CN111389391A - Ce doped-MnO2Preparation method and application of nanoparticles - Google Patents
Ce doped-MnO2Preparation method and application of nanoparticles Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title abstract description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims abstract description 19
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 238000010183 spectrum analysis Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910003144 α-MnO2 Inorganic materials 0.000 description 1
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- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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Abstract
The invention discloses Ce doped-MnO2The preparation method and the application of the nano-particles comprise the following steps: mixing ammonium ceric nitrate with MnSO4·H2Dissolving O in inorganic acid solution and stirring uniformly, wherein the cerium ammonium nitrate and the MnSO4·H2The molar ratio of O is (1: 2) - (3: 1); the second step is that: will be firstTransferring the solution after the one-step treatment to a microwave hydrothermal parallel synthesizer for synthesis reaction, cooling to room temperature after the reaction is finished, filtering, washing and drying the obtained product to obtain amorphous MnO2(ii) a The third step: to form amorphous MnO2Calcining in air atmosphere to obtain Ce doped-MnO2And (3) nanoparticles. The preparation method provided by the invention has the advantages of simple process, easily available raw materials, high yield, good repeatability, good medium and low temperature Catalytic activity and wide temperature window in Selective Catalytic Reduction (SCR) reaction, and high conversion rate.
Description
Technical Field
The invention relates to the field of synthesis of inorganic nano materials, in particular to Ce-doped-MnO2A preparation method and application of nano particles.
Background
Manganese dioxide (MnO)2) Is an important inorganic functional material and is widely applied to the industries of environmental protection, energy, chemical industry and the like at present. MnO2Having a plurality of crystal forms including-MnO2、α-MnO2、-MnO2And β -MnO2Etc., wherein-MnO2Is a twin crystal structure formed by the alternate growth of manganese oxygen octahedral tunnel structures of 1 × 1 and 1 × 22Has good oxidation-reduction performance, and can be used as a catalyst to be applied to the fields of environmental catalysis, synthetic catalysis and the like. According to the existing literature, MnO can be prepared by hydrothermal synthesis, coprecipitation and the like2A material. For example, Ding et al (advanced functional Materials,2006,16, 549-Surfynol 555) uses NaClO4As oxidant, three-dimensional multi-branch-MnO is prepared by hydrothermal synthesis method2(ii) a Cheng et al (Journal of Materials chemistry A,2016,4,16462-3The three-dimensional hexagonally-shaped MnO is synthesized by a hydrothermal synthesis method as an oxidant2(ii) a Shi et al (applied catalysis A: General,2012,433,206-213) in KMnO4Is an oxidizing agent and is used as a catalyst,adopts a coprecipitation method to obtain the-MnO with a three-dimensional flower shape2. MnO prepared by the above synthetic method2The material has a large particle size, the particle diameters are larger than 1 mu m, so that-MnO2The material has a low specific surface area, which results in still an unsatisfactory catalytic activity. Furthermore, MnO synthesized using a solution system2The thermal stability of the material is poor, and-MnO is easily caused2When high-temperature catalytic reaction is carried out, structural collapse occurs, and phase transition is carried out to β -MnO with poor activity2. The above problems cause-MnO2The material shows more general thermal catalytic activity and poorer stability, which greatly limits-MnO2The application of the material in the field of catalysis.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide Ce doped-MnO with simple preparation and good stability2A method for preparing nanoparticles.
Another object of the present invention is to provide Ce-doped-MnO2Ce doped-MnO prepared by nano particle preparation method2The nano-particles can be used as a catalyst for denitration treatment of boiler tail gas.
The invention is realized by the following technical scheme:
ce doped-MnO2A method for preparing nanoparticles, comprising the following steps,
the first step is as follows: mixing ammonium ceric nitrate with MnSO4·H2Dissolving O in inorganic acid solution and stirring uniformly, wherein the cerium ammonium nitrate and the MnSO4·H2The molar ratio of O is (1: 2) - (3: 1);
the second step is that: transferring the solution treated in the first step into a microwave hydrothermal parallel synthesizer for synthesis reaction, cooling to room temperature after the reaction is finished, filtering, washing and drying the obtained product to obtain amorphous MnO2；
The third step: calcining amorphous MnO2 in air atmosphere to obtain Ce doped-MnO2And (3) nanoparticles.
Further, the inorganic acid solution in the first step is hydrochloric acid, nitric acid or sulfuric acid.
Further, the molar concentration of the inorganic acid solution in the first step is 1.5 mol/L-3.0 mol/L.
Further, in the first step, the cerium ammonium nitrate and MnSO4·H2The molar ratio of O is 1: 2.
further, in the first step, the cerium ammonium nitrate and MnSO4·H2The molar ratio of O is 1: 1.
further, in the first step, the cerium ammonium nitrate and MnSO4·H2The molar ratio of O is 3: 1.
further, the temperature of the microwave hydrothermal reaction in the second step is 120-180 ℃, the reaction time is 5-20 min, and the working power is 200-400W.
Further, the calcining temperature in the third step is 250-400 ℃, and the calcining time is 2-3 h.
Further, Ce-doped-MnO obtained in the third step2The diameter of the nano-particles is 3 nm-5 nm.
Ce-doped-MnO2Ce doped-MnO prepared by nano particle preparation method2The nano-particles can be used as a catalyst for denitration treatment of boiler tail gas.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method has the advantages of simple process, easily obtained raw materials, high yield and good repeatability, and the prepared Ce doped-MnO2Nanoparticles having excellent thermal stability.
(2) MnO prepared by the invention2The material is an ultrafine nano particle which has uniform appearance, smaller size and larger specific surface area.
(3) Ce doped-MnO prepared by the invention2The nano-particles can be used as an SCR catalyst, show good medium-low temperature SCR catalytic activity and a wider temperature window, and have the conversion rate of 90 percent at 145 ℃ and the conversion rate of more than 90 percent at 145-395 ℃.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows Ce doped-MnO in example 1 of the present invention2Amorphous MnO prepared by preparation method of nano-particles2X-ray diffraction patterns of (a);
FIG. 2 shows Ce doped-MnO in example 1 of the present invention2Ce doped-MnO prepared by nano particle preparation method2An X-ray diffraction pattern of the nanoparticles;
FIG. 3 shows Ce doped-MnO in example 1 of the present invention2Ce doped-MnO prepared by nano particle preparation method2Scanning electron micrographs of nanoparticles;
FIG. 4 shows Ce doped-MnO in example 1 of the present invention2Ce doped-MnO prepared by nano particle preparation method2SCR catalytic performance plots of nanoparticles.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to Ce doped-MnO2A method for preparing nanoparticles, comprising the following steps,
the first step is as follows: mixing ammonium ceric nitrate with MnSO4·H2Dissolving O in inorganic acid solution, stirring, and mixing with ammonium ceric nitrate and MnSO4·H2The molar ratio of O is (1: 2) - (3: 1); the inorganic acid solution is hydrochloric acid, nitric acid or sulfuric acidThe molar concentration of the inorganic acid solution is 1.5 mol/L-3.0 mol/L cerium ammonium nitrate and MnSO4·H2The molar ratio of O may be 1: 2 or 1: 1 or 3: 1.
the second step is that: transferring the solution treated in the first step into a microwave hydrothermal parallel synthesizer for synthesis reaction, cooling to room temperature after the reaction is finished, filtering, washing and drying the obtained product to obtain amorphous MnO2(ii) a The temperature of the microwave hydrothermal reaction is 120-180 ℃, the reaction time is 5-20 min, and the working power is 200-400W.
The third step: calcining amorphous MnO2 in air atmosphere to obtain Ce doped-MnO2And (3) nanoparticles. The calcining temperature is 250-400 ℃, and the calcining time is 2-3 h. Obtained Ce-doped-MnO2The diameter of the nano-particles is 3 nm-5 nm.
Ce-doped-MnO2Ce doped-MnO prepared by nano particle preparation method2The nano-particles can be used as a catalyst for denitration treatment of boiler tail gas.
Example 1
1.0mmol of ceric ammonium nitrate and 2.0mmol of MnSO4·H2Dissolving O in 1.5 mol/L hydrochloric acid solution, stirring uniformly, transferring the solution to a microwave hydrothermal parallel synthesizer for reaction at 120 ℃, 5min for reaction and 200W for reaction, cooling to room temperature after the reaction is finished, filtering, washing and drying the obtained product, as shown in figure 1, according to the identification result of X-ray powder diffraction, the product is amorphous MnO2. Subjecting the amorphous MnO to2Calcining in air atmosphere at 250 ℃ for 2h to obtain Ce doped-MnO2And (3) nanoparticles. As shown in FIG. 2, from the results of X-ray powder diffraction, it was found that the manganese dioxide had a crystal form of-MnO2. As a result of the scanning electron microscope shown in FIG. 3, it can be seen that-MnO2The particles have uniform appearance and small size, the diameter of the particles is about 3-5 nm, and the particles are ultrafine nanoparticles. Further, as can be seen from the results of the energy spectrum analysis identified in Table 1 below, the Ce element was successfully doped into the Ce-doped-MnO2In the nano-particle crystal lattice, the Ce doped-MnO is successfully synthesized2Ultrafine nanoparticles.
Table 1: identification results of energy spectrum analysis
| Kind of element | Chemical symbol of elements | Elemental content (atomic ratio) |
| Oxygen gas | O | 59.61 |
| Manganese oxide | Mn | 37.29 |
| Cerium (Ce) | Ce | 3.09 |
Adding the above Ce-doped-MnO2Carrying out SCR catalytic reaction on the ultrafine nanoparticles, wherein the test conditions are as follows: the mixed gas contains 700ppm of NO and 700ppm of NH36.5% of O2Ar is used as the balance gas, the total flow of the gas is maintained at 700ml/min, and the corresponding space velocity is 280000h-1。
As can be seen from the SCR performance diagram shown in FIG. 4, under the test condition of high space velocity, the catalyst synthesized in example 1 shows good medium-low temperature SCR catalytic activity, the conversion rate reaches 90% at 145 ℃, and the conversion rate is maintained above 90% within the range of 145-395 ℃, and excellent SCR catalytic activity is shown.
Example 2
2.0mmol of ceric ammonium nitrate and 2.0mmol of MnSO4·H2Dissolving O in 2.0 mol/L nitric acid solution, stirring uniformly, transferring the solution to a microwave hydrothermal parallel synthesizer for synthesis reaction at 150 ℃, reacting for 10min and with the working power of 300W, cooling to room temperature after the reaction is finished, filtering, washing and drying the obtained product to obtain amorphous MnO2. To form amorphous MnO2Calcining in air atmosphere at the temperature of 300 ℃ for 2h to obtain the Ce doped-MnO 2 nano-particles. The results of the X-ray powder diffraction, the scanning electron microscope and the energy spectrum analysis thereof identified in this example are similar to those of example 1, and have the same effects.
Example 3
2.0mmol of ceric ammonium nitrate and 1.0mmol of MnSO4·H2Dissolving O in 2.5 mol/L sulfuric acid solution, stirring uniformly, transferring the solution to a microwave hydrothermal parallel synthesizer for synthesis reaction at 180 ℃, reacting for 15min and with the working power of 400W, cooling to room temperature after the reaction is finished, filtering, washing and drying the obtained product to obtain amorphous MnO2. To form amorphous MnO2Calcining in air atmosphere at 350 ℃ for 2.5h to obtain the Ce doped-MnO 2 nano-particles. The results of the X-ray powder diffraction, the scanning electron microscope and the energy spectrum analysis thereof identified in this example are similar to those of example 1, and have the same effects.
Example 4
3.0mmol of ceric ammonium nitrate and 1.0mmol of MnSO4·H2Dissolving O in 3.0 mol/L hydrochloric acid solution, stirring uniformly, transferring the solution to a microwave hydrothermal parallel synthesizer for synthesis reaction at 180 ℃, reacting for 20min and with the working power of 400W, cooling to room temperature after the reaction is finished, filtering, washing and drying the obtained product to obtain amorphous MnO2. To form amorphous MnO2Calcining in air atmosphere at 400 deg.C for 3 hr to obtain the final productTo Ce doped-MnO 2 nanoparticles. The results of the X-ray powder diffraction, the scanning electron microscope and the energy spectrum analysis thereof identified in this example are similar to those of example 1, and have the same effects.
Ce doped-MnO prepared by the invention2The ultrafine nanoparticles can be used as a selective catalytic reduction catalyst to be applied to denitration treatment of boiler tail gas, and show good medium-low temperature SCR catalytic performance and a wider temperature window.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. Ce doped-MnO2The preparation method of the nano-particles is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
the first step is as follows: mixing ammonium ceric nitrate with MnSO4·H2Dissolving O in inorganic acid solution and stirring uniformly, wherein the cerium ammonium nitrate and the MnSO4·H2The molar ratio of O is (1: 2) - (3: 1);
the second step is that: transferring the solution treated in the first step into a microwave hydrothermal parallel synthesizer for synthesis reaction, cooling to room temperature after the reaction is finished, filtering, washing and drying the obtained product to obtain amorphous MnO2；
The third step: calcining amorphous MnO2 in air atmosphere to obtain Ce doped-MnO2And (3) nanoparticles.
2. The Ce doped-MnO of claim 12The preparation method of the nano-particles is characterized by comprising the following steps: the inorganic acid solution in the first step is hydrochloric acid, nitric acid or sulfuric acid.
3. The Ce doped-MnO of claim 12The preparation method of the nano-particles is characterized in that the molar concentration of the inorganic acid solution in the first step is 1.5 mol/L-3.0 mol/L.
4. The Ce doped-MnO of claim 12The preparation method of the nano-particles is characterized by comprising the following steps: in the first step, the cerium ammonium nitrate and MnSO4·H2The molar ratio of O is 1: 2.
5. the Ce doped-MnO of claim 12The preparation method of the nano-particles is characterized by comprising the following steps: in the first step, the cerium ammonium nitrate and MnSO4·H2The molar ratio of O is 1: 1.
6. the Ce doped-MnO of claim 12The preparation method of the nano-particles is characterized by comprising the following steps: in the first step, the cerium ammonium nitrate and MnSO4·H2The molar ratio of O is 3: 1.
7. the Ce doped-MnO of claim 12The preparation method of the nano-particles is characterized by comprising the following steps: the temperature of the microwave hydrothermal reaction in the second step is 120-180 ℃, the reaction time is 5-20 min, and the working power is 200-400W.
8. The Ce doped-MnO of claim 12The preparation method of the nano-particles is characterized by comprising the following steps: the calcining temperature in the third step is 250-400 ℃, and the calcining time is 2-3 h.
9. The Ce doped-MnO of claim 12The preparation method of the nano-particles is characterized by comprising the following steps: Ce-doped-MnO obtained in the third step2The diameter of the nano-particles is 3 nm-5 nm.
10. The Ce-doped-MnO of any one of claims 1 to 92Ce doped-MnO prepared by nano particle preparation method2The nano-particles can be used as a catalyst for denitration treatment of boiler tail gas.
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