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Keywords = alkaline hydrothermal environments

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17 pages, 1908 KB  
Article
Hydrothermal Synthesis of Zeolites from Volcanic Ash from Ubinas and Its Application in Catalytic Pyrolysis of Plastic Waste
by Jonathan Almirón, Rossibel Churata, María Vargas, Francine Roudet, Katia Valverde-Ponce, Carlos Gordillo-Andia and Danny Tupayachy-Quispe
Processes 2025, 13(11), 3376; https://doi.org/10.3390/pr13113376 - 22 Oct 2025
Viewed by 296
Abstract
The valorization of volcanic ash as a raw material for advanced functional materials offers dual benefits for both the environment and technology. Firstly, it diverts waste from landfills, thereby reducing the environmental footprint of volcanic deposits. Secondly, it contributes to the circular economy [...] Read more.
The valorization of volcanic ash as a raw material for advanced functional materials offers dual benefits for both the environment and technology. Firstly, it diverts waste from landfills, thereby reducing the environmental footprint of volcanic deposits. Secondly, it contributes to the circular economy by transforming an abundant natural residue into a high-value product. In this study, zeolites were synthesized from the ash of the Ubinas volcano via the hydrothermal method in an alkaline medium. A systematic investigation was conducted to ascertain the influence of NaOH concentration and reaction temperature on synthesis efficiency and final material properties. The crystalline phases and morphology of the products were characterized using Fourier Transform Infrared Spectroscopy (FTIR), X-ray Diffraction (XRD), and Scanning Electron Microscopy (SEM), while textural and thermal properties were evaluated through the Brunauer–Emmett–Teller (BET) method and Thermogravimetric Analysis (TGA). The results revealed that both temperature and NaOH concentration significantly affected the physicochemical properties of the zeolites. Four zeolite types were obtained; among them, Zeolite Z4 (synthesized with 3 M NaOH at 150 °C) exhibited the highest adsorption capacity, with a specific surface area of 35.60 m2/g, while Zeolite Z1 (synthesized at 120 °C with 1.5 M NaOH and 27.85 m2/g) displayed superior thermal stability and crystallinity. These variations in thermal and textural properties were reflected in the catalytic pyrolysis performance of polypropylene (PP). Zeolite Z3 (synthesized at 150 °C with 1.5 M NaOH) achieved the highest gaseous product yield (80.2%), despite lacking the expected zeolitic crystalline phases. In contrast, Zeolite Z2 (synthesized at 120 °C with 3 M NaOH) yielded 57.7% gaseous products and stood out for its predominant analcime phase, characteristic of zeolitic materials. In summary, this study demonstrates that volcanic ash-derived zeolites not only enhance synthesis efficiency and functional performance but also represent a sustainable strategy for waste valorization, closing material loops and enabling the recovery of high-calorific gaseous products from plastic waste. Full article
(This article belongs to the Section Chemical Processes and Systems)
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14 pages, 2797 KB  
Article
MoO3 Nanobelts Synthesized from Recycled Industrial Powder and Applied as Electrodes for Energy Storage Applications
by Angelo Di Mauro, Federico Ursino, Giacometta Mineo, Antonio Terrasi and Salvo Mirabella
Nanomaterials 2025, 15(17), 1380; https://doi.org/10.3390/nano15171380 - 8 Sep 2025
Viewed by 748
Abstract
The sustainable development of our society faces significant challenges, including the need for environmentally friendly energy storage devices. Our work is concerned with the conversion of Mo-based recycled industrial waste into active nanocatalysts for energy storage applications. To reach this goal, we employed [...] Read more.
The sustainable development of our society faces significant challenges, including the need for environmentally friendly energy storage devices. Our work is concerned with the conversion of Mo-based recycled industrial waste into active nanocatalysts for energy storage applications. To reach this goal, we employed hydrothermal synthesis, a low-cost and temperature-scalable method. The proposed synthesis produces MoO3 nanobelts (50–200 nm in width and 2–5 µm in length) with a high yield, about 74%. The synthesized nanostructures were characterized in 1 M KOH and 1 M NH4OH, as alkaline environments are a promising choice for the development of eco-friendly devices. To investigate the material’s behaviour cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS) measurements were carried out. From CV curves, it was possible to evaluate the specific capacitance values of 290 and 100 Fg−1 at 5 mVs−1 in 1 M KOH and 1 M NH4OH, respectively. Also, GCD was employed to evaluate the specific capacitance of the material, resulting in 75 and 60 Fg−1 in 1 M KOH and 1 M NH4OH, respectively. CV and GCD analyses revealed that MoO3 nanobelts act as two different types of energy storage devices: supercapacitors and pseudocapacitors. Additionally, EIS allowed us to distinguish between the resistive and capacitive behaviour contributions depending on the electrolyte. Furthermore, it provided a comprehensive electrochemical characterization in different alkaline electrolytes, with the intention of conjugating waste management and sustainable energy storage device production. Full article
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22 pages, 12129 KB  
Article
Metallogenic Age and Tectonic Setting of the Haigou Gold Deposit in Southeast Jilin Province, NE China: Constraints from Magmatic Chronology and Geochemistry
by Zhongjie Yang, Yuandong Zhao, Cangjiang Zhang, Chuantao Ren, Qun Yang and Long Zhang
Minerals 2025, 15(6), 582; https://doi.org/10.3390/min15060582 - 29 May 2025
Viewed by 637
Abstract
Haigou deposit, located in Dunhua City, southeast Jilin Province, NE China, is a large-scale gold deposit. The gold ore body is categorized into two types: quartz-vein type and altered rock type, with the quartz-vein type being predominant. The vein gold ore body primarily [...] Read more.
Haigou deposit, located in Dunhua City, southeast Jilin Province, NE China, is a large-scale gold deposit. The gold ore body is categorized into two types: quartz-vein type and altered rock type, with the quartz-vein type being predominant. The vein gold ore body primarily occurs within the monzonite granite and monzonite rock mass in the Haigou area and is controlled by fault structures trending northeast, northwest, and near north-south. In order to constrain the age and tectonic setting of quartz vein-type gold mineralization, we conducted a detailed underground investigation and collected samples of monzonite granite and pyroxene diorite porphyrite veins related to quartz-vein-type gold mineralization for LA-ICP-MS zircon U-Pb dating and whole-rock main trace element data testing to confirm that monzonite granite is closely related to gold mineralization. Pyroxene diorite porphyry and gold mineralization were found in parallel veins. The zircon U-Pb weighted mean ages of monzonite and pyroxene diorite porphyrite veins are 317.1 ± 3.5 Ma and 308.8 ± 3.0 Ma, respectively, indicating that gold mineralization in monzonite, pyroxene diorite porphyrite veins, and quartz veins occurred in the Late Carboniferous. The monzonite granite and pyroxene diorite porphyrite veins associated with quartz vein-type gold mineralization have high SiO2, high K, and high Al2O3 and are all metaluminous high-potassium calc-alkaline rock series. Both of them are relatively enriched in light rare earth elements (LREE) and macroionic lithophile elements (LILE: Rb, Ba, K, etc.), but deficient in heavy rare earth elements (HREE) and high field strength elements (HFSE: Nb, Ta, P, Ti, etc.), the monzonitic granite Eu is a weak positive anomaly (δEu = 1.15–1.46), the pyroxene diorite porphyre dyke Eu is a weak positive anomaly (δEu = 1.09–1.13), and the Nb and Ta are negative anomalies. The Th/Nb values are 0.28–0.73 and 1.48–2.05, and La/Nb are 2.61–4.74 and 4.59–5.43, respectively, suggesting that diagenetic mineralization is the product of subduction in an active continental margin environment. In recent years, scholarly research on Sr, Nd, and Pb isotopes in Haigou rock masses has indicated that the magmatic source region in the Haigou mining areas is complex. It is neither a singular crustal source nor a mantle source but rather a mixed crust-mantle source, primarily resulting from the partial melting of lower crustal materials, with additional contributions from mantle-derived materials. In summary, the metallogenic characteristics, chronology data, geochemical characteristics, and regional tectonic interpretation indicate that at least one phase of magmatic-hydrothermal gold mineralization was established in the Late Carboniferous as a result of the subduction of the Paleo-Asian ocean plate at the northern margin of the North China Craton. Full article
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22 pages, 13090 KB  
Article
Petrological, Textural, Compositional, and Economic Potential of Carbonatites from the Peshawar Plain Alkaline Igneous Province, Northwestern Himalaya
by Mehboob ur Rashid and Hafiz U. Rehman
Minerals 2025, 15(5), 439; https://doi.org/10.3390/min15050439 - 23 Apr 2025
Viewed by 1151
Abstract
Carbonatites, which are rare mantle-derived igneous rocks that are mainly enriched in carbonate minerals and host relatively higher amounts of rare earth element (REE)-bearing phases, remain subjects of extensive geological research due to their enigmatic origin and potential economic importance. This study aims [...] Read more.
Carbonatites, which are rare mantle-derived igneous rocks that are mainly enriched in carbonate minerals and host relatively higher amounts of rare earth element (REE)-bearing phases, remain subjects of extensive geological research due to their enigmatic origin and potential economic importance. This study aims to describe the petrographic, mineralogical, and some rare-earth element (REE) abundances of four carbonatite bodies (known as Sillai Patti, Loe Shilman, Warsak, and Jambil) exposed in the Peshawar Plain Alkaline Igneous Province (PPAIP), northwestern Himalaya, Pakistan, to identify their economic potential. The observed petrographic, textural features, and chemical compositions of the constituent minerals of the carbonatites were utilized to elucidate the evolutionary processes through which the rocks evolved. The results indicate distinct mineralogical assemblages dominated by calcite, dolomite, apatite, pyroxene, biotite, and feldspar, with accessory opaque and REE-bearing phases, such as pyrochlore, monazite, and britholite. The apatite grains display compositional zoning reflecting their growth under magmatic conditions. The petrographic features of apatite in some carbonatite samples, exhibiting preferred orientation in a particular direction and spongy or murky textures, indicate that the studied rocks underwent post-magmatic deformation or hydrothermal alteration. Calcite and dolomite, coexisting in some carbonatite samples, exhibit significant Mg-Fe variation, which is possibly related to magmatic differentiation. The pyroxene compositions vary from a low-calcium enstatite–ferrosilite series to high-calcium diopside, suggesting variable crystallization environments among the carbonatite bodies studied. The abundance of REE-bearing phases in the studied carbonatites emphasizes their high economic potential. These findings indicate that the PPAIP carbonatites originated from mantle-derived magmas and subsequently experienced metamorphic/metasomatic overprinting during their tectonic evolution. The abundance of REE-rich phases such as apatite, pyrochlore, monazite, and britholite underscores their high economic potential. Full article
(This article belongs to the Special Issue Geochemistry and Geochronology of High-Grade Metamorphic Rocks)
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31 pages, 16566 KB  
Article
The Role of Fluid Chemistry in the Diagenetic Transformation of Detrital Clay Minerals: Experimental Insights from Modern Estuarine Sediments
by Anas Muhammad Salisu, Abdulwahab Muhammad Bello, Abduljamiu O. Amao and Khalid Al-Ramadan
Minerals 2025, 15(3), 317; https://doi.org/10.3390/min15030317 - 19 Mar 2025
Viewed by 1076
Abstract
The diagenetic transformation of detrital clay minerals significantly influences sandstone reservoir quality, with fluid chemistry and temperature playing key roles in dictating transformation pathways during burial diagenesis. While these processes are well-documented in basinal settings, the diagenetic alterations of sediments in dynamic environments [...] Read more.
The diagenetic transformation of detrital clay minerals significantly influences sandstone reservoir quality, with fluid chemistry and temperature playing key roles in dictating transformation pathways during burial diagenesis. While these processes are well-documented in basinal settings, the diagenetic alterations of sediments in dynamic environments like estuaries remain underexplored. This study investigates the impact of fluid composition on the transformation of modern estuarine sediments through hydrothermal experiments using sediments from the Gironde estuary, SW France. A range of natural and synthetic solutions including seawater (SW), 0.1 M KCl (SF1), 0.1 M NaCl, KCl, CaCl2·2H2O, MgCl2·6H2O (SF2), estuarine water (EW), and 0.1 M Na2CO3 (SF3) were used under temperatures from 50 °C to 250 °C for 14 days, with a fixed fluid-to-sediment ratio of 10:1. The results revealed distinct mineralogical transformations driven by fluid composition. Dissolution of detrital feldspars and clay materials began at lower temperatures (<100 °C). The authigenic formation of smectite and its subsequent illitization in K-rich fluids (SW, SF1) occurred between 150 °C and 250 °C, replicating potassium-driven illitization processes observed in natural sandstones. Additionally, chlorite formation occurred through the conversion of smectite in SF2 and EW. Geochemical analysis showed that SF2 produced Mg-rich chlorites, while EW yielded Fe-rich chlorites. This aligns with diagenetic trends in coastal environments, where Fe-rich chlorites are typically associated with estuarine systems. The resulting authigenic illite and chlorite exhibited morphological and chemical characteristics similar to those found in natural sandstones, forming through dissolution-crystallization and solid-state transformation mechanisms. In contrast to illite and chlorite, SF3 produced entirely different mineral phases, including halite and analcime (zeolite), attributed to the high alkalinity and Na-rich composition of the solution. These findings provide valuable insights into the role of fluid chemistry in the diagenetic alteration of modern sediments and their implications for the evolution of sandstone reservoirs, which is critical for energy exploration and transition. Full article
(This article belongs to the Section Clays and Engineered Mineral Materials)
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13 pages, 3194 KB  
Article
Fluorescence Quenching of Graphene Quantum Dots from Orange Peel for Methyl Orange Detection
by Weitao Li, Yang Liu, Xinglong Pang, Yuanhao Huang, Zeyun Dong, Qian Niu, Yuping Xiong, Shang Li, Shuai Li, Lei Wang, Huazhang Guo, Saisai Cui, Shenpeng Hu, Yuenan Li, Tiantian Cha and Liang Wang
Nanomaterials 2025, 15(5), 376; https://doi.org/10.3390/nano15050376 - 28 Feb 2025
Cited by 6 | Viewed by 2024
Abstract
Methyl orange (MO) is an organic synthetic dye widely used in laboratory and industrial applications. In laboratory settings, it serves as an acid–base indicator due to its distinct color change in both acidic and alkaline environments. Industrially, it is primarily utilized in the [...] Read more.
Methyl orange (MO) is an organic synthetic dye widely used in laboratory and industrial applications. In laboratory settings, it serves as an acid–base indicator due to its distinct color change in both acidic and alkaline environments. Industrially, it is primarily utilized in the textile industry for its ultraviolet (UV) absorption properties. However, the discharge and leakage of methyl orange into the environment can cause severe ecological damage and pose potential carcinogenic and teratogenic risks to human health. Therefore, detecting and quantifying the concentration of methyl orange in various matrices is crucial. This study reports the synthesis of graphene quantum dots (GQDs) from orange peel as a precursor, using ethanol and dimethylformamide (DMF) as solvents. Cyan (c-GQDs) and yellow (y-GQDs) graphene quantum dots were synthesized through a bottom-up hydrothermal method. The difference in color is attributed to the redshift caused by the varying ratio of pyridine nitrogen to pyrrole nitrogen. These GQDs exhibited notable optical properties, with c-GQDs emitting cyan fluorescence and y-GQDs emitting yellow fluorescence under UV light. To investigate fluorescence quenching effects, nine commonly used dyes were tested, and all were found to quench the fluorescence of y-GQDs, with methyl orange having the most significant effect. The fluorescence quenching of orange peel-derived GQDs in the presence of methyl orange is attributed to poor dispersion in DMF solution. Additionally, the GQDs possess high specific surface area, abundant surface functional groups, and excellent electronic conductivity, which contribute to their effective fluorescence quenching performance. The average thickness of y-GQDs (the vertical dimension from the substrate upwards) was 3.51 nm, confirming their graphene-like structure. They emitted yellow fluorescence within the wavelength range of 450–530 nm. Notably, a significant linear correlation was found between the concentration of methyl orange and the fluorescence intensity of y-GQDs (regression coefficient = 0.9954), indicating the potential of GQDs as effective sensing materials for organic pollutant detection. Full article
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13 pages, 2340 KB  
Article
The Effect of Fluid Acidity on GeO2 Solubility and Complexation in Aqueous Solutions and Its Implications on Ge Mineralization
by Zhiwei Xu, Haotian Liu, Yan Zhang, Runsheng Han, Zonghui Li and Xing Ding
Minerals 2025, 15(2), 173; https://doi.org/10.3390/min15020173 - 13 Feb 2025
Cited by 1 | Viewed by 1379
Abstract
Germanium (Ge) has been recognized as a critical strategic metal due to its high-technology implications. It is predominantly found in sphalerite within the Pb-Zn deposits, whose genesis is closely related to chloride-bearing hydrothermal activities. However, the dissolution and complexation of Ge in chloride-bearing [...] Read more.
Germanium (Ge) has been recognized as a critical strategic metal due to its high-technology implications. It is predominantly found in sphalerite within the Pb-Zn deposits, whose genesis is closely related to chloride-bearing hydrothermal activities. However, the dissolution and complexation of Ge in chloride-bearing fluids have not yet been well understood. To address this issue, this study investigates the dissolution behavior of Ge and corresponding species in HCl and NaCl aqueous solutions at 150 °C using the solubility method. The results show that the solubility of Ge in HCl solutions reaches 300 ppm and decreases with increasing HCl concentration. In contrast, the solubility of Ge in NaCl solutions is up to 1500 ppm and exhibits no significant dependence on NaCl concentration. The new findings demonstrate that the solubility of Ge in chloride-bearing solutions is primarily controlled by the solution’s pH. As the pH increases, the concentration of Ge dissolved in solutions rises substantially, suggesting that alkaline fluid environments facilitate Ge dissolution and transport. Further analysis of the experimental data indicates that the dominant species of Ge is Ge(OH)40 in acidic chloride-bearing solutions and Ge(OH)5 in neutral-basic chloride-bearing solutions, in which the species Ge(OH)5 promotes higher Ge solubility compared to Ge(OH)40. On account of high solubility in both HCl and NaCl solutions, it is proposed that Ge mineralization is not controlled by the co-precipitation process with Pb and Zn but by subsequent solid–liquid reaction between sphalerite and fluids. These experimental data and computational results not only provide new insights into the dissolution, transport, and precipitation processes of Ge in Earth’s material cycling but also offer novel perspectives for the understanding of Ge mineralization and industrial extraction and recovery of Ge. Full article
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16 pages, 4405 KB  
Article
Density Functional Theory Study on Na+ and K+ Catalysis in the Transformation of Glucose to Fructose and HMF in Hydrothermal Environments
by Long Gao, Qihao Chen, Yanhong Wang, Deyong Che, Baizhong Sun and Shuai Guo
Molecules 2024, 29(20), 4849; https://doi.org/10.3390/molecules29204849 - 13 Oct 2024
Cited by 3 | Viewed by 1684
Abstract
Hydrothermal carbonization (HTC) is an efficient method for converting biomass into biochar. Hydrochar contains catalytic components such as alkali and alkaline earth metals (AAEMs); however, the mechanisms by which highly active metals such as potassium (K) and sodium (Na) catalyze the conversion of [...] Read more.
Hydrothermal carbonization (HTC) is an efficient method for converting biomass into biochar. Hydrochar contains catalytic components such as alkali and alkaline earth metals (AAEMs); however, the mechanisms by which highly active metals such as potassium (K) and sodium (Na) catalyze the conversion of small carbon–water compounds into hydrochar in hydrothermal environments remain unclear. In this study, glucose was used as a small molecule model, and Na+ and K+ were used as catalysts to investigate the catalytic reaction mechanism during the hydrothermal process using density functional theory (DFT). In the presence of different ions at various binding sites, glucose isomerizes into fructose, which subsequently undergoes three consecutive dehydration reactions to form 5-hydroxymethylfurfural (HMF). The results indicate that the catalytic effectiveness of Na+ and K+ in the isomerization of glucose to fructose is optimal when interacting with specific oxygen sites on glucose. For Na+, the interaction with the O1 and O2 oxygens provides the lowest reaction barrier of 37.16 kcal/mol. For K+, the most effective interactions are with the O3 and O4 oxygens and the O5 and O6 oxygens, resulting in reduced reaction barriers of 54.35 and 31.50 kcal/mol, respectively. Dehydration of fructose to HMF catalyzed by Na+ ions, the catalytic effectiveness at different positions is ranked as O5O6 > O1O5, whereas for K+, the ranking is O1O5 > O5O6. This study explores the catalytic effects of Na+ and K+ at different binding sites on the hydrothermal reactions of glucose at the atomic level, offering theoretical support for designing catalysts for the HTC of sludge. Full article
(This article belongs to the Special Issue Renewable Energy, Fuels and Chemicals from Biomass)
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16 pages, 4223 KB  
Article
One-Step Hydrothermally Synthesized Ni11(HPO3)8(OH)6/Co3(HPO4)2(OH)2 Heterostructure with Enhanced Rate Performance for Hybrid Supercapacitor Applications
by Mingjun Jing, Kaige Long, Rui Liu, Xingyu Wang, Tianjing Wu, Yirong Zhu, Lijie Liu, Sheng Zhang, Yang Zhang and Cheng Liu
Batteries 2024, 10(10), 339; https://doi.org/10.3390/batteries10100339 - 24 Sep 2024
Cited by 3 | Viewed by 1761
Abstract
Transition metal phosphate is the prospective electrode material for supercapacitors (SCs). It has an open frame construction with spacious cavities and wide aisles, resulting in excellent electric storage capacity. However, the inferior rate behavior and cycling stability of transition metal phosphate materials in [...] Read more.
Transition metal phosphate is the prospective electrode material for supercapacitors (SCs). It has an open frame construction with spacious cavities and wide aisles, resulting in excellent electric storage capacity. However, the inferior rate behavior and cycling stability of transition metal phosphate materials in alkaline environments pose significant barriers to their application in SCs. Herein, Ni11(HPO3)8(OH)6/Co3(HPO4)2(OH)2 heterostructured materials synthesized through a one-step hydrothermal process exhibiting remarkable rate capability coupled with exceptional cycling endurance. Ni11(HPO3)8(OH)6/Co3(HPO4)2(OH)2 samples exhibit a micron-scale structure composed of sheet-like compositions and unique pore structure. The multistage pore structure is favorable for promoting the diffusion of protons and ions, enhancing the sample’s electrochemical storage capacity. Upon conducting electrochemical tests, it was observed that Ni11(HPO3)8(OH)6/Co3(HPO4)2(OH)2 composite electrode surpassed both the standalone Ni11(HPO3)8(OH)6 and Co3(HPO4)2(OH)2 electrode, achieving a remarkable specific capacity of 163 mAh g−1 with exceptional stability and efficiency at 1 A g−1. Notably, this electrode also exhibits superior rate performance, maintaining 82.5% and 71% of its original full capacity even at 50 A g−1 and 100 A g−1, respectively. Furthermore, it demonstrates superior stability in cycling, retaining a capacity of 92.7% at 10 A g−1 after 5000 cycles. Moreover, Ni11(HPO3)8(OH)6/Co3(HPO4)2(OH)2 and porous carbon (PC) were assembled into a hybrid supercapacitor (HSC). Electrochemical tests reveal an impressive power density of up to 36 kW kg−1 and an exceptional energy density of up to 47.4 Wh kg−1 for the HSC. Moreover, Ni11(HPO3)8(OH)6/Co3(HPO4)2(OH)2//PC HSC exhibits robust capacity retention stability of 92.9% after enduring 10,000 cycles at 3 A g−1, demonstrating its remarkable durability. This work imparts viewpoints into the design of transition metal phosphate heterostructured materials. Full article
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18 pages, 8969 KB  
Article
Petrogenesis and Geodynamic Mechanisms of Porphyry Copper Deposits in a Collisional Setting: A Case from an Oligocene Porphyry Cu (Au) Deposit in Western Yangtze Craton, SW China
by Mimi Yang, Xingyuan Li, Guoxiang Chi, Hao Song, Zhengqi Xu and Fufeng Zhao
Minerals 2024, 14(9), 874; https://doi.org/10.3390/min14090874 - 27 Aug 2024
Cited by 1 | Viewed by 1824
Abstract
The Xifanping deposit is a distinct Cenozoic porphyry Cu (Au) deposit located in the Sanjing porphyry metallogenic belt 100–150 km east of the JinshajFiang fault in the western Yangtze craton. We present new zircon U–Pb–Lu–Hf isotopic studies and geochemical data of the ore-bearing [...] Read more.
The Xifanping deposit is a distinct Cenozoic porphyry Cu (Au) deposit located in the Sanjing porphyry metallogenic belt 100–150 km east of the JinshajFiang fault in the western Yangtze craton. We present new zircon U–Pb–Lu–Hf isotopic studies and geochemical data of the ore-bearing quartz monzonite porphyry from the Xifanping deposit to determine their petrogenesis and geodynamic mechanisms. LA–ICP–MS zircon U–Pb dating yielded precise emplacement ages of 31.87 ± 0.41 Ma (MSWD = 0.86) and 32.24 ± 0.61 Ma (MSWD = 1.8) for quartz monzonite porphyry intrusions, and 254.9 ± 5.1 Ma (MSWD = 1.7) for inherited zircons of the monzonite porphyry. The ore-bearing monzonite porphyry is characterized by high-K calc–alkaline to shoshonite and peraluminous series, relatively enriched in light over heavy REEs, with no distinct Eu anomalies, as well as enrichment in LILEs and depletion of HFSEs, with adakitic affinities. The zircon Lu–Hf isotope data ranged from εHf(t) values of −2.94 to +3.68 (average −0.47) with crustal model (TDM2) ages ranging from 0.88 to 1.30 Ga, whereas the inherited zircons displayed positive εHf(t) values ranging from +1.83 to +7.98 (average +5.82), with crustal model (TDM2) ages ranging from 0.77 to 1.17 Ga. Results suggest that the Xifanping porphyry Cu (Au) deposit is related to two periods of magmatic activities. Early magmas were generated from the Paleo-Tethys oceanic subduction during the Late Permian. The subsequent porphyry magma was likely formed by the remelting of previously subduction-modified arc lithosphere, triggered by the continental collision between the Indian and Asian plates in the Cenozoic. The deep magmas and late hydrothermal fluids took advantage of the early magma transport channels along tectonically weak zones during the transition from an extrusive to an extensional–tensional tectonic environment. Early dikes from remelted and assimilated crust contributed to the two age ranges observed in the porphyry intrusions from the Xifanping deposit. The juvenile lower crust materials of the early magmatic arc were potential sources of the Cenozoic porphyry magmas, which has significant implications for mineral exploration and the geological understanding of porphyry Cu deposits in this region. Full article
(This article belongs to the Section Mineral Deposits)
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15 pages, 2795 KB  
Article
Electrochemical Performance of a Hybrid NiCo2O4@NiFelt Electrode at Different Operating Temperatures and Electrolyte pH
by Ataollah Niyati, Arianna Moranda, Pouya Beigzadeh Arough, Federico Maria Navarra and Ombretta Paladino
Energies 2024, 17(15), 3703; https://doi.org/10.3390/en17153703 - 26 Jul 2024
Cited by 5 | Viewed by 1801
Abstract
Transition metals such as nickel and cobalt as an alternative to Pt and Pd can be used for oxygen evolution reactions (OERs) and hydrogen production reactions (HERs) in alkaline environments, facilitating green hydrogen production as a sustainable alternative to fossil fuels. In this [...] Read more.
Transition metals such as nickel and cobalt as an alternative to Pt and Pd can be used for oxygen evolution reactions (OERs) and hydrogen production reactions (HERs) in alkaline environments, facilitating green hydrogen production as a sustainable alternative to fossil fuels. In this study, an NiCo2O4 catalyst was produced by a sono-hydrothermal method using urea as a hydrolysis agent. The electrochemical performance of the catalyst-coated NiFelt electrode was evaluated at different KOH concentrations (0.25, 0.5, and 1 M) and four operating temperatures in the interval of 20–80 °C. The electrode characteristics were investigated via electrochemical spectroscopy (cyclic voltammetry, EIS, multistep chronopotentiometry, multistep chronoamperometry) using two different reference electrodes (Ag/AgCl and Hg/HgO), to obtain insight into the anodic and cathodic peaks. XRD, SEM, EDS, and TEM analyses confirmed the purity, structure, and nanoscale particle size (20–45 nm) of the NiCo2O4 catalyst. The electrode showed symmetric CV with Ag/AgCl, making this reference electrode more appropriate for capacitance measurements, while Hg/HgO proved advantageous for EIS in alkaline solutions due to reduced noise. The overpotential of the catalyst-coated NiFelt decreased by 108 mV at 10 mA/cm2 compared to bare NiFelt, showing a good potential for its application in anion exchange membranes and alkaline electrolyzers at an industrial scale. Full article
(This article belongs to the Collection Advanced Materials for Energy Conversion and Storage Devices)
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17 pages, 7127 KB  
Article
In Situ Growth of Mn-Co3O4 on Mesoporous ZSM-5 Zeolite for Boosting Lean Methane Catalytic Oxidation
by Yuxuan Zhang, Ruibo Wei, Lin Yang, Jinming Ge, Feiyang Hu, Tingting Zhang, Fangyin Lu, Haiwang Wang and Jian Qi
Catalysts 2024, 14(7), 397; https://doi.org/10.3390/catal14070397 - 23 Jun 2024
Cited by 1 | Viewed by 1876
Abstract
The low-temperature oxidation of methane gas in coal mine exhaust gas is important for reducing the greenhouse effect and protecting the environment. Unfortunately, the carbon–hydrogen bonds in methane molecules are highly stable, requiring higher reaction temperatures to achieve effective catalytic oxidation. However, metal [...] Read more.
The low-temperature oxidation of methane gas in coal mine exhaust gas is important for reducing the greenhouse effect and protecting the environment. Unfortunately, the carbon–hydrogen bonds in methane molecules are highly stable, requiring higher reaction temperatures to achieve effective catalytic oxidation. However, metal oxide-based catalysts face the problem of easy sintering and the deactivation of active components at high temperatures, which is an important challenge that catalysts need to overcome in practical applications. In this work, a series of Mn-Co3O4 active components were grown in situ on ZSM-5 zeolite with mesoporous pore structures treated with an alkaline solution via a hydrothermal synthesis method. Due to the presence of polyethylene glycol as a structure-directing agent, manganese can be uniformly doped into the Co3O4 lattice. The large specific surface area of ZSM-5 zeolite allows the active component Mn-Co3O4 to be uniformly dispersed, effectively preventing the sintering and growth of active component particles during the catalytic reaction process. It is worth mentioning that the Mn-Co3O4/meso-ZSM-5-6.67 catalyst has a methane conversion rate of up to 90% at a space velocity of 36,000 mL·g−1·h−1 and a reaction temperature of 363 °C. This is mainly due to the mesoporous ZSM-5 carrier with a high specific surface area, which is conducive to the adsorption and mass transfer of reaction molecules. The active component has an abundance of oxygen vacancies, which is conducive to the activation of reaction molecules and enhances its catalytic activity, which is even higher than that of noble metal-based catalysts. The new ideas for the preparation of metal oxide-based low-temperature methane oxidation catalysts proposed in this work are expected to provide new solutions for low-temperature methane oxidation reactions and promote technological progress in related fields. Full article
(This article belongs to the Special Issue Feature Papers in "Industrial Catalysis" Section)
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13 pages, 4215 KB  
Article
Oxygen Vacancy-Enhanced Ni3N-CeO2/NF Nanoparticle Catalysts for Efficient and Stable Electrolytic Water Splitting
by Xianghao Meng, Xin Zhao, Yulin Min, Qiaoxia Li and Qunjie Xu
Nanomaterials 2024, 14(11), 935; https://doi.org/10.3390/nano14110935 - 26 May 2024
Viewed by 2556
Abstract
Highly efficient and cost-effective electrocatalysts are of critical significance in the domain of water electrolysis. In this study, a Ni3N-CeO2/NF heterostructure is synthesized through a facile hydrothermal technique followed by a subsequent nitridation process. This catalyst is endowed with [...] Read more.
Highly efficient and cost-effective electrocatalysts are of critical significance in the domain of water electrolysis. In this study, a Ni3N-CeO2/NF heterostructure is synthesized through a facile hydrothermal technique followed by a subsequent nitridation process. This catalyst is endowed with an abundance of oxygen vacancies, thereby conferring a richer array of active sites. Therefore, the catalyst demonstrates a markedly low overpotential of 350 mV for the Oxygen Evolution Reaction (OER) at 50 mA cm−2 and a low overpotential of 42 mV for the Hydrogen Evolution Reaction (HER) at 10 mA cm−2. Serving as a dual-function electrode, this electrocatalyst is employed in overall water splitting in alkaline environments, demonstrating impressive efficiency at a cell voltage of 1.52 V of 10 mA cm−2. The in situ Raman spectroscopic analysis demonstrates that cerium dioxide (CeO2) facilitates the rapid reconfiguration of oxygen vacancy-enriched nickel oxyhydroxide (NiOOH), thereby enhancing the OER performance. This investigation elucidates the catalytic role of CeO2 in augmenting the OER efficiency of nickel nitride (Ni3N) for water electrolysis, offering valuable insights for the design of high-performance bifunctional catalysts tailored for water splitting applications. Full article
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18 pages, 5803 KB  
Article
Shape–Preserved CoFeNi–MOF/NF Exhibiting Superior Performance for Overall Water Splitting across Alkaline and Neutral Conditions
by Yu Liu, Panpan Li, Zegao Wang and Liangjuan Gao
Materials 2024, 17(10), 2195; https://doi.org/10.3390/ma17102195 - 7 May 2024
Cited by 7 | Viewed by 2571
Abstract
This study reported a multi–functional Co0.45Fe0.45Ni0.9–MOF/NF catalyst for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting, which was synthesized via a novel shape–preserving two–step hydrothermal method. The resulting bowknot flake structure on NF [...] Read more.
This study reported a multi–functional Co0.45Fe0.45Ni0.9–MOF/NF catalyst for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting, which was synthesized via a novel shape–preserving two–step hydrothermal method. The resulting bowknot flake structure on NF enhanced the exposure of active sites, fostering a superior electrocatalytic surface, and the synergistic effect between Co, Fe, and Ni enhanced the catalytic activity of the active site. In an alkaline environment, the catalyst exhibited impressive overpotentials of 244 mV and 287 mV at current densities of 50 mA cm−2 and 100 mA cm−2, respectively. Transitioning to a neutral environment, an overpotential of 505 mV at a current density of 10 mA cm−2 was achieved with the same catalyst, showing a superior property compared to similar catalysts. Furthermore, it was demonstrated that Co0.45Fe0.45Ni0.9–MOF/NF shows versatility as a bifunctional catalyst, excelling in both OER and HER, as well as overall water splitting. The innovative shape–preserving synthesis method presented in this study offers a facile method to develop an efficient electrocatalyst for OER under both alkaline and neutral conditions, which makes it a promising catalyst for hydrogen production by water splitting. Full article
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18 pages, 3633 KB  
Article
Evaluation of Hydrothermally Treated Wood Fibre Performance in Cement Mortars
by Petrini Kampragkou, Vasiliki Kamperidou and Maria Stefanidou
Fibers 2024, 12(3), 21; https://doi.org/10.3390/fib12030021 - 26 Feb 2024
Cited by 10 | Viewed by 3262
Abstract
Biofibres’ wide application in mortar enhancement has thus far been restricted by factors related to their chemical composition and hygroscopic nature. Their hydrophilic behaviour increases the water demand of mortar mixtures and diminishes their affinity to the matrix, while further moisture-related fibre degradation [...] Read more.
Biofibres’ wide application in mortar enhancement has thus far been restricted by factors related to their chemical composition and hygroscopic nature. Their hydrophilic behaviour increases the water demand of mortar mixtures and diminishes their affinity to the matrix, while further moisture-related fibre degradation issues may arise. Additionally, natural fibres seem to be susceptible to degradation caused by exposure to alkaline environmental conditions such as those experienced by cement mortars, restricting their utilisation in the construction industry. Therefore, the current study investigates the potential of fibre modification through treatments that would permanently alter their structure and chemical composition to improve their performance. In this study, wood fibres of black pine and beech species were exposed to mild thermal treatment (140 °C 2 h, under a steam atmosphere), characterised in terms of the physical and chemical properties and incorporated in cement mortars, applying the proportion of 1.5% v/v in the mortar, in order to assess their performance as reinforcement material. The mortars’ workability (at a fresh state) was examined, as well as other physical, hygroscopic, thermal, and mechanical characteristics of the mortars at the ages of 28, 90 and 365 days and weathering performance, by subjecting them to different artificial ageing environments (freeze–thaw cycles or outdoor exposure). The results revealed the beneficial role of the treated fibres in dimensional stability, flexural strength, thermal insulation properties and capillary absorption of the mortar specimens, especially during the ageing process, with the black pine fibres showing the greatest improvement. The hydrothermally treated wood fibres seem to help maintain the integrity of cement mortars under all ageing conditions, proving that they could provide low-cost and eco-friendly mortar enhancement pathways. Full article
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