Low-temperature N2 Adsorption Research Articles

Synergistic Effect of Co and Ni Co-Existence on Catalytic Decomposition of Ammonia to Hydrogen—Effect of Catalytic Support and Mg-Al Oxide Matrix

Hydrotalcite-derived mixed metal oxides containing Co and Ni and containing these metals supported on MgO and Al2O3 were prepared and tested as catalysts for the decomposition of ammonia to hydrogen and nitrogen. The obtained samples were characterised in terms of chemical composition (ICP-OES), structure (XRD), textural parameters (low-temperature N2 adsorption–desorption, SEM), form and aggregation of transition-metal species (UV-Vis DRS), reducibility (H2-TPR) and surface acidity (NH3-TPD). The catalytic efficiency of the tested systems strongly depends on the support used. Generally, the alumina-based catalyst operated at lower temperatures compared to transition metals deposited on MgO. For both series of catalysts, a synergistic effect of the co-existence of cobalt and nickel on the catalytic efficiency was observed. The best catalytic results were obtained for hydrotalcite-derived catalysts; however, in the case of these catalysts, an increase in the Al/Mg ratio resulted in a further increase in catalytic activity in the decomposition of ammonia.

The effect of structural preservation conditions on pore structure of marine shale reservoir: a case study of the Wufeng-Longmaxi Formation shale, Southern Sichuan Basin, China

The marine shale within the Sichuan Basin constitutes China’s significant shale gas production, featuring old formation age, high degree of thermal evolution, multiple tectonic movements, and complex structural conditions. However, there are significant differences in the shale gas preservation conditions and reservoir quality in different areas, limiting future large-scale exploration and development. Pore structure significantly influences shale reservoir quality, gas content, and exploration of shale gas occurrence, migration, and enrichment mechanisms. The influence of structural-dominated preservation conditions on shale pore structures is essential to comprehend for effective shale gas exploitation. This study employs field-emission scanning electron microscopy in conjunction with other techniques (low-temperature N2 adsorption, low-temperature CO2 adsorption, and nuclear magnetic resonance) for detailed analyses of the pore structure across varied structural zones, revealing the influence of structural attributes, fault systems, depth of burial, and formation pressure on pore architecture, and examining the relationship between pore structure and shale gas preservation conditions. The results show that stable structural condition is conducive to the development and preservation of shale pores. Structural compression causes inorganic and organic pores to become narrow and elongated due to shrinkage, with a significant increase in microfractures. The porosity of shale with stable structural conditions exhibits markedly increased porosity compared to samples under structural compressions. Under conditions of similar TOC and mineral composition, the pore size distribution (PSD), pore volume (PV), and specific surface area (SSA) of shale after structural compression are significantly lower than those of samples with stable structural conditions. As the burial depth increases, the shale porosity shows a decreasing trend, but the decrease is limited. Burial depth significantly impacts the SSA and PV of high-TOC samples (3%–6%). As the burial depth increases, both SSA and PV show a significant decreasing trend. When the burial depth reaches 4000 m, SSA and PV tend to concentrate. The formation pressure coefficient is an important factor for the development and preservation of shale pores, and porosity is positively correlated with the formation pressure coefficient. Increased formation pressure coefficient indicates superior preservation conditions and enhanced pore development.

Unexpected strong toluene chemisorption over Ag/CeO2 catalysts for total toluene oxidation

The effect of Ag content on the sorption properties and toluene removal activity over Ag/CeO2 catalysts is studied. In this paper, the series of Ag/CeO2 catalysts with Ag content from 1 to 10 wt% are prepared by impregnation method and characterized using a complex of methods: low-temperature N2 adsorption, XRD analysis, TPR-H2, and TEM-HR. For the first time, the strong toluene chemisorption over Ag-containing species accompanied by total oxidation into CO2 is observed. The correlation between the amount of chemisorbed toluene and Ag loading in the catalysts confirms the toluene chemisorption over Ag species and/or Ag-CeO2 interface. The active surface oxygen of ceria oxidizes chemisorbed toluene. The cooperation of active sites on silver and ceria provides both enhanced chemisorption of toluene and its total oxidation. The total removal of toluene (2000 ppm) was achieved at ∼140 °C over 5Ag/CeO2 and 10Ag/CeO2 catalysts due to both chemisorption and total oxidation of toluene.

Influence of coal rock on tight sandstone reservoirs in coal seam roofs: A case study of the lower jurassic in the Taibei sag, Turpan-Hami Basin, China

After shale gas, coalbed methane and gas hydrate, coal measure gas has become an important new unconventional resource, for which exploration to depths of >3000 m are taking place in China. However, owing to unusual geological conditions and as yet inadequate exploration technology the current level of exploration is low. The acidic water medium in coal-bearing strata affects the diagenesis of adjacent tight sandstone reservoirs, thereby influencing reservoir quality. However, the current understanding of the impact mechanism of coal seams on neighboring tight reservoirs is insufficient, constraining the further exploration of coal measure gas. In order to reveal the influence of coal rock on a tight sandstone reservoir in its roof, we study the coal-bearing strata of the Xishanyao Formation in the Taibei Sag of the Turpan-Hami Basin using cast thin sections, physical property tests, XRD analysis, carbon and oxygen isotopes, high-pressure mercury intrusion and low-temperature N2 adsorption. The carbonate cement in the sandstone reservoir of the coal seam roof was formed by the decarboxylation of organic acid. The organic acid, containing CO2 generated by coal rock hydrocarbon generation, has modified the tight sandstone reservoir of the coal seam roof via dissolution. This has improved the physical properties and pore throat structure of the tight sandstone reservoir close to the coal-sandstone interface. The amount of improvement extends to about 2 m into the sandstone. During the upward transport of fluid, the pre-existing carbonate cement dissolves and then precipitates, which causes the CO2 generated by the organic acid decarboxylation to exchange carbon with the carbon isotopes in the pre-existing carbonate cement. Due to the slow upward diffusion rate and limited diffusion distance of the CO2-bearing fluids, the carbonate cement exhibits gradually heavier δ13CPDB values with increasing distance from the coal-sandstone interface.

Physicochemical and Adsorption Characterization of Char Derived from Resorcinol-Formaldehyde Resin Modified with Metal Oxide/Silica Nanocomposites.

A series of metal- and silica-containing carbon-based nanocomposites were synthesized by pyrolysis of a resorcinol-formaldehyde polymer modified with metal oxide/silica nanocomposites (MxOy/SiO2, where M = Mg, Mn, Ni, Cu and Zn) via the thermal oxidative destruction of metal acetates adsorbed on highly dispersed silica (A380). The concentration of metals was 3.0 mmol/g SiO2. The phase composition and morphological, structural and textural properties of the carbon materials were analyzed by X-ray diffraction, SEM, Raman spectroscopy and low-temperature N2 adsorption. Thermal decomposition under a nitrogen atmosphere and in air was analyzed using TG-FTIR and TG-DTG-DSC techniques to determine the influence of the filler on the decomposition process. The synthesized composites show mesoporous structures with high porosity and narrow pore size distributions. It could be shown that the textural properties and the final composition of the nanocomposites depend on the metal oxide fillers of the precursors. The data obtained show that nickel and copper promote the degree of graphitization and a structural order with the highest porosity and largest specific surface area of the hybrid composites. The good adsorption properties of the obtained materials were shown for the recovery of p-chlorophenol and p-nitrophenol from aqueous solutions.

Multiscale Pore Structure Evolution of Different Rank Coals Induced by Chelating Agent Intrusion

Summary China’s coalbed methane (CBM) reservoirs are characterized by low permeability (<1 md). Stimulation with conventional acids is facing the problems of secondary precipitation, high corrosion rates, and fines migration. Chelating agent intrusion was proposed as a promising alternative for conventional acids, while the pore structure evolution induced by it needs to be further clarified. In this study, coal samples with three different ranks were selected and treated with L-glutamic acid N, N-diacetic acid (GLDA). Low-temperature Ar and N2 adsorption tests, mercury intrusion porosimetry (MIP), and scanning electron microscope (SEM) analyses were applied to investigate nanoscale to macroscale pore structure changes. X-ray fluorescence (XRF) spectroscopy tests were conducted to determine the mineralogical change of coal. The results show that chelating agent intrusion can widen fracture width, connect micropores, and create void space in macropores by dissolving carbonate minerals, while the nanoscale pore volumes (PVs) showed a slight decrease due to clay minerals collapse. The fractal dimensions Dm calculated by the MIP results of lignite, bituminous coal, and anthracite coal decreased by 0.2735, 0.1734, and 0.1444, respectively. It is indicated that a pore structure with a diameter of >100 nm of the coal became more unified, which favors the seepage of gas/water. The chelating agent intrusion shows a significant effect on lignite, followed by bituminous and anthracite coal. However, the metal element reduction rate of anthracite coal presents the highest, followed by bituminous coal and lignite. There can be a risk that a long intrusion time would loosen the skeleton of lignite, leading to further reservoir damage. Therefore, bituminous and anthracite coal samples are preferred, as the skeletons of higher-rank coals are more compact. These research findings introduced a potential stimulation method for enhancing CBM recovery and provided references for field application.

Covalent bonding of N-hydroxyphthalimide on mesoporous silica for catalytic aerobic oxidation of p-xylene at atmospheric pressure.

The surface of SBA-15 mesoporous silica was modified by N-hydroxyphthalimide (NHPI) moieties acting as immobilized active species for aerobic oxidation of alkylaromatic hydrocarbons. The incorporation was carried out by four original approaches: the grafting-from and grafting-onto techniques, using the presence of surface silanols enabling the formation of particularly stable O-Si-C bonds between the silica support and the organic modifier. The strategies involving the Heck coupling led to the formation of NHPI groups separated from the SiO2 surface by a vinyl linker, while one of the developed modification paths based on the grafting of an appropriate organosilane coupling agent resulted in the active phase devoid of this structural element. The successful course of the synthesis was verified by FTIR and 1H NMR measurements. Furthermore, the formed materials were examined in terms of their chemical composition (elemental analysis, thermal analysis), structure of surface groups (13C NMR, XPS), porosity (low-temperature N2 adsorption), and tested as catalysts in the aerobic oxidation of p-xylene at atmospheric pressure. The highest conversion and selectivity to p-toluic acid were achieved using the catalyst with enhanced availability of non-hydrolyzed NHPI groups in the pore system. The catalytic stability of the material was additionally confirmed in several subsequent reaction cycles.

Spherical Lignin-Derived Activated Carbons for the Adsorption of Phenol from Aqueous Media.

In this work, a synthesis and activation path, which enabled the preparation of spherical activated carbon from a lignin precursor, characterized by high adsorption capacity in the removal of phenolic compounds from water, was successfully developed. Two industrial by-products, i.e., Kraft lignin and sodium lignosulfonate, were used to form spherical nanometric lignin grains using pH and solvent shift methods. The obtained materials became precursors to form porous activated carbons via chemical activation (using K2CO3 or ZnCl2 as activating agents) and carbonization (in the temperature range of 600-900 °C). The thermal stabilization step at 250 °C was necessary to ensure the sphericity of the grains during high-temperature heat treatment. The study investigated the influence of the type of chemical activator used, its quantity, and the method of introduction into the lignin precursor, along with the carbonization temperature, on various characteristics including morphology (examined by scanning electron microscopy), the degree of graphitization (evaluated by powder X-ray diffraction), the porosity (assessed using low-temperature N2 adsorption), and the surface composition (analyzed with X-ray photoelectron spectroscopy) of the produced carbons. Finally, the carbon materials were tested as adsorbents for removing phenol from an aqueous solution. A conspicuous impact of microporosity and a degree of graphitization on the performance of the investigated adsorbents was found.

Metal-organic frameworks@silk composites as efficient levofloxacin carriers against nosocomial infections and pathogens

This study presents a novel, biodegradable and biocompatible levofloxacin (LVX) release system based on metal-organic frameworks (MOF) and silk. The synergic effect between the silk fibroin and metal-organic frameworks not only provides the matrix for the efficient MOF distribution but, above all, builds an innovative composite material that may be used as a nanocomposite fibre building patients’ hospital clothes and healthcare employees’ uniforms against nosocomial infections and pathogens. In this study, a series of composite zirconium-based MOFs, varied in terms of the defectivity and the presence of functional groups and silk fibroin were tested in terms of LVX release kinetics, biocompatibility and biocidal activity towards all reference Gram-positive and Gram-negative bacteria. The obtained materials were characterized by using various characterization techniques including low-temperature N2 adsorption, scanning electron microscopy, optical microscopy and Fourier Transforms Infrared spectroscopies, and DFT modelling. The results indicate that the developed LVX@UiO-66 25 % HCl@SILK sponge composite material possesses high biocidal activity toward Gram-positive and Gram-negative bacteria. Additionally, in vivo experiments have indicated that developed material may be considered potentially safe for living organisms.

Mineralogical control on the dissolution induced microscopic pore alternations of high-rank coal during CO2 sequestration

The microstructure of deep coal seam plays a crucial role in determining the CO2 geological sequestrations. To investigate the effects of pore and mineral distribution on the changes and mechanisms of coal microstructure under supercritical CO2 (SC–CO2) interactions, we employed low-temperature N2 (LTN2) adsorption, low-temperature CO2 (LTCO2) adsorption, and X-ray diffraction (XRD) techniques to explore the development of microstructures and mineral compositions of coal samples with distinct pore distribution characteristics under SC-CO2 exposure. The results revealed that mineral dissolution under SC-CO2 saturation led to an increase in both specific surface area (SSA) and pore volume (PV) of mesopores, with SSA increasing by 13.6%–332.31% and PV increasing by 4.59%–148.61%. Subsequently, SC-CO2 exposure induced the formation of numerous new pores with diameters smaller than 3 nm within the coal matrix, particularly an abundance of new ultra-micropores (r > 0.5 nm) and large micropores (r > 0.85 nm). This significantly altered the irregularity of pore structure and adsorption capacity, thereby playing a crucial role in CO2 storage. Micropores exhibited much larger SSA and PV than mesopores, underscoring their significant contribution to CO2 geological sequestration. The spatial mineral distribution in coal influences the alteration characteristics of pores, which explains the different microscopic pore structures formed after SC-CO2 exposure. The impact of spatial mineral distribution on SC-CO2-induced pore alteration is analysed, emphasising the intrinsic heterogeneity of minerals within coal as the fundamental factor behind the diversity observed in pore development during CO2 sequestration. Finally, we found that the changes in micropores and mesopores under SC-CO2 exposure are closely related to the initial structure of microscopic pores. The development of micropores under SC-CO2 exposure is associated with the average pore size and fractal dimension of micropores, with the increment in mesopore irregularity increasing with the increase in micropore volume fractal dimension. By studying the influence of mineral and pore distribution on the evolution of coal microstructures, this study provides new insights into pore development under SC-CO2 geological sequestration, which can be valuable for predicting reservoir development in CO2-ECBM.

Liquid-phase adsorption of nitrogen compounds from model diesel fuel on activated carbons

One of the great challenges in deep hydrodesulfurization (HDS) to produce ultra-low-sulfur diesel (ULSD) is the coexisting heterocyclic nitrogen-containing compounds in middle distillates, which significantly inhibit the HDS reactions. This study investigates various activated carbon (AC) samples for selectively removing nitrogen compounds from a model diesel fuel through adsorption. The physical and chemical properties of the AC samples were characterized using low-temperature N2 adsorption–desorption, SEM–EDS, and FT-IR to explore their impact on the adsorption performance. The results indicate that the adsorption performance is influenced not only by the surface area and by the number of oxygen-containing functional groups on the surface but also by the pore diameter distribution. Among all AC samples tested, AC-W exhibited the highest adsorption capacity, achieving a nitrogen removal rate of 97.8% with the addition of 10 wt.% of AC-W. The adsorption capacity was approximately 24.0 mg-N/g-A at a nitrogen equilibrium concentration of 200 ppmw. The adsorption isotherms for total nitrogen and individual nitrogen compounds in the fuel over AC can be described well by the Freundlich isotherm model. An approach for improving the ADN performance of AC is discussed based on the findings in this study.

Reformation of coal reservoirs by microorganisms and its significance in CBM exploitation

The study investigates the variations in surface morphology and micro-nano-scale pore structure of coal matrix during the process of biodegradation. Comprehensive reservoir characterization techniques, including field emission scanning electron microscope, mercury intrusion porosimetry, and low-temperature N2 adsorption, are employed on four anthracite samples. The significance of the relationship between coal reservoir bio-reformation and coalbed methane (CBM) exploitation is proposed. The main findings indicate that organic matter on the surface of the coal matrix can undergo biodegradation, resulting in the generation of new pores. Microbial metabolism does not alter pore type but only modifies pore size and volume of coal. After microbial degradation, there is an increase in average pore width, while both Brunauer-Emmett-Teller specific surface area and Barrett-Joyner-Halenda pore volume decrease. Furthermore, bioconversion leads to a reduction in both surface and volume dimensions of coal, resulting in a smoother coal matrix surface and simplified complexity of its pore structure. This benefits desorption, migration, and exploitation of CBM. These findings further reinforce the pivotal role of microbial-enhanced coalbed methane production technology in improving CBM production and promoting the clean utilization of coal resources.

Cordierite-Supported Transition-Metal-Oxide-Based Catalysts for Ozone Decomposition

Cordierite-based supported noble-metal-free catalysts for ozone decomposition are elaborated. The cordierite ceramic surface is pretreated with oxalic acid and NaOH, and Mn-Cu-Ni oxide catalysts are prepared by the impregnation method. The mass ratio of the supported oxides in the resulting catalysts is MnO2:CuO:NiO = 3:2:1, and their loadings are from 1.8 to 7.0 wt.%. The pretreated supports and catalysts are characterized by low-temperature N2 adsorption, scanning electron microscopy (SEM), powder X-ray diffraction analysis (XRD), and temperature-programmed reduction with H2 (TPR-H2). The catalysts are tested in ozone decomposition with high airflow rates (20 and 50 L/min) and with initial ozone concentrations of 1 and 2 ppm at temperatures in the range of 25–120 °C. It is shown that a combined treatment of cordierite with oxalic acid and NaOH leads to a developed porous structure and stabilization of supported Mn-Cu-Ni oxides in a highly dispersed state. The high activity of catalysts in ozone decomposition at room temperature and high airflow is demonstrated. The developed catalysts can be recommended for application in purification of air from the ozone because of their high catalytic activity, high mechanical stability, and relatively low weight and cost.

Greenhouse Gas Conversion into Hydrocarbons and Oxygenates Using Low Temperature Barrier Discharge Plasma Combined with Zeolite Catalysts

Global warming occurs as a result of the build-up of greenhouse gases in the atmosphere, causing an increase in Earth’s average temperature. Two major greenhouse gases (CH4 and CO2) can be simultaneously converted into value-added chemicals and fuels thereby decreasing their negative impact on the climate. In the present work, we used a plasma-catalytic approach for the conversion of methane and carbon dioxide into syngas, hydrocarbons, and oxygenates. For this purpose, CuCe zeolite-containing catalysts were prepared and characterized (low-temperature N2 adsorption, XRF, XRD, CO2-TPD, NH3-TPD, TPR). The process of carbon dioxide methane reforming was conducted in a dielectric barrier discharge under atmospheric pressure and at low temperature (under 120 °C). It was found that under the studied conditions, the major byproducts of CH4 reforming are CO, H2, and C2H6 with the additional formation of methanol and acetone. The application of a ZSM-12 based catalyst was beneficial as the CH4 conversion increased and the total concentration of liquid products was the highest, which is related to the acidic properties of the catalyst.

Gas production decline trends for Longmaxi shale under thermally stimulated conditions

Recently, thermal treatment has emerged as a promising technology to enhance shale gas recovery efficiency by promoting gas desorption. However, the understanding of gas desorption characteristics from heterogeneous shale matrix under thermal stimulation remains inadequate, which constrains the development of thermal recovery technology. In this study, on-site canister desorption tests were employed to investigate the shale gas desorption patterns of four distinct shale cores, sourced from four various production zones, under two heating stages (50 °C and 110 °C). Additionally, low-temperature N2 adsorption experiments and infrared examination were used to study the microstructure characteristics of shale before and after thermal treatments. The canister desorption tests revealed that the gas production rates increased for all shales under heating conditions, particularly when transitioning from 50 °C to 110 °C. However, the peak gas production rates at the two heating stages exhibited different trends: nearly identical for Shale-1 and Shale-2, decreasing for Shale-3 and increasing for Shale-4. This can be attributed to the different quantities of adsorbed gas present in shale samples, with Shale-4 containing approximately 0.0088 m3, compared to the markedly lower volumes in Shale-1 (0.0053 m3), Shale-2 (0.0040 m3), and Shale-3 (0.0041 m3). Furthermore, the gas production rates followed distinct decline trends at different temperatures: exponentially at 50 °C and following a power law at 110 °C, indicating varying gas desorption dynamics under different thermal conditions. Moreover, the findings from low-temperature N2 adsorption experiments and infrared examination indicated that combustion increased the pore volume and induced thermal cracks and fractures, thereby enhancing shale permeability. These insights highlight the potential of combustion fracturing as a technology to improve gas recovery efficiency.

Effect of TiO2 on Pd/La2O3-CeO2-Al2O3 Systems during Catalytic Oxidation of Methane in the Presence of H2O and SO2.

New results on the effect of TiO2 on Pd/La2O3-CeO2-Al2O3 systems for catalytic oxidation of methane in the presence of H2O and SO2 have been received. Low-temperature N2-adsorption, XRD, SEM, HRTEM, XPS, EPR and FTIR techniques were used to characterize the catalyst. The presence of Ce3+ on the catalytic surface and in the volume near the lantana was revealed by EPR and XPS. After aging, the following changes are observed: (i) agglomeration of the Pd-clusters (from 8 nm to 12 nm); (ii) transformation of part of the TiO2 from anatase to larger particles of rutile; and (iii)-the increase in PdO/Pd-ratio above its optimum. The modification by Ti of the La2O3-CeO2-Al2O3 system leads to higher resistance towards the presence of SO2 most likely due to the prevailing formation of unstable surface sulfites instead of thermally stable sulfates. Based on kinetic model calculations, the reaction pathway over the Pd/La2O3-CeO2-TiO2-Al2O3 catalyst follows the Mars-van Krevelen mechanism. For evaluation of the possible practical application of the obtained material, a sample of Pd/La2O3-CeO2-TiO2-Al2O3, supported on rolled aluminum-containing stainless steel (Aluchrom VDM®), was prepared and tested. Methane oxidation in an industrial-scale monolithic reactor was simulated using a two-dimensional heterogeneous reactor model.

Effect of Pore Size Distribution on Energy Storage of Nanoporous Carbon Materials in Neat and Dilute Ionic Liquid Electrolytes.

This study investigates three carbide-derived carbon (CDC) materials (TiC, NbC, and Mo2C) characterized by uni-, bi-, and tri-modal pore sizes, respectively, for energy storage in both neat and acetonitrile-diluted 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. A distribution of micro- and mesopores was studied through low-temperature N2 and CO2 adsorption. To elucidate the relationships between porosity and the electrochemical properties of carbon materials, cyclic voltammetry, galvanostatic cycling, and electrochemical impedance spectroscopy measurements were conducted using three-electrode test cells. The ultramicroporous TiC-derived carbon is characterized by a high packing density of 0.85 g cm-3, resulting in superior cathodic and anodic capacitances for both neat ionic liquid (IL) and a 1.9 M IL/acetonitrile electrolyte (93.6 and 75.8 F cm-3, respectively, in the dilute IL). However, the bi-modal pore-sized microporous NbC-derived carbon, with slightly lower cathodic and anodic capacitances (i.e., 85.0 and 73.7 F cm-3 in the dilute IL, respectively), has a lower pore resistance, making it more suitable for real-world applications. A symmetric two-electrode capacitor incorporating microporous CDC-NbC electrodes revealed an acceptable cycle life. After 10,000 cycles, the cell retained approximately 75% of its original capacitance, while the equivalent series resistance (ESR) only increased by 13%.

Nanopore Structure and Multifractal Characteristics of Continental Shale Oil Reservoir: A Case Study from Ziliujing Shales in the Sichuan Basin

Thermal maturity of the shales from the Ziliujing Formation of the Jurassic age in the Sichuan Basin is in the hydrocarbon generation window, which makes it a candidate for shale oil and gas development. The meso- and macropore characteristics and heterogeneity of shales are important factors affecting the occurrence and development of oil and gas. However, the meso- and macropores of the Ziliujing shales have not been systematically studied. Thus, the mineral compositions and total organic carbon (TOC) of samples from this formation, as well as its pore structure, are analyzed by low-temperature N2 adsorption technique. Moreover, the heterogeneity of the pores was determined by multifractal analysis. The results show that the Ziliujing shales can be classified into three types according to the distributions of mineral compositions of carbonate and mixed and argillaceous shales. Results revealed that the smallest meso- and macropore volume (PV), the smallest specific surface area (SSA), and the largest average pore diameter (APD) occur in the carbonate shales. However, the largest PV and SSA and the smallest APD are observed in the argillaceous shales. The porosity of carbonate shales is mainly concentrated between 5 nm and 30 nm. Compared with carbonate shales, the porosity with pore sizes less than 30 nm of mixed and argillaceous shales shows a rapid increase. Furthermore, inorganic minerals are the main factors affecting the pore distributions, while TOC shows a weak effect. Herein, clay minerals significantly increase the mesopore volume and the pore number with a size of less than 30 nm. The Dq-q curves reveal that the meso- and macropore distributions of Ziliujing shales show multifractal behavior, but the multifractal characteristics of pores of various shales are distinctly different. The information dimension D1, the Hurst exponent H, and the width of the right side D0–D10 are key indicators to distinguish the local variations within the pore structure of different types of shales. The carbonate shales have the largest multifractal spectra width and the smallest D1 and H, while the opposite trend is found for the argillaceous shales. Clay minerals reduce the heterogeneity of the meso- and macropore distributions and increase the pore connectivity. Nevertheless, the carbonate minerals exhibit a reverse trend. Finally, it was found that TOC does not impact pore complexity as much. Collectively, this study supports our understanding of the occurrence of shale oil within various reservoir facies, thereby providing a guideline for future explorations in the Ziliujing Formation of the Jurassic age in the Sichuan Basin.

Silica-titania mesoporous silicas of MCM-41 type as effective catalysts and photocatalysts for selective oxidation of diphenyl sulfide by H2O2

Abstract Spherical Ti-MCM-41, synthetized by co-condensation method, presented very promising activity in catalytic and photocatalytic oxidation of diphenyl sulfide with H2O2 to obtain diphenyl sulfoxide and diphenyl sulfone. Mesoporous silica materials with various titanium content were analyzed with respect to chemical composition (inductively coupled plasma optical emission spectrometry), structure properties (X-ray diffraction), textural properties (low-temperature N2 adsorption–desorption), morphology (scanning electron microscopy), forms and aggregation introduced titanium species (diffuse reflectance spectroscopy, Raman spectroscopy), and surface acidity (NH3-TPD). Titanium introduced in the samples was present mainly in the form of highly dispersed species, presenting catalytic and photocatalytic activities in diphenyl sulfide oxidation with H2O2. Efficiency of the reaction increased with an increase in titanium loading in the samples and was significantly intensified under UV irradiation. The role of various Ti species in diphenyl sulfide oxidation was presented and discussed.

Influence of supercritical CO2 on fracture network evolution with nanopore structure linkage in high-rank anthracite matrix

It is essential to understand the permeability evolution of coal reservoirs under the interaction of supercritical CO2 (SC-CO2) in order to be successful in both CO2 geological storage and extraction of coalbed methane. However, the influence of nanopore structure characteristics on the permeability evolution of coal exposed to SC-CO2 has not been elucidated. To this end, the quantitative analysis of the pores in high-rank coal was conducted through low-temperature N2 adsorption, low-temperature CO2 adsorption, and Nuclear Magnetic Resonance (NMR). The analysis revealed that micropores and mesopores are the major contributors to the specific surface area and pore volume of the nanopores, respectively. After SC-CO2 interaction, the pore size and pore number of the coal increased significantly, with small pores changing to large ones, mainly due to the dissolution of SC-CO2 with the contribution of gas pressure being negligible. The proportion of micropore and mesopore decreases while that of macropore increases after SC-CO2 treatment, especially SC-CO2 causes macropores to be continuous and increased the connectivity of fractures. The relationship between nanopore structure characteristics and the deformation of the fracture network under SC-CO2 interaction was studied. The results showed that the specific surface area (SSA) of the micropore and the volume fractal dimension (DLN2) of the mesopore were related to the change of fracture porosity, while the surface fractal dimension (DLN1) of the micropore, the specific surface area (SSA) and pore volume of mesopore were related to the change of fracture complexity. This indicated that the evolution of the fracture network under SC-CO2 interaction is related to the nanopore structure characteristics. A mechanical model was established based on the close correlation between nanopore structures characteristics in the matrix and the evolution of fracture networks under SC-CO2 interaction. This mechanical model elucidates the impact of nanopore alteration resulting from mineral dissolution induced by SC-CO2 on the evolution of fracture networks. This research provides a clearer understanding of the evolution in reservoir permeability during CO2 geological sequestration, offering valuable reference for safety assessments.