Catalysts For Combustion Research Articles

Boosting catalytic combustion of diesel soot particles over potassium-promoted CoMn-Co3O4 dual spinel structure catalyst

Catalytic oxidation is an effective method to remove soot particles from diesel exhaust, and the key aspect of this technology is to develop highly effective catalysts. In this work, a potassium-promoted dual spinel structure was prepared for soot elimination with the self-sacrificing template strategy. The highest activity was presented by the CoMn-0.2 H-10%K catalyst under a loose contact mode, with the temperature of soot conversion reaching 90% and turnover frequency value of 365 °C and 3.76×10−3 s−1, respectively. The catalyst was found to have a high content of oxygen vacancy and a superior ability for lattice oxygen migration, which led to elevated performance for soot combustion. The formation of K-OMS-2 at the interface between the CoMn spinel and the Co3O4 spinel was one of the reasons for the elevated lattice oxygen migration at low temperatures. This work provides an effective way to prepare transition metal catalysts for soot combustion.

Chemical compatibility of energetic metal complexes with polymers by thermal analytical techniques

Energetic metal complexes have been established to be effective combustion catalyst for energetic composites and propellants with improved performance. Chemical compatibility is an important aspect in the development of novel energetic composites which are related to safe processing, handling, and storage. In the present paper, the compatibility of energetic metal complexes [Zn(atrz)(DNBA)2(H2O)2]n (complex 1) and [Cd(atrz)(DNBA)2(H2O)2]n (complex 2) with Viton A and epoxy resin as polymer binder are studied by thermal analytical techniques. The compatibility was studied through vacuum stability test (VST), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) according to standardization agreement (STANAG) 4147 method. Furthermore, physicochemical methods including powder X-ray diffraction (PXRD) and Fourier transform infrared spectroscopy (FTIR) are used to support the thermal analytical methods. The VST results indicate that the volume of gases evolved for complex 1/Viton A, complex 1/epoxy resin, complex 2/Viton A, and complex 2/epoxy resin is found to be 0.545 mL/g, 0.86 mL/g, 0.403 mL/g, and 0.884 mL/g, respectively, indicating high compatibility with one another. According to the STANAG 4147 criteria, the DSC/DTG data demonstrate that the difference in Tmax is less than 2 °C for all the admixtures, suggesting that the polymer binders under investigation are compatible with complexes. TG results demonstrate that the mass loss difference is less than 4 % for all admixtures, indicating good compatibility. The essential additional information offered by the supplementary non-thermal FTIR and PXRD techniques confirm that no reaction occurs between metal complex and polymer. SEM micrographs exhibit that metal complex crystals are embedded in the polymer matrix.

Synthesis and testing of active and water resilient low temperature methane combustion catalysts

Synthesis and testing of active and water resilient low temperature methane combustion catalysts

Fabrication of porous and highly defective CeO2-based catalysts for soot combustion with the strategy of soft-template addition and matrix doping by multiple rare earth elements

In this study, aiming to optimize the reactivity of CeO2 for soot combustion, rare earth elements (La, Pr, Sm and Y) co-doped CeO2 catalysts were synthesized via polyvinylpyrrolidone (PVP) and glycine (GNC) combustion methods. The PVP-CeO2-Re catalyst maintains a high specific surface area (82.9 m2 g−1) and abundant porous structure, thus being able to enhance the soot contact efficiency. The co-doping of multiple rare earth ions improves also the redox properties of the catalyst and increases the surface defects/vacancies, which is crucial to form the active surface O2- and O22- species to participate in soot combustion. The oxygen exchange rate over the catalyst with gaseous O2 can be accelerated by raising the temperature, and the exchange mechanism changes from a mixture of the R1 and R2 mechanisms to a domination by the R2 mechanism. Notably, PVP-CeO2-Re catalyst shows not only excellent activity (T50=373 °C) but also good stability. Our work could provide some reference for the design of promising catalysts applied in diesel particulate filters.

Characterizing of Nano Activated Bio-Carbon of Sago Waste as a Homogeneous Combustion Catalyst

Alternative fuels were developed by blending crude coconut oil and bio-carbon nanoparticles. Bio-carbon, derived from sago waste via pyrolysis and ground using a ball mill, underwent FTIR testing to assess its energy absorption capabilities. SEM analysis was conducted to examine the surface morphology of bio-catalyst with and without crude coconut oil. The findings indicate that incorporating bio-catalyst can enhance mechanical properties, facilitating rapid heat absorption, as evidenced by reduced flashpoint and viscosity. In addition, the results show an increase in fuel mass, broadening of molecular contacts, increased reactivity, and increased heat absorption for easier ignition. This phenomenon indicates that bio-carbon of sago waste have great potential for biofuel use as a homogeneous combustion catalyst.

Modulation mechanism of Mn-O strength in α-MnO2 catalyst for high-efficiency catalytic combustion of propane

The cleavage of C-H with high energy impedes the catalytic combustion of propane. Herein, α-MnO2 with modulation of Mn-O strength by changing the calcination temperature was applied in propane catalytic combustion. α-MnO2 calcinated at 350 °C (α-MnO2-350) exhibited superior performance (T20=150 °C, T90= 220 °C) in propane oxidation due to the synergistic effect of oxygen vacancies (OVs) and Lewis acidity. Density functional theory (DFT) calculations revealed that the lowest o-vacancy formation energy on α-MnO2-350 (Evo=0.74 eV) with its lowest Mn-O strength prompted the existence of abundant OVs and propane oxidation. Moreover, the highest Lewis acidity in α-MnO2-350 displayed the strongest propane adsorption, promoting the activation of C-H. The mineralization of propane on α-MnO2-350 dropped steeply after 68 h while could recover to 90 % in long-term water vapor stability test owing to the H2O adsorbed at OVs and the carbonaceous intermediates adsorbed at the Lewis acid sites.

Combustion characteristics of water-oil emulsion droplets with special additives

Relevance. Fuel oil application in power plants is characterized by increased values of underburning and anthropogenic emissions. One way to reduce anthropogenic emissions is the use of oil-water emulsions. Also, additional specialized additives are used to reduce anthropogenic emissions and improve fuel combustion characteristics. Aim. To determine the optimal fuel oil additive to reduce anthropogenic emissions and ignition delay times. Methods. The following additives: ION-M, Rosneft R503V3, Rosneft R502V1 (relative mass concentration 0.5%) were added to the water-oil fuel. The physicochemical properties of fuel oil M-100, as well as the elemental composition of CHNSO, were determined. The rheological characteristics of water-oil fuel compositions were established. Using high-speed photography, the droplet ignition delay times were determined. Using the gas analyzer, it was possible to prevent anthropogenic emissions. Results and conclusions. The results of the study showed that the additive based on a special combination of positively and negatively charged ions (ION M) reduces ignition delay times by 20–60%, when the gas temperature varies in the range from 700 to 900 °C. The addition of the additive based on fatty vegetable acids (P502B3) reduced the ignition delay times by 7–10%, when the temperature changed in the range from 700 to 900 °C relative to water-oil fuel. It was found that when using the P502B1 additive in water-oil fuel, it was possible to reduce the ignition delay times by 15–50%. It was determined that in the presence of combustion catalysts, water binds with heavy hydrocarbons and thus the release of volatile substances occurs faster, i. e. the supplied heat is not wasted on heating water into droplets, but evenly affects the entire volume of fuel. The results of the study of anthropogenic emissions showed that the use of additives when burning water-oil fuel reduces the concentrations of CO, CO2, NO, SO2 by 8, 6, 10 and 13%, respectively, compared to fuel oil.

Effects of graphene organic iron nanocomplex on the pyrolysis and laser ignition performance of TKX-50

Novel graphene iron tannate and graphene iron gallate nanocomplex (G-D-Fe and G-M-Fe) were designed, prepared and characterized by SEM, EDS, FTIR, RAMAN and XPS equipment. The catalytic property of the G-D-Fe and G-M-Fe for energetic TKX-50 was explored by DSC, kinetic calculation and laser ignition. The synthesized G-D-Fe and G-M-Fe present a positive impact on pyrolysis and ignition combustion of TKX-50, resulting in the significantly reduced decomposition temperature, activation energy (Ea) and ignition delay time. After adding G-D-Fe (G-M-Fe), the first and second decomposition peak temperatures (TFDP and TSDP) of TKX-50 were decreased by 42.3 °C (43.9 °C) and 45.0 °C (49.6 °C), respectively. At the conversion degree of 0.2–0.8, the nonlinear kinetic data showed that after adding G-D-Fe and G-M-Fe, the Ea of TKX-50 decreased from 163.5 to 141.3 and 145.4 kJ·mol−1 respectively. Additionally, after adding G-D-Ni and G-M-Ni, the laser ignition delay time of TKX-50 was reduced from 58 ms to 26 ms and 28 ms, respectively. The possible catalytic mechanism of preferred combustion catalyst G-D-Fe was disclosed by in-situ FTIR and gas-phase MS-FTIR analysis. The results are helpful to broaden the catalysts for pyrolysis and ignition combustion of TKX-50 and to disclose the catalytic mechanism.

High-temperature resistant BaO-Y2O3 catalysts with different morphologies for NO decomposition and mechanism study

The high-temperature reaction is a common phenomenon in combustion society, and its catalytic response remain a tremendous challenge hampered by the activity and resistance of the catalyst to high temperatures exceeding 1000 ℃. Three distinct forms of BaO-Y2O3 catalysts—nanosphere, nanorod, and rod—were created using a hydrothermal method and high-temperature annealing to enable direct decomposition of NO. To gather reaction-relevant structural and property information for BaO-Y2O3, we combined reactor activity measurements, chemisorption and DFT studies to elucidate NO high-temperature decomposition process and pinpoint the critical role of oxygen vacancy. We have systematically clarified the increasing favorability of NO decomposition on the nano-catalysts (nanospheres and nanorods) at high temperatures is through stable lattice structure, large specific surface areas, high porosity, and active Ba–O–Y bond. Due to the attraction of electrons gathering in vacancies to NO molecules, oxygen vacancies created in situ at high temperatures, as validated by O2-TPD and density functional theory (DFT) calculations, are advantageous for NO adsorption and decomposition. Moreover, N2 formation pathway over Ba-Y2O3(111) structure is revealed by DFT calculations that NO molecules are apt to be caught by active sites, the region of Ba–O–Y, resulting in the production of N2O2 intermediate and its subsequent bond breaking to N2O as well as N2. In situ DRIFTS experiment further confirms the reaction mechanism via the detected adsorbed species, and clarify the significance of NO2− to O2 formation. In a nutshell, the synthetic combustion catalysts are effective in high-temperature environments that contribute to de-NOx combustion, and the insights into the adsorption configurations of reactant and intermediates unlock fundamental understanding for emissions gas chemistry.

Inhibition effect of sulfation on Pt/TiO2 catalysts in methane combustion

Inhibition effect of sulfation on Pt/TiO2 catalysts in 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.

Efficient catalytic combustion of propane at low temperature based on ignition effect caused by amorphous atomic-layer Pt clusters

Developing highly active catalysts for hydrocarbon combustion at low temperatures is paramount but yet challenging. The crystal form of carrier and the dispersion degree of active species have great influence on propane combustion catalysts, but its internal mechanism is still unclear. In this study, the amorphous atomic-layer Pt clusters (AL) and Pt single atoms (SA) on TiO2 with various crystal phases were prepared and used as propane combustion catalysts, where the as-synthesized Pt/a-TiO2 catalyst with atomic-layer Pt clusters exhibited better catalytic performance. The Pt/a-TiO2-AL could achieve a 90 % propane conversion (T90) at 230 °C, with the highest reaction rate (39.57 × 10−7 mol g−1 s−1) and TOF value (7.72 × 10−2 s−1) at 240 °C. Kinetic studies showed that oxygen had a lower inhibitory effect on Pt/a-TiO2-AL compared to that on the Pt/p-TiO2-AL and Pt/r-TiO2-AL catalysts; simultaneously, the Pt/a-TiO2-AL catalyst presented lower apparent activation energy compared with Pt/a-TiO2-SA. DFT results showed that atomic-layer Pt clusters on TiO2 had the lower formation energy of oxygen vacancy than Pt single atoms due to the synergistic effect between adjacent exposed Pt atoms in the fully exposed atomic-layer Pt clusters, which had a higher activation capacity for oxygen and thus accelerated propane combustion through the ignition effect (rapid activation of oxygen and rapid combustion of propane). Our primary results provide a promising approach for the creation of high-efficiency Pt-based catalysts, specifically tailored for the catalytic combustion of volatile organic compounds (VOCs).

Preparation and properties of nano B/NC/AP@F2602 double-layer energetic fiber

The nano-boron powder (n-B) exhibits remarkable efficacy as a combustion catalyst, making it a prime candidate for use in solid propellant metal burners. Nevertheless, throughout the storage phase, the surface of n-B powder is prone to oxidation and substantial agglomeration, resulting in challenges with ignition and incomplete energy dissipation when utilizing boron powder. In this study, we utilized the coaxial electrospinning technique to produce nanofibers comprised of nano-boron /nitrocellulose/ammonium perchlorate@fluororubber (n-B/NC/AP@F2602), with the nano boron uniformly distributed within the core-shell fibers. In the course of combustion, the fibrous composite of n-B/NC/AP@F2602 undergoes an escalation in the rates of energy output and energy release, owing to the constraints imposed by external F2602((C₂H₂F₂)n and (C₃F₆)n). The n-B/NC/AP@F2602 demonstrates a 1.4-fold increase in peak pressure and a 3.6-fold increase in maximum boost rate when compared to the n-B/NC/AP. The energy performance evaluation results reveal that the mean molecular weight (MC) of combusted products from n-B/NC/AP@F2602 is 29.2 g·mol−1, representing a substantial increase compared to that of n-B/NC/AP. The aforementioned findings exemplify that coaxial electrospinning is an exceedingly efficacious technique for enhancing nanostructures, thereby amplifying the reactivity of energetic particles and offering novel insights into their application in energetic materials.

Nanocrystalline FeMnO3 Powder as Catalyst for Combustion of Volatile Organic Compounds.

The paper shows the obtaining of nanocrystalline iron manganite (FeMnO3) powders and their investigation in terms of catalytic properties for a series of volatile organic compounds. The catalyst properties were tested in the catalytic combustion of air-diluted vapors of ethanol, methanol, toluene and xylene at moderate temperatures (50-550 °C). Catalytic combustion of the alcohols starts at temperatures between 180 °C and 230 °C. In the case of ethanol vapors, the conversion starts at 230 °C and increases rapidly reaching a value of around 97% at 300 °C. For temperatures higher than 300 °C, the degree of conversion is kept at the same value. In the case of methanol vapors, the conversion starts at a slightly lower temperature (180 °C), and the degree of conversion reaches the value of 97% at a higher temperature (440 °C) than in the case of ethanol, and it also remains constant as the temperature increases. Catalytic combustion of the hydrocarbons starts at lower temperatures (around 50 °C), the degree of conversion is generally lower, and it increases proportionally with the temperature, with the exception of toluene, which shows an intermediate behavior, reaching values of over 97% at 430 °C. The studied iron manganite can be recommended to achieve catalysts that operate at moderate temperatures for the combustion of some alcohols and, especially, ethanol. The performance of this catalyst with regard to ethanol is close to that of a catalyst that uses noble metals in its composition.

Mechanistic insights into the deactivation of Pd/BEA methane combustion catalysts by hydrothermal aging

Three Pd/Beta zeolite catalysts with low, intermediate and high support Si/Al2 (SAR) ratios were synthesized for methane combustion in both fresh and hydrothermally aged forms. SAR was found to dramatically influence catalyst performance and hydrothermal stability. Via an array of structural and textural characterizations, it is discovered that (1) at low SAR, catalyst deactivation is due primarily to the transformation of catalytically active PdO to inactive Pd2+-ions via protonolysis; (2) at intermediate SAR, catalyst deactivation during aging is due partly to the protonolysis chemistry, and partly to Al-decoration of the remaining PdO particles; (3) at high SAR, both of these deactivation mechanisms are greatly mitigated, leading to much improved catalyst hydrothermal stability. Our work here demonstrates that PdO particles stabilized by silanol nests, sites that are highly active for methane combustion, can only survive harsh hydrothermal aging at very high support SAR.

Enhanced Ru-O-Ce interaction by solid solution structure of Ru-CexZr1-xO2 catalysts for efficient catalytic combustion of vinyl chloride

Ru-CexZr1-xO2 catalysts, prepared by stepwise precipitation method, were investigated for the catalytic combustion of vinyl chloride (VC). Ru-O-Ce is a highly reactive structure in the redox ability. The Ce-O-Zr solid solution structure enhances the strong metal-support-interaction (SMSI) between Ru and Ce, thereby increasing the content of Ru-O-Ce structure, which can be modulated by the molar ratio of Ce/(Ce + Zr) in the catalyst. Zr doping also enhances the surface acid sites. In situ DRIFTS reveals that Ru-CexZr1-xO2 catalyst avoids chlorine poisoning, and Ru-O-Ce provides sufficient chemically adsorbed oxygen species (CAOS) to promote formation of formate intermediate species. Ru-Ce0.5Zr0.5O2 catalyst exhibited the best catalytic performance with T90 of 227 °C under the reaction conditions of 1000 ppm VC and WHSV of 30,000 mL·g−1·h−1. Moreover, Ru-Ce0.5Zr0.5O2 catalyst exhibited the superior resistance to high temperature, chlorine poisoning and water, and excellent catalytic activity for the catalytic combustion of various VOCs.

Studying the Structure‐Reactivity Relationship of CuO/CeO2 for Catalytic Soot Particulate Combustion: On the Monolayer Dispersion Threshold Effect

AbstractTo elucidate structure‐reactivity relationship and prepare improved catalysts for soot combustion, a series of CuO/CeO2 with different loadings have been fabricated by the impregnation method. With XRD and XPS extrapolation methods, it is disclosed that CuO disperses finely on the CeO2 support to form a monolayer with a capacity around 1.06 mmol 100 m−2, which equals to 2.9 wt. % CuO loading. Below this capacity, CuO is in a sub‐monolayer state. However, above this capacity, CuO micro‐crystallites are formed, and co‐exist with the monolayer CuO. By increasing CuO loading, soot combustion activity of the catalysts increases as well until it reaches the monolayer dispersion capacity. Further increasing the CuO loading to 5 % decreases the activity slightly, and then remains constant. Therefore, an apparent monolayer dispersion threshold effect is observed for soot combustion on CuO/CeO2 catalysts. It is found that the amount of surface‐active O2− sites plays critical role for the catalytic activity. To obtain the most active CuO/CeO2 catalyst, a monolayer amount of CuO should be loaded on the supports.

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.

Cobalt–Magnesium Oxide Catalysts for Deep Oxidation of Hydrocarbons

Co–Mg catalysts for methane combustion were synthesized and studied, revealing the transformation of MgCo2O4 spinel into a CoO–MgO solid solution with oxygen release from the spinel lattice as the calcination temperature increased. Repeated heat treatment of the calcined solid solution at lower temperatures led to spinel regeneration with segregation of the solid solution phase. A TPR of the samples showed the presence of two characteristic peaks, the first of which relates to the transition of Co3+Oh spinel to the Co2+Oh structure of CoO, and the second to the reduction of CoO to Co°. The second peak was observed at 540–620 °C for samples calcined at temperatures below spinel decomposition, and for high-temperature samples at 900–1100 °C. Taking into account the identity of the structure of phases obtained in both cases, the formation of not a true CoO–MgO solid solution, but rather a mixture of ordered oxides (“pseudo-solid solution”) in the low-temperature region, was postulated. A study of the activity of the samples showed the high activity of the spinel systems and a linear relationship between the activation energy of methane oxidation and the heat treatment temperature.

Mesoporous Silica MCM-41 from Fly Ash as a Support of Bimetallic Cu/Mn Catalysts for Toluene Combustion.

The main outcome of this research was to demonstrate the opportunity to obtain a stable and well-ordered structure of MCM-41 synthesized from fly ash. A series of bimetallic (Cu/Mn) catalysts supported at MCM-41 were prepared via grinding method and investigated in catalytic toluene combustion reaction to show the material's potential application. It was proved, that the Cu/Mn ratio had a crucial effect on the catalytic activity of prepared materials. The best catalytic performance was achieved with sample Cu/Mn(2.5/2.5), for which the temperature of 50% toluene conversion was found to be 300 °C. This value remains in line with the literature reports, for which comparable catalytic activity was attained for 3-fold higher metal loadings. Time-on-stream experiment proved the thermal stability of the investigated catalyst Cu/Mn(2.5/2.5). The obtained results bring a valuable background in the field of fly ash utilization, where fly ash-derived MCM-41 can be considered as efficient and stable support for dispersion of active phase for catalyst preparation.