Multiscale Pore Structure Research Articles

Recent Advancements in Fabrication, Separation, and Purification of Hierarchically Porous Polymer Membranes and Their Applications in Next-Generation Electrochemical Energy Storage Devices

Abstract: In recent years, hierarchically porous polymer membranes (HPPMs) have emerged as promising materials for a wide range of applications, including filtration, separation, and energy storage. These membranes are distinguished by their multiscale porous structures, comprising macro-, meso-, and micropores. The multiscale structure enables optimizing the fluid dynamics and maximizing the surface areas, thereby improving the membrane performance. Advances in fabrication techniques such as electrospinning, phase separation, and templating have contributed to achieving precise control over pore size and distribution, enabling the creation of membranes with properties tailored to specific uses. In filtration systems, these membranes offer high selectivity and permeability, making them highly effective for the removal of contaminants in environmental and industrial processes. In electrochemical energy storage systems, the porous membrane architecture enhances ion transport and charge storage capabilities, leading to improved performance in batteries and supercapacitors. This review highlights the recent advances in the preparation methods for hierarchically porous structures and their progress in electrochemical energy storage applications. It offers valuable insights and references for future research in this field.

Facile Synthesis of Silver‐Exchanged Phosphotungstic Acid Immobilized on Sn‐Bi Bimetallic Metal–Organic Frameworks for Enhanced Esterification

ABSTRACTMetal–organic frameworks (MOFs) are ideal supports for the synthesis of porous composite catalysts. In the present study, Sn‐Bi bimetallic metal–organic frameworks (Sn‐Bi‐MOFs) supported silver‐doped phosphotungstic acid (AgPW) catalysts (AgPW@Sn‐Bi‐BDC and AgPW@Sn‐Bi‐BDC (NH2)) were successfully synthesized via a simple in situ impregnation method, which was subsequently applied to catalyze esterification for the production of biodiesel from oleic acid (OA). The physico‐chemical properties of the prepared composite catalysts underwent comprehensive analysis through XRD, FTIR, N2 physisorption, SEM, EDX, NH3‐TPD, Py‐FTIR, TG, and XPS techniques, confirming the successful impregnation of AgPW on the Sn‐Bi‐MOFs framework. Among the catalysts tested, AgPW@Sn‐Bi‐BDC (NH2) exhibited the better catalytic activity than that of Sn‐Bi‐BDC, Sn‐Bi‐BDC (NH2), and AgPW@Sn‐Bi‐BDC, reaching 91.6% of OA conversion with the methanol:OA molar ratio of 20:1 and the catalyst quantity of 0.2 g at 130°C for 4 h. The high activity of AgPW@Sn‐Bi‐BDC (NH2) is attributed to the available multiscale pore structure, high acidity, and the synergistic action of the Brønsted and Lewis acidic sites. Additionally, the esterification with AgPW@Sn‐Bi‐BDC (NH2) followed the first‐order reaction kinetic model, with an Ea of 34.5 kJ/mol. Moreover, the recyclability of the composites was also assessed, demonstrating sustained catalytic activity after four reuses. This approach showed a potential for sustainable and efficient energy production through bimetallic MOFs‐based composite catalysts.

Geological characteristics and volume fracturing adaptability of tight oil reservoirs in the Ordos Basin of China

Abstract In recent years, China’s dependence on foreign crude oil has gradually increased. The Ordos Basin has abundant oil, gas, and coal resource. Tight oil and shale reservoirs have become very important replacement resources. This article studies the geological characteristics and volume fracturing adaptability of the Yanchang Formation tight oil reservoir in the central region of the Ordos Basin, and uses X-ray diffraction experiments to analyze the mineral composition of the reservoir; Utilizing high-pressure mercury intrusion technology to achieve precise quantitative characterization of multi-scale pore structures in reservoirs; Using the Analytic Hierarchy Process, establish a numerical judgment matrix and factor weights to study the adaptability of volume fracturing in the region. The results indicate that the volume fracturing adaptability of tight oil reservoirs in the Ordos Basin is good.

Fabrication of a macro-micro porous structure on PEEK surface by ultrasound-assisted sulfonation

A multiscale porous surface can significantly improve the osseointegration of biomedical implants, but it cannot be facilely achieved on the Poly-ether-ether-ketone (PEEK) surface. In this work, a macro-micro porous structure was prepared on the PEEK surface by ultrasound-assisted sulfonation. The surface morphologies, chemical compositions, functional groups, surface roughness, and wettability of the porous structures at different sulfonation times were characterized by scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectrometer (FTIR), laser scanning confocal microscope (LSCM), and contact angle measurement, respectively. The results demonstrate that a macro-micro porous structure is formed on the PEEK surface, with macropore sizes ranging from 50 to 250 μm and micro-sized pore sizes ranging from 0.2 to 1.5 μm. Moreover, the results of in vitro cellular experiments demonstrate that the macro-micro porous structure can promote cell adhesion and proliferation of BMCSc. The formation mechanism of the multiscale porous structures has also been discussed. This novel approach may provide a simple and effective strategy for surface modification of PEEK to improve its mechanical and biological response.

The design of binder-free self-supporting carbon paper electrode based on biomass derived hierarchical porous carbon/cellulose nanofibers for sustainable flexible supercapacitors

The design and synthesis of advanced electrodes with high conductivity and flexibility are the key to the development of wearable energy storage devices. Herein, a strategy for preparing conductive carbon paper electrode for flexible supercapacitors is reported by vacuum filtration of a mixture of biomass hierarchical porous carbon materials (HPC), cellulose nanofibers (CNFs) from polysaccharide cellulose of plant origin and silver nanowire (AgNWs), in which CNFs serve as substrates for dispersion and crosslinking of HPC. The prepared self-supporting electrode showed multi-scale pore structure and excellent conductivity (14.1 S cm−1). The electrode exhibited the highest specific capacitance of 383 F g−1 at 0.5 A g−1. Even after 10,000 charge and discharge cycles, 95 % of the original capacitance was remained, which means excellent cyclic stability. High strength and flexibility of the as-assembled flexible supercapacitor make the electrochemical performance of this device remain unchanged when bent at any angle. The present research delineates a simple and convenient method to prepare green, efficient and low-cost flexible supercapacitor.

Changes of the Multiscale Pore Structure and Connectivity of Organic-Rich Shale during Hydrous Pyrolysis under Different Temperatures and Pressures

Changes of the Multiscale Pore Structure and Connectivity of Organic-Rich Shale during Hydrous Pyrolysis under Different Temperatures and Pressures

Open-cell ceramic foam filters for melt filtration: Processing, characterization, improvement and application

Open-cell ceramic foams are widely used as filters for the purification of molten metals due to their high permeability and high efficiency for capturing non-metallic inclusions. With the consideration of manufacture and filtration behaviour, most filters are produced by replica methods. The intrinsic multiscale porous structure requires the ceramic foams to have sufficient strength. As a consequence, different processing approaches, material compositions and characterizations are investigated. Meanwhile, to further enhance the filtration performance, the functionalization of ceramic foam filters is often conducted with surface coating. This review summarizes the processing and characteristics of ceramic foam filters (CFFs), the nature and formation of non-metallic inclusions (NMIs), the filtration mechanism and applications of CFFs. The characterization of mechanical and filtration performance, as well as the corresponding strengthening and functionalization methods are also presented.

Superlong Metal-Organic Framework Nanowire Fabricated via Steam-Assisted Conversion.

1D nanomaterials have attracted great attention due to their outstanding anisotropic and linear structures. A facile method is developed to fabricate 1D copper metal-organic framework nanowires (Cu-MOF-NW) through steam-assisted conversion from Cu-MOF precursors. During the steam-assisted conversion, Cu-MOF precursor gradually dissolves in methanol steam, and then recrystallized into Cu-MOF-NW, which shows high aspect ratio of about 600 and identical crystal structure of MOF-74. As-prepared Cu-MOF-NW with multiscale porous structure can effectively remove cationic dyes even in dye mixture. Moreover, Cu-MOF-NW, as an ideal template, is calcined to form Cu nanoparticle-doped carbon nanofiber with maintaining its 1D morphology, which shows excellent electrocatalytic activity for the non-enzymatic sensing of glucose.

Variation of soil pore structure and predication of the related functions following land‐use conversion identified by multi‐scale X‐ray tomography

AbstractLand‐use conversion profoundly influences the soil pore structure, consequently modifying the soil functions. Investigating the variation of multiscale soil pore structure and their associated functions following land‐use change is critical for evaluating land management strategies. However, this topic has not yet been extensively explored in recent studies. In this study, the pore structure of soil following land‐use conversion was quantitatively investigated by multiscale X‐ray tomography. Intact soil aggregates and undisturbed soil cores were collected from paddy fields (PF) and from vegetable fields were converted from paddy fields for 5 years (VF‐5), 13 years (VF‐13), and 20 years (VF‐20), respectively. Results revealed that the connected porosity of both aggregates and soil cores was significantly increased after land‐use conversion. The isolated porosity of soil aggregates increased, while, conversely, it decreased for soil cores. The variance in pore structure was attributed to the development of new pores, including channels created by vegetable roots, fissures, earthworm holes, and packing pores resulting from the decomposition of soil organic matter and the rearrangement of soil particles. The altered pore structure influenced the soil exchangeability and reservation ability. For aggregates, the isolated porosity of PF and VF‐5 accounted for over 70% of the total imaged porosity. These aggregates displayed a larger water and carbon reservation ability, but limited exchangeability of air, water, and nutrients. The isolated porosity of VF‐13 and VF‐20 aggregates accounted for approximately 50% of the total imaged porosity, suggesting they could effectively balance the exchange and storage of air, water, and nutrients. As for soil cores, isolated pores became negligible (<0.2%) following land‐use conversion, leading to the emergence of a drainable pore system suitable for vegetable plantation. These findings offer insights into the development of pore structures and the prediction of soil function variations at multiple scales, both of which are crucial for optimizing soil management protocols.

Interplay of physical and textural properties in porous, nanostructured hard‑carbons as electrode materials for non-Faradic energy storage devices

This work presents a systematic investigation on the non-Faradic energy storage ability of non-graphitizable, porosity engineered hard‑carbon nanostructures as electrode materials. The persistent challenge of inducing and tuning porosity in hard‑carbon nanostructures is overcome here, by utilizing dendritic fibrous nano silica (DFNS) as a sacrificial template for uniform and conformal deposition of carbon through thermal chemical vapor deposition, leading to the formation of porosity tuned, nanostructured hard‑carbon florets (NCF). This strategy enables precisely crafted six varieties of NCF with varying yet monodisperse dimensions (NCF 90, NCF 350, NCF 366, NCF 430, NCF 540 and NCF 600), SSA (494–719 m2/g) and textural features such as pore volume (0.67–1.24 cm3/g) and pore diameter (3.83–5.65 nm). In contrast to current understanding, NCF 366 with defect length of 16 nm, defect density of 2.65 × 1011 cm−2, micro- to mesoscale pore ratio of 0.16 and specific surface area of 535 m2/g achieves the highest energy density of 14.6 Wh/kg and power density 10.0 kW/kg, when compared to NCF 90 with higher SSA (719 m2/g) and pore volume (1.24 cm3/g). Thus, this work manifests the critical contributions of tuning the pore structures and optimizing the relative contributions from multi-scale pore structures to achieve high-performing energy storage devices.

Multi-field and multi-scale dynamic numerical modeling of supercritical CO2 and fly ash mineralization

Fly ash-CO2 mineralization technology can effectively control gas–solid waste emissions and improve the climate environment. However, rationally describing the evolution mechanism of the fly ash-supercritical CO2 mineralization reaction and accurately predicting the efficiency of the mineralization reaction are of great significance for improving and evaluating the supercritical CO2 mineralization sequestration capacity. Fly ash micro- and nanopore multi-scale effects are the key to influencing the supercritical CO2 seepage-mineralization reaction mechanism. None of the current theoretical models consider the pore multi-scale effects, thus the validity and accuracy of predicting and describing the evolutionary mechanism of supercritical CO2 mineralization rates and efficiencies are questionable. To address this scientific issue, a multi-scale continuous pore structure theoretical model was established based on the structural characteristics of fly ash micro- and nanopores. Additionally, a new model of supercritical CO2 multi-field and multi-scale dynamic mineralization theory was developed by considering parameters such as temperature, pressure, and humidity. The accuracy of the model was verified through the mineralization experiments. The new model effectively describes the dynamic evolution mechanism of supercritical CO2 mineralized fly ash. The effects of parameters such as temperature, pressure, water vapor diffusion coefficient, supercritical CO2 permeability, and pore multi-scale effect on the efficiency and mineralization rate were investigated through numerical simulation. The results showed the following: The mineralization efficiency exhibited a parabolic increase with temperature, with 72℃ being the turning point for the growth rate of mineralization efficiency, and 82℃ being the optimal effective temperature to promote the mineralization efficiency of supercritical CO2. A 3.5-fold increase in supercritical CO2 pressure changes the mineralization efficiency by a maximum of only 0.0493 %. Increasing the water vapor diffusion coefficient by 5 orders of magnitude changes the mineralization efficiency by only 8.3 %. The pore attenuation coefficient increases by 3 orders of magnitude, and the supercritical CO2 mineralization efficiency changes by a factor of 2.27. A model that does not account for pore multi-scale effects overestimates the fly ash- supercritical CO2 mineralization efficiency by a factor of 2.47 at a permeability of 3 × 10-10 m2. Therefore, neglecting the pore continuum multi-scale effect can lead to a serious overestimation of the mineralization efficiency of supercritical CO2.

A multi-scale porous scaffold fabricated by a combined additive manufacturing and chemical etching process for bone tissue engineering

It is critical to develop a fabrication technology for precisely controlling an interconnected porous structure of scaffolds to mimic the native bone microenvironment. In this work, a novel combined process of additive manufacturing (AM) and chemical etching was developed to fabricate graphene oxide/poly(L-lactic acid) (GO/PLLA) scaffolds with multiscale porous structure. Specially, AM was used to fabricate an interconnected porous network with pore sizes of hundreds of microns. And the chemical etching in sodium hydroxide solution constructed pores with several microns or even smaller on scaffolds surface. The degradation period of the scaffolds was adjustable via controlling the size and quantity of pores. Moreover, the scaffolds exhibited surprising bioactivity after chemical etching, which was ascribed to the formed polar groups on scaffolds surfaces. Furthermore, GO improved the mechanical strength of the scaffolds.

Multiscale Dynamic Diffusion Model for Ions in Micro- and Nano-Porous Structures of Fly Ash: Mineralization Experimental Research

The leaching concentration of alkaline ions plays a crucial role in the efficiency of the CO2 mineralization reaction in fly ash. The multi-scale structural characteristics of micro–nano pores in fly ash are the primary factors that control the leaching and diffusion rate of alkaline ions. However, the existing theoretical models do not account for the multi-scale pore structure, leading to challenges in accurately describing the ion diffusion in fly ash and predicting the reaction rate and efficiency of CO2 mineralization. To address this issue, a multi-scale dynamic diffusion model of ions was developed based on the micro–nano pore structure of fly ash. This model established the relationship between the ionic leaching rate and pore structure, as well as macroscopic changes over time, which were validated through experiments. Mineralization experiments with varying soaking times and uniaxial compression experiments on mineralized specimens were conducted to investigate the relationships among soaking time, ion leaching concentration, mineralization degree, and mechanical strength. The results elucidated the impact of alkaline ion concentration on the mineralization degree and mechanical strength of fly ash materials, offering theoretical insights to enhance mineralization and material properties.

A hybrid pore-network-continuum modeling framework for flow and transport in 3D digital images of porous media

Understanding flow and transport in multiscale porous media is challenging due to the presence of a wide range of pore sizes. Recent imaging advances offer high-resolution characterization of the multiscale pore structures. However, simulating flow and transport in 3D digital images requires models to represent both the resolved and sub-resolution pore structures. We develop a hybrid pore-network-continuum modeling framework. The hybrid framework treats the smaller pores below the image resolution as a continuum using the Darcy-scale formalism and explicitly represents the larger pores resolved in the images employing a pore network model. We validate the hybrid model against direct numerical simulations for single-phase flow and solute transport and further demonstrate its applicability for simulating two-component gas transport in a shale rock sample. The results indicate that the new hybrid model represents the flow and transport process in multiscale porous media while being much more computationally efficient than direct numerical simulation methods for the range of simulated conditions.

Application and Research of Multi-Scale Dynamic Diffusion Permeability Model in Different Coal Ranks

The spatial scale of coal mining and rock layer control is distributed between 10-10 and 107, spanning 17 orders of magnitude. There are multi-scale pore cracks from millimeter to micro and nanometers in the coal, and the pore size can reach one million times, which makes the coal permeability also show a multi-scale characteristics of millions and time. For the permeability of the coal seam, it is necessary to test and analyze the distribution of micro and nano pores and cracks in the coal [1]. CBM mining is accompanied by the dynamic change of adsorption pressure in coal and the complex deformation of multi-scale heterogeneous structure of coal, and the multi-scale deformation feature of pore fissure structure plays an important role in the transport of methane [2]. However, existing studies focus on treating coal as a homogeneous isotropic medium, without considering the influence of coal multiscale pore structure on permeability. The variation of heterogeneous degree of coal structure with structural scale and its influence on dynamic diffusion and permeability are rarely reported. Li Zhiqiang et al. [3] conducted an experimental-model-mechanism study of CBM gas micro-nano series multi-scale dynamic diffusion permeability. On this basis, the dynamic diffusion and permeability of different coal scales.

Lightweight polyimide/silica aerogel composite foams and their derived carbon foams for excellent flame retardancy, thermal insulation and EMI shielding performance

Multifunctional porous materials demonstrate ubiquitous applications in the fields of flame retardancy, thermal insulation and electromagnetic interference (EMI) shielding. In this work, a series of lightweight polyimide/silica aerogel (PIF/SiA) foams with exceptional thermal stability, flame retardancy and thermal insulation performance were prepared by employing microwave-assisted foaming and thermal imidization treatment, using polyester ammonium salt/silica aerogel (PEAS/SiA) powders as the derivative precursors. The limiting oxygen index and fire growth rate reached as high as 58.2 % and as low as 0.1 kW/(m2·s) for PIF/SiA composite foams, respectively, which was a result of the formation of micro/nano multi-scale pore structure of PIF skeleton and the “pearl-necklace-like” skeletal network of nano SiA. In addition, the PIF/SiA composite foams exhibited excellent thermal insulation and infrared stealth performance, which demonstrate a potential for long service life in fire protection use. Furthermore, the carbonized PIF/SiA (i.e., PICF/SiA) foams possessed enhanced mechanical (improvement of 117.6 %) and EMI shielding performance (specific EMI shielding effectiveness: 8541.9 dB/(g/cm2)) when compared with the original PIF/SiA composite foams. To sum up, a facile method was proposed to fabricate multifunctional PIF-based composite foams and their derived carbon foams for flame retardancy, thermal insulation and EMI shielding applications in high-end engineering sectors.

Multi-scale pore structure characteristics of coal under alternating hydraulic intrusion pressure

Multi-scale pore structure characteristics of coal under alternating hydraulic intrusion pressure

Mussel shell-derived pro-regenerative scaffold with conductive porous multi-scale-patterned microenvironment for spinal cord injury repair

It is well-established that multi-scale porous scaffolds can guide axonal growth and facilitate functional restoration after spinal cord injury (SCI). In this study, we developed a novel mussel shell-inspired conductive scaffold for SCI repair with ease of production, multi-scale porous structure, high flexibility, and excellent biocompatibility. By utilizing the reducing properties of polydopamine, non-conductive graphene oxide (GO) was converted into conductive reduced graphene oxide (rGO) and crosslinked in situ within the mussel shells. In vitro experiments confirmed that this multi-scale porous Shell@PDA-GO could serve as structural cues for enhancing cell adhesion, differentiation, and maturation, as well as promoting the electrophysiological development of hippocampal neurons. After transplantation at the injury sites, the Shell@PDA-GO provided a pro-regenerative microenvironment, promoting endogenous neurogenesis, triggering neovascularization, and relieving glial fibrosis formation. Interestingly, the Shell@PDA-GO could induce the release of endogenous growth factors (NGF and NT-3), resulting in the complete regeneration of nerve fibers at 12 weeks. This work provides a feasible strategy for the exploration of conductive multi-scale patterned scaffold to repair SCI.

Multiscale Pore Structure Evolution of Different Rank Coals Induced by Chelating Agent Intrusion

Summary China’s coalbed methane (CBM) reservoirs are characterized by low permeability (<1 md). Stimulation with conventional acids is facing the problems of secondary precipitation, high corrosion rates, and fines migration. Chelating agent intrusion was proposed as a promising alternative for conventional acids, while the pore structure evolution induced by it needs to be further clarified. In this study, coal samples with three different ranks were selected and treated with L-glutamic acid N, N-diacetic acid (GLDA). Low-temperature Ar and N2 adsorption tests, mercury intrusion porosimetry (MIP), and scanning electron microscope (SEM) analyses were applied to investigate nanoscale to macroscale pore structure changes. X-ray fluorescence (XRF) spectroscopy tests were conducted to determine the mineralogical change of coal. The results show that chelating agent intrusion can widen fracture width, connect micropores, and create void space in macropores by dissolving carbonate minerals, while the nanoscale pore volumes (PVs) showed a slight decrease due to clay minerals collapse. The fractal dimensions Dm calculated by the MIP results of lignite, bituminous coal, and anthracite coal decreased by 0.2735, 0.1734, and 0.1444, respectively. It is indicated that a pore structure with a diameter of >100 nm of the coal became more unified, which favors the seepage of gas/water. The chelating agent intrusion shows a significant effect on lignite, followed by bituminous and anthracite coal. However, the metal element reduction rate of anthracite coal presents the highest, followed by bituminous coal and lignite. There can be a risk that a long intrusion time would loosen the skeleton of lignite, leading to further reservoir damage. Therefore, bituminous and anthracite coal samples are preferred, as the skeletons of higher-rank coals are more compact. These research findings introduced a potential stimulation method for enhancing CBM recovery and provided references for field application.

A computationally efficient modeling of flow in complex porous media by coupling multiscale digital rock physics and deep learning: Improving the tradeoff between resolution and field-of-view

Digital rock physics is at the forefront of characterizing porous media, leveraging advanced tomographic imaging and numerical simulations to extract key rock properties like permeability. However, fully capturing the heterogeneity of natural rocks necessitates imaging increasingly larger sample volumes, presenting a significant challenge. Direct numerical simulations at these scales become either prohibitively expensive or computationally unfeasible due to limitations in resolution and field of view (FOV). This issue is particularly pronounced in carbonate rocks, known for their complex, multiscale pore structures, which exacerbate the resolution-FOV tradeoff. To address this, we introduce a machine learning strategy that merges multiscale imaging data from various resolutions with a 3D convolutional neural network (CNN) model. This approach is innovative in its ability to identify cross-scale correlations, thereby enabling the estimation of transport properties in larger volumes—properties that are difficult to simulate directly—using trainable proxies. The integration of multiscale imaging with deep learning allows for accurate permeability predictions at scales beyond those feasible with traditional direct simulation methods. By employing transfer learning across different scales during the training phase, our multiscale machine learning model achieves robust performance, with an R² exceeding 0.96 when evaluated on diverse lower-resolution domains with larger FOVs. Notably, this method significantly enhances computational efficiency, reducing the computational time by orders of magnitude. Originally developed for the intricate pore structures of carbonate rocks, our approach shows promise for application to a wide range of multiscale porous media, offering a viable solution to the longstanding tradeoff between imaging resolution and FOV in digital rock physics.