WO2022089669A1 - 锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料及其制备方法与在催化氧化甲苯中的应用 - Google Patents

锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料及其制备方法与在催化氧化甲苯中的应用 Download PDF

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WO2022089669A1
WO2022089669A1 PCT/CN2021/141006 CN2021141006W WO2022089669A1 WO 2022089669 A1 WO2022089669 A1 WO 2022089669A1 CN 2021141006 W CN2021141006 W CN 2021141006W WO 2022089669 A1 WO2022089669 A1 WO 2022089669A1
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strontium
ordered mesoporous
composite material
salt
toluene
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French (fr)
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路建美
陈冬赟
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Suzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/656—Manganese, technetium or rhenium
    • B01J23/6562—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention relates to the technical field of nano-composite materials, in particular to a strontium-doped ordered mesoporous lanthanum manganate-supported precious metal palladium composite material, a preparation method thereof, and an application in catalytic oxidation of toluene.
  • VOCs Volatile organic compounds
  • the treatment methods for VOCs mainly include: adsorption, absorption, membrane separation, plasma, photocatalysis, catalytic oxidation, etc.
  • catalytic oxidation method is widely used because of its low operating temperature, high efficiency and low energy consumption.
  • the core problem of this method is to develop and develop catalysts with low temperature, high activity, good thermal stability and low cost.
  • Noble metal catalysts have been widely studied due to their excellent catalytic properties, but since noble metals are prone to agglomeration and deactivation during application, a stable carrier with a large surface area is required to support noble metal materials.
  • Perovskite oxides are abundant in reserves and have good redox ability, and the high calcination temperature during the preparation of perovskite oxides leads to low surface area, and the valence state of manganese is closely related to the performance of toluene catalytic oxidation.
  • the preparation of perovskite oxide lanthanum manganate with high surface area and the adjustment of the valence state of manganese as a support for supporting noble metal catalysts to realize low-temperature catalysis of toluene are worthy of in-depth research.
  • the purpose of the present invention is to provide a strontium-doped ordered mesoporous lanthanum manganate-supported noble metal palladium composite material and a preparation method thereof.
  • the ordered mesoporous lanthanum manganate is prepared by nano-casting and doped with different proportions of lanthanum manganate. Strontium, and then the method of hydrogen reduction is used to load different proportions of precious metal palladium on the surface of lanthanum manganate to achieve efficient catalytic oxidation of toluene.
  • a strontium-doped ordered mesoporous lanthanum manganate-supported noble metal palladium composite material the preparation method thereof comprises the following steps: (1) adding manganese salt, lanthanum to the silicon template In the mixed solution of salt, strontium salt and weak acid, after evaporation, drying, calcination, and alkaline solution etching, the strontium-doped ordered mesoporous lanthanum manganate material is obtained; (2) adding the palladium salt solution to the strontium-doped In the alcohol of the ordered mesoporous lanthanum manganate material, a composite material with strontium-doped ordered mesoporous lanthanum manganate supported precious metal palladium is obtained by heating reaction and hydrogen reduction calcination.
  • a method for low-temperature thermal catalytic treatment of toluene comprising the following steps: (1) adding a silicon template to a mixed solution of manganese salt, lanthanum salt, strontium salt and weak acid, and evaporating, drying, calcining, and etching with alkaline solution to obtain strontium Doping ordered mesoporous lanthanum manganate material; (2) adding palladium salt solution to alcohol containing strontium doped ordered mesoporous lanthanum manganate material, and obtaining ordered mesoporous strontium doped mesoporous material through heating reaction and reduction The lanthanum manganate-supported precious metal palladium composite material; (3) the strontium-doped ordered mesoporous lanthanum manganate-supported precious metal palladium composite material is placed in an environment containing toluene, and heated at a low temperature to complete catalytic oxidation to remove toluene.
  • the manganese salt is manganese nitrate
  • the lanthanum salt is lanthanum nitrate
  • the strontium salt is strontium nitrate
  • the weak acid is citric acid
  • the alkali is sodium hydroxide
  • the palladium salt is sodium chloropalladium
  • the solvent is water; in the sodium hydroxide solution and the sodium chloropalladate solution, the solvent is water; and the alcohol is ethanol.
  • the temperature of evaporation is room temperature, and the time is 10 to 14 hours, and the preferred evaporation temperature is room temperature, and the evaporation time is 12 hours;
  • the temperature was 80 °C, and the drying time was 6 hours;
  • the calcination was carried out in air, and the calcination was heated in two stages.
  • the heating rate of the first stage was 5 °C/min, the temperature was 500 °C, and the time was 5 h; 5°C/min, the temperature is 700°C, and the time is 8h; the etching temperature of the sodium hydroxide solution is 70°C, and the time is 12 hours.
  • the heating reaction is 50-70°C for 6-10 hours, preferably 60°C for 8 hours, and the solvent is simultaneously removed under thermal evaporation of the solvent;
  • the reduction is hydrogen reduction, and the temperature during the reduction treatment is 230-270°C, and the time is 1.5-2.5h, preferably, reduction is calcination in the presence of hydrogen, the calcination temperature is 250°C, the time is 2h, and the heating rate is 5°C/min.
  • step (1) the dosage ratio of silicon template, manganese salt, lanthanum salt, strontium salt and weak acid is 1 g: 4 mmol: (0 ⁇ 3.2) mmol: (0.8 ⁇ 4) mmol: 4 mmol,
  • the prepared strontium-doped ordered mesoporous lanthanum manganate material is La 1-x Sr x MnO 3 , and x is 0-0.8.
  • the mass ratio of palladium salt to La 1-x Sr x MnO 3 in step (2) is (0.01-0.06):1.
  • the silicate is reacted with polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer in the presence of water and hydrochloric acid, and then calcined to obtain a silicon template; the reaction is a reaction at 38°C 24h, and then react at 110 °C for 24 hours; calcination is calcined at 550 °C for 6 hours; further, the silicate is tetraethyl orthosilicate.
  • the method of preparing the ordered mesoporous lanthanum manganate by using the silicon template as the hard template firstly obtains a nanotube array structure with high specific surface area, uniform pore size and good repeatability, which can be used as an excellent carrier to support precious metals Palladium nanoparticles, the higher specific surface area is conducive to the catalytic reaction.
  • the reduction and calcination treatment is carried out in the atmosphere of hydrogen.
  • the precious metals supported by the impregnation method are reduced to nanoparticles during calcination and loaded into the nanotubes doped with strontium manganate to form nanoparticles with uniform loading and small particle size, which can promote Catalytic degradation of toluene.
  • a quantitative strontium-doped ordered mesoporous lanthanum manganate-supported precious metal palladium composite material is placed in a toluene environment with a certain concentration, and a fixed-bed reactor is used to heat and catalyze the composite material. , complete catalytic oxidation of toluene.
  • the invention further discloses the application of the above-mentioned strontium-doped ordered mesoporous lanthanum manganate-supported noble metal palladium composite material in low-temperature catalytic oxidation of toluene.
  • the above-mentioned strontium-doped ordered mesoporous lanthanum manganate-supported precious metal palladium composite material is placed in an environment containing toluene, and a fixed-bed reactor is used to complete the treatment of toluene.
  • the optimum temperature for complete catalytic oxidation of toluene gas at low temperature is 150 °C.
  • the strontium-doped ordered mesoporous lanthanum manganate-supported precious metal palladium composite material disclosed in the present invention has a higher specific surface area and a uniform pore size, and the doping of strontium is beneficial to the increase of the valence state of manganese;
  • the noble metal palladium nanoparticles are loaded on strontium-doped lanthanum manganate, and the interaction between the noble metal and the nanoparticles can improve the performance of catalytic toluene, and realize the catalytic oxidation of toluene at a lower temperature, which has a good application prospect.
  • Figure 1 is a transmission electron microscope (TEM) image of the silicon template.
  • Figure 2 is a scanning electron microscope (SEM) image of the silicon template.
  • Figure 3 is a transmission electron microscope (TEM) image of La 0.8r S 0.2 MnO 3 .
  • Figure 4 is a scanning electron microscope (SEM) image of La 0.8r S 0.2 MnO 3 .
  • Figure 5 is a scanning electron microscope (SEM) image of the ordered mesoporous lanthanum manganate (N-LMO) catalyst.
  • Figure 6 is a scanning electron microscope (SEM) image of the lanthanum manganate (LMO) catalyst.
  • Figure 7 shows the transmission electron microscope (TEM) image of the 2 wt% Pd@La 0.8r S 0.2 MnO 3 composite.
  • Figure 8 is the scanning electron microscope (SEM) image of the 2 wt% Pd@La 0.8r S 0.2 MnO 3 composite.
  • Figure 9 is a graph showing the thermocatalytic effect of strontium-doped ordered mesoporous lanthanum manganate support on toluene gas.
  • FIG. 10 is a graph showing the thermal catalytic effect of the strontium-doped ordered mesoporous lanthanum manganate-supported noble metal palladium composite on toluene gas.
  • Figure 11 is a graph showing the catalytic performance of lanthanum manganate LMO' synthesized without adding citric acid during the preparation process.
  • the preparation method of a strontium-doped ordered mesoporous lanthanum manganate-supported precious metal palladium composite material of the present invention is as follows: (1) adding a silicon template into a mixed solution of manganese nitrate, lanthanum nitrate, strontium nitrate and citric acid, and evaporating , drying, calcining, and etching with sodium hydroxide solution to obtain ordered mesoporous perovskite oxide lanthanum manganate (strontium-doped); (2) adding sodium chloropalladate solution to ethanol solution to disperse uniform manganic acid In lanthanum (strontium doped), the ordered mesoporous perovskite oxide lanthanum manganate supported noble metal palladium composite material is obtained by heating and stirring, and hydrogen reduction and calcination.
  • the raw materials involved in the present invention are all conventional products in the field, and the specific operation method and testing method are conventional methods in the field.
  • Example 1 Preparation of ordered mesoporous La 0.8r S 0.2 MnO 3 , the specific steps are as follows: 4g polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), 130ml ultra Pure water and 20ml of concentrated hydrochloric acid (37wt%) were mixed, then 8.32g of tetraethyl orthosilicate was added, and the reaction was stirred in a water bath for 24 hours at 38°C. Naturally cooled to room temperature, filtered with suction and washed to neutrality, dried at 80 °C, and calcined at 10 °C/min from room temperature to 550 °C for 6 hours after drying to obtain the product silicon template.
  • the obtained solid product was dispersed in a 2 M NaOH solution and refluxed at 70 °C for 6 h to obtain an ordered mesoporous strontium-doped lanthanum manganate, which was used as a La 0.8 Sr 0.2 MnO 3 support.
  • Figure 1 is the TEM image of the silicon template
  • Figure 2 is the SEM image of the silicon template
  • Figure 3 is the TEM image of La 0.8r S 0.2 MnO 3
  • Figure 4 is the SEM image of La 0.8r S 0.2 MnO 3 . It can be seen from the figure that the tubular pore structure is uniform and the distribution is relatively uniform.
  • Example 2 Preparation of lanthanum manganate (LMO) and nano-cast lanthanum manganate (N-LMO), the specific steps are as follows: 4 mmol La(NO 3 ) 3 ⁇ 6H 2 O, 4 mmol Mn(NO 3 ) 2 were dissolved In 5 ml of distilled water and 15 ml of absolute ethanol, a homogeneous solution was obtained, then, 4 mmol of citric acid was added to the above solution and mixed at room temperature for 1 hour, and then the solution was dried in an oven at 80 °C for 6 hours. It was calcined at 500 °C for 5 h in a furnace, and then heated to 700 °C for 8 h. During the entire heating process, the heating rate was 5 °C/min.
  • Lanthanum manganate was obtained as LaMnO 3 support (LMO).
  • FIG. 5 is a SEM image of an ordered mesoporous lanthanum manganate (N-LMO) catalyst
  • FIG. 6 is a SEM image of a lanthanum manganate (LMO) catalyst.
  • Example 3 Preparation of a strontium-doped ordered mesoporous lanthanum manganate-supported noble metal palladium composite material, the specific steps are as follows: a certain amount of sodium chloropalladate solution (1wt%, 2wt%, 4wt%, 6wt%, with La 0.8 Sr 0.2 MnO 3 carrier as the base number) was added to 120 mg La 0.8 Sr 0.2 MnO 3 carrier dispersed in 15 mL of ethanol, and the conventional magnetic stirring was carried out at 60 °C for 8 h to obtain black powder, and then the black powder was mixed in 10 vol% H 2 /N 2 calcined in the atmosphere, the calcination temperature was 250 °C, the calcination time was 2 h, and the heating rate was 10 °C/min to obtain a strontium-doped ordered mesoporous lanthanum manganate-supported precious metal palladium composite material, in which the palladium loading mass accounted for La
  • FIG. 7 is a TEM image of the strontium-doped ordered mesoporous lanthanum manganate-supported precious metal palladium composite material
  • FIG. 8 is a SEM image of the strontium-doped ordered mesoporous lanthanum manganate-supported precious metal palladium composite material. It can be seen from the figure that the morphology of the perovskite oxide is well controlled and does not change significantly after loading the noble metal.
  • Example 4 Synthesis of lanthanum manganate without adding citric acid, the specific steps are as follows: 4 mmol La(NO 3 ) 3 ⁇ 6H 2 O, 4 mmol Mn(NO 3 ) 2 are dissolved in 5 ml of distilled water and 15 ml of Then, the solution was dried in an oven at 80 °C for 6 hours, fully ground, calcined in a muffle furnace at 500 °C for 5 h, and then heated to 700 °C for 8 h . During the entire heating process, the heating rate was 5 °C/min. The lanthanum manganate nanoparticles are obtained, which are denoted as LMO'.
  • Example 5 The thermal catalysis conditions for the strontium-doped ordered mesoporous lanthanum manganate-supported noble metal palladium composite material to toluene gas are: the toluene concentration is 50 ppm, the amount of the catalyst was 50 mg, the catalyst was fixed on a fixed bed reactor through a U-shaped tube, and the catalytic effect of the composite material on toluene gas was analyzed by gas chromatography under heating conditions.
  • FIG. 9 is a graph showing the thermocatalytic effect of strontium-doped ordered mesoporous lanthanum manganate support on toluene gas.
  • FIG. 10 is a graph showing the thermal catalytic effect of the strontium-doped ordered mesoporous lanthanum manganate-supported noble metal palladium composite on toluene gas.
  • Fig. 11 is a graph showing the catalytic performance of lanthanum manganate LMO' synthesized without adding citric acid during the preparation process. It can be seen from Figures 9 and 10 that the present invention can be applied to the conversion of toluene at lower temperatures.
  • Toluene pollution in the air mainly comes from building materials, interior decoration materials, household and office supplies, outdoor industrial waste gas, automobile exhaust, photochemical smog, etc.
  • the specific catalytic effect of toluene is analyzed by gas chromatography.
  • the calculation method of toluene conversion rate is as follows Equation (1): ; C 0 and C are the initial and test concentrations of toluene in the experiment, respectively (tested every 15 minutes).
  • Figure 9 is a comparison of the catalytic effect of strontium-doped ordered mesoporous lanthanum manganate carrier on toluene gas, it can be seen that the introduction of strontium significantly reduces the catalytic reaction temperature;
  • Figure 10 is a strontium-doped ordered mesoporous lanthanum manganate carrier
  • the thermal catalytic effect curve of the noble metal palladium-loaded composite on toluene gas, the loading of noble metal further reduces the catalytic temperature, which indicates that the strong interaction between noble metal and perovskite oxide can promote the degradation of toluene, which can be achieved at 150 °C Toluene was completely converted. Comparing Fig. 9 with Fig. 11, it can be found that the addition of citric acid is beneficial to the catalytic oxidation of toluene.
  • the above analysis shows that the morphology of lanthanum manganate can be successfully controlled by the technical solution of the present invention, and the valence state of manganese can be adjusted by introducing different proportions of strontium into lanthanum manganate, and the strontium-doped lanthanum manganate with higher specific surface area It can be used as a good carrier to uniformly support noble metal palladium nanoparticles, which improves the stability and efficiency of the catalyst under the interaction between the carrier and the noble metal, and realizes the catalytic oxidation of toluene at a lower temperature, which has a good application in the practical application process. prospect.

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Abstract

一种锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料及其制备方法与在催化氧化甲苯中的应用，以La(NO 3) 3•6H 2O，Mn(NO 3) 2，Sr(NO 3) 2作为镧源、锰源、锶源，以硅模板分子筛作为硬模板，以柠檬酸作为络合剂，通过蒸发、干燥、煅烧、氢氧化钠溶液刻蚀得到La 1-xSr xMnO 3纳米管材料；取La 1-xSr xMnO 3作为载体，加入氯钯酸钠金属前驱体，通过搅拌溶剂热蒸发以及氢气还原煅烧得到负载钯的La 1-xSr xMnO 3纳米管复合材料。Pd@La 1-xSr xMnO 3复合材料中锶的引入增加了四价锰的含量从而促进甲苯的催化氧化，实现了在较低温度下的高效催化氧化甲苯，对降解工业生产、生活中所排放的污染气体甲苯有很好的应用前景。

Description

锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料及其制备方法与在催化氧化甲苯中的应用 技术领域
本发明涉及纳米复合材料技术领域，具体涉及一种锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料及其制备方法与催化氧化甲苯中的应用。
 背景技术
挥发性有机物(VOCs)是导致城市雾霾与光化学污染等大气复合污染的重要前体物，对人类健康和生态环境产生重大影响，已经引起了政府和公众的广泛关注。目前针对VOCs的处理方法主要有：吸附、吸收、膜分离、等离子体、光催化、催化氧化法等。其中催化氧化法因具有低操作温度、高效且低能耗而被广泛应用，该方法的核心问题是开发与研制低温、高活性、热稳定性好和价廉的催化剂。贵金属催化剂因具有优异的催化性能而得以广泛研究，但由于贵金属容易发生团聚，在应用过程中会出现失活现象，因此需要具有较大表面积且稳定的载体来支撑贵金属材料。
钙钛矿氧化物储量丰富且具有良好的氧化还原能力，而钙钛矿氧化物的制备过程中煅烧温度高导致其表面积较低，且锰的价态与甲苯催化氧化的性能联系密切，因此如何制备具有高表面积的钙钛矿氧化物锰酸镧以及调整锰的价态并将其作为负载贵金属催化剂的载体来实现甲苯的低温催化值得深入研究。
 技术问题
本发明的目的是提供一种锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料及其制备方法，采用纳米浇铸的方法制备了有序介孔锰酸镧并掺杂了不同比例的锶，再利用氢气还原的方法在锰酸镧的表面负载了不同比例的贵金属钯，以实现高效催化氧化甲苯。
 技术解决方案
为了达到上述目的，本发明采用如下具体技术方案：一种锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料，其制备方法包括以下步骤：(1) 将硅模板加入锰盐、镧盐、锶盐以及弱酸的混合溶液中，经过蒸发、干燥、煅烧、碱溶液刻蚀，得到锶掺杂有序介孔锰酸镧材料；(2) 将钯盐溶液加入到含有锶掺杂有序介孔锰酸镧材料的醇中，通过加热反应、氢气还原煅烧得到有锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料。
一种低温热催化处理甲苯的方法，包括以下步骤：(1) 将硅模板加入锰盐、镧盐、锶盐以及弱酸的混合溶液中，经过蒸发、干燥、煅烧、碱溶液刻蚀，得到锶掺杂有序介孔锰酸镧材料；(2) 将钯盐溶液加入到含有锶掺杂有序介孔锰酸镧材料的醇中，通过加热反应、还原得到有锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料；(3) 将锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料置入含有甲苯的环境中，低温加热，完成催化氧化去除甲苯。
本发明中，锰盐为硝酸锰，镧盐为硝酸镧，锶盐为硝酸锶，弱酸为柠檬酸，碱为氢氧化钠，钯盐为氯钯酸钠；硝酸锰、硝酸镧、硝酸锶以及柠檬酸的混合溶液中，溶剂为水；氢氧化钠溶液以及氯钯酸钠溶液中，溶剂都为水；醇为乙醇。
本发明中，蒸发的温度为室温，时间为10～14小时，优选的蒸发温度为室温，蒸发时间为12小时；干燥的温度为60℃～100℃，时间为4～8小时，优选的干燥温度为80℃，干燥时间为6小时；煅烧在空气中进行，煅烧采取两段式升温，第一阶段升温速率为5℃/min，温度为500℃，时间为5h；第二阶段升温速率为5℃/min，温度为700℃，时间为8h；氢氧化钠溶液刻蚀的温度为70℃，时间为12小时。
本发明中，加热反应为50～70℃反应6～10小时，优选60℃反应8小时，溶剂热蒸发下同时去除溶剂；还原为氢气还原，还原处理时的温度为230～270℃，时间为1.5～2.5h，优选的，还原为氢气存在下煅烧，煅烧的温度为250℃，时间为2h，升温速率为5℃/min。
本发明中，步骤（1）中，硅模板、锰盐、镧盐、锶盐、弱酸的用量比为1 g: 4 mmol: (0～3.2) mmol: (0.8～4)mmol: 4 mmol，制备的锶掺杂有序介孔锰酸镧材料为La 1-xSr xMnO 3，x为0～0.8。
本发明中，步骤 (2) 中钯盐与La 1-xSr xMnO 3的质量比为 (0.01～0.06) :1。
本发明中，将硅酸酯与聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物在水、盐酸存在下进行反应，再煅烧得到硅模板；反应为38℃反应24h，再于110℃反应24小时；煅烧为550℃下煅烧6小时；进一步的，硅酸酯为原硅酸四乙酯。
本发明首先采用硅模板作为硬模板的方法制备有序介孔锰酸镧，获得了具有较高比表面积，均一的孔径大小，重复性好的纳米管阵列结构，可作为优异的载体来负载贵金属钯纳米粒子，较高的比表面积有利于催化反应的进行。还原煅烧处理是在氢气的氛围中进行的，浸渍法负载的贵金属在煅烧中还原为纳米粒子负载到掺锶锰酸镧的纳米管中，形成负载均匀，粒径较小的纳米粒子，可促进催化降解甲苯。本发明在还原煅烧处理后，将定量的锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料置于具有一定浓度的甲苯环境中，采用固定床反应器对其进行加热催化，低温下，完全催化氧化甲苯。
本发明进一步公开了上述锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料在低温催化氧化甲苯中的应用。
本发明公开的低温热催化处理甲苯的方法中，将上述锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料置入含有甲苯的环境中，利用固定床反应器完成甲苯的处理，优选的，低温完全催化氧化甲苯气体的最佳温度为150 ℃。
 有益效果
本发明的优点：本发明公开的锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料具有较高的比表面积，均一的孔径大小，锶的掺杂有利于锰价态的升高；贵金属钯纳米粒子负载到掺锶的锰酸镧上，贵金属与纳米粒子之间的相互作用可提高催化甲苯的性能，实现较低温度下的催化氧化甲苯，具有良好的应用前景。
 附图说明
图1 为硅模板的透射电镜图（TEM）。
图2 为硅模板的扫描电镜图（SEM）。
图3 为La 0.8rS 0.2MnO 3的透射电镜图（TEM）。
图4 为La 0.8rS 0.2MnO 3的扫描电镜图（SEM）。
图5为有序介孔锰酸镧（N-LMO）催化剂的扫描电镜图（SEM）。
图6为锰酸镧(LMO)催化剂的扫描电镜图（SEM）。
图7 为2 wt% Pd@La 0.8rS 0.2MnO 3复合材料的透射电镜图（TEM）。
图8 为2 wt% Pd@La 0.8rS 0.2MnO 3复合材料的扫描电镜图（SEM）。
图9 为锶掺杂有序介孔锰酸镧载体对甲苯气体的热催化效果曲线图。
图10为锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料对甲苯气体的热催化效果曲线图。
图11为制备过程中未添加柠檬酸合成的锰酸镧LMO’的催化性能图。
 本发明的实施方式
本发明一种锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料的制备方法如下：(1) 将硅模板加入硝酸锰、硝酸镧、硝酸锶以及柠檬酸的混合溶液中，经过蒸发、干燥、煅烧、氢氧化钠溶液刻蚀步骤，得到有序介孔钙钛矿氧化物锰酸镧(掺锶)；(2) 将氯钯酸钠溶液加入到在乙醇溶液中分散均匀锰酸镧(掺锶)中，通过加热搅拌，氢气还原煅烧得到有序介孔钙钛矿氧化物锰酸镧负载贵金属钯复合材料。
本发明涉及的原料都为本领域常规产品，具体操作方法以及测试方法为本领域常规方法。
实施例一 有序介孔La 0.8rS 0.2MnO 3的制备，具体步骤如下：将4g聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物（P123）、130ml超纯水和20ml浓盐酸（37wt%）混合，然后加入8.32g原硅酸四乙酯，在38℃下水浴搅拌反应24h，结束后，转移至反应釜中，于110℃下水热反应24小时，自然冷却至室温，将其抽滤并洗涤至中性，于80℃干燥，干燥后以10℃/min由室温升至550℃下煅烧6小时得到产物硅模板。
将3.2 mmol La(NO 3) 3·6H 2O，4 mmol Mn(NO 3) 2，0.8 mmol Sr(NO 3) 2溶解在5ml蒸馏水和15 ml无水乙醇中，得到均匀溶液，然后，将4 mmol柠檬酸加入上述溶液中室温混合1小时，再加入1g 硅模板并混合12小时；然后将溶液在80℃的烘箱中干燥6小时，充分研磨后，在马弗炉中于500℃下煅烧5 h，然后将其加热至700℃煅烧8 h。在整个加热过程中，加热速率为5℃/ min。最后，将所得固体产品分散在2 M NaOH溶液中70 ℃回流6 h，得到有序介孔掺锶锰酸镧，作为La 0.8Sr 0.2MnO 3载体。
附图1为硅模板的TEM图，附图2为硅模板的SEM图，附图3为La 0.8rS 0.2MnO 3的TEM图，附图4为La 0.8rS 0.2MnO 3的SEM图。从图中可以看出管状孔道结构，且分布较均一。
更改La(NO 3) 3·6H 2O、Sr(NO 3) 2的摩尔量，采用同样的方法，得到La 0.5Sr 0.5MnO 3载体、La 0.2Sr 0.8MnO 3载体。
实施例二 制备锰酸镧 (LMO)和纳米浇铸锰酸镧(N-LMO)，具体步骤如下：将4 mmol La(NO 3) 3·6H 2O，4 mmol Mn(NO 3) 2，溶解在5ml蒸馏水和15 ml无水乙醇中，得到均匀溶液，然后，将4 mmol柠檬酸加入上述溶液中室温混合1小时，然后将溶液在80℃的烘箱中干燥6小时，充分研磨后，在马弗炉中于500℃下煅烧5 h，然后将其加热至700℃煅烧8 h。在整个加热过程中，加热速率为5℃/ min。得到锰酸镧，作为LaMnO 3载体 (LMO)。
将4 mmol La(NO 3) 3·6H 2O，4 mmol Mn(NO 3) 2，溶解在5ml蒸馏水和15 ml无水乙醇中，得到均匀溶液，然后，将4 mmol柠檬酸加入上述溶液中室温混合1小时，再加入1g 硅模板并混合12小时；然后将溶液在80℃的烘箱中干燥6小时，充分研磨后，在马弗炉中于500℃下煅烧5 h，然后将其加热至700℃煅烧8 h。在整个加热过程中，加热速率为5℃/ min。最后，将所得固体产品分散在2 M NaOH溶液中70 ℃回流6 h，得到有序介孔锰酸镧，作为LaMnO 3载体(N-LMO)。
附图5为有序介孔锰酸镧（N-LMO）催化剂的SEM图，附图6为锰酸镧(LMO)催化剂的SEM图。
实施例三 锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料的制备，具体步骤如下：将一定量的氯钯酸钠溶液（1wt％、2wt％、4wt％、6wt％，以La 0.8Sr 0.2MnO 3载体为基数）加入到分散在15mL乙醇的120mg La 0.8Sr 0.2MnO 3载体中，在60℃常规磁力搅拌8h，得到黑色粉末，再将黑色粉末在10vol％H 2/N 2气氛中煅烧，煅烧温度为250℃，煅烧时间为2h，升温速率为10℃/min，得到锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料，其中钯负载质量占La 0.8Sr 0.2MnO 3 2%的样品记为2 wt% Pd La 0.8rS 0.2MnO 3。
附图7为锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料的TEM图，附图8为锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料的SEM图。从图中可以看出钙钛矿氧化物的形貌得到很好的控制，并且负载贵金属后未发生明显变化。
实施例四 在不添加柠檬酸的条件下合成锰酸镧，具体步骤为：将4 mmol La(NO 3) 3·6H 2O，4 mmol Mn(NO 3) 2，溶解在5ml蒸馏水和15 ml无水乙醇中，得到均匀溶液，然后，将溶液在80℃的烘箱中干燥6小时，充分研磨后，在马弗炉中于500℃下煅烧5 h，然后将其加热至700℃煅烧8 h。在整个加热过程中，加热速率为5℃/ min。得到锰酸镧纳米颗粒，记为LMO’。
实施例五 锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料对甲苯气体的热催化条件是：甲苯浓度为50 ppm, 催化剂的量为 50毫克，将该催化剂通过U形管固定在固定床反应器上，通过气相色谱分析该复合材料在加热条件下对甲苯气体的催化效果。
附图9 为锶掺杂有序介孔锰酸镧载体对甲苯气体的热催化效果曲线图。附图10 为锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料对甲苯气体的热催化效果曲线图。图11为制备过程中未添加柠檬酸合成的锰酸镧LMO’的催化性能图。由附图9、10可知，本发明可应用于较低温度下甲苯的转化。空气中甲苯污染主要来源于建筑材料、室内装饰材料和生活及办公用品，室外的工业废气、汽车尾气、光化学烟雾等，具体的甲苯催化效果是通过气相色谱分析的，甲苯转化率的计算方法如方程 (1)：
Figure 497749dest_path_image001
；C 0和C分别为实验中甲苯的初始浓度和测试浓度(每15分钟测试一次）。
附图9为锶掺杂有序介孔锰酸镧载体对甲苯气体催化效果的比较，可以看出锶的引入明显降低了催化反应温度；附图10 为锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料对甲苯气体的热催化效果曲线图，贵金属的负载进一步降低了催化温度，这说明贵金属与钙钛矿氧化物之间的强相互作用可促进甲苯的降解，150℃可以实现甲苯完全转化。将附图9与附图11相比可以发现柠檬酸的加入有利于甲苯的催化氧化。
通过以上分析，说明采用本发明的技术方案可以成功控制锰酸镧的形貌，并且在锰酸镧中引入不同比例的锶可以调整锰的价态，具有较高比表面积的掺锶锰酸镧可作为良好的载体均匀的负载贵金属钯纳米粒子，在载体与贵金属的相互作用下提高了催化剂的稳定性和效率，并且实现了较低温度下催化氧化甲苯，在实际应用过程中具有良好的应用前景。

Claims (10)

  1. 一种锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料，其特征在于，所述锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料的制备方法包括以下步骤：
    (1) 将硅模板加入锰盐、镧盐、锶盐以及弱酸的混合溶液中，经过蒸发、干燥、煅烧、碱溶液刻蚀，得到锶掺杂有序介孔锰酸镧材料；
    (2) 将钯盐溶液加入到含有锶掺杂有序介孔锰酸镧材料的醇中，通过加热反应、氢气还原煅烧得到有锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料。
  2. 根据权利要求1所述锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料，其特征在于，锰盐为硝酸锰，镧盐为硝酸镧，锶盐为硝酸锶，弱酸为柠檬酸，碱为氢氧化钠，钯盐为氯钯酸钠。
  3. 根据权利要求1所述锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料，其特征在于，蒸发的温度为室温，时间为10～14小时；干燥的温度为60℃～100℃，时间为4～8小时；煅烧在空气中进行，煅烧采取两段式升温。
  4. 根据权利要求1所述锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料，其特征在于，加热反应为50～70℃反应6～10小时。
  5. 根据权利要求1所述锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料，其特征在于，还原为氢气还原，还原时的温度为230～270℃，时间为1.5～2.5h。
  6. 根据权利要求1所述锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料，其特征在于，硅模板、锰盐、镧盐、锶盐、弱酸的用量比为1 g: 4 mmol: (0～3.2) mmol: (0.8～4)mmol: 4 mmol；钯盐与La 1-xSr xMnO 3的质量比为 (0.01～0.06) :1。
  7. 根据权利要求1所述锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料，其特征在于，将硅酸酯与聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物在水、盐酸存在下进行反应，再煅烧得到硅模板。
  8. 权利要求1所述锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料，其特征在于，在低温催化氧化甲苯中的应用。
  9. 一种低温热催化处理甲苯的方法，其特征在于，包括以下步骤：
    (1) 将硅模板加入锰盐、镧盐、锶盐以及弱酸的混合溶液中，经过蒸发、干燥、煅烧、碱溶液刻蚀，得到锶掺杂有序介孔锰酸镧材料；
    (2) 将钯盐溶液加入到含有锶掺杂有序介孔锰酸镧材料的醇中，通过加热反应、还原得到有锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料；
    (3) 将锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料置入含有甲苯的环境中，低温加热，完成催化氧化去除甲苯。
  10. 根据权利要求9所述的应用，其特征在于，低温加热的温度为140～160℃。
PCT/CN2021/141006 2020-10-26 2021-12-23 锶掺杂有序介孔锰酸镧负载贵金属钯的复合材料及其制备方法与在催化氧化甲苯中的应用 Ceased WO2022089669A1 (zh)

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CN116196921B (zh) * 2022-12-20 2024-06-04 北京工业大学 一种用于天然气车尾气净化的三维有序大孔锰酸镧负载钯单原子催化剂
CN116196921A (zh) * 2022-12-20 2023-06-02 北京工业大学 一种用于天然气车尾气净化的三维有序大孔锰酸镧负载钯单原子催化剂
CN116726911B (zh) * 2023-06-19 2024-06-11 金华职业技术学院 一种Mn5O8臭氧常温分解催化剂及其制备方法
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CN117282470A (zh) * 2023-09-20 2023-12-26 苏州科技大学 一种镍修饰mof材料表面负载钯的复合材料及其制备方法和应用
CN117504871A (zh) * 2023-11-14 2024-02-06 中国环境科学研究院 三维有序大孔结构催化剂、催化剂组合物及应用
CN118719056A (zh) * 2024-07-12 2024-10-01 福州大学 一种用于光热催化氧化Cl-VOCs的酸蚀3DOM多元金属催化剂及其制备方法
CN118719056B (zh) * 2024-07-12 2025-11-21 福州大学 一种用于光热催化氧化Cl-VOCs的酸蚀3DOM多元金属催化剂及其制备方法
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