Search Results (263)

Partial oxidation of methane is a highly attractive route for hydrogen-rich syngas production, provided that high H₂ yields and H₂/CO ratios above 3 can be achieved. Herein, we demonstrate that precise compositional tuning of Ni–Cu bimetallic catalysts supported on Gd-doped CeO₂ enables direct control over defect chemistry and reaction pathways in partial oxidation of methane. A systematic investigation of Ni/Cu ratios was conducted to elucidate composition–structure–activity relationships using X-ray diffraction, Raman spectroscopy, temperature-programmed reduction/oxidation/desorption, and thermogravimetric analysis. While monometallic 5%Ni/GDC and promoted 1%Re4%Ni/GDC exhibited high methane conversion, they failed to deliver optimal hydrogen selectivity. In contrast, introducing Cu within a narrow compositional window fundamentally altered the reaction mechanism. The 2.5%Ni2.5%Cu/GDC catalyst showed limited oxygen vacancy formation and pronounced carbon deposition, leading to inferior catalytic performance. Remarkably, the 3.5%Ni1.5%Cu/GDC catalyst maximized both oxygen vacancy density and surface basicity, thereby selectively activating CO₂- and H₂O-assisted oxidation routes and enforcing the exclusive dominance of indirect POM pathways. This defect-mediated pathway control effectively decoupled methane activation from hydrogen-consuming side reactions while simultaneously promoting hydrogen-forming, CO-consuming reactions, most notably the water–gas shift reaction. As a result, the optimized 3.5%Ni1.5%Cu/GDC catalyst achieved an H₂ yield of 84% with an H₂/CO ratio of 3.11 and maintained stable operation for 40 h on stream at 600 °C. These findings establish Ni–Cu compositional tuning as a powerful strategy for defect engineering and reaction pathway regulation, providing new design principles for efficient and durable partial oxidation of methane catalysts targeting hydrogen-rich syngas production. Full article

Mercury adsorption/oxidation plays a crucial role in mercury transformation during coal combustion. To gain an intuitive understanding of the adsorption/oxidation mechanisms between mercury and fly ash, changes in mercury speciation of fly ash before and after Hg adsorption were investigated using temperature-programmed decomposition–atomic fluorescence spectroscopy (TPD-AFS). The results directly reveal that the primary adsorption/oxidation mechanism between mercury and fly ash is the heterogeneous oxidation reaction of Hg⁰ to HgCl₂. The mercury adsorption capacity exhibits a strong positive correlation with both the unburned carbon (UBC) content and the specific surface area (SSA) of the fly ash, whereas the presence of metal oxides has a negligible effect on mercury adsorption. Higher inlet concentrations of Hg⁰ enhance mercury adsorption, while flue gas components such as N₂, O₂, and CO₂ have minimal influence on mercury adsorption. Full article

The conversion of polycyclic aromatic hydrocarbons (PAHs) to monocyclic aromatic hydrocarbons holds significant importance in the petrochemical and coal chemical industries, as it enables the production of high-value-added chemicals. In this study, we investigated the methane-assisted hydroconversion of PAHs to monocyclic aromatic hydrocarbons with methyl side chains over Zn-based catalysts from Hβ zeolites treated with citric acid (CA) at different concentrations. The CA-modified Hβ catalysts were characterized using X-ray diffraction (XRD), N₂ adsorption–desorption, pyridine–Fourier transform infrared spectroscopy (Py-FTIR), and ammonia temperature-programmed desorption (NH₃-TPD). The results show that low CA concentrations facilitate the removal of amorphous aluminum from the zeolite framework, thereby increasing the specific surface area, pore volume, and pore diameter of the Zn/Hβ catalyst, as well as improving its Lewis/Brønsted (L/B) acid ratio. In contrast, excessive CA treatment causes the undesirable removal of framework aluminum and leads to structural collapse in the mesoporous regions formed at the interfaces between certain crystal aggregates. This, in turn, has a negative impact on the catalyst’s specific surface area, pore volume, pore size distribution, total acidity, and L/B ratio. Experimental data further indicate that the optimal Zn/Hβ catalyst, prepared using Hβ treated with 0.08 M CA, achieves a naphthalene conversion rate of up to 99% and a benzene–toluene–xylene (BTX) selectivity of 60% in the liquid product over a 10 h reaction period. These findings confirm that CA treatment not only enhances the catalytic activity of Zn/Hβ but also significantly improves its operational stability. This work provides new insights into the rational design of catalysts for the efficient conversion of PAHs to monocyclic aromatic hydrocarbons and the utilization of methane resources. Full article

There are many obstacles to the industrial application of CO₂ hydrogenation reduction technology, the most important of which is the high economic cost. The purpose of this study is to explore the interaction mechanism between the active component CuO-ZnO-Al₂O₃(CZA) and the zeolite carrier Zeolite Socony Mobil-5(ZSM-5), screen the simplified preparation method of catalysts with high catalytic performance, and further promote the industrial application of CO₂ hydrogenation reduction technology. In this study, the effects of the gas velocity of the feedstock, the reaction temperature, the content of acidic sites in the carrier, the filling amount of active component, and the mixing mode of the active component and the carrier on catalytic CO₂ hydrogenation reduction were investigated. The structure of the catalysts was analyzed by X-ray diffractometer (XRD), Brunauer-Emmett-Teller (BET), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and transmission electron microscopy (TEM). The catalyst surface properties were analyzed by X-ray photoelectron spectroscopy (XPS), ammonia temperature programmed desorption (NH₃-TPD), hydrogen temperature programed reduction (H₂-TPR) and other characterization methods. The research found that the grinding treatment led to the insertion of CZA between ZSM-5 zeolite particles in CZA@HZ5-20-GB, which was prepared via grinding both CZA and H-ZSM-5 with an Si/Al ratio of 20, inhibiting the action of strongly acidic sites in the zeolite, resulting in only CO and MeOH in the catalytic products, with no Dimethyl Ether (DME) generation. Full article

Advancing catalysts for low-temperature NH₃-SCR enhances their viability as a terminal flue gas denitration solution across diverse operating regimes. A high-performance, hydrothermally stable catalyst for low-temperature SCR was synthesized by depositing MnO_x onto MgAlO_x composite oxide supports. These supports, featuring varied Mg/Al ratios, originated from layered double hydroxide (LDH) precursors. The obtained catalyst with the Mg/Al ratio of 2 (Mn/Mg₂AlO_x) possesses relatively high concentrations of active oxygen species (O_α) and Mn⁴⁺ and exhibits remarkable catalytic performance. The Mn/Mg₂AlO_x catalyst exhibits a wide operating temperature range (100–300 °C) for denitration, achieving over 80% NO_x conversion, along with robust water resistance. The temperature-programed surface reactions and NO oxidation reactions are performed to elucidate the promoting effect of water on N₂ selectivity, which is not only due to inhibition of catalyst oxidation capacity at high temperature but also is related to the competing adsorption of water and NH₃. In situ DRIFTS analysis confirmed that the NH₃-SCR mechanism over Mn/Mg₂AlO_x adheres to the Eley–Rideal (E–R) pathway. These findings highlight the significant promise of Mn/MgAlO_x catalysts for deployment as downstream denitration units within exhaust treatment systems. Full article

In the race for industrialization and urbanization, the concentration of greenhouse gases like CO₂ and CH₄ is growing rapidly and ultimately resulting in global warming. An Ni-based catalyst over MgO support (Ni/MgO) offers a catalytic method for the conversion of these gases into hydrogen and carbon monoxide through the dry reforming of methane (DRM) reaction. In the current research work, 1–4 wt% strontium is investigated as a cheap promoter over a 5Ni/MgO catalyst to modify the reducibility and basicity for the goal of excelling the H₂ yield and H₂/CO ratio through the DRM reaction. The fine catalytic activities’ correlations with characterization results (like X-ray diffraction, surface area porosity, photoelectron–Raman–infrared spectroscopy, and temperature-programmed reduction/desorption (TPR/TPD)) are established. The 5Ni/MgO catalyst with a 3 wt.% Sr loading attained the highest concentration of stable active sites and the maximum population of very strong basic sites. 5Ni3Sr/MgO surpassed 53% H₂ yield (H₂/CO ~0.8) at 700 °C and 85% H₂ yield (H₂/CO ratio ~0.9) at 800 °C. These outcomes demonstrate the catalyst’s effectiveness and affordability. Higher Sr loading (>3 wt%) resulted in a weaker metal–support contact, the production of free NiO, and a lower level of catalytic activity for the DRM reaction. The practical and cheap 5Ni3Sr/MgO catalyst is scalable in industries to achieve hydrogen energy goals while mitigating greenhouse gas concentrations. Full article

Dry reforming of methane (DRM) into synthesis gas (CO + H₂) is one of the most important chemical reactions for industrial hydrogen production. It also enables the synthesis of hydrocarbons (liquid fuels) and other valuable products, providing an effective route for utilizing greenhouse gases. However, a major challenge limiting the implementation and scale-up of DRM is the high cost of stable and active noble metal-based catalysts, or the rapid deactivation of nickel- and cobalt-based catalysts due to coking and sintering of the active metal particles. In this context, the present work demonstrates that combining a highly active and inexpensive component (Ni) with tungsten carbide produces a composite material exhibiting high catalytic activity and resistance to oxidation and coking during DRM. Tungsten carbide was synthesized using a vacuum-free electric arc method, and nickel was subsequently deposited in varying amounts (1–25 wt.%) using the deposition–precipitation method with NaOH (DP). The resulting catalysts were characterized by X-ray diffraction, temperature-programmed reduction and Raman spectroscopy. Their performance was evaluated under DRM conditions, at atmospheric pressure and 800 °C, using different CH₄:CO₂ ratios. The most effective oxidation/(re)carbonization cycle, ensuring catalyst stability during DRM by balancing the rates of carbon formation and removal from the catalyst surface, was achieved with a nickel content of 20 wt.% and a CH₄ to CO₂ ratio of 0.67 in the feed gas mixture. Full article

This field study describes the successful implementation and evaluation of a Polymer-free Delayed Acid System, a next-generation acid retarder system that is chemically superior to traditional emulsified acid systems with an amphoteric-based surfactant. It is a polymer-free system that stimulates ultra-tight carbonate reservoirs in extreme sour and high-temperature conditions. The candidate well, located in an onshore gulf region field, for a major oil and gas company demonstrated chronically unstable production behavior for over two years, with test volumes fluctuating unpredictably between 200 and 400 barrels of oil per day. This indicated severe near-wellbore damage, high skin, and limited matrix permeability (<0.3 mD). The well was chosen for a pilot trial of the Polymer-free Delayed Acid System technology after a thorough formation study, which included mineralogical characterization and capillary diagnostics. The innovative acid retarder formulation, designed for deep matrix penetration and controlled acid–rock reaction, uses intrinsic encapsulation kinetics to significantly increase the acid’s reactivity, allowing it to bypass damaged zones, minimize acid leak-off, and initiate dominant wormhole propagation into the tight formation. The stimulation procedure began with a custom pre-flush designed to change nanoscale wettability and interfacial tension, so increasing acid displacement and assuring effective contact with the formation rock. Real-time injectivity testing and operational data collecting were performed prior to, during, and following the acid job, with pre-stimulation injectivity peaking at 1.2 bpm, indicating poor formation conductivity. Treatment with the Polymer-free Delayed Acid System resulted in a 592% increase in post-stimulation injectivity, indicating significant increases in near-wellbore permeability and successful propagation. However, a substantial operational difficulty arose: the well remained shut down for more than two months following the acid stimulation work due to surface infrastructure delays, notably the scheduling and execution of a flowline cleanup campaign. This lengthy closure slowed immediate flowback analysis and impeded direct assessment of treatment performance because production could not be tracked in real time. Despite this, once the surface system was operational and the well was open to flow, a structured production testing program was carried out over four quarterly intervals. The well regularly produced at an average stable rate of 500 bbl/day, more than doubling pre-treatment performance and demonstrating the long-term effectiveness and mechanical durability of the acid-induced wormhole network. Despite the post-job shut-in, the Polymer-free Delayed Acid System maintained the stimulating impact even under non-ideal settings, demonstrating its robustness. The Polymer-free Delayed Acid System outperforms conventional emulsified acid systems, giving better control over acid placement and reactivity, especially under severe reservoir conditions with bottomhole temperatures reaching 200 °F. This project offers a field-proven methodology that combines advanced chemical engineering, formation-specific design, and live diagnostics, as well as a scalable blueprint for unlocking hydrocarbon potential in similarly complicated, low-permeability reservoirs. Full article

This study examines the surface chemistry of platinum, palladium, rhodium, and ruthenium-substituted lanthanum strontium cobaltate perovskite catalysts in the context of the dry reforming of methane (DRM). The catalysts were synthesized by the solution combustion method and characterized by using a series of techniques. To explore the effect of noble metal ion substitution on the DRM, surface reaction was probed by CH₄/CO₂ TPSR using mass spectroscopy. It was recognized that La_1−xSr_xCo_1−yPd_yO₃ show the best activities for the reaction in terms of the temperature but became deactivated over time. CH₄/CO₂ temperature-programmed surface reactions (TPSRs) were set up to unravel the details of the surface phenomena responsible for the deactivation of the DRM activity on the LSPdCO. The CH₄/CO₂ TPSR analysis conclusively demonstrated the importance of lattice oxygen in the removal of carbon, which is responsible for the stability of the catalysts on the synthesized perovskites upon noble metal ion substitution. Full article

In this study, Mg-Al-Zn, MgO, Al₂O_3, and ZnO were synthesized via the co-precipitation method and evaluated as catalysts for the transesterification reaction of dimethyl carbonate (DMC) and ethanol. The crystal structure, morphological characteristics, pore structure properties, and alkaline properties of the catalysts were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, temperature-programmed desorption of CO₂ (CO₂-TPD), and Fourier transform infrared spectroscopy (FTIR). The surface alkali strength and alkalinity of the solids were determined using the Hammett indicator method and non-aqueous titration. When Al₂O₃ and ZnO are used as catalysts for this transesterification, the conversion rate of dimethyl carbonate is relatively low. When MgO and Mg-Al-Zn are used as catalysts, the conversion rate of dimethyl carbonate is higher. This indicates that the alkali strength of the catalyst for the transesterification reaction needs to be greater than 9.3. Additionally, the activity of the catalysts is also related to the amount of the alkaline sites on the solid surface. The alkali strength of MgO is greater than 11; its excessively high alkali strength will react with CO₂ and H₂O during use, resulting in a reduction in the number of alkaline sites and thus showing unsatisfactory reactivity. The alkaline strength of the Mg-Al-Zn catalyst ranges from 9.3 to 11.0. When used for the first time, the number of alkaline sites decreases, and then the alkalinity remains at a certain value. Therefore, the alkaline strength of the solid catalyst for the transesterification reaction between DMC and ethanol needs to be between 9.3 and 11.0 so that the number of alkaline sites on the catalyst surface remains unchanged and the catalytic activity remains stable. Full article

Hydrogen (H₂) has become a more important alternative source in the current energy transition process. Beyond its role in clean energy production, it also serves as a key reactant in a wide range of industrial chemical transformations, such as hydrogenation and hydroprocessing. A fundamental step in many of these processes is the dissociation of hydrogen on catalyst surfaces. This short review provides an overview of the fundamental mechanisms involved in hydrogen dissociation over catalysts, with a specific emphasis on heterolytic pathways. Meanwhile, the influence of surface coordination environments on hydrogen activation is discussed, focusing on key factors—Lewis acid–base pairs, lattice oxygen and oxygen vacancies, and metal–support interfaces. With recognizing the significance of understanding the reaction mechanisms, we provide a critical review of experimental techniques, including spectroscopy, temperature-programmed methods, and kinetic analysis, that have been successfully applied or appear promising for probing active sites, reaction dynamics, chemisorbed intermediates, and elementary steps. Our goal is to highlight how these techniques contribute to a mechanistic understanding and to outline future directions, making this review a valuable resource for both new and experienced researchers. Full article

The FeZn-MOFs@Al₂O₃ catalyst was synthesized under solvothermal conditions. Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), temperature-programmed desorption of ammonia (NH₃-TPD), and specific Brunauer–Emmett–Teller (BET) surface area and pore volume were used to systematically investigate the effects of different parameters such as molar ratio of iron to zinc, synthesis temperature, and synthesis time on the properties of the materials. The results showed that the optimum synthesis conditions of FeZn-MOFs@Al₂O₃ composites were 140 °C for 1 h, and the optimum molar ratio of Fe³⁺ and Zn²⁺ was 1.3:0.7. Under the aforesaid conditions, FeZn-MOFs@Al₂O₃ had the deacidification rate of vacuum gas oil (VGO) up to 96.3%. The optimum esterification parameters were as follows: the amounts of catalyst and ethylene glycol were, respectively, 2.5 wt% and 4.0 wt% of the sample oil, the reaction temperature was 250 °C, and the reaction time was 1 h. Full article

The dehydration of methanol to produce light olefins and gasoline, known as MTO (methanol-to-olefins) process requires acidic catalysts that maintain their acidity at reaction temperatures. Zeolites, such as SAPOs and ZSM-5, are commonly used for this purpose due to their acidic centers. The initial step in these experiments involves the activation or pretreatment of these solids to remove physically adsorbed water from their pores. Inadequate pretreatment can lead to the destruction of the existing Brönsted sites through the dihydroxylation of surface -OH groups. Therefore, it is crucial to pretreat the zeolites properly to preserve the Brönsted sites. One method is to subject the fresh catalyst to programmed dehydration, which involves desorption at a controlled temperature while monitoring the appearance of water that results from Brönsted site dihydroxylation. The temperature at which the dehydration peak appears determines the optimal reaction temperature. The results presented in this work will demonstrate the progressive deactivation of the catalysts when the reaction temperature exceeds 400 °C. Full article

This work presents a study of the redox properties of CeO₂ particles with (FeCeHS) and without (CeHS) Fe₂O₃ impregnation, as possible innovative catalysts for oxidation and combustion reactions as well as CO₂ activation. The topic, therefore, is part of a broader analysis of environmental catalysis, which aims to reduce the emissions of polluting substances and improve the exploitation of energy resources, with consequent progress in the eco-friendly field. Different laboratory techniques (Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Ultraviolet–Visible (UV-Vis), and Fourier Transform–Infrared (FT-IR) spectroscopies) point out that iron oxide is deposited on the surface of ceria, which maintains its lattice structure, although the particle morphology is slightly changed. Methanol and ethanol adsorption and conversion were evaluated on these catalysts by Temperature Programmed Surface Reaction (TPSR) and by in situ FT-IR spectroscopy of the probe redox properties, evidencing the formation of surface oxidized intermediates and combustion products. The FeCeHS catalyst demonstrates, in our reaction conditions, a good combustion activity in total oxidation of oxygenated molecules, hindering the formation of formaldehyde from methanol and reducing the quantity of CO produced by the partial oxidation reaction. A cooperative effect is suggested by the mixture of these two metals in the oxidation process. Full article

Ammonia is one of the common inorganic pollutants in surface waters. It can come from a wide range of sources through the discharge of wastewater (industry, agriculture, and municipal waters). Catalytic ozonation reaction can efficiently remove ammonia nitrogen without introducing other pollutants and improve the nitrogen selectivity of reaction products by controlling the reaction conditions. Catalysts based on silver nanoparticles (Ag NPs) have shown excellent O₃ decomposition performance; therefore, they are promising catalysts for catalytic ammonia ozonation due to their high reactivity, stability, and selectivity to N₂. In this study, we synthesized well-defined silver nanoparticles (Ag NPs) using a modified alkaline polyol method and then dispersed them on solid oxide supports (Fe₃O₄, TiO₂, and WO₃). Before being deposited on the oxide support, the silver nanoparticles were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and UV-VIS spectroscopy. The obtained catalysts, Ag_Fe₃O₄, Ag_TiO₂, and Ag_WO₃ were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), BET surface area analysis, UV-VIS spectroscopy, temperature-programmed reduction (H₂-TPR), and temperature-programmed desorption (TPD) of CO₂ and NH₃. It has been demonstrated that the nature of the support significantly influences the physicochemical properties of the catalysts, as well as their catalytic performance in ammonia ozonation reaction. Full article