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Gas adsorption is an important tool for the characterisation of porous solids and fine powders. Major advances in recent years have made it necessary to update the 1985 IUPAC manual on Reporting Physisorption Data for Gas/Solid Systems. The aims of the present document are to clarify and standardise the presentation, nomenclature and methodology associated with the application of physisorption for surface area assessment and pore size analysis and to draw attention to remaining problems in the interpretation of physisorption data.

Double-walled metal-organic frameworks (MOFs), synthesized using Zn and Co, are potential porous materials for trace benzene adsorption. Aluminum is with low-toxicity and abundance in nature, in comparison with Zn and Co. Therefore, a double-walled Al-based MOF, named as ZJU-520(Al), with large microporous specific surface area of 2235 m 2  g –1 , pore size distribution in the range of 9.26–12.99 Å and excellent chemical stability, was synthesized. ZJU-520(Al) is consisted by helical chain of AlO 6 clusters and 4,6-Di(4-carboxyphenyl)pyrimidine ligands. Trace benzene adsorption of ZJU-520(Al) is up to 5.98 mmol g –1 at 298 K and P/P 0  = 0.01. Adsorbed benzene molecules are trapped on two types of sites. One (site I) is near the AlO 6 clusters, another (site II) is near the N atom of ligands, using Grand Canonical Monte Carlo simulations. ZJU-520(Al) can effectively separate trace benzene from mixed vapor flow of benzene and cyclohexane, due to the adsorption affinity of benzene higher than that of cyclohexane. Therefore, ZJU-520(Al) is a potential adsorbent for trace benzene adsorption and benzene/cyclohexane separation. Trace benzene poses a risk to the health and safety of humans, resulting in a challenging task. Here authors synthesise double-walled Al-based MOF ZJU-520(Al) with trace benzene adsorption (5.98 mmol g –1 ) and excellent benzene/cyclohexane separation ability.

High-performance membranes exceeding the conventional permeability-selectivity upper bound are attractive for advanced gas separations. In the context microporous polymers have gained increasing attention owing to their exceptional permeability, which, however, demonstrate a moderate selectivity unfavorable for separating similarly sized gas mixtures. Here we report an approach to designing polymeric molecular sieve membranes via multi-covalent-crosslinking of blended bromomethyl polymer of intrinsic microporosity and Tröger’s base, enabling simultaneously high permeability and selectivity. Ultra-selective gas separation is achieved via adjusting reaction temperature, reaction time and the oxygen concentration with occurrences of polymer chain scission, rearrangement and thermal oxidative crosslinking reaction. Upon a thermal treatment at 300 °C for 5 h, membranes exhibit an O 2 /N 2 , CO 2 /CH 4 and H 2 /CH 4 selectivity as high as 11.1, 154.5 and 813.6, respectively, transcending the state-of-art upper bounds. The design strategy represents a generalizable approach to creating molecular-sieving polymer membranes with enormous potentials for high-performance separation processes. Microporous polymers become increasingly attractive as materials for the fabrication of permeable and selective gas separation membranes but separation performance is often limited by broad pore size distribution. Here, the authors design a porous polymer membrane via multi-crosslinking of miscible blends of microporous polymers enabling simultaneous high permeability and selectivity.

Bentonite pellets are recognized as good buffer/backfill materials for sealing technological voids in high-level radioactive waste (HLW) repository. Compared to that of a traditional compacted bentonite block, one of the most important particularities of this material is the initially discrete pellets and the inevitable heterogeneous porosity formed, leading to a distinctive water retention behaviour. In this paper, water retention and mercury intrusion porosimetry (MIP) tests were conducted on pellet mixture (constant volume), single pellet (free swelling) and compacted block (constant volume) of GMZ bentonite, water retention properties and pore structure evolutions of the specimens were comparatively investigated. Results show that the water retention properties of the three specimens are almost similar to each other in the high suction range (> 10 MPa), while the water retention capacity of pellet mixture is lower than those of the compacted block and single pellet in the low suction range (< 10 MPa). Based on the capillary water retention theory (the Young–Laplace equation), a new concept ‘saturated void ratio’ that was positively related to water content and dependent on pore size distribution of the specimen was defined. Then, according to the product of saturated void ratio and water density in saturated void, differences of water retention properties for the three specimens at low suctions were explained. Meanwhile, MIP tests indicate that as suction decreases, the micro- and macrovoid ratios of pellet mixture and compacted block decrease as the mesovoid ratio increases, while all the void ratios of single pellets increase. This could be explained that upon wetting, water is successively adsorbed into the inter-layer, inter-particle and inter-pellet voids, leading to the subdivision of particles and swelling of aggregates and pellets. Under constant volume condition, aggregates and pellets tend to swell and fill into the inter-aggregates or inter-pellets voids. While under free swelling condition, the particles and aggregates in a single pellet tend to swell outward rather than squeezing into the inter-aggregate voids, leading to the expansion of the pores and even formation of cracks. Results including the effects of initial conditions (initial dry density and fabric) and constraint conditions (constant volume or free swelling) on the water retention capacity and pore structure evolution reached in this work are of great importance in designing of engineering barrier systems for the HLW repository.

HighlightsPore size and graphitization engineering of carbon cathode were orientated-designed by regulating the molar ratios of Zn/Co ions.Zn90Co10-APC and its assembled PLG//Zn90Co10-APC LIC both deliver the excellent electrochemical performances.The lack of methods to modulate intrinsic textures of carbon cathode has seriously hindered the revelation of in-depth relationship between inherent natures and capacitive behaviors, limiting the advancement of lithium ion capacitors (LICs). Here, an orientated-designed pore size distribution (range from 0.5 to 200 nm) and graphitization engineering strategy of carbon materials through regulating molar ratios of Zn/Co ions has been proposed, which provides an effective platform to deeply evaluate the capacitive behaviors of carbon cathode. Significantly, after the systematical analysis cooperating with experimental result and density functional theory calculation, it is uncovered that the size of solvated PF6− ion is about 1.5 nm. Moreover, the capacitive behaviors of carbon cathode could be enhanced attributed to the controlled pore size of 1.5–3 nm. Triggered with synergistic effect of graphitization and appropriate pore size distribution, optimized carbon cathode (Zn90Co10-APC) displays excellent capacitive performances with a reversible specific capacity of ~ 50 mAh g−1 at a current density of 5 A g−1. Furthermore, the assembly pre-lithiated graphite (PLG)//Zn90Co10-APC LIC could deliver a large energy density of 108 Wh kg−1 and a high power density of 150,000 W kg−1 as well as excellent long-term ability with 10,000 cycles. This elaborate work might shed light on the intensive understanding of the improved capacitive behavior in LiPF6 electrolyte and provide a feasible principle for elaborate fabrication of carbon cathodes for LIC systems.

The full pore size distribution represents the integrated characteristics of micro‐nano pore‐throat systems in tight reservoirs. And it involves experiments of different scales to fully analyze the microscope properties. In this paper, we established a new approach for full pore size characterization through conducting the high‐pressure mercury intrusion (HPMI) experiments and low‐temperature nitrogen gas adsorption (LTN2GA) experiments. Meanwhile, we studied the petrology feature of the tight sandstones through X‐ray diffraction (X‐rD) and TESCAN Integrated Mineral Analyzer (TIMA). Then, we investigated the HPMI capillary pressure curves and pore size distribution characteristics, as well as the adsorption‐desorption isotherms features and BET‐specific surface area. Finally, the BJH, non‐local density functional theory (NLDFT) and the quenched solid density functional theory (QSDFT) are contrasted for analyzing the adsorption and pore size distribution characteristics. The HPMI method characterizes the macropores distribution accurately, and the micro/mesopores take up of 14.47% of the total pore spaces. The physisorption isotherms take on the combining shape of type II and IV(a), and the hysteresis loops are like type H3 combined with H4. The BET‐specific surface area is inversely proportional to permeability, and the constant of adsorption heat shows consistence with the analysis results of mineral content. QSDFT can characterize the pore size distribution of micro/mesopores more accurately than the BJH, HPMI, and NLDFT method. By combining the pores narrower than 34 nm calculated from QSDFT method and pores larger than 34 nm calculated from HPMI data with mercury intrusion pressure lower than 42.65 MPa, the full pore size distribution features of tight sandstones are accurately characterized. The micro/mesopores from the new combination method are 3.72% more than that calculated from the HPMI data, and it is of great significance for the accurate pore distribution evaluation and development of tight reservoirs. We performed low‐temperature nitrogen gas adsorption (LTN2GA), high‐pressure mercury intrusion (HPMI), and X‐ray diffraction (X‐rD) experiments on different ultra‐low permeability/tight sandstones to accurately characterize the full pore size distribution of this kind of reservoir rocks. By combining the micropore and mesopore distribution calculated by QSDFT with the mesopore and macropore distribution calculated by HPMI, the accurate characterization of full pore size distribution for the ultra‐low permeability/ tight sandstones is achieved.

The three-dimensional arrangement of natural and synthetic network materials determines their application range. Control over the real-time incorporation of each building block and functional group is desired to regulate the macroscopic properties of the material from the molecular level onwards. Here we report an approach combining kinetic Monte Carlo and molecular dynamics simulations that chemically and physically predicts the interactions between building blocks in time and in space for the entire formation process of three-dimensional networks. This framework takes into account variations in inter- and intramolecular chemical reactivity, diffusivity, segmental compositions, branch/network point locations and defects. From the kinetic and three-dimensional structural information gathered, we construct structure–property relationships based on molecular descriptors such as pore size or dangling chain distribution and differentiate ideal from non-ideal structural elements. We validate such relationships by synthesizing organosilica, epoxy–amine and Diels–Alder networks with tailored properties and functions, further demonstrating the broad applicability of the platform. A computational platform describing the spatial and temporal interactions of monomers during the formation of network polymers provides structure–property relationships that are used to synthesize 3D network polymers with tailored functionalities.

The purpose of this article was to quantitatively investigate the pore structure and fractal characteristics of different lithofacies in the upper Permian Dalong Formation marine shale. Shale samples in this study were collected from well GD1 in the Lower Yangtze region for mineral composition, X-ray diffraction (XRD), and nitrogen adsorption–desorption analysis, as well as broad-ion beam scanning electron microscopy (BIB-SEM) observation. Experimental results showed that the TOC (total organic carbon) content and vitrinite reflectance (Ro) of the investigated shale samples were in the ranges 1.18–6.45% and 1.15–1.29%, respectively, showing that the Dalong Formation shale was in the mature stage. XRD results showed that the Dalong Formation shale was dominated by quartz ranging from 38.4% to 54.3%, followed by clay minerals in the range 31.7–37.5%, along with carbonate minerals (calcite and dolomite), with an average value of 9.6%. Based on the mineral compositions of the studied samples, the Dalong Formation shale can be divided into two types of lithofacies, namely siliceous shale facies and clay–siliceous mixed shale facies. In siliceous shale facies, which were mainly composed of organic pores, the surface area (SA) and pore volume (PV) were in the range of 5.20–10.91 m2/g and 0.035–0.046 cm3/g, respectively. Meanwhile, the pore size distribution (PSD) and fractal dimensions were in the range 14.2–26.1 nm and 2.511–2.609, respectively. I/S (illite-smectite mixed clay) was positively correlated with SA, PV, and fractal dimensions, while illite had a negative relationship with SA, PV, and fractal dimensions. I/S had a strong catalytic effect on organic matter for hydrocarbon generation, which was beneficial to the development of organic micropores, so I/S was conducive to pore structure complexity and the increase in SA and PV, while illite easily filled organic pores, which was not beneficial to the improvement of pore space. In clay–siliceous mixed shale facies, which mainly develop inorganic pores such as intergranular pores, SA and PV were in the range of 6.71–11.38 m2/g and 0.030–0.041 cm3/g, respectively. Meanwhile, PSD and fractal dimensions were in the range of 14.3–18.9 nm and 2.563–2.619, respectively. Quartz and I/S showed weak positive correlations with SA, PV, and fractal dimensions. The various compact modes between quartz particles and the disorder of I/S were conducive to the complexity of pore structure and the improvement of SA and PV. The research findings can provide a reference for the optimization and evaluation of shale gas favorable area of the Lower Yangtze Platform.

Nanoporous graphene and related atomically thin layered materials are promising candidates in reverse electrodialysis research owing to their remarkable ionic conductivity and high permselectivity. The synthesis of atomically thin nanoporous membranes with a narrow pore size distribution, however, remains challenging. Here, we report the fabrication of nanoporous carbon membranes via the thermal crosslinking of core–rim structured monomers, that is, polycyclic aromatic hydrocarbons. The mechanically robust, centimetre-sized membrane has a pore size of 3.6 ± 1.8 nm and a thickness of 2.0 ± 0.5 nm. When applied to reverse electrodialysis, the nanoporous carbon membrane offers a high short-circuit current with an output power density of 67 W m−2, which is about two orders of magnitude beyond that of the classic ion-exchange membranes and current prototype nanoporous membranes reported in the literature. Crosslinked and atomically thin porous polycyclic aromatic hydrocarbon membranes therefore represent new scaffolds that will revolutionize the rapidly developing fields of sustainable energy and membrane technology.Mechanically robust, centimetre-sized, molecularly thin nanoporous carbon membranes were fabricated via the thermal crosslinking of core–rim structured monomers, offering a high reverse electrodialysis short-circuit current with a giant output power density of 67 W m−2.

The preparation of atom-thick porous lattice hosting Å-scale pores is attractive to achieve a large ion-ion selectivity in combination with a large ion flux. Graphene film is an ideal selective layer for this if high-precision pores can be incorporated, however, it is challenging to avoid larger non-selective pores at the tail-end of the pore size distribution which reduces ion-ion selectivity. Herein, we develop a strategy to overcome this challenge using an electrochemical repair strategy that successfully masks larger pores in large-area graphene. 10-nm-thick electropolymerized conjugated microporous polymer (CMP) layer is successfully deposited on graphene, thanks to a strong π-π interaction in these two materials. While the CMP layer itself is not selective, it effectively masks graphene pores, leading to a large Li + /Mg 2+ selectivity from zero-dimensional pores reaching 300 with a high Li + ion permeation rate surpassing the performance of reported materials for ion-ion separation. Overall, this scalable repair strategy enables the fabrication of monolayer graphene membranes with customizable pore sizes, limiting the contribution of nonselective pores, and offering graphene membranes a versatile platform for a broad spectrum of challenging separations. The preparation of atom-thick lattices with Å-scale pores is desirable for achieving ion selectivity and high ion flux. Here authors present a cm-scale membrane made of atom-thick graphene film hosting zero-dimensional pores spanning only a few Å, repaired using an in situ electrochemical strategy, yielding high Li + /Mg 2+ separation performance.