CN113769735A - CeO2/MnO2Composite photocatalyst and preparation method and application thereof - Google Patents

CeO2/MnO2Composite photocatalyst and preparation method and application thereof Download PDF

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CN113769735A
CN113769735A CN202111230253.4A CN202111230253A CN113769735A CN 113769735 A CN113769735 A CN 113769735A CN 202111230253 A CN202111230253 A CN 202111230253A CN 113769735 A CN113769735 A CN 113769735A
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ceo
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CN113769735B (en
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董林
于平平
邹伟欣
魏晓倩
濮钰
李婉芹
季稼伟
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Nanjing University
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Abstract

The invention discloses CeO2/MnO2A composite photocatalyst and a preparation method and application thereof, belonging to the technical field of functional materials. In the invention, MnO is added2Rod photocatalyst and Ce (NO)3)3·6H2O is synthesized into CeO with different loading amounts by a green simple solvothermal method2/MnO2Composite photocatalyst prepared by passing CeO2Nanoparticle pair MnO2The modification of the rod-shaped carrier prolongs the service life of a photon-generated carrier, improves the oxidation-reduction capability of the material, optimizes the acid-base property of the surface of the catalyst, is used for catalytically oxidizing toluene under a full spectrum, can promote the adsorption, activation and photocatalytic oxidation of more toluene molecules, and finally discharges carbon dioxide in an environment-friendly manner. The raw materials used in the invention are cheap, the method and the process are simple and convenient, and the prepared productCeO2/MnO2The composite photocatalyst has strong practicability and good economic benefit and environmental protection benefit.

Description

CeO2/MnO2Composite photocatalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to CeO2Nanoparticle modified MnO2A rod catalyst, a preparation method thereof and application of the catalyst in photocatalytic oxidation of toluene.
Background
Volatile Organic Compounds (VOCs) are atmospheric pollutants harmful to humans and their surrounding ecosystems, have certain irritation and toxicity to humans, and also cause photochemical smog, global warming, ozone layer destruction, and other hazards. The photocatalytic oxidation technology can effectively degrade trace VOCs pollutants in an environment-friendly and secondary-pollution-free manner under mild conditions, and has the advantage of efficiently removing VOCs pollutants in a short time. In recent years, the semiconductor manganese oxide (MnO)2) As a common catalyst active component, a certain pore channel structure can be formed, and the catalyst has a good application prospect in the aspect of eliminating VOCs. Cerium oxide (CeO)2) Due to the abundant content, low cost, no pollution and stable chemical property, the photocatalyst has attracted a certain attention in the aspect of photocatalytic oxidation of toluene.
At present, MnO2The application in photocatalysis has the following disadvantages: firstly, the light absorption wavelength range is narrow, and the sunlight utilization rate is low; secondly, the recombination rate of photon-generated carriers is high, and the quantum efficiency is low; thirdly, the nano catalyst is difficult to recover and has high loss. However, manganese oxide ore has a high defect structure and non-ideal matching property, has strong oxidation-reduction performance, has multiple Mn valence states, can release lattice oxygen, can be compounded with various transition metal ions, and has potential in the aspect of catalytic degradation of volatile organic pollutantsHas wide application foreground.
CeO2As a commonly used inorganic n-type semiconductor photocatalytic material, the band gap is wider and can only be excited by ultraviolet light; secondly, the internal charge transfer rate is low, the electron hole pair recombination rate is high, and the photon utilization rate in the photocatalytic chemical reaction process is low. However, Ce3+And Ce4+Flexible valence state switching between the CeO and the CeO2Has excellent oxidation-reduction performance and unique oxygen storage and release capacity, and attracts the attention of a plurality of researchers in the field of photocatalysis.
Thus, by CeO2Modifying MnO2The synergistic effect between the two components is utilized to promote the photocatalytic oxidation performance of the toluene. By constructing CeO2/MnO2The composite photocatalyst can effectively improve the light absorption performance of the composite material and the rapid separation and transfer of photo-generated charges, and can also enhance the photo-oxidation capacity of the composite material. The concrete points are as follows: (1) CeO (CeO)2/MnO2The composite photocatalyst can effectively utilize MnO as a carrier2The rod has larger specific surface area and provides more active sites; (2) effectively enhances the light absorption capacity, reduces the recombination probability of photo-generated electrons and holes, and improves the oxidation capacity of the catalyst. However, to date, there has been no CeO2Modifying MnO2The preparation of the nanorod composite photocatalyst and the research report of the nanorod composite photocatalyst in photocatalytic oxidation of toluene.
Disclosure of Invention
In view of the above problems in the prior art, a first technical problem to be solved by the present invention is to provide CeO2/MnO2A preparation method of the composite photocatalyst; the second technical problem to be solved by the invention is to provide the CeO prepared by the method2/MnO2A composite photocatalyst; the third technical problem to be solved by the present invention is to provide CeO2/MnO2The application of the composite photocatalyst in catalytic oxidation of toluene.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
CeO (CeO)2/MnO2Preparation method of composite photocatalystThe method comprises the following steps:
1) mixing MnSO4·H2O、KMnO4Placing the mixture into a high-pressure kettle according to the mass ratio of 2.48: 1.66, adding ultrapure water, and carrying out constant-temperature thermal reaction; naturally cooling to room temperature after the reaction is finished, centrifugally washing and drying by using ultrapure water, calcining the obtained dried sample, cooling to room temperature after the calcination is finished, taking out a product, and grinding to obtain MnO2A rod photocatalyst;
2) under the condition of room temperature, MnO is added2Rod photocatalyst and Ce (NO)3)3·6H2O is respectively and slowly added into the mixed liquid of the ultrapure water and the acetic acid according to the mass ratio of 0.5: 0.156-0.936; fully stirring for 0.2-1h, and uniformly mixing to obtain a dispersion E, F;
3) dropwise adding the dispersion liquid F into the dispersion liquid E, fully stirring for 0.5h after dropwise adding, heating and stirring the mixed liquid at constant temperature until the mixed liquid is evaporated to dryness, and transferring the mixed liquid into a drying box for drying; placing the obtained dry sample in a muffle furnace for calcining, cooling to room temperature after calcining, taking out the product, and grinding to obtain CeO2/MnO2A photocatalyst material.
Further, in the step 1), the isothermal thermal reaction is kept at 160 ℃ for 4 hours.
Further, in the step 1), the drying temperature is 110 ℃, and the drying time is 12 h.
Further, in step 1), the obtained dried sample was calcined at 300 ℃ for 6 h.
Further, in the step 2), MnO is added at room temperature2Rod photocatalyst and Ce (NO)3)3·6H2O is slowly added into the mixed liquid of the ultrapure water and the acetic acid respectively according to the mass ratio of 0.5: 0.312, and the volume ratio of the ultrapure water to the acetic acid is 20: 1; stirring thoroughly for 0.5h and mixing well to obtain dispersion E, F.
Further, in the step 3), the constant temperature heating mode is oil bath, and the constant temperature heating temperature is 110 ℃.
Further, in the step 3), the drying temperature is 110 ℃, and the drying time is 12 hours.
Further, in step 3), the obtained dried sample is placed in a muffle furnace to be calcined at 350 ℃ for 3 h.
CeO prepared by the above method2Nanoparticle modified MnO2A rod catalyst.
The CeO2Nanoparticle modified MnO2The use of a rod catalyst for the catalytic oxidation of toluene.
Compared with the prior art, the invention has the beneficial effects that:
1) CeO prepared by the invention2/MnO2The photocatalyst has the advantages of green and simple preparation process, low cost, environmental protection and easy large-scale industrial production, and the heterojunction material has excellent environmental stability and potential application prospect in the aspect of catalyzing and eliminating indoor low-concentration volatile organic pollutants.
2) CeO prepared by the invention2/MnO2Composite photocatalyst with Ce simultaneously3+、Ce4+In which Ce is3+And Ce4+Is in the form of a reversible electron pair, which can extend the lifetime of the charge; ce4+Capable of trapping electrons to prevent rapid recombination of electron-hole pairs; ce3+The oxidation capability of the catalyst can be improved, so that the catalytic oxidation degradation of toluene under visible light can be realized.
3) CeO prepared by the invention2/MnO2The composite photocatalyst can be used as a photocatalyst with excellent performance. CeO (CeO)2And MnO with MnO2The synergistic effect generated by coupling is beneficial to enhancing the adsorption/activation of the reactant toluene molecules, improving the utilization rate of visible light, promoting the transmission of photo-generated charges and the catalytic oxidation capacity and finally effectively improving the photocatalytic performance of the composite catalytic material. Thus, CeO2/MnO2The composite photocatalyst has wide prospect in the field of photocatalytic elimination of atmospheric pollutants.
Drawings
FIG. 1 is an XRD and FT-IR spectrum of the prepared sample; in the figure, (a) is an XRD spectrum; (b) is FT-IR spectrum;
FIG. 2 is a UV-vis DRS spectrum of the prepared sample;
FIG. 3 is a TEM spectrum of the prepared sample (a)A pure manganese oxide support; (b) cerium oxide; (c) 10% CeO2/MnO2；(d)10％CeO2/MnO2HRTEM image of (A);
FIG. 4(a) is a photo-amperometric graph of the prepared sample; FIG. 4(b) is an impedance spectrum of the prepared sample;
FIG. 5 is a graph of the oxidation performance of the prepared samples on toluene under full spectrum illumination.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
(1)MnO2Preparation of nanorods
2.48g of hydrated manganese sulfate (MnSO)4·H2O), 1.66g potassium permanganate (KMnO)4) Placing the mixture into a 150mL stainless steel autoclave with a polytetrafluoroethylene inner container, adding 75mL ultrapure water, and carrying out constant temperature thermal reaction at 160 ℃ for 4 hours; naturally cooling to room temperature after the reaction is finished, centrifugally washing for 3 times by using ultrapure water, and drying the obtained sample for 12 hours at the constant temperature of 110 ℃; calcining the obtained dried sample in a muffle furnace at 300 ℃ for 6h, cooling to room temperature after calcination, taking out the product, and grinding to obtain MnO2And (5) storing the nanorods for later use.
(2) Preparation of 5% CeO2/MnO2Composite material
Under room temperature conditions, 0.5g of MnO2Slowly adding the rod into a mixed solution (volume ratio is 20: 1) of 40mL of ultrapure water and 2mL of acetic acid, and fully stirring for 0.5h until the mixture is uniformly mixed to obtain a dispersion liquid E; then 0.156g of Ce (NO) is proportionally mixed3)3·6H2Slowly adding O into the mixed solution (the volume ratio is 20: 1) of another portion of ultrapure water of 20mL and acetic acid of 1mL, and fully stirring for 0.5h until the mixture is dissolved to obtain a dispersion liquid F; dropwise adding the dispersion liquid F into the dispersion liquid E, fully stirring for 0.5h after dropwise adding, uniformly mixing reactants, transferring the reaction liquid into a beaker, heating and stirring at the constant temperature of 110 ℃ until evaporation is carried out, and transferring the reaction liquid into an oven to dry for 12h at the constant temperature of 110 ℃; calcining the obtained dried sample in a muffle furnace at 350 ℃ for 3h, cooling to room temperature after calcination, taking out the product, and grinding to obtain the CeO with the load of 5%2/MnO2Photocatalyst and process for producing the sameA material.
Example 2
(1)MnO2Preparation of nanorods
2.48g of hydrated manganese sulfate (MnSO)4·H2O), 1.66g potassium permanganate (KMnO)4) Placing the mixture into a 150mL stainless steel autoclave with a polytetrafluoroethylene inner container, adding 75mL ultrapure water, and carrying out constant temperature thermal reaction at 160 ℃ for 4 hours; naturally cooling to room temperature after the reaction is finished, centrifugally washing for 3 times by using ultrapure water, and drying the obtained sample for 12 hours at the constant temperature of 110 ℃; calcining the obtained dried sample in a muffle furnace at 300 ℃ for 6h, cooling to room temperature after calcination, taking out the product, and grinding to obtain MnO2And (5) storing the nanorods for later use.
(2) Preparation of CeO with 10% of load2/MnO2Composite material
Under room temperature conditions, 0.5g of MnO2Slowly adding the rod into a mixed solution (volume ratio is 20: 1) of 40mL of ultrapure water and 2mL of acetic acid, and fully stirring for 0.5h until the mixture is uniformly mixed to obtain a dispersion liquid E; then 0.312g of Ce (NO) is proportionally mixed3)3·6H2Slowly adding O into the mixed solution (volume ratio is 20: 1) of another portion of ultrapure water of 20mL and acetic acid of 1mL, and fully stirring for 0.5h until the mixture is dissolved to obtain a dispersion liquid F; dropwise adding the dispersion liquid F into the dispersion liquid E, fully stirring for 0.5h after dropwise adding, uniformly mixing reactants, transferring the reaction liquid into a beaker, heating and stirring at the constant temperature of 110 ℃ until evaporation is carried out, and transferring the reaction liquid into an oven to dry for 12h at the constant temperature of 110 ℃; calcining the obtained dried sample in a muffle furnace at 350 ℃ for 3h, cooling to room temperature after calcination, taking out the product, and grinding to obtain the CeO with the load of 10%2/MnO2A photocatalyst material.
Example 3
(1)MnO2Preparation of nanorods
2.48g of hydrated manganese sulfate (MnsO)4·H2O), 1.66g potassium permanganate (KMnO)4) Placing the mixture into a 150mL stainless steel autoclave with a polytetrafluoroethylene inner container, adding 75mL ultrapure water, and carrying out constant temperature thermal reaction at 160 ℃ for 4 hours; naturally cooling to room temperature after the reaction is finished, centrifugally washing for 3 times by using ultrapure water, and drying the obtained sample for 12 hours at the constant temperature of 110 ℃; drying the obtained powderCalcining the dried sample in a muffle furnace at 300 ℃ for 6h, cooling to room temperature after calcination, taking out the product, and grinding to obtain MnO2And (5) storing the nanorods for later use.
(2) Preparation of 30% CeO2/MnO2Composite material
Under room temperature conditions, 0.5g of MnO2Slowly adding the rod into a mixed solution (volume ratio is 20: 1) of 40mL of ultrapure water and 2mL of acetic acid, and fully stirring for 0.5h until the mixture is uniformly mixed to obtain a dispersion liquid E; then 0.936g of Ce (NO) is proportionally mixed3)3·6H2Slowly adding O into the mixed solution (volume ratio is 20: 1) of another portion of ultrapure water of 20mL and acetic acid of 1mL, and fully stirring for 0.5h until the mixture is dissolved to obtain a dispersion liquid F; dropwise adding the dispersion liquid F into the dispersion liquid E, fully stirring for 0.5h after dropwise adding, uniformly mixing reactants, transferring the reaction liquid into a beaker, heating and stirring at the constant temperature of 110 ℃ until evaporation is carried out, and transferring the reaction liquid into an oven to dry for 12h at the constant temperature of 110 ℃; calcining the obtained dried sample in a muffle furnace at 350 ℃ for 3h, cooling to room temperature after calcination, taking out the product, and grinding to obtain the CeO with the load of 30%2/MnO2A photocatalyst material.
Comparative example 1MnO2Preparation of nanorods
2.48g of hydrated manganese sulfate (MnSO)4·H2O), 1.66g potassium permanganate (KMnO)4) Placing the mixture into a 150mL stainless steel autoclave with a polytetrafluoroethylene inner container, adding 75mL ultrapure water, and carrying out constant temperature thermal reaction at 160 ℃ for 4 hours; naturally cooling to room temperature after the reaction is finished, centrifugally washing for 3 times by using ultrapure water, and drying the obtained sample for 12 hours at the constant temperature of 110 ℃; calcining the obtained dried sample in a muffle furnace at 300 ℃ for 6h, cooling to room temperature after calcination, taking out the product, and grinding to obtain MnO2And (5) storing the nanorods for later use.
Comparative example 2CeO2Preparation of nanoparticles
A certain mass of Ce (NO)3)3·6H2Calcining O in a muffle furnace at 350 ℃ for 3h, cooling to room temperature after calcination, taking out the product, and grinding to obtain CeO2And (5) storing the nanoparticles for later use.
The sample was characterized by X-ray diffraction (XRD), fourier-infrared spectroscopy (FT-IR), ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), and Transmission Electron Microscopy (TEM), with the following results:
MnO can be seen from the XRD pattern of the prepared sample2The characteristic peaks of the rod catalyst support are quite distinct. With CeO2Increase in nanoparticle loading, CeO2Gradually increased in diffraction peak intensity of (1), MnO2Does not change, indicating that CeO2The nanoparticles are supported in such a way that MnO is not deeply or destructively supported on the surface2The crystal lattice of the support. The FT-IR spectrum of the prepared sample shows that hydroxyl, carbon species and the like are adsorbed on the surface of the sample.
In the UV-vis DRS spectrum of FIG. 2, the absorption intensities of the prepared sample to different wavelengths reflect the absorption capacity of the sample to light. With respect to CeO2Sample, Compound CeO2/MnO2The light absorption capacity of the light-absorbing material is greatly improved.
In the TEM spectrum of FIG. 3, MnO2Rod-like structure of photocatalyst and CeO2The appearance of the nano-scale particles is clearly displayed. By comparing 10% CeO in FIG. (d)2/MnO2In the HRTEM image of (1), d-0.24 nm corresponds to MnO2(211) crystal face of the rod photocatalyst, d ═ 0.31nm corresponding to CeO2The (111) crystal face of the nanoparticles fully confirms the CeO2Nanoparticles in MnO2Successful loading on the nanorods.
Fig. 4(a) is a photo-amperometric graph of the prepared sample, the photo-current intensity corresponding to the separation efficiency of photo-generated holes and charges of the sample. By comparison of photocurrent intensity between different samples, 10% CeO2/MnO2Shows the strongest photocurrent intensity, indicating 10% CeO2/MnO2The catalyst has optimal photoproduction hole and electron separation efficiency, and is beneficial to improving the photocatalytic oxidation toluene reaction activity of the sample, which is consistent with the oxidation toluene performance diagram result of the prepared sample shown in the figure 5; FIG. 4(b) is an impedance spectrum of 5% CeO of the prepared sample2/MnO2Shows the minimum Nyquist radius, indicated at 5% CeO2/MnO2With minimal ac impedance during the reaction.
FIG. 5 is a graph of the oxidation performance of toluene under full spectrum illumination of the prepared samples, showing the conversion of toluene under full spectrum illumination of a xenon lamp in mobile phase toluene gas (50 ppm). CeO (CeO)2/MnO2The toluene conversion rate of the compound is far higher than that of pure CeO2Nanoparticles, and meanwhile, the comparison of the conversion rate of toluene among samples with different loading amounts can find that the activity shows a variation trend similar to 'rising before falling' of volcano chart. Wherein, 10% of CeO2/MnO2The highest toluene conversion was exhibited. Compared with MnO2Toluene Oxidation Activity of rods, 10% CeO2/MnO2Besides higher toluene conversion rate, the catalyst also shows more excellent structural stability, and can keep high reaction activity for a longer time in the reaction process. By CeO2Nanoparticles and MnO2The coupling of the rods can greatly improve the performance of deep oxidation toluene of the photocatalytic material.
The results show that CeO2Nanoparticle pair MnO2The modification of the rod promotes the coupling between the two, the formed heterojunction structure fully utilizes the synergistic effect between the two, and the activity and the performance stability of the oxidized toluene are greatly improved by improving the light absorption rate and the separation efficiency of photon-generated carriers. The catalyst can realize high-efficiency and high-stability conversion of low-concentration methylbenzene under the normal temperature condition, the conversion rate is kept at 86.80-87.78%, effective utilization of light energy is realized, the high sensitivity to low-concentration pollutants enables the application scenes of the catalyst to be wider, and high-efficiency clean conversion of indoor pollutants can be realized.

Claims (10)

1. CeO (CeO)2/MnO2The preparation method of the composite photocatalyst is characterized by comprising the following steps:
1) mixing MnSO4·H2O、KMnO4Placing the mixture into a high-pressure kettle according to the mass ratio of 2.48: 1.66, adding ultrapure water, and carrying out constant-temperature thermal reaction; after the reaction is finished, naturally cooling to room temperature, and using ultrapure waterCentrifugally washing and drying, calcining the obtained dried sample, cooling to room temperature after calcination, taking out the product, and grinding to obtain MnO2A rod photocatalyst;
2) under the condition of room temperature, MnO is added2Rod photocatalyst and Ce (NO)3)3·6H2O is respectively and slowly added into the mixed liquid of the ultrapure water and the acetic acid according to the mass ratio of 0.5: 0.156-0.936; fully stirring for 0.2-1h, and uniformly mixing to obtain a dispersion E, F;
3) dropwise adding the dispersion liquid F into the dispersion liquid E, fully stirring for 0.5h after dropwise adding, heating and stirring the mixed liquid at constant temperature until the mixed liquid is evaporated to dryness, and transferring the mixed liquid into a drying box for drying; placing the obtained dry sample in a muffle furnace for calcining, cooling to room temperature after calcining, taking out the product, and grinding to obtain CeO2/MnO2A composite photocatalyst is provided.
2. The CeO of claim 12/MnO2The preparation method of the composite photocatalyst is characterized in that in the step 1), the constant-temperature thermal reaction is kept for 4 hours at a constant temperature of 160 ℃.
3. The CeO of claim 12/MnO2The preparation method of the composite photocatalyst is characterized in that in the step 1), the drying temperature is 110 ℃, and the drying time is 12 hours.
4. The CeO of claim 12/MnO2The preparation method of the composite photocatalyst is characterized in that in the step 1), the obtained dried sample is calcined for 6 hours at 300 ℃.
5. The CeO of claim 12/MnO2The preparation method of the composite photocatalyst is characterized in that MnO is added under the room temperature condition in the step 2)2Rod photocatalyst and Ce (NO)3)3·6H2O is slowly added into the mixed liquid of the ultrapure water and the acetic acid respectively according to the mass ratio of 0.5: 0.312, and the volume ratio of the ultrapure water to the acetic acid is 20: 1; fully stirring for 0.5h and mixingThe mixture was homogenized to obtain a dispersion E, F.
6. The CeO of claim 12/MnO2The preparation method of the composite photocatalyst is characterized in that in the step 3), the constant-temperature heating mode is oil bath, and the constant-temperature heating temperature is 110 ℃.
7. The CeO of claim 12/MnO2The preparation method of the composite photocatalyst is characterized in that in the step 3), the drying temperature is 110 ℃, and the drying time is 12 hours.
8. The CeO of claim 12/MnO2The preparation method of the composite photocatalyst is characterized in that in the step 3), the obtained dried sample is placed in a muffle furnace to be calcined for 3 hours at the temperature of 350 ℃.
9. CeO prepared by the method of any one of claims 1 to 82/MnO2A composite photocatalyst is provided.
10. The CeO of claim 92/MnO2The application of the composite photocatalyst in catalytic oxidation of toluene.
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