 was found to be more water tolerant than a silica‐supported catalyst due to Si−O−Si(CH3)3 groups retained from hexamethyldisilazane (HMDS) derivatization of SOMS.

Function and structural stability of protein adsorbed to swellable organosilica

Abstract Swellable organically modified silica (SOMS) is a mesoporous sol-gel derived material that spontaneously swells >6 mL/g upon addition organic liquids. Adsorption of 8 different proteins to swollen-state SOMS was studied as a function of adsorbate molecular size and solution pH. Adsorption capacity was dependent on molecular size with the highest capacity of 690 mg/g measured for wheat germ acid phosphatase (58 kDa), a mid-size protein. Adsorption capacities were generally independent of pH suggesting protein-protein interactions do not play a major role in the adsorption mechanism. Rate of adsorption was measured at different protein loadings and fit to a pseudo second-order rate equation. Adsorption rates were independent of loading state when the pH was near a protein's isoelectric point (pI), but varied when the pH differed from the pI of adsorbate. Adsorption was found to irreversible for all proteins when rinsed with buffer solution or ethanol. Infrared spectroscopy of adsorbed cytochrome c and myoglobin indicated that both proteins maintain a native folded state that is stabilized to thermal denaturation. Adsorbed streptavidin was found to bind FITC-biotin (63% binding site saturation) suggesting that adsorbed proteins are accessible to small molecules in bulk solution. Acid phosphatase showed catalytic activity when adsorbed to swollen SOMS, however, specific activity of the bound enzyme was 10-fold lower compared to free enzyme in solution. Adsorption to SOMS appears to be a one-step, reagent-free method to irreversibly immobilize small to mid-sized proteins. Data supports an adsorption mechanism where protein molecules become sterically entrapped in the flexible mesoporous material.

Aqueous-phase hydrodechlorination of trichloroethylene over Pd-based swellable organically-modified silica (SOMS): Catalyst deactivation due to chloride anions

Swellable-organically modified silica (SOMS) has been demonstrated to be an efficient catalyst scaffold for catalytic treatment of water contaminated with trichloroethylene (TCE). In this study, deactivation characteristics of Pd-incorporated SOMS for aqueous-phase hydrodechlorination (HDC) of TCE were investigated. Pd/SOMS catalysts were exposed to highly-concentrated chloride solutions (up to 1 M NaCl or 0.01 M HCl) to examine the deactivation resistant behavior of Pd/SOMS. The commonly used HDC catalyst Pd/Al2O3 was also studied for comparison purposes. Pd/SOMS and Pd/Al2O3 in their pristine and treated states were tested for aqueous-phase HDC of TCE and characterized by several techniques including N2 physisorption, inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray photoelectron spectroscopy, extended X-ray absorption fine structure spectroscopy (EXAFS), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of adsorbed CO. The aqueous-phase treatments had a pronounced adverse effect on the textural properties of Pd/Al2O3, although the effect was independent of the type of the chloride precursor, NaCl or HCl. Treating Pd/Al2O3 with chloride-containing solutions lowered the catalytic activity due to formation of Pd-Cl complexes and active metal leaching. The leached Pd obtained from the treatment solution was shown to be inactive for aqueous-phase HDC of TCE. While Pd/Al2O3 underwent severe deactivation due to the chloride treatments, Pd/SOMS exhibited resistance to chloride deactivation and metal leaching. The chloride treatments did not impact the textural properties of Pd/SOMS. The achieved deactivation resistance was attributed to the novel characteristics of the SOMS support.

Swellable Organically Modified Silica (SOMS) as a Catalyst Scaffold for Catalytic Treatment of Water Contaminated with Trichloroethylene

The properties of a swellable organically modified silica (SOMS) scaffold allowed us to synthesize “smart” catalysts with tunable accessibility of the active sites induced by organic swelling agents. Pd nanoparticles (NPs) deposited inside the swollen matrix of SOMS were shown to be selectively located on the interior surface, a surface which is only available through swelling. Techniques such as near ambient-pressure X-ray photoelectron spectroscopy (NAP–XPS) and cryogenic scanning electron microscopy (SEM) were employed to characterize Pd/SOMS in its swollen as well as unswollen state because their conventional counterparts do not preserve the swollen state of Pd/SOMS during spectral acquisition. The results obtained depicted significant differences between the unswollen and swollen state of Pd/SOMS. The most important difference is that Pd NPs became accessible on the surface after exposure to an organic compound. This indicates that the accessibility of the active sites can be controlled by changing the reaction environment, hence allowing a tunable accessibility induced by organic swelling agents. The effects of the extent of swelling on the catalytic activity were investigated by performing catalytic activity experiments in the presence of an organic swelling agent. Hydrodechlorination (HDC) of trichloroethylene (TCE), an important method of catalytic water abatement, was chosen as a model reaction. The catalytic performance was found to be proportional to the concentration of the organic swelling agent, indicating that the accessibility of active sites is related to the concentration of organic compounds. While the unavoidable reaction product HCl inhibited the commonly used HDC catalyst 1%Pd/Al2O3, 1%Pd/SOMS was able to maintain its rate throughout the reaction under the same conditions, indicating its resistance to the inhibition. Overall, a silica-based catalyst with tunable accessibility of the active sites induced by changes in the reaction environment can have significant implications for heterogeneous catalysis.

Formation of carbonaceous deposits on Pd-based hydrodechlorination catalysts: Vibrational spectroscopy investigations over Pd/Al2O3 and Pd/SOMS

The widespread utilization and commercialization of hydrodechlorination (HDC) over Pd-based catalysts as a remediation technique has been impeded because of catalyst deactivation problems such as formation of carbonaceous deposits under the reductive environment of HDC. In this study, we investigated the use of a novel animated material, swellable organically-modified silica (SOMS), as a catalyst scaffold for HDC of trichloroethylene (TCE) to develop a catalytic system resistant to carbon formation. The state of aggregation of adsorbed TCE on Pd/SOMS was characterized. It was found that the unique nature of SOMS scaffold caused condensation of adsorbents in the SOMS matrix. This is of particular importance considering the fact that the increase of local concentration of reactants due to condensation may enhance the kinetics of catalytic reactions. To determine the resistance to the formation of carbonaceous materials under reaction conditions, in-situ vibrational spectroscopy experiments (diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and laser Raman spectroscopy) were undertaken over Pd-incorporated SOMS in the absence and presence of water vapor in the reactant stream. The commonly used HDC catalyst Pd/Al2O3 was also studied for comparison purposes. Formation of carbonaceous deposits of different nature were observed over Pd/Al2O3 whereas no detectable carbon formation was observed over Pd/SOMS. It was confirmed that surface hydroxyl groups which are in basic character act as coking agents. The carbon formation resistant behavior of Pd/SOMS is closely related to the nature and low concentration of surface hydroxyl groups.

Adsorption of short chain carboxylic acids from aqueous solution by swellable organically modified silica materials

The adsorption of C2–C6 short chain carboxylic acids was measured for swellable organically modified silicas (SOMS), hydrophobic polysilsesquioxane based materials prepared via the sol–gel process. Adsorption was measured for SOMS materials that were either hydrophobic or incorporated variable amounts of quaternary amine groups to serve as ion exchange sites. Batch equilibrium experiments were performed for carboxylic acids and alcohols to standard hydrophobic SOMS. Results show that SOMS has partition coefficients for short chain alcohols that are approximately 3× greater than liquid–liquid extraction into octanol, and 10× greater for the extraction of short chain carboxylic acids. Affinity for valeric acid was similar to commercially available Amberlite XAD-4 resins, however the organosilica derived sorbent had a 3× higher total adsorption capacity which was attributed to the ability of the pores to expand. Column experiments using SOMS were used to measure breakthrough curves for valeric acid across a wide range of concentrations. The isotherm for dynamic adsorption was linear indicating that capacity to adsorb valeric acid was controlled by equilibrium and not limited by set pore volume capacity. Addition of quaternary amine sites to SOMS improved adsorption affinity of valeric acid at low concentrations, but those modifications reduced the swelling of the matrix and lowered capacity at higher concentrations. Overall, SOMS was found to be poorly suited to extract organic acids at concentrations < 10 mM, but has high capacity for adsorption at higher concentrations (up to 700 mg/g). Adsorbed valeric acid could be recovered by solvent rinse.

Effect of high-temperature on the swellable organically-modified silica (SOMS) and its application to gas-phase hydrodechlorination of trichloroethylene

Pd catalysts supported on swellable organically-modified silica (SOMS) and high-temperature-treated swellable organically-modified silica (H-SOMS) were characterized and tested for gas-phase hydrodechlorination (HDC) of trichloroethylene (TCE) conditions. The high-temperature treatment on SOMS resulted in an increase in surface area and pore diameter as well as significant improvement of Pd dispersion on H-SOMS with smaller Pd particle sizes compared to the Pd/SOMS catalyst. Although the high-temperature treatment led to some alteration of the SOMS polysiloxane network, the hydrophobicity and organic vapor adsorption characteristics of SOMS were preserved. The reduction and oxidation characteristics of Pd on SOMS and HSOMS were investigated in situ using XANES technique. It was found that the Pd sites in the pores of SOMS was accessible to small molecules such as H2, facilitating the reduction of PdOx, whereas oxidation of metallic Pd was limited even at higher temperatures when O2 was used. This effect was only observed over Pd/SOMS catalyst. For Pd/H-SOMS, because the pores were more widely open than Pd/SOMS, both reduction and oxidation of Pd were observed. Finally, the catalytic activity of Pd/H-SOMS for gas-phase HDC of TCE was significantly better than Pd/SOMS. When water was added to the reactant stream (TCE+H2O), both Pd/SOMS and Pd/H-SOMS maintained its catalytic performances due to hydrophobic property of the supports.

Adsorption of Gas Phase Organic Compounds by Swellable Organically Modified Silica

Swellable organically modified silica (SOMS) is a sol–gel derived material that spontaneously expands >2.5× upon contact with organic liquids, absorbing 7.8 mL/g. Adsorption of gas-phase volatile organic compounds by SOMS was measured to examine how the capability to swell affects capacity and rate of organic vapor absorption. Static adsorption capacities of SOMS for organic vapors at saturated vapor pressure ranged from 0.7 to 1.05 g/g, which was higher than values for other sorbents (powdered activated carbon, Amberlite XAD-4, Tenax TA, OptiPore, and organophilic zeolite). Rates of adsorption by SOMS were similar to those of XAD-4, a porous polymer with similar surface chemistry, and slower than that of activated carbon. Sequential coadsorption of multiple compounds by SOMS was measured, yielding enhanced adsorption capacity attributed to adsorption-induced pore expansion. The sequential adsorption of phenol and acetone vapor (p = p0) led to a total capacity of 5.7 g/g. Adsorption of organic vapors was ...

Hydrodechlorination of trichloroethylene over Pd supported on swellable organically-modified silica (SOMS)

The catalytic activity and resistance to poisoning of Pd catalysts supported on swellable organically-modified silica (SOMS) were investigated for hydrodechlorination (HDC) of trichloroethylene (TCE). The promising catalytic activity of 1% Pd/SOMS sample was attributed to the high affinity of SOMS for organics and its high hydrophobicity. While latter characteristic repels water, the adsorptive capacity for organics allows TCE dissolved in aqueous media to concentrate inside the pores, in the vicinity of the active sites, thus helping the kinetics. In the liquid phase, using a continuous flow reactor, higher TCE conversion was obtained over the 1% Pd/SOMS compared to the commercial 1% Pd/Al2O3 catalyst. When the pores of 1% Pd/SOMS sample were fully opened by pre-treating it with ethanol prior to the reaction, HDC activity was seen to significantly increase. In the gas phase, the extent of adsorption was less, reducing the concentration of reactants near the active sites. As a result, 1% Pd/SOMS was less active than 1% Pd/Al2O3 for HDC of TCE. To determine their resistance to poisoning, 1% Pd/SOMS and 1% Pd/Al2O3 catalysts were poisoned ex-situ with Li2S. The ex-situ poisoned Pd/SOMS sample maintained its catalytic activity for HDC of TCE. However, a significant loss in catalytic activity of the Pd/Al2O3 catalyst was observed after poisoning. Protection from aqueous phase sulfide poisoning was attributed to the hydrophobicity of the Pd/SOMS, which would exclude anionic species from the embedded Pd particles. The XPS, STEM and ICP-OES results indicated that when Pd/Al2O3 and Pd/SOMS were treated with 1M HCl, most of the Pd metal was leached from the Pd/Al2O3 catalyst in contrast to Pd/SOMS, which had negligible leaching. Overall, due to hydrophobicity and high affinity for organics, SOMS has potential as a catalyst scaffold for different reactions in groundwater remediation applications.

Absorption of dissolved organic species from water using organically modified silica that swells

Organically modified silica that rapidly and reversibly swells to >3 times their dry volume have been recently described. Here, these organosilica materials were demonstrated to have the ability absorb trichloroethylene (TCE), perchloroethylene (PCE), methyl t-butyl ether (MTBE), toluene, naphthalene, acetone, 1,4-dioxane, and 1-butanol from water. Direct experimental comparisons indicated that swellable organically modified silica (SOMS) has in many instances greater capacity than activated carbon and molecular sieves and possesses the ability to capture a wide range of dissolved polar and non-polar organic contaminants. The absorption of organic species to SOMS is enhanced by matrix expansion leading to non-selective capture of organics beyond what could only be attributed to physisorption. This process appears to be facilitated by initial adsorption events unlatching the collapsed matrix leading to the opening of nanometer-scale pores within the tensioned SOMS material, thus providing volume for absorption. Partition coefficients for the absorption of organic species from water by SOMS ranged from 2.8 × 10 5 to 1.0 × 10 2, and vary depending on polarity of the contaminant, concentration, and the total mass of contaminant absorbed. Maximum capacity exceed three times the dry weight of the absorbent under conditions of high contaminant concentration. SOMS was repeatedly regenerated with mild thermal treatment (60–110 °C) in air to evaporate absorbates from the matrix which could be subsequently collected. Only a slight decrease in effectiveness is observed after regeneration. Absorption is equally effective from salt water. Minimal loss of capacity and affinity is lost when extracting environmentally relevant concentrations of TCE from a topsoil/water mixture, presumably due to a molecular sieving effect.

Remediation of Dissolved Organic Pollutants in Water Using Organosilica-Based Materials that Rapidly and Reversibly Swell

AbstractA sol-gel derived organosilica material that energetically swells when exposed to organic molecules was tested as a means to extract dissolved organic species from water. Swellable organically modified silica (SOMS) was demonstrated to be effective at removing butanol, methyl t-butyl ether (MTBE), tetrachloroethylene, trichloroethylene, ethanol, and toluene from lab grade water, salt water, and natural waters. Partition coefficients for the absorption of organic species from water by SOMS ranged from 2.8�105 – 1.0�102, and vary depending on polarity of the contaminant, concentration, and the total mass of contaminant absorbed. Absorption of organic species to SOMS appears to be enhanced by matrix expansion of nanometer sized pores leading to non-selective capture of organics beyond what could be attributed to physisorption.