Selective Catalytic Reduction Of NOx Research Articles

Modulating the Activity and SO2 Resistance of α-Fe2O3 Catalysts for NH3-SCR of NOx via Crystal Facet Engineering.

The development of Fe-based catalysts for the selective catalytic reduction of NOx by NH3 (NH3-SCR of NOx) has garnered significant attention due to their exceptional SO2 resistance. However, the influence of different sulfur-containing species (e.g., ferric sulfates and ammonium sulfates) on the NH3-SCR activity of Fe-based catalysts as well as its dependence on exposed crystal facets of Fe2O3 has not been revealed. This work disclosed that nanorod-like α-Fe2O3 (Fe2O3-NR) predominantly exposing (110) facet performed better than nanosheet-like α-Fe2O3 (Fe2O3-NS) predominantly exposing (001) facet in NH3-SCR reaction, due to the advantages of Fe2O3-NR in redox properties and surface acidity. Furthermore, the results of the SO2/H2O resistance test at a critical temperature of 250 °C, catalytic performance evaluations on Fe2O3-NR and Fe2O3-NS sulfated by SO2 + O2 or deposited with NH4HSO4 (ABS), and systematic characterization revealed that the reactivity of ammonium sulfates on Fe2O3 catalysts to NO(+O2) contributed to their improved catalytic performance, while ferric sulfates showed enhancing and inhibiting effects on NH3-SCR activity on Fe2O3-NR and Fe2O3-NS, respectively; despite this, Fe2O3-NR showed higher affinity for SO2 + O2. This work set a milestone in understanding the NH3-SCR reaction on Fe2O3 catalysts in the presence of SO2 from the aspect of crystal facet engineering.

Synthesis‐structure‐catalysis relations in CHA zeolites applied for selective catalytic reduction of NOx with ammonia

Microporous aluminosilicate zeolites are useful industrial catalysts. However, their hydrothermal synthesis is a multistep process with complicated and unclear reactions, limiting their rational functional design. Herein, we compare the formation pathway and the structural and catalytic properties of several CHA zeolites to obtain fundamental knowledge for intentionally controlling the catalytic function of zeolites. Three CHA zeolites were synthesized using different starting silica/alumina sources in the presence of tetraethylammonium hydroxide as an inexpensive organic structure‐directing agent. FAU zeolite and an amorphous synthesis gel prepared using two different methods were used as starting materials. The obtained CHA zeolites were applied for exhaust gas purification (selective catalytic reduction of NOx with ammonia, NH3‐SCR), and their structural characteristics and formation pathways were investigated using a combination of analytical methods. Stepwise gel preparation (SGP), which divides the compositional control of the amorphous synthesis gel, promotes the decomposition of the initial additive (zeolite seed), resulting in the formation of CHA zeolites with abundant micropores and paired Al sites. This structural feature obtained using the SGP method improves the catalytic durability of the NH3‐SCR reaction. The present relationship, including different crystallization phenomena, structures, and catalytic abilities, provides useful insights into rational zeolite synthesis and its application.

Assembling copper and cerium into TNU-9-type periodic microporous organosilicas for the selective catalytic reduction of NOx by NH3

TNU-9-type periodic microporous organosilicas material containing Ce and Cu was assembled by organic-inorganic hybrid method and then calcined to acquire CuCex@PMO-TNU-9 catalyst. The effect of cerium on the structure-performance relationship was studied. The results indicated that the (CuCex@PMO-TNU-9 x = 1.0, 1.5 and 2.0) catalysts were successfully prepared, whereas CuCe2.5@PMO-TNU-9 was not successfully prepared due to the excess of the precursor resulting in the difference of hydrolysis rate between the organosilane precursor and white carbon black. The CuCe2@PMO-TNU-9 catalyst showed higher NH3-SCR activity than Cu@PMO-TNU-9, which was because that the interaction between Ce and Cu could form Cu2++Ce3+↔Cu++Ce4+ redox cycle, which promoted the oxidation of NO to NO2, forming “fast SCR” reaction. More importantly, CuCe2@PMO-TNU-9 catalyst had excellent the resistance of H2O and SO2 due to the excellent hydrophobicity of the TNU-9 zeolite and the sacrificial site Ce protecting the active site Cu.

Asymmetric oxygen vacancy promotes CO-SCR performance on defect-engineered Rh/CeCuOx catalyst

Selective Catalytic Reduction of NOx with CO (CO-SCR) is a process that purifies both NO and CO pollutants through a catalytic reaction. Specifically, the cleavage of NO on the catalyst surface is crucial for promoting the reaction. During the reaction, the presence of oxygen vacancies can extract oxygen from NO, thereby facilitating the cleavage of NO on the catalyst surface. Thus, the formation of oxygen vacancies is key to accelerating the CO-SCR reaction, with different types of oxygen vacancies being more conducive to their generation. In this study, Rh/CeCuOx catalysts were synthesized using the co-crystallization and impregnation methods, and asymmetric oxygen vacancies were induced through hydrogen thermal treatment. This structural modification was aimed at regulating the behavior of NO on the catalyst surface. The Rh/Ce0.95Cu0.05Ox-H2 catalyst exhibited the best performance in CO-SCR, achieving above 90 % NO conversion at 162 °C. Various characterization techniques showed that the H2 treatment effectively reduced some of the CuO and Rh2O3, creating asymmetric oxygen vacancies that accelerated the cleavage of NO on the catalyst surface, rather than forming difficult-to-decompose nitrates. This study offers a novel approach to constructing oxygen vacancies in new CO-SCR catalysts.

Investigation of Co–Mn–Ce Ternary Composite Oxide Catalyst for Low-Temperature Selective Catalytic Reduction of NOx with NH3

Investigation of Co–Mn–Ce Ternary Composite Oxide Catalyst for Low-Temperature Selective Catalytic Reduction of NOx with NH3

Enhanced low-temperature activity of Mn-based catalysts for NH3 selective catalytic reduction of NO through CE-modulated redox and TiO2 shell construction

Manganese-based catalysts presented great challenges for the wide operating window in the selective catalytic reduction of NOx with NH3 (NH3-SCR). Aiming at enhancement of the SCR performance, a series of MnCeOx (MnyCe1) and MnxCe1@TiO2 catalysts were prepared. Impressively, the Mn1Ce1 catalyst exhibited excellent low-temperature activity, achieving over 80 % conversion of NO within the temperature range of 85–350 °C, but the N2 selectivity decreased with the increasing temperature. Upon coating a TiO2 shell, the temperature window with N2 selectivity exceeding 80 % was significantly widened to 85–350 °C since the weak redox ability limited the NH3 oxidation to undesired N2O. High surface area, together with abundant acid sites and chemical adsorbed oxygen that formed via the interaction between Mn4+/Mn3+, Ce4+/Ce3+ and Ti4+/Ti3+, contributed to the superior catalytic performance of MnxCe1@TiO2. In addition, through in situ DRIFTS analysis, both Eley-Rideal and Langmuir-Hinshelwood reaction routes were observed. This work would provide an efficient and low-cost strategy for preparing Mn-based catalysts with excellent low-temperature activity for NOx removal.

Effect of sulfation on the catalytic performance of Mn-Co composite oxide catalyst for the selective catalytic reduction of NOx by NH3

The effect of sulfation on the catalytic performance of Mn-Co composite oxide catalyst for the selective catalytic reduction of NOx by NH3 (NH3-SCR) has been investigated. Different concentrations of SO2 have been used to sulfate Mn-Co composite oxide catalyst. The catalyst sulfated with 30 ppm SO2 showed the widest activity temperature window, over which 80% NOx conversion was obtained in the temperature range of 80–350 °C. The sulfation leads to the appropriate redox property of Mn-Co composite oxide, thus improving the N2 selectivity. Meanwhile, the sulfation contributes to the generation of more Brønsted acid sites, which is crucial for the enhanced activity. In situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS) demonstrated that the adsorbed NH3 species on both Lewis acid and Brønsted acid sites, monodentate nitrite, bidentate nitrate and cis-nitrite species are the reactive intermediates in the NH3-SCR reaction. This study provides an idea for the regulating the activity temperature window of NH3-SCR catalyst to adapt to its practical application.

Plasma-assisted manipulation of vanadia nanoclusters for efficient selective catalytic reduction of NOx

Supported nanoclusters (SNCs) with distinct geometric and electronic structures have garnered significant attention in the field of heterogeneous catalysis. However, their directed synthesis remains a challenge due to limited efficient approaches. This study presents a plasma-assisted treatment strategy to achieve supported metal oxide nanoclusters from a rapid transformation of monomeric dispersed metal oxides. As a case study, oligomeric vanadia-dominated surface sites were derived from the classic supported V2O5-WO3/TiO2 (VWT) catalyst and showed nearly an order of magnitude increase in turnover frequency (TOF) value via an H2-plasma treatment for selective catalytic reduction of NO with NH3. Such oligomeric surface VOx sites were not only successfully observed and firstly distinguished from WOx and TiO2 by advanced electron microscopy, but also facilitated the generation of surface amide and nitrates intermediates that enable barrier-less steps in the SCR reaction as observed by modulation excitation spectroscopy technologies and predicted DFT calculations.

Revealing the roles of Zr on enhanced H2-SCR performances on Pt/TiO2 catalyst

The development of Hydrogen Internal Combustion Engine (H2-ICEs) to replace conventional fuel engines is expected to be an effective way to reduce CO2 emissions, but some NOx emitted from the H2-ICEs still should be eliminated by the selective catalytic reduction of NOx with H2 (H2-SCR). Large amount of platinum oxide existed on Pt/TiO2 leads to its low H2-SCR activity. In contrast, the Zr-modified Pt/TiO2 catalysts exhibit a higher NOx conversion and N2 selectivity in a wider temperature window (100–180 °C) than those of Pt/TiO2. The appropriately weakened strong interaction between Pt and TiO2 by Zr induces more Pt0 species, which are active sites for the activation of NOx and H2 in H2-SCR reaction. More oxygen vacancies caused by the formation of Zr-Ov-Ti3+ bands involve in the activation of NOx and the adsorption of nitrates (NOx−) species. Furthermore, in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTs) demonstrates that Pt/ZrxTi1-x catalysts possess more adsorbed NOx− species and a faster reduction rate for them. Monodentate and bridged nitrates are considered to be more reactive with H2 than bidentate nitrates at relatively low temperatures. This work provides directions for the development of high-performance H2-SCR catalysts and the modulation of the conversion temperature.

In situ DRIFTS study and mechanism analysis of selective catalytic reduction of NOx by NH3 over ions doping MnCeOx/GR catalyst

The present study demonstrates an innovative approach of doping MnCeOx/GR catalyst with three transition metal ions, namely Fe3+, Co3+, and Ni2+. Subsequently, the catalyst exhibiting superior performance was carefully selected. Meanwhile, the micro-reaction process of MnCeOx/GR and ion-doped MnCeOx/GR catalysts were established by in situ DRIFTS. The phenomena occurred in the experiment process were thoroughly examined through the application of various characteristic analysis, for instance, XRD, Raman, BET, XPS, H2-TPR, and NH3-TPD to analyze that Co3+ doping had a good improvement of activity and N2 selectivity on MnCeOx/GR catalyst at low temperature. This was evidenced by the activity test experiments, which revealed that CoMnCeOx/GR catalyst has the highest NO conversion within 150–225 °C temperature range, surpassing 90 %. Our findings showed that Co3+ doping not only enhanced redox capability and surface acidity, but also raised the relative Mn4+, Ce3+, and Oα content compared to MnCeOx/GR catalyst, which eventually contributed that the reactant molecules can be more effectively adsorbed onto the catalyst, thereby enhancing activation of NH3 and O2, thus improving efficiency of CoMnCeOx/GR catalyst. Additionally, it was proved that the Eley-Rideal and Langmuir-Hinshelwood mechanisms co-existed on CoMnCeOx/GR catalyst in a competitive way by in situ DRIFTS test.

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.

Phosphotungstic Acid as a Dechlorination Agent Collaborates with CeO2 for Synergistic Catalytic Elimination of NOx and Chlorobenzene.

The development of efficient technologies for the synergistic catalytic elimination of NOx and chlorinated volatile organic compounds (CVOCs) remains challenging. Chlorine species from CVOCs are prone to catalyst poisoning, which increases the degradation temperature of CVOCs and fails to balance the selective catalytic reduction of NOx with the NH3 (NH3-SCR) performance. Herein, synergistic catalytic elimination of NOx and chlorobenzene has been originally demonstrated by using phosphotungstic acid (HPW) as a dechlorination agent to collaborate with CeO2. The conversion of chlorobenzene was over 80% at 270 °C, and the NOx conversion and N2 selectivity reached over 95% at 270-420 °C. HPW not only allowed chlorine species to leave as inorganic chlorine but also enhanced the Bro̷nsted acidity of CeO2. The NH4+ produced in the NH3-SCR process can effectively promote the dechlorination of chlorobenzene at low temperatures. HPW remained structurally stable in the synergistic reaction, resulting in good water resistance and long-term stability. This work provides a cheaper and more environmentally friendly strategy to address chlorine poisoning in the synergistic reaction and offers new guidance for multipollutant control.

Spatial Distribution of Brønsted Acid Sites Determines the Mobility of Reactive Cu Ions in the Cu-SSZ-13 Catalyst during the Selective Catalytic Reduction of NOx with NH3.

The formation of dimer-Cu species, which serve as the active sites of the low-temperature selective catalytic reduction of NOx with NH3 (NH3-SCR), relies on the mobility of CuI species in the channels of the Cu-SSZ-13 catalysts. Herein, the key role of framework Brønsted acid sites in the mobility of reactive Cu ions was elucidated via a combination of density functional theory calculations, in situ impedance spectroscopy, and in situ diffuse reflectance ultraviolet-visible spectroscopy. When the number of framework Al sites decreases, the Brønsted acid sites decrease, leading to a systematic increase in the diffusion barrier for [Cu(NH3)2]+ and less formation of highly reactive dimer-Cu species, which inhibits the low-temperature NH3-SCR reactivity and vice versa. When the spatial distribution of Al sites is uneven, the [Cu(NH3)2]+ complexes tend to migrate from an Al-poor cage to an Al-rich cage (e.g., cage with paired Al sites), which effectively accelerates the formation of dimer-Cu species and hence promotes the SCR reaction. These findings unveil the mechanism by which framework Brønsted acid sites influence the intercage diffusion and reactivity of [Cu(NH3)2]+ complexes in Cu-SSZ-13 catalysts and provide new insights for the development of zeolite-based catalysts with excellent SCR activity by regulating the microscopic spatial distribution of framework Brønsted acid sites.

Role of Vanadium in Thermal and Hydrothermal Aging of a Commercial V2O5-WO3/TiO2 Monolith for Selective Catalytic Reduction of NOx: A Case Study

In recent years, increased attention to air pollutants such as NOx has led the scientific community to focus meaningfully on developing strategies for NOx reduction. Selective catalytic reduction of NOx by ammonia (NO SCR by NH3) is currently the main method to remove NOx from diesel engine exhaust emissions. The catalysts with typical V2O5-WO3/TiO2 (VWTi) composition are widely used in NH3-SCR for their high NOx conversion activity, low cost, and robustness, especially concerning sulfur poisoning. However, in real diesel engine working conditions, the thermal and hydrothermal aging of catalysts can occur after several hours of operation at high temperature, affecting the catalytic performance. In this study, the stability of a commercial VWTi monolith, self-supported and containing glass fibers and bentonite in its matrix, was investigated as a case study. In laboratory conditions, NO SCR tests were performed for 50 h in the range of 150 to 350 °C. Subsequently, the VWTi monolith was thermally and hydrothermally aged at 600 °C for 6 h. The thermal aging increased the NOx conversion, especially at low temperature (<250 °C), while the hydrothermal aging did not affect the SCR. The differences in NOx conversion before and after aging were associated with the change in vanadium and tungsten oxide surface coverage and with the reduction in the surface area of catalysts. In order to correlate the change in SCR activity with the modifications occurring after aging processes, the monolithic samples were characterized by several techniques, namely XRD, SSA and pore analysis, TPR, XPS, Raman, TGA and SEM/EDX.

Structure and activity relationships of AMn2O4 (A = Mg and Zn) spinels in selective catalytic reduction of NOx with NH3

Mn-based spinel as a catalyst for low-temperature selective catalytic reduction with ammonia (NH3-SCR) has been widely studied. However, most researchers have focused on double transition metal Mn-based spinel and the reports about doping with non-transition metal are not common. Herein, Mg2+ and Zn2+ with similar ionic radii were used to prepare high purity MgMn2O4 and ZnMn2O4 (named MMO and ZMO) to study their structure and activity relationships in NH3-SCR. It was found that the denitration performance of the two showed significant differences at low temperature despite have a very similar crystal structure. A series of characterization methods and first-principles calculations demonstrates that the relatively weak bonding strength and basic adsorption sites of MMO catalyst are the key factors contributing to its superior reactivity at low temperatures. This work provides novel insights and ideas in comprehending the catalytic function of non-transition metal-doped Mn-based spinels in NH3-SCR reactions.

Enhancement of low-temperature activity of γ-Fe2O3-modified V2O5-MoO3/TiO2 catalysts for selective catalytic reduction of NOx with NH3

In this study, a series of γ-Fe2O3-modified V2O5-MoO3/TiO2 (VMT) catalysts was prepared by wet impregnation method. The γ-Fe2O3-modified catalysts exhibited excellent catalytic performance, and 1.25 wt% γ-Fe2O3 content improved the deNOx efficiency at 150 °C from 54% (unmodified VMT catalyst) to 84% (modified catalyst). BET, XRD, XPS, NH3-TPD, H2-TPR, and in situ DRIFTs were employed to characterize the physicochemical properties and reaction mechanisms of the catalysts. The introduction of γ-Fe2O3 increased the V5+/V4+ ratio, surface chemisorbed oxygen content, redox ability, and a number of acid sites in the prepared catalysts. XPS confirmed the addition of γ-Fe2O3 introduced new charge transfer pathways (Fe3+/Fe2+ ↔ V5+/V4+). In situ DRIFTs suggested that the addition of γ-Fe2O3 to the catalyst significantly increased the adsorption capacity of catalyst for NH3 and NOx, while also exerting a strong activating effect on the adsorbed NH3. Furthermore, selective catalytic reduction over the VMT and 5PEG@1.25Fe-VMT catalysts followed the Eley-Rideal (E-R) mechanism. At temperatures above 200 °C, the 5PEG@1.25Fe-VMT catalyst also followed the Langmuir-Hinshelwood (L-H) mechanism.

Study of rare Earth tailings modified by Mn for selective catalytic reduction of NOx by NH3

Study of rare Earth tailings modified by Mn for selective catalytic reduction of NOx by NH3

Deciphering the improvement in (H2-)C3H6-SCR performance of Ag/Al2O3 catalysts prepared from warm-water-treated alumina: A NMR-assisted identification of the Ag anchoring sites of the alumina support

Lean exhausts aftertreatment has been the subject of numerous investigations due to ever stringent regulations on pollutants emissions such as that of NOx. Among aftertreatment technologies, the selective catalytic reduction of NOx by the hydrocarbons (HC-SCR) has been studied intensively, in particular by using Ag/Al2O3 materials. The present work highlights that pretreatment of pristine Al2O3 in warm water prior to Ag deposition allows to prepare catalysts of significantly higher (H2-)C3H6-SCR performance compared to conventional Ag/Al2O3 catalysts. In addition, NOx-TPD-C3H6-SCR structure-activity correlations indicate that optimum composition of the Ag/Al2O3 catalysts can be improved by about 50% in terms of Ag content for the first time. Unprecedented in-depth NMR investigations allow for the identification of the alumina sites of importance in the anchoring of Ag. These sites are µ1-OH groups located near the (100)/(110)l edge and then near the (110)b/(100) edge of Al2O3 crystallites and bonded to octahedrally coordinated Al species.

Exploring the role of Cu/Mn-BTC catalyst in the selective catalytic reduction of NOx by C3H6: Synthesis to in-situ DRIFTS study

The choice of reducing agents and their impact on catalytic performance are important aspects of selective catalytic reduction (SCR) technology. Marking the inaugural use of C3H6 as a reducing agent with the BTC catalyst, a bimetallic organic framework (xCu-Mn-BTC) was prepared and tested as a catalyst for NOx reduction under oxygen-enriched conditions. The results showed that NO conversion was influenced by the ratio of Cu and Mn metals, among which 3.2Cu-Mn-BTC exhibited the highest denitrification performance (80 % NOx conversion and 94 % N2 selectivity) at 300 °C. From the characterization results, Cu was successfully incorporated into the BTC framework and 3.2Cu-Mn-BTC became spherical grains with smaller particle sizes. The high catalytic activity of 3.2Cu-Mn-BTC was due to the presence of more adsorbed oxygen Oα (89.7 %) and Cu2+ (63 %) species than in the other catalysts. The TPR peak of xCu-Mn-BTC shifted to a lower temperature and showed better reducibility. The Py-FTIR study shows that xCu-Mn-BTC contained more Lewis acid but no Brønsted acid, because Cu increased the concentration of Lewis acid on the catalytic surface (42 to 46 mmol/g), and Lewis acid plays an important role in the C3H6-SCR of NOx.

Sustainable preparation of highly efficient copper ferroaluminosilicate CHA zeolite for selective catalytic reduction of NOx with NH3

Copper aluminosilicate CHA zeolite has been widely applied in selective catalytic reduction of NOx with NH3 (NH3-SCR), but the formation of CuOx clusters in the zeolite catalyst strongly influence the catalytic activity at the relatively high temperatures. In this work, we have employed the coal fly ash (CFA) as a starting source for one-pot synthesis of CHA zeolite. Because the CFA contains Fe, Al, and Si species, it is finally obtained copper ferroaluminosilicate CHA zeolite (Cu/Fe-Al-CHA). Interestingly, the introduction of Fe species in the Cu/Fe-Al-CHA zeolite significantly hinders the formation of CuOx clusters in the aged zeolite catalyst, compared with a conventional Cu/Al-CHA zeolite. As a result, the activities at the temperatures of 350–450 °C in NH3-SCR over the Cu/Fe-Al-CHA zeolite is a little higher than those over the conventional Cu/Al-CHA zeolite. Characterizations of the samples show that the presence of Fe species in the CHA framework results in shifts of Cu species to high energies, compared with the conventional Cu/Al-CHA zeolite. These results mean that there are stronger interactions between Cu species and Cu/Fe-Al-CHA zeolite framework than those between Cu species and Cu/Al-CHA zeolite framework. Because the starting source is the CFA, a solid waste in the environment, it can be regarded as a sustainable preparation of highly efficient Cu/Fe-Al-CHA zeolite catalysts, which might offer a new opportunity to prepare highly efficient zeolite-based catalysts with an environmentally friendly manner.