Selective Catalytic Reduction Of NOx Research Articles

Knowledge-Driven Experimental Discovery of Ce-Based Metal Oxide Composites for Selective Catalytic Reduction of NOx with NH3 through Interpretable Machine Learning.

Mining the scientific literature, combined with data-driven methods, may assist in the identification of optimized catalysts. In this paper, we employed interpretable machine learning to discover ternary metal oxides capable of selective catalytic reduction of nitrogen oxides with ammonia (NH3-SCR). Specifically, we devised a machine learning framework utilizing extreme gradient boosting (XGB), identified for its optimal performance, and SHapley Additive exPlanations (SHAP) to evaluate a curated database of 5654 distinct metal oxide composite catalytic systems containing cerium (Ce) element, with records of catalyst composition and preparation and reaction conditions. By virtual screening, this framework precisely pinpointed a CeO2-MoO3-Fe2O3 catalyst with superior NOx conversion, N2 selectivity, and resistance to H2O and SO2, as confirmed by empirical evaluations. Subsequent characterization affirmed its favorable structural, chemical bulk properties and reaction mechanism. Demonstrating the efficacy of combining knowledge-driven techniques with experimental validation and analysis, our strategy charts a course for analogous catalyst discoveries.

Effect of Mo on the selective catalytic reduction of NOx with NH3 in the magnetic separation of rare earth tailings

Effect of Mo on the selective catalytic reduction of NOx with NH3 in the magnetic separation of rare earth tailings

Theoretical insight into H2O impact on V2O5/TiO2 catalysts for selective catalytic reduction of NOx.

H2O in flue gas causes the deactivation of V2O5/TiO2 catalysts for selective catalytic reduction (SCR) of NOx with NH3 at low temperatures. Developing water resistance requires understanding the theoretical mechanism of H2O impact on the catalysts. The aim of this work was to clarify the adsorption process of H2O and the deactivation mechanism induced by H2O through density functional theory (DFT). The process of H2O adsorption was studied based on a modeled V2O5/TiO2 catalyst surface. It was found that H2O had a strong interaction with exposed titanium atoms. Water adsorption on the catalyst surface significantly alters the electronic structure of VOx sites, transforming Lewis acid sites into Brønsted acid sites. Exposed titanium sites contribute to the decrease of Lewis acidity via adsorbed water. Ab initio thermodynamic calculations show that H2O adsorption on V2O5/TiO2 is stable at low coverage but less favorable at high coverage. Adsorption of NH3 is the most critical step for the SCR of NOx, and the adsorption of H2O can hinder this process. The H2O coverage below 15% of adsorption sites could enhance the NH3 adsorption rate and have a limited effect on the acidity, while higher coverage impeded the adsorption ability of VOx sites. This work provided electron-scale insight into the adsorption impact of H2O on the surface of V2O5/TiO2 catalysts, presented thermodynamic analysis of the adsorption of H2O and NH3, paving the way for the exploration of V2O5/TiO2 catalysts with improved water resistance.

Phosphorus poisoning and regeneration of the Cu-LTA catalyst for the selective catalytic reduction of NOx with NH3

In this study, the phosphorus poisoning and regeneration of the Cu-LTA catalyst for the selective catalytic reduction of NOx with NH3 (NH3-SCR) were investigated.

Heteropoly acid-grafted iron oxide catalysts for efficient selective catalytic reduction of NOx with NH3

A series of heteropoly acid-grafted Fe2O3 catalysts (i.e., HPA/Fe2O3) for selective catalytic reduction of NOx with NH3 (NH3-SCR) were investigated.

Experimental Investigation of Mass Transfer in NH3 SCR Over Self-Supporting Cu-ZSM-5 Foam

Selective catalytic reduction of NOx by NH3 is an emerging technology for emission control applications worldwide. The development of structured catalysts for process intensification is of growing interest in catalytic...

Elucidating the role of the state of Pd in the H2-SCR of NOx by operando XANES and DRIFTS

Characterization of a Pd/V2O5/TiO2 catalyst by operando XAS and DRIFTS links the Pd state to reactive intermediates and resulting products for the selective catalytic reduction of NOx by H2.

Cu-SAPO-56, a potential catalyst for the selective catalytic reduction of NOx by NH3

A novel Cu-exchanged catalyst, Cu-SAPO-56 prepared by direct ion exchange method, was studied for NH3-SCR reaction. Cu-SAPO-56 exhibits excellent NH3-SCR activity and hydrothermal stability. The NOx conversion of Cu-SAPO-56 maintains more than 90 % at a wide temperature range between 250 °C and 400 °C even after a rigorous steam treatment (800 °C for 16 h or 50 °C for 24 h). The isolated Cu2+ ions located in double 6-ring of AFX structure are determined as the catalytic active sites. Both of Cu content and Si content in Cu-SAPO-56 play critical roles in NH3-SCR activity and hydrothermal stability. The excellent catalytic performance and strong hydrothermal stability exhibits the huge application potential of Cu-SAPO-56 for NH3-SCR reaction.

Selective catalytic reduction of NOX with CH4 over In/SSZ-13 zeolites: The enhancement of high-temperature catalytic activity by Ce modification

The selective catalytic reduction of nitrogen oxides by methane (CH4/NOX-SCR) is a potential technique for the abatement of the NOX emissions from lean-burn GDI engines, due to the excellent thermal stability of CH4. This work focuses on the promotion of In/SSZ-13 catalysts by Ce modification for the CH4/NOX-SCR performance at high temperatures. A series of In/SSZ-13 and Ce-In/SSZ-13 catalysts were prepared using the wetness impregnation method. The effects of Ce modification on the catalytic performance were analysed in detail using the scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectrum and temperature-programmed desorption/reduction techniques. The results show that the Ce modification significantly enhances the high-temperature activity of the In/SSZ-13 catalysts for the NOX-SCR reaction, especially for the 5 wt% Ce-15 wt% In/SSZ-13 sample which has more than 75% NOX conversion at 390–700 °C. In addition, the Ce modification enhances the water vapor tolerance of the catalyst sample. The Ce modification increases not only the concentration of surface chemisorption oxygen species, but also the relative amount of InO+ species which serve as the main active sites for CH4 activation. Furthermore, the incorporation of Ce into In/SSZ-13 greatly promotes NOX adsorption on the catalyst surface. Most importantly, the Ce modification makes In species well-dispersed on the catalyst surface and thus suppresses the formation of bulk In2O3 species which are more active for the CH4 non-selective oxidation. The combination of all these effects results in the Ce-In/SSZ-13 samples with the superior catalytic activity.

Oxalic acid-mediated regeneration strategy and mechanism of phosphorus poisoned CeO2/TiO2 catalysts for selective catalytic reduction of NOx with NH3

The development of the regeneration strategies can extend the service life of deactivated catalysts and improve resource efficiency. In this work, an acid treatment method was proposed to regenerate the P-poisoned CeO2/TiO2 (PCeTi) catalyst for ammonia selective catalytic reduction (NH3-SCR) of NOx. Catalytic activity test results showed that acid treatment could achieve the efficient regeneration of PCeTi catalyst, the regenerated PCeTi mediated with oxalic acid (PCeTi-OA) catalyst showed a 90% mineralization temperature (T90) of 236 °C (T90 for fresh CeTi was 232 °C) and retained the promotional effect of P species at the high temperature (>350 °C). The characterization results showed that most of the P species on the PCeTi catalyst were removed after regeneration, which restored the majority of the original Ce-O active structure, thereby promoting the Ce4+/Ce3+ redox cycling and inducing the formation of new oxygen vacancies. At the same time, the residual P-O structures and new oxygen vacancies could provide a large amount of acid sites, which was favorable for the adsorption and activation of NH3. The recovered redox properties and the increased surface acidity of the PCeTi-OA catalyst were responsible for its recovered low temperature activity and superior high temperature activity, respectively.

Unexpected Low Temperature Activity with Low N2 O Emission of Stabilized Al-rich Zeolite Beta for Selective Catalytic Reduction of NOx.

The low temperature activity of Fe-loaded zeolites as selective catalytic reduction of NOx by NH3 (NH3 -SCR) catalysts is a critical drawback for practical application. Here, we found unexpected improvement of low temperature activity by our proposed post-synthetic treatment. An Al-rich zeolite beta (Si/Al=5) is employed as the catalyst support, and the parent sample is dealuminated for higher hydrothermal stability, followed by the liquid-mediated stabilization treatment and impregnation. It is found that stabilized samples feature excellent low temperature activity and high N2 selectivity even for a long-term operation, along with the ability to maintain high NOx conversion after aging. The improved SCR activity should be attributed to abundant acid sites in Al-rich framework and better stabilization of monomeric iron species after the stabilization treatment. Furthermore, the low yield of side product N2 O is probably due to the absence of the generation of NH4 NO3 during NH3 -SCR catalyzed by Fe-loaded zeolites.

Generating silicon-rich AFX zeolite using rigid diquaternary alkylammonium structure directing agent towards stable selective catalytic reduction of NOx by NH3

New synthetic protocols to manipulate Si/Al ratios of small pore zeolites hold promise to find better selective NOx reduction catalyst using NH3 as reducing agent (NH3-SCR). AFX zeolite as NH3-SCR catalyst is currently impeded by the insufficient hydrothermal stability owing to the low Si/Al ratio. In this contribution, we report the synthesis of AFX zeolite using N,N-(1,4-phenylenebis(methylene))bis(N,N,N-triethylammonium) as organic structure directing agent (OSDA) to increase the framework Si/Al ratio to 7.8, giving rise to a marked enhancement of hydrothermal stability to withstand hydrothermal aging at 850 °C for up to 10 h. The increase in Si/Al ratio for AFX zeolite minimizes catalytic cycle driven by Brønsted acid site and broadens high temperature operation window (150–515 °C) for Cu-exchanged catalyst. Moreover, the hydrothermally aged Cu-AFX catalyst exhibits comparable catalytic activity to that of the fresh catalyst owing to Cu predominant distribution close to the 6-MR.

New Insights into the Effect of Ce Doping on the Catalytic Performance and Hydrothermal Stability of Cu-USY Zeolite Catalysts for the Selective Catalytic Reduction of NO with NH3

5Cu-USY and Ce-doped 5Cu8Ce-USY zeolite catalysts were prepared by the conventional impregnation method. The obtained catalysts were subjected to the hydrothermal ageing process. The catalytic performance of the selective catalytic reduction of NOx with NH3 (NH3-SCR) was evaluated on both fresh and aged catalysts. Physical/chemical characterizations such as X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS) were performed, along with detailed in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) experiments including CO adsorption, NH3 adsorption, and NO + O2 reactions. Results showed that, for the 5Cu-USY catalyst, hydrothermal ageing treatment could somehow improve the low-temperature SCR activity, but it also led to significant formation of unfavorable byproducts NO2 and N2O. Such an activity change can be attributed to hydrothermal ageing inducing the migration of isolated Cu+ species in the sodalite cavities towards the super cages of the USY zeolites. The increased content of Cu+ species in the super cages was beneficial for the low-temperature activity improvement, but, at the same time, it also facilitated ammonia oxidation at high temperatures. Ce doping after hydrothermal ageing has a “double-edged sword” effect on the catalytic performance. First of all, Ce doping can inhibit Cu species migration by self-occupying the internal cage sites; thus, the catalytic performance of 5Cu8Ce-USY-700H remains stable after ageing. Secondly, Ce doping introduces a CuOx–CeO2 strong interaction, which facilitates lattice oxygen mobility by forming more oxygen vacancies so as to increase the concentration of surface active oxygen. These changes, on the one hand, could help to promote further oxidative decomposition of nitrate/nitrite intermediates and improve the catalytic performance. But, on the other hand, it also causes the byproduct generation to become more severe.

Low temperature NH3 selective catalytic reduction of NOx over CeOx-biochar catalyst prepared by air oxidation

A highly efficient CeOx-BC0.6 (BC: biochar. 0.6: mass ratio of Ce/(BC + Ce)) catalyst was prepared by air oxidation for low temperature NH3 selective catalytic reduction of NOx. The catalytic performance, characterization and reaction mechanism of the CeOx-BC0.6 were investigated. The results showed that NOx conversion and N2 selectivity of CeOx-BC0.6 catalyst obtained by calcining in air were above 90 % at 150–300 °C and 100,000 h−1. The surface oxygen groups, acid sites and oxygen vacancies were generated by air oxidation treatment, which promoted the adsorption and activation of reactants. NH3 and NOx were adsorbed on the catalyst surface in the form of NH4+, NH3+, nitrite and nitrate adspecies. The redox cycles of ketonic carbonyl/phenol (CO/C–OH) pairs and Ce4+/Ce3+ pairs were responsible for the activation of NH3 and NOx. NH2NO and NH4NO2 were the main active intermediates. The reaction of NH3 selective catalytic reduction of NOx over CeOx-BC0.6 mainly followed Eley-Rideal mechanism. These results will promote the understanding of mechanism of NH3 selective catalytic reduction of NOx for biochar-based catalyst prepared by air oxidation.

Gas-expanded pore MOF derived Sm/MnOx catalysts enable ultralow-temperature selective catalytic reduction of NOx

Employing physical manipulation in macroscopic manner to achieve fine-tuning of solid mutiple-component interface and then improving of corresponding catalytic efficiency was still highly desirable but challengeable topic in design of advanced heterogeneous catalysts. Herein, a physical CO2 gas-intermediate pore-expanding strategy was deliberately integrated in the preparation of Mn-MOF precursor to facilitate the incorporation of Sm, which was employed to obtain derived Sm/MnOx catalyst with fine-tuned catalytic interface for NH3-Selective Catalytic Reduction (NH3-SCR) of NOx. Based on in-situ DRIFT analyses, DFT calculations was integrated to image that more sites exposed on the compact Sm-O-Mn interface would greatly lower the adsorption energies (Eads) for reactant and reaction intermediate. On such fine-tuned Sm-O-Mn interface, a distinct catalytic performance for NH3-SCR of NOx with 95% conversion was achieved at ultra-low temperature of 50 °C, which could be ranged in the best level compared to literature reports.

Low-temperature selective catalytic reduction of NOx with NH3: Exploring the mechanism of enhancing H2O tolerance through methylation functionalization and structural regulation in IPAx-Mn-BTC

In the selective catalytic reduction (SCR) of NOx with NH3, it is crucial to design low-temperature de-nitrification (de-NOx) catalysts with high H2O tolerance. Here, we developed a type of low-temperature de-NOx catalyst (IPAx-Mn-BTC) with strong H2O tolerance through methyl functionalization. In the presence of the optimal catalyst (IPA50-Mn-BTC), the NOx conversion only decreased from 97% to 90% after introducing 6% H2O for 6 h at low temperature of 150 °C. The results of in-situ DRIFTS and density functional theory calculations confirm that the de-NOx reaction process and the generation of intermediate states that occur on the surface of the IPA50-Mn-BTC are not affected by H2O. The elimination of the small pore size (< 4.3 nm) and the diminished H2O adsorption energy resulted from methyl functionalization are the key factors behind the improved H2O tolerance. This work provides a new approach for designing low-temperature de-NOx catalysts with high H2O tolerance.

Vanadium in strongly correlated electron system Ni1-xVxWO4: Paradoxically boosted deNOx reaction under SOx environment via modulating electron correlation

The persistent challenge of NOx selective catalytic reduction degradation in the presence of SOx has remained unresolved for decades. In this study, we report a paradoxical boosted denitration performance more than 20% under the SOx environment through controlling the charge state of V utilizing strongly correlated electron systems (SCES) in Ni1−xVxWO4. Substitutional doped V at the Ni site, and the computed charge gap from DFT confirms the SCES. Through the manipulation of the strong correlation between V and Ni, V preserves the between + 2–3 charge state in the presence of SOx. Furthermore, we achieved a stable oxidation/reduction cycle and higher denitration efficiency by altering the oxidation point of (NH4)HSO4-contaminated Ni1−xVxWO4. This results from deliberate decrease in Coulombic repulsion between Ni and V, improving electron transfer for catalytic performance. This revelation offers a resolution of exceptional denitration performance within SOx in industrial exhaust systems, exploiting the foundational principles of SCES.

Enhancement of Fe-Nb interaction by acid modification over SO42--FeOx-Nb2O5 catalyst for NH3 selective catalytic reduction of NOx

A series of iron-based composite oxide catalysts, modified with acid and niobium, were produced for the purpose of selective catalytic reduction of NOx with NH3 (NH3-SCR) via co-precipitation. The obtained SO42--FeOx-Nb2O5 (S-FeNbOx) catalyst exhibited significantly better SCR performance than the unmodified FeOx catalyst, with a NOx conversion above 90% and N2 selectivity higher than 95% in the temperature range of 275–450 °C. The characterization results suggest that the addition of Nb not only modifies the electronic structure and alleviates the reducibility but also enhances the surface acidity of the catalysts. The sulfuric acid modification of FeOx-Nb2O5 catalyst promotes the formation of redox-acid sites. The in situ Diffuse Reflectance Infrared Fourier Transform spectroscopy (DRIFTs) results revealed that the combining sulfuric acid and niobium modifications resulted in a significant increase in the amount of Brønsted acid sites, and also led to a blue shift of the band related to the Lewis acid sites, implying the existence of a synergistic effect of the two modification methods. The creation of redox-acid sites significantly enhances the adsorption and activation capacity of NH3 on the catalyst surface. These results suggest that the NH3-SCR reaction to primarily follow the Eley-Rideal (E-R) mechanism on the catalyst.

Continuous Unsteady-State De-NOx System via Tandem Water-Gas Shift, NH3 Synthesis, and NH3-SCR under Periodic Lean/Rich Conditions.

The development of urea-free and platinum group metal (PGM)-free catalytic systems for automotive emission control is a challenging task. Herein, we report a new de-NOx system using cyclic feeds of rich and lean gas mixtures with PGM-free catalysts. Initial catalyst screening tests showed that Cu/CeO2 with 5 wt % Cu loading was the most suitable for the water-gas shift reaction (WGS, CO + H2O → CO2 + H2), followed by the selective NH3 synthesis by the NO + H2 reaction. The unsteady-state system under alternating feeds of rich (0.1% NO + 0.5% CO + 1% H2O) and lean (0.1% NO + 2% O2 + 1% H2O) gas mixtures over a mixture of Cu/CeO2 and Cr-exchanged mordenite (CrMOR) showed higher NOx conversion than the steady-state (0.1% NO + 0.35% CO + 0.6% O2 + 1% H2O) reaction between 200 and 500 °C. The de-NOx mechanism under periodical rich/lean conditions was studied by operando infrared (IR) experiments. In the rich period, the WGS reaction on the Cu/CeO2 catalyst yield H2, which reduces NO to NH3 on the Cu/CeO2 catalyst. NH3 is then captured by the Brønsted acid sites of CrMOR. In the subsequent lean period, the adsorbed NH3 acts as a reductant for the selective catalytic reduction of NOx catalyzed by the Cr sites of CrMOR. This study demonstrates a new urea-free and PGM-free catalytic system that can provide an alternative de-NOx technology for automotive catalysis under periodic rich/lean conditions.

Sulfur and Water Resistance of Carbon-Based Catalysts for Low-Temperature Selective Catalytic Reduction of NOx: A Review

Low-temperature NH3-SCR is an efficient technology for NOx removal from flue gas. The carbon-based catalyst designed by using porous carbon material with great specific surface area and interconnected pores as the support to load the active components shows excellent NH3-SCR performance and has a broad application prospect. However, overcoming the poor resistance of H2O and SO2 poisoning for carbon-based catalysts remains a great challenge. Notably, reviews on the sulfur and water resistance of carbon-based low-temperature NH3-SCR catalysts have not been previously reported to the best of our knowledge. This review introduces the reaction mechanism of the NH3-SCR process and the poisoning mechanism of SO2 and H2O to carbon-based catalysts. Strategies to improve the SO2 and H2O resistance of carbon-based catalysts in recent years are summarized through the effect of support, modification, structure control, preparation methods and reaction conditions. Perspective for the further development of carbon-based catalysts in NOx low-temperature SCR is proposed. This study provides a new insight and guidance into the design of low-temperature SCR catalysts resistant to SO2 and H2O in the future.