Decrease In Specific Surface Area Research Articles

Deactivation mechanism of NiWS/SAPO-11 catalyst in hydroisomerization of n-hexadecane: Insights into coke deposition behavior and active phase migration

The application of non-noble metal supported catalysts in the hydroisomerization of long-chain n-alkanes is a novel field, and there is currently not any research available on the deactivation process of these catalysts. We investigated into the deactivation mechanism of NiWS/SAPO-11 catalyst in the hydroisomerization of n-hexadecane in this work for the first time. Specifically, coke deposition behavior and active phase migration were investigated. The reduction of catalytic efficiency of the catalyst was partially aided by the decrease in specific surface area, pore volume, and acid density. From the perspective of the active phase, the clusters of NiWS active phase migrated as the reaction time increased, mostly resulting in an increase in both the stacking number and the length of active phase slabs. The migration of active phase increased the distance between active phase clusters and metal sites, and decreased the utilization ratio of active metal atoms. From the perspective of coke deposition, the coke formed on the catalyst includes soft coke and hard coke. The formation and evolution of coke on the catalyst were investigated. The soft coke (aliphatic compounds) progressively transformed into hard coke (polycyclic aromatic hydrocarbons and graphite-like), and the coke gradually migrated from the external surface of the catalyst to the pore channels as the reaction time increased. It is expected to provide theoretical basis and reference value for the deactivation research and design of non-noble metal supported hydroisomerization catalyst.

Capturing low-concentration benzene: Design and mechanism of high-performance Cu1-Ox,Ny-C single-atom adsorbents

Common adsorbents, such as active carbons, zeolites, and metal–organic frameworks (MOFs), struggle to capture low concentrations of benzene. Single-atom adsorbents (SAAs), boasting exceptional atomic utilization efficiency and precisely tailored electronic structures, offer a promising solution. This study first designed Cu1-Ox,Ny-C SAAs and explored their enhanced benzene adsorption through density functional theory (DFT). Particularly, a crucial link between the SA coordination configuration and its affinity for benzene was established. Next, Cu1-Ox,Ny-C was synthesized from the MOF MIL-101(Cr) and extensively characterized using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure (XAFS) spectroscopy, etc. to determine the coordination configuration of Cu single atoms. Finally, a thorough evaluation of the Cu1-Ox,Ny-C’ capacity and stability was conducted. Theoretical analysis revealed that Cu single atoms within the Ox,Ny-C matrix act as the primary adsorption sites for benzene. Notably, O and N atoms work synergistically: oxygen atoms promote adsorption, while nitrogen atoms mainly stabilize single-atom sites. Cu1-Ox,Ny-C was successfully synthesized, and characterization revealed that Cu1-O2,N2(trans)-C and Cu1-O3,N1-C were the dominant coordination configurations. Remarkably, despite a fourfold decrease in specific surface area compared to MIL-101(Cr), Cu1-Ox,Ny-C exhibited a threefold increase in chemisorption capacity for low-concentration benzene. Moreover, it exhibits excellent resistance to H2O and can be effectively reused. This study demonstrates a valuable strategy for designing and creating highly efficient SAAs for capturing low concentrations of benzene.

Structural modification of CNT-C xerogel through synthesis parameters

This study focuses on the synthesis of porous carbonaceous structures by drying resorcinol-formaldehyde (RF) gels under ambient conditions and then carbonizing them in an inert atmosphere. This avoids the expensive drying processes like supercritical drying or freeze drying. However, drying under ambient conditions does cause structural shrinkage and a reduction in porosity and specific surface area. Therefore, the goal of this study was to compensate for these structural degradations by adjusting other synthesis and process parameters, such as solvent exchange, drying condition, content of water, catalyst, and CNT in the gel. In the present study, different organic solvents such as t-butanol, ethanol, and acetone were used to replace the water in the hydrogels at a certain R/F molar ratio (1:2). The experimental results showed that t-butanol, with its low surface tension, resulted in a structure with a high specific surface area and pore volume. Regarding the catalyst dosage, by changing the R/C molar ratio between 71 and 849, the best structural properties were obtained using R/C∼200. Increasing the water content from 15 to 30 mL led to a decrease in specific surface area and pore volume. Drying the gel at an oven temperature of 85 °C resulted in the highest specific surface area, pore volume, and mean pore diameter. Increasing the dosage of carbon nanotubes (CNTs) in the range of 20–150 mg led to an increase in total pore volume and mean pore diameter. The results of this work can be a step forward towards the industrialization of these materials in various applications.

Catalytic transfer hydrogenation with methanol over Pt/C catalyst for synergistic hydrothermal hydrogenation of palmitic acid

Achieving hydrothermal hydrogenation and deoxygenation of bio-oil with high water content such as microalgae-based bio-oil still faces significant challenges. Traditional upgrading processes require a large amount of H2. The objective of current research uses methanol and formic acid as a hydrogen donor to achieve the hydrothermal hydrodeoxygenation of palmitic acid (a model of microalgae-based bio-oil) to prepare pentadecane over Pt/C catalyst without the need for additional H2 supply. The research findings have shown that the H2 supply mechanism of methanol and formic acid in synergy with palmitic acid hydrothermal hydrodeoxygenation is obviously different. Formic acid is directly decomposed to produce H2, while methanol undergoes aqueous steam reforming to produce H2 in synergy with palmitic acid hydrodeoxygenation. More importantly, methyl palmitate, a typical model compound of the first-generation biodiesel, achieved efficient deoxygenation without the addition of H2 and hydrogen donors. At 300 °C, the yield of pentadecane reached 91.25 % within 150 min. The hydrothermal stability test shows that the decrease in Pt content and specific surface area (SBET), as well as the destruction of pore structure, are the main reasons for the decrease in activity of the Pt/C catalyst after cycling. The H2 production efficiency of hydrogen donors possesses a significant impact on the hydrodeoxygenation of palmitic acid and therefore more efficient catalysts need to be developed.

Solidification and leaching behaviours of heavy metal Pb in MSW incineration fly ash and its thermal stability at various thermal treatment temperatures

The fly ash generated by municipal solid waste (MSW) incineration contains heavy metals, which pose a significant environmental threat. Thermal treatment emerges as a potential technique for reducing and detoxifying MSW incineration fly ash, but the optimal thermal treatment temperature remains unclear. This study explores the thermal stability of MSW incineration fly ash under various thermal treatment temperatures (1000 °C − 1500 °C). Additionally, the solidification and leaching behaviors of heavy metal Pb were investigated. The results revealed distinctive trends: the mass residual rate showed the fastest decline between 1200 °C and 1273 °C, while the volume residual rate showed the fastest decline between 1100 °C and 1200 °C. The solidification rate of heavy metal Pb decreased as the treatment temperature increased. With the decrease of specific surface area, the leaching rate of heavy metal Pb exhibited a gradual decline, but it sharply surged at the fluid temperature. This was because the encapsulation effect of Pb by calcium silicate iron manganese complex was weakened and an increase in kinds of Pb oxides(Pb2O3, Pb3O4) that can react with glacial acetic acid in the leachate. Thus, it was not advisable to treat the MSW incineration fly ash around the fluid temperature. The optimal thermal treatment temperature was suggested to be 1200 °C, as it achieves goals such as volume reduction, detoxification and low energy consumption. These provide useful theoretical guidelines for the thermal treatment of MSW incineration fly ash.

Reignition characteristics of lignite affected by pre-oxidation and liquid nitrogen cold soaking

The propensity of residual oxidized coal to be reignited within enclosed fire areas in coal mines under liquid nitrogen (LN2) cold soaking remains unclear. Therefore, scanning electron microscopy (SEM), low-temperature nitrogen adsorption (LTNA), and thermogravimetric (TG) experiments were conducted to characterize the pore structure and secondary oxidation of oxidized cold-soaked coal. The results indicate that pre-oxidation or cold soaking alone can promote the generation and merging of pores and make the pore structure more complex, especially when pre-oxidized. However, pore evolution is suppressed and then improves when lignite is simultaneously subjected to pre-oxidation and cold soaking. In particular, the macropore volume and specific surface area decrease and then increase. The cryogenic shrinking of the LN2 results in the collapse of the loose coal matrix, which subsequently blocks the macropores. In contrast, vaporization expansion enhances pore connectivity with continuous LN2 injections, transforming mesopores into macropores, especially in the pore ranges of 2–5 nm and >50 nm. Additionally, pre-oxidation or cold soaking alone improves the oxidizing activity and combustion performance of raw coal. However, continuous cold soaking initially increases and subsequently decreases the characteristic temperatures and activation energy of oxidized coal. Oxidization at 200 °C with one cold soaking can further lower reignition propensity. The average activation energy of oxidized coal decreases by 22.9%–29 % when soaked more than three times. The improvement in combustion property is closely related to the increasing number of macropores because a larger pore volume and specific surface area are conducive to oxygen diffusion and adsorption. Therefore, pre-oxidation and cold soaking promote and inhibit the reignition of coal when performed simultaneously. These results provide theoretical guidance for rational liquid-nitrogen injection to control coal fires.

Hydrogen-rich syngas upgrading via CO2 adsorption by amine-functionalized Cu-BTC: the effect of different amines.

Syngas produced from supercritical water gasification typically contain a high amount of CO2 along with H2. In order to improve the quality of syngas, amine-functionalized copper benzene-1,3,5-tricarboxylate (Cu-BTC) was synthesized as an effective adsorbent for selective removal of CO2 from syngas to increase the concentration of H2. The amines used in this study included monoethanolamine (MEA), ethylenediamine (EDA), and polyethyleneimine (PEI). The fundamental physicochemical character of adsorbents, CO2 adsorption capacity, and CO2/H2 selectivity were analyzed. The physicochemical characterization indicated that the structure of amine-functionalized Cu-BTC was partially damaged, which resulted in a decrease in specific surface area and pore volume. On the other hand, the enlarged pore size was beneficial for the mass transfer of gas in the adsorbent. Among these adsorbents, Cu-BTC/PEI exhibited the maximum CO2 adsorption capacity of 3.83mmol/g and the highest CO2/H2 selectivity of 19.74. It was found that the adsorption pressure is the most significant factor for the CO2 adsorption capacity. Lower temperature and higher pressure were favored for CO2 adsorption capacity and CO2/H2 selectivity, so physical adsorption by Cu-BTC played a dominant role. Moreover, Cu-BTC/PEI can be well-regenerated with stable adsorption efficiency after five consecutive cycles. These findings suggested that Cu-BTC/PEI could be a promising alternative adsorbent for CO2 capture from syngas.

STUDY OF CATALYTIC BEHAVIOURS OF THE SPINEL STRUCTURE NdxMg1- xAl2O4 COMPOSITION WITH ZSM-5 ZEOLITE IN ETHYLBENZENE DISPROPORTIONATION

Nanosized (10–15 nm) powders of spinel structures NdxMg1–xAl2O4 were obtained by low-temperature combustion of aluminium, magnesium, neodymium nitrate solutions, diethylmalonate, and hydrazine monohydrate with further calcination of nanopowders at 1000 °C, which were used in the preparation of catalytic compositions with ZSM-5 zeolite. The obtained catalytic compositions were characterized by X-ray diffraction, pyridine adsorption, and low-temperature nitrogen adsorption. The acidic properties and porosity of the catalysts were altered by controlling the concentration of nanopowder (1.0–7.0 wt.%) in the catalytic composition. The interaction of the modifier with HZSM-5 zeolite leads to a decrease in specific surface area and pore volume, as well as reduse of strong Bronsted acid sites (B) and an increase in the concentration of medium Lewis acid sites (L), resulting in a change in the B/L ratio from 3.61 to 0.23. The ongoing variations contributed mainly to an enhancement of the para-selectivity of the catalytic composition in the ethylbenzene disproportionation reaction. The catalytic composition of 5% Nd0.1Mg0.9Al2O4 with a pore volume of 0.15 cm3/g and an acid site B/L ratio of 0.27 demonstrates a maximum selectivity to p-diethylbenzene of 75.6% with a conversion of ethylbenzene of 23.7%.

The Removal of Phosphorus from Wastewater Using a Sewage Sludge Biochar: A Column Study

This scientific study investigated the adsorption capabilities of biochar samples derived from municipal sewage sludge pellets. Sewage sludge was pyrolyzed at various temperatures (400, 500, and 600 °C), and the biochar’s properties, including specific surface area, pore volume, and pore size distribution, were assessed. The results indicate that the sewage sludge biochar samples are mesoporous materials with significant potential for good adsorption performance. Despite showing a decrease in specific surface area compared to that achieved with pyrolysis at 400 °C, samples pyrolyzed at 600 °C demonstrated an increase in mesopore surface area, enhancing their adsorption potential. Two filtration experiments, conducted at a flow rate of 8 mL/min, revealed that the column containing sewage sludge pyrolyzed at 600 °C retained phosphorus the most effectively during the first and second experiments (with retention efficiencies of 87% and 78%, respectively). The study concludes that municipal sewage sludge biochar could be a promising material for the removal of phosphorus from wastewater and represents a viable solution for sustainable environmental development.

Quantitative sulfur poisoning of nanocrystal PtO2/KL-NY and its deactivation mechanism for benzene catalytic oxidation

The present study involved the synthesis of a kaolin-based NaY zeolite (KL-NY) supported nanocrystal PtO2 (5–10 nm) catalyst, which exhibited complete benzene conversion at 195 °C. However, a certain amount of sulfur species led to severe deactivation of the catalyst. This deactivation was mainly caused by the reduction of active lattice oxygen. XPS, H2-TPR and HRTEM results confirmed that adsorbed sulfur species competitively consumed active lattice oxygen, resulting in a transition of partial PtO2 to PtO. Generated PtO cannot actively participate in the oxidation reaction due to its weaker oxidation property, indicating a decrease of active species induced by sulfur poisoning. Furthermore, Al2O3 outside the KL-NY framework can adsorb sulfur species and form Al2(SO4)3, leading to an increase in acid sites. Due to the weak acid-tolerance of KL-NY, partial porous structure destruction occurred with a decrease in specific surface area and pore volume, thereby negatively impacting catalyst performance.

Enhancing interfacial synergies for the preparation of high mechanical strength and interconnected porosity of alumina extrudates through pre-wetting method

The forming of catalyst supports is a crucial step in the application of industrial catalysts. Alumina, a widely employed catalyst support, is often shaped using nitric acid as a peptizer to enhance mechanical strength. However, the use of large amounts of nitric acid typically results in a decrease in specific surface area and damage to the pore structure due to chemical corrosion. In this work, we present a more practical approach that is pre-filling the open pores of pseudo-boehmite powder with water instead of directly filling them with nitric acid solution. The binder with a small quantity of nitric acid plays a synergistic role in functioning as a glue on the particle surfaces. And through this method, high-strength (231 N cm−1) alumina support can be prepared more efficiently through extrusion. Besides, the pore structure of the extrudates was characterized by multi-scale methods, including nitrogen physical sorption and XRM (X-ray microscopy), which revealed abundant interconnected hierarchical pores deriving from the pre-wetting shaping process. This proposed approach enables the attainment of high mechanical strength and interconnected porosity for alumina extrudates with less use of acid, which holds a significant practical application value.

Removal of COD from petroleum refinery wastewater by adsorption using activated carbon derived from avocado plant

In the present work, removing of COD from wastewater generated via Al-Diwanya petroleum refinery plant located in Iraq by adsorption with activated carbon (AC) derived from avocado seeds was successfully performed via a two-step approach. In the first step, AC was prepared from avocado seeds via impregnating with H3PO4 at 400 °C where effects of H3PO4 concentration and calcination time on the specific surface area of AC were studied. Additionally, properties of the prepared AC were examined by XRD, SEM, and FTIR to knowledge the features of the internal structure of AC. Results showed that the prepared AC has mesopores structure with pore diameters in the range between 30.07 and 50.8 µm. Increasing the weight percent of H3PO4 led to an increase in the specific surface area of AC to reach a maximum value beyond which a decrease in the specific surface area was happened with further increasing in H3PO4 percent. Increasing the time resulted in an increase in the AC specific surface area to reach a maximum value beyond which a decrease in specific surface area was happened. The best value of AC specific surface area was 436.6 m2/g which obtained at 70 %H3PO4 and 4 h. At the second step, the performance of the prepared AC in removing of COD by adsorption process was evaluated via studying the effects of three operating parameters, namely adsorbent dosage (1–5 g/L), pH (3–9), and shaking speed (100–400 rpm) on the removal of COD(RE%) using a response surface methodology (RSM). Increasing AC dosage led to an increase in RE% while increasing each of pH and shaking speed resulted in lowering RE%. The optimum conditions for higher RE% were AC dosage of 5 g/L, pH of 3, and shaking speed of 100 rpm in which a removal efficiency of 94.54 % was obtained. The degradation of COD with time was found to obey a second order kinetic confirming the chemisorption is the rate limiting step in the adsorption process.

Effect of PAM on Surface Hydrophobicity of Montmorillonite and Difference of Interface Adsorption: An Experimental and Simulation Study.

How to realize efficient treatment of coal slime generated by a coal washing operation is an urgent problem to be solved in this industry. The presence of clay minerals, especially highly hydrophilic montmorillonite (MMT), is the key to the poor treatment effect of coal slime. Polyacrylamide (PAM) is very popular as a polymer agent to improve the treatment of coal slime. However, when it is used to treat coal slime with a high content of MMT, the selection of PAM type and the mechanism of action are still lacking. In this study, the effects of different types of PAM on the treatment of coal slime water containing MMT are considered by sedimentation and press filtration tests. The interaction mechanism of PAM on the MMT surface is studied by using ζ-potential, Brunauer-Emmett-Teller (BET) analysis, low-field nuclear magnetic resonance, density functional theory (DFT), and molecular dynamics (MD) simulations. The results show that the three PAM can improve the sedimentation and filtration effect of coal slime water, and the performance is CPAM > NPAM > APAM. The ζ-potential of the MMT (001) surface increases under the action of three PAM, and the effect of CPAM is the most significant. The adsorption of PAM on the MMT (001) surface has the ability to neutralize the surface charge of MMT. The flocculation of MMT particles under PAM results in an increase of particle size and a decrease of specific surface area. Meanwhile, the pore volume of MMT decreases, and the average pore size increases. In addition, PAM mainly removes vicinal water on the MMT surface. The active sites of the MMT surface and PAM are calculated by DFT. The adsorption of three PAM structural units on the MMT Na-001 surface and non-001 surface is nonbonding interaction, and the adsorption energy of CPAM is the largest. And the left shift of εp of the O atom on the MMT surface is conducive to the stable adsorption of CPAM. The MD results show that the concentration of water molecules on the surface of MMT Na-001 decreases after PAM is adsorbed on the MMT Na-001 surface, indicating that PAM can keep water molecules away from the surface of MMT, which means that the hydrophobicity of the MMT surface is enhanced. This study has guiding significance for the selection of PAM and the development of new flocculants in the treatment of coal slime with a high content of MMT.

Application of Infrared Pyrolysis and Chemical Post-Activation in the Conversion of Polyethylene Terephthalate Waste into Porous Carbons for Water Purification.

In this study, we compared the conversion of polyethylene terephthalate (PET) into porous carbons for water purification using pyrolysis and post-activation with KOH. Pyrolysis was conducted at 400-850 °C, followed by KOH activation at 850 °C for samples pyrolyzed at 400, 650, and 850 °C. Both pyrolyzed and post-activated carbons showed high specific surface areas, up to 504.2 and 617.7 m2 g-1, respectively. As the pyrolysis temperature increases, the crystallite size of the graphite phase rises simultaneously with a decrease in specific surface area. This phenomenon significantly influences the final specific surface area values of the activated samples. Despite their relatively high specific surface areas, pyrolyzed PET-derived carbons prove unsuitable as adsorbents for purifying aqueous media from methylene blue dye. A sample pyrolyzed at 650 °C, with a surface area of 504.2 m2 g-1, exhibited a maximum adsorption value of only 20.4 mg g-1. We propose that the pyrolyzed samples have a surface coating of amorphous carbon poor in oxygen groups, impeding the diffusion of dye molecules. Conversely, post-activated samples emerge as promising adsorbents, exhibiting a maximum adsorption capacity of up to 127.7 mg g-1. This suggests their potential for efficient dye removal in water purification applications.

Towards a low-cost solid oxide electrolyte based on local mineral

The demand for critical minerals is showing significant growth as a response to various applications in energy transition devices such as those involving solid oxide electrolytes. Thus, in the present work a dense and conductor material was prepared following appropriate sintering of a low-cost local natural mineral (NM). Comprehensive morphological, textural, and microstructural characterizations were carried out in order to study the densification of NM samples shaped as thin layers obtained by casting method using polyethylene oxide (PEO) as a plasticizer and distilled water. It was found that sintering at 1000 °C was enough to achieve densification without any change of material structure, as indicated by significant decrease of specific surface area and porosity. Furthermore, the effect of temperature on electrical conductivity was measured by impedance spectroscopy (IS) under dry air by increasing temperatures and total conductivity value at about 8.48 × 10−2 S cm−1 was reached at 950 °C. Such promising intrinsic electrical conductivity, in addition to appropriate material densification, paves the way for possible application of such an available and low-cost natural minerals as solid oxide electrolyte.

Sulfur-tolerant mechanism in catalytic combustion of toluene over Co/5Mg-γ-Al2O3 catalyst: Dual functions of MgO

Using toluene catalytic combustion as a probe reaction, simulating quantitative sulfur poisoning by in situ thermal decomposition of ammonium sulfate solution, the study used MgO modified γ-Al2O3 to support cobalt-based catalyst, and the result displayed that the catalyst exhibited excellent sulfur poisoning resistance. The successful construction of MgO-Al2O3 heterogeneous interface weakened the interaction between Co and Al and reduced the production of inactive CoAl2O4. Besides that, it fixed sulfur species and formed MgSO4 to protect active components. The dual function of MgO have been proved by various characterization experiments. The modification of γ-Al2O3 by the appropriate amount of MgO could improve the catalytic activity of Co/γ-Al2O3. Meanwhile, T100 increased from 300 °C to 330 °C after 1.6 wt% sulfur poisoning and we concluded that the decrease in catalytic performance was not caused by the loss of active Co, but by the decrease of specific surface area and lattice oxygen activity.

Reducing rare earth loss by adding acetic acid in the aluminum removal process of rare earth leaching solution

The ionic-type rare earth ore, abundant in medium and heavy rare earth elements, is a strategic mineral resource. The removal of aluminum from ionic rare earth leaching solution results in over 8% loss of rare earths. Preliminary research has found that adding acetic acid (HAc) during aluminum removal process can effectively reduce the loss of rare earth elements. In this paper, through the calculation of the species distribution in the La2(SO4)3-Al2(SO4)3-HAc-H2O system, it is found that HAc forms an AlOH-Ac+ complex with aluminum ions, with a proportion of up to 70%, which will increase the initial precipitation pH of aluminum hydroxide. Furthermore, HAc and lanthanum form a LaAc2+ complex, and the proportion can reach more than 20%. Moreover, the zeta potential, FT-IR, and XPS tests of aluminum hydroxide, obtained by neutralization precipitation, revealed that the complexation of HAc and aluminum can reduce the precipitation rate of aluminum hydroxide, so that its particle size increases, the specific surface area decreases, and the van der Waals force adsorption sites are reduced. HAc can be chemically adsorbed on aluminum hydroxide, thereby increasing the zeta potential of aluminum hydroxide and ultimately reducing its electrostatic adsorption effect on rare earths. Additionally, the complexation of HAc and rare earth elements can reduce the local supersaturation of rare earth hydroxides and decline the coprecipitation of rare earth elements. Finally, under a precipitation endpoint pH of 5.2, HAc concentration of 0.006 mol/L, aluminum concentration of 0.2 g/L, rare earth concentration of 0.8 g/L, magnesium ion concentration of 0.5 g/L and magnesium oxide slurry concentration of 0.45 mol/L, the aluminum removal efficiency obtained with rare earth leaching solution reached 98.47%, and the rare earth loss efficiency was 2.62%. Compared with the control, the rare earth loss efficiency was reduced by 5.59%. This paper provides guidance for the efficient and green development of ionic-type rare earth ore.

Reactivity of kaolinitic clays calcined in the 650 °C–1050 °C temperature range: Towards a robust assessment of overcalcination

Using calcined clays as supplementary cementitious materials is one of the main solutions available for a substantial and widespread reduction of the clinker factor in cement. Thus, understanding the phenomena governing their production process and reactivity is crucial for a successful technological deployment. In this study, the mineralogical and physical changes experienced by kaolinitic clays calcined within 650 and 1050 °C were explored, with emphasis on the identification of overcalcination. It was observed that the decrease in reactivity above the optimum calcination temperature is associated with the formation of Al–Si spinel and a decrease in specific surface area, which is linked to a modification of the pore size distribution within the particles. Differential scanning calorimetry (DSC) was identified as the most robust, and repeatable technique to identify an overcalcined kaolinitic clay. In combination with thermogravimetric analysis (TGA), it can provide a complete calcination process overview, relevant for quality control purposes.

Thermal behavior of minerals in shale and its influence on evolution of gas-flow channels under thermal shock

Thermal shock-induced damage can significantly enhance the connectivity of the rock's fracture network. Thermal Enhanced Recovery (TER) technology holds promising potential for application in shale gas production. Nevertheless, there is still a lack of direct experimental studies focusing on the evolution of shale's gas-flow channels and the mechanism of thermal fracturing in shale under the influence of thermal shock. In this study, we initially investigated the impact of thermal shock on various minerals in shale through X-ray diffraction (XRD) analysis and scanning electron microscope (SEM) imaging, and examined the mass and heat variation with temperature using Thermogravimetry-Differential Scanning Calorimetry (TG-DSC) testing. Subsequently, we assessed the alterations in shale's internal structure due to thermal shock through low-temperature gas (N2) adsorption (LTGA) analysis, and observed the distribution and expansion patterns of shale fractures under thermal shock using computed tomography (CT). Finally, we evaluated the changes in shale permeability before and after thermal shock. The findings indicate that quartz, feldspar, and clay exhibit relatively stable behavior in shale under thermal shock, whereas carbonate and pyrite are prone to crack. Under the combined influence of mineral cracking and thermal stress, the internal pore structure of shale tends to enlarge in size while reducing in surface area. The substantial decrease in pore specific surface area highlights the considerable reduction in gas adsorption capacity. Furthermore, fractures expand along the bedding planes as surface fractures. The expansion of pores and fractures promotes the formation of primary gas-flow channels. In addition, the aforementioned test results demonstrate a high level of consistency, specifically highlighting a distinct threshold temperature (500 °C) for the alteration of various physical parameters of shale during thermal shock. This study is anticipated to offer insights into the implementation of TER technology in the oil and gas industry.

The electronic structure regulation improving xylene gas sensing properties in p-type Zn-doped α-Fe2O3 nanoparticles

Xylene is a highly carcinogenic inert gas, and achieving highly selective detection toward xylene gas is crucial for environmental protection and physical health. Herein, α-Fe2O3 nanoparticles doped with different Zn contents (ZF-0, ZF-1, ZF-2 and ZF-3) have been prepared through a feasible solvothermal and subsequent annealing treatment. The successful doping of Zn has been confirmed through EDS, XPS and XRD characterizations. After Zn doping, the baseline resistance in air reduces, the band gap and specific surface area decrease, but oxygen vacancy defects increase for α-Fe2O3 nanoparticles. When applied as gas sensors, all as-prepared α-Fe2O3 samples show typical p-type semiconductor gas sensing behaviors. Especially, the ZF-2 sample with appropriate amount of Zn doping exhibits an excellent xylene gas sensing selectivity. Meanwhile, the ZF-2 sensor shows a high response, fast response/recovery speed, well stability and repeatability and a detection limit of 5 ppm at 240 °C. The acceptor level and oxygen vacancy defects in ZF-2 nanoparticles promote the catalytic oxidation of xylene gas by p-type Zn-doped α-Fe2O3 oxide semiconductors, thereby resulting in better xylene gas sensing performance.