Apparent Pore Size Research Articles

Cadmium oxide nanoparticles doped with nickel and silver: Photocatalytic activity for environmental remediation

In this work, we used a co-precipitation approach to create CdO nanoparticles that were co-doped with nickel (Ni) and silver (Ag). X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) were employed to assess the structural attributes of the nanoparticles that were synthesized. Co-doping with Ni and Ag resulted in a steady rise in nanoparticle crystallite size, increasing from 20.97 nm to 32.16 nm. Following the co-doping procedure, FESEM pictures demonstrated a morphological shift from tiny, rock-like formations in pure CdO to bigger rock-like structures. Energy-dispersive X-ray spectroscopy (EDX) was utilised to explore the compositional characteristics of Ni and Ag-doped CdO nanoparticles. The existence of particles’ agglomerations was observed, which may have limited the real surface area available for gas adsorption and resulted in smaller apparent pore sizes in the Brunauer-Emmett-Teller (BET) investigation. Diffused Reflectance Spectroscopy (DRS) revealed a decline in the band gap from 2.45eV to 2.30eV, which was most likely caused by structural changes caused by cadmium ion replacement or the occupancy of interstitial spaces within the lattice by nickel and silver ions. The chemical and electronic states of the atoms were assessed using X-ray photoelectron spectroscopy (XPS), which examined the formation of defects in the form of oxygen vacancies, which contributed to accelerated photocatalytic performance. The deterioration of Crystal Violet (CV) dye during sunlight exposure utilising co-doped CdO nanoparticles vs pristine CdO is being evaluated in the evaluation of photocatalytic activity. Notably, co-doped nanoparticles improved photocatalytic activity significantly, with CV degradation reaching up to 95 % within 180 min of exposure. The potential of Ni and Ag impregnated CdO nanoparticles as effective photocatalysts for environmental remediation applications is highlighted in this study.

Improved water vapor corrosion resistance of SiC bricks via in situ formation of microporous Yb2Si2O7 bonding phase

AbstractSiC‐based lining refractories used in incinerators faced serious hot water vapor corrosion. The pores in SiC‐based refractories played a crucial role in corrosion resistance because both the penetration of water vapor and the expulsion of corrosion products depended on diffusion channels provided by pores. The in situ microporous Yb2Si2O7 bonding phase formed in the SiC bricks after sintering at 1550°C under air atmosphere, which simultaneously decreased the apparent porosity and pore size. The optimization of pore structures reduced the permeability to gases of SiC bricks by 37.5%, which prevented the penetration of hot water vapor into SiC bricks. The microporous Yb2Si2O7‐bonded SiC bricks presented only .15% permanent linear change and showed good thermal shock resistance after corrosion at 1000°C for 100 h under hot water vapor atmosphere. Some SiC particles in the refractories could be adopted as high‐temperature pore‐forming agents; the gaseous oxidation products of SiC bricks, including SiO(g) and CO(g), contributed to the generation of microporous Yb2Si2O7 (pore size ≤5 μm) and SiC whiskers during sintering, which obviously improved mechanical properties and water vapor corrosion resistance of SiC bricks.

An NMR-Based Procedure for Evaluating the Apparent Surface Relaxivity and Pore Size Distribution of Soils

An NMR-Based Procedure for Evaluating the Apparent Surface Relaxivity and Pore Size Distribution of Soils

Effect of structural characteristics on functional properties of textured vegetable proteins

Meat analogues are predominantly composed of a pre-structured form of protein called textured vegetable protein (TVP) that is designed to mimic the fibrous structure of animal muscle meat. Limited information is available regarding the link between structural characteristics of TVPs and their functional properties. This study investigated the relationships between the structural characteristics of commercial TVPs and (a) their rehydration behaviour, as well as (b) the mechanical properties and serum release (cooking loss and expressible liquid) of patties prepared from these TVPs. The micro- and macrostructural features of thirteen commercial TVPs were quantified using X-ray microtomography. Apparent density (205–1042 kg m−3), porosity (27.1–80.9%), pore size (251–4790 μm), wall thickness (108–657 μm), and wall density (597–1515 kg m−3) varied largely across samples. In the early stages of water absorption, thicker walls promoted the absorption of larger volumes of water. In contrast, the maximum water absorption capacity as well as water holding capacity were higher for TVPs with thinner walls and higher porosity, highlighting the impact of structural features of TVPs on water absorption during rehydration. Significant positive correlations between cooking loss and expressible liquid indicated that patties with higher serum release during cooking also tended to release more during compression. TVPs with thicker walls resulted in stiffer patty batters, and TVPs with smaller pores resulted in stiffer grilled patties. We conclude that the structural characteristics of TVPs influence their rehydration behaviour and various functional properties of patties made with them.

An Apparent Permeability Model in Organic Shales: Coupling Multiple Flow Mechanisms and Factors.

It is of great significance to study shale apparent permeability under the action of multiple flow mechanisms and factors because shale reservoirs possess complex pore structures and flow mechanisms. In this study, the confinement effect was considered, with the thermodynamic properties of gas being modified, and the law relating to the conservation of energy adopted to characterize bulk gas transport velocity. On this basis, the dynamic change of pore size was assessed, from which shale apparent permeability model was derived. The new model was verified by three steps: experimental and molecular simulation results of rarefied gas transport, shale laboratory data, and comparison with different models. The results revealed that, under the conditions of low pressure and small pore size, the microscale effects became obvious, which significantly improved gas permeability. Through comparisons, the effects of surface diffusion and matrix shrinkage, including the real gas effect, were obvious in the smaller pore sizes; nevertheless, the stress sensitivity effect was stronger in larger pore sizes. In addition, shale apparent permeability and pore size decreased with an increase in permeability material constant and increased with increasing porosity material constant, including internal swelling coefficient. The permeability material constant had the greatest effect on gas transport behavior in nanopores, followed by the porosity material constant; however, the internal swelling coefficient had the least effect. The results of this paper will be important for the prediction and numerical simulation of apparent permeability relating to shale reservoirs.

Determination of Apparent Pore Size Distributions of Organic Matter and Inorganic Matter in Shale Rocks Based on Water and N2 Adsorption

Determination of Apparent Pore Size Distributions of Organic Matter and Inorganic Matter in Shale Rocks Based on Water and N₂ Adsorption

Customized biochar for soil applications in arid land: Effect of feedstock type and pyrolysis temperature on soil microbial enumeration and respiration

Biochar is rapidly gaining worldwide interest as an agro-technology for increasing soil health and carbon storage. This study investigated the physicochemical characteristics and impact on soil microbes of biochar amendments from three feedstock sources: date palm leaves (D), mesquite plants (M) and sludge compost (S.C.); pyrolyzed at 450 ℃, 600 ℃ and 750 ℃. Scanning electron microscopy images showed an apparent pore size increase with increasing pyrolysis temperature. The increase in pyrolysis temperature decreased O-H and C-O bonds and increased the proportion of C-C bonds, as obtained from the Fourier transform infrared spectroscopy studies. Thermostability was highest at a pyrolysis temperature of 750 ℃, with distinct thermal decomposition profiles for each of the three feedstock materials used, as indicated by the dynamic thermal gravimetric analysis. The SC biochars showed the highest mineral content (45–66%) with significantly higher water-soluble and total concentrations of mineral elements. The SC samples also showed the presence of possible soil contaminants such as Pb and As, and its use as a soil amendment is not recommended, even though the SC at 450 ℃ was the only nonalkaline biochar in this study. The M feedstock produced biochar with the highest surface area (600 m2 g−1) and carbon content based on loss on ignition (94.98%); nevertheless, the M biochar reduced soil microbial enumeration and respiration. This reduction increased with increasing pyrolysis temperature. Therefore, the M biochar feedstocks are not recommended for improving soil health and may be tested in the future as a microbial inhibitor for soil-borne plant pathogens. Considering the physicochemical properties and the biochar impact on soil, D at 600 ℃ was the best biochar selected for further studies as a soil amendment. The large differences in biochar physicochemical properties and their effect on soil microbes observed in this study suggest that the feedstock type and pyrolysis temperatures must be considered during biochar amendment production for improving soil health in arid-land agroecosystems.

Effect of pH variation and annealing on covalently assembled nanodiamond films

This work examines the effect of using low-ionic strength zwitterionic buffer and post-deposition thermal annealing on the microstructure and thermal conductivity of continuous nanocrystalline diamond films that are deposited via the directed covalent assembly of detonation nanodiamonds. Variation of the zwitterionic buffer pH was found to tune the surface coverage, film thickness, thermal conductivity, and film morphology as quantified by apparent porosity and pore size distribution. The sequential annealing of these films up to 400 °C, showed the anticipated severance of amide bonds holding the nanodiamonds together, followed by the detrimental aggregation of the nanodiamonds to segregated islands, losing film continuity and increasing apparent porosity. The change in thermal conductivity with annealing was subjective to buffer pH, suggesting that the morphology changes associated with annealing may have a complex relationship with thermal conductivity. The thermal conductivity data were further analyzed using a phonon hopping model to quantify the degree of phonon movement across boundaries. Overall, the results demonstrate a way to achieving porous, low-cost nanocrystalline diamond thin films with tunable film morphology and thermal conductivity.

Custom-tailoring tight nanocomposite membranes for advanced reclamation of hairwork dyeing effluent

A novel combination of custom-tailoring tight nanocomposite membrane process with dual-stage pretreatment incorporating flocculation and ultrafiltration has been experimentally conceived for the advanced reclamation of seriously contaminated hairwork dyeing effluent (HDE). The hybrid system exhibited impressive advantages of qualified recycle rate of HDE (91.2%) and minimal environmental impact when taking both bearable membrane fouling and appropriate long-term separation performance into consideration. It was observed that after partial alternative doping of M-tolidine-H and continuous incorporating of carbon quantum dots, both skin features (smoothness, hydrophilicity and charge) and nanoporous loose body (porosity and apparent pore size) of the resultant membranes were improved synergistically. As a consequence, the optimal TFN-CQDs membrane showed high water permeance of 4.31 L m−2 h−1 bar−1, rejection for small-sized organics (≥97.3%) and salt (≥96.4%) and good antifouling ability (86.2% of flux recovery ratio) operated for 72 h, which were superior than those of most other reported permeate membranes. Besides, the economical and feasible pretreatment steps including less dosage (only 100 mg L−1) of biodegradable CLF-10 flocculant and cheap UF module made the optimized reuse process more attractive. Overall, this study has taken a concrete step forward on the road of realizing zero liquid discharge and advanced reclamation of HDE.

Effect of a plasma synthesized polypyrrole coverage on polylactic acid/hydroxyapatite scaffolds for bone tissue engineering.

Composite biomaterials are solids that contain two or more different materials, combining the properties of their components to restore or improve the function of tissues. In this study, we report the generation of electrospun matrices with osteoconductive properties and porosity using the combination of a biodegradable polyester, polylactic acid (PLA), and hydroxyapatite (HA). Additionally, we report the effects of modifying these matrices through plasma polymerization of pyrrole on the growth and osteogenic differentiation of rabbit bone marrow stem cells. Cells were isolated, seeded and cultured on biomaterials for periods between 7 and 28 days. The matrices we obtained were formed by nano and microfibers containing up to 35.7wt% HA, presenting a variety of apparent pore sizes to allow for the passage of nutrients to bone cells. Scanning electron microscopy showed that the fibers were coated with polypyrrole doped with iodine, and MTT assay demonstrated this increased cell proliferation and significantly improved cell viability due to the adhesive properties of the polymer. Our results show that PLA/HA/Pyrrole/Iodine matrices are favorable for bone tissue engineering.

Microstructure and properties evolution of silicon-based ceramic cores fabricated by 3D printing with stair-stepping effect control

A ceramic core is the key component in the manufacture of the hollow turbine blades of aeroengines. Compared with the traditional injection molding method, 3D printing is more suitable for manufacturing ceramic cores with a complex geometry at high precision. However, the stair-stepping effect is inevitable in the 3D printing process and affects the surface roughness and strength of the ceramic core. In this study, to explore the influence of nano-silica content on the microstructure and properties of the ceramic core, silicon-based ceramic cores were fabricated with the addition of nano-silica powder by digital light processing and subsequent sintering at 1200 °C. The results showed that the apparent porosity and pore size of the ceramic core gradually decreased as both the nano-silica powder content and bulk density increased. Meanwhile, the printing interlayer spacing was significantly reduced, resulting in a low surface roughness, high flexural strength, and creep-resistance. To simulate the entire casting process of a superalloy blade, the thermal deformation behavior of the ceramic core was observed by heating and cooling cycles performed in a thermal dilatometer at 1540 °C. The total linear shrinkage decreased as the nano-silica powder content increased, which was mainly due to the phase transformation of cristobalite and the densification of the ceramic core sintered at 1200 °C. The low surface roughness and linear shrinkage as well as high flexural strength of the ceramic core can contribute to the excellent quality of cast superalloy blades.

Calcium Aluminate Cement Blends Containing Bioactive Glass and Strontium for Biomaterial Applications

In this work blends based on calcium aluminate cement (CAC) containing bioactive glass (BG) (5, 7.5 and 10 wt%) and strontium oxide (1 wt%) were produced aiming improve their bioactivity and the capacity to stimulate the bone regeneration. In the first part, the blends containing only BG were characterized as theoretical density, microhardness, uniaxial cold crush strength after SBF and apparent porosity and pore size distribution before and after SBF treatment. In the second part, bioactivity and cell culture tests were also conducted in the blends containing BG and strontium oxide. The addition of 7.5 wt% of BG in homogeneous calcium aluminate cement (CH) improved its mechanical properties as microhardness and uniaxial cold crushing strength. The blends were more bioactive due to the presence of a highly soluble amorphous phase as confirmed by means of SEM/EDX mainly for 7.5 wt% BG without and with Sr from 1 day in SBF. FTIR analyses indicated the formation the apatite-like phase by means of increase of intensity of the PO43- peaks after SBF treatment. All blends allowed the development of the osteoblastic phenotype and the formation of mineralized matrix increased due to the inclusion of BG and Sr promoting the osteogenesis process.

Acid-Induced Gelation of Enzymatically and Nonenzymatically Cross-Linked Caseins-Texture Properties, and Microstructural Insights.

Casein gels consist of a fractal organized network of aggregated casein particles. The gel texture thereby depends on the structure, the spatial distribution, and the interaction forces of the network's elementary building blocks. The aim of this study was to explore the technofunctional consequences of a possible specificity of Maillard reaction-induced cross-linking reactions on casein with respect to texture and microstructure of acid gels. Therefore, sodium caseinate glycated with lactose in the dry state (60 °C, aw 0.5) was compared with casein samples cross-linked with methylglyoxal, with glutaraldehyde, or via microbial transglutaminase, respectively, at similar levels of protein cross-linking as confirmed by size-exclusion chromatography under denaturing conditions. Casein gels prepared by acidification with glucono-δ-lactone were characterized concerning pH kinetics during gelation, mechanical texture properties under large deformation, and water-holding capacity, while viscometric properties of casein suspensions were obtained prior to gelation. The gel microstructure was captured by confocal laser scanning microscopy and evaluated by means of image texture analysis. All protein cross-linking reactions studied led to an enhanced gel strength which was accompanied by an increased interconnectivity of the gel network and a decrease in apparent pore sizes. Gels with more densely packed strands, as was the case for enzymatically modified casein, exhibited pronounced mechanical stability. The spontaneous destabilization of the gel network upon prolonged glycation reactions, which was not obviously displayed by microstructural features but connected to an increased viscosity and pronounced pseudoplastic flow of the unacidified suspension, suggests a limitation of particle rearrangements and the weakening of interparticle protein-protein interactions by additional structure attributes formed during the early Maillard reaction (glycoconjugation).

The Impact of the Amount of Water Used in Activation Solution and the Initial Temperature of Paste on the Rheological Behaviour and Structural Evolution of Metakaolin-Based Geopolymer Pastes

This study aimed to determine the impact of the initial temperature of the paste (from 5 °C to 35 °C) and the addition of water, which reflects a decrease in the molarity of activation solutions (AS) by diluting 10 M NaOH with distillate water, on the rheological properties of geopolymer pastes. Additionally, this resulted in changes to the physical–mechanical properties of geopolymers after curing. A higher amount of water in the AS composition and higher initial paste temperature led to an increase in the spread values up to 28% and decreases viscosity. A smaller amount of water in the AS composition and a higher initial paste temperature accelerated the speed of the geopolymer structure formation up to 1.5 times during the curing period, increased compressive strength and reduced apparent porosity and pore size. X-ray diffraction confirmed the compressive strength test results and revealed that the lower amount of water in the AS and the higher initial paste temperature for the geopolymer preparation significantly affected the mineral formation and physical and mechanical properties of the samples.

Relating nanofiltration membrane morphology to observed rejection of saccharides

Nanofiltration for the fractionation of uncharged solutes has become more interesting in recent times, due to the goal of valorizing side-streams and by-products of the food industry. Since the membranes suitable for this purpose are mainly utilized for demineralization processes, the specifications given by the manufacturer are insufficient for the prediction of the rejection of uncharged solutes. Nine membranes with a molecular weight cut-off between 150 and 1000 Da were investigated showing differences in their rejection of fructose at a transmembrane pressure difference ΔpTM of 1.0 MPa. These values were correlated with the root-mean-square roughness Sq and apparent pore size dap determined by atomic force microscopy, while the determined contact angle Θ did not influence the rejection. Thereby, a correlation between membrane morphology and rejection behavior was established.

Predicting intraparticle diffusivity as function of stationary phase characteristics in preparative chromatography

Diffusion inside pores is the rate limiting step in many preparative chromatographic separations and a key parameter for process design in weak interaction aqueous chromatographic separations employed in food and bio processing. This work aims at relating diffusion inside porous networks to properties of stationary phase and of diffusing molecules. Intraparticle diffusivities were determined for eight small molecules in nine different stationary phases made from three different backbone materials. Measured intraparticle diffusivities were compared to the predictive capability of the correlation by Mackie and Meares and the parallel pore model. All stationary phases were analyzed for their porosity, apparent pore size distribution and tortuosity, which are input parameters for the models. The parallel pore model provides understanding of the occurring phenomena, but the input parameters were difficult to determine experimentally. The model predictions of intraparticle diffusion were of limited accuracy. We show that prediction can be improved when combining the model of Mackie and Meares with the fraction of accessible pore volume. The accessible pore volume fraction can be determined from inverse size exclusion chromatographic measurements. Future work should further challenge the improved model, specifically widening the applicability to greater accessible pore fractions (> 0.7) with corresponding higher intraparticle diffusivities (Dp/Dm > 0.2). A database of intraparticle diffusion and stationary phase pore property measurements is supplied, to contribute to general understanding of the relationship between intraparticle diffusion and pore properties.

The improvement in properties and environmental safety of fired clay bricks containing hazardous waste electroplating sludge: The role of Na2SiO3

The introduction of electroplating sludge in the manufacturing of clay brick can be considered a feasible method to consume it, while physical-mechanical performances would degrade significantly and the potential leachability of heavy metals remain. This study proposed an alternative to remedy these negative impacts by adding Na2SiO3. The addition of Na2SiO3 decreased water absorption and promoted compressive strength substantially. Water absorption of bricks fired at 1050 °C for 3 h decreased from 6.05 to 0.56% and compressive strength increased dramatically from 22 to 46 MPa with the adding amount of Na2SiO3 raising from 0 to 20 wt%. The porosity analysis demonstrated the apparent porosity, surface area, pore volume, and pore size decreased significantly, especially at 1050 °C. The mineralogical phase analysis showed the Na2SiO3 reacted with quartz and formed albite, and the albite played an important role in decreasing porosity and enhancing mechanical property. Additionally, Na2SiO3 decreased the leachability of heavy metals, it was mainly due to the decrease in water absorption, surface area, pore volume, and pore size. Prolonging the firing time can also decrease water absorption and enhance compressive strength in the presence of Na2SiO3. These results proved that the addition of Na2SiO3 is a feasible strategy for enhancing the properties and environmentally safe of fired bricks when solid waste was introduced to produce bricks or ceramics.

Permeability anisotropy and relative permeability in sediments from the National Gas Hydrate Program Expedition 02, offshore India

Gas and water permeability through hydrate-bearing sediments essentially governs the economic feasibility of gas production from gas hydrate deposits. Characterizing a reservoir's permeability can be difficult because even collocated permeability measurements can vary by 4–5 orders of magnitude, due partly to differences between how various testing methods inherently measure permeability in different directions and at different scales. This study uses a customized flow anisotropy cell to investigate geomechanical and hydrological properties of hydrate-bearing sediments focusing on permeability anisotropy (i.e., horizontal, kh, to vertical, kv, permeability ratio) and relative permeability. Two cores recovered during India's National Gas Hydrate Program Expedition 02 (NGHP-02) are tested in this study. Near in situ effective vertical stress, ∼ 2 MPa, the permeability anisotropy is approximately kh/kv = 1.86 for the “seal core” (from a fine-grained non-reservoir overburden sedimentary section) and kh/kv = 4.24 for the gas hydrate reservoir core with tetrahydrofuran (THF) hydrate saturation Sh = 0.8. Permeability anisotropy increases exponentially with effective vertical stress, as described by kh/kv = α(σv/MPa)β, with α = 1.6, β = 0.22 for seal sediment and α = 3, β = 0.5 for THF hydrate-bearing sediment. Results imply the measured permeability from permeameter tests with vertical flow may underestimate the reservoir's flow performance, which is mainly horizontal (radial) toward a vertical well. Hydrate in sediment increases the gas-entry pressure and residual water saturation, but decreases the water retention curve's shape factor (m), resulting in a steeper curve. Distributions of available pore space sizes for flow in sediment with and without THF hydrate (Sh = 0.8) follow a log-normal distribution. Hydrate formation decreases the apparent mean pore size from ∼10 μm to ∼2 μm, without evidently changing the pore size distribution's standard deviation. Gas hydrate dissociation increases effective permeability and relative permeability to gas.

Characterization of modified zeolite as microbial immobilization media on POME anaerobic digestion

As the world’s biggest palm oil producer, Indonesia generates also huge amount of Palm Oil Mill Effluent (POME) wastewater and causes serious problem in environment. In conventional method, POME was converted into biogas using lagoon system which required extensive land area. Anaerobic Fluidized Bed Reactor (AFBR) proposes more effective biogas producing with smaller land area. In the proposed system, a immobilization media would be main factor for enhancing productivity. This research studied on characterization of Lampung natural zeolite as immobilization media in the AFBR system for POME treatment. Various activation method such as physical and chemical were attempted to create more suitable material which has larger surface area, pore size distribution as well as excellent surface structures. The physical method was applied by heating up the material till 400°C while HCl was used on the chemical activation. Based on the result, the chemical activation increased the surface area significantly into 71 m2/g compared to physical as well as original zeolite. The strong acid material was quite effective to enforce the impurities within zeolite pore structure compared to heating up the material. According to distribution data, the Lampung zeolite owned the pore size with the range of 3 – 5 μm which was mesopore material. The pore size was appropriate for immobilization media as it was smaller than size of biogas microbial. The XRD patterns verified that chemical activation could maintain the zeolite structure as the original. Obviously, the SEM photograph showed apparent structure and pore size on the modified zeolite using chemical method. The testing of modified zeolite on the batch system was done to evaluate the characterization process. The modified zeolite using chemical process resulted fast reduction of COD and stabilized the volatile fatty acid as the intermediate product of anaerobic digestion, especially in the beginning of the process. Therefore, the chemical activation process was most suitable to produce the immobilization media from Lampung natural zeolite for POME waste treatment

Water adsorption and its impact on the pore structure characteristics of shale clay

Abstract Water is considered ubiquitous within the shale reservoirs and mainly stored in the hydrophilic clay minerals. The water distribution characteristics and its effect on pore structure are important for the gas-in-place of shale systems. In this work, water vapor adsorption on montmorillonite (Mt), kaolinite (Kaol) and illite (Il) were performed to investigate the behaviors of water adsorption on shale clay. Subsequently, the moisture-equilibrated samples were conducted with N2 gas-adsorption techniques to investigate the effect of adsorbed water on pore structure characteristics, such as apparent pore size distribution (APSD), N2 BET specific surface area (N2-BET SSA) and pore volume (PV). The results show that the water uptake isotherms of our samples have the sigmoidal-shaped profiles and GAB model provides a good fit for the adsorption behavior. In addition, The APSD curves under different relative humidity (RH) conditions have validated the condensation effect and indicated that the small pores (approximately smaller than 5 nm) are blocked by the capillary water and will disappear on the APSD curves at RH of 98% while the large nanopores (> 5 nm) are covered with water film, these effects will lead dramatically decrease of N2-BET SSA. Taking Mt and Il samples as the examples, the N2-BET SSA has declined to 33.51% and 33.66% compared with the dry conditions when Sw approaches to 50%. Meanwhile, these effects also indicate that the gas storage for clay minerals is massively overestimating under dry condition, the contribution to methane adsorption might be negligible in the actual shale reservoir.