NH3 Oxidation Research Articles

Theory-driven design of graphene schiff base iron nanocomplex as catalyst for composite propellant

New graphene Schiff base iron nanocomplexes (S-792-Fe, S-550-Fe, and S-590-Fe) were designed and fabricated based on investigations of reactions mechanisms of AP pyrolysis, structural analysis of new materials and simulation results of quantum mechanics to deal with the long-standing contradiction between safety and performance for composite propellent combustion catalyst. By taking traditional catalyst Catocene as the benchmark, the S-550-Fe nanocomplexes exhibited competitive catalytic performances, much better anti-migration properties and significantly reduced impact and electrostatic sensitivities. After adding S-550-Fe, the burning rate of propellant enhanced from 13.87 to 19.77 mm s−1 at 15 MPa, and the impact and electrostatic sensitivities are improved to 50.2 cm and 172.12 mJ, respectively. The excellent catalytic performance of S-550-Fe is closely related to its molecular structure, which is manifested by an increase in charge density and a decrease in NH3 oxidation energy barriers. The promotion effects of S-550-Fe on desorption and oxidation of NH3 from the surface of AP is conducive to the rapid and complete pyrolysis of AP, which is reflected in the improvement of combustion rate and temperature gradient. The theory-driven design mode of this work may provide new pathways to tune combustion behaviors of composite propellants from the view of molecular-level insights.

Highly Sensitive Room-Temperature Detection of Ammonia in the Breath of Kidney Disease Patients Using Fe2Mo3O8/MoO2@MoS2 Nanocomposite Gas Sensor.

A novel Fe2Mo3O8/MoO2@MoS2 nanocomposite is synthesized for extremely sensitive detection of NH3 in the breath of kidney disease patients at room temperature. Compared to MoS2, α-Fe2O3/MoS2, and MoO2@MoS2, it shows the optimal gas-sensing performance by optimizing the formation of Fe2Mo3O8 at 900°C. The annealed Fe2Mo3O8/MoO2@MoS2 nanocomposite (Fe2Mo3O8/MoO2@MoS2-900°C) sensor demonstrates a remarkably high selectivity of NH3 with a response of 875% to 30ppm NH3 and an ultralow detection limit of 3.7 ppb. This sensor demonstrates excellent linearity, repeatability, and long-term stability. Furthermore, it effectively differentiates between patients at varying stages of kidney disease through quantitative NH3 measurements. The sensing mechanism is elucidated through the analysis of alterations in X-ray photoelectron spectroscopy (XPS)signals, which is supported by density functional theory (DFT) calculations illustrating the NH3 adsorption and oxidation pathways and their effects on charge transfer, resulting in the conductivity change as the sensing signal. The excellent performance is mainly attributed to the heterojunction among MoS2, MoO2, and Fe2Mo3O8 and the exceptional adsorption and catalytic activity of Fe2Mo3O8/MoO2@MoS2-900°C for NH3. This research presents a promising new material optimized for detecting NH3 in exhaled breath and a new strategy for the early diagnosis and management of kidney disease.

Promoting effects of cerium oxide on catalysts performance for selectivity catalytic oxidation of NH3 over RuOx/TiO2

Cerium oxide (CeO2) was added to modified Ru/TiO2 catalyst by a two-step impregnation method for selective catalytic oxidation of ammonia (NH3-SCO). The low-temperature NH3 oxidation activity and N2 selectivity of the 1Ru/xCe-TiO2 catalyst were investigated with the result that both SCO activity and N2 selectivity were influenced by the amount of Ce. Specifically, the presence of 5 wt% CeO2 demonstrated a great promoting effect on both parameters, reaching an NH3 conversion and N2 selectivity of 97 % and 93 % at 180 ℃, respectively. Various characterization methods indicated that the presence of CeO2 regulates the dispersion of the 1Ru/xCe-TiO2 catalysts, changes the amount, strength and ratio of strong and weak acid sites on the catalyst surface, and promotes the formation of Ru-O-Ce bonds through the interaction between Ce and Ru species, which facilitates electron transfer and oxygen vacancy formation, thereby enhancing the oxidation ability of the catalysts. Furthermore, the results of in situ diffuse reflectance infrared Fourier transform spectroscopy indicated that the NH3-SCO reaction over the 1Ru/xCe-TiO2 catalysts follows the “internal” selective catalytic reduction (i-SCR) mechanism, involving the oxidation of NH3 into nitric oxide (NO) species and the reaction of -NH2 with in situ-formed NO to form N2.

Catalytic performance and mechanism of PtxVW catalyst for selective catalytic oxidation of high-concentration NH3

It is foreseeable that a high-concentration NH3 may exist in exhaust gas of NH3-fuel engines, which may result in some negative damages to ecological environment. Herein, a series of PtxVW catalysts with extremely low Pt doping amounts were synthesized with the aim to remove high-concentration NH3 efficiently via selective catalytic oxidation (SCO) method. The results showed that, Pt0.04VW catalyst (0.04 wt% Pt) achieved a complete NH3 conversion at 250 ºC. Both catalytic activity and N2 selectivity of Pt0.04VW catalyst were much superior over Pt/Al2O3 catalyst (1 wt% Pt) in a wide temperature range of 250–450 ºC. XPS, Raman and H2-TPR results indicated that Pt existed in the lattice of VOx and formed Pt-V bimetallic oxides. The interaction between Pt and V played a key role in the NH3-SCO reactions. DFT calculation demonstrated that dual electron transfer pathways between Pt and V atoms in PtxVW catalysts were beneficial for NH3 coordination on Lewis acid sites, then enhancing NH3-SCO reactions. In-situ DRIFTS and NH3-TPD product analysis suggested that NH3-SCO reactions on Pt0.04VW catalyst surface abide by internal selective catalytic reduction (i-SCR) and hydrazine mechanisms. Moreover, coordinated NH3 species on Lewis acid sites, bidentate nitrate species were the main intermediates in NH3-SCO reactions over Pt0.04VW catalyst.

Performance of ammonia catalytic combustion over Cu-CeOx catalyst and the impact of oxygen concentration

Ammonia has long been regarded as a high-quality zero-carbon fuel; however, limitations in its combustion characteristics have restricted its practical applications. Catalytic combustion is considered an effective solution to overcome the challenges associated with ammonia combustion. In this study, we successfully synthesized a copper-cerium binary catalyst (Cu-CeOx) using the sol-gel method, demonstrating outstanding performance for NH3 catalytic combustion. Through in-situ DRIFTS results, we observed that the 15Cu-CeOx catalyst exhibits both i-SCR and -NH mechanisms. The oxygen concentration affects the N2 selectivity by modulating the overoxidation of NH3. Under high oxygen concentrations, high temperatures promote the excessive oxidation of NH3, and ammonia combustion through the i-SCR mechanism. Conversely, the oxygen concentration was equal to NH3 reaction stoichiometry, the overoxidation of NH3 is limited, and ammonia combustion proceeds through the NH mechanism, resulting in higher N2 selectivity.

Ammonia and toluene oxidation: Mutual activating effect of copper and cerium on catalytic efficiency

Copper and cerium containing hydrotalcite-like precursors Cux-Cey-Mg-Al were synthesized by mutual co-precipitation followed by calcination at 800 °C. The obtained mixed metal oxides were studied as catalysts for selective ammonia oxidation (NH3-SCO) and toluene combustion. Various techniques, such as temperature-programmed reduction with hydrogen, temperature-programmed desorption of toluene, scanning electron microscopy and reactive frontal chromatography were used to characterize the catalysts. Series 800-Cux-Ce2.5 showed the highest catalytic efficiency in both reactions, allowing complete NH3 and C7H8 conversion below 350 °C and 500 °C, respectively. CeO2 crystallites (12–18 nm), as well as dispersed CuO oxide forms were found in the most active samples. Both phases affect pollutants conversion, however, for ammonia oxidation the occurrence of Cu2+ is essential, while for toluene oxidation, the formation of Ce4+ is sufficient. Over the most active sample (800-Cu5-Ce2.5) the complete conversion in mutual oxidation of NH3 and toluene was achieved below 450 °C.

CaMnO3 perovskite-derived porous γ-MnO2 for highly efficient oxidation of NH3 and NO

Selective dissolution is highly promising for tailoring the structures and functions of metal oxides toward various applications. Here, we demonstrate a successful fabrication of porous γ-MnO2 by selectively dissolving Ca in a CaMnO3 perovskite (CMO) via dilute HNO3 treatment. The perovskite-derived γ-MnO2 (denoted as CMO-72 h) outperformed drastically the pristine CaMnO3 and a commercial γ-MnO2 in the catalytic oxidation of NH3 and NO, two representative gaseous pollutants in the atmosphere. Physicochemical characterization by X-ray photoelectron spectroscopy and temperature-programmed techniques (including H2-TPR, O2-TPD and NH3-TPD) suggests that the excellent catalytic performance of CMO-72 h is associated with its low–temperature reducibility and abundant surface–active oxygen species. Specifically, acid treatment led to the oxidation of Mn3+ to Mn4+ on the surface, increasing significantly the Mn4+/Mn3+ ratio from 0.76 (for CMO) to 1.45 (for CMO-72 h) and, meanwhile, generating additional surface oxygen vacancies. As a result, O2 molecules can be easily adsorbed and activated on the CMO-72 h, leading to improved performance in NH3 and NO oxidation. This study may offer new opportunities in the synthesis of high-performance Mn oxide catalysts for environmental applications.

Designing ammonia oxidation catalysts via physical mixing of Pt/SiO2 and Cu/ZSM-5

Ammonia (NH3) is emerging as a carbon-neutral fuel alternative; however, its use poses environmental and health risks due to NH3 slip. The NH3-selective catalytic oxidation (NH3-SCO) process, which converts NH3 into N2 and H2O, offers a solution. However, it faces challenges with respect to the formation of byproducts, particularly N2O and NOx. This study focuses on designing NH3-SCO catalysts to enhance low temperature NH3 conversion efficiency while minimizing undesired byproducts. Pt/SiO2 catalysts were synthesized with adjusted Pt particle sizes to improve the NH3-SCO activity and were physically mixed with Cu/ZSM-5 to overcome the low N2 selectivity of Pt-based catalysts by utilizing the selective catalytic reduction (SCR) ability of Cu/ZSM-5. Pt1Cu3 catalyst, a physical mixture of Pt/SiO2 and Cu/ZSM-5 in a 1:3 mass ratio, was found to be the most effective, achieving complete NH3 oxidation at 250 ℃ while maintaining a high N2 selectivity of approximately 80%. Further investigation revealed that the performance of the Pt1Cu3 catalyst was significantly influenced by the arrangement and physical proximity of the Pt/SiO2 and Cu/ZSM-5 catalysts, with a closely contacted mixture showing synergistic effects that enhanced activity and selectivity. These results suggest that the Pt1Cu3 catalyst offers a promising solution for NH3 emission control by utilizing a balanced approach that combines SCO and SCR reactions.

Neural network potential-based molecular investigation of pollutant formation of ammonia and ammonia-hydrogen combustion

This study developed neural network potentials (NNPs) specifically designed for ammonia and ammonia-hydrogen combustion systems for the first time. The NNPs were employed to perform reactive molecular dynamics (RMD) simulations, combining the precision of density functional theory (DFT) calculations with the efficiency of empirical force fields. NNP-based RMD simulations provide a more detailed and comprehensive understanding of chemical reaction mechanisms. The impacts of different equivalence ratios and hydrogen addition on ammonia combustion as well as NOX and N2O formation were analysed. The results indicate that both the addition of hydrogen and the reduction of equivalence ratios contribute to enhancing ammonia combustion. The primary reason is the enhancement of the oxidative environment within the system, leading to a significant increase in the frequency of reactions associated with oxidising radicals such as OH, O, and HO2. This is also the cause for the increased production of NO and NO2, because the formation of NO depends on the oxidation of NH and NH2, while NO2 is formed through the oxidation of NO. An interesting finding is that the addition of hydrogen decelerates the generation of N2O, while reducing the equivalence ratio promotes N2O production. This phenomenon is attributed to the additional H radicals generated during hydrogen decomposition, which hinders the binding between NH and NO, resulting in a reduction in the formation of the precursor HN2O required for N2O formation.

Promoting effect of polyoxometallic acid modification on the NH3-SCR performance of Mn-based catalysts

The strong oxidation capabilities of Mn sites render Mn-based catalysts showing high activities of selective catalytic reduction (SCR) at temperatures < 250℃, but simultaneously lead to the generation of by-product N2O with strong greenhouse effect. The activity-N2-selectivity trade-off was a prevalent observation in the development of Mn-based SCR catalysts. Here, a polyoxometallic acid enhancement strategy was devised to simultaneously promote the N2 selectivity and low-temperature SCR (LT-SCR) activity of Mn-based metal oxide catalysts, where the introduction of uniformly dispersed phosphomolybdic acid (HPMo) tuned the oxidation capabilities and enhanced NH3 adsorption-storage capability of catalysts. The combination of transient reaction, in-situ DRIFTS analysis and DFT calculations revealed that the main origin of N2O on the Mn-based catalysts was the deep oxidation of NH3, which was inhibited by the interaction between HPMo and Mn sites. Additional NH3 molecules adsorbed by the abundant acid sites supplied by HPMo further facilitated the SCR reaction. This strategy could guide the design of high-activity and high-selectivity LT-SCR catalysts for industrial denitration.

Insights into the Construction of Robust Pt Clusters with Satisfactory Stability on CeO2 for the Catalytic Oxidation of CO.

Improving the efficiency of platinum group metals (Pt, Pd, Rh, etc.) in catalytic oxidation reactions remains an urgent topic. The conflict between the low-temperature activity and high-temperature stability of noble metals can hardly reach a consensus. For instance, Pt cluster catalysts supported on CeO2 with high low-temperature activity will suffer from deactivation due to the redispersion under high-temperature lean-burn reaction conditions. Herein, two Pt1/CeO2 prepared by the incipient wetness impregnation method using different Pt precursors possessed varied Pt-O and Pt-O-Ce coordination numbers (CNs). They showed various priorities in CO oxidation versus NH3 selective catalytic oxidation, materials with higher CNPt-O-Ce selectively catalyzing NH3 oxidation to N2 more superior, conversely materials with lower CNPt-O-Ce performing better in CO oxidation. After activation by H2 reduction, both formed massive Pt clusters on the CeO2 surface but showed drastically distinct stability in lean-burn CO oxidation reactions. By summarizing the experimental results of high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, Raman spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy, etc., it is beyond doubt that the difference in the initial states of Pt1 due to distinct precursors indeed determine the redispersion behavior of the reduced Pt clusters on CeO2. Materials with lower CNPt-O-Ce and higher CNPt-O are more likely to form robust Pt clusters, as they are not conducive to Pt anchoring, thus restricting the reversible structural evolution occurring under lean-burn CO oxidation and reductive conditions. This approach serves as a guide for the convenient and efficient construction and exploration of robust Pt cluster catalysts.

Impact of mild hydrothermal aging on kinetics of NH[formula omitted], NO, SO[formula omitted] and CO oxidation reactions on Cu/SSZ-13 catalyst

Cu/SSZ-13 is a catalyst commonly used for selective catalytic reduction (SCR) of nitrogen oxides (NOx) in diesel engine exhaust. Standard configurations are based on SCR preceded by an oxidation catalyst, however, a close-coupled SCR configuration appears relevant for upcoming regulations addressing cold-start emissions. Two often discussed ion-exchanged Cu sites in Cu/SSZ-13 are denoted ZCuOH and Z2Cu, where Z represents an Al atom in the zeolite framework. Mild hydrothermal aging (HTA) causes Cu redistribution within the catalyst; ZCuOH sites transform into more stable Z2Cu species. In this work, the effect of mild HTA on NH3, NO, SO2, and CO oxidation is studied on a commercial Cu/SSZ-13 sample. Temperature-programmed reaction experiments, performed in a lab reactor, and previously published catalyst characterization data using H2-TPR, NH3-TPD, and DRIFTS were used to build and validate a mathematical model. It couples the kinetics of the oxidation reactions with ZCuOH and Z2Cu concentration evolution during mild HTA. The model uses two distinct rate coefficients for ZCuOH and Z2Cu sites, allowing prediction of the catalyst activity during aging. The results suggest that the rate coefficients for the studied reactions on Z2Cu are effectively nil, so the observed activity in NH3, NO, SO2, and CO oxidation can be attributed solely to ZCuOH sites.

Molecular Complexes for Catalytic Ammonia Oxidation to Dinitrogen and the Cleavage of N−H Bonds

AbstractThe molecular complexes described herein use main‐group elements or transition metals to control the stoichiometric cleavage of N−H bonds of ammonia (NH3) and/or catalyze chemical and electrochemical NH3 oxidation to dinitrogen (N2). We highlight the phenomenon of coordination‐induced bond weakening and a variety of N−H bond cleavage mechanisms of NH3 including H atom abstraction, inter‐ and intra‐molecular deprotonation reactions, oxidative addition, and σ‐bond metathesis that have been demonstrated with molecular systems. We provide an overview of the molecular complexes reported for the rapidly developing field of NH3 oxidation catalysis to form N2. These systems exhibit several diverse structure types and innovative ligands to support transition metals capable of activating NH3 and mediating a challenging chemical transformation that requires breaking strong N−H bonds and forming an N−N bond en route to N2 formation.

Biochar reduces gaseous emissions during poultry manure composting: Evidence from the evolution of associated functional genes

Biochar has demonstrated the potential in mitigating pollutant gaseous emission during composting. However, little is known about the difference among biochars derived from different plant feedstocks on the critical genes' expression and microbial communities’ succession for gaseous emissions. In this study, the effects of biochar (from wood chips, cornstalks, and rice husks) on gaseous emissions during chicken manure composting were investigated. Environmental factors, bacterial communities, and functional genes related to CH4, N2O, NH3, and H2S emissions were analyzed to reveal the reduction pathways of different biochar amendments during composting. Results showed that all biochar treatments improved the seed germination index of the compost from unmature (55.74%) to mature (70.28–75.23%). The CH4, N2O, NH3, and H2S emissions from all biochar-treated composts were reduced by 18.93–27.47%, 35.74–52.82%, 1.26–36.38%, and 8.57–24.14%, respectively, and the cornstalk biochar had the highest emission reduction performance. Temperature, pH, and NH4+ were the major environmental factors that affected Lactobacillus and Bacillus activities, which critically influenced the CH4, N2O, NH3, and H2S emissions during composting. Furthermore, cornstalk biochar mainly improved pmoA for CH4 reduction, whereas wood chip biochar increased amoA for NH3 oxidation. Rice husk biochar mostly decreased nirS and nirK and increased norB, narG, and nosZ during N2O reduction. Cornstalk biochar also increased dsrB and decreased aprA during H2S reduction. Overall, cornstalk biochar was determined to be an optimal additive for simultaneously improving compost maturity and reducing gaseous pollutant emissions during chicken manure composting. This study verified the mechanisms of three plant derived biochars in pollutant gas control in composting, and thus provided evidence for facilitating the sustainable development of composting technologies.

NOx emissions during oxygen-enriched combustion of sewage sludge and corresponding hydrochar

This study proposed an oxygen-enriched combustion technology for the resource utilization of hydrochar prepared from sewage sludge (SS) through hydrothermal carbonization (HTC). However, its application potential relies heavily on NOx emissions. To investigate NOx emissions during oxygen-enriched combustion of hydrochars prepared at different temperatures (200 °C, 240 °C, and 280 °C), real-time NOx concentrations were recorded under varying conditions, including different carrier gases (N2 and CO2), temperatures (600 °C, 800 °C, and 1000 °C), and oxygen concentrations (20 %, 30 %, and 40 %). In comparison to air combustion processes, the NOx emissions during the devolatilization stage were considerably depressed in oxygen-enriched combustion. A high concentration of CO2 inhibited NH3 production and HCN oxidation, and generated increased amounts of CO to facilitate NOx reduction. Elevated temperatures also reduced the NOx release during the oxygen-enriched combustion of SS and hydrochar, as the accelerated oxygen consumption weakened the oxidation reactions of HCN and NH3; the enhanced reduction reaction rate and increased CO production also promoted NOx reduction. Elevated oxygen concentrations, however, promoted NOx release owing to the increased NH3 and HCN oxidation by an increased number of oxidizing groups. Additionally, the reduction of reducing gases and rapid char combustion hindered NOx reduction. The NOx-N conversion of the hydrochars was much lower than that of SS under different conditions. HTC effectively reduced the nitrogen content of SS, with nitrogen in HC-280 existing as stable heterocyclic -N. HC-280 showed significantly less nitrogen conversion at low temperatures (9.03 % reduction at 600 °C) and high oxygen concentrations (2.01 % reduction at 40 % O2) compared to SS, highlighting the potential of combining HTC and oxygen-enriched combustion.

Enhanced photocatalytic ammonia oxidation over WO3@TiO2 heterostructures by constructing an interfacial electric field

WO3 nanorods and xWO3@TiO2 (WO3/TiO2 mass ratio (x) = 1−5) photocatalysts were synthesized using the hydrothermal and sol-gel methods, respectively. The photocatalytic activities of xWO3@TiO2 for NH3 oxidation first increased and then decreased with a rise in TiO2 content. Among them, the heterostructured 3WO3@TiO2 photocatalyst showed the highest NH3 conversion (58 %) under the simulated sunlight irradiation, which was about two times higher than those of WO3 and TiO2. Furthermore, the smallest amounts of by-products (i.e., NO and NO2) were produced over 3WO3@TiO2. The enhancement in photocatalytic performance (i.e., NH3 conversion and N2 selectivity) of 3WO3@TiO2 was mainly attributed to the formed interfacial electric field between WO3 and TiO2, which promoted efficient separation and transfer of photogenerated charge carriers. Based on the results of reactive species trapping and active radical detection, photocatalytic oxidation of NH3 over 3WO3@TiO2 was governed by the photogenerated holes and superoxide radicals. This work combines two strategies of morphological regulation and interfacial electric field construction to simultaneously improve light utilization and photogenerated charge separation efficiency, which promotes the development of full-spectrum photocatalysts for the removal of ammonia.

The spatiotemporal heterogeneity of fertosphere hotspots impacted by biochar addition and the implications for NH3 and N2O emissions

The fertosphere, as the interfaces between fertilizer granular and soil particles, represents a key hotspot for nitrogen transformation processes, particularly for ammonia (NH3) and nitrous oxide (N2O) emissions. Understanding the heterogeneity of the fertosphere, especially when incorporating organic amendments like biochars, is crucial for predicting NH3 and N2O emissions after soil fertilization. In this study, we investigated the effects of three types of biochar (pristine, aged, and acid-washed biochar) on heterogeneity of fertosphere induced by localized urea application. pH-specific planar optodes were employed to visualize pH gradients in fertosphere hotspots with high spatial and temporal resolution. In addition, we conducted thorough measurements of the gradient distribution of electric conductivity (EC), mineral N, aqueous NH3 in soil and enzyme activities relevant to nitrification. Concurrently, NH3 and N2O emissions from the soil were continuously monitored at a high temporal resolution. Initially, urea-induced fertosphere exhibited significant NH3 emissions, primarily attributed to the pH elevation resulting from urea hydrolysis. However, after 6 days, NH3 emissions subsided, and there was a notable sharp increase in N2O emissions. Importantly, compared to urea application alone, the inclusion of pristine biochar led to a delay in soil pH decline with a 19% rise in NH3 emission. Aged biochar, characterized by a higher content of oxygen functional groups, demonstrated increased NH4+/NH3 adsorption capacity and enhanced ammonia monooxygenase (AMO) activity in soil, resulting in an 18% reduction in NH3 emission. While a slight decrease of 5% in NH3 cumulative emission was observed in the acid-washed biochar treatment. Notably, biochar could potentially promote nitrification-derived N2O emissions due to the accumulation of NH3 oxidation products (NH2OH). These findings could contribute to refining N transformation models for fertilized soils, and optimizing N fertilizer application strategies.

Selective oxidation of ammonia nitrogen to nitrogen gas by Fe2+/PMS/Cl−: The role of reactive chlorine species

Ammonia nitrogen (NH4+-N) can pose a threat to ecosystems and human health. Many methods have been used for the removal of NH4+-N. In particular, reactive chlorine species (RCS, including Cl·, Cl2·−, and ClO·) show superior performance for the selective oxidation of NH4+-N to nitrogen gas (N2). Herein, Fe2+/peroxymonosulfate (PMS)/Cl− process was proposed to generate RCS for the conversion of NH4+-N to N2, in which Fe2+ was used as the activator of PMS in the presence of Cl−. Fe2+, PMS, and Cl− concentrations could affect the removal of NH4+-N in Fe2+/PMS/Cl− process. Fe2+/PMS/Cl− exhibited good performance in removing NH4+-N at pH 3.5–8.0. At all investigated conditions, NH4+-N was mainly converted to N2, and N2 selectivity was more than 90 %. Under optimal conditions, 50 % of NH4+-N was removed in 5 min, and the removal efficiency reached the maximum of 96 % within 120 min with the high N2 selectivity of 100 %. The electron spin resonance tests, scavenging experiments, and probe experiments demonstrated the generation of RCS in Fe2+/PMS/Cl− reaction system. Experimental results and model analysis consistently proved that ClO· and Cl· were crucial radicals during the selective oxidation of NH4+-N, especially ClO·. Fe2+/PMS/Cl− system could remove NH4+-N and COD simultaneously in real wastewater. This study can provide an efficient strategy for the removal of NH4+-N.

Catalytic elimination of NOx and CH3SH over synergistic reaction induced active sites

The synergistic elimination of hazardous NOx and CH3SH is of significance in various industrial production processes. However, the synergistic elimination mechanism is ambiguous and the efficient synergistic catalysts have never been reported. Herein, the synergistic reaction is originally demonstrated over CuOx modified CeO2/TiO2 catalysts via coupling with selective catalytic reduction of NOx by NH3 and catalytic oxidation of CH3SH. CuOx modification notably improves the acidity and redox ability, and promotes the absorption and oxidation of CH3SH, thus generating more CO2 rather than toxic CO and HCN by-products. Moreover, the CH3SH oxidation reaction induces the formation of SO42- on CeOx sites that contribute to NOx reduction reaction via improving the reactivity of adsorbed NH4+ species with nitrogen oxide species. This work provides insights into the synergistic catalytic elimination of NOx and CH3SH, and guides the development of environmental catalysis techniques for eliminating multiple pollutants in actual complex operating conditions.

Distinct effects of Na on Cu-based Beta zeolites for the selective catalytic reduction of NOx with NH3

The distinct impact of Na on the NH3-SCR activity of Cu-based Beta zeolites was explored by incorporating Cu onto Na and H-type Beta zeolites via ion-exchange and impregnation methods. The characterization results revealed that an appropriate amount of Na facilitated the exchange of Cu ions into the Beta zeolites, leading to enhanced acidity and NOx adsorption properties. The CuNa-Beta catalysts obtained through ion-exchange, exhibited decreased NH3 oxidation activity at elevated temperatures while demonstrated enhanced NO oxidation activity at lower temperatures, resulting in the improved NOx conversion. However, when the Cu loading was conducted by the impregnation method, Na remained in the Cu/Beta zeolites caused the transformation of Cu to CuOx, resulting in the inferior NH3-SCR performance. These findings demonstrated the significant influence of co-cation Na and preparation methods on Cu locations and NH3-SCR performance of Cu-based Beta zeolites.