Catalytic Decomposition Of N2O Research Articles

Highly active Mn-VO-Co sites by cobalt doping on cryptomethane for enhanced catalytic decomposition of N2O.

Direct catalytic decomposition has shown great promise in controlling the greenhouse gas N2O. Herein, we synthesize a series of cobalt-doped cryptomethane (OMS-2) catalysts for N2O catalytic decomposition by a mild one-step sol-gel method. The Co0.1-OMS-2 exhibits superior catalytic performance with 90% N2O conversion at 398 °C, which is attributed to the formation of the Mn-VO-Co structure served as active sites. The increased electron density on oxygen vacancies promotes the electron transfer between oxygen vacancies and N2O molecules, in turn facilitating the adsorption and activation of N2O. Moreover, Co doping reduces the formation energy of oxygen vacancies. However, excessive Co doping results in the decrease of highly active Mn-VO-Co sites and the formation of Co3O4, which makes Co0.3-OMS-2 exhibit poor catalytic activity. The DFT calculation illustrates that Langmuir-Hinshelwood is the primary reaction mechanism over Co0.1-OMS-2. This study broadens the materials applicable for the catalytic decomposition of N2O, offering an effective approach to modulate the electronic structure at oxygen vacancies.

Enhanced Nitrous Oxide Decomposition on Zirconium-Supported Rhodium Catalysts by Iridium Augmentation.

The effective elimination of N2O from automobile exhaust at low temperatures poses significant challenges. Compared to other materials, supported RhOx catalysts exhibit high N2O decomposition activities, even in the presence of O2, CO2, and H2O. Metal additives can enhance the low-temperature N2O decomposition activities over supported RhOx catalysts; however, the enhancement mechanism and active sites require further investigation. In this study, we demonstrate the significant enhancement of the low-temperature N2O decomposition activity of a monoclinic ZrO2-supported Rh catalyst [Rh(1)/ZrO2] with Ir addition in the presence of N2O + O2 + CO2 + H2O. The promotional effect of Ir and the active sites on N2O decomposition in Rh(1)-Ir(1)/ZrO2 (Rh = 1 wt % and Ir = 1 wt %) were investigated by kinetic studies and in situ spectroscopic methods, including X-ray absorption spectroscopy, ambient-pressure X-ray photoelectron spectroscopy, and ultraviolet-visible spectroscopy. These results indicate that both surface Rh and Ir species in Rh(1)-Ir(1)/ZrO2 were active sites for N2O catalytic decomposition at low temperatures, and Ir augmentation promoted the desorption of gaseous O2, which are regarded as key steps in N2O decomposition.

A review of chemical kinetic mechanisms and after-treatment of amino fuel combustion.

Ammonia is a highly promising carbon-neutral fuel. The use of ammonia as a fuel for internal combustion engines can reduce fossil energy consumption and greenhouse gas emissions. However, the high ignition energy required for ammonia and the slow flame propagation rate result in low combustion efficiency when ammonia is used directly in internal combustion engines. The combination of ammonia with highly reactive fuels improves combustion quality and increases efficiency. However, the combustion of these combined fuels generates particulate matter, CO, hydrocarbon, and significant amounts of NOx. Therefore, pollutant emissions must be reduced through after-treatment technologies. In this paper, a series of combustion and post-treatment challenges faced by amino fuel combustion in internal combustion engines are extensively discussed and the combustion reaction mechanisms of different amino fuels are also analyzed. The paper then reviews five key technologies applicable to the reprocessing of amino fuels, including selective catalytic reduction, selective catalytic reduction filter technology, electrochemical methods for NOx removal, direct catalytic decomposition of N2O, and ammonia sliding catalysts. An in-depth discussion of the catalytic materials and reaction mechanisms involved in these technologies is also provided in this paper. Finally, the paper summarizes the main technical challenges that must be addressed for the future application of amino fuels in internal combustion engines. These discussions can serve as an essential reference for developing and applying critical technologies for combustion control and pollutant treatment of amino fuels.

Uniform and fully exposed Rh clusters on defect-rich CeO2 enable efficient catalytic N2O decomposition

Uniform and fully exposed Rh clusters on defect-rich CeO2 enable efficient catalytic N2O decomposition

Assessing the role of oxygen vacancies on N2O catalytic decomposition over CaMn1-xFexO3-δ perovskites

Catalytic decomposition of N2O using redox perovskites can efficiently mitigate industrial emissions of this molecule. Here, we have selected the CaMn1-xFexO3-δ (CMF) oxides as catalysts to explore the role of oxygen vacancies on N2O decomposition, because for these materials the thermodynamics of oxygen non-stoichiometry is known in detail Perovskites with two levels of Fe-doping, CMF73 (30 % at.) and CMF91 (10 % at.), were prepared and extensively characterized. Higher conversion is obtained over CMF73, which also presents good stability. In the presence of N2O, variation of temperature prompts this perovskite to quickly adjust the value of δ by reversible release/uptake of O2. In parallel, surface vacancies can participate in the breaking of the N-O bond, as a part of a regenerative catalytic cycle yielding N2 and O2. A simple kinetic model shows good correlation between the number of oxygen vacancies, estimated by δ, and the catalytic activity, explaining the better performance of CMF73.

A new denitrification strategy based on high-temperature catalytic coatings Y2O3-BaO-ZrO2 without using ammonia in a lab-scale natural gas combustion furnace

Catalytic decomposition of NO at high temperatures without the use of ammonia, offers an eco-friendly and sustainable solution for denitrification in industrial combustion or heating processes. To simulate a complex combustion flue gas, we designed a lab-scale natural gas industrial combustion furnace specifically for assessing the impacts of Y2O3-BaO-ZrO2 catalyst coated on SiC plates on NO emissions. Various factors including the plate number, excess air ratio, combustion power, and coating position were considered. Results demonstrated that arranging the Y2O3-BaO-ZrO2 coated plates shifted the high-temperature zone of the furnace downstream. When the excess air ratio was below 1.05, the catalytic coating significantly reduced NO emission concentration at the furnace outlet by over 40 %. However, this reduction coincided with a substantial presence of unburned CO in flue gases. Placing the coated SiC plates in the constant temperature zone of 1100–1200 °C within the middle of furnace offered significant advantages in NO removal, particularly as the combustion power increased. Based on a 60-h durability evaluation of Y2O3-BaO-ZrO2 coating, the observed good high-temperature thermal and chemical stabilities further enhanced the coating’s potential for industrial application. The possible mechanism of the reduction NO by CO over coating surfaces were analyzed by in situ optical measurements. After calculation, using 12 kg Y2O3-BaO-ZrO2 catalysts might decrease at least 642 kg of ammonia consumption under ideal conditions, and significantly reduce the investment cost on existing flue gas denitrification equipment. Therefore, the investigated technology is a green and sustainable denitrification strategy, which would potentially provide a novel approach towards attaining ultra-low NO emissions.

Effects of Zn loading on ZnxCo1−xCo2O4 spinel catalysts for low-temperature catalytic decomposition of N2O in the presence of inhibitors

The recent advancement of NH3-based fuel demands the development of catalysts that can decompose N2O at low temperatures and are stable against various inhibitors. Zn-doped cobalt spinel (ZnxCo1−xCo2O4) catalysts have demonstrated superior activity for N2O decomposition at low temperatures. However, their optimization and deactivation mechanisms with respect to Zn loading when inhibitors are present require further investigation. Herein, we reviewed the effects of Zn loading on catalysts at low temperatures without or with the presence of inhibitors (3 vol% O2, 6 vol% H2O, 200 ppm NO). The results showed that adding an appropriate amount of Zn into Co3O4 spinel catalysts improves their N2O decomposition activity. The Zn-induced enhancement of the catalysts’ redox properties, and reducibility was the underlying mechanism behind the activity promotion. The presence of structural defects created through the addition of Zn enhanced the catalyst’s resistance to O2. The deactivation by H2O and NO upon the addition of Zn could be correlated with the reduced availability of surface Co species and Co2+ as adsorption-active sites and the stronger bond of Co with –NO, respectively. This study underscores the importance of controlling the Zn loading as a bulk redox promoter in ZnxCo1−xCo2O4 spinel catalysts for practical applications.

Application of Mesoporous/Hierarchical Zeolites as Catalysts for the Conversion of Nitrogen Pollutants: A Review

Mesoporous/hierarchical zeolites (HZs) are a relatively new group of materials, and interest in their application in catalysis is continuously growing. This paper presents recent achievements in the application of mesoporous zeolites in catalytic reactions of nitrogen pollutant conversion. The analysis presented includes processes such as selective catalytic reduction of NOx with ammonia (NH3-SCR, DeNOx), selective catalytic oxidation of ammonia (NH3-SCO, AMOx), and catalytic decomposition of N2O. Different zeolite topologies and methods of their modification focused on mesoporosity generation (e.g., desilication, dealumination, steaming, self-assembly techniques, and application of hard and soft templates) are reviewed and compared with respect to catalytic processes. Special attention is paid to the role of porous structure and acidity, as well as the form of deposited transition metals, in the catalytic activation of modified zeolites in the elimination of nitrogen pollutants from flue gases.

Facile Synthesis of N-doped Co3O4 Catalyst for Catalytic Decomposition of N2O under Simulated Real Tail Gases

Facile Synthesis of N-doped Co3O4 Catalyst for Catalytic Decomposition of N2O under Simulated Real Tail Gases

High-temperature treatment promotes N2O decomposition over Fe-impregnated Al-rich SSZ-13 zeolites

Fe/SSZ-13 catalysts were prepared via the impregnation method and calcined at different temperatures. The catalytic activity of Fe/SSZ-13 catalysts in the N2O catalytic decomposition reaction was greatly influenced by the calcination temperature. As the calcination temperature rose to 800 °C, the catalytic efficiency of N2O decomposition performance gradually improved. Nevertheless, if the temperature of calcination exceeded 800 °C, the efficiency diminished as a result of the disintegration of the molecular sieve framework. Various characterization methods were used to investigate the impact of calcination temperature on iron species. The results showed that the high-temperature treatment could promote the dispersion and reduction of Fe2O3 particles on the catalyst surface, which led to the generation of more active species (such as Fe3O4 and FeO) and provided more oxygen vacancies which favored the N-O breakage, thus improving the N2O decomposition activity.

Enhancement of N2O decomposition performance by co-doping of Ni and Y to Co3O4 catalyst

Co3O4, Y2O3-Co3O4 and NiO-Y2O3-Co3O4 samples were prepared by the simple co-precipitation method, and their N2O catalytic decomposition performance was evaluated. Experimental results disclose that the order of catalytic activity among the three catalysts is NiO-Y2O3-Co3O4 > Y2O3-Co3O4 >> Co3O4. N2O conversion over NiO-Y2O3-Co3O4 catalyst reached 100 % at 360 °C, which was 20 °C and 60 °C lower than those over Y2O3-Co3O4 and Co3O4, respectively. In addition, NiO-Y2O3-Co3O4 catalyst shows better water resistance compared with Co3O4 and Y2O3-Co3O4. Systems-based characterization techniques, it is confirm that Y and Ni were successfully doped into Co3O4, where Y was on the surface and Ni was mainly in the bulk phase. Due to the co-doping of Y and Ni, NiO-Y2O3-Co3O4 catalyst has smaller average particle size and reinforced surface alkalinity. Furthermore, the surface modification of Y enhances the electron-donating capacity of Co2+ and oxygen desorption ability, while bulk phase doping of Ni facilitates the reduction of Co3+ to Co2+ and weakens Co-O bond in Co3O4, which endow NiO-Y2O3-Co3O4 sample with lower Ea for N2O decomposition. Therefore, NiO-Y2O3-Co3O4 catalyst exhibits the best N2O catalytic decomposition performance.

Enhanced N2O decomposition on Rh/ZrO2 catalysts through the promotional effect of palladium

Supported rhodium oxide (RhOx) catalysts have emerged as highly promising for effectively catalytic decomposition of N2O, hence contributing to the mitigation of greenhouse gas emission and combating global warming. Supported RhOx catalysts outperform catalysts employing zeolites and composite metal oxides even under challenging conditions involving O2, H2O, and CO2. This study explores the augmentation of Rh/ZrO2 (RhOx supported on monoclinic ZrO2) catalyst efficiency through the addition of palladium (Pd) to yield RhPd/ZrO2. The augmented catalyst demonstrates notable improvements in N2O decomposition under both N2O-only and more realistic conditions (N2O + O2 + H2O + CO2). Various techniques, including high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption spectroscopy, were employed to investigate the structural characteristics of Rh and Pd species on ZrO2. Kinetic studies further delved into the promotional effect, revealing that the introduction of Pd enhanced the catalytic activity of RhOx catalysts by augmenting their thermal reduction capability. This enhancement proved beneficial in facilitating the efficient progression of the rate-determining step for N2O catalytic decomposition, namely the thermal reduction of the catalyst to produce gaseous O2, particularly at low temperatures. These results highlight the potential of Pd-mediated improvements in Rh/ZrO2 catalysts for sustainable and efficient N2O decomposition.

Boosting N2O Catalytic Decomposition by the Synergistic Effect of Multiple Elements in Cobalt-Based High-Entropy Oxides.

Nitrous oxide (N2O) has a detrimental impact on the greenhouse effect, and its efficient catalytic decomposition at low temperatures remains challenging. Herein, the cobalt-based high-entropy oxide with a spinel-type structure (Co-HEO) is successfully fabricated via a facile coprecipitation method for N2O catalytic decomposition. The obtained Co-HEO catalyst displays more remarkable catalytic performance and higher thermal stability compared with single and binary Co-based oxides, as the temperature of 90% N2O decomposition (T90) is 356 °C. A series of characterization results reveal that the synergistic effect of multiple elements enhances the reducibility and augments oxygen vacancy in the high-entropy system, thus boosting the activity of the Co-HEO catalyst. Moreover, density functional theory (DFT) calculations and the temperature-programmed surface reaction (TPSR) with isotope labeling demonstrate that N2O decomposition on the Co-HEO catalyst follows the Langmuir-Hinshelwood (L-H) mechanism with the promotion of abundant oxygen vacancies. This work provides a fundamental understanding of the synergistic catalytic effect in N2O decomposition and paves the way for the novel environmental catalytic applications of HEO.

Density Functional Theory Study of Mechanism of Reduction of N2O by CO over Fe-ZSM-5 Zeolites

Nitrous oxide (N2O) is an industrial waste gas (e.g., from the production of adipic acid), which damages the ozone layer and causes the greenhouse effect. Density functional theory calculations were employed to investigate the mechanism of direct catalytic decomposition of N2O and selective catalytic reduction (SCR) of N2O by CO over Fe-ZSM-5 zeolites. Two stable Fe-active sites with six-membered ring structures on Fe-ZSM-5 were considered. The calculations indicate that the decomposition of N2O is affected by the coordination environment around Fe and can occur through two reaction pathways. However, there is invariably a more considerable energy hurdle for the initiation of the second stage of N2O decomposition. When CO participated in the reaction, it showed good reactivity and stability, the reaction energy barriers of the rate-limiting step were reduced by roughly 20.57 kcal/mol compared to the direct catalytic decomposition of N2O. CO exhibited a superior electron-donating ability and orbital hybridization performance during the reaction, which enhanced the cyclicity of the N2O reduction catalytic process. Our calculations confirmed the significant role of CO in N2O reduction over Fe-ZSM-5 observed in previous studies. This study provides a valuable theoretical reference for exploring CO-SCR methods for N2O reduction over Fe-based zeolite catalysts.

New insights into the effect of polyvinyl alcohol on Co3O4 spinel oxide catalyst for N2O decomposition

Polyvinyl alcohol (PVA)-assisted precipitation method offered surface modification Co3O4 spinel oxides which were applied to catalytic N2O decomposition. PVA was added in the preparation process and endowed catalysts with changes in surface metal ions valance state properties, i.e. Co2+ ions which served as active centers. Co3O4 adding PVA (Co3O4-P) showed superior performance for catalytic N2O decomposition with a high gas hourly space velocity of 400,000 h−1. Co2+ ion quantities were positively correlated to catalytic performance which was inseparable from PVA superhydrophobicity and reducibility during the preparation process. Moreover, density functional theory (DFT) calculation revealed N2O preferable adsorption on Co2+ sites whether near oxygen vacancies or not, which indirectly affirmed the reason Co3O4-P with superior catalytic N2O decomposition property. Our research gave more evidence to N2O decomposition active sites from atom-scale for Co3O4 spinel oxides and provided a novel pathway for high-performance catalyst preparation.

Low-temperature direct decomposition of NO over Rh/NC-MnFe catalyst: activity, stability and mechanism

As the ideal NO removal technology, the biggest challenge associated with the direct catalytic decomposition of NO is the development of highly active deNOx catalysts at low temperatures.

Roles of Re and Cs Promoters and Organochlorine Moderators in the Synthesis of Ethylene Oxide on Ag‐based Catalysts

AbstractC2H4−O2 reactions form ethylene oxide (EO) on Ag nanoparticles dispersed on α‐Al2O3 and promoted with alkali and other elements, with Re and Cs most frequently used in practice. Traces of alkyl chlorides (e. g., C2H5Cl) and alkanes in much larger amounts are added to reactants to balance the rate of deposition and removal (and the coverage) of Cl adatoms (Cl*) on Ag surfaces. Such Cl adlayers retain Ag surface ensembles that form O2‐derived intermediates that favor EO synthesis, but typically decrease O2 activation rates. A series of Ag/α‐Al2O3 catalysts (with and without Re or Cs) are used here to examine the role of promoters and Cl moderators through an analysis of the effects of reaction conditions and C2H5Cl levels using convection‐reaction constructs and a mechanistic formalism that considers O2 (as chemisorbed O2*) as the reactant in EO synthesis through one electrophilic O‐atom, with the second O‐atom (O*) acting as a unselective nucleophile that must be scavenged by a sacrificial reductant (C2H4 or EO); such channels are precluded by any intervening O2 dissociation events (that form two O*). O2 consumption rates in C2H4−O2 reactions decrease 10‐fold upon exposing Ag/α‐Al2O3 to C2H5Cl, evincing persistent Cl* species that block active sites and require >104 C2H4 oxidation turnovers to be removed. Activation barriers do not change but relative rates of epoxidation versus combustion increase in the presence of this refractory Cl* adlayer, which reduces the number and shrinks the size of available site ensembles without altering their intrinsic reactivity for O2 activation to form O2* but attenuating rates of its subsequent dissociation. Refractory O* adlayers also form on Ag surfaces, as shown by the accumulation of persistent O* species upon exposing reduced Ag particles to N2O. Inter‐atom repulsive forces weaken O* binding and destabilize N2O decomposition transition states to eventually allow stable N2 and O2 evolution for catalytic N2O decomposition, which occurs at landing ensembles formed at interstices of refractory adlayers. Cl* forms denser adlayers than O*, as evidenced by a 10‐fold decrease not only to C2H4−O2 rates but also to N2O stoichiometric and catalytic rates and O* uptakes. The occasional evolution of O2, which forms larger landing ensembles that more readily form 2O* from O2, occurs with higher frequency from O* than mixed O*/Cl* adlayers, and this effect of Cl* to inhibit (O−O)* dissociation is demonstrated in CO probe reaction studies, which show that highly reactive bound dioxygen species are retained to a greater extent when adlayers comprise both Cl* and O*. Re and Cs do not influence the nature of such adlayers but increase and decrease, respectively, the number of acid sites and selectivity losses via EO combustion. Their respective domains may also block a modest fraction of Ag surfaces without consequences on intrinsic O2 activation rates or EO selectivities. The effects of Re beyond those reported here may emerge upon synthetic protocols that alter Re location and Ag−Re intimacy to enable channels which utilize both O‐atoms in epoxidation.

Multiple cobalt species on HZSM-5 cooperative catalyzing N2O decomposition

As a strong greenhouse gas with a wide lifespan, nitrous oxide (N2O) reduction emissions are imperative. Transition metal oxides, especially cobalt oxides, possess superior N2O catalytic decomposition properties. A series of cobalt-incorporated HZSM-5 (Co/HZ) catalysts were synthesized by citric acid-complexion impregnation and were systematically investigated by N2O decomposition and characterizations. Co content and calcination temperature influenced cobalt species distribution and active site amount. Multiple cobalt species were found and cooperatively catalyzed N2O decomposition. Co2+ ions in cobalt species are regarded as active sites in N2O decomposition and the 10Co/HZ-800 catalyst showed better N2O catalytic decomposition performance, O2, and NO tolerance. The 10Co/HZ-800 catalyst was subjected to in situ diffuse reflectance infrared Fourier-transform spectroscopy (in situ DRIFTS) for surveying N2O adsorption patterns on the surface under different temperatures and atmospheres.

In-situ polymerization intercalation of montmorillonite to achieve Co3O4 barrier dispersion for direct catalytic decomposition of N2O

Herein, the Co-MMT (Co3O4-montmorillonite) catalysts were prepared by coordination-deposition (Co(0.015)-MMT-2(CD)) and deposition-precipitation method (Co(0.015)-MMT-2 (DP)) for the N2O direct decomposition, respectively. The structure, texture, and surface properties of the catalysts are characterized by XRD, TEM, FT-IR, Raman, XPS, and so on. The results show that compared with Co(0.015)-MMT-2(DP), Co(0.015)-MMT-2(CD) achieves barrier dispersion of active phase (Co3O4) by using the layer structure of montmorillonite and has a smaller Co3O4 crystal size, richer oxygen vacancy and higher content of Co2+Oh. In addition, the results of DFT calculation and kinetic calculation indicate that Co2+Oh possesses higher reaction activity than Co2+Td and Co3+Oh, and the TOF value of Co(0.015)-MMT-2(CD) at 400 ℃ is 3 times higher than that of Co(0.015)-MMT-2(DP). Therefore, the Co(0.015)-MMT-2(CD) catalyst shows excellent catalytic activity and tolerance to impurity gases (H2O, NO, and O2), and it can maintain 100% conversion at least 50 h for the direct catalytic decomposition of N2O.

Waste eggshell to valuable Co3O4/eggshell material as an efficient catalyst for catalytic decomposition of N2O under simulated real tail gases

Co3O4 shows excellent catalytic activity for N2O decomposition, in which it is urgently needed to develop novel efficient catalysts/supports with cheap and environmentally-friendly properties. Herein, Co3O4 nanoparticles decorated eggshell catalysts (Co3O4/eggshell-GR, Co3O4/eggshell-IM, and Co3O4/eggshell-DP) were prepared using simple grinding, impregnation, and deposition-precipitation methods, where waste eggshells were used as an effective support and reaction-promoter. The results indicated that the preparation methods significantly influenced the catalytic activity of Co3O4/eggshell catalysts; the highest activity was obtained over the Co3O4/eggshell-DP. The activity of Co3O4/eggshell-DP was comparable to that of pure Co3O4. More importantly, its specific activity was about 7.3 times that of Co3O4 at 400 °C. The examined Co3O4/eggshell-DP also displayed outstanding stability and anti-poisoning property in NO, O2, and/or H2O-containing atmospheres. It was also verified that the excellent activity of Co3O4/eggshell-DP correlated with the unique structure of the eggshell and the close incorporation between CaCO3 and Co3O4. The Co3O4/eggshell-DP catalyst owned abundant Co3O4 nanoparticles, more Co3+ species, and excellent redox performance, promoting the conversion of N2O at a lower temperature. The presence of abundant surface basic sites and a larger amount of oxygen vacancies also facilitated the catalytic efficiency of Co3O4/eggshell-DP.