Pore Cavity Research Articles

Exploring the Effect of Ionic Liquid Conformation on the Selective CO2 Capture of Supported Ionic Liquid-Phase Adsorbents Based on ZIFs.

The CO2 adsorption capacity and the CO2/N2 selectivity of a series of Supported Ionic Liquid-Phase adsorbents (SILPs), including the novel inversely structured SILP "Inverse SILPs", are thoroughly investigated. ZIF-8, ZIF-69 and ZIF-70 were involved as the solid matrix, while ILs, having tricyanomethanide (TCM) as an anion and alkyl-methylimidazolium of different alkyl chain lengths (C2, C6, C8) as a cation, were used as the liquid constituents of the SILPs. The ultimate target of the work was to ratify a few recently reported cases of enhanced CO2 absorptivity in ILs due to their incorporation in ZIFs and to corroborate phenomena of CO2/N2 selectivity improvements in ZIFs, due to the presence of ILs. This ambiguity originates from the vague assumption that the pores of the ZIF are filled with the IL phase, and the free pore volume of a SILP is almost zero. Yet, through the integration of theoretical predictions with N2 porosimetry analysis of an actual sample, it is suggested that a thin layer of IL covered the exterior surface of a ZIF crystal. This layer could act as an impermeable barrier for N2, inhibiting the gas molecules from reaching the empty cavities laying underneath the liquid film during porosimetry analysis. This consideration is based on the fact that the solubility of N2 in the IL is very low, and the diffusivity at 77 K is negligible. In this context, the observed result reflects an averaged adsorptivity of both the IL phase and the empty pores of the ZIF. Therefore, it is incorrect to attribute the adsorption capacity of the SILP solely to the mass of the IL that 'hypothetically' nests inside the pore cavities. In fact, the CO2 adsorption capacity of SILPs is always less than the average adsorptivity of an ideal ZIF/IL mixture, where the two phases do not interact. This reduction occurs because some ZIF pores may become inaccessible, particularly when the IL forms a layer on the pore walls, leaving only a small empty core accessible to CO2 molecules. Additionally, the IL layer masks the active sites on the ZIF's pore walls. It should also be noted that the CO2/N2 selectivity increases only when the ZIF's pores are completely filled with the IL phase. This is because ILs have a higher CO2/N2 selectivity compared to the bare ZIF.

Sub-nanometer size level regulation of biomimetic channels in porous membrane for high-capacity removal of toxic dye contaminants

Organic dyes are an important chemical with a market demand of millions of tons. However, their massive emissions, especially alkaline dye contaminants, have caused serious disruption of the ecosystem and even cancers. Inspired by bionic mass transfer, several amino acid fragments (carboxylic acid, γ-aminobutyric acid, and glutamic acid) are introduced into the 2.5 nm-pore size cavity through in-situ polymerization. The flexible amino acid chains facilitate the transport of guest molecules into the channels, accelerating their movement within the porous framework. These flexible chains are implanted into a 2.5 nm pore cavity, forming a 0.8–1.5 nano-meter-sized confinement space, bringing about the strong absorption capability for alkaline contaminants. Notably, LNU-74-glutamic acid achieves an ultra-fast absorption rate for toxic dye contaminants (4.74 g g−1h−1), as well as the highest capacity per unit area among all reported porous adsorbents, including porous carbons, metal–organic frameworks, porous polymers. After encapsulation in commercial polymer, the mixed-matrix membrane reveals (LNU-74-glutamic acid@MMM) a rejection rate greater than 98 % in various real water environments at permeation flux of ∼320 L m−2h−1, including strong acid/alkali, river water, and seawater.

Planar Group Functionalization of Quasi-Discrete Pores in Metal-Organic Frameworks for Enhanced Isomeric Separation in Simulated Moving Bed Processes.

The efficient separation of 4-methyl-1-pentene (4MP1) from its structural isomers is crucial for industrial applications but remains challenging due to the similar physicochemical properties of these compounds. This study introduces a novel strategy using metal-organic frameworks (MOFs), specifically an engineered variant of ZIF-108, which demonstrates remarkable improvements in the thermodynamic and kinetic properties for 4MP1 separation. By substituting the methyl groups in ZIF-8 with planar nitro groups, we achieved a strategic resizing of the pore windows and cavity dimensions in ZIF-108. This adjustment not only enhanced the molecular affinity and selectivity toward 4MP1 but also facilitated a diffusion rate that is 164 times faster than that observed in ZIF-8. These properties significantly elevated the performance of ZIF-108 in simulated moving bed (SMB) processes, achieving up to 96.5% recovery of high-purity 4MP1, outperforming traditional adsorbents. Comprehensive characterization, including density functional theory (DFT) calculations and molecular dynamics (MD) simulations, provided insights into the interactions and the stability of the adsorption process. The findings suggest that the strategic modification of the pore architecture in MOFs holds significant potential for optimizing the separation processes of industrially relevant mixtures.

Influence of pore structures on friction and wear properties of iron-based oil-containing composites under dry and self-lubricated sliding conditions

This study successfully prepares iron-based oil-containing materials with connected porous structures using TiH2 and nylon 66 short fibers as pore-forming agents. The dehydrogenation of TiH2 can produce large pore cavities and the nylon 66 short fiber with a highly regular shape has a unique advantage in pore channel production. Compared to the iron-based specimen without the pore-forming agent, the oil content of the iron-based specimen with the two pore-forming agents increases by 33.86 %. The tribologica23ee3l properties of the iron-based oil-containing materials under dry and self-lubricated sliding conditions are evaluated using the MM-200 ring-block sliding tribometer and the HDM-20 end-face friction and wear tester, respectively. Special emphasis is given to the effect of pore structures on wear patterns. The results showed that the material's surface is subjected to significant shear failure under dry sliding conditions, leading to the closure of pores due to plastic deformation during the initial sliding. The connected pore structure is a non-dense region, allowing shear damage to occur in the deeper subsurface of the matrix and increasing the material's wear rate. Under self-lubricated conditions, the connected pore structure facilitates the rapid release of lubricating oil, improves the initial lubrication state, and delays pore closure. As compared with dry friction, the wear rate can be reduced by two orders of magnitude under self-lubricating conditions. At a sliding speed of 0.46 m/s, an appropriate load (about 900 N) can enhance the material's ability to continuously and rapidly supply oil.

Partial Water Intrusion and Extrusion in Hydrophobic Nanopores for Thermomechanical Energy Dissipation.

Forced wetting (intrusion) and spontaneous dewetting (extrusion) of hydrophobic/lyophobic nanoporous materials by water/nonwetting liquid are of great importance for a broad span of technological and natural systems such as shock-absorbers, molecular springs, separation, chromatography, ion channels, nanofluidics, and many more. In most of these cases, the process of intrusion-extrusion is not complete due to the stochastic nature of external stimuli under realistic operational conditions. However, understanding of these partial processes is limited, as most of the works are focused on an idealized complete intrusion-extrusion cycle. In this work, we show an experimental system operating under partial intrusion/extrusion conditions and present a simple model that captures its main features. We rationalize these operational conditions in terms of the pore entrance and cavity size distributions of the material, which control the range of intrusion/extrusion pressures.

Suitable Pore Confinement with Multiple Interactions in a Low-Cost Zeolitic Imidazolate Framework for Efficient Xe Capture and Separation

The increasing industrial demand for the noble gases xenon (Xe) and krypton (Kr), along with growing environmental concerns on their radionuclides, has made the efficient separation and purification of Xe and Kr a critical issue. Leveraging advanced porous materials to achieve highly efficient adsorptive Xe/Kr separation has been recognized as an energy-saving and economical alternative to the widely used cryogenic distillation technology. Herein, we present a stable, low-cost, and easily scalable zeolitic imidazolate framework (ZIF) material, ZIF-4, for effective xenon adsorption and separation. ZIF-4 possesses uniformly distributed pore cavities with ideally matched pore size (4.3 Å) with that of Xe atom (4.047 Å), providing appropriate pore confinement for Xe binding. Sorption isotherms of ZIF-4 demonstrate the remarkably high Xe uptake (1.64 mmol/g at 0.2 bar and 298 K) and excellent Xe/Kr separation selectivity (16.2 for IAST selectivity of 20/80 Xe/Kr gas mixtures). Breakthrough experiments further validate the efficient separation performance of ZIF-4 in both binary Xe/Kr (20/80) gas mixtures and under dilute conditions. Single-crystal X-ray diffraction studies of activated and Xe-loaded ZIF-4 crystals reveal that the flexible pore cavities of ZIF-4 can self-adaptively adsorb and accommodate Xe atoms through the rotation of imidazolate rings, forming multiple Xe···H and Xe···π interactions to create strong binding sites for Xe capture and discrimination. The stability, economic feasibility, and scalability of ZIF-4 underscore its significant potential for industrial Xe/Kr separation.

Utilization of Alkali-Activated Rice Husk Ash for Sustainable Peat Stabilization

Abstract Peat is formed from organic matter (OM) in wetlands under an anaerobic environment. Peat is considered weak and problematic soil because of high-water retaining capability, high compressibility, and low shear strength. The cement is generally used to stabilize peat, but cement production is energy intensive and contributes 7–8 % of total carbon dioxide to the atmosphere. Nowadays, there is a need to use a potential “greener” alternative that is sustainable in the long term. Therefore, this research assesses the feasibility of rice husk ash (RHA)–based alkali-activated binder (AAB)–stabilized peat with varying fiber content (6–73 %) and OM (21–79 %). The RHA-based AAB was prepared by adding bauxite powder (as alumina source) to RHA in proportion to keep constant silica to alumina ratio (silica/alumina = 3). The samples were prepared using sodium hydroxide (NaOH) of molarities 3, 6, and 9 to activate the binder with percentages 10, 20, and 30 % by weight of dry peat and alkali (A) to binder (B) ratio chosen as 0.5, 0.7, and 0.9. The results illustrate that the factors like pH of pore solution, the molarity of NaOH, binder content, A/B ratio, OM, and curing affect the unconfined compressive strength (UCS) of treated peat. The maximum UCS of 962, 873, and 668 kPa was found at an optimum combination of molarity (6M), binder content (20 %), and A/B ratio (0.7) for sapric, fibric, and hemic peat. It was seen that OM has a negative impact, whereas the curing period positively impacts the UCS of treated peat. Furthermore, the cumulative mass loss of fibric peat (13.6 %) is more than hemic (11.4 %) and sapric (10.6 %) peat. The X-ray diffraction patterns and field emission scanning electron microscopy micrographs confirm the cementitious minerals that fill pore spaces or cavities to form a smooth and dense gel responsible for strength gain.

Kajian Penyebab Rembesan pada Bendungan Situ Lembang di Kabupaten Bandung Barat

A dam is a construction structure built to hold back the flow of water from upstream to downstream. Geographically, the Situ Lembang Dam is located in Kertawangi Village, Cisarua District, West Bandung Regency, the Situ Lembang Dam has a length of 350 m. One of the problems with dams is seepage. Seepage is defined as the property of a porous material that allows fluid in the form of water to flow through the pore cavity. The aim of this research is to determine the effect of variations in hydrostatic height on seepage that occurs in the dam body. The material forming the dam body is a type of organic clay. Almost all of the instrumentation equipment at 'Situ Lembang' no longer functions. This research uses laboratory simulations to review seepage patterns and seepage discharge against variations in hydrostatic height. Seepage discharge (Qf) is calculated using 3 methods, namely the Dupuit method, Schaffernak method, and Cassagrande method. The hydrostatic height variations reviewed are H10, H15, and H20.

Adsorption enhances CH4 transport-driven hydrate formation in size-varied ZIF-8: Micro-mechanism for CH4 storage by adsorption-hydration hybrid technology

The adsorption-hydration hybrid technology holds significant potential for future CH4 storage applications. However, the transport of CH4/H2O and the mechanisms governing hydrate formation within metal-organic framework (MOF) systems remain unclear. In this study, the mechanism of CH4 adsorption, transport, and hydrate formation within ZIF-8 pores of different sizes was delineated utilizing the magnetic resonance imaging (MRI) technique. Primarily, CH4 undergoes physisorption within the inner cavity of ZIF-8, facilitating diffusion through the pores, which preferentially accumulate in larger pore spaces. Due to favorable interactions between CH4 and pre-absorbed water on the ZIF-8 surface, ZIF-8–01 and ZIF-8–02 preferentially facilitate substantial hydrate formation within larger pore spaces. The continuous hydrate growth depletes CH4 in the pore space, enabling two-way migration of adsorbed CH4 to support ongoing hydrate formation. This limited availability of adsorption sites within ZIF-8 induces the diffusion of surrounding CH4 into smaller pore spaces, facilitating the conversion of bound water. The size of the particles considerably influences the transport of physically adsorbed CH4 and impacts hydrate formation. Similar patterns are observed in the adsorption mass transfer coefficients of ZIF-8–01 and ZIF-8–02, which range from 0.0038 to 0.0044 and 0.0031 to 0.0124, respectively. The presence of more adsorption vacancies in the early stage leads to rapid diffusion adsorption of CH4 owing to strong adsorption effects. As adsorption within ZIF-8 pore cavities approaches saturation, increased water transport elevates internal gas-liquid two-phase resistance, slowing the kinetics of late-stage CH4 adsorption. At 6 MPa, CH4 with a larger particle size preferentially overcomes the gas-liquid energy barrier, expediting transport and promoting hydrate formation. Furthermore, the optimal particle sizes of ZIF-8 substantially influence physisorption and significantly improve the kinetics of hydrate formation.

Improving the proton conductivity of MOF materials by regulating the pore space

The construction of metal-organic frameworks (MOFs) with structural tunability, designability, and high stability is crucial in proton conduction studies. In this paper, MOF-801 and UiO-66 were used as precursors. A solvothermal synthesis method was employed to modulate the pore space of composite MOFs. The hydrogen-bonding network and structure within the pore cavities are adjusted by varying the molar ratios of fumaric acid and terephthalic acid to improve the proton transfer rate and proton conductivity of the materials. A total of 14 materials, MOF/MOG-801&UiO-66-X (X is the molar ratio of fumaric acid and terephthalic acid) were synthesised, the variation of proton conductivity with temperature of which was investigated at different tempertures and humidities. The results shows that MOG-801&UiO-66–1:1 has the best proton conductivity with 0.12 S cm−1 at 353 K and 100 % RH, which is 5 times higher than that of MOF-801&UiO-66–1:3 (2.54 × 10−2 S cm−1), 11 times higher than that of MOF-801 and 22 times higher than that of UiO-66. Based on the calculated activation energy and structural characterisation, the proton conduction mechanism of the composite was investigated. This work opens up novel research fields for the design of new proton-conducting MOF materials.

Microbial carbonate reservoir characteristics and their depositional effects, the IV Member of Dengying Formation, Gaoshiti-Moxi area, Sichuan Basin, Southwest China

Previous scientific research on reservoirs of the Deng IV Member in the Gaoshiti-Moxi area, the main production area of the Anyue gas field with reserves of tens of billions of cubic metres, has focused on karst palaeogeomorphology reconstruction, the facies distribution on platform margins, and their effects on creating favourable reservoirs. However, the quality of microbial carbonate reservoirs is also closely related to their original depositional environments on both inner and marginal platforms. Therefore, this paper attempts to reveal favourable microbial carbonate reservoir characteristics and the sedimentary effects on their distribution and prediction based predominantly on a synthetic analysis of the sequence stratigraphy and depositional facies. The results show that favourable reservoirs of the Deng IV Member are classified into three types according to their reservoir spaces: fracture-cavity, pore-cavity and pore reservoirs. Secondary dissolution pores and cavities are primary reservoir spaces developed mainly in nonskeletal grain dolomites with sparry cements, thrombolites, and stromatolites. The physical properties of the fracture-cavity and pore-cavity types of reservoirs are better than those of pore reservoirs and have porosities between 1 and 5% and permeabilities between 0.01 × 10–3 and 1 × 10–3 μm2. Vertically, favourable reservoirs are developed mainly in parasequence set 6 (PSS6) and PSS7 and are laterally distributed in well zone MX9-MX19-MX1 for the fracture-cavity type, MX105-MX110-GS20 for the pore-cavity type and MX17-MX107-MX41-MX102-GS102 for the pore type. Moreover, depositional effects on reservoirs in terms of depositional sequences, seismic facies, microfacies and microfacies associations indicate that to some extent, the fracture-cavity type of reservoir is constrained by the top boundaries of PSS7, PSS2, parasequence 17 (PS17) and PS14; the pore-cavity type of reservoir is constrained by the top boundaries of PSS7, PSS4, PS18 and PS12; and the pore type of reservoir is constrained by the top boundaries of PSS7, PSS6, PSS3, PSS2, PS18, PS17, PS14, and PS12. Seismic facies associated with shoals and mound-flat complexes are related to the facies distributions of pore cavities and pore reservoirs. MA1, MA3, MA7, and MA8 are predominant microfacies associations of favourable reservoirs of the Deng IV Member in the Gaoshiti-Moxi area. The above results are significant for further petroleum exploration and exploitation of ultradeep microbial carbonate reservoirs in this area.

PROPUESTA DE MODIFICACIÓN AL MODELO DE ARYA-PARIS PARA LA ESTIMACIÓN DE LA CURVA DE RETENCIÓN DE AGUA EN EL SUELO

This contribution addresses drawbacks highlighted in the literature such as the disadvantage of using the concept of cylindrical capillary bundle (CCP) with uniform sizes to represent the geometry of the pore space and the lack in the consideration of surface forces and the non-inclusion of water retention in the angular pore cavities, which often leads to underestimation of the dry range of the CCRAS.

Sequestration of Pb2+ from aqueous solution using bio-based-alkaline modified sorbent from waste Irvingia gabonensis seed husk

Abstract The unmodified and modified Irvingia gabonensis (IG) were characterized with Fourier transform infrared (FTIR), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), thermogravimetric analyzer (TGA), and scanning electron microscope (SEM). The experimental conditions revealed the optimum adsorption efficiency was achieved at pH 6 within 30 min. FTIR spectra showed an observable shift in peaks attributed to the pretreatment with NaOH that necessitated the breakdown of the organic compounds. It was established from the SEM image under different magnifications that the surface morphology of the biosorbent consists of heterogeneous layers and pore cavities which acted as potential sites for Pb2+ adsorption. However, there was a considerable increase in the BET surface area, pore size, and pore width on the modified biosorbent compared to the unmodified biosorbent though this did not translate into higher adsorption capacity. The experimental data were best fitted with the Temkim isotherm model suggesting heterogeneous uptake of Pb2+ onto the base-modified Irvingia gabonensis seed husk. The maximum adsorption capacity was 2.58 mg/g and the kinetic model is best described with the pseudo-second-order reaction suggesting a chemical adsorption mechanism. The two error functions (HYBRID and MPSD) suggested the pseudo-second-order reaction mechanism in the adsorption of Pb2+ onto the base-modified Irvingia gabonensis.

Cavity and entrance pore development in ant plant hypocotyls.

Some genera of Rubiaceae in South-eastern Asia are known as typical ant plants. They have large domatia, which form in well-developed hypocotyls in which ants nest. Previously, cavity formation processes were described; however, these reports were dependent on tissue sections of different individuals of different ages. No continuous time-course analyses were done because cavity formation occurs inside the thick tissues of highly swollen domatia. Here we observed cavity formation processes in ant plants by using X-ray computed tomography (CT) imaging and revealed previously overlooked features of cavity formation. Firstly, the cavity pore occurs at the hypocotyl base in not only gravity-dependent but also basal position-dependent manner. Secondly, the cavity forms prior to the start of short tunnel formation between the cavity and the pore. The cavity axis is parallel to the longitudinal axis of the hypocotyl; however, the short tunnel axis between the pore and cavity depends on gravity. Non-invasive CT scanning is a very powerful method to analyze deeply hidden morphogenic processes in organs.

Nanoarchitectonics of lithium ion pathways through pores in a carbon framework for improving the storage capability and reversibility of lithium metal anode

The utilization of lithium (Li) metal as an anode has attracted significant attention for high‐energy Li batteries. Unfortunately, uncontrollable Li dendrite cannot be avoided during Li plating and stripping. Much intensive research has been conducted to suppress the dendritic growth by confinement of metallic Li in host architectures. Recently, zeolitic imidazolate frameworks (ZIFs) with a porous features have been used to explore a new approach to storing the Li metal with the advantages of their structural and chemical stability, large surface areas, and large pore cavities. Herein, we investigate the storage capability of metallic Li in a porous carbon framework derived from ZIFs as a function of carbonization temperature. Diversities in pore volumes and channels, the degree of crystallinity, the amount of residual zinc (Zn) metal, and the electrical conductivity can all be controlled by temperature. We demonstrate that well‐connected pore channels and adequate electrical conductivity secure the Li‐ion pathways and that well‐distributed Zn clusters in porous carbon trigger the outward growth of metallic Li from inside the frameworks, resulting in a relatively low overpotential and long‐lasting cyclability. Our findings can provide practical insight into advanced electrode design for next‐generation Li metal batteries.

Highly Robust Metal-Organic Framework for Efficiently Catalyzing Knoevenagel Condensation and the Strecker Reaction under Solvent-Free Conditions.

Metal-organic frameworks (MOFs) have been recognized as one of the most promising porous materials and offer great opportunities for the rational design of new catalytic solids having great structural diversity and functional tunability. Despite numerous inherent merits, their chemical environment instability limits their practical usage and demands further exploration. Herein, by employing the mixed-ligand approach, we have designed and developed a robust 3D Co-MOF, [Co2(μ2-O)(TDC)2(L)(H2O)2]·2DMF (H2TDC = 2,5-thiophenedicarboxylic acid, L = 3,3'-azobispyridine), IITKGP-50 (IITKGP stands for the Indian Institute of Technology Kharagpur), which exhibited excellent framework robustness not only in water but also in a wide range of aqueous pH solutions (pH = 2-12). Taking advantage of superior framework robustness and the presence of high-density open metal sites, IITKGP-50 was further explored in catalyzing the two-component Knoevenagel condensation reaction and three-component Strecker reactions. Moreover, to verify the size selectivity of IITKGP-50, smaller to bulkier substrates in comparison with the MOF's pore cavity (8.1 × 5.6 Å2) were employed, in which relatively lesser conversions for the sterically bulkier aldehyde derivatives confirmed that the catalytic cycle occurs inside the pore cavity. The easy scalability, lower catalyst loading compared to that of benchmark MOFs, magnificent conversion rate over a wide range of substrates, and excellent recyclability without significant performance loss made IITKGP-50 a promising heterogeneous catalyst candidate.

Synergistic effect of silica aerogel and titanium dioxide in porous polyurethane composite coating with enhanced passive radiative cooling performance

Passive daytime radiative cooling is a promising technology that can mitigate the increasing issues of global warming and urban heat island effects. In this work, a series of porous polyurethane (PPU) composite coatings containing silica aerogel (SA) and/or titanium dioxide (T) were prepared though a wet phase inversion method. The effects of the filler types on relevant properties of composite coatings, such as pore microstructure, radiative cooling, mechanical, and hydrophobic performances, were systematically investigated. The typical PPU-SA10@T10 composite coating showed an interleaving porous structure, and the incorporated SA and T fillers were uniformly stacked in the pore cavities. Taking advantages of the strong light-back scattering and molecular oscillation functions, the solar reflectance, thermal emittance in the atmospheric transparency window, and the net cooling power of the PPU-SA10@T10 coating reached 0.917, 0.973, and 87.8 W/m2, respectively, which results in a sub-ambient cooling of 7.8 °C at midday under a solar irradiance of ∼640 W/m2. Moreover, the PPU-SA10@T10 coating possessed well balanced mechanical properties and superior hydrophobicity (water contact angle was 121.7°). The present work provides a viable way for developing radiative cooling coating with desirable mechanical properties and water-repellency.

Exclusive Recognition of CO2 from Hydrocarbons by Aluminum Formate with Hydrogen-Confined Pore Cavities.

Exclusive capture of carbon dioxide (CO2) from hydrocarbons via adsorptive separation is an important technology in the petrochemical industry, especially for acetylene (C2H2) production. However, the physicochemical similarities between CO2 and C2H2 hamper the development of CO2-preferential sorbents, and CO2 is mainly discerned via C recognition with low efficiency. Here, we report that the ultramicroporous material Al(HCOO)3, ALF, can exclusively capture CO2 from hydrocarbon mixtures, including those containing C2H2 and CH4. ALF shows a remarkable CO2 capacity of 86.2 cm3 g-1 and record-high CO2/C2H2 and CO2/CH4 uptake ratios. The inverse CO2/C2H2 separation and exclusive CO2 capture performance from hydrocarbons are validated via adsorption isotherms and dynamic breakthrough experiments. Notably, the hydrogen-confined pore cavities with appropriate dimensional size provide an ideal pore chemistry to specifically match CO2 via a hydrogen bonding mechanism, with all hydrocarbons rejected. This molecular recognition mechanism is unveiled by in situ Fourier-transform infrared spectroscopy, X-ray diffraction studies, and molecular simulations.

Free-Standing Metal–Organic Framework Membranes Made by Solvent-Free Space-Confined Conversion for Efficient H2/CO2 Separation

Metal-organic frameworks (MOFs) are promising candidates for the advanced membrane materials based on their diverse structures, modifiable pore environment, precise pore sizes, etc. Nevertheless, the use of supports and large amounts of solvents in traditional solvothermal synthesis of MOF membranes is considered inefficient, costly, and environmentally problematic, coupled with challenges in their scalable manufacturing. In this work, we report a solvent-free space-confined conversion (SFSC) approach for the fabrication of a series of free-standing MOF (ZIF-8, Zn(EtIm)2, and Zn2(BIm)4) membranes. This approach excludes the employment of solvents and supports that require tedious pretreatment and, thus, makes the process more environment-friendly and highly efficient. The free-standing membranes feature a robust and unique architecture, which comprise dense surface layers and highly porous interlayer with large amounts of irregular-shaped micron-scale pore cavities, inducing satisfactory H2/CO2 selectivities and exceptional H2 permeances. The ZIF-8 membrane affords a considerable H2 permeance of 2653.7 GPU with a competitive H2/CO2 selectivity of 17.1, and the Zn(EtIm)2 membrane exhibits a high H2/CO2 selectivity of 22.1 with an excellent H2 permeance (6268.7 GPU). The SFSC approach potentially provides a new pathway for preparing free-standing MOF membranes under solvent-free conditions, rendering it feasible for scale-up production of membrane materials for gas separation.

Bohemian sandstone for restoration of cultural heritage sites: 3D microstructure and mass transport properties

We characterised the microstructure of sandstone from the Msene locality (Czech Republic) by combining X-ray computed micro-tomography, back-scattered electron imaging, chemical composition analysis and textural analysis and gas permeation. Both, 2D and 3D images were commonly processed by linking an anisotropic non-linear diffusion filter and a segmentation method based on power watershed. This approach guaranteed binarised outputs that were almost the same in wide ranges of spatial-filter and power-watershed parameters, i.e., subjective choices of the parameters played the negligible role. The rock pore structure was found to be statistically homogeneous and almost isotropic with perfectly connected pore space. We also partitioned the void and solid phases into either grains or pores and throats, which enabled us to study characteristic sizes and connectivity of partitioned regions. By comparing pore and throat sizes, we demonstrated the significant convergent-divergent nature of the pore space because the throat size covered at most one half of the total surface area per pore (cavity). In addition, we calculated coordination numbers for all pores (cavities) to verify almost perfect connectivity of internal pores with those at the external surface. Effective (macroscopic) transport properties of the reconstructed pore space were simulated and the results were validated by experimentally observing steady state flow of inert gas. These findings appear to be a favorable starting point for future investigation of consolidation procedures. The well-connected pore structure with minimum occurrence of dead-end pores suggests that the consolidation agent is very likely to flood the whole pore space.