Search Results (22)

The development of deep coalbed methane (buried depth > 2000 m) in the Yan’an block of Ordos Basin is limited by low permeability, the pore structure of the coal reservoir, and the gas–water occurrence relationship. It is urgent to clarify the key control mechanism of pore structure on gas migration. In this study, based on high-pressure mercury intrusion (pore size > 50 nm), low-temperature N₂/CO₂ adsorption (0.38–50 nm), low-field nuclear magnetic resonance technology, fractal theory and Pearson correlation coefficient analysis, quantitative characterization of multi-scale pore–fluid system was carried out. The results show that the multi-scale pore network in the study area jointly regulates the occurrence and migration process of deep coalbed methane in Yan’an through the ternary hierarchical gas control mechanism of ‘micropore adsorption dominant, mesopore diffusion connection and macroporous seepage bottleneck’. The fractal dimensions of micropores and seepage are between 2.17–2.29 and 2.46–2.58, respectively. The shape of micropores is relatively regular, the complexity of micropore structure is low, and the confined space is mainly slit-like or ink bottle-like. The pore-throat network structure is relatively homogeneous, the difference in pore throat size is reduced, and the seepage pore shape is simple. The bimodal structure of low-field nuclear magnetic resonance shows that the bound fluid is related to the development of micropores, and the fluid mobility mainly depends on the seepage pores. Pearson’s correlation coefficient showed that the specific surface area of micropores was strongly positively correlated with methane adsorption capacity, and the nanoscale pore-size dominated gas occurrence through van der Waals force physical adsorption. The specific surface area of mesopores is significantly positively correlated with the tortuosity. The roughness and branch structure of the inner surface of the channel lead to the extension of the migration path and the inhibition of methane diffusion efficiency. Seepage porosity is linearly correlated with gas permeability, and the scale of connected seepage pores dominates the seepage capacity of reservoirs. This study reveals the pore structure and ternary grading synergistic gas control mechanism of deep coal reservoirs in the Yan’an Block, which provides a theoretical basis for the development of deep coalbed methane. Full article

Highly over-mature marine shales are distributed worldwide with substantial resource potential, yet their pore structure characteristics and controlling mechanisms remain poorly understood, hindering accurate shale gas resource prediction and efficient development. This study focuses on the Cambrian Niutitang Formation shales in the Upper Yangtze region of South China. To decipher the multiscale pore network architecture and its genetic constraints, we employ scanning electron microscopy (SEM) pore extraction and fluid intrusion methods (CO₂ and N₂ adsorption, and high-pressure mercury intrusion porosimetry) to systematically characterize pore structures in these reservoirs. The results demonstrate that the shales exhibit high TOC contents (average 4.78%) and high thermal maturity (average Ro 3.64%). Three dominant pore types were identified: organic pores, intragranular pores, and intergranular pores. Organic pores are sparsely developed with diameters predominantly below 50 nm, displaying honeycomb, slit-like, or linear morphologies. Intragranular pores are primarily feldspar dissolution voids, while intergranular pores exhibit triangular or polygonal shapes with larger particle sizes. CO₂ adsorption isotherms (Type I) and low-temperature N₂ adsorption curves (H3-H4 hysteresis) indicate wedge-shaped and slit-like pores, with pore size distributions concentrated in the 0.5–50 nm range, showing strong heterogeneity. Pore structure shows weak correlations with TOC and quartz content but a strong correlation with feldspar abundance. This pattern arises from hydrocarbon generation exhaustion and graphitization-enhanced organic pore collapse under high compaction stress, which reduces pore preservation capacity. The aulacogen tectonic setting engenders proximal sediment provenance regimes that preferentially preserve labile minerals such as feldspars. This geological configuration establishes optimal diagenetic conditions for the subsequent development of meso- and macro-scale of dissolution pores. Our findings demonstrate that feldspar-rich shales, formed in a proximal depositional system with well-developed inorganic pores, serve as favorable reservoirs for the exploration of highly over-mature marine shale gas. Full article

This study explores the impact of scandium (Sc) as a promoter on the catalytic performance of 4Ni/MCM-41 catalysts for the partial oxidation of methane (POM). 4Ni+Sc/MCM-41 catalysts were synthesized with varying Sc loadings of 0, 0.2, 0.4, 0.6, and 0.8 wt.%. These catalysts were characterized using several techniques, including N₂ physisorption, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), Raman spectroscopy, thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). All catalysts exhibited a mesoporous structure characterized by narrow slit-shaped pores. Among them, the 4Ni+0.2Sc/MCM-41 catalyst showed the most consistent pore size distribution. The addition of Sc (scandium) facilitated the formation of strongly interacting nickel species, which enhanced the initial catalytic activity. However, a trade-off was observed between initial activity and long-term stability. The optimal Sc loading was determined to be 0.2 wt.%. This catalyst achieved the highest methane conversion rate of 63.9%, a hydrogen yield of 60%, and an H₂/CO ratio of 2.7 while also demonstrating superior stability during extended operation. The 4Ni+0.2Sc/MCM-41 catalyst showed only a 7% weight loss in the thermogravimetric analysis (TGA), which shows that it will stay stable even after being used for a long time. The improved performance of the Sc-promoted catalysts is attributable to the increased availability of active sites, enhanced stability, and better dispersion of nickel. These efforts aim to create more sustainable and efficient methods for hydrogen production, minimizing the negative effects associated with traditional processes. By advancing these technologies, we can further support the transition to a cleaner energy future. Full article

The analysis of the impact of the star polymer topology on depletion interaction potentials, depletion forces, and monomer density profiles is carried out analytically using field theory methods and techniques as well as molecular dynamic simulations. The dimensionless depletion interaction potentials and the dimensionless depletion forces for a dilute solution of ideal star polymers with three and five legs (arms) in a $\mathsf{\Theta }$-solvent confined in a slit between two parallel walls with repulsive surfaces and for the case where one of the surfaces is repulsive and the other inert are obtained. Furthermore, the dimensionless layer monomer density profiles for ideal star polymers with an odd number ($\tilde{f}$ = 3, 5) of arms immersed in a dilute solution of big colloidal particles with different adsorbing or repelling properties in respect of polymers are calculated, bearing in mind the Derjaguin approximation. Molecular dynamic simulations of a dilute solution of star-shaped polymers in a good solvent with N = 901 (3 × 300 + 1 -star polymer with three arms) and 1501 (5 × 300 + 1 -star polymer with five arms) beads accordingly confined in a slit with different boundary conditions are performed, and the results of the monomer density profiles for the above-mentioned cases are obtained. The numerical calculation of the radius of gyration for star polymers with $\tilde{f}$ = 3, 5 arms and the ratio of the perpendicular to parallel components of the radius of gyration with respect to the wall orientation for the above-mentioned cases is performed. The obtained analytical and numerical results for star polymers with an odd number ($\tilde{f}$ = 3, 5) of arms are compared with our previous results for linear polymers in confined geometries. The acquired results show that a dilute solution of star polymer chains can be applied in the production of new functional materials, because the behavior of these solutions is strictly correlated with the topology of polymers and also with the nature and geometry of confined surfaces. The above-mentioned properties can find extensive practical application in materials engineering, as well as in biotechnology and medicine for drug and gene transmission. Full article

The Middle and Upper Permian Dalong and Gufeng Formations in South China have recently been considered as potential gas-producing shales. However, their pore structure characteristics remain poorly understood. To investigate the pore structure and fractal characteristics of the pores in these two formations, a suite of shale samples from the Dalong and Gufeng Formations in the western Hubei Province, South China were analyzed by multiple techniques, namely, TOC content, X-ray diffraction (XRD) mineralogy analysis, optical microscopy observations, major elemental analysis, field emission-scanning electron microscopy (FE-SEM), and low-pressure gas adsorption measurements (N₂ and CO₂). The identified major shale lithofacies include siliceous mudstone, carbonaceous mudstone, argillaceous-siliceous mixed mudstone, and calcareous-siliceous mixed mudstone. SEM images show that the dominant pore types include the pores between brittle minerals, slit-shaped pores between clay sheets, and secondary organic matter (OM) pores within solid bitumen. The pore size distribution is dominated by micropores and mesopores (<30 nm), which are the major contributors to total pore volume and surface area for the Dalong and Gufeng Formations. Based on the Frenkel–Halsey–Hill (FHH) method, fractal dimensions (D₁, D₂) calculated from the nitrogen adsorption data have a range of from 2.489 to 2.772 (D₁) and from 2.658 to 2.963 (D₂), and are higher in the Gufeng Formation (average TOC = 8.3 wt.%) due to a higher TOC content comparing to the Dalong Formation (average TOC = 6.2 wt.%). The pore development and fractal characteristics are primarily controlled by organic matter (OM), carbonate minerals, and clay minerals for both the Dalong and Gufeng Formations. Shale samples with high TOC content, low carbonate content, and high clay content tend to develop more heterogeneous micropores and mesopores, which is ascribed to the generation of clay-related and OM-hosted pores, along with the destruction of primary pores by pore-filling carbonate cements. Full article

The shale reservoirs of the Lower Cambrian Qiongzhusi Formation are widely distributed in the Sichuan Basin and have abundant gas resources. However, the shale lithofacies of the Qiongzhusi Formation are complex due to frequent sea level changes. The reservoir pore structure characteristics and gas content of different shale lithofacies vary significantly, which makes identifying the ‘sweet spot’ a challenging task. In this study, core observation and X-ray diffraction (XRD) were used to analyze the lithofacies types and characteristics of the study area. The pore types of different shale lithofacies were observed using field emission-scanning electron microscopy. Pore structures were studied using low-temperature gas (including N₂ and CO₂) physisorption, and the pore volume (PV), specific surface area (SSA) and pore structure were systematically characterized. The primary factors influencing pore formation in different types of shale lithofacies were analyzed by combining geochemical experiments and mineral contents. The results indicate that the lithofacies of the Qiongzhusi Formation shale in the study area can be classified into five categories according to mineral compositions: Siliceous argillaceous shale (CM-1), Argillaceous siliceous mixed shale (M-2), Argillaceous siliceous shale (S-3), Siliceous rock (S) and Calcareous siliceous shale (S-2). Pores are abundant in S-3 shale, M-2 shale and CM-1 shale. The S-3 shale is more enriched in organic pores and clay mineral pores compared to other lithofacies shales, and the pore morphology is mainly wedge-shaped and plate-like. M-2 shale and CM-1 shale are rich in clay minerals and mainly develop clay mineral pores and are mainly wedge-shaped and plate-like. The S shale and S-2 shale mainly develop interparticle pores and clay mineral pores, which are mainly slit-like. The results show that TOC, pyrite content, quartz and feldspar mineral content, clay mineral type and content affect the pore structure in the study area. Quartz and feldspar content have a negative effect on micropore and mesopore volumes. TOCs have a weak positive correlation with micropore volume and micropore SSA. Clay mineral content has significant positive effects on the PV and SSA of micropores and mesopores, indicating that clay mineral content is the main factor affecting the pore structure of shale. Full article

Organic geochemistry experiments, X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), N₂ adsorption, CO₂ adsorption, and two-dimensional nuclear magnetic resonance (2D NMR) were performed on ten Chang 7 shale samples (Longdong area, Ordos Basin) to elucidate their pore structure and the characteristics of oil occurrence. Moreover, the factors influencing free oil were discussed, and an occurrence model was established. FE-SEM analysis reveals that the pore types include interparticle pores, intraplatelet pores within clay aggregates, rare fracture pores, and organic matter (OM) pores. The pores are predominantly slit-shaped. The development of micropores was mainly contributed to by OM. Quartz and clay minerals influence the development of macropores and mesopores, feldspar mainly controls macropore development, and pyrite most strongly affects micropore development. Micropores and mesopores constitute the main total pore specific surface area, while mesopores and macropores are the main contributors to the total pore volume. Pores > 2 nm are the main storage spaces for shale oil, and free oil mainly occurs in pores > 20 nm. Adsorbed oil and free oil were assessed by NMR T₁–T₂ mapping. The adsorbed oil signal intensities range from 7.5–23.4 a.u. per g of rock, and the free oil signal intensities range from 4.4–23.2 a.u. per g of rock. The free oil proportions are 15.9–70.6% (average of 44.2%). The free oil proportion is negatively correlated with the clay mineral content and total organic carbon (TOC) content but positively correlated with the saturated hydrocarbon content and volume of pores > 20 nm. The results of this study could help optimize favorable shale oil target areas. Full article

Characterizing materials with low surface areas or with very small sample sizes requires innovative approaches beyond traditional N${}_2$ and Ar adsorption measurements. The measurement of Kr adsorption isotherms is often employed to serve this purpose, yet its potential remains limited by the lack of models for the interpretation of the experimental results in terms of pore size distribution. In this work, simulated adsorption isotherms of Kr onto graphite in slit-shaped pores are generated with a Grand Canonical Monte Carlo method. The pore size distributions of nuclear-grade graphite samples and activated carbon are modelled by fitting simulated isotherms to the experimental data. The resulting distributions are favourably compared with those generated by commercially available modelling packages, based on the use of N₂ adsorption isotherms using GCMC and BJH methods. The new GCMC-Kr kernel developed in this study offers an alternative method for the evaluation of the distribution of pore sizes in nuclear graphite and other low surface area materials, which can be employed when N₂ and Ar adsorption measurements cannot be carried out. Full article

A new species of hornshark is described from northwestern Australia based on six whole specimens and a single egg case. Heterodontus marshallae n. sp. was previously considered to be conspecific with H. zebra from the Western Pacific. The new species differs from H. zebra in the sequence of its NADH2 gene, several morphological characters, egg case morphology and key coloration features. Despite the coloration being similar between H. marshallae n. sp. and H. zebra, i.e., pale background with 22 dark brown bands and saddles, they differ consistently in two key aspects. Firstly, the snout of H. marshallae n. sp. has a dark semicircular bar, usually bifurcated for most of its length vs. a pointed, triangular shaped dark marking in H. zebra. Secondly, H. zebra has a dark bar originating below the posterior gill slits and extending onto anterior pectoral fin, which is absent in H. marshallae n. sp. The Heterodontus marshallae n. sp. is endemic to northwestern Australia and occurs in deeper waters (125–229 m) than H. zebra (0–143 m). Full article

One of the main challenges of photocatalysis is to find a stable and effective photocatalyst, that is active and effective under sunlight. Here, we discuss the photocatalytic degradation of phenol as a model pollutant in aqueous solution using NUV-Vis (>366 nm) and UV (254 nm) in the presence of TiO₂-P25 impregnated with different concentrations of Co (0.1%, 0.3%, 0.5%, and 1%). The modification of the surface of the photocatalyst was performed by wet impregnation, and the obtained solids were characterized using X-ray diffraction, XPS, SEM, EDS, TEM, N₂ physisorption, Raman and UV-Vis DRS, which revealed the structural and morphological stability of the modified material. BET isotherms are type IV, with slit-shaped pores formed by nonrigid aggregate particles and no pore networks and a small H3 loop near the maximum relative pressure. The doped samples show increased crystallite sizes and a lower band gap, extending visible light harvesting. All prepared catalysts showed band gaps in the interval 2.3–2.5 eV. The photocatalytic degradation of aqueous phenol over TiO₂-P25 and Co(X%)/TiO₂ was monitored using UV-Vis spectrophotometry: Co(0.1%)/TiO₂ being the most effective with NUV-Vis irradiation. TOC analysis showed ca. 96% TOC removal with NUV-Vis radiation, while only 23% removal under UV radiation. Full article

Exploring the relationship between formation pressure and shale pore evolution is helpful for the enrichment and development of marine shale gas accumulation theory. The thermal evolution experiment was carried out on the Xiamaling Formation (Pr3x) lowly matured marine shale, which has a similar sedimentary environment to the Longmaxi Formation (S1l) highly matured marine shale. Comparative experiments of open and semi-closed pyrolysis and multiple pore structure characterization techniques, including CO₂ and N₂ physisorption, mercury intrusion porosimetry, and field emission scanning electron microscopy, were conducted. The marine shale pore evolutionary model under formation pressure is proposed by characterizing pore evolution, and hydrocarbon expulsion and retention for shales under and without formation fluid pressures. The results show that the existence of formation pressure increases the percentage of quartz and reduces the content of clay minerals. The change in formation pressure has no obvious effect on the maturity evolution of shale samples. With the increase of formation pressure, the pore morphology of shale gradually changes from narrow slit pores to ink bottle-shaped pores. The retained hydrocarbons in shale mainly occupy the mesopore space, and the existence of formation pressure promotes hydrocarbon expulsion, especially the hydrocarbon expulsion in the mesopore. In addition, formation pressure improves pore connectivity, especially in the high-over mature stage of shale. With the increase of formation pressure, the micropore volume decreases slightly, the mesopore volume increases significantly, and the macropore volume changes have two stages. Full article

Shale oil has become a global hotspot of unconventional exploration and development. In this study, the latest drill core and experiment analyses of the Qingshankou Formation in the northern Songliao Basin were used to evaluate its lithofacies classification, sedimentary environment, pore types, pore-throat structure characterization, and shale oil potential. Lithofacies classification was determined according to the total organic carbon (TOC) content, sedimentary structure, and rock mineral content. Laminae genesis and micro-sedimentary structures indicate the deposition of fine-grained sedimentary rocks (FGSRs) in a semi-deep to deep lacustrine environment; however, evidence also suggests partial reworking by storm events and bottom current flows. FGSRs mostly comprise type I kerogen, with small amounts of type II₁. The average vitrinite reflectance of the FGSRs was 1.37%, indicating middle to high stages of thermal maturation within the oil generation window. The N₂ adsorption experiment indicated that silty mudstone (SM), silty fine mixed sedimentary rock (SFMR), and argillaceous fine mixed sedimentary rock (AFMR) had ink-bottle-shaped and slit-shaped pores, and the lithofacies were dominated by mesopores, accounting for 77.4%, 71.9%, and 80.8% of the total pore volume, respectively. Mercury injection capillary pressure analysis indicated that SM and SFMR had an average pore-throat radius of 0.01–0.04 μm, whereas AFMR and CM were dominated by nanopores, mainly distributed in the range of 0.004–0.0063 μm. Based on the comprehensive studies of TOC content, pore development, and brittleness, we concluded that organic-rich laminated SM and SFMR should be the focus of shale oil exploration of the Qingshankou Formation in the northern Songliao Basin, followed by organic-rich or organic-moderate laminated and layered AFMR, as well as calcareous fine mixed sedimentary rocks. Full article

The Silurian Longmaxi (S₁l) marine shale and Jurassic Dongyuemiao (J₁d) lacustrine shale in the Sichuan Basin, West China have attracted considerable attention from the oil-and-gas industry in China. Currently, the differences in pore types and pore structures between them are poorly understood, which has limited shale-resource exploration in the Sichuan Basin. This paper systemically compares the pore characteristics of Longmaxi shale and Dongyuemiao shale and investigates their impact on shale-gas enrichment by integrating field-emission scanning electron microscopy (FE–SEM), X-ray diffraction (XRD), low-pressure gas (CO₂ and N₂) adsorption and mercury-intrusion porosimetry, high-pressure sorption isotherms, gas-saturation measurement, molecular-dynamics simulation, etc. The results show that the S₁l organic-rich marine shale and the J₁d lacustrine shale have different pore types and pore structures. The S₁l shale is dominated by organic pores, mainly micropores and mesopores with ink-bottle-like pore shapes, while the J₁d shale is primarily composed of clay-mineral pores, mainly mesopores and macropores with slit- or plate-like pore shapes. Organic pores can provide considerable storage space for shale-gas enrichment in S₁l marine shale, which also determines the adsorption capacity of shale reservoirs. Although organic pores are not the most prevalent in the Dongyuemiao lacustrine shale, they also play an important role in enhancing reservoir quality and absorbed-gas enrichment. Clay-mineral pores contribute weakly to the storage space of J₁d-lacustrine-shale reservoirs. Mesopores are the most important form of storage space in both S₁l shale and J₁d shale, contributing significantly to shale-gas enrichment. Micropores are secondary in importance in S₁l marine shale, while macropores are secondary contributors to pore volume in J₁d lacustrine shale. Full article

The Lower Paleozoic marine shale in southern China has undergone several strong tectonic transformations in an extensive region outside the Sichuan Basin. Although some shale strata underwent strong deformation, they still contain a significant amount of shale gas. The gas preservation mechanism in the strongly deformed shale has become the focus of attention. In this paper, the Lower Cambrian gas-bearing shale samples with a strong deformation taken from an exploration well in northern Chongqing, China, were investigated on their pore types and structure, with the aim to reveal the reason for the gas preservation. The pore types of the Lower Cambrian shale are dominated by microfractures and interparticle (interP) pores occurring mainly between clay minerals and between organic matter (OM) and clay minerals, while pores within OM that can be observed by FE-SEM (field emission-scanning electron microscopy) are rare. The shale has a low porosity, with an average of 1.56%, which is mainly controlled by the clay mineral content. The adsorption experiments of low pressure N₂ (LPNA) and CO₂ (LPCA) indicate that the shale is rich in micropores and small mesopores (<2–3 nm) provided mainly by OM, but mesopores with a size range of 3–50 nm are underdeveloped. The shale, as revealed by LPNA data, has dominant slit-like or plate-like pores and an obvious low-pressure hysteresis (LPH), indicating a low gas diffusion. The deformed shale samples with a removal of OM by oxidation and their isolated kerogen further indicate that the LPH is completely related to OM, without any relationship with minerals, while an undeformed shale sample, taken from another well for a comparison, has no obvious LPH for both of its OM-removed sample and kerogen. Based on a comprehensive analysis of the relative data, it is suggested that the nanopores related to OM and clay minerals in the shale were significantly altered owing to the deformation, with a result of the pores being squeezed into the slit-like shape and converted into micropores. This extraordinary pore structure of the shale formed during the deformation process should be the main preservation mechanism of shale gas. Full article

A quad-band circularly-polarized antenna, for applications of a global navigation satellite system (GNSS), 5G, and WIFI-6E, is designed, fabricated, and measured. The proposed antenna is formed by an L-shaped radiator, a rectangular frame ground with an L-shaped stub, and a rectangular strip at the opposite corner. The microstrip antenna can generate four frequency bands, covering WIFI-6E (5925–7125 MHz), 5G n77 (3300–4200 MHz), n78 (3300–3800 MHz), and the GNSS bands. This antenna generates right hand circular polarization (RHCP) waves in the low frequency band (0.95–2.11 GHz), covering GPS, BDS, GLONASS, and GALILEO applications. Moreover, an L-shaped aperture and three rectangular slits are cut on the ground to broaden the axial-ratio bandwidth at the upper band. A prototype is fabricated and measured to verify the performance of this design. It is shown that the agreement between the simulation and measurement is satisfactorily good. The measured −10 dB bandwidths for each band are 75.8% (0.95–2.11 GHz), 55.8% (3.05–5.39 GHz), 39.9% (5.84–8.19 GHz) and 10.3% (9.14–10.68 GHz), respectively. While the measured 3 dB axial-ratio bandwidths are 59.4% (1.16–2.14 GHz), 35.8% (3.23–4.64 GHz), 8.4% (5.70–6.20 GHz), and 2.6% (7.51–7.71 GHz), the measured gains are 4.56, 2.28, 4.26, and 4.30 dBi at 1.5 GHz, 3.8 GHz, 6 GHz, and 7.6 GHz, respectively. Full article