Pore Walls Research Articles

Effect of density value and gradient distribution on the deformation mechanism of foamed concrete

Foamed concrete is an essential material in engineering that can be categorized into two types based on density distribution, namely uniform foamed concrete (UFC) and gradient foamed concrete (GFC). However, there exists a research gap concerning the mesoscopic deformation mechanism of UFC and GFC. The objective of this research is to bridge this gap by examining the quasi-static compression characteristics of UFCs with three distinct densities and GFCs with different density sequences. The results reveal that the strength of pore walls significantly influences the failure mechanism of UFCs with varying densities. Specifically, UFCs with low density exhibit weak pore-wall strength, leading to stress concentration at the pore-wall junction. During compression, these weak pore walls are widely dispersed within the specimen, resulting in a powdering failure mode. Conversely, UFCs with high density possess stronger pore walls, which prevent the powdering failure mode by maintaining adequate pore-wall strength. Nevertheless, the existence of a dominant crack within the specimen results in a splitting failure mode. In the context of GFCs, deformation occurs in a sequence from low to high density, with each layer exhibiting a failure mode corresponding to its density. Note that the last-deforming layer in this brittle gradient foam cannot attain the strength of the corresponding uniform foam. This is due to the failure of the second layer, which results in uneven contact surfaces and prompts the third layer to crack simultaneously. Finally, a statistical model is developed to forecast the compressive Stress–strain curve of foamed concrete, demonstrating remarkable agreement with experimental data.

Investigation of the confinement effect on fluid-phase behavior in shale oil reservoirs during CO2 injection process

AbstractDue to the confinement effect of nanopores, the fluid-phase behavior of shale oil reservoirs is much different from that of conventional reservoirs. The accurate description of the phase change characteristics of fluid in nanopores is the basis to design development plan, production system, and EOR methods of shale oil reservoirs. In this study, molecular dynamics simulation was employed to analyze the phase behavior of single-component system and hydrocarbon–CO2 mixture system in organic nanopores. The results show that the confinement effect on the phase change pressure of the single-component system is influenced by the distribution of the electron cloud. The phase change pressure of hydrocarbons with even distribution of the electron cloud would be increased, while that of CO2 would be decreased due to the instantaneous dipole moment. In addition, as the length of carbon chains increases, the confinement effect on hydrocarbons becomes stronger. When the temperature increases, the confinement effect becomes weaker. In the hydrocarbon–CO2 mixture system, when the occurrence condition changes from bulk to the nanopore of 5 nm, the bubble point pressure decreases by 39.21–68.85%, and the critical temperature and pressure decrease by 75.98% and 7.13%, respectively. On the whole, the P–T phase envelope is shrunken under the confinement effect. CO2 is much easier to be miscible with shale oil in nanopores. Moreover, full mixing and keeping in single liquid phase of CO2–hydrocarbons mixture system can reduce the adsorption of hydrocarbons on organic pore walls. Therefore, CO2 injection could be a feasible method to enhance oil recovery in the matrix of shale oil reservoirs.

Three-dimensional observation of porous materials prepared from iron tailings and their pore wall site adsorption function

Porous materials are widely used to treat phosphorus-containing wastewater due to their structural characteristics and loading site functionality. The use of iron tailings as a raw material during the preparation of these materials can effectively reduce production costs. In this study, a porous material was prepared according to a one-step method using solid waste iron tailings. High-temperature phase transition technology was used to construct crystallographic sites on the pore walls of the material to improve the phosphorus removal efficiency. The pore structure, pore wall characteristics, and internal crystal growth in the three-dimensional space of the material were characterized using X-ray microscopy (micro-CT) scanning, and the voxel data for the internal structural were analyzed. The results showed that the material had a clear internal skeletal structure, a uniform distribution of internal pores, and crystal phases in three-dimensional space. The pore ratio in the three-axis direction was greater than 50%, with connected pores accounting for more than 95% of the pores. The wall thickness distribution was uniform, but the pore size distribution and ellipticity ratio varied significantly due to the different pore structures and quantities. A connected structure was formed when the thin walls of adjacent pores ruptured, and there were magnesioferrite and hematite crystal sites with fractal growth in the pore wall framework. The adsorption capacity of the porous material for phosphorus pollutants was investigated using photometry, and the highest removal rate was found to be 68.13%. This analysis suggests that the presence of rough pore walls, a high specific surface area, and crystal sites within the pore walls enhance the adsorption performance of the material. Further research along this line could explore the potential of developing new low-cost materials for pollution treatment.

A sustainable pore wall strengthening for strong and fire-retardant nanopolymerised wood

Cellulose aerogels prepared by the directional freezing method show huge potential in the field of thermal insulation materials, tissue engineering, and building blocks. However, poor mechanical strength and fire resistance limit their application in buildings and engineering. Inspired by the chemical crosslinking of wood cell walls, we propose a sustainable wall-strengthening strategy for robust cellulose aerogels with high mechanical strength, superior thermal insulation, and flame-retardant performance, denoted as nanopolymerised wood. Specifically, oriented cellulose aerogel, prepared from cellulose nanofibers and polyvinyl alcohol, is impregnated with Na2SiO3 solution and then thermally crosslinked to obtain nanopolymerised wood. The cellulose nanofibers served as a supporting skeleton, while polyvinyl alcohol and Na2SiO3 acted as fillers and adhesives, respectively. This combination densifies the pore walls, resulting in an enhanced compressive strength of the nanopolymerised wood to 64.2 MPa. The directional channels with high interfacial thermal resistance lead to a low radial thermal conductivity of 0.027 W·m−1·K−1. Furthermore, the covalently crosslinked silicates provide nanopolymerised wood with outstanding fire-retardant and self-extinguished properties. The biodegradable components, good mechanical properties, superior thermal insulation, and fire-retardant performance of nanopolymerised wood make it a promising material for sustainable buildings and machine envelopes.

A Nanocavitation Approach to Understanding Water Capture, Water Release, and Framework Physical Stability in Hierarchically Porous MOFs.

Chemically stable metal-organic frameworks (MOFs) featuring interconnected hierarchical pores have proven to be promising for a remarkable variety of applications. Nevertheless, the framework's susceptibility to capillary-force-induced pore collapse, especially during water evacuation, has often limited practical applications. Methodologies capable of predicting the relative magnitudes of these forces as functions of the pore size, chemical composition of the pore walls, and fluid loading would be valuable for resolution of the pore collapse problem. Here, we report that a molecular simulation approach centered on evacuation-induced nanocavitation within fluids occupying MOF pores can yield the desired physical-force information. The computations can spatially pinpoint evacuation elements responsible for collapse and the chemical basis for mitigation of the collapse of modified pores. Experimental isotherms and difference-electron density measurements of the MOF NU-1000 and four chemical variants validate the computational approach and corroborate predictions regarding relative stability, anomalous sequence of pore-filling, and chemical basis for mitigation of destructive forces.

Characterization of Water Structure and Phase Behavior within Metal-Organic Nanotubes.

Water behavior under nanoconfinement varies significantly from that in the bulk but also depends on the nature of the pore walls. Hybrid compound offers the ideal system to explore water behavior in complex materials, so a model metal-organic nanotube (UMONT) material was utilized to explore the behavior of water between 100 and 293 K. Single-crystal X-ray and neutron diffraction revealed the formation of a filled Ice-I arrangement that was previously predicted to only occur under high pressures. 17O NMR spectra suggest that the onset of melting for the water in the UMONT channels occurs at 98 K and the presence of ice-like water up to 293 K, indicating that the complete ice-water transition does not occur before dehydration of the material. Overall, the water behavior differs significantly from hydrophobic single-walled carbon nanotubes indicating precise control over water can be achieved through rational design of hybrid materials.

Application of ZnO Nanoparticles Encapsulated in Mesoporous Silica on the Abaxial Side of a Solanum lycopersicum Leaf Enhances Zn Uptake and Translocation via the Phloem.

Foliar application of nutrient nanoparticles (NPs) is a promising strategy for improving fertilization efficiency in agriculture. Phloem translocation of NPs from leaves is required for efficient fertilization but is currently considered to be feasible only for NPs smaller than a cell wall pore size exclusion limit of <20 nm. Using mass spectrometry imaging, we provide here the first direct evidence for phloem localization and translocation of a larger (∼70 nm) fertilizer NP comprised of ZnO encapsulated in mesoporous SiO2 (ZnO@MSN) following foliar deposition. The Si content in the phloem tissue of the petiole connected to the dosed leaf was ∼10 times higher than in the xylem tissue, and ∼100 times higher than the phloem tissue of an untreated tomato plant petiole. Direct evidence of NPs in individual phloem cells has only previously been shown for smaller NPs introduced invasively in the plant. Furthermore, we show that uptake and translocation of the NPs can be enhanced by their application on the abaxial (lower) side of the leaf. Applying ZnO@MSN to the abaxial side of a single leaf resulted in a 56% higher uptake of Zn as well as higher translocation to the younger (upper) leaves and to the roots, than dosing the adaxial (top) side of a leaf. The higher abaxial uptake of NPs is in alignment with the higher stomatal density and lower density of mesophyll tissues on that side and has not been demonstrated before.

Alternating current assisted preparation of three-dimensional graphene aerogels and the application in electromagnetic interference shielding

Three-dimensional (3D) graphene aerogels (GA) have obtained significant attention across various fields due to their lightweight and porous properties. Nevertheless, the development of a scalable and environmentally friendly method for synthesizing self-supported 3D GA remains a challenge. In this study, we introduced an innovative method for the preparation of 3D GA using alternating current (AC) strategy, which fully used the characteristic of AC's constantly changing current direction to attract graphene oxide (GO) particles to the electrode surface and subsequently reduced them to reduced GO (rGO). Ultimately, GA is self-assembled on the electrode surface under repeated cycles. An applied AC signal with optimal parameters produced a porous GA with an oxygen content of 10.76 at%, which is 66.67% less than that of the original GO. When applying GA to electromagnetic interference (EMI) shielding, it provides a maximum specific shielding effectiveness of 9100 dB cm2 g−1 at X-band due to the repeated reflection and absorption of electromagnetic waves (EMWs) by the abundant pore wall. Furthermore, the shielding effectiveness can be significantly improved to 68.60 dB at the X-band for a multilayer GA. Notably, it is worth emphasizing that this AC-assisted synthesis method has proven its adaptability to various metal electrodes, such as cost-effective iron and copper. Importantly, this method avoids the high-temperature treatments and the use of environmentally hazardous chemicals. It is envisaged that this environmentally friendly and low-cost approach will greatly facilitate the cost-effective production of 3D GA with diverse applications.

G-POSS connected double network starch gels for protein release

Starch is one of the most frequently preferred natural polymers in hydrogel synthesis. Herein, we combined two strategies of associating brittle and ductile networks in a structure and incorporating inorganic particles into the polymeric gel to design mechanically enhanced nanocomposite double network (DN) starch gels. For the first time in the literature, nanocomposite starch gels (s-NC) were designed by cross-linking starch chains with 8-armed glycidyl-polyhedral oligomeric silsesquioxane (g-POSS) units. Fourier Transform Infrared Spectroscopy and Energy Dispersive X-Ray Spectroscopy analyses have proven that g-POSS is included in the gel structure and is homogeneously distributed throughout the network. More stable d-NC-DMA and d-NC-VP gels were obtained by incorporating N,N-dimethylacrylamide (DMA), or 1-vinyl-2-pyrrolidinone (VP) units, respectively, into g-POSS-linked starch gels, and the reaction kinetics were followed in situ. In SEM images, it was observed that d-NC-DMA had smaller pores and thicker pore walls compared to s-NC and d-NC-VP starch gels, and its mechanical strength was shown to be much superior by rheological tests, compression, and tensile analyses. In addition to increasing the mechanical strength of the gels, the potential of starch in protein release applications using amylase sensitivity has been demonstrated in vitro experiments using the model protein BSA.

Turning on Singlet Oxygen Generation by Outer‐Sphere Microenvironment Modulation in Porphyrinic Covalent Organic Frameworks for Photocatalytic Oxidation

AbstractSinglet oxygen (1O2) is ubiquitously involved in various photocatalytic oxidation reactions; however, efficient and selective production of 1O2 is still challenging. Herein, we reported the synthesis of nickel porphyrin‐based covalent organic frameworks (COFs) incorporating functional groups with different electron‐donating/‐withdrawing features on their pore walls. These functional groups established a dedicated outer‐sphere microenvironment surrounding the Ni catalytic center that tunes the activity of the COFs for 1O2‐mediated thioether oxidation. With the increase of the electron‐donating ability of functional groups, the modulated outer‐sphere microenvironment turns on the catalytic activity from a yield of nearly zero by the cyano group functionalized COF to an excellent yield of 98 % by the methoxy group functionalized one. Electronic property investigation and density‐functional theory (DFT) calculations suggested that the distinct excitonic behaviors attributed to the diverse band energy levels and orbital compositions are responsible for the different activities. This study represents the first regulation of generating reactive oxygen species (ROS) based on the strategy of outer‐sphere microenvironment modulation in COFs.

Turning on Singlet Oxygen Generation by Outer-Sphere Microenvironment Modulation in Porphyrinic Covalent Organic Frameworks for Photocatalytic Oxidation.

Singlet oxygen (1 O2 ) is ubiquitously involved in various photocatalytic oxidation reactions; however, efficient and selective production of 1 O2 is still challenging. Herein, we reported the synthesis of nickel porphyrin-based covalent organic frameworks (COFs) incorporating functional groups with different electron-donating/-withdrawing features on their pore walls. These functional groups established a dedicated outer-sphere microenvironment surrounding the Ni catalytic center that tunes the activity of the COFs for 1 O2 -mediated thioether oxidation. With the increase of the electron-donating ability of functional groups, the modulated outer-sphere microenvironment turns on the catalytic activity from a yield of nearly zero by the cyano group functionalized COF to an excellent yield of 98 % by the methoxy group functionalized one. Electronic property investigation and density-functional theory (DFT) calculations suggested that the distinct excitonic behaviors attributed to the diverse band energy levels and orbital compositions are responsible for the different activities. This study represents the first regulation of generating reactive oxygen species (ROS) based on the strategy of outer-sphere microenvironment modulation in COFs.

Effect of nanoparticles and surfactants on properties and microstructures of foam and foamed concrete

The stability of foam is an important factor affecting the stability and strength of foamed concrete. In this study, the foams were prepared by coupling the effects of nanoparticles and surfactants. Multiple methods were employed to investigate the properties and microstructures of various foams and their impacts on properties of foamed concrete. Results reveal that the addition of nanoparticles increased the foam density while decreased the foaming multiplicity, water secretion rate and settling distance, irrespective of surfactant types. Nanoparticles can be combined with the groups of surfactants by electrostatic force, which limits the gas-liquid contact area and the coarsening of bubble and thus stabilizes the foams. Generally, nano-silica (NS) stabilized the foams better than nano-calcium carbonate (NC). Nanoparticle-modified foams reduced the fluidity and increased the viscosity of foamed concrete, and owing to the more irregular and rougher surface, NC had more noticeable effect on fluidity and viscosity than NS. Nanoparticles can change the Ca/Si ratio of pore wall of the foamed concrete and affect the cement hydration, therefore enhancing the strength of foamed concrete to some extent.

Molecular simulation of the adsorption and diffusion properties of CH4 and CO2 in the microporous system of coal

Micropores are the main adsorption sites for gases in coal. The research of the adsorption and diffusion pattern of gases in micropores is important for CO2-ECBM engineering and other measures to improve production. In this study, a multiscale microporous system with intramolecular pores, intermolecular pores, and slit pores is proposed. Adsorption and diffusion characteristics of CH4 and CO2 in different microporous systems were investigated. The results show that the adsorption of different microporous systems is basically consistent at low pressures (<2 MPa). Upon further increase in pressure, adsorption increases with increasing slit pore size. Gas molecules in coal are preferentially adsorbed in the intramolecular and intermolecular pores, and gas molecules in the slit pores are preferentially adsorbed in the slit pore walls. The increase in gas pressure and slit pore size decreases the proportion of gases adsorbed in the intramolecular and intermolecular pores and also increases the proportion adsorbed in the slit pores. Increase in size of the slit pores and decrease in adsorption will result in an increase in self-diffusion coefficients of gases. The results of self-diffusion coefficients of pores with different scales indicate that slit pores have the largest self-diffusion coefficients, followed by the intermolecular pores, and the smallest for the intramolecular pores. The isosteric heat of gases tends to decrease and then increase with increasing adsorption. The increase of slit pore size will decrease interaction energy. This study gives a reference for adsorption and diffusion mechanisms of gases in microporous systems, as well as a basis for gas injection displacement studies.

Modular Gating of Ion Transport by Postsynthetic Charge Transfer Complexation in a Metal-Organic Framework.

Nature's design of biological ion channels that demonstrates efficient gating and selectivity brings to light a very promising model to mimic and design for achieving selective and tunable ion transport. Functionalized nanopores that permit modulation of the pore wall charges are a compelling approach to gain control over the ion transport mechanism through the pores. This makes way for employing a noncovalent supramolecular approach for attaining charge reversal of the MOF pore walls using donor-acceptor pairs that can demonstrate strong charge transfer interactions. Herein, robust Zr4+-based mesoporous MOF-808 was postsynthetically modified into an anion-selective nanochannel (MOF-808-MV) by modification with dicationic viologen-based motifs. Charge modulation and even reversal of the MOF-808-MV pore walls were then explored taking advantage of strong charge transfer interactions between the grafted dicationic viologen acceptor moieties and anionic, π-electron-rich donor guest molecules such as pyranine (PYR) and tetrathiafulvalene tetrabenzoic acid (TTF-TA). Tunability of the MOF pore charge from positive to neutral to negative was achieved via simple methodologies such as diffusion control in case of guest molecule like PYR and by pH modulation for pH-responsive guest like TTF-TA. This results in a concomitant modulation in the selectivity of the nanochannel, rendering it from anion-selective to ambipolar to cation-selective. Furthermore, as a real-time application of this ion channel, Na+ ion conductivity (σ = 3.5 × 10-5 S cm-1) was studied at ambient temperature.

Molecular simulation of the impact of surface roughness on carbon dioxide adsorption in organic-rich shales

This study investigates the adsorption behavior of carbon dioxide in organic nanopores with different surface roughness. The nanopores are constructed by sinusoidally corrugating the graphite slit pore walls. By computing the density distributions, adsorption quantities and orientation of carbon dioxide under various pressure and roughness conditions, we elucidate the impacts of surface roughness on carbon dioxide adsorption in organic nanopores. The Langmuir-Freundlich adsorption model is utilized to fit the isotherms of CO2 adsorption under three different roughness conditions. the results show that increasing surface roughness led to the increase in the adsorption of carbon dioxide, as the relative roughness increased from 0% to 12.92%, the average CO2 adsorption capacity increased by 0.003 mmol/m2. Both the adsorbed layer density and monolayer maximum adsorption capacity increased concurrently with escalating roughness. Moreover, carbon dioxide molecules preferentially aligned parallel to the rough organic surface within the adsorption layer, consistent with the smooth graphitic wall configuration. All simulations, observations, and calculations were performed through grand canonical Monte Carlo (GCMC) simulations. These findings provide insights into the influence of surface roughness on CO2 adsorption, especially in organic nanopores, which has substantial implications for carbon capture and geological sequestration applications. The results could facilitate optimization of strategies for efficient, secure geological CO2 storage.

Protein-stabilized Pickering emulsion interacting with inulin, xanthan gum and chitosan: Rheological behavior and 3D printing

Physical stability and lipid digestion of protein-stabilized Pickering emulsions interacting with polysaccharides have been emphasized in our previous investigation. However, the polysaccharide coating and micelle protection of protein-based stable Pickering emulsion and its three-dimensional (3D) printing properties have not been thoroughly studied. The rheological properties and 3D printing properties of gelatin-catechin nanoparticles (GCNPs) stabilized Pickering emulsion were studied by using different charged polysaccharides, such as inulin (neutral), Xanthan gum (XG, anion), and chitosan (cation) as stable materials. The microstructure analysis of polysaccharide-stabilized Pickering emulsion (PSPE) showed that the order of pore wall thickness was GC-Chitosan > GC-XG > GC-Inulin. The network structure of GC-Chitosan was thickened, allowing the 3D printed product to have a good surface texture and adequate support. Rheological analysis showed that PSPEs in extrusion (shear thinning), self-support (rigid structure), and recovery (the outstanding thixotropy) of the three stages exhibited good potential of 3D printing. 3D printing results also showed that GC-Chitosan had the best printing performance. Therefore, polysaccharide-stabilized Pickering emulsions can provide a basis for the development of 3D printed food products.

Molecular Self‐Assembly of Au Nanoparticles on a Porous Cellulose Membrane Template for Highly Sensitive Colorimetric Detection of Glucose

AbstractA sensitive glucose colorimetric detection system (Au@QCM) based on quaternized cellulose membrane (QCM) and enzyme‐mimicking Au nanoparticles (AuNPs) was successfully developed via a simple molecular self‐assembly strategy. The positively charged QCM functioned as a template to guide the negatively charged citric acid‐reduced AuNPs uniformly distributed on the surfaces along the pore walls of its porous structure, and thus gave AuNPs an ordered interconnected three‐dimensional network. This electrostatic interaction could effectively prevent the aggregation of the AuNPs and greatly increase their exposed surface area, thus endow the Au@QCM with highly active catalytic properties towards glucose oxidation with glucose oxidase (GOx). The experimental studies showed that the color change of redox indicator 3,3′,5,5′‐tetramethylbenzidine (TMB) can be clearly observed with naked eyes and the absorbance of the oxidized TMB (at 653 nm) was directly proportional to the concentration of glucose. Au@QCM could achieve a sensitive glucose detection with a limit of detection of 0.55 μM and linear response in the range of 0.01–0.5 mM. Besides, it also had good applicability in real samples detection and excellent selectivity to glucose. This novel detection system significantly improved detection performance compared to previous work based on cellulose‐based strips loaded with GOx and horseradish peroxides.

Limiting Thickness of Pore Walls Formed in Processes of Anode Etching of Heavily Doped Semiconductors

Limiting Thickness of Pore Walls Formed in Processes of Anode Etching of Heavily Doped Semiconductors

Modulating Skeletons of Covalent Organic Framework for High-Efficiency Gold Recovery.

Covalent organic frameworks (COFs) have attracted considerable attention as adsorbents for capturing and separating gold from electronic wastes. To enhance the binding capture efficiency, constructing hydrogen-bond nanotraps along the pore walls was one of the most widely adopted approaches. However, the development of absorbing skeletons was ignored due to the weak binding ability of the gold salts (Au). Herein, we demonstrated skeleton engineering to construct highly efficiently absorbs for Au capture. The strong electronic donating feature of diarylamine units enhanced the electronic density of binding sites (imine-linkage) and thus resulted in high capacities over 1750 mg g-1 for all three COFs. Moreover, the absorbing performance was further improved via the ionization of diarylamine units. The ionic COF achieved 90 % of the maximal adsorption capacity, 1.63 times of that from the charge-neutral COF within ten minutes, and showed remarkable uptakes of 1834 mg g-1 , exceptional selectivity (97.45 %) and cycling stability. The theoretical calculation revealed the binding sites altering from imine bonds to ionic amine sites after ionization of the frameworks, which enabled to bind the AuCl4 - via coulomb force and contributed to enhanced absorbing kinetics. This work inspires us to design molecular/ionic capture based on COFs.

Modulating Skeletons of Covalent Organic Framework for High‐Efficiency Gold Recovery

AbstractCovalent organic frameworks (COFs) have attracted considerable attention as adsorbents for capturing and separating gold from electronic wastes. To enhance the binding capture efficiency, constructing hydrogen‐bond nanotraps along the pore walls was one of the most widely adopted approaches. However, the development of absorbing skeletons was ignored due to the weak binding ability of the gold salts (Au). Herein, we demonstrated skeleton engineering to construct highly efficiently absorbs for Au capture. The strong electronic donating feature of diarylamine units enhanced the electronic density of binding sites (imine‐linkage) and thus resulted in high capacities over 1750 mg g−1 for all three COFs. Moreover, the absorbing performance was further improved via the ionization of diarylamine units. The ionic COF achieved 90 % of the maximal adsorption capacity, 1.63 times of that from the charge‐neutral COF within ten minutes, and showed remarkable uptakes of 1834 mg g−1, exceptional selectivity (97.45 %) and cycling stability. The theoretical calculation revealed the binding sites altering from imine bonds to ionic amine sites after ionization of the frameworks, which enabled to bind the AuCl4− via coulomb force and contributed to enhanced absorbing kinetics. This work inspires us to design molecular/ionic capture based on COFs.