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Catalysts for Catalytic Oxidation of Formaldehyde and Reaction Mechanism

Yuan Su , Keming Ji , Jiayao Xun , Liang Zhao , Kan Zhang , Ping Liu

Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (9) : 1560 -1570.

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Progress in Chemistry ›› 2021, Vol. 33 ›› Issue (9) : 1560-1570 DOI: 10.7536/PC200810
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Catalysts for Catalytic Oxidation of Formaldehyde and Reaction Mechanism
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Abstract

Formaldehyde is the main indoor pollutant, which has teratogenicity and carcinogenicity. Catalytic oxidation of formaldehyde has high conversion efficiency without secondary pollution, therefore related research has been increasingly concerned. This paper introduces noble metal and non-noble metal catalysts in detail. The effects of active components, support and catalyst promoters on the physicochemical properties and reaction performance of the catalyst are discussed. The influence factors of catalytic reactions, such as preparation methods, and the level of water content in the reactants are discussed. Besides, the main factors of catalyst deactivation are analyzed. The results show that the number of reactive oxygen species, surface hydroxyl groups, oxygen vacancies, as well as the adsorption, desorption and storage capacity of the reactants are the key factors affecting the catalytic activity. Noble metal catalysts, especially Pt catalysts, have better catalytic performance and can fully convert formaldehyde at lower temperature. Non-noble metal catalysts have variable valence states and abundant raw material resources, is cheap and easy to obtain, and could have enough catalytic activity through reasonable design of catalyst, therefore its application prospect is broad.

Contents

1 Introduction

2 Influence of active components on catalytic performance

2.1 Noble metals active components

2.2 Non-noble metal active components

3 Influence of supports on catalytic performance

3.1 Single metal oxide supports

3.2 Composite metal oxide supports

4 Influence of promoters on catalytic performance

4.1 Alkali metal promoters

4.2 Transition metal promoters

5 Other factors affecting catalytic performance

5.1 Effects of preparation method

5.2 Effects of water

5.3 Effects of catalytic deactivation

6 Conclusion

Graphical abstract

Keywords

formaldehyde / catalytic oxidation / noble metal catalysts / catalytic mechanism / deactivation

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Yuan Su, Keming Ji, Jiayao Xun, Liang Zhao, Kan Zhang, Ping Liu. Catalysts for Catalytic Oxidation of Formaldehyde and Reaction Mechanism. Progress in Chemistry, 2021, 33(9): 1560-1570 DOI:10.7536/PC200810

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1 Introduction

Formaldehyde (HCHO) is an important indoor gas pollutant, which is colorless, has a pungent odor, and is slightly denser than air. Indoor formaldehyde mainly comes from polyformaldehyde in decoration materials such as plywood and artificial wood[1,2]. As a protoplasmic toxic substance, formaldehyde can act on the amino part of protein, destroy its structure and produce methylphthalein protein, which is a primary carcinogen. Long-term exposure to formaldehyde-rich environments can stimulate sensory organs, cause memory loss and sleep disorders, damage the nervous system, and cause leukemia and cancer[3⇓~5]. For the sake of social green development and human health, it is of great significance to remove indoor formaldehyde pollution.
There are mainly biological purification, ventilation, adsorption, plasma purification, photocatalytic oxidation and catalytic oxidation to eliminate indoor formaldehyde[6][7][8⇓⇓~11][12,13][14⇓~16]. Among them, the biological purification method converts formaldehyde into organic acids, sugars and amino acids through plant metabolism. The treatment process of this method is slow, and the purification ability is greatly affected by environmental factors and plant physiological state, so it is suitable for the auxiliary means of formaldehyde purification[17]. The ventilation method is to reduce the concentration of formaldehyde through indoor and outdoor air exchange, which is simple and easy to implement, but it is difficult to apply to places with inconvenient ventilation and cold environment. The principle of adsorption method is simple and widely used, but there is an inherent problem of adsorption saturation, which makes it difficult to play a long-term and stable purification role. Plasma air purification technology has good purification effect and strong treatment capacity, but the process has high energy consumption and may cause secondary pollution. Photocatalytic oxidation technology is to use light energy to excite semiconductor materials, so that electrons and holes in them participate in the redox process. This method has been widely studied, and some technologies have been put into use. However, due to the limitation of light intensity and light source characteristics, its application scenarios are limited. Catalytic oxidation method is to oxidize formaldehyde into non-toxic and harmless H2O and CO2 by using oxygen in the air under the action of catalyst. This process has high formaldehyde conversion efficiency, large treatment capacity, relatively low cost, no secondary pollution, complete treatment and no adsorption saturation, and has a good effect on the treatment of low concentration formaldehyde pollution, which has become a hot research topic for scholars at home and abroad (Figure 1). In this paper, the catalytic oxidation of formaldehyde as the research object, combined with the catalytic reaction mechanism, the research progress of noble metal catalysts and non-noble metal catalysts were reviewed in detail, and the development trend and application of catalysts for catalytic oxidation of formaldehyde were prospected.

2 Effect of Active Components on Catalytic Performance

2.1 Noble metal active component

Noble metal elements have unfilled d electron orbitals, which can promote the adsorption and electron transfer of oxygen molecules, thus dissociating to form surface active oxygen species[18⇓⇓~21]. In the heterogeneous catalytic oxidation of volatile organic compounds such as benzene, chlorobenzene and toluene, the advantages of supported noble metal nanoparticles (NPs) catalysts have been widely recognized[22⇓~24][25,26][27,28]. In 2005, Zhang et al. First used noble metal elements in formaldehyde oxidation reaction, using Pt/TiO2 as catalyst, and the reaction products were CO2 and H2O[29]. Subsequent studies showed that the introduction of noble metal elements could increase the number of active oxygen and lattice defects on the surface of the catalyst, and promote the low-temperature adsorption of formaldehyde[30,31].
The noble metal elements commonly used in formaldehyde oxidation catalysts include Pt, Rh, Pd, Au, Ag, etc. The type, content and valence state of the supported noble metal are the key factors affecting the catalytic activity of the catalyst[32⇓⇓~35][36⇓~38][39⇓~41][42⇓~44][45⇓⇓~48][38,49,50][21,42,51][21,34,47]. In terms of element types, Zhang et al. And Peng et al. Prepared a series of catalysts with TiO2 as the carrier and Pt, Rh, Pd, Au, Mn, Cu as the active metals[49][50]. The reaction evaluation results showed that the activity of Pt/TiO2 catalyst was the best, followed by Rh/TiO2 and Pd/TiO2, while the activity of non-noble metal catalysts Mn/TiO2 and Cu/TiO2 was poor. Among them, the Pt in the Pt/TiO2 catalyst has better dispersion on the support, smaller particle size and more exposed active sites. In terms of valence state, Huang et al. Introduced NaBH4 with strong reducibility into the catalyst preparation process, and prepared Pt/TiO2 catalysts containing 0 valence Pt[21,52]. The results show that the reduced Pt nanoparticles have small particle size and uniform dispersion, which can promote the adsorption of oxygen. The activity of the catalyst with 0.1% Pt loading after reduction was comparable to that of the catalyst with 1% Pt loading without reduction, and the conversion of 10 ppm formaldehyde reached 99.1% at room temperature. Chen et al. Also confirmed that the Pt metal on the surface of the Pt/ZSM-5 catalyst after reduction treatment had good dispersion and small particle size, and the conversion of formaldehyde reached 95% after 100 hours of reaction at room temperature[34]. In view of the influence of the valence state of noble metals on the reaction performance, Fang et al studied the Ag/TiO2 catalyst and found that the partially oxidized Agδ+(0<δ<1) could accelerate the decomposition of intermediates, and 7 ppm formaldehyde could be completely oxidized in 200 min at room temperature[47]. The related research of our group shows that the intermediate valence + 2 Pt has better catalytic performance than 0 and + 4 Pt in the Pt/TiO2 catalyst[53].
The catalytic oxidation of formaldehyde over noble metal catalysts usually follows the Mars-van Krevelen (MvK) mechanism[54,55]. As shown in Figure 2 of the early study, in the formaldehyde oxidation reaction, HCHO is first oxidized to surface dioxymethylene (DOM), and then oxidized to formate species. The surface formate species decomposes to adsorbed CO and H2O,CO, which react with oxygen to form gas-phase CO 2[56]. Among these, the conversion of formic acid to CO is considered to be the rate-determining step in the catalytic oxidation of HCHO[56,57]. On this basis, Liu et al studied the reaction mechanism of formaldehyde catalytic oxidation over Au/CeO2 catalysts[43]. During the reaction, the active oxygen species are transferred from the Au2O3 to formaldehyde to form HCOOH and Au0, and then HCOOH is converted into formate and — H, and — H reacts with — OH on the support surface to form H2O. When HCOOH is completely oxidized, it is converted into CO2 and H2O. When it is not completely oxidized, HCOOH is converted into carbonate and oxycarbonate by removing — H, and then decomposed into CO2 and H2O, but carbonate is easy to accumulate and cause catalyst deactivation. Xu et al. Found that the energy levels of 110 and 100 crystal planes of the CeO2 nanorod support in the Au/CeO2 catalyst are low, which is conducive to the formation of oxygen vacancies. Nano and sub-nano gold particles can weaken the Ce — O bond and further promote the oxidation of HCHO[51]. Sun et al. explored the role of O2 in the oxidation of formaldehyde by in situ diffuse reflectance infrared spectroscopy[18]. It was found that in the absence of O2, HCHO could be converted to DOMs and formates, and the surface hydroxyl groups were consumed in this process, and an obvious CO vibration peak was observed. After the introduction of O2, it was found that DOM was rapidly converted to formate and CO was converted to CO2 under the action of oxygen.

2.2 Non-noble metal active component

Compared with noble metals, non-noble metals such as Mn, Co and Ce are relatively abundant, cheap and easy to obtain, and their oxides have variable valence States, which are conducive to the migration and storage of surface oxygen and suitable for catalytic oxidation of formaldehyde. As early as 2002, Sekine compared the catalytic performance of various non-noble metal oxides for formaldehyde oxidation at low temperature[58]. The results showed that ZnO, La2O3 and V2O5 had low catalytic activity, and the conversion of formaldehyde was less than 10%, while MnO2 had good catalytic activity, and the conversion of formaldehyde was more than 90%.
Mn atoms have the outer electronic structure of 3d54s2, and their oxides can form [MnO6] octahedron, which is the basic structural unit to form one-dimensional tunnel, two-dimensional layered or three-dimensional network crystal structure with common edges, common corners or common planes, thus forming a variety of crystal types of manganese oxides such as α, δ, γ, λ, β and ε (Fig. 3)[59⇓~61][61]. Zhang et al. Investigated the activity of four crystalline forms of MnO2 catalysts, namely α, δ, λ and β, and found that the layered structure of δ-MnO2 provided more active sites, which improved the adsorption and diffusion rate of formaldehyde, and the complete conversion of formaldehyde could be achieved at 80 ℃, while the complete conversion temperatures of α-, λ- and β-MnO2 catalysts were 125 ℃, 200 ℃ and 150 ℃, respectively[62]. Some studies on the crystal forms and faces of MnO2 further confirm that the (001) face of layered δ-MnO2 is conducive to the desorption of H2O, and the (100) face of α-MnO2 is conducive to the adsorption and activation of O2.The (310) crystal face of α-MnO2 has higher surface energy, which is beneficial to the adsorption and activation of O2 and H2O, and can improve the HCHO oxidation activity[63][64]. It is also believed that the pore structure of cryptomelane (0.26 nm) is similar to the dynamic diameter of formaldehyde molecule (0.243 nm), which can show high catalytic activity[65]. Wang et al. explored the formaldehyde catalytic reaction mechanism of MnOx catalyst in dry atmosphere in combination with MvK reaction mechanism[66]. It was found that the gas-phase oxygen molecules first adsorbed on the oxygen vacancies on the surface of the catalyst and decomposed into active oxygen species Oads. At the same time, the Mn3+ was oxidized into Mn4+,Oads electrons by the Oads and released into O-. The HCHO adsorbed on the surface of the catalyst reacts with the O- to generate a HCOOH intermediate,HCOOH is further decomposed into H+ and HCOO-,HCOO- which react with Oads to form HCO 3 -,The HCO 3 - reacts with the H+ and decomposes into CO2 and H2O.
When manganese oxides have some special morphologies, their unique microstructure and texture properties are also beneficial to improve the reaction performance of catalysts. Boyjoo et al. Prepared hollow microsphere MnO2 catalyst, which has large specific surface area, highly dispersed mesoporous structure, and a large number of oxygen vacancies on the surface, which promotes the migration of oxygen species[67]. Bai et al. Prepared 3D mesoporous MnO2 catalyst by template method. The catalyst has a large specific surface area, and the Mn4+ of its (110) crystal face provides the main active site for formaldehyde oxidation, so it has good catalytic performance[68].
Cobalt oxide and cerium oxide have large specific surface area, abundant oxygen vacancies and other structural properties, have redox ability and good catalytic activity and stability, and are also commonly used catalysts for formaldehyde oxidation[69]. Bai et al. Prepared three kinds of catalysts with different microstructure, including nano-Co3O4, 2D-Co3O4 and 3D-Co3O4, and investigated their reaction performance[70]. The catalytic activity increases in the order of nano-Co3O4<2D-Co3O4<3D-Co3O4, and the 3D-Co3O4 catalyst has three-dimensional ordered mesoporous structure, large specific surface area, high proportion of Co3+ species and more anionic lattices, which is conducive to the adsorption and activation of oxygen. The studies of Xie et al. And Ma et al. Also confirmed that the Co3+ species are the main active sites of the catalyst for catalytic oxidation[71][72]. Ma et al. Synthesized CeO2 nanospheres by hydrothermal method, with a specific surface area of 148.6 m2/g, while the specific surface area of ordinary CeO2 is only 57.8 m2/g[46]. When the reaction temperature was 200 ℃ and the concentration of formaldehyde in the feed gas was 1012.5 mg/m3, the conversion of formaldehyde was 85% over the CeO2 catalyst, while that over the conventional CeO2 catalyst was only 44%. Valence changes of transition metals can promote the generation of reactive oxygen species[73]. Wang et al. Prepared Co3O4 with nano-ribbon structure, and studied the catalytic oxidation mechanism of Co3O4 catalyst[74]. It was found that the transfer of active oxygen species was accelerated by the synergistic effect of Co3+/Co2+ and oxygen molecule/oxygen vacancy redox, the oxygen vacancy reduced the chemisorption energy of oxygen molecule, and the O2 adsorbed on the catalyst surface was activated by the delocalized electrons of oxygen vacancy to form active oxygen species (ROS).When HCHO molecules are adsorbed on the surface of the catalyst, HCHO is rapidly oxidized by the adsorbed oxygen to form formate, which then reacts with ROS to form CO2 and H2O. The nanobelt-structured Co3O4 catalyst can achieve complete conversion of 260 ppm formaldehyde within 30 min.
The introduction of other transition metal elements into the transition metal oxide catalyst can modify the key physical and chemical properties of the catalyst, such as microstructure, particle size and crystal defects, and promote the adsorption of reactants and the activation of oxygen, thus improving the catalytic performance[75⇓⇓⇓⇓~80]. Shi et al. Introduced Mn element into the preparation process of Co3O4 and prepared MnxCo3-xO4 solid solution catalyst[79]. The results showed that the surface area of the catalyst was increased after doping, and the oxygen species adsorption capacity and low temperature reduction ability of the catalyst were significantly improved.Under the conditions of 75 ℃, relative humidity of 50%, space velocity of 60 000 h-1, formaldehyde could be completely converted. Wu et al. Prepared MnCo3Ox catalysts doped with rare earth metals such as Ce, La and Pr[78]. The results showed that the MnCo3CeOx solid solution was formed after doping Ce, which enhanced the interaction of metal elements and improved the redox cycling ability of the catalyst surface, and 100 ppm formaldehyde could be completely converted at room temperature. Fan et al. Prepared Fe-Ce-O solid solution ultrafine nanoparticles (7 ~ 12.9 nm) and supported them on SBA-15 to prepare FeOx-CeOx/SBA-15 catalysts[81]. The catalyst has a high specific surface area of 500 m2·g-1,Ce3+, good dispersion of active components and abundant surface oxygen vacancies, and shows good catalytic activity in the oxidation of formaldehyde with low concentration (9.8μg·L-1) at 30 ℃ and 60 ℃, and the conversion of formaldehyde is 65% and 94.9%, respectively.

3 Effect of Support on Catalytic Performance

3.1 Monometallic oxide support

The composition, morphology, structure and surface properties of supports can affect the dispersion of active metals and the interaction between metals, and then affect the catalytic performance of catalysts. Transition metal oxides are commonly used as catalytic supports for formaldehyde oxidation catalysts[82⇓~84]. Huang et al prepared supported Pt-based catalysts with TiO2, CeO2, Al2O3, MgO and ZrO3 as carriers, and found that when TiO2 was used as the carrier, the active metal Pt had better dispersion and smaller particle size[21]. Generally speaking, the small particle size and uniform dispersion of active metals are beneficial to the exposure of active sites and the improvement of catalyst activity[50].
The silica-alumina compound carrier represented by molecular sieve has large specific surface area, strong formaldehyde adsorption energy and storage capacity of reaction intermediates. Among them, Beta, SBA-15, ZSM-5 and other molecular sieves have been used in the preparation of noble metal catalysts, which show good catalytic activity in the oxidation of formaldehyde[40,45,85,86].
Carbon nanomaterials are widely used in catalysis, energy storage, adsorption and separation due to their good conductivity, large specific surface area and easy functionalization. Among them, activated carbon, graphene oxide and carbon nanotubes have large specific surface area, contain a large number of hydroxyl groups and oxygen vacancies on the surface, and have good catalytic stability, so they are widely used as catalyst carriers for formaldehyde oxidation[87,88][89,90][91,92]. Wang et al. Prepared C @ MnO catalyst with core-shell structure[93]. The results showed that MnO and carbon spheres were tightly combined to form adsorption sites, and there was a synergistic effect between the active sites, and there were unsaturated MnOx species, which promoted the adsorption and catalytic reaction of formaldehyde, and the complete conversion of 60 ppm formaldehyde could be achieved under the reaction conditions of 30℃,60 000 h-1. Lu et al. Prepared supported MnO2 catalysts with graphene as the carrier, and the study showed that the activation energy of supported MnO2 was significantly reduced, and the hybrid graphene-manganese interlayer region provided an important reaction interface.The electron transfer of Mn4+ and Mn3+ in the redox cycle promotes the activation and transfer of oxygen, promotes the regeneration of surface hydroxyl groups and the exposure of active sites on the surface of the catalyst, and improves the catalytic oxidation performance of the catalyst[90][94].
Palygorskite, diatomite and other minerals and macromolecular polymers have large specific surface area, structural lattice defects and abundant surface hydroxyl and oxygen species, which have good formaldehyde adsorption and storage capacity[95,96]. Rong et al. Obtained a MnO2/PET catalyst by impregnating ultrathin MnO2 nanosheets with a thickness of 1 to 2 nm in polyethylene terephthalate[97]. When the concentration of formaldehyde was 200 ppm, the conversion of formaldehyde was 81% at room temperature. After the catalyst was deactivated, it could be regenerated by drying at 105 ℃.
Some catalysts with special morphology also showed good catalytic performance in the oxidation of formaldehyde. Qi et al showed that the TiO2 support with macroporous/mesoporous structure had large specific surface area (158 m2/g) and suitable pore size (6 ~ 12 μm), and Pt nanoparticles could be uniformly dispersed inside and outside the pores, which was conducive to improving the formaldehyde adsorption capacity of the catalyst, and the formaldehyde conversion rate in the reaction could reach 90. 6%[98]. Lu et al. Prepared Ag/MnO2 nanorods by impregnation method[48]. The catalyst has good reduction performance and abundant active surface oxygen species, and the conversion of formaldehyde reaches 100% under the reaction conditions of 60 deg C, 300 ppm of formaldehyde concentration and 36 000 h-1 of space velocity. Liu et al. Found that in the 3D Au/CeO2 catalyst, the reaction intermediate formate is not easy to accumulate, the active site is not easy to be occupied, and the complete conversion of formaldehyde can be achieved at 75 ℃[43]. Yu et al. prepared three kinds of Pt/MnO2 catalysts with different microscopic morphologies of cocoon, sea urchin and nest, and their morphologies and catalytic performances are shown in Figure 4. The study shows that the specific surface area of the nest Pt/MnO2 catalyst is only 56.9 m2/g, but the surface of the MnO2 has a pore structure that is easy to adsorb formaldehyde[32]. The catalyst has the best activity and can realize the complete conversion of formaldehyde at 70 deg C. In contrast, the specific surface area of the cocoon-shaped Pt/MnO2 catalyst is as high as 247.6 m2/g, but the MnO2 has a high degree of crystallization, which hinders the adsorption of formaldehyde molecules.

3.2 Composite metal oxide carrier

Compared with the single metal oxide support, the introduction of other components into the support to form a composite support can affect its specific surface area, surface structure, and adsorption, storage, and redox properties[83,93][85,99][80,99][44,100]. Yan et al. Prepared a graphene oxide (GO) supported Pt/GOFe catalyst[101]. Among them, Pt is well dispersed on the surface of the Fe2O3 nanosheet, and there are a large number of oxygen-adsorbing functional groups and π-π bonds on the surface, which promotes the mass transfer of oxygen molecules and the formation of active oxygen species, facilitates the generation and decomposition of intermediate formate, and improves the activity of the catalyst. The catalytic mechanism of this reaction process is shown in Figure 5.
Li et al. Prepared Co-doped Au/Co-LDHs (double-layered hydroxides) nanosheet catalysts by in-situ precipitation method[44]. The results show that there is an electronic synergy between the doped Co and Au nanoparticles as well as the surface hydroxyl groups, which promotes the adsorption and activation of oxygen, and the conversion of formaldehyde increases from 86. 6% to 96. 2% at room temperature. Yan et al. Prepared flower-like layered Pt/NiAl-LDHs catalyst by hydrothermal method. The surface of the catalyst is rich in oxygen species, which can completely oxidize 223 ppm formaldehyde at room temperature and maintain activity after 7 cycles[83]. Yan et al. Prepared CeO2/AlOOH supported Pt catalysts by microemulsion method[99]. The results showed that the oxygen storage capacity of the CeO2 was enhanced due to the strong interaction between Ce and Pt in the catalyst, which provided more active oxygen species for the reaction and promoted the adsorption of formaldehyde.The concentration of formaldehyde was reduced from 230 ppm to 19 ppm in 60 min.

4 Effect of Promoter on Catalytic Performance

4.1 Alkali metal promoter

Alkali metals as catalyst promoters are widely used in ammonia synthesis, benzyl alcohol oxidation and water-gas shift reactions, which effectively improve the reaction performance of catalysts and provide a feasible idea for the improvement of formaldehyde oxidation catalysts. Flytzani-Stephanopoulos et al. Have shown that alkali metal ions can promote the dispersion of noble metals on the surface of catalytic supports[102,103]. Zhang et al. Found that Pt-O-alkali metal species were formed after the introduction of alkali metal Na into the Pt/TiO2 catalyst, which promoted the spontaneous dispersion of noble metals and the generation of hydroxyl groups, facilitated the decomposition of intermediate formate, and improved the catalytic activity. The catalytic reaction path was HCHO→CHOO-+—OH→CO2+H2O, and the reaction between formate species and hydroxyl was easier than the decomposition of formate species to CO species[33]. The studies of Nie et al. And Xiang et al. Have also confirmed the above view[104][105]. Related studies also showed that alkali metal modification could promote the dispersion of noble metals, increase the contact area of active sites, the number of surface hydroxyl groups and surface oxygen vacancies, increase the surface area and pore volume of mesopores, promote the mass transfer of formaldehyde, and improve the adsorption/storage capacity of catalysts for formaldehyde[106][85]. In order to clarify the effect of the introduction of alkali metal on the catalytic activity of formaldehyde, Wang et al studied the decomposition mechanism of formaldehyde on the surface of Pt/NaxTiO2 catalyst at room temperature in detail by in-situ infrared characterization[107]. The results show that HCHO reacts with nucleophilic oxygen under the action of water molecules to form DOM. Formate was formed by the Camizaro disproportionation reaction of DOMs adsorbed on the surface of the catalyst, and then three reaction pathways were followed: First, formate was dehydrated to produce strongly adsorbed CO, which reacted with active oxygen produced by noble metals to form CO2. The other is that the strongly adsorbed CO reacts with the surface hydroxyl of the catalyst to form carbonate or bicarbonate. Carbonate or bicarbonate generates CO2 under the action of active oxygen. Thirdly, when sodium hydroxide is added in the preparation process of the catalyst, the pH value rises, formate is dehydrated to generate weakly adsorbed CO, and the weakly adsorbed CO is more likely to react with active oxygen to generate CO2.
In the aspect of non-noble metal catalyst modification, Huang et al. Prepared an alkali metal modified scandium nanosheet catalyst, and confirmed that the catalyst had the advantages of large surface area, strong adsorption capacity and high surface hydroxyl content. The conversion rate of formaldehyde could reach 95. 3% at room temperature, and the reaction still had good catalytic performance after 200 H[108]. Fang et al. explored the formaldehyde catalytic reaction mechanism of the δ-MnO2 catalyst after adding alkali metal K. The study showed that HCHO was first adsorbed on the surface of the δ-MnO2 and formed formic acid species in a bridging manner, and formate species were oxidized to CO2 or carbonate species by active oxygen on the surface.Carbonate can be further decomposed into CO2 and H2O,K+, which can increase the average oxidation state (AOS) value of Mn and the proportion of surface adsorbed oxygen, improve the reducing ability of oxygen species, and promote the formation of formate and carbonate in HCHO oxidation reaction[109]. In addition, Rong et al. Found that alkali metal K can significantly reduce the activation energy of lattice oxygen of the catalyst and improve the activity of lattice oxygen, and the change of activation energy of the catalyst is shown in Figure 6[110]. Fan et al. prepared Co3O4 catalysts with NH3·H2O, potassium hydroxide, NH4HCO3, K2CO3 and KHCO3 as precipitants respectively[111,112]. The results showed that the use of KHCO3 as a precipitant could increase the molar ratio of Co3+/Co2+ on the surface of the catalyst, increase the number of oxygen vacancies on the surface, promote the regeneration of hydroxyl groups on the catalyst surface, and accelerate the oxidation of intermediates. The catalyst could completely convert 100 ppm formaldehyde at 90 ℃. Li et al. Found that the catalytic mechanism of Ir/TiO2 catalyst was HCHO→HCOO-+—OH→CO2+H2O after the introduction of alkali metal, which confirmed that the introduction of alkali metal increased the number of hydroxyl and active oxygen on the surface of the catalyst, in which active oxygen could promote the formation of formate and — OH could promote the decomposition of formate[113].

4.2 Transition metal promoter

The transition metals commonly used in the modification of formaldehyde oxidation catalysts mainly include Ni, Fe and Ce. Li et al. prepared a Fe-modified Ag/MnO2 catalyst, and the structure and reaction mechanism of the catalyst are shown in Figure 7[100]. Fe doping changed the electron cloud density of Ag nanoparticles, enhanced the interaction between the support and Ag, and improved the oxygen adsorption and activation ability of the catalyst. When the concentration of formaldehyde was 230 ppm at room temperature, the formaldehyde conversion of the modified catalyst increased from 76% to 100%. Ding et al. Prepared Ni-doped Pt-Ni/ZSM-5 catalyst by ion exchange method[86]. The results showed that the doping of Ni improved the interfacial chemical properties of the catalyst, the dispersion of Pt increased from 79% to 81%, and the proportion of hydroxyl groups on the surface of the catalyst increased from 52. 1% to 82. 4%.Under the condition of 50 ppm formaldehyde, the conversion of formaldehyde reached 90%, and the stability time was more than 100 H. The study of Shi et al also showed that the binding energy of the active component Pt of the Ce-doped Pt/TiO2 catalyst increased, the diameter of Pt nanoparticles decreased from 2. 9 nm to 2. 2 nm, the dispersion of Pt nanoparticles increased from 15. 63% to 45. 33%, the number of oxygen vacancies increased, the ratio of adsorbed oxygen to lattice oxygen increased, and the activity of the catalyst improved[114].

5 Other factors affecting catalytic performance

5.1 Influence of preparation method

The preparation methods and conditions of catalysts affect the physical and chemical properties of catalysts, such as morphology, lattice defects, metal valence, active metal particle size and the number of surface oxygen species, and then affect the catalytic performance. Cui et al. And Tang et al. Prepared catalysts for catalytic oxidation of formaldehyde by impregnation method, colloidal precipitation method, co-precipitation method and sol-gel method[115][73]. Among them, the catalyst prepared by coprecipitation method has stronger interaction between the support and the metal, more hydroxyl groups on the surface, more lattice oxygen on the surface of the catalyst, and better catalyst activity. Li et al. Prepared the CeO2 support by sol-gel method and surfactant-template method. The study showed that the specific surface area of the catalyst prepared by surfactant-template method could reach 150~270 m2/g, while the specific surface area of the CeO2 prepared by sol-gel method was only 37 m2/g[42]. The CeO2 support with large specific surface area forms AuxCe1-xO2-δ solid solution with Au, and the catalyst has abundant oxygen vacancies, which is beneficial to the adsorption of formaldehyde. The conversion of 500 ppm formaldehyde over the catalyst can reach 92.3% at 37 ℃.
Catalyst preparation conditions are also important factors affecting the performance of catalysts. In the process of preparing Pt4+/SiO2 catalyst, Wu et al found that the particle size of Pt on the surface of SiO2 after vacuum calcination was less than 1 nm, which was much smaller than that of Pt after calcination in air atmosphere (8.4 nm)[116]. Kim et al. Investigated the reduction conditions of the Pt/TiO2 catalyst. The results showed that when the reduction temperature was too high, the content of zero-valent Pt in the catalyst decreased and the content of high-valent Pt increased. The optimal reduction temperature was 873 K[82]. Tian et al. Studied the effect of synthesis temperature on the morphology, crystal phase, specific surface area, pore size and other chemical properties of manganese oxides[117]. As shown in fig. 8, with the increase of synthesis temperature, the crystallinity of manganese oxide gradually increases, the morphology of the catalyst changes from cotton-like nanospheres (80 ℃) to fibrous structure (100 ℃) and octahedral structure (140 ℃), and the specific surface area of the catalyst gradually increases from 28 m2/g to 154 m2/g. Due to the influence of morphology, surface area and surface reducibility, the catalyst has the best activity when the synthesis temperature is 120 ℃. Zhou et al. explored the effects of hydrothermal temperature, pH value and anion type on the crystal structure of MnO2, and found that the reaction temperature and anion type affected the morphology and phase structure of the final product, and the activity of cryptomelane MnO2 catalyst was better than other catalysts[118].

5.2 Effect of water in the reaction

Huang et al. Found that when the humidity of the reaction environment is too high, excessive water will compete with formaldehyde for adsorption, resulting in a decrease in the conversion rate of the reaction[21][66,80]. However, some studies have shown that water molecules are not only beneficial to the activation of oxygen and the decomposition of carbonate, but also can promote the breaking of noble metal-Cl bonds and inhibit the poisoning of catalysts[119]. Shi et al. Found that in the Ag-MnOx-CeO2 catalyst, water vapor can promote the decomposition of formaldehyde to form formate[80]; In Ag/HZSM-5 catalyst, water molecules with similar polarity to formaldehyde easily occupy the active sites of the catalyst and compete with formaldehyde for adsorption, which affects the catalytic activity. Ma et al. Also investigated the effect of steam on the performance of different transition metal modified MCo2O4(M=Mn, Ce and Cu) catalysts, and the H2O-TPD characterization results of the catalysts are shown in Figure 9[120]. The results showed that for the CuCo2O4 catalyst, water vapor adsorbed on the surface of the catalyst to form active H-OH, which could promote the generation of active oxygen. However, the active sites of HCHO oxidation were covered by H-OH and free OHs formed by H2O on the surface of MnCo2O4 and CeCo2O4 catalysts, which accelerated the deactivation of catalysts.

5.3 Factors affecting inactivation

With the increase of reaction time, the pore structure of the catalyst may collapse, poisoning, and the intermediate products occupy the active sites, which may lead to the deactivation of the catalyst. In the process of formaldehyde oxidation, the disappearance of active oxygen species and the occupation of active sites by formates are the main reasons for the deactivation of the catalyst[43,120]. By heating at high temperature, the accumulated reaction intermediates such as DOM and formate can be rapidly decomposed, the surface oxygen species can be replenished, and the activity of the catalyst can be restored[121]. In addition, noble metal poisoning is an important factor that inhibits the activity of noble metal catalysts. Zhu et al. Investigated the effects of halogen elements such as F-, Cl-, Br- and I- on the activity of Pt/TiO2 catalysts[122]. As shown in Figure 10, the research shows that the halogen ions are strongly adsorbed on the surface of Pt nanoparticles and transfer the electrons to the 5d empty electron orbitals of Pt atoms to form coordination bonds with Pt atoms on the surface, resulting in poisoning of Pt nanoparticles, inhibiting the adsorption and activation of oxygen molecules by Pt nanoparticles, and reducing the catalytic activity. The deactivation rate of the catalyst increases with the increase of the diameter of halogen ions.

6 Conclusion

In the catalytic oxidation of formaldehyde, noble metal catalysts can promote the adsorption of oxygen molecules and the formation of active oxygen species, and effectively catalyze the oxidation of formaldehyde. Among them, Pt catalyst has better catalytic performance and has been widely studied. Through the reduction treatment, the active phase of the intermediate valence noble metal is obtained, which is beneficial to the improvement of the reaction performance of the catalyst. Commonly used non-noble metal catalysts include manganese-based, cobalt-based and cerium-based oxide catalysts, whose active components promote the formation of intermediate products through valence conversion. Element doping and structural modification of catalysts can affect the texture properties, active site distribution and electronic environment of catalysts, and improve the reaction performance of catalysts. Transition metal oxides are commonly used as catalyst supports for formaldehyde oxidation, and their surface hydroxyl groups and oxygen vacancies are beneficial to the reaction. Molecular sieves, carbon materials, macromolecular polymers and other carriers have good formaldehyde adsorption and storage capacity, which are the focus of recent research. Some carriers with special morphology can promote the dispersion of active phase, increase the number of active sites exposed, and improve the adsorption, diffusion and storage capacity of formaldehyde molecules. The addition of alkali metal promoter can promote the regeneration of surface hydroxyl groups, increase the number of oxygen vacancies, improve the adsorption and storage capacity of formaldehyde, and accelerate the oxidative decomposition of intermediates. The addition of transition metal promoters can enhance the interaction between metal elements by using the electronic synergistic effect, improve the interfacial chemical properties of the catalyst, and improve the adsorption and activation capacity of oxygen and formaldehyde.

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Funding

project of leading talents in emerging industries of Shanxi province(E0SW986201)

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