Microporous Environment Research Articles

Alkylation of lignin-derived aromatic oxygenates with cyclic alcohols on acidic zeolites

Moderately strong BAS and spacious microporous environments (i.e., large-pore acidic zeolites HBEA and HY) are important criteria for efficient alkylation of phenols with cyclic alcohols and alkenes, while very strong BAS appear to be responsible for catalyst deactivation. BAS confined in HBEA and HY pores show substantially higher turnover frequencies compared to solids without molecularly sized pore constraints. HBEA favors the formation of mono-alkylates, while enhanced formation of di-alkylates is observed on HY. Dehydration of alcohols always dominates over the alkylation at the onset of the reaction. Carbenium ions, the direct electrophile for aromatic oxygenates, are produced mainly from the adsorption and protonation of olefins. The present study shows that for the alkylation of phenols and cyclic alcohols in apolar liquids, the alcohol concentration should be kept low to avoid the formation of unreactive surface dimers and mitigate their inhibitory effects on olefin adsorption and protonation.

Computational Framework to Evaluate the Hydrodynamics of Cell Scaffold Geometries.

The fluid dynamics of microporous materials are important to many biomedical processes such as cell deposition in scaffold materials, tissue engineering, and bioreactors. Microporous scaffolds are frequently composed of suspensions of beads that have varying topology which, in turn, informs their hydrodynamic properties. Previous work has shown that shear stress distributions can affect the response of cells in microporous environments. Using computational fluid dynamics, we characterize localized differences in fluid flow attributes such wall shear stress and velocity to better understand the fluid dynamics underpinning microporous device function. We evaluated whether bead packings with similar void fractions had different fluid dynamics as characterized by the distribution of velocity magnitudes and wall shear stress and found that there are differences despite the similarities in void fraction. We show that another metric, the average distance to the nearest wall, can provide an additional variable to measure the porosity and susceptibility of microporous materials to high shear stress. By increasing our understanding of the impact of bead size on cell scaffold fluid dynamics we aim to increase the ability to predict important attributes such as loading efficiency in these devices.

Crystallographic Elucidation of Stimuli-Controlled Molecular Rotation for a Reversible Sol-Gel Transformation.

To get an idea about the most probable microporous supramolecular environment in the gel state, gelator molecule 1 has been crystallized from its gelling solvent (dimethylformamide). Crystal structure analysis of 1 shows a strong π···π stacking interaction between the electron-deficient pentafluorophenyl ring and electron-rich naphthyl ring. The gelling solvent situated in the "molecular pocket" stitches the gelators through weak H-bonding interactions to facilitate the formation of an organogel. Scanning electron microscopy analysis exhibits a ribbonlike fibrous morphology that resembles the supramolecular arrangement of 1 in its crystalline state, as evidenced by powder X-ray diffraction. In the presence of external stimuli (tetrabutylammonium fluoride), the organogel of 1 disassembles into sol. This sol-gel transformation phenomenon has been explained on the basis of X-ray single-crystal analysis. Single crystals obtained from the sol state show that naphthylic -OH of 1 gets deprotonated, resulting in C-C bond rotation that plays a major role in the sol-gel transformation. Gelator 1 exhibits weak green fluorescence in the gel state, whereas it shows highly intense yellow fluorescence in the sol state. Furthermore, a reversible sol-gel transformation associated with changes in the spectroscopic properties has been observed in the presence of acids and fluoride ions, respectively.

Evaluation of the Textural Parameters of Zeolite Beta in LDPE Catalytic Degradation: Thermogravimetric Analysis Coupled with FTIR Operando Studies

Zeolite-based catalysts are globally employed in many industrial processes, such as crude-oil refining and bulk chemical production. In this work, the cracking of low-density polyethylene (LDPE) was thoroughly followed in a FTIR operando study to examine the catalytic efficiency of purely microporous zeolites β of various textural characteristics. To provide complementary and valuable information on the catalytic activity of the zeolite β studied, the thermogravimetric analysis results were compared with yields of the products generated under operating conditions. The reaction products were analyzed via GC–MS to determine the hydrocarbon chain distribution in terms of paraffin, olefins, and aromatics. The individual impact of textural and acidic parameters on catalytic parameters was assessed. The accumulation of bridging hydroxyls of high strength in the zeolite β benefited the decrease in polymer decomposition temperature. Through a strategic comparison of purely microporous zeolites, we showed that the catalytic cracking of LDPE is dominated by the acidic feature inherent to the microporous environment.

Computational modelling of flow in a microporous environment of a natural reservoir with consideration of the topological structure

The article presents the initial stage of developing a hybrid mathematical model for describing the recovery of oil from a natural sand reservoir. The hybrid model means that part of the computational domain (microchannel structure in the space between particles) is calculated by one- dimensional models is based on the hydraulic circuit theory, and another part (large cracks and caverns) is calculated by computational fluid dynamics methods (CFD). The article also describes a unique algorithm for building a network model based on preliminary CFD calculation. The last section of the article presentation compares of results of calculation CFD and network models.

Interplay of Tri- and Bidentate Linkers to Evolve Micropore Environment in a Family of Quasi-3D and 3D Porous Coordination Polymers for Highly Selective CO2 Capture.

In the design and construction of porous materials, these with exceptional structure and composition are often highly expected, as they may offer unique nanopore space for desired applications. Here, a new family of quasi-3D and a 3D porous coordination polymers (PCPs) (termed NTU-43 to NTU-50) were constructed via an evolution strategy from a layered structure (termed NTU-42). Single gas adsorption isotherms of CO2, N2, and CH4 display the dependency of gas capacity on optimized effects of pore size, functionality, and charged framework of these quasi-3D PCPs, where NTU-45 and NTU-46, the two with NH2-BDC and OH-BDC bidentate linkers (NH2-BDC = 2-aminoterephthalic acid and OH-BDC = 2-hydroxyterephthalic acid) have demonstrated outstanding ability for selective CO2 uptake. To the best of our knowledge, this is the first time to well explore the synergistic effects toward gas adsorption on a platform of quasi-3D frameworks. More importantly, the efficient CO2 capture from CO2/CH4 and CO2/N2 mixtures has been also validated by breakthrough experiments under continuous and dynamic conditions at 298 K.

Porous chitosan adhesives with L-DOPA for enhanced photochemical tissue bonding

L-3,4-dihydroxyphenylalanine (L-DOPA) is a naturally occurring catechol that is known to increase the adhesive strength of various materials used for tissue repair. With the aim of fortifying a porous and erodible chitosan-based adhesive film, L-DOPA was incorporated in its fabrication for stronger photochemical tissue bonding (PTB), a repair technique that uses light and a photosensitiser to promote tissue adhesion. The results showed that L-DOPA did indeed increase the tissue bonding strength of the films when photoactivated by a green LED, with a maximum strength recorded of approximately 30 kPa, 1.4 times higher than in its absence. The addition of L-DOPA also did not appreciably change the swelling, mechanical and erodible properties of the film. This study showed that strong, porous and erodible adhesive films for PTB made from biocompatible materials can be obtained through a simple inclusion of a natural additive such as L-DOPA, which was simply mixed with chitosan without any chemical modifications. In vitro studies using human fibroblasts showed no negative effect on cell proliferation indicating that these films are biocompatible. The films are convenient for various surgical applications as they can provide strong tissue support and a microporous environment for cellular infusion without the use of sutures. Statement of significanceTissue adhesives are not as strong as sutures on wounds under stress. Our group has previously demonstrated that strong sutureless tissue repair can be realised with chitosan-based adhesive films that photochemically bond to tissue when irradiated with green light. The advantage of this technique is that films are easier to handle than glues and sutures, and their crosslinking reactions can be controlled with light. However, these films are not optimal for high-tension tissue regenerative applications because of their non-porous structure, which cannot facilitate cell and nutrient exchange at the wound site. The present study resolves this issue, as we obtained a strong and porous photoactivated chitosan-based adhesive film, by simply using freeze drying and adding L-DOPA.

Diffusive Escape of a Nanoparticle from a Porous Cavity.

Narrow escape from confinement through a nanochannel is the critical step of complex transport processes including size-exclusion-based separations, oil and gas extraction from the microporous subsurface environment, and ribonucleic acid translocation through nuclear pore complex channels. While narrow escape has been studied using theoretical and computational methods, experimental quantification is rare because of the difficulty in confining a particle into a microscopic space through a nanoscale hole. Here, we studied narrow escape in the context of continuous nanoparticle diffusion within the liquid-filled void space of an ordered porous material. Specifically, we quantified the spatial dependence of nanoparticle motion and the sojourn times of individual particles in the interconnected confined cavities of a liquid-filled inverse opal film. We found that nanoparticle motion was inhibited near cavity walls and cavity escape was slower than predicted by existing theories and random-walk simulations. A combined computational-experimental analysis indicated that translocation through a nanochannel is barrier controlled rather than diffusion controlled.

Imine-linked polymer/silica composites for CO2 sequestration

The silica supported imine polymers are synthesized using a facile single step Schiff-base condensation. The formation of imine linkage on silica support is confirmed using FT-IR and solid state 13C NMR. The crystallinity and surface morphology of the materials are examined by PXRD and SEM analyses. The thermal stability of the materials is confirmed from TGA analysis. N2 sorption isotherms for Si-TPA-1 and Si-TPA-2 exhibit surface area of 105.8 m2/g and 404.5 m2/g respectively. The adsorption isotherms exhibit meso- and microporous environments of Si-TPAs. The CO2 uptake capacity of Si-TPAs are around 38.86 mg/g - 121. 85 mg/g. The experimental adsorption data is fitted with Langmuir and Freundlich adsorption isotherm models. The thermodynamic parameters emphasis that the adsorption process is spontaneous and exothermic physisorption. Isosteric heats of adsorption for Si-TPAs are around 38.5–32.5 kJ/mol. The high selectivity of CO2 over N2 is obtained for both Si-TPAs at 273 K and also high selectivity of CO2 over CH4 is achieved at 298 K.

Covalent organic framework with high capacity for the lithium ion battery anode: insight into intercalation of Li from first-principles calculations

Covalent organic frameworks (COFs) generally have high stability, large charge capacity and wide ion diffusion paths, and they may serve as the potential electrode materials for lithium ion batteries. Here we explored the structural, electronic, and lithium-storage properties of the newly synthesized NUS-2 COF material by first-principles calculations. The present results indicate that the micropore environment and the presence of the carbonyl oxygens in the NUS-2 COF can prevent the formation of lithium dimer and the aggregation of lithium bulk, which can improve lithiation efficiency. The predicted maximum theoretical capacity is as high as 742.8 mAh g−1 and the average cell voltage varies from 3.35 V for Li@NUS-2 to 2.04 V for 14Li@NUS-2, suggesting that the NUS-2 COF material should be a quite suitable lithium-storage anode material.

Effect of Surface Ionization of Doped MnO2 on Capacitive Deionization Efficiency.

Associating MnO2 with carbonaceous supports profoundly enhances capacitive deionization (CDI) efficiency. A fundamental question of how the surface chemistry of MnO2 itself influences CDI efficiency is not yet fully understood. In this study, the effect of surface ionization on the CDI efficiencies of Fe-, Co-, and Ni-doped α-MnO2 (<0.1 mol %) as a model cathode material was studied. A pattern that CDI efficiency decreased with increasing negative surface charge density resulting from surface deprotonation was noted. This is likely attributed to the appreciable co-ion expulsion occurring at a highly ionized surface in the mesopores of MnO2. It is thus concluded that the combination of surface charge modification and a microporous environment would be important for CDI efficiency enhancement by minimizing co-ion exclusion effect. In the former case, structural stress adjustment by doping elements would be a practical route to regulate the p Ka1 and p Ka2 values and consequently the degree of surface ionization of MnO2.

Microfluidic-enabled bottom-up hydrogels from annealable naturally-derived protein microbeads

Naturally-derived proteins, such as collagen, elastin, fibroin, and gelatin (denatured collagen) hold a remarkable promise for tissue engineering and regenerative medicine. Gelatin methacryloyl (GelMA), synthesized from the methacryloyl modification of gelatin, mimicking the structure of extracellular matrix, has widely been used as a universal multi-responsive scaffold for a broad spectrum of applications, spanning from cell therapy to bioprinting and organoid development. Despite the widespread applications of GelMA, coupled stiffness and porosity has inhibited its applications in 3D cellular engineering wherein a stiff scaffold with large pores is demanded (e.g., at concentrations >10 wt%). Taking advantage of the orthogonal thermo-chemical responsivity of GelMA, we have developed microfluidic-assisted annealable GelMA beads, that are first stabilized by temperature-mediated physical crosslinking, flowed to form a scaffold structure, and then chemically annealed using light to fabricate novel bead-based 3D GelMA scaffolds with high mechanical resilience. We show how beaded GelMA (B-GelMA) provides a self-standing microporous environment with an orthogonal void fraction and stiffness, promoting cell adhesion, proliferation, and rapid 3D seeding at a high polymer concentration (∼20 wt%) that would otherwise be impossible for bulk GelMA. B-GelMA, decorated with methacryloyl and arginylglycylaspartic acid (RGD) peptide motifs, does not require additional functionalization for annealing and cell adhesion, providing a versatile biorthogonal platform with orthogonal stiffness and porosity for a myriad of biomedical applications. This technology provides a universal method to convert polymeric materials with orthogonal physico-chemical responsivity to modular platforms, opening a new horizon for converting bulk hydrogels to beaded hydrogels (B-hydrogels) with decoupled porosity and stiffness.

Influence of confining environment polarity on ethanol dehydration catalysis by Lewis acid zeolites

Lewis acidic Sn centers isolated within Beta zeolite frameworks catalyze bimolecular ethanol dehydration to diethyl ether, yet with kinetic behavior sensitive to the hydrophobic character of their confining microporous voids. Sn sites in open ((HO)-Sn-(OSi)3) and closed (Sn-(OSi)4) configurations, quantified from infrared spectra of adsorbed CD3CN before and after reaction, convert to structurally similar intermediates during ethanol dehydration catalysis (404 K) and revert to their initial configurations after regenerative oxidation treatments (21% O2, 803 K). Dehydration rate data (404 K, 0.5–35 kPa C2H5OH, 0.1–50 kPa H2O) measured on ten low-defect (Sn-Beta-F) and high-defect (Sn-Beta-OH) zeolites were described by a rate equation that was derived from mechanisms identified previously by density functional theory calculations and simplified using microkinetic modeling to identify kinetically-relevant pathways and intermediates. Polar hydroxyl defect groups located in the microporous environments that confine Sn sites preferentially stabilize reactive (ethanol-ethanol) and inhibitory (ethanol-water) dimeric intermediates over monomeric ethanol intermediates. As a result, equilibrium constants (404 K) for ethanol-water and ethanol-ethanol dimer formation are 3–4× higher on Sn-Beta-OH than on Sn-Beta-F, consistent with insights from single-component (302 K) and two-component (303 K, 403 K) ethanol and water adsorption measurements. Intrinsic dehydration rate constants (404 K) were identical, within error, among Sn-Beta-OH and Sn-Beta-F zeolites; thus, measured differences in dehydration turnover rates solely reflect differences in prevalent surface coverages of inhibitory and reactive dimeric intermediates at active Sn sites. The confinement of Lewis acidic binding sites within secondary microporous environments of different defect density confers the ability to discriminate surface intermediates on the basis of polarity, providing a design strategy to accelerate turnover rates and suppress inhibition by water.

Ethylene formation by dehydration of ethanol over medium pore zeolites

In this work, the role of pore arrangement of 10-ring zeolites ZSM-5, TNU-9 and IM-5 on their catalytic properties in ethanol transformation were investigated. Among all the studied catalysts, the zeolite IM-5, characterized by limited 3-dimensionality, presented the highest conversion of ethanol and the highest yields of diethyl ether (DEE) and ethylene. The least active and selective to ethylene and C3+ products was zeolite TNU-9 with the largest cavities formed on the intersection of 10-ring channels. The catalysts varied, however, in lifetime, and their deactivation followed the order: IM-5>TNU-9>ZSM-5. The processes taking place in the microporous zeolite environment were tracked by IR spectroscopy and analysed by the 2D correlation analysis (2D COS) allowing for an insight into the nature of chemisorbed adducts and transition products of the reaction. The cage dimension was found as a decisive factor influencing the tendency for coke deposition, herein identified as polymethylated benzenes, mainly 1,2,4-trimethyl-benzene.

Xylenes transformation over zeolites ZSM-5 ruled by acidic properties

The studies presented in this work offer an insight into xylene isomerization process, followed by 2D COS analysis, in the terms of different acidity of microporous zeolites ZSM-5. The isomerisation reaction proceeded effectively over zeolites ZSM-5 of Si/Al equal of 12 and 32. Among them, the Al-poorer zeolite (Si/Al=32) was found to offer the highest conversion and selectivity to p-xylene with the lowest number of disproportionation products, both in ortho- and meta-xylene transformation. Further reduction of Brønsted acidity facilitated the disproportionation path (zeolites of Si/Al=48 and 750). The formation of intermediate species induced by the diffusion constraints for m-xylene in 10-ring channels was rationalized in the terms of the methylbenzenium ions formation inside the rigid micropore environment. Finally, both microporous character of zeolite and the optimised acidity were found to be crucial for high selectivity to the most desired product i.e. p-xylene. The analysis of asynchronous maps allowed for concluding on the order of the appearance of the respective products on the zeolite surface.

Molecular simulation of CO2/CH4 adsorption in brown coal: Effect of oxygen-, nitrogen-, and sulfur-containing functional groups

The CO2/CH4 adsorption behaviors in brown coal at the temperatures of 298, 313, and 373K and in the pressure range of 0.005–10MPa were investigated by molecular dynamics (MD), density functional theory (DFT), and grand canonical Monte Carlo (GCMC) simulations. The absolute adsorption isotherms of single-component CH4 and CO2 exhibit type-I Langmuir adsorption behavior showing a negative influence of temperature. For the binary CO2/CH4 mixture, brown coal shows super high selectivity of CO2 over CH4 at pressures below 0.2MPa, which then decreases quickly and finally tends to be constant when the pressure increases. The high competitive adsorption of CO2 originates from the effects of (i) the large electrostatic contributions, (ii) the conducive micropore environment with pore sizes below 0.56nm, and (iii) the stronger adsorption of CO2 with respect to CH4. These effects are strengthened by the high-density oxygen-containing, pyridine, and thiophene functional groups contained in brown coal, which provide abundant and strong adsorption sites for CO2, but show weaker affinity to CH4. Furthermore, the influence of various nitrogen- and sulfur-containing functional groups on the CO2 adsorption capacity was also investigated. The results indicate that the basicity of the oxygen- and nitrogen-containing groups has a large influence on the CO2 adsorption, while for the sulfur functional groups the determining factor is the polarity.

Equilibria model for pH variations and ion adsorption in capacitive deionization electrodes

Ion adsorption and equilibrium between electrolyte and microstructure of porous electrodes are at the heart of capacitive deionization (CDI) research. Surface functional groups are among the factors which fundamentally affect adsorption characteristics of the material and hence CDI system performance in general. Current CDI-based models for surface charge are mainly based on a fixed (constant) charge density, and do not treat acid-base equilibria of electrode microstructure including so-called micropores. We here expand current models by coupling the modified Donnan (mD) model with weak electrolyte acid-base equilibria theory. In our model, surface charge density can vary based on equilibrium constants (pK's) of individual surface groups as well as micropore and electrolyte pH environments. In this initial paper, we consider this equilibrium in the absence of Faradaic reactions. The model shows the preferential adsorption of cations versus anions to surfaces with respectively acidic or basic surface functional groups. We introduce a new parameter we term “chemical charge efficiency” to quantify efficiency of salt removal due to surface functional groups. We validate our model using well controlled titration experiments for an activated carbon cloth (ACC), and quantify initial and final pH of solution after adding the ACC sample. We also leverage inductively coupled plasma mass spectrometry (ICP-MS) and ion chromatography (IC) to quantify the final background concentrations of individual ionic species. Our results show a very good agreement between experiments and model. The model is extendable to a wide variety of porous electrode systems and CDI systems with applied potential.

A new method for calculating gas content of coal reservoirs with consideration of a micro-pore overpressure environment

When the gas content of a coal reservoir is calculated, the reservoir pressure measured by well logging and well testing is generally used for inversion calculation instead of gas pressure. However, the calculation result is not accurate because the reservoir pressure is not equal to the gas pressure in overpressure environments. In this paper, coal samples of different ranks in Shanxi and Henan are collected for testing the capillary pressure of coal pores. Based on the formation process of CBM reservoirs and the hydrocarbon generation and expulsion history of coal beds, the forming mechanisms of micro-pore overpressure environments in coal reservoirs were analyzed. Accordingly, a new method for calculating the gas content of coal reservoirs with consideration of a micro-pore overpressure environment was developed. And it was used to calculate the gas content of No. 1 coal bed of the 2nd member of Lower Permian Shanxi Fm in the Zhongmacun Coal Mine in Jiaozuo, Henan. It is indicated that during the formation and evolution of coals, some solid organic matters were converted into gas and water, and gas–water contact is surely formed in pores. In the end, capillary pressure is generated, so the gas pressure in micro-pores is much higher than the hydrostatic column pressure, which results in a micro-pore overpressure environment. Under such an environment, gas pressure is higher than reservoir pressure, so the gas content of coal reservoirs calculated previously based on the conventional reservoir pressure evaluation are usually underestimated. It is also found that the micro-pore overpressure environment exerts a dominating effect on the CBM content calculation of 3–100 nm pores, especially that of 3–10 nm pores, but a little effect on that of pores >100 nm. In conclusion, this new method clarifies the pressure environment of CBM gas reservoirs, thereby ensuring the calculation accuracy of gas content of coal reservoirs.

One-pot synthesis of triptycene-based porous organic frameworks with tailored micropore environments for highly efficient and selective amine adsorption

Triptycene-based porous organic frameworks (POFs) with high BET (Brunauer–Emmett–Teller) surface areas and tailored micropore environments were prepared using a facile external knitting strategy. The functionalized POFs exhibited very high aliphatic amine vapor uptakes of up to 5 times their own weight and more than 30 times selectivity for aliphatic amines over n-hexane; thus, they provide new opportunities for environment-related applications. Triptycene-based porous organic frameworks (POFs) with high BET (Brunauer–Emmett–Teller) surface and tailored micropore environments were prepared through a facile external knitting strategy. The functionalized POFs exhibited very high aliphatic amine vapor uptakes of up to 5 times of their own weight, and more than 30 times selectivity for aliphatic amines over n-hexane, and thus they open up new opportunities for environment-related applications.

The state of iron sites in the calcined FeAlPO4-5 and its tuning to the property of microporous AlPO4-5 molecular sieve

The dispersion and coordination is critical to the nature of metal phases. This article describes an approach of single Fe sites preparing under microporous environment via calcination of the Fe incorporated FeAlPO4-5 as well as the tuning to the property of AlPO4-5 molecular sieve. The UV, Raman, EPR spectroscopies and H2-TPR characterization revealed through the extraction of framework Fe inside the micropore by calcination, extra-framework Fe sites were generated, the dispersion of which was higher than Fe sites of impregnated Fe2O3/AlPO4-5, and it indicated that part of Fe sites of FeAlPO4-5 can be with coordination vacancy. It is notable that the presence of single Fe sites was directly observed by Cs-corrected STEM micrograph. NH3-TPD and toluene-TPD results both exhibited an enhanced acidity and π bond adsorption ability of FeAlPO4-5 toward AlPO4-5 and the impregnated sample Fe2O3/AlPO4-5. Finally, the FeAlPO4-5 turned out to perform higher thiophene desulfurization rate against AlPO4-5 and impregnated sample, which can be related to the improvement in the adsorption ability and reactivity for the single Fe sites inside the microporous environment.