4.6 Review

Research Progress of the Selective Catalytic Reduction with NH3 over ZSM-5 Zeolite Catalysts for NOx Removal

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Bifunctional ZnO/HZSM-5 Catalysts in Direct Hydrogenation of CO2 to Aromatics; Influence of Preparation Method

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Summary: The incorporation of ZnO in HZSM-5 zeolites was achieved through five different methods, and the influence of these methods on the performance of ZnO/HZSM-5 catalysts in the direct hydrogenation of CO2 to aromatics was evaluated. The introduction of ZnO led to a decrease in surface area and micropore volume, except when ZnO was added to the synthesis gel. The high amount of Bronsted acidity was found to enhance CO2 conversion and aromatics synthesis, and the addition of ZnO decreased weak acid sites while increasing strong acid sites. The CO2 conversion followed a specific sequence, with the ZnO/ZSM-5-HS catalyst showing outstanding aromatics selectivity and CO2 conversion.

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Synthesis of Hierarchical Micro-mesoporous ZSM-5 Zeolite and its Catalytic Activity in Benzylation of Mesitylene

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Summary: Hierarchical micro-mesoporous ZSM-5 zeolite was synthesized by using corn plant stem pith powder as a hard template. The addition of pith powder increased the porosity of the zeolites, resulting in better catalytic performance with higher conversion rate and selectivity in the formation of 2-Benzyl-1, 3, 5-trimethylbenzene. The presence of hierarchical pores and strong acidity in C-ZSM-5 contributed to its improved selectivity and stability.

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Study on the role of Fe species and acid sites in NH3-SCR over the Fe-based zeolites

Dan Yu et al.

Summary: Fe-doped ZSM-5 zeolite catalysts were studied for their activity and characteristics changes in the NH3 selective catalytic reduction of NOx. The results showed that the SCR activity was mainly dependent on active Fe species rather than acidity. Fe-oxo related Lewis sites played an important role in the low-temperature SCR reaction, while high Bronsted acidity was not necessary for high SCR activity. The study also revealed the conversion of inactive free Fe2+ ions to isolated Fe3+ species during high-temperature calcination and thermal aging, which was inhibited by water.
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Positive Effect of Ce Modification on Low-Temperature NH3-SCR Performance and Hydrothermal Stability over Cu-SSZ-16 Catalysts

Yuqian Liang et al.

Summary: Cu-exchanged SSZ-16 zeolite catalysts were modified with Ce to improve their hydrothermal stability. Increasing Ce contents significantly enhanced the stability, with CuCe0.87-SSZ-16 showing the best performance. Characterization measurements revealed that Ce modification strengthened the structural stability and increased the active Cu2+-2Z species, contributing to the improved hydrothermal stability.

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Denitrification performance and sulfur resistance mechanism of Sm-Mn catalyst for low temperature NH3-SCR

Junlin Xie et al.

Summary: MnOx and Sm-Mn catalysts prepared by coprecipitation method demonstrated excellent activities and sulfur resistances in the selective catalytic reduction of NOx by NH3 at temperatures between 50 and 300 degrees C with excess oxygen. 0.10Sm-Mn catalyst showed superior catalytic activity and sulfur resistance. The addition of Sm affected the phases, morphology structures, gas adsorption, reaction process, and specific surface areas, resulting in enhanced NO conversion, N-2 selectivity, and sulfur resistance. Extensive investigations were conducted on the reaction mechanism and the impact of SO2 on the catalysts.

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Highly ordered mesoporous MnOx catalyst for the NH3-SCR of NOx at low temperatures

Shiyu Xu et al.

Summary: MnOx catalysts with 3D structure (Mn-HT) were prepared using KIT-6 as a template by the hard-template method, and their catalytic performance for the selective catalytic reduction of NOx by NH3 was investigated at low temperatures. It was found that the template KIT-6 prepared at different hydrothermal temperatures significantly affected the catalytic performance of Mn-HT catalysts. Among them, Mn-140 catalyst prepared using the template obtained at a hydrothermal temperature of 140 degrees C exhibited the highest catalytic performance. Characterizations showed that Mn-140 catalyst possessed high reducibility with abundant surface oxygen species and Mn4+ species. NH3-TPD and in situ DRIFTS demonstrated that there were more Lewis acid sites and Bronsted acid sites on the surface of Mn-140 catalyst, promoting the adsorption and activation of NH3 and efficiently reducing NOx mainly by the Eley-Rideal (E-R) mechanism, accompanied by the Langmuir-Hinshelwood (L-H) mechanism.

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A review of comparison between the traditional catalyst and zeolite catalyst for ammonia-selective catalytic reduction of NOx

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Summary: Emission plays a crucial role in air pollution and its impact on living organisms. Selective Catalytic Reduction (SCR) is a commonly used technology to reduce Nitrogen Oxides (NOx) emissions in internal combustion engines. This review examines various catalysts used in SCR, including metal-based catalysts and zeolite-based catalysts, and explores their performance and characteristics in terms of GHSV, efficiency at different temperature ranges, percentage doping, and NOx conversion efficiency. The review concludes that zeolite catalysts show excellent deNOx efficiency, with 2 to 4 wt% doping of Cu achieving around 95% deNOx and doping of Fe widening the operating temperature range.
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Deactivation of Cu SCR catalysts based on small-pore SSZ-13 zeolites: A review

Boji Wang et al.

Summary: Increasingly stringent regulation towards nitrogen oxides (NOx) emission worldwide calls for efficient technologies such as selective catalytic reduction (SCR) with NH3. Transition metals supported on small-pore zeolites, especially Cu-SSZ-13, have been successfully applied to NOx abatement in road transport and can be extended to stationary sources. However, the stability and activity of such catalysts need to be revisited and tuned to accommodate the complex operating conditions in various industries. This review critically discusses the poisoning and deactivation mechanisms of zeolite-based SCR catalysts, aiming to establish the link between current catalysts and the demands in industries.

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Recent progress in novel zeolite catalysts for selective catalytic reduction of nitrogen oxides

Anqi Guo et al.

Summary: This paper summarizes recent advancements in the development and application of novel zeolites as selective catalytic reduction (SCR) catalysts for nitrogen oxides (NOx) abatement from lean-burn heavy-duty vehicles. It focuses on the synthesis, structure-performance relationship, and potential application of small-pore zeolites as catalysts in SCR with NH3 as the reductant. The post-synthetic modifications of small-pore zeolites, Cu-free small-pore zeolites, and mechanistic understandings of NH3-SCR chemistry over small-pore zeolite catalysts are also discussed, along with the potential of several novel small-pore zeolites for real application in NH3-SCR and the development of new SCR systems.

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Mechanistic investigation of Sm doping effects on SO2 resistance of W-Zr-ZSM-5 catalyst for NH3-SCR

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Summary: A series of xSm-WZZ catalysts were prepared to improve the SO2 resistance and regeneration performance of diesel engine NH3-SCR catalysts. The 1Sm-WZZ catalyst exhibited the best SO2 and H2O resistance and slightly improved the NH3-SCR activity.
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Summary: NOx emission is a major cause of acid rain and photochemical smog, which have had a serious impact on the ecological environment, production, and daily life. Effective reduction of NOx emissions has become an important topic, with selective catalytic reduction (SCR) being the main research direction due to its high efficiency. Carbon-based materials, known for their large surface area, well-developed pore structure, and strong adsorption capacity, are widely used as catalyst carriers in SCR. This paper reviews recent research achievements in using activated carbon, carbon nanotube, graphene, and other carbon materials as SCR catalyst carriers, and summarizes the catalytic efficiency of these catalysts. The differences in properties due to different modification and preparation methods, as well as the effects of H2O and SO2 on the catalysts, are discussed. Challenges in the industrial application of carbon-based catalysts and future research directions are also highlighted.

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ZSM-5 core-shell structured catalyst for enhancing low-temperature NH3-SCR efficiency and poisoning resistance

Zhaoying Di et al.

Summary: By constructing a core-shell ZSM-5@CeO2 support and loading copper, the NH3-SCR performance, as well as the tolerance to H2O and SO2, was improved. The Cu/(ZSM-5@CeO2) catalyst showed superior activity with the lowest T-90 at 215°C, attributed to the interaction between CeO2 shell and copper ions, which enhanced the redox properties. The ZSM-5 core provided more acid sites for improved ammonia adsorption. The CeO2 shell preferentially reacted with SO2, leading to high sulfur tolerance. This study provides a strategy for designing and applying NH3-SCR zeolite catalysts.

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An in-situ DRIFTs study of Mn doped FeVO4 catalyst by one-pot synthesis for low-temperature NH3-SCR

Heng Xie et al.

Summary: Manganese-doped FeVO4 catalysts were synthesized using a novel one-pot method, and the effect of Mn doping on FeVO4 in the selective catalytic reduction of NOx with NH3 was studied extensively. The 0.3Mn-FeV catalyst demonstrated superior deNOx performance, reaching 100% NOx conversion rate at 250 degrees C. Various characterization techniques revealed that Mn doping improved the crystal size, acidity, and redox properties of the catalyst, facilitating NH3 activation and maintaining V species in a higher oxidation state for enhanced performance in the SCR reaction.
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Significant promoting effect of La doping on the wide temperature NH3-SCR performance of Ce and Cu modified ZSM-5 catalysts

Jian Yang et al.

Summary: The La-doped Ce-Cu/Z5 catalyst demonstrated excellent SCR activity and stability in the selective catalytic reduction of NOx via ammonia. Its performance is attributed to the promotion of oxygen vacancy formation and optimization of the surface redox cycle, facilitating the efficient SCR reaction.

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Pengfei Li et al.

Summary: This study reports the fabrication of a cobalt-doped trimetallic catalyst through pyrolysis of a metal-organic framework, which shows excellent performance in NH3 selective catalytic reduction, high water and sulfur resistance, and good stability. The results suggest the potential for developing a high stability catalyst for low-temperature selective catalytic reduction of NOx with NH3.

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Jie Yang et al.

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Hongyan Xue et al.

Summary: M/ZSM-5 (M = Mn, Co, Cu) samples were prepared by impregnation and their catalytic performance in NH3-SCR of NO was tested. Cu/ZSM-5 exhibited the highest activity, followed by Mn/ZSM-5, and Co/ZSM-5 was the least active. In-situ DRIFTS analysis revealed the nature and evolution of surface species. Coordinated NH3, NH4+, and amide (-NH2) species derived from NH3 adsorption were found to be relevant for NH3-SCR, while bridged nitrate species derived from NOx adsorption were identified as the main active species. Bridged nitrate was more abundant and thermally more stable on Cu/ZSM-5, consistent with its higher activity compared to Mn/ZSM-5 and Co/ZSM-5. Different mechanisms, including Eley-Rideal and Langmuir-Hinshelwood, were observed for Mn/ZSM-5 at different temperatures, while both pathways coexisted for Co/ZSM-5 and Cu/ZSM-5.

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Green synthesis of ZSM-5 zeolite for selective catalytic reduction of NO via template-free method from tailing residue

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