Gas Sorption Research Articles

Streamlined In Situ X-ray Crystallography of Gas Sorption State as Realized through the De Novo Development of a Novel Crystal Mount

Streamlined In Situ X-ray Crystallography of Gas Sorption State as Realized through the De Novo Development of a Novel Crystal Mount

ZIF-8 Porous Liquids with Different Sterically Hindered Solvents and Porous Guests for Catalytic Conversion of Carbon Dioxide.

Utilizing carbon dioxide (CO2) as a raw material is an effective way to reduce carbon emissions, and developing catalytic systems with high catalytic activity and stability is crucial for the efficient utilization of CO2. Porous liquids (PLs) with both permanent pores and fluidity have great potential in the fields of catalysis, gas sorption, and storage. Nevertheless, the catalytic performance of PLs is affected by many factors; therefore, further study is needed. Herein, we proposed a general strategy to construct a series of type III PLs with different chemical structures of sterically hindered solvents and different microstructures of porous guests. Benefiting from the unique microstructures, the as-prepared PLs exhibit great potential in catalyzing the reaction of CO2 with propylene oxide under suitable conditions. Moreover, their catalytic activity exceeds that of pure sterically hindered solvents without a porous guest loading. The influences of the nucleophilicity of the anion of the sterically hindered solvent and the microstructure of the porous guests on the catalytic activity and the catalytic stability of the PLs were analyzed. Meanwhile, the mechanism of the catalytic conversion of CO2 was proposed, which is of great significance for the design and development of the subsequent PL catalysts.

Fractal Modelling of Heterogeneous Catalytic Materials and Processes.

This review considers the use of fractal concepts to improve the development, fabrication, and characterisation of catalytic materials and supports. First, the theory of fractals is discussed, as well as how it can be used to better describe often highly complex catalytic materials and enhance structural characterisation via a variety of different methods, including gas sorption, mercury porosimetry, NMR, and several imaging modalities. The review then surveys various synthesis and fabrication methods that can be used to create catalytic materials that are fractals or possess fractal character. It then goes on to consider how the fractal properties of catalysts affect their performance, especially their overall activity, selectivity for desired products, and resistance to deactivation. Finally, this review describes how the optimum fractal catalyst material for a given reaction system can be designed on a computer.

Resolving optimal ionomer interaction in fuel cell electrodes via operando X-ray absorption spectroscopy

To bridge the gap between oxygen reduction electrocatalysts development and their implementation in real proton exchange membrane fuel cell electrodes, an important aspect to be understood is the interaction between the carbon support, the active sites, and the proton conductive ionomer as it greatly affects the local transportations to the catalyst surface. Here we show that three Pt/C catalysts, synthesized using the polyol method with different carbon supports (low surface area Vulcan, high surface area Ketjenblack, and biomass-derived highly ordered mesoporous carbon), revealed significant variations in ionomer-catalyst interactions. The Pt/C catalysts supported on ordered mesoporous carbon derived from biomass showed the best performance under the gas diffusion electrode configuration. Through a unique approach of operando X-ray Absorption Spectroscopy combined with gas sorption analysis, we were able to demonstrate the beneficial effect of mesopore presence for optimal ionomer-catalyst interaction at both molecular and structural level.

Construction of a Fluorinated-Anion Pillared Metal-Organic Framework Exhibiting Dual-Pore Architecture for Simultaneous Enhancement of C2H2 Adsorption Capacity and Selectivity.

Physisorption-based separation processes represents a promising alternative to the conventional thermally driven methods, such as cryogenic separation. However, a significant challenge lies in balancing the trade-off between adsorption capacity and selectivity of adsorbents. In this study, we introduce a novel fluorinated-anion pillared metal-organic frameworks (APMOFs) featuring a dual-pore architecture, constructed using a pyridine-oxazole bifunctional ligand. The inherent low symmetry of the ligand leads to significant distortion of the fluorinated-anion pillars, resulting in a distinctive type of APMOFs characterized by dual-pore architecture. On pore structure with constrict pore width is enriched with a high density of anion fluorinated pillars, offering numerous active sites advantageous for enhancing separation selectivity. Concurrently, the other pore structure exhibits larger dimensions, facilitating increased gas molecule accommodation and thereby augmenting adsorption capacity. Gas sorption studies reveal a substantial C2H2 adsorption capacity and a high C2H2/CO2 separation selectivity. Breakthrough experiments confirm its exceptional separation performance, while theoretical investigations elucidate a sequential adsorption process within these APMOFs, underscoring the efficacy of this strategy in overcoming trade-off limits in adsorbents.

Engineering of the High‐Power Laser‐Induced Synthesis of Ni‐Based Metal‐Organic Framework: Investigation of its Optical Properties, Computational Methodology, Electrocatalytic Performances, and Glucose‐Sensing Ability

AbstractMetal‐organic frameworks (MOFs) are porous materials with numerous chemical and structural possibilities. Due to their ease of modification, well‐organized structure, and diverse guest molecule chemistry, MOFs are ideal platforms for uncovering improved functional material design characteristics. Quantitative analysis of glucose is crucial, especially in some food products, for quality control as well as evaluation of the glucose levels helps diagnose and treat diabetes. Recent glucose sensing devices have relied heavily on MOFs and other nanomaterials to enable user‐friendly and safe non‐invasive sensing methods. Nevertheless, the conventional synthesis methods involve multi‐day reactions, cooling, and depressurization processes. This study demonstrates the unprecedented high‐power laser‐induced rapid synthesis (LIRS) of Ni‐based MOF nanospheres with interconnected nano‐rods and noncentrosymmetric primitive triclinic crystalline structure, highlighting their multifunctional usage in sensing and gas sorption applications. Ab initio simulations show excellent agreement with the experimental physical and gas sorption properties. Furthermore, the Ni‐MOF‐based biosensor accurately measures glucose real‐life beverage samples, yielding promising glucose detection biosensor results with a low limit of the detection (LOD) of 13.96 µM and high sensitivity of 120.606 µA mM−1 cm−2.

Switching from Molecules to Functional Materials: Breakthroughs in Photochromism With MOFs.

Photochromic materials with properties that can be dynamically tailored as a function of external stimuli are a rapidly expanding field driven by applications in areas ranging from molecular computing, nanotechnology, or photopharmacology to programable heterogeneous catalysis. Challenges arise, however, when translating the rapid, solution-like response of stimuli-responsive moieties to solid-state materials due to the intermolecular interactions imposed through close molecular packing in bulk solids. As a result, the integration of photochromic compounds into synthetically programable porous matrices, such as metal-organic frameworks (MOFs), has come to the forefront as an emerging strategy for photochromic material development. This review highlights how the core principles of reticular chemistry (on the example of MOFs) play a critical role in the photochromic material performance, surpassing the limitations previously observed in solution or solid state. The symbiotic relationship between photoresponsive compounds and porous frameworks with a focus on how reticular synthesis creates avenues toward tailorable photoisomerization kinetics, directional energy and charge transfer, switchable gas sorption, and synergistic chromophore communication is discussed. This review not only focuses on the recent cutting-edge advancements in photochromic material development, but also highlights novel, vital-to-pursue pathways for multifaceted functional materials in the realms of energy, technology, and biomedicine.

State of the art on solid–gas sorption based long-term thermochemical energy storage

Solid-gas sorption thermochemical heat storage technology is an innovative and promising solution for storing heat over long periods. The review focuses on the construction of composite sorption thermochemical heat storage materials and binary mixed salt materials with porous matrix as the supporting materials, which can further improve the hydration rate and cycle stability of single hydrated salt. Furthermore, the heat storage capabilities of the metal halide/ammonia working pair make it suitable for extreme environments, surpassing the limitations of water-based working pairs in terms of low-temperature adaptability. It is worth noting that common solid–gas reactors and measures to enhance heat and mass transfer are also reviewed. Meanwhile, the efficient open and closed heat storage systems and their optimization schemes are introduced, and the feasibility of the practical operation of the heat storage systems is evaluated comprehensively from the technical and economic perspectives, and the future research challenges are prospected.

Scale-span feature of surface analysis, macromolecular and pore structure in coal: Implications for inherent evolutionary mechanism of morphological microstructure

Morphological microstructural evolution of tectonic coal determines CBM storage and transportation mechanism as well as the occurrence of coal and gas outburst. Scale-span morphological feature of original and tectonic coals was characterized by AFM, Raman spectrum and physisorption method. The results demonstrate that metamorphism could remold the surface property of coal from rugged band to flat porous structure with pore form factor from 0.572 to 0.831, promoting the formation of regular and round pores. Tectonism facilitates ability of gas sorption in coal, breaking the basic structural integrity. Metamorphism could facilitate the ordered macromolecular structural evolution on recombination and aromatization as well as condensation; besides, tectonism may promote the evolution and development of microcrystalline structure in advance. The aforementioned results have revealed essential differences in morphological microstructure between original and tectonic coals, which are of great guiding significance to safe mining of CBM and prediction of coal and gas outburst.

Modelling across Multiple Scales to Design Biopolymer Membranes for Sustainable Gas Separations: 2-Multiscale Approach

The majority of materials used for membrane-based separation of gas mixtures are non-renewable and non-biodegradable, and the assessment of alternative bio-based polymers requires expensive and time-consuming experimental campaigns. This effort can be reduced by adopting suitable modelling approaches. In this series of works, we propose various modelling approaches to assess the CO2/CH4 separation performance of eight different copolymers of 3-hydroxybutyrate and 3-hydroxyvalerate (PHBV) using a limited amount of experimental data for model calibration. In part 1, we adopted a fully atomistic approach based on Molecular Dynamics (MD), while, in this work, we propose a multiscale methodology where a molecular description of the polymers is bridged to a macroscopic prediction of its gas sorption behaviour. PHBV structures were simulated using MD to obtain pressure–volume–temperature data, which were used to parametrise the Sanchez–Lacombe Equation of State. This, in turn, allows for the evaluation of the CO2 and CH4 solubility in the copolymers at various pressures and compositions with little computational effort, enabling the estimate of the sorption-based selectivity. The gas separation performance obtained with this multiscale technique was compared to results obtained with a fully atomistic model and experimental data. The solubility–selectivity for the CO2/CH4 mixture is in reasonable agreement between the two models and the experimental data. The multiscale method presented is a time-efficient alternative to fully atomistic methods and detailed experimental campaigns and can accelerate the introduction of renewable materials in different applications.

Cationic effect study in acetate-based ionic liquids/ZIF-8 composites for CO2 sorption

Several strategies can be considered for the mitigation of carbon dioxide (CO2) emissions to the atmosphere, and among them is its post-combustion capture/separation from flue gas emitted from coal-fired power plants. In this work, six imidazolium, ammonium- and DABCO-based ionic liquids (ILs) containing the acetate anion were used to impregnate the metal-organic framework (MOF) ZIF-8. The cationic effect was studied to determine how the different cationic families and side alkyl chain size influence the gas sorption performance of the produced IL@MOF composites. The combination of different characterization techniques confirmed IL impregnation, and that the composite materials were microporous and crystalline. Single-component CO2 and nitrogen (N2) sorption-desorption equilibrium measurements were performed at 303 K for ZIF-8 and the IL@ZIF-8 materials. At the low-pressure regime (0–1 bar), synergy was observed for the imidazolium-based composites, especially for the one with the long-side alkyl chain. The ideal CO2/N2 selectivity was calculated for post-combustion composition, and, at 1 bar, [C10MIM][Ac]@ZIF-8 was over four times more selective than ZIF-8, while the selectivity of [C2MIM][Ac]@ZIF-8 at this pressure almost tripled when compared to the MOF. A chemical reaction between CO2 and the imidazolium ILs explained the results.

Deformation-induced gas adsorption and self-desorption dynamics of a carbon nano-network: Molecular dynamics modeling focusing on CO2 capture

Gas adsorption and separation/desorption are two pivotal stages in gas capture, demanding additional energy for liberating gas molecules from the adsorbent. Hence, it’s essential to engineer an adsorbent with minimal energy consumption yet effective gas adsorption–desorption characteristics. Accordingly, this research introduces a carbon nano-network (CNN) material capable of inhaling and exhaling gases via self-deformation. Molecular dynamics simulations demonstrate that the gas adsorption–desorption capabilities of CNN can be efficiently regulated by its deformation. While the size of CNN minimally affects the gas sorption rate, a larger CNN necessitates a prolonged duration to achieve saturation under identical gas conditions. Incorporating elongated appendages in CNN enhances both its stability during contraction and its efficiencies in gas adsorption and desorption. We discerned that attaining a critical gas density within a confined space is imperative to initiate self-desorption of CNN. Specifically, if the gas density dips below this critical threshold–set at 5.2 times that of CO2 at room temperature (300 K) and atmospheric pressure (1 Bar)–CNN exhibits no self-desorption capability. Nevertheless, even a marginal elevation in gas density triggers and maintains self-desorption with a consistently surpassing desorption ratio of 98 %. This discovery offers valuable insights for designing automatic self-desorption materials or apparatuses.

Polyphosphonate covalent organic frameworks

Herein, we report polyphosphonate covalent organic frameworks (COFs) constructed via P-O-P linkages. The materials are synthesized via a single-step condensation reaction of the charge-assisted hydrogen-bonded organic framework, which is constructed from phenylphosphonic acid and 5,10,15,20‐tetrakis[p‐phenylphosphonic acid]porphyrin and is formed by simply heating its hydrogen-bonded precursor without using chemical reagents. Above 210 °C, it becomes an amorphous microporous polymeric structure due to the oligomerization of P-O-P bonds, which could be shown by constant-time solid-state double-quantum 31P nuclear magnetic resonance experiments. The polyphosphonate COF exhibits good water and water vapor stability during the gas sorption measurements, and electrochemical stability in 0.5 M Na2SO4 electrolyte in water. The reported family of COFs fills a significant gap in the literature by providing stable microporous COFs suitable for use in water and electrolytes. Additionally, we provide a sustainable synthesis route for the COF synthesis. The narrow pores of the COF effectively capture CO2.

Correlating the structure of quinone-functionalized carbons with electrochemical CO2 capture performance

Electrochemical carbon dioxide capture is emerging as an energy-efficient alternative to traditional carbon capture technology. In particular, redox-active molecules that can capture carbon dioxide when electrochemically reduced and release carbon dioxide when electrochemically re-oxidized are under active development. To prepare a carbon capture device, these molecules can be incorporated into a solid electrode in a battery-like cell. In this work, we explore the scope of a recently developed method where anthraquinones are covalently attached to porous carbon supports to obtain electrodes for electrochemical carbon dioxide capture. We functionalize four different porous carbon materials with varying porosities and surface chemistries, and use gas sorption analysis and solid-state NMR spectroscopy to probe the location of the grafted anthraquinones. All four functionalized materials show electrochemically mediated capture and release of carbon dioxide, and we explore the factors that determine their performance. While the anthraquinone-functionalized mesoporous carbon, f-CMK-3, showed the highest quinone loading, it showed poor quinone utilization for CO2 capture and poor long-term cycling stability. In contrast, the predominantly microporous functionalized carbon, f-YP-80F, showed a higher quinone utilization and improved cycling stability. This work can guide the design of functionalized carbon electrodes for electrochemical carbon dioxide capture.

Microstructure analysis of cement-biochar composites

The use of biochar as a concrete constituent has been proposed to reduce the massive carbon footprint of concrete. Due to the low density and complex porosity of biochar, microstructural analysis of Portland cement-biochar composites is challenging. This causes challenges to the improvement of the micro-scale understanding of biochar composite behavior. This work advances the microstructural understanding of Portland cement composites with 0, 5, and 25 volume percent (vol%) of cement replaced with wood biochar by applying common characterization techniques of mercury intrusion porosimetry (MIP), gas sorption, scanning electron microscopy, and isothermal heat flow calorimetry (HFC) in conjunction with 1H nuclear magnetic resonance (NMR) and micro-X-ray computed tomography (XCT) analysis techniques. The combination of these techniques allows a multi-scale investigation of the effect of biochar on the microstructure of cement paste. NMR and XCT techniques allow the observation and quantification of the pore space. HFC and MIP confirmed that biochar absorbs moisture and reduces the effective water-cement ratio. Gas sorption, MIP, and NMR shows that 5 vol% replacement does not significantly affect the gel and capillary pore structures. Results from XCT (supported by MIP and NMR) show that biochar can reduce the formation of larger pores. Importantly, XCT results suggest that biochar can act as a flaw in the microstructure which could explain reductions in the mechanical properties. Overall, the mechanical properties already analyzed in the literature are consistent with the microstructural changes observed, and these results highlight the need to carefully tailor the volume fraction of biochar to control its effect on the paste microstructure.

Comparison of Gravimetric Determination of Methane Sorption Capacities of Coals for Using Their Results in Assessing Outbursts in Mines

The gravimetric method for determining coal gas sorption has many advantages and limitations. The article presents the influence of various factors on the results of methane sorption on coal. In mining practice, in addition to sorption properties of coal, knowledge of methane sorption capacity and effective diffusion coefficient determined when assuming a unipore sorption/desorption model are crucial for predicting sudden releases of methane from coal seams to a mine ventilation environment. In Poland, determining sorption capacities of coals for methane is mandatory when starting mining operations in new parts of coal deposits threatened by outbursts. Traditionally, gravimetric microbalances, such as intelligent gravimetric analysis (IGA), are used to determine adsorption capacity and desorption rate. Recently, newer microbalances XEMIS have been introduced to the market. Two gas laboratories, AGH in Krakow and CLP-B in Jastrzebie-Zdroj, respectively, compared experimental adsorption isotherms using XEMIS microbalances with mutually exchanged coal samples. Both sorption capacity at the pressure of 1 bar (a1bar) and effective diffusion coefficient (De) were independently determined for the coal samples tested. The results obtained are comparable despite the use of different microbalance XEMIS models. The conducted studies and comparative evaluation of the results allowed for assessing procedures for determining sorption properties using XEMIS microbalances. The exchange of laboratory experiences also allowed for the identification of methodology factors crucial for the development of a uniform procedure for conducting similar studies with XEMIS microbalance. The proposed factors for testing the sorption behavior of methane in coal structures may be helpful in mining practice.

Tuning (Photo)Electronic Properties of an Electron Deficient Porous Polymer via n-Doping with Tetrathiafulvalene.

Charge-transfer complex formation within the pores of porous polymers is an efficient way to tune their electronical properties. Introduction of electron accepting guests to the electron donating hosts to conduct their p-doping is intensively studied in this context. However, the vice versa scenario, n-doping by treating the electron deficient (i.e., n-type) porous polymers with electron donating dopants, is rare. In this work, synthesis of an n-type phenazine based conjugated microporous polymer and its exposure to strong electron donating tetrathiafulvalene (TTF) dopants are presented. The fundamental physical characterizations (e.g., elemental analysis, gas sorption) showed that the vacuum impregnation technique is a good approach to load the guest molecules inside the pores. Moreover, the formation of charge-transfer complexes between the phenazine building blocks of the polymeric network and TTF dopants are confirmed via spectral techniques such Fourier transform infra-red, UV-vis, steady-state/time-resolved photoluminescence, and transient absorbance spectroscopies. Effect of the doping to the electronical properties is monitored by employing photoelectrochemical measurements, which showed lower charge-transfer resistivity and nearly doubled photocurrents after the doping. The study is, therefore, an important advancement for the applicability of (n-type) porous polymeric materials in the field of photo(electro)catalysis and organic electronics.

Competitive sorption of CH₄ and CO₂ on coals: Implications for carbon geo-storage

Geological carbon storage, particularly within coal seams, is recognized as a viable strategy for achieving net-zero emissions. However, following CO₂ injection into the coal seam, limited studies have addressed the competitive sorption dynamics of CH₄ and CO₂ on coal, despite the natural presence of CH₄ in these formations. In this work, sorption experiments were conducted using two types of coal: sub-bituminous coal and anthracite. Initially, pure CH4 and CO2 gases were employed to conduct individual sorption tests. Subsequently, the competitive sorption of CH4 and CO2 was evaluated using pre-mixed binary gas mixtures with varying CH4/CO2 ratios. Further, the displacement effect of CO2 on CH4 was investigated by injecting CO2 into coal samples that had been pre-adsorbed with CH4. The data reveal that, for both coals, the ideal selectivity calculated from pure gas measurements underestimates the corresponding values from real multicomponent systems. Anthracite demonstrates a higher selectivity for CO₂ over CH₄ during both adsorption and desorption processes when compared to the ideal selectivity calculated from pure gas sorption data. Conversely, the sub-bituminous coal initially shows lower selectivity for CO₂ than for CH₄ during adsorption, but this trend reverses and intensifies during desorption. If competitive sorption effects are neglected, coal selectivity for CO₂ over CH₄ under the examined conditions would be underestimated by a factor of 1.5 to 2.5. Due to the competitive sorption effects between CH₄ and CO₂, the Langmuir equilibrium constants for gas mixtures are influenced by compositional changes, leading to dynamic deviations from those observed under pure gas conditions. This finding contrasts with the traditional extended Langmuir model, which presumes that the equilibrium constants remain unchanged regardless of gas composition. In addition, the displacement study underscores the efficacy of CO2 in displacing CH4, with higher CO2 ratios intensifying displacement effects. The study highlights the substantial impact of real multicomponent scenarios on coal selectivity for CO₂ and CH₄, offering deeper insights into predicting competitive sorption behavior between CO₂ and CH₄ during CO₂-enhanced coalbed methane recovery and carbon storage processes.

Insights on influence of polymer molecular weight on gas sorption, transport and plasticization in glassy 6FDA-DAM polyimide membranes

It is well-known that spinning of defect-free asymmetric polyimide hollow fibers is promoted by using high polymer molecular weight. On the other hand, effects of polymer molecular weight on microstructure and separation performance of dense film 6FDA-based polyimide membranes relevant to sheath layers of composite membranes are less well-explored. In this work, gas sorption, diffusion and permeation of CO2, N2 and CH4 for 6FDA-DAM dense films are considered for 45 kDa and 176 kDa weight average molecular weights. Such molecular weights are relevant for practical hollow fiber spinning of membranes. Earlier results for polystyrene samples show similar trends in dual mode sorption model results like those noted here for the 6FDA-DAM polyimide case; however, effects on permeation like those considered here were not addressed for the polystyrene case. Here we also address actual pure and mixed gas CO2 and CH4 permeation and show higher free volumes, higher gas permeability but lower 50:50 CO2/CH4 selectivity associated with the higher molecular weight sample. Analysis using the self-consistent dual-mode sorption and transport models help understand the observed trends. Our results suggest denser packing of polymer segments exists in the Henry's law environment of the low molecular weight sample. Moreover, the higher polymer segmental packing in the Henry's law environment suppresses CO2 plasticization with a dual-mode microstructure controlling separation performance and plasticization behavior for this important member of the 6FDA polyimide family. We show evidence of effects of charge transfer complexes as possible main features in these trends. These dense film results help guide future work on dense sheath layers on composite hollow fiber membranes.

Construction of Coordination Spaces with Narrow Pore Windows in Co-Based Metal-Organic Frameworks toward CO2/N2 Separation.

Carbon emission reduction is an important measure to mitigate the greenhouse effect, which has become a hotspot in global climate change research. To contribute to this, here, we fabricated two Co-based metal-organic frameworks (Co-MOFs), namely, {[Co3(NTB)2(bib)]·(DMA)2·(H2O)4}n (DZU-211) and {[Co3(NTB)2(bmip)]·(DMA)2}n (DZU-212) (H3NTB = 4,4',4″-nitrilotribenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane, bmip = 1,3-bis(2-methyl-1H-imidazol-1-yl)propane) to realize efficient CO2/N2 separation by dividing coordination spaces into suitable pores with narrow windows. DZU-211 reveals a 3D open porous framework, while DZU-212 exhibits a 3D double-fold interpenetrated structure. The two MOFs both possess large coordination spaces and small open pore sizes, via the bib ligand insertion and framework interpenetration, respectively. Comparatively, DZU-211 reveals superior selective CO2 uptake properties due to its more suitable pore characteristics. Gas sorption experiments show that DZU-211 has a CO2 uptake of 52.6 cm3 g-1 with a high simulated CO2/N2 selectivity of 101.7 (298 K, 1 atm) and a moderate initial adsorption heat of 38.1 kJ mol-1. Moreover, dynamic breakthrough experiments confirm the potential application of DZU-211 as a CO2 separation material from postcombustion flue gases.