Search Results (20)

Unique fractal characteristics are significantly controlled by shale lithofacies, mineralogical characteristics, and OM features, which in turn determine reservoir properties and gas-bearing capacity. However, a comprehensive understanding of fractal features has remained insufficient. This study presents a systematic investigation into the full-scale pore size distribution for the Wufeng–Longmaxi shales in Sichuan Basin which employed low-pressure CO₂ adsorption (CO₂GA), N₂ adsorption (N₂GA), and mercury injection capillary pressure (MICP), as well as field emission scanning electron microscope (FE-SEM) techniques. The fractal dimensions of pores across different pressure ranges were revealed by different fractal models. The results demonstrate that the shale pores are dominated by micro- to mesopores and partial extremely larger pores, contributed primarily by organic matter (OM) pores and microcracks, respectively. Fractal dimensions follow a consistent increasing order: D_C < D_N1 < D_N2 < D_M or D_C < D_N1 < D_M < D_N2, suggesting that larger pores with diameters lager than 5 nm are more heterogeneous and complex compared to the pores less than 5 nm (smaller pores). This is because smaller pores are predominantly composed of OM pores, while larger pores comprise a mixture of OM pores, mineral-related pores, and microcracks. Different fractal dimensions, in turn, are influenced by distinct factors. The D_C value exhibits a positive correlation with micropore volume. D_N1 and D_N2 values are positively correlated with the content of brittle minerals and TOC, while they show negative correlations with the content of clay minerals. Notably, D_M values do not demonstrate a significant correlation with shale compositions, primarily owing to the development of microcracks. Fractal dimensions, particularly D_N1 and D_N2, are significantly controlled by the lithofacies of shale. The highest D_N1 and D_N2 values occur in the siliceous shale lithofacies, and the mixed shale lithofacies exhibit moderate D_N1 and D_N2 values, whereas the lowest D_N1 and D_N2 values primarily occur in clay-rich shale lithofacies. Different fractal dimensions show various correlations with shale gas content. The Langmuir volume as well as total gas content exhibit significant correlations with D_N1 and D_N2 values, while they exhibit no obvious correlations with D_C and D_M values. This implies that pores with diameters of 1.8–55 nm serve as primary storage sites for both adsorbed and free gas. The findings can significantly improve the cognition of adsorbed gas and free gas behavior in shale reservoirs. Full article

Contamination of heavy metals, particularly chromium from industrial activities, represents a critical challenge for public health and the environment. The aim of this study is to evaluate the adsorption performance of green mesoporous silica (GMS-24 h), synthesized through a sustainable process from industrial sodium silicate, and its derivative functionalized with amino groups (GMS-24 h–NH₂) for the removal of Cr(III) in aqueous systems. FTIR and CP–MAS NMR characterization confirmed the surface modification and textural property improvement of green mesoporous silica. The adsorption experiments, carried out under varying pH and Cr(III) concentration conditions, were fitted to the Langmuir and Freundlich models. The results showed that GMS-24 h reached a maximum capacity of 303 mg·g⁻¹ at pH 3, while GMS-24 h–NH₂ achieved 370 mg·g⁻¹ at pH 5. The evaluated adsorbents showed up to a 44% increase in efficiency. Preliminary kinetic studies indicated that the pseudo-second-order model accurately describes the process (R² > 0.99), with the rapid stabilization of the system. Diffusion analysis indicated combined mechanisms, with an additional chelation step (N → Cr) in GMS-24 h–NH₂. These findings suggest that GMS–NH₂ has the potential to be a sustainable and economical adsorbent for the remediation of wastewater from the tanning industry in León, Guanajuato, Mexico. Full article

Tectonic deformation can substantially change the pore characteristics and the resulting methane adsorption capacity of shales; thus, it strongly influences shale gas exploration and development in structurally complex areas of southern China. Two sets of shales with identical lithofacies that were derived from either structurally stable or deformed regions were collected at Fuling Field to evaluate the response of their pore properties and methane adsorption behavior to tectonic deformation through field emission scanning electron microscopy (FE-SEM), low-pressure gas (CO₂/N₂) adsorption, and high-pressure methane adsorption experiments. Three primary shale lithofacies were identified in each set of shales: organic-lean (OL) siliceous-rich argillaceous (CM-1) shale lithofacies, organic-moderate (OM) argillaceous/siliceous mixed (M-2) shale lithofacies, and organic-rich (OR) argillaceous-rich siliceous (S-3) shale lithofacies. In the stable region, organic matter (OM) pores dominated the pore types of OR S-3 shales, whereas the primary pore types of OL CM-1 shales were clay cleavage micro-fractures. OM M-2 shales exhibited a composite type of OM pores and clay cleavage micro-fractures. Compared with structurally stable shales, the original OM-hosted and clay-related pores in structurally deformed shales were extensively compacted or even closed due to tectonic compression during structural deformation. Despite pore collapse, two new types of tectonic micro-fractures were generated and found to be well developed in deformed shales through the rupture of brittle minerals in OR S-3 shales and the deformation of clay minerals in OL CM-1 shales. Simultaneously, organic matter–clay aggregates that formed during tectonic compression constituted a distinctive structure in deformed OM M-2 shales. As a result, the deformed shales displayed a decrease in their micropore and mesopore volumes, as well as a decrease in their pore surface areas, because of strong tectonic compression accompanied by an increase in the macropore volume due to the development of tectonic micro-fractures. Furthermore, the large pore surface areas in structurally stable shales could supply abundant adsorption sites and facilitate the enrichment of adsorbed gas. The expanded macropore volumes in structurally deformed shales could provide more storage spaces that are favorable for the accumulation of free gas. Full article

Coal gangue, a prevalent solid waste in the coal industry, has long been a significant concern due to its substantial production volume and potential environmental hazards. However, it contains valuable components such as silica and alumina, making it a promising raw material for synthesizing cementitious materials. This study focused on the synthesis of coal gangue-based magnesium silicate hydrate (M-S-H) and calcium silicate hydrate (C-S-H) through mechanical–thermal–chemical composite activation treatment. The cementitious activity of coal gangue samples and the characterization of the resulting cementitious materials were analyzed using ICP-AES, FTIR, XRD, SEM, and DSC-TG. Results indicated that calcination temperature, calcination time, the Ca/Si molar ratio, and the Mg/Si molar ratio were key factors influencing the cementitious activity of coal gangue, exhibiting a positive correlation with the dissolution amounts of Si⁴⁺ and Al³⁺. When kaolin in coal gangue was fully decomposed into active Al₂O₃ and SiO₂, the cementitious activity of coal gangue reached its peak. M-S-H and C-S-H were successfully synthesized after 7 days of curing at room temperature, significantly reducing the synthesis time. The synthesized M-S-H and C-S-H exhibited large specific surface areas, good mechanical properties, and well-developed pore structures, making them suitable as mesoporous materials that provide numerous active sites for adsorbing metal ions. Full article

This paper presents an original method for synthesizing Zn-doped mesoporous silica (KCC-1) via a one-pot microemulsion method followed by hydrothermal treatment. Zn incorporation into the silica matrix was achieved by varying Zn/Si molar ratios from 1% to 8%. The Zn-doping effect on KCC-1 morphological and structural properties was investigated using several characterization techniques, providing new insights into the Zn-doping behavior and coordination environment. X-ray fluorescence (XRF) spectra confirmed the stoichiometric doping of silica nanoparticles for samples obtained with a precursor concentration of 1%, 3%, and 6%. An attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy highlighted that Zn was included into the KCC-1 matrix rather than chemically adsorbed onto the surface. Scanning electron microscopy (SEM) images clearly showed that a low Zn content preserves the KCC-1 fibrous morphology. An X-ray diffraction (XRD) analysis confirmed the amorphous nature of the doped nanoparticles, suggesting a structural disorder of the silica framework at higher Zn concentrations. X-ray photoelectron spectroscopy (XPS) revealed that Zn–(OH)₂ bonds increased at a 6% Zn/Si molar ratio, confirming the disordered inclusion of Zn at this doping limit. X-ray absorption near-edge structure (XANES) data revealed that in Zn-doped silica at 3% and 6%, Zn primarily exists in a coordination state similar to zinc-silicates and the amorphous Zn-hydroxyapatite-like phase. Full article

Zr-containing silica residue (ZSR) is an industrial by-product of ZrOCl₂ production obtained through an alkali fusion process using zircon sand. In this study, low-cost and efficient Zr-doped mesoporous silica adsorption materials (Zr-MCM-41 and Zr-SBA-15) were prepared in one step via the hydrothermal synthesis method using ZSR as the silicon source for the removal of methylene blue (MB) from dye-contaminated wastewater. The samples were characterized using X-ray fluorescence (XRF) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetry (TG), and N₂ adsorption–desorption measurements. The findings indicate that the synthesized Zr-MCM-41 and Zr-SBA-15 possess highly ordered mesoscopic structures with high specific surface areas of 910 and 846 m²/g, large pore volumes of 1.098 and 1.154 cm³/g, and average pore diameters of 4.18 and 5.35 nm, respectively. The results of the adsorption experiments show that the adsorbent has better adsorption properties under alkaline conditions. The adsorption process obeys the pseudo-quadratic kinetic model and the Freundlich adsorption isotherm model, indicating the coexistence of physical and chemisorption processes. The maximum adsorption capacities of Zr-MCM-41 and Zr-SBA-15 are 618.43 and 516.58 mg/g, respectively, as calculated by the Langmuir model (pH = 9, temperature of 25 °C). Compared with mesoporous silica prepared with sodium silicate as the silicon source, Zr-MCM-41 and Zr-SBA-15 have different structural properties and better adsorption properties due to Zr doping. These findings indicate that ZSR is the preferred silicon source for preparing mesoporous silica, and the mesoporous silica prepared using Zr silicon slag is a promising adsorbent and has great application potential in wastewater treatment. Full article

Emissions of volatile organic compounds (VOCs) such as benzene, toluene, xylene, styrene, hexane, tetrachloroethylene, acetone, acetaldehyde, formaldehyde, isopropanol, etc., increase dramatically with accelerated industrialization and economic growth. Most VOCs cause serious environmental pollution and threaten human health due to their toxic and carcinogenic nature. Adsorption on porous materials is considered one of the most promising technologies for VOC removal due to its cost-effectiveness, operational flexibility, and low energy consumption. This review aims to provide a comprehensive understanding of VOC adsorption on various porous adsorbents and indicate future research directions in this field. It is focused on (i) the molecular characterization of structures, polarity, and boiling points of VOCs, (ii) the adsorption mechanisms and adsorption interactions in the physical, chemical, and competitive adsorption of VOCs on adsorbents, and (iii) the favorable characteristics of materials for VOCs adsorption. Porous adsorbents that would play an important role in the removal of benzene and other VOCs are presented in detail, including carbon-based materials (activated carbons, active carbon fibers, ordered mesoporous carbons, and graphene-based materials), metal-organic frameworks, covalent organic frameworks, zeolites, and siliceous adsorbents. Finally, the challenges and prospects related to the removal of VOCs via adsorption are pointed out. Full article

A siliceous material in which a framework order was established with a surfactant with sixteen carbon atoms in alkyl chains, MCM-41-C16, was synthesised, surface-modified, and tested regarding the selected physical properties. The pristine material was extracted in an acidic aqueous alcohol and then lined with different surface groups. The properties of four adsorbents were investigated using XRD, X-ray photoelectron spectroscopy, and N2 physisorption techniques. The unit–cell constant was determined from X-ray diffractograms, being in fixed relation to the edge length of the hexagonal frame. The specific surface areas of mesopores and whole crystallites were determined from low-temperature N2-physisorption isotherms. The novelty of this work is a mathematical model of a crystalline microstructure explaining the sizes and shapes of crystalline grains in relation to adsorption features, proposed and successfully tested with the aforementioned experimental data. The roughness of the surface is different from one that is necessary to explain the experimental characteristics quantitatively. Full article

Mesoporous materials containing heteroelements have a huge potential for use as catalysts, exchangers, and adsorbents due to their tunable nanometer-sized pores and exceptionally large internal surfaces accessible to bulky organic molecules. In the present work, ordered mesoporous silica containing Ni atoms as active sites was synthesized by a new low-temperature method of condensation of silica precursors on a micellar template from aqueous solutions in the presence of nickel salt. The homogeneity of the resulting product was achieved by introducing ammonia and ammonium salt as a buffer to maintain a constant pH value. The obtained materials were characterized by nitrogen sorption, X-ray and neutron diffraction, scanning electron microscopy, infrared spectroscopy, and thermal analysis. Their morphology consists of polydisperse spherical particles 50–300 nm in size, with a hexagonally ordered channel structure, high specific surface area (A_BET = 900–1200 m²/g), large pore volume (V_p = 0.70–0.90 cm³/g), average mesopore diameter of about 3 nm, and narrow pore size distribution. Adsorption tests for methylene blue show sorption capacities reaching 39–42 mg/g at alkaline pH. The advantages of producing nickel silicates by this method, in contrast to precipitation from silicon alkoxides, are the low cost of reagents, fire safety, room-temperature processing, and the absence of specific problems associated with the use of ethanol as a solvent, as well as the absence of the inevitable capture of organic matter in the precipitation process. Full article

Vinasse was successfully utilized to synthesize carbon–silica composite with a low-cost silica source available in Thailand (sodium silicate, Na₂SiO₃) and most commonly used source, tetraethyl orthosilicate (TEOS). The composites were prepared by a simple one-step sol–gel process by varying the vinasse (as carbon source) to silica source (Na₂SiO₃ or TEOS) weight ratio. The resulting composites were characterized by N₂ adsorption, moisture and ash contents, pH, pH_pzc, bulk density, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX). The composites had highest surface area of 313 and 456 m²/g, with average mesopore diameters of 5.00 and 2.62 nm when using Na₂SiO₃ and TEOS as the silica sources, respectively. The adsorption of a non-steroidal anti-inflammatory drug, ibuprofen, was investigated. The contact time to reach equilibrium was 60 min for both composites. The adsorption kinetics were fitted by a pseudo-second-order model with the correlation coefficient R² > 0.997. The adsorption isotherms were well described by the Langmuir model (R² > 0.992), which indicates monolayer adsorption. The maximal adsorption capacities of the Na₂SiO₃- and TEOS-based composites were as high as 406 and 418 mg/g at pH 2, respectively. The research results indicate that vinasse and a low-cost silica source (Na₂SiO₃) show great potential to synthesize adsorbents through a simple method with high efficiency. Full article

Nonylphenol (NP) is considered to be an environmentally toxic, endocrine-disrupting chemical that affects humans and ecosystems. Adsorption is one of the most promising approaches for the removal of nonylphenol contamination from water. Herein, in order to design an adsorbent with high adsorption capacity, magnesium silicate with different Mg/Si ratios was successfully synthesized by a sol–gel method at 60 °C. Magnesium silicate with a Mg/Si ratio of 1:6 was found to possess the best adsorption performance, with maximum 4−NP sorption 30.84 mg/g under 25 °C and 0.2 g/L adsorbent dose. The adsorption was negatively affected by increasing adsorbent dose and temperature. The kinetics and isotherm of 4−NP adsorption by Mg/Si were well described by the pseudo−second−order and Sips model, respectively, and behavior was proven to be physisorption−enhanced by a chemical effect. Detailed characterization by XRD, BET, and SEM confirmed that the magnesium silicate possesses an amorphous, mesoporous structure. The study will contribute to the applicability of cheap magnesium silicate for removal of NP contamination in water. Full article

Aluminum silicate powder was prepared using two different syntheses: (1) co-precipitation and (2) two-step sol-gel method. All synthesized powders were characterized by various techniques including XRD, FE-SEM, FT-IR, BET, porosimeter, and zetasizer. The particle morphology of the synthesized aluminum silicate powder was greatly different depending on the synthesis. The synthesized aluminum silicate powder by co-precipitation had a low specific surface area (158 m²/g) and the particle appeared to have a sharp edge, as though in a glassy state. On the other hand, synthesized aluminum silicate powder by the two-step sol-gel method had a mesoporous structure and a large specific surface area (430 m²/g). The aluminum silicate powders as adsorbents were characterized for their adsorption behavior towards Pb (II) ions and methylene blue in an aqueous solution performed in a batch adsorption experiment. The maximum adsorption capacities of Pb (II) ions and methylene blue onto the two-step sol-gel method powder were over four-times and seven-times higher than that of the co-precipitation powder, respectively. These results show that the aluminum silicate powder synthesized with a two-step sol-gel method using ammonia can be a potential adsorbent for removing heavy metal ions and organic dyes from an aqueous solution. Full article

Ordered mesoporous Santa Barbara amorphous (SBA-15) materials have high surface areas and are widely used in adsorption, separation, filtration, and heterogeneous catalytic processes. However, SBA-15 surfaces contain hydroxyl groups that are unsuited to the adsorption of organic pollutants; thus, SBA-15 must be chemically modified to promote its adsorption activity. In this study, amino-functionalized nanoporous SBA-15 was fabricated by employing sodium silicate as a precursor. The structural characteristics of the prepared composites were examined using thermogravimetric analysis, X-ray diffraction, Fourier transform infrared spectrometry, field-emission scanning electron microscopy, transmission electron microscopy, and surface area analysis. The prepared SBA-15 had a large pore size (6.46–7.60 nm), large pore volume (1.037–1.105 cm³/g), and high surface area (546–766 m²/g). Functionalization caused a reduction in the SBA-15 pore volume and surface area, whereas amino groups that promoted an interaction between adsorbates and solids facilitated solute adsorption. The adsorption of tannic acid (TA) onto amino-modified silica composites (SBA-15 and 3-aminopropyltriethoxysilane (SBA-15/APTES) and SBA-15 and pentaethylenehexamine (SBA-15/PEHA)) was studied. Their adsorption capacities were affected by solution temperature, solution pH, agitation speed, adsorbent dosage, and initial TA concentration. The maximum adsorption capacities for SBA-15/APTES and SBA-15/PEHA were 485.18 and 413.33 mg/g, respectively, with SBA-15/APTES exhibiting ultrafast removal of TA (98.61% removal rate at 15 min). In addition, this study explored the thermodynamics, adsorption isotherms, and kinetics. A comparison of two types of amino-functionalized SBA-15 was used for the first time to adsorb TA, which providing valuable information on TA adsorption on high adsorption capacity materials in water media. Full article

It is of both fundamental and practical importance to develop effective adsorbents for removing phosphate from aqueous solutions continuously. In this study, magnetic amorphous lanthanum silicate alginate hydrogel beads (MALS-B) were prepared and used for phosphate removal. Mesoporous silica materials with highly ordered and hexagonal channel structures were synthesized from natural mineral rectorite (REC) at room temperature. On this basis, amorphous lanthanum silicate (ALS) was synthesized by theone-pot method using a silicon source from REC and a commercial lanthanum source. Further, MALS-B were synthesized from sodium alginate (SA) with ALS and Fe₃O₄ as the incorporated adsorbable and magnetic nanoparticles via a simple cross-linking method in CaCl₂ solution. The synthesized hydrogel beads were characterized by various techniques. ALS and Fe₃O₄ existed relatively independently in MALS-B, where ALS provided adsorption sites and Fe₃O₄ provided magnetism. They played a synergistic role in phosphate removal. The saturation magnetization value of MALS-B was 17.38 emu/g, enabling theirfacile separation from aqueous solutions after phosphate adsorption. MALS-B exhibited a preferable adsorption capacity of 40.14 mg P/g for phosphorus compared to other hydrogel beads based on adsorption experiments. More significantly, MALS-B exhibited excellent selectivity for phosphate in aqueous solutions with various interfering ions and possessed a high affinity to phosphate in a wide pH range. MALS-B showed the treatment volume of 480 BV when effluent phosphate concentration was below 0.5 mg/L in fixed-bed column adsorption. The adsorption mechanism was also revealed. Our work demonstrates that MALS-B can serve as a promising adsorbent for continuous phosphate adsorption. Full article

Three mesoporous, siliceous materials, i.e., SBA-15 (Santa Barbara Amorphous), PHTS (Plugged Hexagonal Templated Silica) and MCM-41 (Mobil Composition of Matter), functionalized with a sulfonic acid derivative, were successfully prepared and applied as the carriers for the poorly water-soluble drug, ticagrelor. The siliceous carriers were characterized using nitrogen sorption analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM) and elemental analysis. The adsorption studies were conducted in acetonitrile. At the highest equilibrium concentrations, the amount of ticagrelor Q_e that adsorbed onto the examined silicas was in the range of 83 to 220 mg/g, increasing in the following order: PHTS-(CH₂)₃-SO₃H < SBA-15-(CH₂)₃-SO₃H < MCM-41-(CH₂)₃-SO₃H. The equilibrium adsorption data were analyzed using the Freundlich, Jovanovich, Langmuir, Temkin, Dubinin-Radushkevich, Dubinin-Astakhov and Redlich-Peterson models. In order to find the best-fit isotherm for each model, a nonlinear fitting analysis was carried out. Based on the minimized values of the ARE function, the fit of the isotherms to the experimental points for ticagrelor adsorption onto the modified silicas can be ordered as follows: SBA-15-(CH₂)₃-SO₃H (Redlich-Peterson > Dubinin-Astakhov > Temkin), PHTS-(CH₂)₃-SO₃H (Redlich-Peterson > Temkin > Dubinin-Astakhov), MCM-41-(CH₂)₃-SO₃H (Redlich-Peterson > Dubinin-Astakhov > Langmuir). The values of adsorption energy (above 8 kJ/mol) indicate the chemical nature of ticagrelor adsorption onto propyl-sulfonic acid-modified silicas. The results of release studies indicated that at pH 4.5, modified SBA-15 and MCM-41 carriers accelerate the drug dissolution process, compared to the dissolution rate of free crystalline ticagrelor. Intriguingly, modified PHTS silica provides prolonged drug release kinetics compared to other siliceous adsorbents and to the dissolution rate of crystalline ticagrelor. A Weibull release model was employed to describe the release profiles of ticagrelor from the prepared carriers. The time necessary to dissolve 50% and 90% of ticagrelor from mesoporous adsorbents at pH 4.5 increased in the following order: SBA-15-(CH₂)₃-SO₃H < MCM-41-(CH₂)₃-SO₃H < PHTS-(CH₂)₃-SO₃H. Full article