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Research Progress on Water Resistance of Transition Metal-Based MOF Denitration Catalysts AITranslate

Menglin Wang1; Xuewen Li1; Jinling Wang1; Yundong Liang2; Yaru Li1; Xianbiao Wang1;
1.School of Materials Science and Chemical Engineering，Anhui Jianzhu University，Hefei 230601，China
2.Anhui Shiqing Environmental Protection Technology Co.，Ltd.，Hefei 231121，China
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Publisher: Youke Publishing Co., Ltd
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Abstract AITranslate

The rapid advancement of industrialization and urbanization in recent years has significantly intensified global environmental challenges. Among these, nitrogen oxide （NOx） emissions stand as a key factor contributing to environmental issues such as acid rain, photochemical smog, stratospheric ozone depletion, and the greenhouse effect. As NOx emissions continue to rise with global industrial output, the development of effective control and reduction technologies has become an urgent priority. Selective catalytic reduction （SCR） technology, particularly ammonia-based SCR （NH3-SCR）, has emerged as one of the most efficient methods for removing NOx from flue gases. In this process, NH3 serves as a reducing agent to selectively convert NOx to harmless N2 and H2O over a solid catalyst. Therefore, the catalyst is essential for lowering the activation energy, enhancing the reaction rate and selectivity, while expanding the reaction temperature window. In the quest for advanced catalysts, metal-based metal-organic frameworks （MOFs）, composed of metal ions or clusters with organic ligands, have attracted increasing attention as potential SCR catalysts due to their unique pore structures, high specific surface areas, and controllable chemical environments. MOFs provide a large number of active sites for reactions, effectively improving catalytic reaction efficiency. Incorporating transition metals such as manganese （Mn）, copper （Cu）, and iron （Fe） endows MOFs with outstanding redox properties, making them promising candidates for catalytic NOx removal. Furthermore, the modular nature of MOFs allows for precise structural tuning, enabling the design of tailored catalysts for gas-phase reactions such as NH3-SCR. Despite these advantages, most of MOF catalysts are sensitive to moisture. During real flue gas treatment processes, they are frequently exposed to high-humidity environments, which can lead to MOF deactivation, commonly referred to as the “water poisoning” phenomenon. This is primarily attributed to the hydrolysis of metal-ligand coordination bonds, the collapse of the MOF framework, or the blockage of active sites by water molecules. Such drawbacks severely limit the long-term stability and industrial applicability of MOF-based catalysts. To overcome these limitations, researchers have delved into the mechanisms underlying MOF water poisoning and developed effective strategies to enhance water resistance. This review systematically summarized recent advances in water-resistant modification techniques for transition metal-based MOF denitrification catalysts in NH3-SCR applications. Three main strategies were discussed. The first involved introducing hydrophobic functional groups onto MOF surface or organic ligands to repel water molecules and prevent hydrolytic degradation. The second focused on strengthening metal-ligand bonds through ligand selection or secondary metal doping to enhance the stability of the coordination framework. The third employed surface protection techniques, such as coating MOF particles with hydrophobic polymers or constructing core-shell structures, to physically isolate the active core from moisture. Specifically, for Mn-based MOFs, researchers had devoted efforts to optimizing pore structures and regulating metal ion distribution, thereby preventing pore blockage by water molecules, enhancing water resistance, and increasing the availability of active sites. Additionally, the introduction of a second metal （such as Fe or Ce） could strengthen the coordination framework and enhance catalytic synergistic effects, while the incorporation of hydrophobic groups could protect active sites from moisture. Cu-based MOFs had been successfully modified by forming hydrophobic coatings or integrating hydrophobic polymers, effectively mitigating structural degradation under humid conditions. For Fe-based MOFs, doping with other metals or surface hydrophobic modification had further improved their inherent thermal stability and redox capabilities, enabling them to maintain high activity and structural stability in moisture-rich environments. This review systematically analyzed the mechanisms of water-induced deactivation, summarized modification strategies, and delved into the structure-performance relationships of transition metal-based metal-organic framework denitrification catalysts. These insights provided a solid foundation for the rational design of next-generation MOF catalysts with enhanced water resistance, catalytic efficiency, and long-term durability. Looking forward, the development of durable, high-performance MOF catalysts would play a pivotal role in advancing NH3-SCR technology, reducing NOx emissions, and promoting clean air and sustainable development. This review aimed to offer valuable references for the design and application research of future water-resistant denitrification catalysts.

KeyWords AITranslate

NH3-selective catalytic reduction （SCR） denitration water poisoning transition metal-based metal-organic frameworks （MOFs） catalyst water resistance

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Basic Information:

DOI：10.13373/j.cnki.cjrm.XY25060013

Chinese Library Classification Number:X51

Citation Information:

The rapid advancement of industrialization and urbanization in recent years has significantly intensified global environmental challenges. Among these, nitrogen oxide （NOx） emissions stand as a key factor contributing to environmental issues such as acid rain, photochemical smog, stratospheric ozone depletion, and the greenhouse effect. As NOx emissions continue to rise with global industrial output, the development of effective control and reduction technologies has become an urgent priority. Selective catalytic reduction （SCR） technology, particularly ammonia-based SCR （NH3-SCR）, has emerged as one of the most efficient methods for removing NOx from flue gases. In this process, NH3 serves as a reducing agent to selectively convert NOx to harmless N2 and H2O over a solid catalyst. Therefore, the catalyst is essential for lowering the activation energy, enhancing the reaction rate and selectivity, while expanding the reaction temperature window. In the quest for advanced catalysts, metal-based metal-organic frameworks （MOFs）, composed of metal ions or clusters with organic ligands, have attracted increasing attention as potential SCR catalysts due to their unique pore structures, high specific surface areas, and controllable chemical environments. MOFs provide a large number of active sites for reactions, effectively improving catalytic reaction efficiency. Incorporating transition metals such as manganese （Mn）, copper （Cu）, and iron （Fe） endows MOFs with outstanding redox properties, making them promising candidates for catalytic NOx removal. Furthermore, the modular nature of MOFs allows for precise structural tuning, enabling the design of tailored catalysts for gas-phase reactions such as NH3-SCR. Despite these advantages, most of MOF catalysts are sensitive to moisture. During real flue gas treatment processes, they are frequently exposed to high-humidity environments, which can lead to MOF deactivation, commonly referred to as the “water poisoning” phenomenon. This is primarily attributed to the hydrolysis of metal-ligand coordination bonds, the collapse of the MOF framework, or the blockage of active sites by water molecules. Such drawbacks severely limit the long-term stability and industrial applicability of MOF-based catalysts. To overcome these limitations, researchers have delved into the mechanisms underlying MOF water poisoning and developed effective strategies to enhance water resistance. This review systematically summarized recent advances in water-resistant modification techniques for transition metal-based MOF denitrification catalysts in NH3-SCR applications. Three main strategies were discussed. The first involved introducing hydrophobic functional groups onto MOF surface or organic ligands to repel water molecules and prevent hydrolytic degradation. The second focused on strengthening metal-ligand bonds through ligand selection or secondary metal doping to enhance the stability of the coordination framework. The third employed surface protection techniques, such as coating MOF particles with hydrophobic polymers or constructing core-shell structures, to physically isolate the active core from moisture. Specifically, for Mn-based MOFs, researchers had devoted efforts to optimizing pore structures and regulating metal ion distribution, thereby preventing pore blockage by water molecules, enhancing water resistance, and increasing the availability of active sites. Additionally, the introduction of a second metal （such as Fe or Ce） could strengthen the coordination framework and enhance catalytic synergistic effects, while the incorporation of hydrophobic groups could protect active sites from moisture. Cu-based MOFs had been successfully modified by forming hydrophobic coatings or integrating hydrophobic polymers, effectively mitigating structural degradation under humid conditions. For Fe-based MOFs, doping with other metals or surface hydrophobic modification had further improved their inherent thermal stability and redox capabilities, enabling them to maintain high activity and structural stability in moisture-rich environments. This review systematically analyzed the mechanisms of water-induced deactivation, summarized modification strategies, and delved into the structure-performance relationships of transition metal-based metal-organic framework denitrification catalysts. These insights provided a solid foundation for the rational design of next-generation MOF catalysts with enhanced water resistance, catalytic efficiency, and long-term durability. Looking forward, the development of durable, high-performance MOF catalysts would play a pivotal role in advancing NH3-SCR technology, reducing NOx emissions, and promoting clean air and sustainable development. This review aimed to offer valuable references for the design and application research of future water-resistant denitrification catalysts.

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GB/T 7714-2015 [1] Menglin Wang, Xuewen Li, Jinling Wang, et al. Research Progress on Water Resistance of Transition Metal-Based MOF Denitration Catalysts[J]. Chinese Journal of Rare Metals, 2026, 50(8): 1324-1337. DOI:10.13373/j.cnki.cjrm.XY25060013.
MLA [1] Menglin Wang, et al., "Research Progress on Water Resistance of Transition Metal-Based MOF Denitration Catalysts." Chinese Journal of Rare Metals, vol. 50, no. 8, 2026, pp. 1324-1337, https://doi.org/10.13373/j.cnki.cjrm.XY25060013.
APA [1] Menglin Wang, Xuewen Li, Jinling Wang, Yundong Liang, Yaru Li, & Xianbiao Wang. (2026). Research Progress on Water Resistance of Transition Metal-Based MOF Denitration Catalysts. Chinese Journal of Rare Metals, 50(8), 1324-1337. https://doi.org/10.13373/j.cnki.cjrm.XY25060013
IEEE [1] Menglin Wang, Xuewen Li, Jinling Wang, Yundong Liang, Yaru Li, and Xianbiao Wang, "Research Progress on Water Resistance of Transition Metal-Based MOF Denitration Catalysts," Chinese Journal of Rare Metals, vol. 50, no. 8, pp. 1324-1337, 2026, doi: 10.13373/j.cnki.cjrm.XY25060013. keywords: {NH-selective catalytic reduction （SCR）;denitration;water poisoning;transition metal-based metal-organic frameworks （MOFs） catalyst;water resistance}