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Application of Transition Metal Based MOF Materials in Selective Catalytic Reduction of Nitrogen Oxides

Wei Zhang , Kang Xie , Yunhao Tang , Chuan Qin , Shan Cheng , Ying Ma

Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (12) : 2638 -2650.

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Progress in Chemistry ›› 2022, Vol. 34 ›› Issue (12) : 2638-2650 DOI: 10.7536/PC220422
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Application of Transition Metal Based MOF Materials in Selective Catalytic Reduction of Nitrogen Oxides
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Abstract

Selective catalytic reduction (SCR) technology is the most widely used industrial denitration technology at present, the development of catalyst system with excellent activity and anti-poisoning performance is the focus of researchers. Transition metal oxides and metal organic framework (MOF) materials have been widely studied and applied in the field of denitration catalysts because of their excellent redox performance, and researchers found that the combination of transition metal oxides and MOF materials can further improve the denitration activity of the catalyst. This paper summarizes the research progress of a series of single transition metal based MOF denitration catalysts and composite transition metal based MOF denitration catalysts mainly used in NH3-SCR reaction in recent years, and expounds the strengthening methods of water resistance, sulfur poisoning resistance and thermal stability of transition metal based MOF denitration catalysts, The main research directions of transition metal based MOF denitration catalysts in the future are prospected: new transition metal based MOF denitration catalysts with excellent denitration activity, water and sulfur resistance and thermal stability can be prepared by comprehensively utilizing the characteristics of different transition metal oxides and combined with the strong interaction between metal oxides. Further, transition metal based MOF denitration catalyst can be prepared by combining experiment and simulation to selectively catalyze the reduction of nitrogen oxides to meet the needs of industrialization.

Contents

1 Introduction

2 Transition metal based MOF denitration catalyst

2.1 Mono-transition metal based MOF denitration catalysts

2.2 Double-transition metal based MOF denitration catalysts

3 Enhancement of antitoxicity of transition metal based MOF denitration catalysts

3.1 Enhancing the water resistance of transition metal based MOF denitration catalysts

3.2 Enhancing the sulfur resistance of transition metal based MOF denitration catalysts

4 Method for enhancing thermal stability of transition metal based MOF denitration catalysts

4.1 Adding metal clusters

4.2 Optimizing the molar ratio of metal ions to organic ligands

5 Conclusion and Prospect

Graphical abstract

Keywords

selective catalytic reduction / metal organic framework / transition metal oxide / poison resistance / thermal stability

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Wei Zhang, Kang Xie, Yunhao Tang, Chuan Qin, Shan Cheng, Ying Ma. Application of Transition Metal Based MOF Materials in Selective Catalytic Reduction of Nitrogen Oxides. Progress in Chemistry, 2022, 34(12): 2638-2650 DOI:10.7536/PC220422

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1 Introduction

As one of the main air pollutants, nitrogen oxides (NOx) can cause a series of environmental problems such as acid rain, haze and greenhouse effect, in addition to causing harm to human health[1][2]. At present, the methods to control the emission of nitrogen oxides mainly include selective catalytic reduction, selective non-catalytic reduction, electron beam, liquid absorption, adsorption, catalytic oxidation, catalytic decomposition, etc. Among them, selective catalytic reduction (SCR) technology has become the most widely used denitrification technology because of its high denitrification efficiency and low production cost[3][4][5][6][7,8,9].
V-Ti catalyst is the most widely used industrial catalyst in SCR denitrification system at present, but it still has some shortcomings, such as high operating temperature, easy poisoning and deactivation of V active sites, and the traditional catalyst carrier has some problems, such as small specific surface area and difficult to control porosity, which limit the industrial application[10][11]. In contrast, metal-organic frameworks (MOF) have the advantages of large specific surface area, regular crystal structure and controllable size, and transition metal oxides have strong redox ability due to the easy loss or abstraction of electrons from the d-electron shell of metal cations, which can show good denitrification performance in low-temperature NH3-SCR reactions[12][13][14]. In recent years, there have been a large number of reports on the modification of MOF materials by transition metal oxides to improve their redox performance and denitrification efficiency. In this pap, that application and characteristics of Mn, Fe, Cu single transition metal-based MOF catalyst in NH3-SCR denitrification are reviewed, and the research progress in the preparation of double transition metal-based MOF catalyst by using different transition metal elements to enhance denitrification performance is further summarized.The methods to enhance the water and sulfur resistance and thermal stability of transition metal-based MOF catalysts were described, and the potential research directions of transition metal-based MOF catalysts were finally prospected to promote their industrial application.

2 Transition metal-based MOF denitration catalyst

2.1 Ingle transition metal based MOF denitration catalyst

The combination of specific transition metal oxides and MOF materials to prepare catalysts can not only improve the dispersion of active components, but also enhance the interaction between active components and supports, and further improve the denitrification activity of transition metal based MOF catalysts[15]. In this paper, the research progress in the preparation of denitration catalysts by combining single transition metal oxides with MOF materials in recent years is reviewed, which provides a reference for the research and preparation of new MOF denitration catalysts in the future.

2.1.1 Mn-based MOF denitration catalyst

As a transition metal element in the seventh subgroup of the fourth period, Mn has a valence electron configuration of 3d54s2. The electrons in the d orbit of Mn in the oxide move in a half-filled state and are easy to jump to other energy levels to provide free electrons, so Mn has multiple valence States such as + 7, + 6, + 4, + 3 and + 2, and each oxidation state can be converted at low temperature to promote the redox reaction[16,17]. In recent years, researchers have found that the coordinated unsaturated metal sites (CUSs) of catalysts can be used as active sites to participate in the adsorption of reaction gases when they use Mn oxides to modify MOF materials to enhance their low-temperature denitrification activity.Among them, CUSs have the strongest binding ability with NH3 and high interaction energy with NO2, which can promote the "fast SCR" reaction and accelerate the catalytic removal of nitrogen oxides[18,19][20]. Meanwhile, NO and O2 have similar affinities for the Mn2+ site, implying that competitive adsorption may occur between the two components. In addition, during the co-adsorption of NH3, H2O, and SO2 on the Mn-MOF surface,Both H2O and SO2 may negatively affect the NH3-SCR reaction because of competitive adsorption on CUSs,And SO2 is easier to replace NH3 than H2O, so the enhancement of sulfur resistance of Mn-based MOF catalyst needs to be further studied.
In addition, the vacuum of the reaction atmosphere and the drying time of the catalyst are also important factors affecting the activity of CUSs[21]. In the air atmosphere, the denitration efficiency of Mn-MOF is low because the vacuum degree is too low and the catalyst drying time is insufficient, and the molecules such as CH3OH, H2O or DMF adsorbed on the CUSs cannot be completely removed. However, in the N2 atmosphere, the higher vacuum degree and sufficient drying time effectively prevented the CUSs on the surface of the catalyst from being passivated, thus obtaining a higher denitrification efficiency. Therefore, further optimizing the reaction conditions of Mn-based MOF denitration catalyst is an effective way to improve its denitration activity.
To sum up, various oxidation States of Mn in Mn-based MOF denitration catalyst can be converted freely at low temperature, and its CUSs have strong adsorbability to NH3-SCR reaction-related gases, so Mn-based MOF denitration catalyst has excellent low-temperature denitration performance. However, the strong adsorption of SO2 is easy to poison the active sites of the catalyst, and the reaction conditions such as the vacuum degree of the reaction atmosphere and the drying time of the catalyst are also important factors affecting the denitrification efficiency of the catalyst.Therefore, the protection of CUSs by optimizing the reaction conditions is beneficial to improve the denitrification activity at low temperature, and the inhibition of SO2 and H2O on CUSs needs to be further studied.

2.1.2 Fe-based MOF denitration catalyst

As a transition metal element in the seventh main group of the fourth period, the valence electron arrangement outside the core of Fe is 3d64s2, which is easy to accept the lone pair electrons in reactive gas molecules such as NO during the denitration reaction, and there are a large number of oxygen vacancies in Fe oxides, which is beneficial to the adsorption and activation of reactive gases such as NO and NH3, thus promoting the NH3-SCR reaction[22,23].
In recent years, the application of MIL-100 (Fe) in the field of denitrification has attracted great attention from the academic community. The surface of MIL-100 (Fe) has both NH 4 + and coordinated NH3, and on the active sites of iron oxide,NO can be oxidized to NO2 and then react with NH 4 + to produce N2 and H2O. At the same time, iron species (the reduction process of Fe3++e-↔Fe2+) can also accelerate the activation of reactive gases such as NO and NH3[24]. In addition, Lewis acid sites and Brønsted acid sites coexist on MIL-100 (Fe) and participate in the denitration reaction, among which Lewis acid sites play a more important role in the activation of reactants, so the NH3-SCR reaction of the catalyst mainly follows the E-R mechanism[25]. The reaction process can be divided into two parts: NO oxidation and "fast SCR" reaction. First, NO and O2 combine on Lewis acid sites to produce nitrate, which in turn reacts with additional NO to produce NO2 with lower barrier energy, thus promoting the oxidation process. In turn, the NH3 adsorbed on the Lewis acid site is activated by N binding with NO2 to decompose into N2 and H2O, forming a "fast SCR" reaction.
Reaction temperature is also one of the important factors affecting the catalytic activity of Fe-based MOF denitration catalyst. At higher temperature, vacuum heating will produce more unsaturated Fe2+/Fe3+ sites on MIL-100 (Fe), and lead to the transformation of Fe3+ into Fe2+, which can effectively improve the conversion rate of NO[26]. When Shi et al. Used MIL-100 (Fe) as a NH3-SCR denitration catalyst, they found that the denitration efficiency of the catalyst was close to 100% at 300 ° C relative to the low temperature range[27]. Therefore, it is an effective way to improve the catalytic activity of MIL-100 (Fe) by optimizing the optimal reaction temperature region.
In the MIL-100 (Fe) denitration system, SO2 and H2O preempted the active sites on the catalyst surface and did not completely deactivate the catalyst. When the introduction of the SO2 and the H2O is stopped, the high-concentration NH3 and NO mixed gas molecules near the active sites on the surface of the catalyst push out or consume the SO2/H2O through physical or chemical action,Resulting in the exposure of the active site occupied by SO2/H2O to the NH3/NO atmosphere, such that the conversion of NOx conversion is slightly elevated[28]. Therefore, MIL-100 (Fe) also has strong anti-poisoning performance.
In summary, the Fe-based MOF denitration catalyst has the following advantages: (1) Fe oxide has a multi-valence valence electron structure and abundant oxygen vacancies, which is beneficial to the adsorption and activation of reaction gases such as NO and NH3. (2) Lewis acid sites and Brønsted acid sites on the surface of the catalyst can effectively promote the "fast SCR" reaction. (3) The reduction of Fe species enables NO, NH3 molecules to be largely converted into active elements favorable for the 4NO+4NH3+O2→4N2+6H2O reaction, thereby increasing the conversion rate of nitrogen oxides. (4) The catalyst can still show good stability in the presence of H2O and SO2. Therefore, it is of great significance to further carry out the basic research of Fe-based MOF denitration catalyst for expanding the low temperature active temperature range of the catalyst, strengthening the sulfur resistance and hydrothermal stability.

2.1.3 Cu-based MOF denitration catalyst

As a transition metal element in the first subgroup of the fourth period, the valence electron configuration of Cu is 3d104s1, and its valence is + 2, + 1 and 0. Its oxide has excellent redox ability and good dispersion on the surface of the support, so the MOF catalyst modified by Cu oxide has a good application prospect in the low temperature denitrification process[29][30].
Cu-BTC is a widely studied denitration catalyst at present. After heat treatment at high temperature, CUSs, which are beneficial to the adsorption of small gas molecules, can be generated on the surface of the ordered mesoporous framework of Cu-BTC, and at the same time, the sp3 hybrid orbital of Cu-BTC can promote the adsorption and conversion of NH3, NO and other molecules by accepting electrons, which makes the adsorbed molecules produce electron migration when contacting with it[31][32]. In recent years, researchers have found that treating Cu-BTC with organic acids can further improve its catalytic activity. The main reasons are as follows: (1) Organic acids compete with H3BTC to occupy the coordination site first, which reduces the complexity of the catalyst framework and delays the crystal growth[33,34]; (2) a small amount of organic acid molecules are ionized in the solvent environment, which can effectively hinder the deprotonation of the organic ligand; (3) Organic acids have a selective inhibitory effect on crystal growth in specific directions. The above factors eventually lead to the change of the morphology and topology of the Cu-BTC catalyst, which improves the exposure of the catalyst CUSs, thereby improving the catalytic activity[35]. In addition, the thermosensitive organic ligand of Cu-BTC catalyst will directly affect the number of active sites on the surface of the catalyst. When the reaction temperature is too high, the thermosensitive organic ligand will decompose and deactivate the catalyst, so the thermal stability of the catalyst is poor[36,37]. Therefore, in order to make Cu-BTC widely used in the field of industrial denitrification, it is necessary to carry out in-depth research on the enhancement method of thermal stability.
In addition, Cu-MOF-74 denitration catalyst modified by Cu oxide has large specific surface area and good dispersion of active sites, which is conducive to the adsorption of reaction gases, so it has also received some attention[38]. Due to the Jahn-Teller distortion of the Cu2+ octahedron, the coordination environment of the Cu2+ in the Cu-MOF-74 structure is changed, and the Cu2+—O bond is elongated. This change will make the residual solvent molecules on the surface of the catalyst easier to be completely desorbed, so that the MOF structure exposes more active sites to promote the denitration reaction. The NO conversion rate of Cu-MOF-74 reaches 97.8% at 230 ℃[39]. In addition, although the competitive adsorption of H2O and NH3 on the acid sites will lead to the occupation of some active sites on the surface of Cu-MOF-74 by H2O, which will reduce its denitrification activity, with the increase of reaction temperature, the H2O occupying the active sites will be removed, which will restore the activity of the catalyst, so the Cu-MOF-74 catalyst also shows strong water resistance.
In summary, the good redox performance and dispersion of Cu oxides, as well as the abundant CUSs on the catalyst surface and the sp3 hybrid orbital promoting electron transfer, are beneficial to the adsorption and reaction of reaction gas molecules. However, the poor thermal stability of Cu-based MOF denitration catalyst is the main reason for limiting its industrial application, so it is necessary to carry out research on high temperature resistant metal binder to reinforce the organic framework structure to enhance its thermal stability.

2.1.4 Other transition metal-based MOF denitration catalyst

Recent studies have shown that MOF materials modified by transition metal elements such as Co, Ni and V also have excellent catalytic performance for denitrification.
Jiang et al. Found that the petal-shaped Co-MOF-74 synthesized by hydrothermal method was rich in a large number of CUSs which were beneficial to the adsorption of reaction gas, thus increasing the contact frequency between gas molecules and reaction active sites, and the modification of Co could also effectively reduce the adsorption strength of SO2 on the surface of Co-MOF-74, thus significantly improving its sulfur resistance[35][21]. Therefore, the use of Co-modified MOF denitration catalyst is an effective way to enhance its sulfur resistance.
Sun et al. Reported a crystalline porous Ni-MOF catalyst synthesized by a hydrothermal method, and found that preheating it in a N2 atmosphere contributed to the formation of surface Ni active sites and the high dispersion of Ni-O species on the surface of the catalyst, so that the catalyst could achieve a denitration efficiency of more than 92% in a wide working temperature window of 275 – 440 ° C[12]. In addition, the Ni-MOF also shows excellent thermal stability, and the Ni-MOF can still maintain a stable crystal structure when the reaction temperature reaches 440 ℃[22,28]. Therefore, the addition of Ni in MOF denitration catalyst is helpful to enhance its thermal stability and obtain a wide denitration active temperature range.
Li et al. Synthesized MIL-88B (V) denitration catalyst by hydrothermal method using V and MOF materials, and found that the staggered and closely arranged structure in MIL-88B (V) could make the density of V3Ox unit clusters higher and the distance between adjacent V3Ox unit clusters smaller.As a result, a large number of V5+ ions and V-O-V bonds are introduced, which are beneficial to the formation of Brønsted acid sites. Therefore, clarifying the interaction mechanism between MOF structure and V ions in V-based MOF denitration catalysts is an effective way to further improve the denitration performance of transition metal-based MOF catalysts[40]. However, the high temperature stability of MIL-88B (V) is poor, and the structure of the catalyst will change at a higher reaction temperature, which makes the stable conversion window of the denitration reaction relatively narrow, so effective methods are still needed to improve its thermal stability.
At present, the research on single transition metal based MOF denitration catalyst at home and abroad mainly focuses on the modification of MOF by transition metal elements such as Mn, Fe and Cu (Table 1). Among them, Mn-based MOF and Cu-based MOF catalysts have abundant CUSs, and Fe-based MOF catalysts have abundant oxygen vacancies, which are beneficial to further improve the denitrification activity of the catalysts, but their sulfur resistance and thermal stability need to be further improved. Because doping Co in MOF can enhance the sulfur resistance, adding Ni can obtain excellent thermal stability, and combining with V can also introduce abundant acid sites, the use of Co, Ni, V and other metals to modify Mn, Fe, Cu and other transition metal-based MOF to construct composite transition metal-based MOF denitration catalysts brings a new opportunity to enhance the sulfur resistance and thermal stability of low-temperature denitration catalysts.

2.2 Double transition metal based MOF denitration catalyst

Bimetallic MOF materials mainly have the following advantages: (1) Different metal ions can differentially adsorb reactive gases such as NO and NH3, which is beneficial to improve the selectivity of the catalyst for surface adsorbed molecules, thus promoting the NH3-SCR reaction[41]. (2) Different metal ions are beneficial to produce more active sites because of their different volume and valence, and promote the dispersion of metal active sites on the surface of the catalyst[42]. (3) The interaction of different metal ions has the advantages of improving catalytic activity, enhancing stability and reducing reaction temperature[43]. Compared with the single transition metal-based MOF denitration catalyst, the MOF denitration catalyst modified by two metal elements can make use of the characteristics of metal oxides and the synergistic effect between metals (Figure 1).Therefore, the bimetallic composite MOF catalyst has broad development prospects in the field of NH3-SCR denitration[44].

2.2.1 Transition metal-rare earth metal mixed type MOF denitration catalyst

Rare earth metal elements have good activity, and the outermost electron structure is the same, which is two s electrons. When they combine with other elements, they are easy to lose two s electrons and one electron in the next outer 5d orbit or one electron in the 4F layer to become trivalent rare earth (RE3+) ions.So as to promote the redox process, the rare earth metal can be compounded with the single transition metal-based MOF catalyst to enhance its low-temperature denitration activity[45,46][47].
Among the rare earth metal elements, because Ce has strong redox characteristics, the MOF denitration catalyst modified by Ce oxide can not only retain the porous structure and lattice phase characteristics of the original catalyst,Moreover, the nano CeO2 encapsulated in the catalyst can accelerate the generation of surface chemisorbed oxygen and significantly promote the formation of NO2 species related to the "fast SCR" reaction, so the catalytic activity of MOF denitration catalyst modified by Ce oxide can be significantly improved[48]. The CeO2/MIL-100(Fe) denitration catalyst synthesized by Wang et al. Using the impregnation method has a higher catalytic activity for NH3-SCR as well as a wider working temperature window than MIL-100 (Fe)[49]. In addition, the preparation method is an important factor affecting the performance of Ce-modified MOF catalyst, and different preparation methods will lead to different metal-to-metal connection morphology in MOF, showing different redox characteristics[50]. For example, Zhang et al. Synthesized MnCe @ MOF denitration catalyst by impregnation method and in-situ doping method respectively. Compared with the impregnation method, the in-situ doping method leads to the intercalation of Mn-Ce into the MOF lattice structure and the decrease of Mn concentration, thus reducing the redox performance of the catalyst[51]. It can be seen that the MnCe @ MOF catalyst prepared by the impregnation method has a higher NO conversion.

2.2.2 Transition metal-transition metal hybrid MOF denitration catalyst

As an active component of that catalyst, Mn can be well disper on the surface of a carrier, and the multiple valence state of the Mn oxide can improve the oxidation-reduction capability of the catalyst; meanwhile, the Mn oxide can be combine with other transition metal oxides,The denitration activity of MOF catalyst is further improved by the strong interaction between metals, so the optimization of MOF denitration catalyst preparation mainly focuses on the addition of Mn element[52][53,54]. The appropriate atomic ratio of metal elements can promote the coordination of metal ions with solvent molecules such as DMF or H2O, and expose more CUSs, thus improving the denitrification activity of the catalyst, so the atomic ratio of metal elements is an important factor affecting the denitrification performance of Mn-based composite MOF catalyst[55⇓~57]. Moreover, the synergistic effect between Mn and metal ions such as Cu and Fe is also helpful to enhance the denitration activity of the catalyst[58]. For example, after Mn ions are uniformly added into the Cu-BTC crystal, the Mn @ Cu-BTC material has a pore structure and distribution that can significantly inhibit the adsorption of H2O because the Mn ions can fine-tune the pore size of the catalyst, so the SCR performance of Mn @ Cu-BTC is significantly improved compared with Cu-BTC[59]. In addition, MIL-100 (Fe-Mn) prepared by doping Mn and Fe on MIL-100 at the same time has a higher NOx conversion rate than MIL-100[60]. At the same time, the trace sulfate formed on the surface of MIL-100 (Fe-Mn) can also increase the number of acid sites, so that the catalyst has higher SCR denitrification activity in the atmosphere of H2O and SO2. It can be seen that Mn and many metal elements can produce good interaction to enhance the removal of nitrogen oxides, which is helpful to prepare MOF denitrification catalysts with excellent catalytic activity and anti-poisoning performance.
At present, there are more and more reports on the preparation of MOF catalysts using Mn and other non-Mn transition metal oxides, and it has been confirmed that the interaction between other non-Mn transition metal oxides can also prepare highly active MOF catalysts for the removal of nitrogen oxides. The results show that there is a good interaction between Cu+ and Fe active sites, and the integrity of the characteristic structure and surface morphology of the Fe-based MOF catalyst is not affected by the incorporation of Cu+, and the structure still has a polyhedral crystal morphology, so the Fe-based MOF catalyst modified by Cu+ can effectively improve its catalytic activity[61]. For example, Shi et al. Synthesized Cu+/MIL-100(Fe) by hydrothermal method, and the specific surface area and porosity of the catalyst decreased slightly with the increase of Cu+ load, indicating that Cu2O had been successfully introduced into the catalyst framework and formed highly dispersed nanoparticles.The higher surface mobility of these Cu2O nanoparticles resulted in the generation of more Cu active sites, so the catalytic activity of Cu+/MIL-100(Fe)) was significantly promoted by Cu species, and the NO conversion rate increased with the increase of Cu content[62]. Similarly, because the Cu2O crystal has high surface mobility in the catalyst framework, and there is a good synergistic effect between the Cu+ and the Ni2+,The Cu+/Ni-MOF prepared by Cu+ modification has more Cu active sites and larger specific surface area than Ni-MOF, thereby improving the low-temperature NH3-SCR denitration activity of the catalyst[63].
At present, there are many studies on the preparation of MOF denitration catalyst by using transition metal elements, and there are also some elements with potential denitration value that can be used for MOF modification (Figure 2), so the preparation of MOF denitration catalyst needs further systematic and comprehensive research. In addition, the deactivation of catalyst by alkali metal deposition is one of the main reasons for inhibiting the denitration activity of the catalyst, but some studies have shown that some alkali metals may also be beneficial to the enhancement of activity under specific conditions. For example, because Na can promote the adsorption and dissociation of NO, the addition of 2 ~ 10 wt% Na to the Rh/Al2O3 catalyst can effectively improve the CO-SCR denitrification activity[64]; Cs can increase the density charge of oxygen, thereby promoting the strong interaction between the catalyst and the C-H group, and enhancing the adsorption characteristics of the catalyst to the reaction gas, so the denitration catalyst prepared by Cs can be used for C4H10-SCR reaction to effectively remove NO[65]. It can be seen that alkali metal elements such as Na and Cs can also promote the denitration activity of the catalyst. However, the alkali metal poisoning mechanism of transition metal-based MOF denitration catalysts is still unclear, so the effect of alkali metal elements such as Na and Cs on the active sites of MOF needs to be further studied.

3 Enhancement of anti-poisoning performance of transition metal-based MOF denitration catalyst

In the process of NH3-SCR denitrification, SO2/H2O is the key factor causing the deactivation of transition metal-based MOF denitrification catalyst, which limits the industrial application[113,114]. This section summarizes the current research progress on enhancing the water and sulfur resistance of transition metal-based MOF denitration catalysts and puts forward the corresponding prospects.

3.1 Method for strengthening water resistance of transition metal based MOF denitration catalyst

The competitive adsorption of H2O will preempt the active sites of transition metal-based MOF denitration catalysts, reducing their number and leading to catalyst deactivation, but this deactivation is generally reversible[115]. There is also an irreversible deactivation of transition metal-based MOF catalysts by water vapor. The chemical adsorption and decomposition of H2O on the catalyst surface will produce a large number of hydroxyl (-OH) species, which can combine with exposed CUSs, thus reducing the number of denitrification active sites on the catalyst surface.And this part of hydroxyl can only fall off at high temperature (252 ~ 502 ℃), while the thermal stability of MOF denitration catalyst is poor, and the MOF material has been decomposed at high temperature, so the irreversible deactivation caused by H2O seriously weakens the denitration activity of transition metal-based MOF catalyst[58][116][117]. In addition, the presence of water vapor can significantly reduce the adsorption capacity of the catalyst to the reaction gas and destroy the crystal structure of MOF[118]. Therefore, it is of great significance to take appropriate measures to reduce the inhibition of water vapor on transition metal-based MOF denitration catalyst to improve the denitration activity of the catalyst.
At present, there are two main methods to improve the water resistance of MOF catalysts: one is to form hydrophobic units around the coordination center or on the working surface of the crystal through self-assembly synthesis to prevent the corrosion of water molecules.The addition of hydrophobic functional groups to IRMOF1 by Wu et al. Effectively reduced the substitution of water molecules for carboxyl and active center sites, maintained the large specific surface area and structural stability of IRMOF1, and thus enhanced the water resistance of IRMOF1[119][120]. The second is to add an active agent on the catalyst surface to reduce the contact of water molecules. Wang et al. Used two methods to improve the water resistance of Mn-MOF-74 denitration catalyst. One method is to cover the surface of the catalyst with surfactant P123 or PVP, and the other method is to introduce hydrophobic groups (—CH3) into the ligand of the catalyst to synthesize Mn-MOF-74-CH3[121,122][11]. Mn-MOF-74 modified with respect to PVP and -CH3,P123 exhibited better surfactant dispersion with more uniform particle size (Fig. 3). The NO conversion of P123-Mn-MOF-74 can still reach 92.1% after adding 5%H2O to the feed gas. Therefore, the addition of surfactant can significantly improve the water resistance of MOF denitration catalyst compared with the addition of hydrophobic group.
In addition to the above two main methods to improve the water resistance of MOF catalysts, the metal doping modification method is also beneficial to reduce the inhibition of water vapor on transition metal-based MOF denitration catalysts. Li et al. Prepared Ni-MOF-5 by doping Ni2+ into MOF-5 framework using solvothermal method[123]. Compared with undoped MOF-5, Ni-MOF-5 has a larger specific surface area and porosity, and the incorporation of Ni2+ effectively prevents other species from entering the crystal structure of MOF, which significantly improves the water resistance of the material and opens up a new way to improve the water stability of MOF denitration catalyst.

3.2 Method for strengthening sulfur resistance of transition metal based MOF denitration catalyst

Sulfur poisoning deactivation of catalysts is one of the main reasons for inhibiting the activity of transition metal-based MOF denitration catalysts. Generally, the competitive adsorption of SO2 can separate NH3 from the adsorption sites, resulting in harmful side reactions between NH3 and NOx. In addition, the oxidation of SO2 in flue gas into SO3 can react with NH3 to form ammonium sulfate (AS) and ammonium bisulfate (ABS), which block the pores of the catalyst and cover the active sites. The pyrolysis temperatures of AS and ABS are 513 ℃ and 350 ℃, respectively. When the thermal drive is used to eliminate AS/ABS, the thermal stability of the MOF catalyst will be seriously affected. Therefore, effective methods should be taken to enhance the sulfur resistance of the transition metal-based MOF denitration catalyst[124⇓~126].
Recent studies have shown that the addition of Ce, Co and other elements to transition metal-based MOF denitration catalysts can effectively improve the sulfur resistance of the catalysts. Chen et al. Found that adding Ce to Mn-based denitration catalyst could effectively improve the structural stability of the catalyst, and the synthesized Mn-Ce mixed oxide had abundant chemisorbed oxygen and active sites[127]. After the SO2 is introduced, the Ce(SO4)2 is formed earlier than the Mn(SO4)2,So that the MnOx is protected from SO2, and the removal mechanism of SO2 is shown in Fig. 4. Jiang et al. Found through experiments that doping Co into Mn-MOF-74 would lead to the weakening of the surface SO2 adsorption strength of the catalyst, thus effectively improving the SO2 anti-poisoning performance of the catalyst[58].
In summary, the Ce-doped transition metal-based MOF denitration catalyst can reduce the inhibition of SO2 on the catalyst by reducing sulfate deposition through oxidation and scavenging, and the Co-doped transition metal-based MOF denitration catalyst can reduce the surface SO2 adsorption intensity of the catalyst to improve its sulfur resistance. In addition, when alkaline earth metal elements (Ba, Ca, Mg) and noble metal elements (Pd, Pt, Ru) are used to modify other types of denitration catalysts, they are also conducive to strengthening the sulfur resistance, so the above elements can be used to carry out modification research when strengthening the sulfur resistance of MOF denitration catalysts[128].

4 Method for enhancing thermal stability of transition metal based MOF denitration catalyst

Although the existing transition metal-based MOF denitration catalyst has excellent denitration activity at low temperature, the denitration temperature of industrial NH3-SCR generally reaches 300 ~ 420 ℃[129]. As the temperature rises above 350 ℃, the skeleton structure of most transition metal-based MOF materials will be damaged to varying degrees, resulting in catalyst deactivation. Therefore, improving the thermal stability of transition metal-based MOF denitration catalysts is the key to achieve their industrial applications. The following is a review of the methods to improve the thermal stability of transition metal-based MOF denitration catalysts[130].

4.1 Introducing metal cluster

At present, the most widely used method to improve the thermal stability of MOF is to introduce highly symmetrical polynuclear metal clusters into MOF[131]. This method can not only establish strong bonds between metal clusters and linkers, but also provide directionality, so that symmetry-adapted linkers can naturally extend and move away from each other, and finally make MOF have high thermal stability[132]. However, for many binuclear MOFs, the bonding of low molecular clusters is relatively weak, resulting in poor thermal stability of many MOF materials with cage structure. In order to solve the above problems, Gao et al. Found that the thermal stability of MOF can be significantly improved by using low-symmetry metal clusters and low-symmetry ligands to prepare MOF materials through the interaction between linkers[133]. The experimental results show that the prepared MOF material (NJU-Bai62) still has good stability at 450 ℃, which is comparable to the high thermal stability MOF materials with polynuclear metal clusters (core ≥ 3) or rod-like structures (Fig. 5). Therefore, the above method provides a new way to construct stable MOF materials.

4.2 Optimize the molar ratio of metal ion to organic ligand

Most of the research results show that the thermal decomposition temperature of MOF denitration catalyst is lower than 400 ℃, and the different synthesis conditions will directly affect the specific surface area, gas adsorption performance and thermal stability of the catalyst[134⇓~136][137,138]. In order to further improve the thermal stability of MOF materials, Wang et al. Prepared MOF-5 by solvothermal method with different molar ratios of Zn2+ and organic ligand H2BDC, and studied the effects of the molar ratio of Zn2+ to organic ligand and the synthesis temperature on the thermal stability of MOF-5[139]. With the increase of synthesis temperature and the molar ratio of Zn2+/H2BDC, the crystal morphology of MOF-5 changed from flake to cube, the coordination mode changed from monodentate to multidentate, and the thermal stability increased gradually. When the molar ratio of Zn2+/H2BDC is 2 ∶ 1, the thermal stability of the catalyst is the highest, and the thermal decomposition temperature is 490 ℃. In addition, the organic ligands have different configurations and coordination modes at different reaction temperatures. Due to the weak monodentate coordination ability of the acid, the effective coordination between the metal ion and the organic ligand could not be achieved at low reaction temperature, resulting in poor crystal morphology of MOF-5. At higher temperature, the polydentate type of acid promotes the coordination of metal ions and organic ligands, thus improving the coordination reaction activity of metal ions and organic ligands, and finally making MOF-5 obtain a stable cubic or hexahedral structure[140]. Therefore, with the increase of synthesis temperature, the coordination ability of acid increases, which is helpful to enhance the thermal stability of MOF-5 framework structure[141]. Therefore, optimizing the molar ratio of related metal ions to organic ligands and selecting the appropriate synthesis temperature to prepare MOF materials are conducive to improving the thermal stability of transition metal-based MOF denitration catalysts in a higher temperature range.
To sum up, transition metal-based MOF denitration catalysts can not be widely used in the field of industrial denitration due to the poor thermal stability of MOF materials.At present, the structural stability of MOF catalysts at high temperature is mostly improved by introducing metal clusters and optimizing the molar ratio of metal ions to organic ligands, but the above methods are costly and the modification methods are not universally applicable, so they can not be used for large-scale production and application of denitrification catalysts. Combined with the previous description of single transition metal-based MOF denitration catalyst, it can be seen that Ni-based MOF denitration catalyst has excellent thermal stability, so it is expected to synthesize denitration catalyst with high thermal stability by combining Ni and its oxides as modifiers with single transition metal-based MOF materials such as Mn, Fe and Cu.

5 Conclusion and prospect

Transition metal-based MOF denitration catalysts have attracted wide attention in the research and application of denitration catalysts because of the good redox properties of transition metal oxides and MOF materials. Single transition metal-based MOF denitration catalysts have their own characteristics, among which Mn, Fe, Cu and other transition metal-based MOF denitration catalysts have efficient denitration activity at low temperature, Co-based MOF denitrification catalysts have good sulfur resistance, Ni-based MOF catalysts have excellent thermal stability, and denitration catalysts with better performance can be synthesized by constructing double transition metal-based MOF materials. In addition, the water and sulfur resistance and thermal stability of transition metal-based MOF denitration catalysts can be improved by metal doping, addition of active agents and optimization of the molar ratio of metal ions to organic ligands. However, there are still many problems in the industrial application of transition metal-based MOF denitration catalyst in the selective catalytic reduction of nitrogen oxides. Future research on the performance enhancement of transition metal-based MOF denitration catalyst needs to consider the following aspects.
(1) a novel transition metal-based MOF denitration catalyst with excellent performance and suitable for industrial application is prepared by comprehensively utilizing the characteristics of different transition metal oxides and combining the strong interaction between the metal oxides.
(2) At present, the fourth period transition metal elements such as Mn, Fe and Cu are mainly used in the preparation of transition metal-based MOF denitrification catalysts, while other period elements also have great application potential.
(3) At present, most of the studies on enhancing the water and sulfur resistance of transition metal-based MOF denitration catalysts are carried out independently under specific experimental conditions, and the modification methods are different, so it is necessary to comprehensively utilize the enhancement methods of water and sulfur resistance to develop transition metal-based MOF denitration catalysts with high water and sulfur tolerance.
(4) The thermal stability of MOF denitration catalyst is generally poor, which makes it impossible to be used in the field of industrial denitration. In the future, effective methods such as metal doping modification can be considered to further enhance the structural stability of transition metal-based MOF denitration catalysts in high temperature environment.
(5) The cost of optimizing the preparation of transition metal-based MOF denitration catalyst is high and the experimental period is long only by experimental research, so the research on the modification method of catalyst combined with simulation can promote the development of industrial denitration technology.

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Funding

national natural science foundation of China(52006016)

state scholarship fund awarded by China scholarship(201808430112)

natural science foundation of Hunan province(2020JJ4098)

natural science foundation of Hunan province(2021JJ40573)

Key projects of scientific research project of Hunan Provincial Department of Education(21A0216)

Changsha Municipal Natural Science Foundation(kq2014104)

young teachers growth plan project of CSUST(2019QJCZ044)

key laboratory of renewable energy electric technology of Hunan province(2018ZNDL004)

key laboratory of renewable energy electric technology of Hunan province(2020ZNDL001)

2022 Graduate research and innovation project at Changsha University of Science and Technology(CXCLY2022092)

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