Pore Walls Research Articles

MnO2@CS modified catalytic membrane for simultaneous organics removal and membrane fouling mitigation via peroxymonosulfate activation

The integration of advanced oxidation process and ultrafiltration membrane has been regarded as an effective method to improve pollutants removal and mitigate membrane fouling simultaneously in the field of wastewater treatment. Hence, a novel catalytic membrane microreactor, referred to as MnO2@CS-UF, was synthesized via coupling MnO2 modified carbon spheres (MnO2@CS) with membrane. The mesoporous structure of MnO2@CS guaranteed adequate water transfer channels and also contributed to more exposure of active sites. With MnO2@CS uniformly dispersed, the MnO2@CS-UF membrane showed increased hydrophilicity, higher permeability and superior peroxymonosulfate (PMS)-activation capability. With synergistic effect of pore interception and catalytic degradation, MnO2@CS-UF showed excellent organic pollutants removal (MB removal of about 100 % in 5 min), and had a prominent mitigation effect on membrane fouling caused by model NOM. In addition, MnO2@CS-UF/PMS system showed excellent catalytic filtration performance in the treatment of actual secondary effluent (SE). MnO2@CS-UF/PMS system could effectively remove fluorescent organics, and the removal rates of I-V region were 36.3 %, 72.3 %, 67.7 %, 73.5 % and 71.4 %, respectively. The permeance decline of MnO2@CS-UF was also effectively alleviated, with irreversible and reversible resistances reduced by 61.0 % and 23.2 % than UF membranes, individually. High-valent manganese-oxo species and singlet oxygen played a leading role in contaminants elimination, whereas radical oxidation acted as auxiliary contributors. Standard blocking became the dominant fouling pattern for MnO2@CS-UF/PMS, demonstrating that the MnO2@CS catalytic layer ensured the synthesis of vast active substances, prevented foulant adhesion on pore walls and alleviated the growth of cake layer. These results illustrated that the integration of MnO2@CS catalytic degradation and membrane filtration was feasible to improve the permeate quality and mitigate membrane fouling in wastewater reclamation.

Effect of contact angle on the pressure needed for a liquid to permeate a cylindrical pore

Effective separation of two immiscible liquids with filters requires a difference in the pressures to permeate between the two liquids, and setting the applied pressure between these two pressures. To help design such filters, we present an equation that enables the calculation of the pressure for a liquid phase to permeate through a smooth pore in the shape of a truncated cone as a function of (a) the contact angle of the liquid on the filters and (b) the angle of the pore wall. The equation was derived by considering the interfacial energy required to push a liquid meniscus from the top of the pore to the bottom, and then to exceed the maximum curvature required at the exit. This equation was tested experimentally by adding a hydrostatic head with water on the 3D-printed filters of acrylate polymer while systematically varying the pore radii and contact angle with water. Experimental results showed an increased pressure to permeate with higher contact angles while the equation predicted the opposite. We hypothesized that the reason for the disagreement was the assumption of a smooth pore. For a liquid on a rough pore wall, the curvature of the meniscus is not solely determined from the microscopic contact angle and the pore wall angle, but the liquid would adopt a lower curvature meniscus. Therefore, the developed equation was modified after reflecting the lower curvature, which showed much better agreement with the experimental results. The remaining discrepancy from the theory was attributed to the pressure fluctuation from the fluid flow occurring while adding water.

Enhanced Recovery of Oil Mixtures from Calcite Nanopores Facilitated by CO2 Injection.

Slow production, preferential recovery of light hydrocarbons, and low recovery factors are common challenges in oil production from unconventional reservoirs dominated by nanopores. Gas injection-based techniques such as CO2 Huff-n-Puff have shown promise in addressing these challenges. However, a limited understanding of the recovery of oil mixtures on the nanopore scale hinders their effective optimization. Here, we use molecular dynamics simulations to study the recovery of an oil mixture (C10 + C19) from a single 4 nm-wide calcite dead-end pore, both with and without CO2 injection. Without CO2 injection, oil recovery is much faster than expected from oil vaporization and features an undesired selectivity, i.e., the preferential recovery of lighter C10. With CO2 injection, oil recovery is accelerated and its selectivity toward C10 is greatly mitigated. These recovery behaviors are understood by analyzing the spatiotemporal evolution of C10, C19, and CO2 distributions in the calcite pore. In particular, we show that interfacial phenomena (e.g., the strong adsorption of oil and CO2 on pore walls, their competition, and their modulation of transport behavior) and bulk phenomena (e.g., solubilization of oil by CO2 in the middle portion of the pore) play crucial roles in determining the oil recovery rate and selectivity.

Modeling enzymatic and electrochemical cascade reactions at the three‐phase interface enzyme electrode

AbstractThe enzyme electrode based on enzymatic and electrochemical cascade reactions is a golden approach for detecting various biomarkers. How the interfacial architectures of a promising three‐phase interface enzyme electrode can influence the cascade reactions and electrode performance, however, remains unclear. In this study, a mathematical model has been developed to describe intraphase and interphase mass transfer, coupled with cascade reactions. The results reveal that the interfacial architectures determine the mass transfer of oxygen (substrate of oxidase) and H2O2 (enzymatic product) in the cascade reactions, hence affecting the electrode current. Generally, thinner pore walls facilitate the mass transfer of oxygen, thereby enhancing the enzymatic kinetics and H2O2 production. Meanwhile, smaller pore sizes shorten the diffusion pathway of H2O2 to the electrode surface, thereby increasing the electrocatalytic reaction rate. This work provides an efficient in silico tool for the design of high‐performance three‐phase enzyme electrodes.

Effect of movability of water on the low-velocity pre-Darcy flow in clay soil

Water seepage in soil is a fundamental problem involving various scientific and engineering fields. According to the literature, low-velocity water seepage in low-permeability porous media, such as clay, does not follow Darcy's law, also known as pre-Darcy flow. The formation of immovable water due to water adsorption on the pore wall is believed to be responsible for the formation of pre-Darcy flow. However, this view lacks direct solid evidence. To investigate the pre-Darcy water flow in clay, head permeability experiments are conducted on six clay samples with different densities. The results indicate that water seepage in clay at low hydraulic gradients does not follow Darcy's law. A clear nonlinear relationship between flow velocity and hydraulic gradient is observed. Water flow in clay can be divided into the pre-Darcy flow and Darcy flow regions by the critical hydraulic gradient, which is 10–12 for the Albic soil with dry density between 1.3 g/cm3 and 1.8 g/cm3. According to the disjoining pressure theory, immovable water due to water adsorption on the pore wall is the primary reason for water flow deviating from Darcy's law in clay. The results indicate that the percentage of movable water ranges from 39.7% to 59.3% for the six samples at a hydraulic gradient of 1. As the hydraulic gradient increases, the percentage of moveable water also increases. Additionally, there is a strong correlation between the percentage of movable water and the variation in hydraulic conductivity with the hydraulic gradient. Furthermore, a quantitative relationship between the percentage of movable water and the hydraulic conductivity has been established. The results of this study suggest that water adsorption on the pore wall not only affects the water movability, but is also closely related to the pre-Darcy flow phenomenon in clay.

Study on the Effects of Wettability and Pressure in Shale Matrix Nanopore Imbibition during Shut-in Process by Molecular Dynamics Simulations.

Shut-in after fracturing is generally adopted for wells in shale oil reservoirs, and imbibition occurring in matrix nanopores has been proven as an effective way to improve recovery. In this research, a molecular dynamics (MD) simulation was used to investigate the effects of wettability and pressure on nanopore imbibition during shut-in for a typical shale reservoir, Jimsar. The results indicate that the microscopic advancement mechanism of the imbibition front is the competitive adsorption between "interfacial water molecules" at the imbibition front and "adsorbed oil molecules" on the pore wall. The essence of spontaneous imbibition involves the adsorption and aggregation of water molecules onto the hydroxyl groups on the pore wall. The flow characteristics of shale oil suggest that the overall push of the injected water to the oil phase is the main reason for the displacement of adsorbed oil molecules. Thus, shale oil, especially the heavy hydrocarbon component in the adsorbed layer, tends to slip on the walls. However, the weak slip ability of heavy components on the wall surface is an important reason that restricts the displacement efficiency of shale oil during spontaneous imbibition. The effectiveness of spontaneous imbibition is strongly dependent on the hydrophilicity of the matrix pore's wall. The better hydrophilicity of the matrix pore wall facilitates higher levels of adsorption and accumulation of water molecules on the pore wall and requires less time for "interfacial water molecules" to compete with adsorbed oil molecules. During the forced imbibition process, the pressure difference acts on both the bulk oil and the boundary adsorption oil, but mainly on the bulk oil, which leads to the occurrence of wetting hysteresis. Meanwhile, shale oil still existing in the pore always maintains a good, stratified adsorption structure. Because of the wetting hysteresis phenomenon, as the pressure difference increases, the imbibition effect gradually increases, but the actual capillary pressure gradually decreases and there is a loss in the imbibition velocity relative to the theoretical value. Simultaneously, the decline in hydrophilicity further weakens the synergistic effect on the imbibition of the pressure difference because of the more pronounced wetting hysteresis. Thus, selecting an appropriate well pressure enables cost savings and maximizes the utilization of the formation's natural power for enhanced oil recovery (EOR).

Covalent Organic Frameworks as a Versatile Platform for Iron‐Catalyzed sp3 C−H Activation and Cross‐Coupling via Decarboxylative Oxidation

AbstractThis work demonstrates the oxidative cross‐coupling of cinnamic acids with toluene using FeCl3 immobilized on a covalent organic framework (COF) pore wall, resulting in the synthesis of 1,3‐arylpropene derivatives. This iron‐based heterogeneous catalytic system affords the desired products in moderate yields ranging from 51 % to 65 %. Investigations using COFs with varying pore sizes indicate that larger pores facilitate the reaction, suggesting a spatial requirement for this transformation within the catalyst. The correlation between pore size and reaction efficiency provides insights into developing tailored catalysts to match the spatial requirements of the transformation. This version emphasizes the novelty of the study and the synthesis of 1,3‐arylpropene derivatives. It also clarifies that the iron‐based heterogeneous catalytic system is responsible for the reaction. Additionally, it provides a more detailed explanation of the findings regarding pore size and spatial requirements.

Adsorption behavior of CO2/H2S mixtures in calcite slit nanopores for CO2 storage: An insight from molecular perspective

It is acknowledged that injecting CO2 into oil reservoirs and saline aquifers for storage is a practical and affordable method for CO2 sequestration. Most CO2 produced from industrial exhaust contains impurity gases such as H2S that might impact CO2 sequestration due to competitive adsorption. This study makes a commendable effort to explore the adsorption behavior of CO2/H2S mixtures in calcite slit nanopores. Grand Canonical Monte Carlo (GCMC) simulation is employed to reveal the adsorption of CO2, H2S as well as their binary mixtures in calcite nanopores. Results show that the increase in pressure and temperature can promote and inhibit the adsorption capacity of CO2 and H2S in calcite nanopores, respectively. CO2 exhibits stronger adsorption on calcite surface than H2S. Electrostatic energy plays the dominating role in the adsorption behavior. Electrostatic energy accounts for 97.11% of the CO2-calcite interaction energy and 56.33% of the H2S-calcite interaction energy at 10 MPa and 323.15 K. The presence of H2S inhibits the CO2 adsorption in calcite nanopores due to competitive adsorption, and a higher mole fraction of H2S leads to less CO2 adsorption. The quantity of CO2 adsorbed is lessened by approximately 33% when the mole fraction of H2S reaches 0.25. CO2 molecules preferentially occupy the regions near the pore wall and H2S molecules tend to reside at the center of nanopore even when the molar ratio of CO2 is low, indicating that CO2 has an adsorption priority on the calcite surface over H2S. In addition, moisture can weaken the adsorption of both CO2 and H2S, while CO2 is more affected. More interestingly, we find that pure CO2 is more suitable to be sequestrated in the shallower formations, i.e., 500–1500 m, whereas CO2 with H2S impurity should be settled in the deeper reservoirs.

Stress-Relief Engineering in a N-Doped C-Modified Hierarchical Nanoporous Si Anode with a Microcurved Pore Wall Structure for Enhanced Lithium Storage.

The commercialization of alloy-type anodes has been hindered by rapid capacity degradation due to volume fluctuations. To address this issue, stress-relief engineering is proposed for Si anodes that combines hierarchical nanoporous structures and modified layers, inspired by the phenomenon in which structures with continuous changes in curvature can reduce stress concentration. The N-doped C-modified hierarchical nanoporous Si anode with a microcurved pore wall (N-C@m-HNP Si) is prepared from inexpensive Mg-55Si alloys using a simple chemical etching and heat treatment process. When used as the anode for lithium-ion batteries, the N-C@m-HNP Si anode exhibits initial charge/discharge specific capacities of 1092.93 and 2636.32 mAh g-1 at 0.1 C (1 C = 3579 mA g-1), respectively, and a stable reversible specific capacity of 1071.84 mAh g-1 after 200 cycles. The synergy of the hierarchical porous structure with a microcurved pore wall and the N-doped C-modified layer effectively improves the electrochemical performance of N-C@m-HNP Si, and the effectiveness of stress-relief engineering is quantitatively analyzed through the theory of elastic bending of thin plates. Moreover, the formation process of Li15Si4 crystals, which causes substantial mechanical stress, is investigated using first-principles molecular dynamic simulations to reveal their tendency to occur at different scales. The results demonstrate that the hierarchical nanoporous structure helps to inhibit the transformation of amorphous LixSi into metastable Li15Si4 crystals during lithiation.

Influence of tool-edge radius on the nano-cutting process of non-continuous surfaces in single-crystal silicon

Pore deformation and damage are caused by the compression of the cutting tool during the machining of porous materials. Tool-edge radius is a key factor in the nano-cutting of pores and significantly influences the resulting deformation and damage. In this paper, the molecular dynamics simulations were conducted to investigate nano-cutting process of the non-continuous surface in single-crystal silicon. Surface morphology, pore wall deformation, cutting forces, and subsurface damage were calculated and discussed under different tool-edge radii. The results indicated that the change of the tool-edge radius greatly affect the machining quality of non-continuous surface. Cutting forces and accumulated material above the pores increase with increasing tool-edge radius, and the side of the tool entering the pore is more susceptible to damage than the opposite side. Additionally, normal force was identified as the primary cause of damage on the side of the tool entering the pore. The longitudinal damage depth on the side of the tool entering the pore increases with the tool-edge radius. Comprehensive analysis of material distribution, pore wall deformation and damage indicates that a smaller tool-edge radius is more conducive to pore processing.

Hydrogen Adsorption in Porous Geological Materials: A Review

The paper adopts an interdisciplinary approach to comprehensively review the current knowledge in the field of porous geological materials for hydrogen adsorption. It focuses on detailed analyses of the adsorption characteristics of hydrogen in clay minerals, shale, and coal, considering the effect of factors such as pore structure and competitive adsorption with multiple gases. The fundamental principles underlying physically controlled hydrogen storage mechanisms in these porous matrices are explored. The findings show that the adsorption of hydrogen in clay minerals, shale, and coal is predominantly governed by physical adsorption that follows the Langmuir adsorption equation. The adsorption capacity decreases with increasing temperature and increases with increasing pressure. The presence of carbon dioxide and methane affects the adsorption of hydrogen. Pore characteristics—including specific surface area, micropore volume, and pore size—in clay minerals, shale, and coal are crucial factors that influence the adsorption capacity of hydrogen. Micropores play a significant role, allowing hydrogen molecules to interact with multiple pore walls, leading to increased adsorption enthalpy. This comprehensive review provides insights into the hydrogen storage potential of porous geological materials, laying the groundwork for further research and the development of efficient and sustainable hydrogen storage solutions.

Alumina Incorporation in Self-Supported Poly(ethylenimine) Sorbents for Direct Air Capture.

Self-supported branched poly(ethylenimine) scaffolds with ordered macropores are synthesized with and without Al2O3 powder additive by cross-linking poly(ethylenimine) (PEI) with poly(ethylene glycol) diglycidyl ether (PEGDGE) at -196 °C. The scaffolds' CO2 uptake performance is compared with a conventional sorbent, i.e., PEI impregnated on an Al2O3 support. PEI scaffolds with Al2O3 additive show narrow pore size distribution and thinner pore walls than alumina-free materials, facilitating higher CO2 uptake at conditions relevant to direct air capture. The PEI scaffold containing 6.5 wt % Al2O3 had the highest CO2 uptake of 1.23 mmol/g of sorbent under 50% RH 400 ppm of CO2 conditions. In situ DRIFT spectroscopy and temperature-programmed desorption experiments show a significant CO2 uptake contribution via physisorption as well as carbamic acid formation, with lower CO2 binding energies in PEI scaffolds relative to conventional PEI sorbents, likely a result of a lower population of primary amines due to the amine cross-linking reactions during scaffold synthesis. The PEI scaffold containing 6.5 wt % Al2O3 is estimated to have the lowest desorption energy penalty under humid conditions, 4.6 GJ/tCO2, among the sorbents studied.

Diameter dependence of transport through nuclear pore complex mimics studied using optical nanopores

The nuclear pore complex (NPC) regulates the selective transport of large biomolecules through the nuclear envelope. As a model system for nuclear transport, we construct NPC mimics by functionalizing the pore walls of freestanding palladium zero-mode waveguides with the FG-nucleoporin Nsp1. This approach enables the measurement of single-molecule translocations through individual pores using optical detection. We probe the selectivity of Nsp1-coated pores by quantitatively comparing the translocation rates of the nuclear transport receptor Kap95 to the inert probe BSA over a wide range of pore sizes from 35 nm to 160 nm. Pores below 55 ± 5 nm show significant selectivity that gradually decreases for larger pores. This finding is corroborated by coarse-grained molecular dynamics simulations of the Nsp1 mesh within the pore, which suggest that leakage of BSA occurs by diffusion through transient openings within the dynamic mesh. Furthermore, we experimentally observe a modulation of the BSA permeation when varying the concentration of Kap95. The results demonstrate the potential of single-molecule fluorescence measurements on biomimetic NPCs to elucidate the principles of nuclear transport.

Diameter dependence of transport through nuclear pore complex mimics studied using optical nanopores.

The nuclear pore complex (NPC) regulates the selective transport of large biomolecules through the nuclear envelope. As a model system for nuclear transport, we construct NPC mimics by functionalizing the pore walls of freestanding palladium zero-mode waveguides with the FG-nucleoporin Nsp1. This approach enables the measurement of single-molecule translocations through individual pores using optical detection. We probe the selectivity of Nsp1-coated pores by quantitatively comparing the translocation rates of the nuclear transport receptor Kap95 to the inert probe BSA over a wide range of pore sizes from 35 nm to 160 nm. Pores below 55 ± 5 nm show significant selectivity that gradually decreases for larger pores. This finding is corroborated by coarse-grained molecular dynamics simulations of the Nsp1 mesh within the pore, which suggest that leakage of BSA occurs by diffusion through transient openings within the dynamic mesh. Furthermore, we experimentally observe a modulation of the BSA permeation when varying the concentration of Kap95. The results demonstrate the potential of single-molecule fluorescence measurements on biomimetic NPCs to elucidate the principles of nuclear transport.

Al2O3 Thin Layer Formed inside Porous Membrane Using Spray Synthesis Method and Its Application

Aluminum oxide (Al2O3) films have been investigated for use in various applications, and numerous deposition techniques have been reported. The spray synthesis method has the advantage of forming a thin layer of crystal at low temperatures using the appropriate precursors. A precursor prepared by diluting Methylaluminoxane with N-methyl pyrrolidone was sprayed onto a porous membrane while varying conditions such as the substrate temperature, feeding speed, and spray amount. The solution penetrated the film during spray application, and the ultra-thin layers deposited on the side wall of the internal pores were observed using a cross-sectional transmission electron microscope (XTEM). The lattice image obtained using the TEM and the composition analysis conducted using a scanning TEM and an energy-dispersive X-ray spectroscope suggest that this thin layer is a layer of Al2O3. The formation of Al2O3 occurred at lower temperatures than in previous reports. This is a major advantage for applications with low-melting-point materials. The most suitable spraying conditions were determined based on the state of deposition on the surface and inside the membrane. These conditions were applied to a three-layer separator for lithium-ion batteries and their effect on thermal stability was investigated. Through heating experiments and XRD analysis, it was confirmed that the shrinkage and melting of the separator are suppressed by spraying. This process can be expected to have wide applications in low-melting-point materials such as polyolefin.

Fabrication and properties of hydroxyapatite/chitosan composite scaffolds loaded with periostin for bone regeneration

This paper reports a facile fabrication method of hydroxyapatite/chitosan (HAp/CS) composite scaffold with 3D porous structure without using any chemical cross-linkers. The HAp particles had an urchin-like hollow microstructure and high surface area, which was uniformly dispersed into the pore walls of the HAp/CS scaffold. The addition of HAp can efficiently enhance the mechanical properties and bioactivity of the HAp/CS scaffold. Moreover, periostin was successfully loaded onto the HAp/CS scaffold. When applied to the repair of bone defect in a rat mandibular model, the HAp/CS scaffold loaded with periostin can enhance osteointegration and accelerate bone regeneration. Our research combines periostin with the HAp/CS composite material, which provides a novel strategy to improve bone regeneration and has great application prospect in bone repair fields.

Nuclear magnetic resonance study on wettability of shale oil reservoir

In order to identify and evaluate reservoir wettability, so as to select suitable mining methods to improve oil recovery, wettability evaluation through one-dimensional (1D) and two-dimensional (2D) nuclear magnetic resonance (NMR) technology combined with physical simulation experiments was carried out in this study, and the feasibility of the experimental method was verified by contact Angle method. According to the principle of hydrophilic inorganic content and hydrophobic organic content of shale, the wettability can be evaluated through vacuum self-imbibition oil and self-imbibition water physical simulation experiments combined with 1D NMR technology, that is, total water absorption can be considered as inorganic content, organic content can be obtained by subtracting total water absorption from total oil absorption, and adsorbed oil content can be obtained by subtracting pore volume from total oil absorption. In addition to the wettability measurement by contact Angle method to verify the experimental method, the occurrence ratio of adsorbed oil can also be verified twice by 2D NMR spectrum. The results show that the error between the proportion of adsorbed oil measured by 2D NMR spectrum and that measured by self-imbibition method is within 4%. In the saturated oil-bound water state, the bound water is within the relaxation interval of 1<T1<10 ms and 1<T2<10 ms, and the oil signal is within the relaxation interval of T1>10 ms and T2>10 ms. And the relaxation time of aqueous phase moved to the right compared with that in the saturated water state, the interaction force between water and the pore wall was weakened, showing the characteristics of free fluid, and the rock sample became oil-wet, which was consistent with the wettability results measured by contact Angle. Therefore, the wettability of rock samples can be evaluated by 1D NMR technique combined with vacuum imbibition method, or by analyzing the changes of NMR spectra of aqueous phase in completely saturated water and saturated oil-bound water.

Ultrashort Peptide Grafting on Mesoporous Films and Its Impact on Ionic Mesopore Accessibility.

An approach for direct in-pore solid-phase ultrashort peptide synthesis on mesoporous films using the amino acids arginine, leucine, and glycine is presented. Although the number of grafted amino acids remains low, the ionic mesopore accessibility can be gradually adjusted. The addition of arginine in up to five reaction cycles leads to a progressive increase in positive mesopore charge density, which gradually increases the anionic mesopore accessibility at acidic pH. At basic pH, the remaining silanol groups at the pore wall still dominate counter-charged cation mesopore accessibility. Thus, specific peptide sequence design is demonstrated to be a sensitive tool for molecular transport control in nanoscale pores. Overall, the direct in-pore solid-phase ultrashort peptide synthesis on mesoporous films using the sequences of different amino acids opens up exciting opportunities for the development of innovative materials with precisely tailored properties and functions based on specific peptide sequence design.

Phosphorus removal of coal-based bottom ash: Performance evaluation and mechanism exploration

In this paper, the phosphorus removal efficiency and capability and pore structure and composition of coal-based bottom ash before and after phosphorus removal are studied to reveal the phosphorus removal mechanism. The results show that the phosphorus removal rate of bottom ash increases with the increase of pH value; When the pH value is 8, the phosphorus removal rate can reach more than 95%. The highest desorption rate is only 2.42% and the pseudo-second order model can be better fitted with the phosphorus removal process of bottom ash, indicating chemical adsorption is the control mechanism. The maximum phosphorus removal capacity is 5.54 mg/g. After phosphorus removal the fractal dimension and porosity decrease, and the specific surface area increases, indicating that the complexity of the pore structure decreases, and the roughness of the pore wall increases. The characteristic peak of brushite (CaHPO4·2H2O) in the XRD spectrum and HPO42− at 2362 cm−1, 985 cm−1 and 800-650 cm−1 appear, respectively. In the XRF results, P2O5/SiO2 ratio increases from 0.008 to 0.089, but SO3/SiO2 ratio decreases from 0.047 to 0.027. The phosphorus removal mechanism of coal-based bottom ash lies in its complex pore structure and the precipitation reaction between soluble Ca2+ and HPO4− in the sewage.

Polymeric liquids in mesoporous photonic structures: From precursor film spreading to imbibition dynamics at the nanoscale

Polymers are known to wet nanopores with high surface energy through an atomically thin precursor film followed by slower capillary filling. We present here light interference spectroscopy using a mesoporous membrane-based chip that allows us to observe the dynamics of these phenomena in situ down to the sub-nanometer scale at milli- to microsecond temporal resolution. The device consists of a mesoporous silicon film (average pore size 6 nm) with an integrated photonic crystal, which permits to simultaneously measure the phase shift of thin film interference and the resonance of the photonic crystal upon imbibition. For a styrene dimer, we find a flat fluid front without a precursor film, while the pentamer forms an expanding molecular thin film moving in front of the menisci of the capillary filling. These different behaviors are attributed to a significantly faster pore-surface diffusion compared to the imbibition dynamics for the pentamer and vice versa for the dimer. In addition, both oligomers exhibit anomalously slow imbibition dynamics, which could be explained by apparent viscosities of six and eleven times the bulk value, respectively. However, a more consistent description of the dynamics is achieved by a constriction model that emphasizes the increasing importance of local undulations in the pore radius with the molecular size and includes a sub-nanometer hydrodynamic dead, immobile zone at the pore wall but otherwise uses bulk fluid parameters. Overall, our study illustrates that interferometric, opto-fluidic experiments with mesoporous media allow for a remarkably detailed exploration of the nano-rheology of polymeric liquids.