CN111250147B - Mn2MoO4/SBA-15 composite catalyst material and preparation method thereof - Google Patents
Mn2MoO4/SBA-15 composite catalyst material and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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Abstract
Mn (manganese)2MoO4the/SBA-15 composite material is characterized in that: bimetallic oxide Mn2MoO4Mn loaded on the surface and in the pore channels of the molecular sieve SBA-152MoO4The total loading on SBA-15 was 20%; mn as described above2MoO4The preparation method of the/SBA-15 composite material comprises the following step of mixing (NH)4)6Mo7O24•4H2O and C4H6MnO4•4H2Dissolving O in concentrated hydrochloric acid, adding distilled water, adding SBA-15 while stirring, adding surfactant polyethylene glycol 4000(PEG) with the mass fraction of 10% -15%, heating and stirring on a magnetic stirrer with the rotation speed of 100r/min to paste, drying in vacuum, grinding, and calcining at high temperature. The invention effectively controls Mn2MoO4Loading on SBA-15, Mn produced2MoO4Mn in SBA-152MoO4The size is small, the load uniformity on SBA-15 is good, agglomeration does not occur, the catalytic activity is high and can reach 98.8%, the time for degrading sulfapyridine is short, the stability of the catalytic performance is good, the sulfapyridine can be recycled, the catalytic activity can still reach more than 95% after being reused for 10 times, the stability is kept stable and not reduced, and the stability in recycling is excellent.
Description
Technical Field
The invention relates to the technical field of advanced oxidation, in particular to Mn2MoO4An SBA-15 composite material and a preparation method thereof.
Background
Antibiotics are widely applied to prevention and treatment of bacterial infectious diseases of human beings and livestock, so that various bacteria can generate antibodies, and meanwhile, residual antibiotics in medical and medical wastewater can also be used as pollutants to cause serious threats to human bodies, animals and environment protection after entering the environment. The antibiotic is difficult to be degraded by microorganisms and is difficult to be absorbed by the nature. Thus, the residual resistance to organisms in the environment will be increasing if no reasonably effective measures are taken. Research on antibiotic pollution by the Chinese academy of sciences shows that more than 5 ten thousand tons of antibiotics are discharged into the water and soil environment in China in a year. Therefore, a fast and efficient method for degrading residual antibiotics in water is urgently needed. Sulfonamides are a class of widely used synthetic antibiotics, are main potential pollutants introduced into the environment, are spread in the environment, pose threats to the health of human beings and animals, and also damage the ecological environment. Therefore, it is highly desirable to have a highly sensitive and reliable degradation of such compounds.
The advanced oxidation technology utilizes the generation of free radicals (SO) with extremely strong activity in the reaction4·－、OH·－Etc.) to oxidize and decompose organic pollutants in the water body, so that most of the organic pollutants are rapidly degraded into carbon dioxide and water. There are many methods for catalyzing persulfate to generate sulfate radical, among which, at present, the homogeneous catalyst-Fe is widely used2+Although the persulfate activation method has the advantages of high oxidation efficiency, strong oxidation capacity, good selectivity, wide application range and the like, the method also has the defects that metal ions can be remained in a single metal or metal oxide in the catalysis process, the catalyst is not easy to recycle, secondary pollution is easy to cause and the like. To overcome the above disadvantages, heterogeneous advanced oxidation techniques have been developed, such as the use of metals or their oxides (Fe)3O4、Co3O4Etc.) are immobilized on a suitable support to produce a supported catalyst composite. In the process of preparing the compound, the technical problems to be overcome are that the carrier and the catalyst are not suitable, the suitability between the carrier and the catalyst is poor, the catalyst cannot be successfully loaded on the carrier or the loading capacity is low, and the particle size of the catalyst on the carrier cannot growPoor dispersion, easy agglomeration, reduced catalytic activity after the catalyst is loaded on a carrier, easy shedding from the carrier in the use process, poor stability, short service life and the like.
Disclosure of Invention
The invention aims to provide Mn with excellent catalytic degradation performance on sulfonamides2MoO4the/SBA-15 composite material.
Another object of the present invention is to provide the above Mn2MoO4A preparation method of the/SBA-15 composite material.
The purpose of the invention is realized by the following technical scheme:
mn (manganese)2MoO4the/SBA-15 composite material is characterized in that: bimetallic oxide Mn2MoO4Mn loaded on the surface and in the pore channels of the molecular sieve SBA-15 and loaded on the surface2MoO4The grain diameter of the bimetal oxide is 20-50nm, and Mn in the pore channel2MoO4The grain diameter of the bimetal oxide is 8-12nm, and Mn2MoO4The total loading on SBA-15 was 20%.
Further, the above Mn2MoO4The preparation method of the/SBA-15 composite material is characterized by comprising the following steps: will be (NH)4)6Mo7O24·4H2O and C4H6MnO4·4H2Dissolving O in concentrated hydrochloric acid, adding distilled water to form a mixed solution A, adding SBA-15 into the mixed solution A while stirring to form a mixed solution B, adding surfactant polyethylene glycol 4000(PEG) with the mass fraction of 10% -15% into the mixed solution B, forming a mixed solution C with the assistance of ultrasonic waves for 5min, heating and stirring on a magnetic stirrer with the rotation speed of 100r/min to be pasty, stirring at the temperature of 60 ℃, preventing the reduction of dispersity caused by too fast heating, then performing vacuum drying, grinding and then performing high-temperature calcination.
The inventors found that (NH) is converted to4)6Mo7O24·4H2O and C4H6MnO4·4H2Dissolving O in acidic environment in the presence of concentrated hydrochloric acid, and adding surfactant polyethyleneThe glycol 4000 can enable the system to be in a highly dispersed state, is favorable for forming stable bimetallic oxide, promotes metal ions to fully enter an SBA-15 orbit, controls the grain growth of the metal ions, and forms uniformly distributed small-grain-size bimetallic oxide.
Further, the above (NH)4)6Mo7O24·4H2O、C4H6MnO4·4H2The dosage ratio of O and distilled water is as follows: 0.4461g, 1.2879g, 30mL, the concentration of concentrated hydrochloric acid is 11.48mol/L, and the volume ratio of concentrated hydrochloric acid to distilled water is 1: 3.
furthermore, the mass-volume ratio of SBA-15 to the mixed liquid A is 1g:30-40 ml.
Further, the dosage ratio of the polyethylene glycol 4000 to the distilled water in the mixed solution A is 1-1.5: 10.
Further, (NH)4)6Mo7O24·4H2O and C4H6MnO4·4H2Dissolving the O in concentrated hydrochloric acid, diluting with distilled water to obtain a mixed solution A, performing ultrasonic treatment for 10-20min, and performing ultrasonic treatment for 40-45 min when adding SBA-15 into the mixed solution A.
Further, the mixed solution C is heated and stirred on a magnetic stirrer with the constant temperature of 55 ℃ until the suspension becomes a pasty material, and the stirring speed is 100 r/min.
Further, the above vacuum drying is to dry the pasty material in a vacuum drying oven at a constant temperature of 100 ℃ for 12 h.
Further, the high-temperature calcination is specifically to take out the dried material, cool the material, grind the material into powder, put the powder into a strip-shaped ceramic boat, and calcine the material in a tube furnace at 700-900 ℃ for 4-5 h at a heating rate of 10 ℃/min.
Most specifically, Mn2MoO4The preparation method of the/SBA-15 composite material is characterized by comprising the following steps:
(1) will be (NH)4)6Mo7O24·4H2O and C4H6MnO4·4H2Dissolving O in concentrated hydrochloric acid, and addingDissolving with distilled water under ultrasonic for 10-20min to obtain mixed solution A, (NH)4)6Mo7O24·4H2O、C4H6MnO4·4H2The dosage ratio of O, concentrated hydrochloric acid and distilled water is 0.4461g, 1.2879g, 10mL and 30mL, and the concentration of the concentrated hydrochloric acid is 11.48 mol/L;
(2) adding SBA-15 into the mixed liquid A while stirring, and then carrying out ultrasonic treatment for 40-45 min to form mixed liquid B, wherein the stirring speed is 100r/min, and the mass volume ratio of the SBA-15 to the mixed liquid A is 1g:30-40 mL;
(3) adding polyethylene glycol 4000 into the mixed solution B while stirring, and performing ultrasonic treatment for 5min to form a mixed solution C, wherein the stirring speed is 100r/min, and the ratio of the polyethylene glycol 4000 to the distilled water in the mixed solution A is 1-1.5: 10.
(4) Placing the mixed solution C on a magnetic stirrer at 60 ℃, heating and stirring until the suspension becomes pasty material, wherein the stirring speed is 100 r/min;
(5) drying the pasty material in a vacuum drying oven at constant temperature of 100 ℃ for 12 h;
(6) and taking out the dried material, cooling, grinding into powder, putting into a strip-shaped ceramic boat, and calcining in a tube furnace at 700-900 ℃ for 4-5 h at a heating rate of 10 ℃/min.
Mn2MoO4Mn in the preparation of the/SBA-15 composite2MoO4The loading capacity is low, the catalytic performance of the composite material is poor, and when the composite material is repeatedly used, the catalytic performance of the composite material is seriously attenuated, so that the degradation rate of the sulfonamide pollutants is reduced; mn2MoO4Agglomeration is easy to occur, mesoporous channels of SBA-15 are blocked, and the ordered mesoporous structure is damaged, so that the specific surface area is reduced, the mesoporous structure is reduced, the mesoporous aperture is reduced, and the catalytic activity is reduced. The preparation method of the invention overcomes the technical problems just by matching the steps, and successfully ensures that Mn is obtained2MoO4Loaded on SBA-15 and effectively controls Mn2MoO4Loading on SBA-15 such that Mn2MoO4Mn in/SBA-15 composite material2MoO4High load, noThe catalyst is agglomerated and uniformly dispersed on the surface and in a pore channel of the SBA-15, has excellent catalytic activity on PMS, and has the advantages that the bimetallic oxides mutually inhibit the leaching of ions, and meanwhile, the bimetallic oxide with stable bimetallic oxide is formed in a mesoporous track by combining with a specific firing temperature, the binding force between the bimetallic oxide and the SBA-15 is large, and the ion leaching is less; in the aspect of repeated use, the mesoporous track provides a bearing environment for metal, and is simpler and more convenient to recycle.
The invention has the following technical effects:
the invention provides Mn2MoO4/SBA-15 composite catalyst material, Mn2MoO4The composite material has the advantages of small size, large specific surface area, no agglomeration, capability of providing more active sites for catalytic reaction, excellent catalytic performance in a large-range pH change environment, good catalytic stability, catalytic activity of 98.8 percent, short time for degrading Sulfapyridine (SPY), reusability, capability of being used for 10 times, capability of keeping the catalytic activity of 95 percent, stability and stability, and excellent repeated use stability.
The preparation method effectively controls Mn2MoO4The loading capacity on SBA-15 is 20%, and the prepared Mn2MoO4Mn in SBA-152MoO4The size is small, the particle size of the metal ions loaded on the surface of the SBA-15 is 20-50nm, the particle size of the bimetallic ions loaded on the mesoporous track is about 10nm, the loading uniformity of the bimetallic oxide on the surface of the SBA-15 and the mesoporous track is good, agglomeration does not occur, the catalytic activity is high and can reach 98.8%, the time for degrading sulfapyridine is short, the catalytic performance is excellent in acidic, neutral and alkaline environments, the catalytic performance is better along with the increase of pH, the stability of the catalytic performance is good, the catalytic activity can be recycled for 10 times, the catalytic activity can still reach over 95%, the stability is kept and is not reduced, the ion leaching rate is low, and the recycling stability is excellent.
Drawings
FIG. 1: mn2MoO4X-ray diffraction (XRD) pattern of/SBA-15Spectra.
FIG. 2: mn2MoO4Scanning Electron Microscope (SEM) picture of/SBA-15.
FIG. 3: mn2MoO4High resolution Transmission Electron Microscopy (TEM) image of/SBA-15.
FIG. 4: a graph of degradation effect of sulfapyridine by different means.
FIG. 5: mn2MoO4the/SBA-15 composite catalyst has a relation curve diagram of the catalytic degradation sulfapyridine effect and the rate constant of PMS with different concentrations.
FIG. 6: mn2MoO4A degradation curve diagram of PMS catalyzed by the SBA-15 composite catalyst for sulfapyridine with different concentrations.
FIG. 7: mn in different amounts2MoO4A relation curve diagram of PMS (poly-p-sulfapyridine) degradation rate and degradation rate constant catalyzed by the SBA-15 composite catalyst.
FIG. 8: mn at different pH conditions2MoO4A relation curve diagram of degradation rate and degradation rate constant of PMS to sulfapyridine catalyzed by SBA-15 catalyst.
FIG. 9: mn2MoO4A relationship graph of the recycling of the/SBA-15 composite catalyst and the degradation rate.
FIG. 10: mn2MoO4Ion leaching rate curve diagram of the/SBA-15 composite catalyst in the recycling process.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-mentioned disclosure.
Example 1
Mn (manganese)2MoO4The preparation method of the/SBA-15 composite material comprises the following steps:
(1) will be (NH)4)6Mo7O24·4H2O and C4H6MnO4·4H2Dissolving O in concentrated hydrochloric acid, adding distilled water, and ultrasonic dissolving for 15min to obtain mixed solution A, (NH)4)6Mo7O24·4H2O、C4H6MnO4·4H2The dosage ratio of O, concentrated hydrochloric acid and distilled water is 0.4461g, 1.2879g, 10mL and 30mL, and the concentration of the concentrated hydrochloric acid is 11.48 mol/L;
(2) adding SBA-15 into the mixed solution A while stirring, and carrying out ultrasonic treatment for 45min to form mixed solution B, wherein the stirring speed is 100r/min, and the mass volume ratio of the SBA-15 to the mixed solution A is 1g: 35 mL;
(3) adding polyethylene glycol 4000 into the mixed solution B while stirring, and performing ultrasonic treatment for 5min to form a mixed solution C, wherein the stirring speed is 100r/min, and the ratio of the polyethylene glycol 4000 to the distilled water in the mixed solution A is 1.5: 10.
(4) Placing the mixed solution C on a magnetic stirrer at 55 ℃, heating and stirring until the suspension becomes a pasty material, wherein the stirring speed is 100 r/min;
(5) drying the pasty material in a vacuum drying oven at constant temperature of 100 ℃ for 12 h;
(6) and taking out the dried material, cooling, grinding into powder, putting into a strip ceramic boat, and calcining in a tube furnace at 800 ℃ for 4.5h at a heating rate of 10 ℃/min.
Example 2
Mn (manganese)2MoO4The preparation method of the/SBA-15 composite material comprises the following steps:
(1) will be (NH)4)6Mo7O24·4H2O and C4H6MnO4·4H2Dissolving O in concentrated hydrochloric acid, adding distilled water, and ultrasonic dissolving for 20min to obtain mixed solution A, (NH)4)6Mo7O24·4H2O、C4H6MnO4·4H2The dosage ratio of O, concentrated hydrochloric acid and distilled water is 0.4461g, 1.2879g, 10mL and 30mL, and the concentration of the concentrated hydrochloric acid is 11.48 mol/L;
(2) adding SBA-15 into the mixed solution A while stirring, and carrying out ultrasonic treatment for 40min to form mixed solution B, wherein the stirring speed is 100r/min, and the mass volume ratio of the SBA-15 to the mixed solution A is 1g:30 mL;
(3) adding polyethylene glycol 4000 into the mixed solution B while stirring, and performing ultrasonic treatment for 5min to form a mixed solution C, wherein the stirring speed is 100r/min, and the ratio of the polyethylene glycol 4000 to the distilled water in the mixed solution A is 1: 10.
(4) Placing the mixed solution C on a magnetic stirrer at 55 ℃, heating and stirring until the suspension becomes a pasty material, wherein the stirring speed is 100 r/min;
(5) drying the pasty material in a vacuum drying oven at constant temperature of 100 ℃ for 12 h;
(6) and taking out the dried material, cooling, grinding into powder, putting into a strip ceramic boat, and calcining in a tube furnace at 700 ℃ for 5h at a heating rate of 10 ℃/min.
Example 3
Mn (manganese)2MoO4The preparation method of the/SBA-15 composite material comprises the following steps:
(1) will be (NH)4)6Mo7O24·4H2O and C4H6MnO4·4H2Dissolving O in concentrated hydrochloric acid, adding distilled water, and ultrasonic dissolving for 20min to obtain mixed solution A, (NH)4)6Mo7O24·4H2O、C4H6MnO4·4H2The dosage ratio of O, concentrated hydrochloric acid and distilled water is 0.4461g, 1.2879g, 10mL and 30mL, and the concentration of the concentrated hydrochloric acid is 11.48 mol/L;
(2) adding SBA-15 into the mixed solution A while stirring, and carrying out ultrasonic treatment for 42min to form mixed solution B, wherein the stirring speed is 100r/min, and the mass volume ratio of the SBA-15 to the mixed solution A is 1g: 40 mL;
(3) adding polyethylene glycol 4000 into the mixed solution B while stirring, and performing ultrasonic treatment for 5min to form a mixed solution C, wherein the stirring speed is 100r/min, and the ratio of the polyethylene glycol 4000 to the distilled water in the mixed solution A is 1.2: 10.
(4) Placing the mixed solution C on a magnetic stirrer at 55 ℃, heating and stirring until the suspension becomes a pasty material, wherein the stirring speed is 100 r/min;
(5) drying the pasty material in a vacuum drying oven at constant temperature of 100 ℃ for 12 h;
(6) and taking out the dried material, cooling, grinding into powder, putting into a strip ceramic boat, and calcining in a tube furnace at 900 ℃ for 4h at a heating rate of 10 ℃/min.
Figure 1 is a sequence of scan images of XRD at large and small angles, respectively. FIG. 1a is a XRD large angle scan of the product at a scan speed of 1 deg./min and 2 theta of 10 deg. -80 deg.. Comparing the XRD large-angle map with standard card PDF #72-0285, and showing strong MnMoO in the image4Characteristic peak of 25.766 ° (100.0) and a relatively broad scanning diffraction peak, indicating MnMoO4Has been absorbed by the mesopores of SBA-15 and forms a stable structure, forming the target material MnMoO4the/SBA-15 composite material. Fig. 1b is an XRD small angle scanning image of the product at a scanning speed of 0.2 °/min of 0 ° to 5 °, and it is found that a certain reduction of the characteristic peak of the mesoporous track can be clearly found under the small angle scanning, because the mesoporous property of the molecular track is reduced due to the effective adhesion of the bimetal oxide inside the mesoporous track.
FIG. 2 shows Mn2MoO4SEM image of/SBA-15 composite catalyst, from which Mn can be seen2MoO4The bimetal particles are loaded on the surface of the SBA-15, are uniformly, neatly and stably arranged and are adhered, the bimetal particles are found to be uniform in size and have the particle size of 20-50nm, the growth of the bimetal oxide crystals loaded in the mesoporous track of the molecular sieve SBA-15 is limited by the pore size of the SBA-15 mesoporous and under the action of a surfactant, the particle size of the bimetal oxide crystals is controlled, the particle size is about 10nm, pore blocking does not occur, the specific surface area of the catalyst is effectively increased, and therefore more catalytic active sites can be provided.
FIG. 3 is Mn2MoO4High-resolution Transmission Electron Microscope (TEM) image of the/SBA-15 composite catalyst, and Mn was observed in FIG. 3(b)2MoO4The nanoparticles were uniformly dispersed in the SBA-15 channels. Mn on SBA-152MoO4Is ordered. Because the small-particle metal oxide is loaded on the surface and in the pore channels of the SBA-15 and is brokenThe ordered mesoporous structure of the SBA-15 part is damaged, and the mesoporous aperture is reduced, which is similar to Mn2MoO4The small angle XRD measurement results of the SBA-15 are consistent; the structure of the electrons of the molecular sieve and the metal oxide is changed, so that the bimetallic oxide formed by Mo and Mn is more stable, the binding force between the bimetallic oxide and SBA-15 is large, the leaching of metal ions is reduced, and the prepared Mn2MoO4the/SBA-15 composite catalyst has better stability and high-efficiency catalytic performance.
Example 4
Mn2MoO4the/SBA-15 composite catalyst catalyzes PMS to degrade sulfapyridine:
with Mn2MoO4SBA-15 as catalyst, Potassium Monopersulfate (PMS) as oxidant, Mn2MoO4In the SBA-15 catalytic reaction mode, PMS is catalyzed to generate sulfate radicals, sulfapyridine is used as a target compound, and the generation of the sulfate radicals plays an important role in the degradation process of the sulfapyridine.
50mL of sulfapyridine Solution (SPY) 100. mu. mol/L was placed in a small 100mL beaker with a magnetic stirrer and Mn was added2MoO4SBA-15, in respective amounts
Placing on a magnetic stirrer, stirring uniformly at room temperature in a dark place to reach sulfapyridine adsorption-desorption balance, and taking the balance concentration as initial concentration (C) of degradation0) Immediately adding 500 μ L PMS with concentration of 0.25 μmol/L and starting timing, sampling 1.0mL at certain time intervals and immediately adding into a sample tube containing 200 μ L sodium thiosulfate inactivating agent, shaking, filtering with 0.22 μm water phase filter membrane, loading into a centrifuge tube for use, and analyzing with HPLC-2010C high performance liquid chromatograph with ultraviolet detector wavelength of 254nm, Agilent Eclipse XDB-C18(150mm × 4.6mm,5.0 μm), mobile phase composition of 35% methanol and 65% water (volume ratio), column temperature of 25 deg.C, mobile phase flow rate of 0.3mL/min, and Inductive Coupling Plasma (ICP) technique to measure Mn2+And Mo2+The detection time is 8 min.
1. Mn in different amounts2MoO4Influence of the/SBA-15 composite catalyst on degradation Performance:
according to example 4, different Mn were used2MoO4The addition amount of SBA-15 is the addition amount in 1L sulfapyridine solution, and the obtained results are shown in the following table 1:
as can be seen from Table 1, the Mn of the present invention is present in a constant concentration and amount of sulfapyridine and PMS2MoO4When the dosage of the SBA-15 is gradually increased within the range of 0.6 g/L-1.2 g/L, the degradation effect of sulfapyridine is better and better, and then the dosage is continuously increased, so that the degradation effect is reduced, as shown in figure 7 (a). The inset in fig. 7(b) shows the kinetics of sulfapyridine degradation; these figures illustrate the sulfapyridine degradation and first order kinetic model lnCt/C0＝–k1t corresponds well, where CtAnd C0The sulfapyridine concentrations at time t and t ═ 0, respectively. FIG. 7(b) clearly shows that the concentration of sulfapyridine and the amount of PMS are constant with Mn2MoO4The kinetic rate constant increases and then decreases for an increase in the mass of/SBA-15. When Mn is present2MoO4The rate constant k when SBA-15 increases from 0.04g to 1.2g/L1Reaches a maximum value after which the value of the rate constant is dependent on Mn2MoO4The increase in/SBA-15 decreased. Higher catalyst usage can increase the number of adsorption sites and provide more active sites for PMS activated sulfate radical generation, thus resulting in a significant increase in oxidative degradation rate. However, when the amount of the catalyst is increased to a certain amount, the catalyst is inhibited from each other by further increasing the amount of the catalyst, resulting in Mn2MoO4The degradation rate in the system consisting of the/SBA-15 catalyst and PMS is reduced, and the corresponding final degradation rate is also inhibited.
2.Mn2MoO4The catalytic activity of the/SBA-15 composite catalyst in different pH environments is as follows:
the same degradation SPY process as in example 4 was carried out under different initial pH conditions, the degradation results are shown in FIG. 8(a), and C at different times during the degradation of sulfapyridine was determined by analyzing the previous experiment when the pH was 3, 5, 7 and 9, respectivelytAnd C0The ratio of (a) to (b). The pH value can be seen to have obvious influence on the degradation of sulfapyridine, and the degradation effect of the sulfapyridine is better and better along with the increase of the pH value; from FIG. 8(b) when the pH is increased from 3 to 9, the rate constant k1Mn is shown to be rising2MoO4the/SBA-15 composite catalyst is optimal in catalyzing and degrading sulfapyridine in a system under an alkaline condition. Thus, Mn can be obtained by analysis2MoO4The rate of degrading sulfapyridine by activating PMS by the/SBA-15 composite catalyst is increased along with the increase of pH.
3.Mn2MoO4SBA-15 stability test:
(1) after finishing degrading sulfapyridine each time, centrifuging the suspension, pouring out supernatant, washing with triple distilled water for three times, and washing away sulfapyridine attached to the surface of the catalyst; washing with absolute ethyl alcohol for three times, (washing PMS and degradation products attached to the surface of the catalyst, finally washing with triple distilled water for three times, washing with absolute ethyl alcohol attached to the surface of the catalyst, pouring out supernatant, drying in a 100 ℃ oven until the catalyst is completely dehydrated, and then putting the catalyst into next degradation for use2MoO4The specific degradation rate of the SBA-15 in the degradation of sulfapyridine by PMS is shown in figure 9. The degradation rate of sulfapyridine is not obviously reduced in 10 times of continuous repeated use, and Mn2MoO4The SBA-15 still shows good catalytic activity in the process of repeated use, which indicates that the activation reaction of PMS can be carried out in a mesoporous track, degradation products can be uniformly dispersed, and the service life of the catalyst is prolonged. And the carbonaceous deposits on the surface of the catalyst are effectively removed through high-temperature drying after each experiment to activate the catalytic active site, so that the degradation efficiency of sulfapyridine is kept in a relatively stable range.
(2) As can be seen from FIG. 10, Mn was used in the first 3 reuses2+And Mo2+The ion leaching rate is very high, the ion leaching rate is reduced along with the increase of the cycle number, but the degradation rate is not changed greatly, because the metal ions entering the aqueous solution come from the metal ions loaded on the surface of the SBA-15, and the bimetal in the SBA-15 mesoporous track plays a main catalytic role all the time. Experiments show that Mn2MoO4the/SBA-15 composite catalyst can repeatedly and continuously degrade sulfapyridine, and has high degradation efficiency and good stability.
Comparative example 1
Sintering Mo and Fe: the Mo and Fe oxide products are prepared respectively, and can degrade sulfapyridine within 90min to a certain extent, but the catalytic action of oxides prepared by mixing and burning Mo and Fe on sulfapyridine is far worse than that of oxides of Mo or Fe alone, the sulfapyridine content for detection is not reduced within 90min through high performance liquid chromatography, after loading, a specific bimetal oxidation peak cannot be obtained through XRD scanning of the products, and the loading effect of the product loaded on SBA-15 is poor; the catalytic performance of the bimetallic oxide/SBA-15 composite catalyst cannot be predicted because any metal with a degrading effect on sulfonamides can be used for preparing the bimetallic oxide/SBA-15 composite catalyst, and the material found by the inventor is generated by continuous bimetallic combination and is obtained by measuring and judging the catalytic efficiency, the repeated use efficiency and the ion leaching rate in various aspects.
Claims (9)
1. Mn (manganese)2MoO4the/SBA-15 composite material is characterized in that: bimetallic oxide Mn2MoO4Mn loaded on the surface and in the pore channels of the molecular sieve SBA-15 and loaded on the surface2MoO4The grain diameter of the bimetal oxide is 20-50nm, and Mn in the pore channel2MoO4The grain diameter of the bimetal oxide is 8-12nm, and Mn2MoO4The total loading on SBA-15 was 20%.
2. An Mn as claimed in claim 12MoO4The preparation method of the/SBA-15 composite material is characterized by comprising the following steps: is (NH)4)6Mo7O24• 4H2O and C4H6MnO4• 4H2Dissolving O in concentrated hydrochloric acid, adding distilled water to form a mixed solution A, adding SBA-15 into the mixed solution A while stirring to form a mixed solution B, adding surfactant polyethylene glycol 4000 with the mass fraction of 10% -15% into the mixed solution B, forming a mixed solution C with the assistance of ultrasonic waves for 5min, heating and stirring the mixed solution C on a magnetic stirrer with the rotation speed of 100r/min to be pasty, stirring the mixed solution C at the temperature of 55 ℃, then drying the mixed solution in vacuum, grinding the mixed solution C, and calcining the mixed solution C at a high temperature.
3. An Mn as claimed in claim 22MoO4The preparation method of the/SBA-15 composite material is characterized by comprising the following steps: said (NH)4)6Mo7O24• 4H2O、C4H6MnO4• 4H2The dosage ratio of O and distilled water is as follows: 0.4461g, 1.2879g, 30mL, the concentration of concentrated hydrochloric acid is 11.48mol/L, and the volume ratio of concentrated hydrochloric acid to distilled water is 1: 3.
4. an Mn as claimed in claim 22MoO4The preparation method of the/SBA-15 composite material is characterized by comprising the following steps: the mass-volume ratio of the SBA-15 to the mixed liquid A is 1g:30-40 ml.
5. An Mn as claimed in claim 22MoO4The preparation method of the/SBA-15 composite material is characterized by comprising the following steps: the dosage ratio of the polyethylene glycol 4000 to the distilled water in the mixed solution A is 1-1.5: 10.
6. An Mn as claimed in claim 22MoO4The preparation method of the/SBA-15 composite material is characterized by comprising the following steps: said (NH)4)6Mo7O24• 4H2O and C4H6MnO4• 4H2Dissolving the O in concentrated hydrochloric acid, diluting with distilled water to obtain a mixed solution A, performing ultrasonic treatment for 10-20min, and performing ultrasonic treatment for 40-45 min when adding SBA-15 into the mixed solution A.
7. An Mn as claimed in claim 22MoO4The preparation method of the/SBA-15 composite material is characterized by comprising the following steps: the vacuum drying is to dry the pasty material in a vacuum drying oven with a constant temperature of 100 ℃ for 12 h.
8. An Mn as claimed in claim 22MoO4The preparation method of the/SBA-15 composite material is characterized by comprising the following steps: the high-temperature calcination is specifically to take out the dried material, cool the material, grind the material into powder, put the powder into a strip ceramic boat, and calcine the material in 700-900 ℃ air for 4-5 h in a tube furnace at a heating rate of 10 ℃/min.
9. Mn (manganese)2MoO4The preparation method of the/SBA-15 composite material is characterized by comprising the following steps:
(1) will be (NH)4)6Mo7O24• 4H2O and C4H6MnO4• 4H2Dissolving O in concentrated hydrochloric acid, adding distilled water, and ultrasonic dissolving for 10-20min to obtain mixed solution A, (NH)4)6Mo7O24• 4H2O、C4H6MnO4• 4H2The dosage ratio of O, concentrated hydrochloric acid and distilled water is 0.4461g, 1.2879g, 10mL and 30mL, and the concentration of the concentrated hydrochloric acid is 11.48 mol/L;
(2) adding SBA-15 into the mixed liquid A while stirring, and carrying out ultrasonic treatment for 40-45 min to form mixed liquid B, wherein the stirring speed is 100r/min, and the mass volume ratio of the SBA-15 to the mixed liquid A is 1g:30-40 mL;
(3) adding polyethylene glycol 4000 into the mixed solution B while stirring, and performing ultrasonic treatment for 5min to form a mixed solution C, wherein the ratio of the polyethylene glycol 4000 to the distilled water in the mixed solution A is 1-1.5: 10;
(4) placing the mixed solution C on a magnetic stirrer, heating and stirring until the suspension becomes pasty material;
(5) drying the pasty material in a vacuum drying oven at constant temperature of 100 ℃ for 12 h;
(6) and taking out the dried material, cooling, grinding into powder, putting into a strip-shaped ceramic boat, and calcining in a tube furnace at 700-900 ℃ for 4-5 h at a heating rate of 10 ℃/min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1048341A1 (en) * | 1999-04-26 | 2000-11-02 | Ford Global Technologies, Inc. | Catalyst made from a mixture of particles of platinum on alumina and manganese-zirconium composite oxide |
| CN101973590A (en) * | 2010-10-21 | 2011-02-16 | 北京师范大学 | Preparation method for small-size mesoporous metal oxide |
| CN105727984A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Ni/Mo bimetal oxide catalyst, preparation method and application thereof |
| CN108187659A (en) * | 2017-12-21 | 2018-06-22 | 万华化学集团股份有限公司 | Support type non-stoichiometric molybdenum tungsten bi-metal oxide catalyst and its application |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1048341A1 (en) * | 1999-04-26 | 2000-11-02 | Ford Global Technologies, Inc. | Catalyst made from a mixture of particles of platinum on alumina and manganese-zirconium composite oxide |
| CN101973590A (en) * | 2010-10-21 | 2011-02-16 | 北京师范大学 | Preparation method for small-size mesoporous metal oxide |
| CN105727984A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Ni/Mo bimetal oxide catalyst, preparation method and application thereof |
| CN108187659A (en) * | 2017-12-21 | 2018-06-22 | 万华化学集团股份有限公司 | Support type non-stoichiometric molybdenum tungsten bi-metal oxide catalyst and its application |
Non-Patent Citations (2)
| Title |
|---|
| Multiple regulations of Mn-based oxides in boosting peroxymonosulfate activation for norfloxacin removal;Jianan Li et al.;《Applied Catalysis A, General》;20190722;第584卷;第117170页 * |
| 钴锰双金属氧化物催化过硫酸氢钾降解酸性橙7的研究;徐浩 等;《中国环境科学》;20171231;第37卷(第8期);第2963-2969页 * |
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