Catalytic Combustion Of Methane Research Articles

Crystalline phase-modulated PtOx nanoparticles exhibit superior methane combustion performance and sulfur poisoning resistance: Multi-interaction regulation

Up to now, methane combustion catalysts generally suffer from issues such as poor reaction stability and susceptibility to sulfur poisoning, which have become the key factors restricting their application, so it is necessary to construct catalysts with excellent chemical stability of the active center and strong sulfur resistance. Here, we showed the crystal phase-modulated state of PtOx nanoparticles (PtOx NPs) on TiO2 and investigated their effects on the reactivity of methane catalytic combustion and anti-SO2 poisoning properties. It was found that Pt/r-TiO2 showed superior activity, stability, and resistance to SO2 poisoning. Transmission electron microscope (TEM) images showed that the PtOx NPs on the surface of r-TiO2 were much more stable than a-TiO2 for the reason that the Ostwald ripening of PtOx NPs on a-TiO2 was facilitated due to the strong metal-support interaction (MSI) between PtOx NPs and TiO2 and the low migration energy of the PtOx NPs on TiO2, while they were moderate of Pt/r-TiO2, and then the active sites were stabilized during methane combustion. The activity was controlled by the size and electronic structure of PtOx NPs, which were stable on the surface of r-TiO2 with a higher Pt4+ content, and the density functional theory (DFT) calculations further revealed the role of r-TiO2 in increasing the quantities of surface oxygen vacancies. Moreover, the SO2 tolerance of Pt/r-TiO2 was also the best among all kinds of Pt-based catalysts prepared, which was attributed to the minimal adsorption energy (Ead) of SO2 on r-TiO2, and the absence of sulfate and sulfite deposition on the Pt/r-TiO2 catalyst confirmed by TGA and in-situ DRIFTS studies on SO2 adsorption. In this research, the anti-SO2 poisoning and reaction stability were realized by adjusting the interaction between SO2, active components, and supports, which provided a new insight for the design of stable Pt-based SO2-resistant catalysts.

Creating Atomically Iridium-Doped PdOx Nanoparticles for Efficient and Durable Methane Abatement.

The urgent environmental concern of methane abatement, attributed to its high global warming potential, necessitates the development of methane oxidation catalysts (MOC) with enhanced low-temperature activity and durability. Herein, an iridium-doped PdOx nanoparticle supported on silicalite-1 zeolite (PdIr/S-1) catalyst was synthesized and applied for methane catalytic combustion. Comprehensive characterizations confirmed the atomically dispersed nature of iridium on the surface of PdOx nanoparticles, creating an Ir4f-O-Pdcus microstructure. The atomically doped Ir transferred more electrons to adjacent oxygen atoms, modifying the electronic structure of PdOx and thus enhancing the redox ability of the PdIr/S-1 catalysts. This electronic modulation facilitated methane adsorption on the Pd site of Ir4f-O-Pdcus, reducing the energy barrier for C-H bond cleavage and thereby increasing the reaction rate for methane oxidation. Consequently, the optimized PdIr0.1/S-1 showed outstanding low-temperature activity for methane combustion (T50 = 276 °C) after aging and maintained long-term stability over 100 h under simulated exhaust conditions. Remarkably, the novel PdIr0.1/S-1 catalyst demonstrated significantly enhanced activity even after undergoing harsh hydrothermal aging at 750 °C for 16 h, significantly outperforming the conventional Pd/Al2O3 catalyst. This work provides valuable insights for designing efficient and durable MOC catalysts, addressing the critical issue of methane abatement.

Promoting effect and kinetic analysis of Fe-Co bimetallic doping on the LaMnO3 catalytic activity for methane combustion

To enhance the catalyst’s properties, a modified sol–gel method is developed in this study, and a unique perovskite catalyst, LaMnxFeyCo1-x-yO3, is successfully synthesized by doping Fe-Co into the lattice of LaMnO3. The catalytic activity of the synthesized catalysts is initially determined by applying them to methane oxidation. Then, the structural, chemical, and surface properties of these catalysts are systematically evaluated utilizing XRD, BET, O2-TPD, H2-TPR, SEM, and XPS analyses. The modified LaMn0.8Fe0.15Co0.05O3 is shown to exhibit excellent activity (T90 at 486.5 ℃) in methane catalytic combustion, comparable to several standard noble metal materials. Experimental findings indicate that such perovskite structures have a larger specific surface area, an elevated molar ratio of Mn4+, desirable low-temperature reducibility, and excellent oxygen mobility relative to the original LaMnO3. Meanwhile, more efficient electron transfer from Mn4+/Mn3+ redox cycles, as well as the emergence of oxygen defects, significantly contribute to the robust interaction between Fe-Co and LaMnO3. Further reaction kinetic analysis is conducted to determine changes in species components and identify possible catalytic pathways. Notably, Fe-Co co-doping leads to an improvement in the increase of lattice oxygen and CH4 adsorption. In addition, the MVK kinetic mechanism governs methane combustion over LaMn0.8Fe0.15Co0.05O3. This study provides new insights into enhancing energy conversion performance and efficient utilization of ventilation air methane (VAM) through the implementation of highly efficient perovskites.

Hydrophobic Modification of Small-Pore Pd-SSZ-13 Zeolites for Catalytic Methane Combustion

Hydrophobic Modification of Small-Pore Pd-SSZ-13 Zeolites for Catalytic Methane Combustion

Highly Active and Stable Pd/MgAl2O4 Catalysts for Methane Catalytic Combustion

Mesoporous MgAl2O4 is synthesized via a novel sol–gel combustion method and the concentration of oxygen defects on the surface is modulated through varying the calcination temperature (850, 900, 1000, and 1100 °C). Notably, the 1Pd/MgAl2O4‐1000 catalyst exhibits superior catalytic activity and stability. The turnover frequency (TOF) for 1Pd/MgAl2O4‐1000 is 0.079 and 0.058 s−1 under dry conditions (300 °C) and wet conditions (380 °C), respectively. The results of H2 temperature‐programmed reduction and X‐Ray photoelectron spectroscopy reveal that the principal active species within the Pd/MgAl2O4‐y catalyst is PdO. Specifically, the Pd–MgAl2O4‐1000 catalyst exhibits the lowest temperature reduction peak (120 °C) and the highest redox capability. Additionally, O2 temperature‐programmed oxidation further elucidates that PdOx species in the Pd/MgAl2O4‐1000 catalyst is prone to decomposition and the resultant palladium metal is readily reoxidized. Consequently, the rapidity of the redox cycle between PdO and Pd0 emerges as a pivotal factor in CH4 catalytic combustion. Furthermore, a correlation analysis among catalyst particle size, oxygen defect concentration, and TOF is conducted. The findings illustrate a distinct volcano‐shaped curve in the relationship between oxygen defect concentration and TOF for the 1Pd/MgAl2O4−y catalysts. A comparable trend is also evident in the correlation between Pd particle size and TOF.

Acid treatment enhances the methane combustion activity of LaFeO3 perovskite catalyst

The catalytic combustion of methane has gained much attention as a sustainable technology, due to concerns about the environmental impact of unburnt methane emissions from the natural gas vehicles. Researchers have explored alternatives to precious metal catalysts for methane combustion, with a focus on perovskite oxides known for their excellent activity and sintering-resistance capacity. In this study, LaFeO3 perovskite material was synthesized and subsequently subjected to a nitric acid etching treatment to modify its surface. It was found that the acid preferentially dissolved La cations from LaFeO3 surface while the perovskite phase was unchanged, as a consequence, the etched LaFeO3 shows improvement in methane combustion activity. The best performance was achieved in the sample with one-hour surface etched treatment, which suggests that the appropriate surface reconstruction induced by acid treatment promotes the formation of more active Fe sites on the surface and reduces the energic barriers of methane activation. This work presents a straightforward and effective approach to tailor the exposed surface properties of perovskites, thereby enhancing their activity in hydrocarbon combustion reactions.

Thermally stable Pd/CeO2@SiO2 with a core-shell structure for catalytic lean methane combustion.

Noble metal catalysts exhibit high catalytic activity in lean CH4 combustion at low temperatures. However, the high surface energy of noble metal nanoparticles makes them susceptible to deactivation due to migratory-aggregation during the catalytic process. Herein, a core-shell structure with a Pd/CeO2 core and a SiO2 shell (denoted as Pd/CeO2@SiO2) was designed and prepared to enhance the thermal stability for catalytic lean CH4 combustion. A series of characterization methods demonstrated the successful encapsulation of SiO2 and the modified thermal stability. The results of activity tests indicated that Pd/CeO2@SiO2 exhibited the optimal catalytic performance. After seven runs, Pd/CeO2@SiO2 achieved 90% conversion of CH4 at 385 °C compared to Pd/CeO2 at 440 °C. The remarkable catalytic performance was attributed to the synergistic effect of strengthened metal-support interactions and the core-shell structure. On the one hand, the migration and aggregation of Pd nanoparticles were limited due to the protection of the SiO2 shell layer. On the other hand, the SiO2 shell layer further enhanced the interactions between the Pd nanoparticles and CeO2, thus promoting the formation of PdxCe1-xO2-δ solid solutions and active oxygen species, which were beneficial for the improvement of the stability and redox capacity of the catalyst.

A novel Fe2O3/Al2O3 porous media catalyst prepared by ultrasonic-assisted impregnation for low-concentration methane catalytic combustion

Porous media (PM) catalytic combustion offers a potential strategy for stable and efficient combustion of low-concentration methane (LCM). Herein, a porous media catalyst loaded with Fe2O3 as the active component (Fe2O3/Al2O3) was developed by ultrasonic-assisted impregnation for LCM catalytic combustion in a four-layer porous media burner. The influences of the gas flows, velocities, equivalence ratios, and PM arrangement patterns on the temperature distribution, combustion stability, methane conversion, and emissions were investigated in detail. The results indicated that the Fe2O3/Al2O3 catalyst possessed exceptional catalytic activity and thermal stability at medium-to-high temperatures, which broadened the limiting equivalence ratio for CH4 stationary combustion to 0.43 with the CH4 conversion exceeding 99 %. LCM enabled higher combustion stability in the PM burner with a gradually varied configuration, achieving steady combustion for more than 120 min under the lean combustion condition (0.43 equivalence ratio and 50 L/min). The high-quality flue gas from LCM catalytic combustion with an average temperature over 600 ℃, lower CO (< 150 ppm) and NOx emissions (< 10 ppm) could serve for the comprehensive utilization of power generation, heating, and cooling. The catalytic oxidation of LCM on the Fe2O3 surface was primarily divided into four steps with the second-step CH4 dehydrogenation in CH4 dissociation being the dominant rate-limiting step. This work proves that the catalyst fabricated by ultrasonic-assisted impregnation can effectively break through the lean combustion threshold, which provides a valiant reference for the clean and efficient utilization of LCM.

In Situ Synthesis of Encapsulated Pd@silicalite-2 for Highly Stable Methane Catalytic Combustion.

Methane emissions from vehicles have made a significant contribution to the greenhouse effect, primarily due to its high global warming potential. Supported noble metal catalysts are widely employed in catalytic combustion of methane in vehicles, but they still face challenges such as inadequate low-temperature activity and deactivation due to sintering under harsh operating conditions. In the present work, a series of encapsulated structured catalysts with palladium nanoparticles confined in hydrophobic silicalite-2 were prepared by an in situ synthesis method. Based on various characterization methods, including XRD, HR-TEM, XPS, H2-TPR, O2-TPD, H2O-TPD, CH4-TPR, Raman, and in situ DRIFTS-MS, it was confirmed that PdOx nanoparticles were mainly encapsulated inside the silicalite-2 zeolite, which further maintained the stability of the nanoparticles under harsh conditions. Specifically, the 3Pd@S-2 sample exhibited high catalytic activity for methane oxidation even after harsh hydrothermal aging at 750 °C for 16 h and maintained long-term stability at 400 °C for 130 h during wet methane combustion. In situ Raman spectroscopy has confirmed that PdOx species act as active species for methane oxidation. During this reaction, methane reacts with PdOx to produce CO2 and H2O, while simultaneously reducing PdOx to metallic Pd species, which is further reoxidized by oxygen to replenish the PdOx catalyst.

Catalytic combustion of lean methane over different Co3O4 nanoparticle catalysts

Three types of Co3O4 catalyst, namely Co3O4 nanoparticles (denoted as Co3O4-NPs, ∼12 nm in diameter), Co3O4 nanoparticles encapsulated in mesoporou s SiO2 (denoted as Co3O4@SiO2), and Co3O4 nanoparticles inside microporous SiO2 hollow sub-microspheres (denoted as Co3O4-in-SiO2), were explored to catalyze the combustion of lean methane. It was found that the methane conversion over the three catalysts has the order of Co3O4-NPs ≈ Co3O4@SiO2 > Co3O4-in-SiO2 due to the different catalyst structure. The comparison experiments at high temperatures indicate the Co3O4@SiO2 has a significantly improved anti-sintering performance. Combined with the TEM and BET measurements, the results prove that the presence of the mesoporous SiO2 layer can maintain the catalytical activity and significantly improve the anti-sintering performance of Co3O4@SiO2. In contrast, the microporous SiO2 layer reduces the catalytical activity of Co3O4-in-SiO2 possibly due to its less effective diffusion path of combustion product. Thus, the paper demonstrates the pore size of SiO2 layer and catalyst structure are both crucial for the catalytical activity and stability.

AOx–MnOx (A = Ni, Cu, Fe, or Co) Nanocatalysts Fabricated by the Mechanochemical Preparation Method for Lean Methane Catalytic Combustion Assisted by a DBD Plasma Reactor

AO<i>_x</i>–MnO<i>_x</i> (A = Ni, Cu, Fe, or Co) Nanocatalysts Fabricated by the Mechanochemical Preparation Method for Lean Methane Catalytic Combustion Assisted by a DBD Plasma Reactor

Highly active SiO2-supported palladium nanoparticles prepared by a modified ammonia evaporation method for lean methane oxidation

By optimizing the ammonia evaporation (AE) method, highly active palladium nanoparticles were successfully deposited on fumed silica (f-SiO2) and exhibited excellent catalytic activity for the catalytic combustion of methane (CCM). It was manifested that the timing of ammonia introduction was of great importance in determining the particle sizes and electronic states of palladium nanoparticles, the desilication degree of SiO2 support material, and the redox properties and methane affinity of the Pd/f-SiO2-AE catalysts. The optimal Pd/f-SiO2-AE-2 catalyst, which converted 90% of lean methane at 333 °C at GHSV of 30,000 h − 1, performed better than its AE-1- and IM-prepared counterparts. In combination with complementary characterizations, DFT calculations and designed experiments, it was revealed that the uniformly dispersed palladium nanoparticles endowed the Pd/f-SiO2-AE-2 catalyst with more accessible sites. Moreover, the presence of Pd4+ species effectively promoted the methane adsorption capacity of the main active PdO phase, which was another critical reason for the outstanding performance. In addition, the necessity of the ammonia evaporation step was also elucidated by designed experiments. More importantly, taking the universality of this optimized AE method into consideration, our work thus put forward an effective and simple procedure to fabricate highly-active palladium nanoparticles for catalyst designers.

Methane Combustion over Zeolite-Supported Palladium-Based Catalysts

The emission of methane leads to the increase in the methane concentration in the atmosphere, which not only wastes resources but also intensifies the greenhouse effect and brings about serious environmental problems. Catalytic combustion can completely convert methane into carbon dioxide and water at low temperatures. However, the catalytic activities of the conventional supported palladium catalysts (e.g., Pd/Al2O3 and Pd/ZrO2) are easy to decrease or the two catalysts can even be deactivated under actual harsh reaction conditions (high temperatures, steam- and sulfur dioxide-containing atmospheres, etc.). Recently, noble metal catalysts supported on zeolites with ordered pores and good thermal stability have attracted much attention. This review article summarizes the recent progress on the development and characteristics of zeolite-supported noble metal catalysts for the combustion of methane. The effects of framework structures, silica/alumina ratios, acidity, doping of alkali metals or transition metals, particle sizes and distributions, and their locations of/in the zeolites on methane combustion activity are discussed. The importance of developing high-performance catalysts under realistic operation conditions is highlighted. In addition, the related research work on catalytic methane combustion in the future is also envisioned.

Properties and mechanisms of low concentration methane catalytic combustion in porous media supported with transition metal oxides

Low concentration methane (LCM) from coal mining is hardly utilized by combustion or oxidation due to its low concentration and fluctuation. Herein, a porous media catalytic combustion technology was presented to investigate the catalytic combustion properties of LCM in porous media by developing three porous media catalysts (Fe2O3/Al2O3, CuO/Al2O3 and Co3O4/Al2O3) supported with transition metal oxides (Fe2O3, CuO and Co3O4) as active components. While the catalytic combustion mechanism was proposed by density functional theory (DFT) calculations. The results indicated that Fe2O3/Al2O3 exhibited superior high-temperature catalytic activity and thermal stability, which was capable of broadening the limit equivalence ratio of CH4 stationary combustion to 0.46 with the CH4 conversion rate over 98 %. DFT calculations revealed that the Fe atoms on the (001) surface of Fe2O3 crystals were the active center during the catalytic process, causing the adsorption and dissociation of CH4 and O2 molecules. The lattice oxygen of Fe2O3 was engaged in the formation of CO and CO2 and the adsorbed oxygen from O2 molecules dissociation facilitated H2O generation, which heightened the conversion of CH4. This study provides a promising avenue for the high-efficiency and clean utilization of LCM.

Methane Catalytic Combustion under Lean Conditions over Pristine and Ir-Loaded La1-xSrxMnO3 Perovskites: Efficiency, Hysteresis, and Time-on-Stream and Thermal Aging Stabilities.

The increasing use of natural gas as an efficient, reliable, affordable, and cleaner energy source, compared with other fossil fuels, has brought the catalytic CH4 complete oxidation reaction into the spotlight as a simple and economic way to control the amount of unconverted methane escaping into the atmosphere. CH4 emissions are a major contributor to the 'greenhouse effect', and therefore, they need to be effectively reduced. Catalytic CH4 oxidation is a promising method that can be used for this purpose. Detailed studies of the activity, oxidative thermal aging, and the time-on-stream (TOS) stability of pristine La1-xSrxMnO3 perovskites (LSXM; X = % substitution of La with Sr = 0, 30, 50 and 70%) and iridium-loaded Ir/La1-xSrxMnO3 (Ir/LSXM) perovskite catalysts were conducted in a temperature range of 400-970 °C to achieve complete methane oxidation under excess oxygen (lean) conditions. The effect of X on the properties of the perovskites, and thus, their catalytic performance during heating/cooling cycles, was studied using samples that were subjected to various pretreatment conditions in order to gain an in-depth understanding of the structure-activity/stability correlations. Large (up to ca. 300 °C in terms of T50) inverted volcano-type differences in catalytic activity were found as a function of X, with the most active catalysts being those where X = 0%, and the least active were those where X = 50%. Inverse hysteresis phenomena (steady-state rate multiplicities) were revealed in heating/cooling cycles under reaction conditions, the occurrence of which was found to depend strongly on the employed catalyst pre-treatment (pre-reduction or pre-oxidation), while their shape and the loop amplitude were found to depend on X and the presence of Ir. All findings were consistently interpreted, which involved a two-term mechanistic model that utilized the synergy of Eley-Rideal and Mars-van Krevelen kinetics.

Towards Low Temperature Operation of Catalytic Gas Sensors: Mesoporous Co3O4-Supported Au-Pd Nanoparticles as Functional Material.

It is shown that the operating temperature of pellistors for the detection of methane can be reduced to 300 °C by using Au-Pd nanoparticles on mesoporous cobalt oxide (Au-Pd@meso-Co3O4). The aim is to reduce possible catalyst poisoning that occurs during the high-temperature operation of conventional Pd-based pellistors, which are usually operated at 450 °C or higher. The individual role of Au-Pd as well as Co3O4 in terms of their catalytic activity has been investigated. Above 300 °C, Au-Pd bimetallic particles are mainly responsible for the catalytic combustion of methane. However, below 300 °C, only the Co3O4 has a catalytic effect. In contrast to methane, the sensor response and the temperature increase of the sensor under propane exposure is much larger than for methane due to the larger heat of combustion of propane. Due to its lower activation energy requirement, propane exhibits a higher propensity for oxidation compared to methane. As a result, the detection of propane can be achieved at even lower temperatures due to its enhanced reactivity.

Effects of Pd doped Cu surface on CO2 and H2O formation in methane total oxidation

To achieve the goal of green and low-carbon sustainable development, the catalytic combustion of methane is particularly important. Based on the density functional theory, CO2 and H2O formation in the process of CH4 oxidation has been calculated on Cu25, Pd2Cu23 and Pd6Cu19. The results show that the addition of Pd changes the adsorption site of some reactive species and increased the adsorption strength. For Cu25, the optimal reaction path is CH*+O* → C*+OH*(+O*) → CO*+O* → CO2*. For Pd2Cu23 and Pd6Cu19, the optimal reaction path is CH*+O* → CHO* → CO*+H*(+O*) → CO2*. Adding Pd significantly reduces the energy barrier when water is generated, and the optimal reaction paths are OH*+OH*→H2O*+O*. Studying on noble metal doping on the activity of Cu catalyst at atomic level is able to provide guidance for the development of catalyst for methane efficient conversion.

Promoting effect of Pt on the activity and stability of Pd/MgFe2O4 for catalytic combustion of methane

Catalytic combustion is a promising way to remove low-concentration methane. Developing catalysts with good low-temperature activity and excellent catalytic stability toward catalytic combustion of methane is critical but challenging. In this work, we report that the addition of Pt into the 1Pd/MgFe2O4 in a suitable amount (4 wt%) can result in a significant enhancement in the catalytic activity and stability. High and stable methane combustion performances were achieved at 395 °C on 4Pt–1Pd/MgFe2O4 catalyst under WHSV of 30,000 mL/(g–h) during 20 h on stream. With comprehensive characterizations by using ICP, XRD, TPO, XPS, STEM and EDS, we reveal that the high catalytic activity and stability is due to that the addition of Pt could decrease the size of metallic nanoparticles, increase the proportion of Pd0 and adsorbed oxygen species. These results provide guidance for designing highly active and stable Pd-based catalysts for catalytic combustion of methane.

Simplified modelling of a fixed bed reactor for catalytic methane combustion

Simplified modelling of a fixed bed reactor for catalytic methane combustion

Designing main-group catalysts for low-temperature methane combustion by ozone

The catalytic combustion of methane at a low temperature is becoming increasingly key to controlling unburned CH4 emissions from natural gas vehicles and power plants, although the low activity of benchmark platinum-group-metal catalysts hinders its broad application. Based on automated reaction route mapping, we explore main-group elements catalysts containing Si and Al for low-temperature CH4 combustion with ozone. Computational screening of the active site predicts that strong Brønsted acid sites are promising for methane combustion. We experimentally demonstrate that catalysts containing strong Bronsted acid sites exhibit improved CH4 conversion at 250 °C, correlating with the theoretical predictions. The main-group catalyst (proton-type beta zeolite) delivered a reaction rate that is 442 times higher than that of a benchmark catalyst (5 wt% Pd-loaded Al2O3) at 190 °C and exhibits higher tolerance to steam and SO2. Our strategy demonstrates the rational design of earth-abundant catalysts based on automated reaction route mapping.