Selective Catalytic Reduction Catalyst Research Articles

Research Progress in the Composition and Performance of Mn-Based Low-Temperature Selective Catalytic Reduction Catalysts

NH3 selective catalytic reduction (NH3-SCR) is the most prevalent and effective method for removing nitrogen oxides. Over the past few decades, manganese (Mn)-based catalysts have demonstrated strong catalytic activity and have been extensively studied for low-temperature NH3-SCR reactions. This paper provides an in-depth introduction to four forms of Mn-based catalysts: single manganese oxide-based catalysts, binary Mn-based metal oxide catalysts, ternary and multivariate Mn-based metal oxide catalysts, and nano-Mn-based catalysts. Advances have been made in enhancing Mn-based catalysts’ redox performance and acidity, increasing the active component’s dispersion, lowering binding energy, enlarging specific surface area, raising the Mn4+/Mn3+ ratio, and enriching surface adsorbed oxygen by optimizing preparation methods, altering the oxidation state of active components, modifying crystal phases, and adjusting morphology and dispersion, along with various metal modifications. The mechanism of low-temperature NH3-SCR reactions has been elucidated using various characterization techniques. Finally, the research directions and future prospects of Mn-based catalysts for low-temperature NH3-SCR reactions are discussed, aiming to accelerate the commercial application of new Mn-based catalysts.

Effect of modified Fe2O3/activated carbon catalysts for low-temperature CO selective catalytic reduction of NOx in underground diesel vehicle exhaust

The elimination of CO and NOx has practical significance for the control of exhaust pollutants from underground diesel vehicles. Catalytic reduction of NO by CO (CO-SCR) using activated carbon (AC) catalysts is considered a cost-effective and environmentally friendly denitrification method. In this study, Fe2O3/AC-based catalysts were prepared using an impregnation method and modified with different metals to investigate their impact on catalyst performance. The results demonstrated that the catalyst exhibited the highest denitrification efficiency when loaded with 10% Fe. The Mn-doped 10Fe/AC catalyst exhibited the best catalytic performance, with the highest NO conversion of 97.5% and CO removal rate of 83.3% at 240 °C. The effects of loading Mn, Ce, and La on the physical and chemical properties of the catalysts were analyzed using various characterization tools, and the reaction mechanism of the catalysts was investigated by in situ DRIFTS technique. The findings revealed that the strong synergistic interaction occurring between Mn and Fe led to an increase in the surface-adsorbed oxygen (Oα) and Fe3+, which produced more oxygen vacancies on the catalyst, thus improving the redox properties. The in-situ DRIFT results indicated that the addition of Mn enhanced the adsorption capacity of active NO and CO. For the CO-SCR reaction on Fe-Mn/AC catalyst, the E-R mechanism was followed at low temperature and the L-H mechanism was followed at high temperature.

Multi-objective optimization of chemical reaction characteristics of selective catalytic reduction in denitrification of diesel engine using ELM-MOPSO methodology

This study systematically investigated the effects of structural parameters in a two-stage selective catalytic reduction (SCR) catalyst on ammonia storage, NO conversion efficiency, and ammonia slip using computational fluid dynamics (CFD) simulations. The rank ordering of the correlations between structural parameters and performance metrics was determined by gray relational analysis (GRA). Both the catalyst diameter and the upstream catalyst porosity had correlations exceeding 0.9, making them key parameters affecting SCR performance. An extreme learning machine (ELM) prediction model was trained using data obtained from CFD simulations. The prediction performance of this ELM model was then evaluated using statistical metrics. Finally, the optimized Pareto frontier diagram was obtained through the multi-objective particle swarm optimization (MOPSO) algorithm, and the optimal results were selected for further CFD modeling analysis. The results showed that the upstream NO conversion efficiency of the SCR system was improved by 7.7 %, the downstream NO conversion efficiency was improved by 18.67 %, the ammonia slip was reduced by 71.97 %, and the upstream ammonia storage capacity was improved by 6.83 % compared with the original model.

Migration of Platinum Nanoparticles via Volatile Platinum Dioxide during Lean High-Temperature Ageing of Diesel Oxidation Catalysts

When platinum-containing diesel oxidation catalysts (DOC) are exposed to high temperatures under lean conditions, the platinum nanoparticles form volatile platinum dioxide on the catalyst surface. The exhaust flow carries the volatile platinum dioxide to the downstream aftertreatment catalyst, such as the selective catalytic reduction (SCR) catalyst, that is responsible for reducing the nitrogen oxides (NOx) emissions and can negatively impact its performance, by promoting the parasitic oxidation of ammonia. Here we investigate the factors such as exposure time, temperature and DOC design characteristics for their impact on the platinum dioxide migration, by characterising the amount of platinum deposited on the SCR catalyst at very low levels (<5 ppm), using inductively coupled plasma optical emission spectroscopy (ICP-OES) fire assay technique. Our results indicate that well-dispersed platinum, not associated with palladium, is most prone to platinum dioxide migration. We also compare several methods to suppress the platinum dioxide migration from the DOC, such as sintering of the platinum nanoparticles, stabilising the platinum nanoparticles via interaction with palladium or covering the platinum nanoparticles with a high surface area capture layer to trap the volatile platinum dioxide.

Effect of crystalline TiO2 on V2O5WO3/TiO2 as tunable low-temperature shift De-NOx catalyst

Based on the crystalline size of anatase TiO2, a series of tunable low-temperature shift V2O5-WO3/TiO2 (VW/Ti) catalysts for NH3 selective catalytic reduction (NH3-SCR) of NOx were prepared by impregnation process. These catalysts contained a loading amount of 2 wt% WO3 and either 2 or 5 wt% V2O5. The tunable low-temperature shift De-NOx performance of the VW/Ti catalysts was significantly enhanced and dramatically decreased after heat treatment of TiO2 from 100 °C to 700 °C (Ti100 ∼ Ti700). Nearly 100 % De-NOx efficiency was achieved at a gas hourly space velocity (GHSV) of 60,000 h−1. A notable shift from higher to lower temperatures was observed from V2W2/Ti100 to V2W2/Ti600; however, the activity was lost for V2W2/Ti650 to V2W2/Ti700. When the V2O5 loading increased from 2 wt% to 5 wt%, the V5W2/Ti600 showed the highest De-NOx efficiency at 225 °C, demonstrating a remarkable synergistic effect compared to the V2W2/Ti100 catalyst, which achieved maximum efficiency at 375 °C. The De-NOx performance and low-temperature shift effect of these catalysts were elucidated by considering TiO2 crystalline size, the synergistic effect between V2O5 content and TiO2, and the V4+/V5+ oxidation state of V2O5 in the catalyst. Additionally, the high crystalline TiO2-based V2W2/Ti600 catalyst prepared in this study is expected to effectively decompose NOx at low temperatures, in contrast to the low crystalline TiO2-based V2W2/Ti100 catalyst.

Comparing low-temperature NH3-SCR activity, operating temperature window and kinetic properties of the Mn-Fe-Nb/TiO2 catalysts prepared by different methods

In order to overcome the shortcomings of traditional V-based catalysts, such as poor low-temperature activity, narrow temperature window, and toxicity. Therefore, the Mn-Fe-Nb/TiO2 catalysts were prepared using impregnation (IM), citric acid complexation (CA), co-precipitation (CP), hydrothermal synthesis (HY), and sol–gel (SG) methods to develop novel NH3 selective catalytic reduction (NH3-SCR) catalysts with excellent low-temperature activity, a wide temperature window, and environmental friendliness. Their NH3-SCR catalytic activity was evaluated, followed by a detailed analysis of their morphology, structure, specific surface area, chemical state, redox properties, acidity, and interactions using X-ray diffraction (XRD), Bruaner-Emmet-Teller (BET), Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR), NH3 temperature-programmed desorption (NH3-TPD), and Fourier transform infrared spectroscopy (FTIR) techniques. The 5Mn-7Fe-4Nb/TiO2-SG catalyst, prepared via sol–gel, exhibited the highest denitrification (de-NOx) activity and the widest operating temperature window, achieving over 80% Nitric oxide (NO) conversion at 180–350 °C and a peak conversion of 97% at 250 °C. The XRD, BET, SEM, and HR-TEM characterization results showed that the catalyst prepared using the sol–gel method had the smallest particles, the highest specific surface area, and the greatest dispersion. XPS and NH3-TPD results revealed that the catalyst prepared using the sol–gel method possessed the highest surface adsorbed oxygen (Oα) content and the largest number of acidic sites. H2-TPR and FTIR analyses indicated that the catalyst prepared using the sol–gel method enhanced the reduction capacity and possessed the strongest interaction forces among support-active-promoter components. Steady-state kinetic tests confirmed that in the NH3-SCR reaction, the rate-determining step was the adsorption activation of NO on the catalyst surface. The sol–gel method reduced the activation energy for de-NOx reactions, enhancing the low-temperature activity of the catalyst.

The preferential occupying effect regulated atomically dispersed Cu site over Cu-SSZ-13 for enhancing NH3-SCR performance

The development of highly active catalysts for selective catalytic reduction of NOx with ammonia (NH3-SCR) at broad temperature range are desirable but challenging. Herein, a preferential occupying effect of Cd regulates atomically dispersed Cu site is proposed for NH3-SCR. Benefiting from the modulation effect of Cd, the temperature of NO conversion above 90 % for Cu-Cd-SSZ-13 is broadened to 160–550 ℃, and hydrothermal stability is significantly improved. The Cd ions prefer to occupy eight-membered rings (8 MRs) favor the generation of Z2Cu2+ at 6 MRs, and the electronegativity of Z2Cu2+ increases due to the introduction of Cd, thus boosting NH3-SCR process by reducing formation energy of key intermediate (NH4NO2) at active Z2Cu2+ site. Noticeably, the preferential occupying of Cd enhances the intrinsic stability of Z2Cu2+ by inhibiting its transformation into inactive CuOx. This work sheds new insight for regulating atomically dispersed Cu site to enhance NH3-SCR performance.

Effect of Tourmaline Addition on the Anti-Poisoning Performance of MnCeOx@TiO2 Catalyst for Low-Temperature Selective Catalytic Reduction of NOx.

In view of the flue gas characteristics of cement kilns in China, the development of low-temperature denitrification catalysts with excellent anti-poisoning performance has important theoretical and practical significance. In this work, a series of MnCeOx@TiO2 and tourmaline-containing MnCeOx@TiO2-T catalysts was prepared using a chemical pre-deposition method. It was found that the MnCeOx@TiO2-T2 catalyst (containing 2% tourmaline) exhibited the best low-temperature NH3-selective catalytic reduction (NH3-SCR) performance, yielding 100% NOx conversion at 110 °C and above. When 100-300 ppm SO2 and 10 vol.% H2O were introduced to the reaction, the NOx conversion of the MnCeOx@TiO2-T2 catalyst was still higher than 90% at 170 °C, indicating good anti-poisoning performance. The addition of appropriate amounts of tourmaline can not only preferably expose the active {001} facets of TiO2 but also introduce the acidic SiO2 and Al2O3 components and increase the content of Mn4+ and Oα on the surface of the catalyst, all of which contribute to the enhancement of reaction activity of NH3-SCR and anti-poisoning performance. However, excess amounts of tourmaline led to the formation of dense surface of catalysts that suppressed the exposure of catalytic active sites, giving rise to the decrease in catalytic activity and anti-poisoning capability. Through an in situ DRIFTS study, it was found that the addition of appropriate amounts of tourmaline increased the number of Brønsted acid sites on the catalyst surface, which suppressed the adsorption of SO2 and thus inhibited the deposition of NH4HSO4 and (NH4)2HSO4 on the surface of the catalyst, thereby improving the NH3-SCR performance and anti-poisoning ability of the catalyst.

Promoting metal oxides–zeolite electron interaction on MnCeOx/HY catalyst for boosting nitrogen oxides reduction

The MnOx-CeO2 metal oxides are considered as promising alternative catalysts for selective catalytic reduction with NH3 (NH3-SCR) to remove NOx due to its excellent low temperature performance. However, their strong oxidative ability can lead to NH3 over-oxidation, narrowing the active temperature range and reducing N2 selectivity. Moreover, their weak surface acidity hampers medium to high-temperature activity and alkali metal resistance. Hence, in this study, MnCeOx metal oxides were coupled with HY zeolite to create MnCeOx/HY, demonstrating excellent NH3-SCR performance. The high dispersion of metal oxides on the zeolite surface and their close integration promoted strong electron interaction, effectively reducing oxygen vacancies and surface adsorbed oxygen concentrations. Consequently, the oxidative ability of active metal oxides was appropriately weakened, suppressing undesirable side reactions. MnCeOx/HY also notably suppressed NO adsorption and nitrate formation, promoting the catalytic reaction solely through the E-R mechanism and enhancing N2 selectivity. The abundant strong acid sites on the zeolite surface facilitates NH3 adsorption at moderate to high temperatures, notably expanding the active temperature window. Furthermore, the acid sites of HY zeolite serve as sacrificial sites, preferentially reacting with alkali metals, thus exhibiting excellent resistance to alkali metal poisoning on MnCeOx/HY. Combining with the DFT results, the structure-activity relationships in this study also reveal the importance of the effective synergy between acid sites and redox sites for optimal catalytic performance, offering valuable insights into the development of highly active and alkali-resistant denitrification catalysts.

TiO2-Supported Catalysts in Low-Temperature Selective Reduction of NOx with NH3: A Review of Recent Progress

Selective catalytic reduction (SCR) stands out as a pivotal method for curbing NOx emissions from flue gas. The support, crucially, for SCR efficacy, loads and interacts with the active components within the catalyst. The catalysts could be amplified by the denitration performance of the catalyst by enhancements in support pore structure, acidity, and mechanical robustness. These improvements ensure efficient interaction between the support and active materials, thereby optimizing the structure and property of the catalysts. TiO2 is the most commonly used support of the NH3-SCR catalyst. The catalyst with TiO2 support has poor thermal stability and a narrow temperature range, which can be improved. This paper reviews the research progress on the effects of various aspects of TiO2 support on the NH3-SCR catalyst’s performance, focusing on the TiO2 crystal type, TiO2 crystal surface, different TiO2 structures, TiO2 support preparation methods, and the effects of TiO2-X composite support on the NH3-SCR catalyst’s performance. The reaction mechanism, denitrification performance, and anti-SO2/H2O poisoning performance and mechanism of TiO2 support with different characteristics were described. At the same time, the development trend of the NH3-SCR catalyst using TiO2 as the support is prospected. It is hoped that this work can provide optimization ideas for SCR catalyst research.

Acid sites-CeOx doping CrZrCeOx catalyst with high SO2 resistance for marine SCR application: Surface analysis and mechanism study

This paper mainly talked about acid sites-CeOx doping CrZrCeOx catalyst with high SO2 resistance for marine NH3– SCR (selective catalytic reduction). The NO removal efficiency of the Cr:Zr:Ce = 8:2:1 catalyst reached 90 % with 500 ppm SO2 and 85 % with 1000 ppm SO2 for 20 h, respectively. It was inferred that the main roles of CeOx species were acid sites but not redox sites. CeOx addition promoted the SCR performance and SO2 resistance, which significantly changed the adsorbed species on the surface. CeOx acted as sacrifice sites to protect CrOx actives sites through reducing the combination of Cr and sulfates. The Cr:Zr:Ce = 8:2:1 catalyst followed Langmuir-Hinshelwood (L-H) mechanism and the reaction process was derived in this paper. It indicated that the Cr:Zr:Ce = 8:2:1 catalyst would be a promising marine SCR catalyst with good SO2 resistance in the future.

Two-dimensional transition metal-sulfide-modified V2O5-WS2/TiO2 catalysts for SCR: Comprehensive mechanistic insights into the in situ inhibition of SO3 generation

The by-product SO3, generated by the conventional catalyst V2O5-WO3/TiO2 employed in selective catalytic reduction (SCR) systems, has garnered attention in pollution control efforts. Studies on existing control have predominantly concentrated on the tail gas section, with insufficient understanding of in-situ suppression theories and methods at the source of SO3 generation. We propose for the first time the introduction of low-valence reduced sulfur to synthesize a novel SCR catalyst, V2O5-WS2/TiO2, which elucidates the remarkable effect and in-situ mechanism of action in inhibiting SO3 formation at its source. Compared to conventional catalysts, the new catalysts showed enhanced SO3 inhibition, particularly at 350 °C, where SO3 production was 64.1 % and 33.9 % lower than that with VTi and VW/Ti catalysts, respectively. This was due to their reduced surface area, smaller pore volume, and fewer alkaline sites, which hindered SO2 adsorption and oxidation. The results revealed that S2− on the catalyst surface reacts with V5+, reducing it to V4+ and V3+. This reaction hinders the interaction between V5+-OH and adsorbed SO2, thereby reducing the formation of VOSO4 intermediates. Furthermore, the WS bond in WS2 impedes the formation of intermediate HSO4−, and the reduction of these intermediates ultimately leads to a decrease in SO3 generation. Additionally, the incompletely depleted S2− reacts with the final SO3 produced, forming SO2 and SO42−, which further decreases the SO3 generation rate and supports the maintenance of a reduced state on the catalyst surface. It is evident that low-valence reduced sulfur plays a crucial role in inhibiting SO3 generation.

SCR + ASC systems control by backward induction with adaptive grid and different disturbance scenarios

The purpose of this study is to enhance control strategies for selective catalytic reduction (SCR) and ammonia slip catalyst (ASC) systems, aiming to effectively reduce NOx emissions from automotive engines during realistic driving cycles. Despite the effectiveness of these after-treatment systems (ATS), their dynamic and non-linear characteristics present significant challenges in achieving precise control. Therefore, this research proposes a hybrid approach that combines backward induction (BI) as the primary optimization technique with model predictive control (MPC) framework for real-time application. The article introduces a reduced-state control-oriented model of the SCR + ASC system, which is embedded into the BI algorithm to calculate optimal control actions within a finite horizon. Additionally, it is proposed an alternative approach for adapting the grid of model states within the BI algorithm, effectively reducing the computational cost. This adjustment enables the algorithm to operate in real-time with near-optimal results, as confirmed by experimental validation. Lastly, the study explores how different degrees of knowledge regarding system disturbances impact the strategy’s performance, examining three distinct scenarios: constant prediction horizon, probabilistic description, and full knowledge of the prediction horizon.

Insight into the Alkali Resistance Mechanism of CoMnHPMo Catalyst for NH3 Selective Catalytic Reduction of NO

Insight into the Alkali Resistance Mechanism of CoMnHPMo Catalyst for NH3 Selective Catalytic Reduction of NO

Experimental study of ammonia storage characteristics of selective catalytic reduction for diesel engine based on Cu-based catalysts

In this paper, the ammonia storage characteristics of Cu-based zeolite catalysts at different exhaust temperatures in heavy-duty diesel engines were experimentally investigated. The data such as exhaust temperature, rotational speed, torque, urea consumption, NOx concentration at selective catalytic reduction (SCR) inlet and outlet, ammonia storage, and NH3 leakage of the diesel engine were recorded respectively. The trend of ammonia storage characteristics of the SCR system was analyzed using the urea injection stopping time as the cut-off point. Both the SCR catalyst ammonia storage volume and the time to saturation of ammonia storage volume decreased with the increase in exhaust temperature. The maximum value of ammonia storage was 9.58 g at 193 °C and 1.08 g at 376 °C. The saturation time decreased from 466.4 s to 96.8 s. The increase in catalyst activity at high temperatures increased the rate of denitrification reaction, but it was observed that the ammonia slippage occurred earlier from 450 s to 100 s, which was mainly due to a more active ammonia desorption reaction at high temperatures. The larger ammonia storage at low temperatures made the effect on NOx conversion efficiency more significant, and the effect of exhaust temperature gradually increased when the temperature was further increased.

Effect of Mn or Fe on CrMoOx /TiO2 selective catalytic reduction catalyst

Developing a high-efficiency catalyst with both superior low-temperature activity and good sulfur and water resistance is still challenging for the NH3 selective catalytic reduction (SCR). Herein, a series of Mn- and Fe-doped CrMoOx/TiO2 catalysts were elaborately designed and the Cr3Mo6Mn2/TiO2 catalyst exhibits the best NOx conversion rate, reaching 81. 8 % at 90 ℃ and closing to 100 % at 150 ℃, and the NOx conversion reach ∼71 % at 150 ℃ for 30 h in presence of H2O+SO2. A series of characterization studies revealed that the abundance of Lewis acidic sites on the catalysts and the protective effect of Mo are conducive to the enhancement of SO2+H2O resistance. cr3Mo6Mn2/TiO2 dominates the SCR reaction through the Eley-Rideal (E-R) pathway between adsorbed NH4+/NH3 and gaseous NOx, generating N2 and H2O. This work provides a new strategy for improving the tolerance of chromium-based oxide catalysts to sulfur dioxide and water at low temperatures.

Sb-loaded MnOx/TiO2/CNTs catalysts for selective catalytic reduction of NOx: insight to the SO2 and H2O tolerance

PurposeThis paper aims to synthesize and test Mn-Sb/TiO2-CNT catalysts with different Sb/Mn molar ratios to be used in NH3-SCR reaction.Design/methodology/approachA series of Sb-loaded carbon nanotubes (CNTs)-based Mn/TiO2 catalysts were prepared by the incipient wetness co-impregnation method and tested for the selective catalytic reduction (SCR) of NOx with NH3.FindingsThe Sb-loaded Mn/TiO2-CNTs catalyst outperformed other catalysts and presented the highest activity in the temperature regime of 100–400°C. The catalyst loaded with Sb also showed good SO2 and H2O resistance and exhibited better thermal stability. A stepwise study of SO2 addition evidenced that Mn-Sb/TiO2-CNTs catalyst exhibited better SO2 resistance than the base catalyst Mn/TiO2, where the Sb doping greatly inhibited the sulphating of active phase of the catalyst.Originality/valueIn Sb-loaded catalysts, the formed SOx species fused with SbOx instead of MnOx. This favoured interaction of SO2 with SbOx successfully prevents the MnOx from being sulphated by SO2 which substantially improves the SO2 tolerance of Sb-loaded catalysts.

Insights into the Acidic Site in Manganese Oxide in Terms of the Sulfur and Water Tolerance of Low-Temperature NH3 Selective Catalytic Reduction.

A critical constraint impeding the utilization of Mn-based oxide catalysts in NH3 selective catalytic reduction (NH3-SCR) is their inadequate resistance to water and sulfur. This vulnerability primarily arises from the propensity of SO2 to bind to the acidic site in manganese oxide, resulting in the formation of metal sulfate and leading to the irreversible deactivation of the catalyst. Therefore, gaining a comprehensive understanding of the detrimental impact of SO2 on the acidic sites and elucidating the underlying mechanism of this toxicity are of paramount importance for the effective application of Mn-based catalysts in NH3-SCR. Herein, we strategically modulate the acidity of the manganese oxide catalyst surface through the incorporation of Ce and Nb. Comprehensive analyses, including thermogravimetry, NH3 temperature-programmed desorption, in situ diffused reflectance infrared Fourier transform spectroscopy, and density functional theory calculations, reveal that SO2 exhibits a propensity for adsorption at strongly acidic sites. This mechanistic understanding underscores the pivotal role of surface acidity in governing the sulfur resistance of manganese oxide.

Unraveling the significance of acid sites in determining NH3-SCR mechanisms over WO3 catalyst: A combined experimental and computational study

With regard to the catalysts for NH3 selective catalytic reduction (NH3-SCR), the acid sites distribution can affect the adsorption of reactants and formation of intermediates, thus determining the reaction routines. In this work, a representative acidic component, monoclinic-WO3 (m-WO3), was used to probe the combination strategy of experimental and theoretical research, aiming at systematic understanding on the full-process mechanisms. Macro-scale characterizations, Temperature Programmed Desorption (TPD) and Temperature Programmed Reduction (TPR), are associated with the Density Functional Theory (DFT) calculations, by which W ion (Lewis acid site) is affirmed as the active sites. By comparing the energy barriers of possible pathways with DFT calculations, we identify that NH2NO and NHNOH are responsible active intermediates. Both Langmuir-Hinshelwood (L-H) and Eley-Rideal (E-R) pathways may take place on acid sites and the former on Lewis acid site is optimal, which agrees well the in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) analysis. This study offers a reasonable prototype for precisely examining the correlation between the catalyst and mechanisms of NH3-SCR catalysts.

Insights into Na+/Ca2+ poisoning mechanisms of Zr-modified and unmodified La-Mn perovskite oxide catalysts for NH3-SCR reaction

The presence of alkali metal/alkaline earth metal in fuel gas is one of the important reasons for the deactivation of catalyst for selective catalytic reduction of NOx with NH3 (NH3-SCR). In this work, the Na+/Ca2+ poisoning mechanisms of Zr-modified and unmodified La-Mn perovskite oxides for NH3-SCR reaction were studied. It is found that the deposition of Na+ into LaMnO3 (LM) catalyst has a much larger effect than that of Ca2+, while such a result is opposite for the Na+/Ca2+-deposited La0.8Zr0.2MnO3 (ZLM) catalysts. The deposition of Na+/Ca2+ compounds can block the pores and affect the adsorption and activation of NH3 on the catalysts. After Zr modification, the catalyst with a higher Mn4+ content shows a better redox property and increased acid sites. These acidic sites can trap Na+, thereby delaying the catalyst poisoning and causing a better activity of ZLM catalyst than LM catalyst. The deposition of Ca2+ in the form of CaCO3 on the catalyst surface leads to a serious pore blockage, showing a poor resistance to Ca2+. After regeneration, the pores of the catalyst are dredged, and the active sites originally occupied by Na+/Ca2+ are released, resulting in an recovery of catalyst activity. The recovery of adsorbed oxygen and Mn4+ content is the key factor for returning the SCR activity.