Methane combustion over palladium catalyst within the confined space of MFI zeolite

Isolated cationic Pd species encapsulated in MFI zeolite,i.e.,Pd@MFI,have been successfully prepared via in situ hydrothermal route followed by oxidative treatment.The as-prepared Pd@MFI samples are investigated as promising catalysts in the reaction of methane combustion.Typically,Pd@H-ZSM-5 shows remarkable activity in methane catalytic combustion with a low apparent activation energy value of 70.7 kj/mol as well as good catalytic stability even in excess water vapor.Detailed characterization results demonstrate the strong interaction between Pd sites and zeolite framework in Pd@ZSM-5 and the efficient stabilization of isolated Pd sites by zeolite thereof.Spectroscopy analyses reveal that the presence of BrΦnsted acid sites is beneficial to methane adsorption and its subsequent activation on adjacent Pd sites,constructing cooperation between Bronsted acid sites and Pd sites within the confined space of MFI zeolite toward high-efficiency methane catalytic combustion.The reaction mechanism of methane combustion catalyzed by Pd@H-ZSM-5 model catalyst is finally discussed.

Catalytic performance for methane combustion of supported Mn-Ce mixed oxides

A series of supported Mn-Ce mixed oxide catalysts were prepared by the impregnation method and used for the oxidation of methane. The catalysts were characterized by N2 adsorption （BET）, X-ray diffraction （XRD）, laser Raman spectrum （LRS）, and temperature programmed reduction （TPR） techniques. The XRD and LRS results confirmed the high dispersion of active components or formation of solid solution between manganese and cerium oxides in the bulk and on the surface of mixed oxide catalysts. The reducibility was remarkably promoted by the stronger synergistic interaction between the two oxides from H2-TPR measurements. As expected, all the experimental mixed oxide catalysts showed excellent activity for methane combustion at low temperature. Especially, for the catalyst with Mn-Ce ratio 3：7, methane conversion reached 92% at a temperature as low as 470 ℃.

Catalytic performance enhancement by alloying Pd with Pt on ordered mesoporous manganese oxide for methane combustion

Ordered mesoporous Mn2O3 (meso‐Mn2O3) and meso‐Mn2O3‐supported Pd, Pt, and Pd‐Pt alloy x(PdyPt)/meso‐Mn2O3; x = (0.10?1.50) wt%; Pd/Pt molar ratio (y) = 4.9?5.1 nanocatalysts were prepared using KIT‐6‐templated and poly(vinyl alcohol)‐protected reduction methods, respectively.The meso‐Mn2O3 had a high surface area, i.e., 106 m2/g, and a cubic crystal structure. Noble‐metalnanoparticles (NPs) of size 2.1?2.8 nm were uniformly dispersed on the meso‐Mn2O3 surfaces. AlloyingPd with Pt enhanced the catalytic activity in methane combustion; 1.41(Pd5.1Pt)/meso‐Mn2O3gave the best performance; T10%, T50%, and T90% (the temperatures required for achieving methaneconversions of 10%, 50%, and 90%) were 265, 345, and 425 °C, respectively, at a space velocity of20000 mL/(g?h). The effects of SO2, CO2, H2O, and NO on methane combustion over1.41(Pd5.1Pt)/meso‐Mn2O3 were also examined. We conclude that the good catalytic performance of1.41(Pd5.1Pt)/meso‐Mn2O3 is associated with its high‐quality porous structure, high adsorbed oxygen species concentration, good low‐temperature reducibility, and strong interactions between Pd‐Pt alloy NPs and the meso‐Mn2O3 support.

Effect of CeO_2 preparation method and Cu loading on CuO/CeO_2 catalysts for methane combustion

CeO2 was synthesized by sol-gel, hydrothermal, nitrate thermal decomposition methods, respectively, and used as support to prepare CuO/CeO2 catalysts. According to characterization and reaction results, preparation method of CeO2 had a great influence on the physicochemical properties and activities of CuO/CeO2 catalysts. CuO with high dispersion and strong interaction with CeO2 was highly active in methane combustion, while CuO particles less associated with CeO2 showed less activity. The CuO catalyst supported on CeO2 which was prepared via nitrate thermal decomposition method showed the largest area, the smallest particle size, the highest dispersion of copper species and strong support metal interactions. Therefore, it presented the highest redox ability and activity for methane combustion. Activities of the catalysts with different copper content kept increasing until 5% Cu loading and from then on kept constant. Moreover, methane conversion decreased as methane space velocities increased on CuO/CeO2 catalyst. Addition of CO2 to the feed did not produce a significant effect on the catalytic activity, but the presence of H2O provoked a remarkable decrease on the activity of CuO/CeO2 catalyst.

Surfactant-aided hydrothermal preparation of La(2-x)Sr_xCuO_4 single crystallites and their catalytic performance on methane combustion

Perovskite-like oxide La2-xSrxCuO4 （x = 0, 1） single crystallites with microrod-like morphologies and tetragonal crystal structures were prepared hydrothermally at 240 ℃ with poly（ethylene glycol） （PEG） or hexadecyltrimethyl ammonium bromide （CTAB） as a surfactant and after calcination at 850 ℃. The physicochemical properties of the materials were characterized by means of XRD, BET, SEM, TEM/SAED （selected-area electron diffraction）, XPS and H2-TPR techniques. It is found that doping Sr2＋ to La2CuO4 lattice enhanced the catalytic activity for methane combustion and the LaSrCuO4 catalyst derived from PEG is the best among the tested ones. It is concluded that factors, such as adsorbed oxygen species concentration, reducibility and surface area, determined the catalytic performance of such single-crystalline materials.

Preparation,characterization and catalytic behavior of Pt-Cu nanoparticles in methane combustion

Fine and well dispersed Pt-Cu bimetallic nanoparticles stabilized by polyvinyl pyrrolidone （PVP） were synthesized by alkaline polyol method. The molar ratio of Pt to Cu was 1 ： 1. Further, the Pt-Cu bimetallic nanoparticles were supported on alumina and their catalytic behavior in methane combustion was investigated. The as-prepared as well as the supported Pt-Cu nanoparticles were characterized by transmission elec- tron microscopy （TEM）, X-ray photoelectron spectroscopy （XPS）, fractal analysis and X-ray diffraction （XRD）. The dependence of methane combustion on the morphology and surface composition of Pt-Cu nanoparticles was analyzed based on the experimental results.

Preparation of LaFe_(0.95)Pd_(0.05)O_3 perovskites and their catalytic performances in methane combustion

The physic-chemical properties of LaFe0.95Pd0.05O3 perovskites were strongly dependent on the temperature of calcination. Most of the organic substances and inorganic impurities were readily removed at 723 K but single-phase and well crystallized perovskite structure was formed at 873 K. With further raising the calcination temperature, the crystallite size of LaFe0.95Pd0.05O3 increased considerably. The LaFe0.95Pd0.05O3 sample that calcined at 1073 K showed only comparable activity as the reference LaFeO3 catalyst, in particular below 923 K, but pre-treatment with the reaction gas at 1223 K resulted in significantly enhanced activity due to the generation of active PdO species on the surface. The hysteresis feature upon heating-cooling cycle further confirmed the strong interaction between Pd and LaFeO3 in the perovskite structure.

Effect of Fe_2O_3 Loading Amount on Catalytic Properties of Monolithic Fe_2O_3/Ce_(0.67)Zr_(0.33)O_2-Al_2O_3 Catalyst for Methane Combustion

Ce0.67Zr0.33O2-Al2O3 solid solution was prepared by the co-precipitation method. Fe2O3-based catalysts supported on the solid solution were obtained by the impregnation method. The article revealed that the optimal loading amount of Fe2O3 on Ce0.67Zr0.33 O2-Al2O3 in our experimental condition for catalytic combustion of methane was 8% （ mass fraction）. The prepared catalysts were characterized by BET, TPR, XRD analyses, and their catalytic activity was investigated after being calcined at 873 K and after being aged in water gas at 1273 K. When the loading amount of Fe203 was 8% （ mass fraction）, the catalyst held the highest activity, and the best temperature speciality and thermal stability. The complete-conversion temperature of methane for fresh and aged sample was 788 and 838 K, respectively. The range between the light-off temperature and the complete-conversion temperature was only 15 K. The characterization results of XRD indicated that Fe2O3 was well dispersed on the Ce0.67Zr0.33O2-Al2O3 matrix. The results of BET and TPR were in good harmony with the catalytic activity results.

Synthesis of La-hexaaluminate catalyst for methane combustion by a reverse SDS microemulsion

La-hexaaluminate catalyst for methane catalytic combustion was synthesized by a reverse microemulsion. Pseudo-temary phase diagrams of a quaternary microemulsion system of sodium dodecyl sulfate （SDS）, n-pentanol, n-octane, and water （or Al（NO3）3 solution） were presented. The effects of alcohol chain length, cosurfactant-to-surfaqtant rat!0, and salt concentration on the formation and stability of the microemul- sion system were studied. The phenomenon that the conductivity changed with water supported the phase behavior of the microemulsion system. La（MnffFex）Al12_xO19_a catalysts, applied in methane combustion and with high-temperature stability, were synthesized within the stable areas of the phase diagram of the microemulsion system, when SDS was chosen as surfactant, n-pentanol as cosurfactant, and n-octane as oil phase. The physical properties and structure of the catalysts were characterized by BET method, transmission electron microscope （TEM）, and X-ray diffraction （XRD）. A micro-fixed-bed reactor was used to measure the catalytic activity of hexaaluminates in methane combustion. The results show that the reverse microemulsions can be used to produce discrete La-hexaaluminate nanoparticles that display excellent methane combustion activity owing to their high surface area and high thermal stability.

Surface for methane combustion:O(^3P)+CH4→OH+CH3

Kinetic investigations including quasi-classical trajectory and canonical unified statistical theory method calculations are carried out on a potential energy surface for the hydrogen-abstraction reaction from methane by atom O(^3P).The surface is constructed using a modified Shepard interpolation method.The ab initio calculations are performed at the CCSD(T)level.Taking account of the contribution of inner core electrons to electronic correlation interaction in ab initio electronic structure calculations,modified optimized aug-cc-pCVQZ basis sets are applied to the all-electrons calculations.On this potential energy surface,the triplet oxygen atom attacks methane in a near-collinear H-CH3 direction to form a saddle point with barrier height of 13.55 kcal/mol,which plays a key role in the kinetics of the title reaction.For the temperature range of 298-2500 K,our calculated thermal rate constants for the O(^3P)+CH4→OH+CH3 reaction show good agreement with relevant experimental data.This work provides detailed mechanism of this gas-phase reaction and a theoretical guidance for methane combustion.

Methane Combustion and TPR/TPO Properties of Pd/Ce_xZr_ 1-xO_2/Al_2O_3 Catalysts

The effects of ceria and zirconium oxides additions to alumina-supported palladium catalysts on methane combustion behavior were investigated. The structure and TPR/TPO properties were studied by XRD, TPR, TPO techniques. The results show that the addition of Ce-Zr oxides improves the thermal stability of alumina and PdO. The Pd/Ce0.2Zr0.8/Al2O3 exhibits the highest activity and thermal stability for methane combustion.

LaMnO_(3)(La_(0.8)Sr_(0.2)MnO_(3))Perovskites for Lean Methane Combustion:Effect of Synthesis Method

The effect of the preparation method on the properties of LaMnO3 and La0.8Sr0.2MnO3 perovskite was studied. Materials were prepared by four methods: sol-gel, chemical combustion, solvothermal and spray pyrolysis and characterized. The effect of the synthesis method on the texture, acid-base character of the surface, reducibility with hydrogen, oxygen desorption, surface composition and catalytic activity for combustion of lean methane was studied. It was found that synthesis method affects physicochemical properties of obtained materials-solvothermally produced materials exhibit well-developed surface area, presence of reactive oxygen species on surface and high catalytic activity for CH4 combustion. Generally, LaMnO3 and La0.8Sr0.2MnO3 perovskites show catalytic activity for lean CH4 combustion comparable or higher than the activity of 0.5 wt.% Pt/Al2O3 but lower than 1 wt.% Pd/Al2O3.

Synergistic effect of bimetallic RuPt/TiO_(2) catalyst in methane combustion

Designing metal compounds based on their structure and chemical composition is essential in achieving desirable performance in methane oxidation,because of the synergistic effect between different metal elements.Herein,a bimetallic Ru-Pt catalyst on TiO_(2) support(RuPt-O/TiO_(2)) was prepared by in situ reduction followed by calcination in air.Compared with monometallic catalysts(Ru-O/TiO_(2) and Pt-O/TiO_(2)),the synergistic effect of mixed metals endowed bimetallic catalysts with excellent stability and outstanding performance in methane oxidation,with a reaction rate of 13.9×10^(-5)mol^(-1)_(CH_(4))·g^(-1)_(Ru+Pt)·s^(-1)at 303℃.The varied characterization results revealed that among the bimetallic catalysts,RuO_(2)was epitaxially grown on the TiO_(2) substrate owing to lattice matching between them,and part of the PtO_(x) adhered to the RuO_(2) surface,in addition to a single PtO_(x) nanoparticle with 4 nm in size.Consequently,Pt mainly existed in the form of Pt2+and Pt4+and a small amount of zero valence in the bimetallic catalyst,prompting the adsorption and activation of methane as the first and rate-controlling step for CH_(4) oxidation.More importantly,the RuO_(2) species provided additional oxygen species to facilitate the redox cycle of the PtO_(x) species.This study opens a new route for structurally designing promising catalysts for CH4oxidation.

Nano-sized alumina supported palladium catalysts for methane combustion with excellent thermal stability

Pd/Al_(2)O_(3)catalysts supported on Al_(2)O_(3)of different particle sizes were synthesized and applied in methane combustion.These catalysts were systematically characterized by Brunauer-Emmett-Teller (BET),X-ray diffraction (XRD),high resolution-transmission electron microscopy (HR-TEM),high-angle annular dark?eld-scanning transmission electron microscopy (HAADF-STEM),H_(2)-temperature-programmed reduction (H_(2)-TPR),O_(2)-temperature-programmed oxidation (O_(2)-TPO),X-ray photoelectron spectroscopy (XPS),and X-ray absorption?ne structure (XAFS).The characterization results indicated that nanosized Al_(2)O_(3)enabled the uniform dispersion of palladium nanoparticles,thus contributing to the excellent catalytic performance of these nano-sized Pd/Al_(2)O_(3)catalysts.Among them,Pd/Al_(2)O_(3)-nano-10 (Pd/Al_(2)O_(3)supported by alumina with an average particle size of 10 nm)showed superior catalytic activity and stability for methane oxidation under harsh practical conditions.It maintained excellent catalytic performance for methane oxidation for50 hr and remained stable even after harsh hydrothermal aging in 10 vol.%steam at 800℃ for 16 hr.Characterization results revealed that the strong metal-support interactions and physical barriers provided by Al_(2)O_(3)-nano-10 suppressed the coalescence ripening of palladium species,and thus contributed to the superior sintering resistance of the Pd/Al_(2)O_(3)-nano-10 catalyst.

Component regulation in novel La-Co-O-C composite catalyst for boosted redox reactions and enhanced thermal stability in methane combustion

A novel La-Co-O-C (LC-C) composites were prepared via a facile co-hydrothermal route with oxides and glycerol and further optimized for methane catalytic activity and thermal stability via component regulation.It was demonstrated that Co3O_(4)phase was the main component in regulation.The combined results of X-ray photoelectron spectroscopy (XPS),temperature-programmed desorption of oxygen (O_(2)-TPD),temperature-programmed reduction of hydrogen (H_(2)-TPR),temperature-programmed desorption of ammonia/carbon dioxide (NH_(3)/CO_(2)-TPD) revealed that component regulation led to more oxygen vacancies and exposure of surface Co_(2)+,lower surface basicity and optimized acidity,which were beneficial for adsorption of active oxygen species and activation of methane molecules,resulting in the excellent catalytic oxidation performance.Especially,the (3.5)LC-C (3.5 is Co-to-La molar ratio) showed the optimum activity and the T50and T90(the temperature at which the CH_(4)conversion rate was 50%and 90%,respectively) were 318 and 367℃,respectively.Using theoretical calculations and in situ diffuse reflection infrared Fourier transform spectroscopy characterization,it was also found that the catalytic mechanism changes from the “Rideal-Eley” mechanism to the “Two-term” mechanism depending on the temperature windows in which the reaction takes place.Besides,the use of the “Flynn-Wall-Ozawa” model in thermoanalytical kinetics revealed that component regulation simultaneously optimized the decomposition activation energy,further expanding the application scope of carboncontaining composites.

Influence of preparation method on performance of a metal supported perovskite catalyst for combustion of methane

A different method was employed for the preparation of a metal supported perovskite catalyst for the catalytic combustion of methane.The prepared metallic catalysts were characterized by means of X-ray diffractometer(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),and also by ultrasonic and thermal shock tests and catalytic activity.It was found that the process factors during the preparation,e.g.the preparation of the catalyst precursor and the coating slurry,the calcination te...

Progress and key challenges in catalytic combustion of lean methane

As a primary type of clean energy,methane is also the second most important greenhouse gas after CO_(2)due to the high global warming potential.Large quantities of lean methane(0.1–1.0 vol%)are emitted into the atmosphere without any treatment during coal mine,oil,and natural gas production,thus leading to energy loss and greenhouse effect.In general,it is challenging to utilize lean methane due to its low concentration and flow instability,while catalytic combustion is a vital pathway to realize an efficient utilization of lean methane owing to the reduced emissions of polluting gases(e.g.,NOxand CO)during the reaction.In particular,to efficiently convert lean methane,it necessitates both the designs of highly active and stable heterogeneous catalysts that accelerate lean methane combustion at low temperatures and smart reactors that enable autothermal operation by optimizing heat management.In this review,we discuss the in-depth development,challenges,and prospects of catalytic lean methane combustion technology in various configurations,with particular emphasis on heat management from the point of view of material design combined with reactor configuration.The target is to describe a framework that can correlate the guiding principles among catalyst design,device innovation and system optimization,inspiring the development of groundbreaking combustion technology for the efficient utilization of lean methane.

La-Hexaaluminate Catalyst Preparation and Its Performance for Methane Catalytic Combustion

The La-hexaaluminate catalysts with high performance ration method with the buffer solution of NH4HCO3 and NH4OH were synthesized by the modified controllable co-precipimixture as the precipitation agent. The physicochemical properties of catalysts were characterized by the means of BET, XRD, and TPR techniques. With methane catalytic combustion as the probe reaction, the catalytic performances were also tested on a fixed bed, continual flow system. The resuits show that it is a good method to obtain chemical homogeneous hexaaluminate materials by the buffer solution as the precipitation agent. The La-hexaaluminate can be formed at low temperatures ranging from 1050 to 1200 ℃. The cerium introduction plays a great role in the methane catalytic combustion on La-Mn hexaaluminate because of its high oxygen storage capacity property and the well synergic effect between Ce and Mn. However, the CeO2 appears in hexaaluminate through the XRD pattern, which reveals that Ce can not enter the crystal lattice position. Mn introduction improves the methane catalytic activity to a large extent due to its high redox property. When Mn atomic substitution amount for A1 is 2, the hexaaluminate shows the highest activity, and the catalyst possesses good H2 consumption and redox performance. Mn can easily occupy the hexaaluminate crystal position, which reveals that the Mn substitute La-hexaaluminate is a promising high temperature methane combustion catalyst with high activity and good stability.

Multi sites vs single site for catalytic combustion of methane over Co3O4(110):A first-principles kinetic Monte Carlo study

Single-atom catalysts have been applied in many processes recently.The difference of their kinetic behavior compared to the traditional heterogeneous catalysts has not been extensively discussed yet.Herein a complete catalytic cycle of CH4 combustion assuming to be confined at isolated single sites of the Co3O4(110)surface is computationally compared with that on multi sites.The macroscopic kinetic behaviors of CH4 combustion on Co3O4(110)is systematically and quantitatively compared between those on the single site and multi sites utilizing kinetic Monte Carlo simulations upon the energetic information from the PBE+U calculation and statistic mechanics.The key factors governing the kinetics of CH4 combustion are disclosed for both the catalytic cycles respectively following the single-site and multi-site mechanisms.It is found that cooperation of multi active sites can promote the activity of complete CH4 combustions substantially in comparison to separated single-site catalyst whereas the confinement of active sites could regulate the selectivity of CH4 oxidation.The quantitative understanding of catalytic mechanism paves the way to improve the activity and selectivity for CH4 oxidation.

Catalytic combustion of methane over Pd/SnO_2 catalysts

SnO2‐supported Pd catalysts were prepared and the effects of the support calcination temperature on the subsequent catalytic activity during methane combustion were investigated.The physicochemical properties of the Pd/SnO2were characterized by X‐ray diffraction,high‐resolution transmission electron microscopy,X‐ray photoelectron spectroscopy,oxygen temperature‐programmed desorption and CH4temperature‐programmed surface reaction.Only crystalline Pd species were found on the catalysts fabricated from the supports calcined above800°C.It was also determined that lattice geometry matching between PdO and SnO2in the catalyst made with a support calcined at1200°C facilitated oxygen activation from SnO2to vacant oxygen sites on the PdO/Pd surface via the back‐spillover of oxygen.This effect in turn enhanced the catalytic combustion process.The activity of this material was clearly increased compared with the catalysts that did not exhibit lattice matching between the PdO and support.