CN112642421B - MnCeO X Metal oxide and method for producing the same - Google Patents
MnCeO X Metal oxide and method for producing the same Download PDFInfo
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 143
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 143
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 230000005855 radiation Effects 0.000 claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 67
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000002604 ultrasonography Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 15
- 239000001301 oxygen Substances 0.000 abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 abstract description 15
- 239000003054 catalyst Substances 0.000 description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002351 wastewater Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
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- CQPFMGBJSMSXLP-ZAGWXBKKSA-M Acid orange 7 Chemical compound OC1=C(C2=CC=CC=C2C=C1)/N=N/C1=CC=C(C=C1)S(=O)(=O)[O-].[Na+] CQPFMGBJSMSXLP-ZAGWXBKKSA-M 0.000 description 7
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- 238000005457 optimization Methods 0.000 description 3
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- -1 Mn 2+ Chemical class 0.000 description 1
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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
- B01J23/002—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
-
- B01J35/40—
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention provides a MnCeO x A metal oxide and a preparation method thereof. The preparation method of the metal oxide comprises the following steps: dissolving Mn salt and Ce salt which are precursors of metal oxide in water to obtain a mixture A, then carrying out catalytic oxidation on the mixture A by using low-frequency ultrasonic radiation of 20kHz-40kHz for 15min, and adding a precipitant solution into the mixture A subjected to the low-frequency ultrasonic radiation to obtain a mixture B; and (3) carrying out solid-liquid separation, drying and roasting on the mixture B to obtain the metal oxide. In the metal oxide, ce 4+ With Ce 3+ The ratio of (C) to (C) is 3-4:1, mn 4+ With Mn 3+ The ratio of (2) is 1.7-2.4:1. The preparation method can effectively adjust MnCeO x Ce in metal oxide 4+ /Ce 3+ 、Mn 4+ /Mn 3+ Optimizing the surface active oxygen component and improving the MnCeO x Catalytic performance of metal oxides.
Description
Technical Field
The invention belongs to the field of novel material preparation, and in particular relates to MnCeO x A metal oxide and a preparation method thereof.
Background
The transition metal-rare earth metal oxide composite is a high-efficiency catalyst and can be used for catalyzing, oxidizing and decomposing pollutants in the environment. Wherein MnCeO x Is of great interest. The catalyst obtained by different preparation methods has huge difference in structure and performance.
The prior art improves the catalytic performance of the transition metal-rare earth metal oxide composite from the perspective of optimizing the particle size of the catalyst. For example, ultrasonic-assisted coprecipitation is currently of great concern; the ultrasonic-assisted coprecipitation method is a novel efficient catalyst preparation method, and can shorten the catalyst preparation time and improve the catalyst particle size to be more uniform and smaller. The ultrasonic wave assisted preparation of the catalyst utilizes the mechanical effect of the ultrasonic wave, and can promote better dispersion, thereby obtaining more uniform catalyst particles.
It has not been found that by optimizing MnCeO x The ratio of Mn ions to Ce ions in each valence state can improve MnCeO x The report of catalytic activity is not found, but rather the report that the optimization of the ratio of Mn ions to Ce ions in each valence state in MnCeOx can be achieved by introducing low-frequency ultrasound for a specific time.
Disclosure of Invention
The invention aims to provide a method for effectively adjusting MnCeO x The ratio relation of Ce (IV)/Ce (III) and Mn (IV)/Mn (III) in the metal oxide optimizes the MnCeO of the surface active oxygen component x A method for producing a metal oxide; mnCeO prepared by the preparation method x The metal oxide is preferably used as a catalyst.
In order to achieve the above object, the present invention provides a MnCeO x A method for producing a metal oxide, wherein the method comprises:
1) Dissolving Mn salt and Ce salt which are precursors of metal oxide in water to obtain a mixture A, adding a precipitant solution into the mixture A, and carrying out catalytic oxidation by using low-frequency ultrasonic radiation for 13-17min to obtain a mixture B; the frequency of the low-frequency ultrasonic wave is 20kHz-48kHz;
2) Solid-liquid separation, drying and roasting of the mixture B to obtain the MnCeO x A metal oxide.
In the above preparation method, preferably, the time of the low-frequency ultrasonic irradiation is 15min. The optimization effect of the ratio relation of Ce (IV)/Ce (III) and Mn (IV)/Mn (III) of low-frequency ultrasonic radiation for 15min is better, and the prepared MnCeO x The catalytic performance of the metal oxide is better.
In the above preparation method, the frequency of the low-frequency ultrasonic wave is preferably 20 to 40kHz, for example 28kHz. Too high and too low frequency ultrasound is unfavorable for realizing the catalytic oxidation reaction initiated by the low frequency ultrasound, however, the different frequencies of the low frequency ultrasound in the usable frequency range have no obvious influence on the adjustment of the ratio relationship of Ce (IV)/Ce (III) and Mn (IV)/Mn (III).
In the above preparation method, preferably, the concentration of Mn salt in the mixture A is 0.1 to 0.4mol/L.
In the above preparation method, the concentration of Ce salt in the mixture A is preferably 0.1 to 0.4mol/L.
In the above preparation method, preferably, the molar ratio of Mn in the Mn salt to Ce in the Ce salt is 1:1.
In the above preparation method, preferably, the Mn salt includes a divalent Mn salt and KMnO 4 At least one of (a) and (b); wherein the divalent Mn salt can be MnCl 2 But is not limited thereto.
In the above preparation method, preferably, the Ce salt includes CeCl 4 。
In the above preparation method, preferably, the concentration of the precipitant in the precipitant solution is 0.5 to 2mol/L; for example 1mol/L.
In the above preparation method, preferably, the amount of the precipitant solution is such that the precipitant solution is added to the mixture a until the pH of the mixture of the two (i.e., the mixture of the precipitant solution and the mixture a after the low-frequency ultrasonic irradiation) is 11. In a preferred embodiment, 1mol/L sodium hydroxide solution is used as precipitant solution, the volume ratio of precipitant solution to mixture A being 1:50.
In the above preparation method, preferably, the precipitant includes at least one of NaOH and KOH; more preferably NaOH.
In the above preparation method, preferably, the precipitant solution is added dropwise.
In the above preparation method, preferably, the mixture B is subjected to an aging treatment before being subjected to solid-liquid separation; more preferably, the high frequency ultrasonic radiation is continuously applied during the aging treatment; wherein the frequency of the high-frequency ultrasonic wave is 100-800kHz; further preferably, the high frequency ultrasonic radiation is applied for 45min to 4h; most preferably, the high frequency ultrasonic radiation is applied for 45 minutes. High-frequency ultrasonic waves are introduced in the aging treatment stage of catalyst preparation, so that the average particle size can be effectively controlled, and the nano-sized catalyst with uniformly dispersed average particle size is prepared.
In one embodiment, the preparation method comprises the following steps:
1) Dissolving Mn salt and Ce salt which are precursors of metal oxide in water to obtain a mixture A, dropwise adding a precipitant solution into the mixture A until the pH value of the mixture A is 11, and then carrying out catalytic oxidation by using low-frequency ultrasonic radiation of 20kHz-40kHz for 15min to obtain a mixture B;
wherein the molar ratio of Mn in the Mn salt to Mn in the Ce salt is 1:1; the concentration of Mn salt in the mixture A is 0.1-0.4mol/L; the concentration of Ce salt in the mixture A is 0.1-0.4mol/L; the concentration of the precipitant in the precipitant solution is 1mol/L; wherein, the liquid crystal display device comprises a liquid crystal display device,
mn salt is MnCl 2 And KMnO 4 At least one of (a) and (b); ce salt is CeCl 4 The method comprises the steps of carrying out a first treatment on the surface of the The precipitant is NaOH;
2) Aging the mixture B for 45min, continuously applying high-frequency ultrasonic radiation of 100-800kHz during the aging treatment, and carrying out solid-liquid separation, drying and roasting on the aged mixture B to obtain the MnCeO x A metal oxide; the MnCeO x The average particle diameter of the metal oxide is nano-sized.
In the above-described production method, it is preferable that the average particle diameter of the produced MnCeOx metal oxide is controlled by controlling the frequency of high-frequency ultrasonic waves when high-frequency ultrasonic radiation is applied, specifically:
when the frequency of high-frequency ultrasonic is controlled to be not lower than 100kHz, the prepared MnCeO x The average particle size of the metal oxide is not more than 420nm;
when the frequency of high-frequency ultrasonic is controlled to be not lower than 200kHz, the prepared MnCeO x The average particle size of the metal oxide is not more than 300nm;
when the frequency of high-frequency ultrasonic is controlled to be not lower than 300kHz, the prepared MnCeO x The average particle size of the metal oxide is not more than 270nm;
when the frequency of high-frequency ultrasonic is controlled to be not lower than 500kHz, the prepared MnCeO x The average particle size of the metal oxide is not more than 190nm;
when the frequency of high-frequency ultrasonic is controlled to be not lower than 800kHz, the prepared MnCeO x The average particle diameter of the metal oxide is not more than 90nm.
More preferably, when the frequency of the high frequency ultrasound is to be appliedWhen the rate is controlled between 100kHz and 200kHz, the prepared MnCeO x The average particle size of the metal oxide is 420nm-300nm; when the frequency of high-frequency ultrasonic wave is controlled between 200kHz and 300kHz, the prepared MnCeO x The average particle size of the metal oxide is 300nm-270nm; when the frequency of high-frequency ultrasonic wave is controlled between 300kHz and 500kHz, the prepared MnCeO x The average particle size of the metal oxide is 270nm-190nm; when the frequency of high-frequency ultrasonic is controlled to be 500-800kHz, the average particle size of the prepared MnCeOx metal oxide is 190-90 nm.
Further preferably, when the frequency of the high-frequency ultrasonic wave is controlled to 100kHz, mnCeO is prepared x The average particle size of the metal oxide is 420nm; when the frequency of high-frequency ultrasonic wave is controlled at 200kHz, the prepared MnCeO x The average particle diameter of the metal oxide is 300nm; when the frequency of high-frequency ultrasonic wave is controlled at 300kHz, the prepared MnCeO x The average particle diameter of the metal oxide is 270nm; when the frequency of high-frequency ultrasonic wave is controlled at 500kHz, the prepared MnCeO x The average particle diameter of the metal oxide is 190nm; when the frequency of high-frequency ultrasonic wave is controlled at 800kHz, the prepared MnCeO x The average particle diameter of the metal oxide was 90nm.
The above preferred scheme gives the frequency selection basis of high-frequency ultrasound for the first time, and realizes the selection of proper high-frequency ultrasound frequency according to the requirement on the average particle size of the prepared product.
In the above preparation method, preferably, the intensity of the low-frequency ultrasound is 3.0-12W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the intensity of the low-frequency ultrasound is 3.0-8.0W/cm 2 . The application of relatively high intensity low frequencies is more advantageous for low frequency ultrasound initiated catalytic oxidation reactions.
In the above preparation method, preferably, the intensity of the high-frequency ultrasonic wave is 0.5 to 1.5W/cm 2 。
In the above preparation method, preferably, the baking temperature is 500 ℃.
In the above preparation method, preferably, the baking time is 4 to 12 hours, for example, 4 hours.
In the above preparation method, the temperature of the drying may be 120 ℃, but is not limited thereto.
In the above preparation method, the drying time may be 12 hours, but is not limited thereto.
In the above preparation method, deionized water may be selected as the water in step 1), but is not limited thereto.
In the above preparation method, the solid-liquid separation may be achieved by means of centrifugation, but is not limited thereto.
In the above preparation method, after the solid-liquid separation, the solid product after the solid-liquid separation may be washed before drying, and in a preferred embodiment, washing is performed with distilled water for not less than 3 times.
In the above preparation method, preferably, the method further comprises the step of adding the MnCeO x The metal oxide is ground.
The invention also provides MnCeO prepared by the preparation method x A metal oxide, wherein the MnCeO x Ce of metal oxide 4+ With Ce 3+ The ratio of (C) to (C) is 3-4:1, mn 4+ With Mn 3+ The ratio of (2) is 1.7-2.4:1.
Above MnCeO x Among the metal oxides, preferably, the average particle diameter of the metal oxide is not more than 420nm; more preferably, the average particle size is not more than 300nm; further preferably, the average particle diameter is not more than 270nm; still more preferably, the average particle size is not more than 190nm; most preferably, the average particle size is not greater than 90nm.
Above MnCeO x Among the metal oxides, the metal oxide preferably has an average particle diameter of 420nm to 300nm; more preferably, the average particle diameter is 300nm to 270nm; further preferably, the average particle diameter is preferably 270nm to 190nm; still more preferably, the average particle diameter is 190nm to 90nm.
Above MnCeO x Among the metal oxides, the metal oxide preferably has an average particle diameter of 420nm; more preferably, the average particle diameter is 300nm; further preferably, the average particle diameter is 270nm; still more preferably, the average particle diameter is 190nm; most preferably, the average particle size is 90nm.
The inventionMing provides a preparation method for realizing MnCeO by means of low-frequency ultrasonic x Adjusting the ratio relation of Ce (IV)/Ce (III) and Mn (IV)/Mn (III) in the metal oxide, and optimizing the surface active oxygen component; the high intensity of ultrasonic energy at low frequency causes the cleavage of water molecules to form strong oxidants such as hydroxyl radicals and hydrogen peroxide, thereby initiating oxidation reactions which can be enhanced by the presence of metal oxide particles in the solution as catalysts. During the preparation of the catalyst, ultrasonic wave is introduced to bring about an autocatalytic effect (in other words, catalytic oxidation reaction occurs simultaneously during the preparation, and the added metal oxide reacts differently under the action of the ultrasonic wave than without the ultrasonic wave, so that the valence state of the prepared product changes, in MnCeO x In (i.e. initially added Mn ions, ce ions (e.g. Mn 2+ ,Mn 7+ ,Ce 4+ ) Oxidation-reduction reaction is carried out, and Mn ions and Ce ions with different proportions and different valence states are generated. By these valence and ratio changes, catalysts with different activities are brought, and the low frequency ultrasound time is a core factor affecting the ion ratio of different valence states.
The preparation method provided by the invention focuses on adjusting MnCeO x The ratio relation of Ce (IV)/Ce (III) and Mn (IV)/Mn (III) in the metal oxide optimizes the surface active oxygen component, and provides a brand new MnCeO x A method for preparing metal oxide. The technical scheme provided by the invention realizes the adjustment of the proportional relation of Ce (IV)/Ce (III) and Mn (IV)/Mn (III) by regulating and controlling the time of low-frequency ultrasonic radiation, and optimizes the prepared MnCeO x A surface active oxygen component of the metal oxide; mnCeO prepared by using the method x The catalytic activity of the metal oxide is improved, and the metal oxide is more suitable for being used as a catalyst. The technical scheme provided by the invention realizes MnCeO by utilizing low-frequency ultrasound with specific duration x Partial catalytic oxidation of Mn and Ce elements in metal oxide and partial change of the obtained MnCeO x Oxidation-reduction potentials of Mn and Ce elements in the metal oxide, so that the improvement of the proportional relation of Ce (IV)/Ce (III) and Mn (IV)/Mn (III) and the optimization of the surface active oxygen component are realized, and the promotion of catalytic activity is facilitated; at the same time, the bookThe technical proposal provided by the invention promotes CeO 2 The (200 crystal face) exposure is beneficial to migration of lattice oxygen from the lattice structure to the surface and promotion of catalytic activity. In addition, mnCeO prepared by the invention x The metal oxide also has a certain amount of oxygen vacancies, and the presence of oxygen vacancies also contributes to the MnCeO to a certain extent x Activity of metal oxide.
Drawings
FIG. 1A shows MnCeO provided in example 1 x HRTEM images of (a).
FIG. 1B shows MnCeO provided in example 1 x Energy distribution profile of HRTEM images of (a).
FIG. 1C shows MnCeO provided in example 1 x Diffraction fringe patterns of HRTEM images of (a).
FIG. 2A is a MnCeO provided in example 1 x SEM images of (a).
FIG. 2B is a MnCeO provided in example 1 x Ce element profile of (c).
FIG. 2C is a MnCeO provided in example 1 x Mn element distribution diagram of (C).
FIG. 2D is a MnCeO provided in example 1 x O element profile of (c).
FIG. 3A is a MnCeO provided in example 1 x Is a XPS graph of (C).
FIG. 3B is a MnCeO provided in example 1 x Is a Ce3d XPS graph of (c).
FIG. 3C is a MnCeO provided in example 1 x XPS map of Mn2p of (C).
FIG. 3D is a MnCeO provided in example 1 x XPS for O1s of (C).
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The present embodiment provides a MnCeO x Metal oxide, mnCeO x The preparation method of the metal oxide comprises the following steps:
1) Will 3.95g KMnO 4 、7.41g MnCl 2 And 23.28g CeCl 4 Dissolving in 250mL of deionized water to obtain a mixture A, dropwise adding 2mol/L NaOH solution into the mixture A until the pH value of the mixture A is 11, and then carrying out catalytic oxidation by using low-frequency ultrasonic radiation of 28kHz for 15min to obtain a mixture B; wherein the intensity of the low-frequency ultrasonic wave is 5W/cm 2 ；
2) Aging the mixture B for 1h, continuously applying 300kHz high-frequency ultrasonic radiation for 45min during aging, centrifuging, washing (3 times of distilled water washing), drying at 120 ℃ for 12h, and roasting at 500 ℃ for 4h to obtain the MnCeO x A metal oxide; wherein the intensity of the high-frequency ultrasonic wave is 0.6W/cm 2 。
Detection of MnCeO provided in this example x The average grain size of the metal oxide is detected to be MnCeO x The average particle size of the metal oxide is 270nm, and CeO on the surface of the metal oxide x The average particle diameter of the particles is 2.9nm, and the particles of the active substance are small.
MnCeO provided for this embodiment x The metal oxide is subjected to crystal phase structure analysis, and MnCeO x HRTEM images of metal oxides are shown in fig. 1A-1C; as can be seen from FIG. 1C, there are 2.04A, 2.70A and 3.11A lattice fringes corresponding to CeO, respectively 2 And (111) crystal planes (220), (200), and (111). Since the crystal plane (111) has the smallest surface energy, it is the most stable crystal plane, which is advantageous in maintaining the stability of the crystal. The crystal face (200) can further improve the catalytic activity due to its higher surface energy. Thus, the catalyst having an exposed crystal face of (200) was successfully prepared by ultrasonic impregnation, and this structure facilitates the migration of lattice oxygen from the lattice structure to the surface. Whereas the catalyst prepared by the conventional method does not exhibit a (200) crystal plane. In addition, the formation of oxygen vacancies at the (200) crystal plane is also relatively superior to the (220) and (111) crystal planes.
Testing of MnCeO provided in this example x As a result of SEM images of the metal oxide, as shown in fig. 2A to 2D, the surface of the MnCeOx metal oxide was rough and the elements were uniformly distributed.
Testing of MnCeO provided in this example x XPS graphs of metal oxides, the results are shown in fig. 3A-3D; as can be seen from the view of figure 3A,the corresponding peak at 641.356eV position is Mn2p 3/2 Further can be classified into Mn 3+ (643.194eV)、Mn 4+ (641.554 eV). Wherein Mn is 4+ The ratio of Mn is 67.73% (based on the total Mn element content of 100%) 4+ With Mn 3+ The ratio of (2) to (1) is about 2:1, which is a sufficient indication that ultrasound plays a catalytic oxidation role during the reaction. FIG. 3B shows Ce3d, where u ` 、v ` Marked by Ce 3+ ，u ``` ,u `` ,u,v ``` ,v `` V denotes Ce 4+ Wherein Ce is 4+ The ratio of Ce is 80.3 percent (based on the total content of Ce element is 100 percent) 4 + With Ce 3+ The ratio of about 4:1.
FIG. 3C shows XPS peak of O1s, 529.231eV belonging to vacancy oxygen e O latt The 530.966eV peak belongs to surface active oxygen O surface The 532.654eV peak belongs to adsorption of molecular oxygen O ads The MnCeO provided in this example is shown x The metal oxide has a certain vacancy oxygen and surface active oxygen.
Example 2
The present embodiment provides a MnCeO x Metal oxide, mnCeO x Preparation method of metal oxide and MnCeO provided in example 1 x The preparation methods of the metal oxides are only different in that the ultrasonic frequency of the high-frequency ultrasonic radiation is different, and the ultrasonic frequency of the high-frequency ultrasonic radiation in the embodiment is 150kHz.
MnCeO provided in the present embodiment x In the metal oxide, the average particle diameter was 372nm.
Example 3
The present embodiment provides a MnCeO x Metal oxide, mnCeO x Preparation method of metal oxide and MnCeO provided in example 1 x The preparation methods of the metal oxides are only different in that the ultrasonic frequency of the high-frequency ultrasonic radiation is different, and the ultrasonic frequency of the high-frequency ultrasonic radiation in the embodiment is 500kHz.
MnCeO provided in the present embodiment x The average particle diameter of the metal oxide was 190nm.
Example 4
This practice isThe embodiment provides a MnCeO x Metal oxide, mnCeO x Preparation method of metal oxide and MnCeO provided in example 1 x The preparation methods of the metal oxides are different only in that the ultrasonic frequency of the high-frequency ultrasonic radiation is different, and the ultrasonic frequency of the high-frequency ultrasonic radiation in the embodiment is 105kHz.
MnCeO provided in the present embodiment x The average particle diameter of the metal oxide was 408nm.
Example 5
The present embodiment provides a MnCeO x Metal oxide, mnCeO x Preparation method of metal oxide and MnCeO provided in example 1 x The preparation methods of the metal oxides are different only in that the ultrasonic frequency of the high-frequency ultrasonic radiation is different, and the ultrasonic frequency of the high-frequency ultrasonic radiation in the embodiment is 800kHz.
MnCeO provided in the present embodiment x The average particle diameter of the metal oxide was 88nm.
Example 6
This comparative example provides a MnCeO x Metal oxide, mnCeO x Preparation method of metal oxide and MnCeO provided in example 1 x The preparation methods of the metal oxides are only different in low-frequency ultrasonic irradiation time, and the low-frequency ultrasonic irradiation is performed for 13min in the embodiment.
Example 7
This comparative example provides a MnCeO x Metal oxide, mnCeO x Preparation method of metal oxide and MnCeO provided in example 1 x The preparation methods of the metal oxides are only different in low-frequency ultrasonic irradiation time, and the low-frequency ultrasonic irradiation is performed for 17min in the embodiment.
Comparative example 1
This comparative example provides a MnCeO x Metal oxide, mnCeO x The preparation method of the metal oxide comprises the following steps:
1) Will 3.95g KMnO 4 ，7.41g MnCl 2 And 23.28g CeCl 4 Dissolving in 250mL deionized water to obtain a mixture A, and dripping 2mol/L NaOH solution into the mixture A until the pH value of the mixture11, and then stirring for 15min by a magnetic heating stirrer to obtain a mixture B;
2) And (3) aging the mixture B for 2 hours, centrifuging, washing (washing with distilled water for 3 times), drying at 120 ℃ for 12 hours, and roasting at 500 ℃ for 4 hours to obtain the MnCeOx metal oxide.
Detection of MnCeO provided in this example x The average particle size of the metal oxide was found to be 102 μm by examination, and the average particle size of the MnCeOx metal oxide was 28nm, which is significantly larger than that of example 1.
Comparative example 2
This comparative example provides a MnCeO x Metal oxide, mnCeO x Preparation method of metal oxide and MnCeO provided in example 1 x The preparation methods of the metal oxides are only different in the low-frequency ultrasonic irradiation time, and the comparative example is low-frequency ultrasonic irradiation for 10min.
MnCeO provided in this comparative example x In metal oxide, ce 4+ /Ce 3+ The ratio of Mn is 4.7:1 4+ /Mn 3+ The ratio of (2) to (1) is 2.5.
Comparative example 3
This comparative example provides a MnCeO x Metal oxide, mnCeO x Preparation method of metal oxide and MnCeO provided in example 1 x The preparation methods of the metal oxides are only different in the low-frequency ultrasonic irradiation time, and the comparative example is low-frequency ultrasonic irradiation for 30min.
MnCeO provided in this comparative example x In metal oxide, ce 4+ /Ce 3+ The ratio of Mn is 2.8:1 4+ /Mn 3+ The ratio of (2) to (1) is 2.9.
Experimental example 1
This experimental example provides MnCeO provided in example 1, example 6, example 7, comparative example 1, comparative example 2, comparative example 3 x The catalytic performance test of the metal oxide is specifically as follows:
and testing the capability of the catalyst to be tested in catalyzing oxydol to oxidize dye wastewater, wherein the reaction is carried out at room temperature, the concentration of acid orange 7 pollutants in the dye wastewater is 20mg/L, the pH value of the dye wastewater is=3.5, the adding amount of oxydol is 40mg/L and the adding amount of the catalyst is 1.0g/L based on the dye wastewater.
MnCeO provided in example 1 x The metal oxide catalyzes hydrogen peroxide to oxidize dye wastewater, and the removal rate of acid orange 7 is 86%; mnCeO provided in example 6 x The metal oxide catalyzes hydrogen peroxide to oxidize dye wastewater, and the removal rate of acid orange 7 is 78%; mnCeO provided in example 7 x The metal oxide catalyzes hydrogen peroxide to oxidize dye wastewater, and the removal rate of acid orange 7 is 76%; mnCeO provided in comparative example 1 x The metal oxide catalyzes hydrogen peroxide to oxidize dye wastewater, and the removal rate of acid orange 7 is 58%; mnCeO provided by comparative example 2 x The metal oxide catalyzes hydrogen peroxide to oxidize dye wastewater, and the removal rate of acid orange 7 is 63%; mnCeO provided by comparative example 3 x The removal rate of acid orange 7 is 48% when the metal oxide catalyzes hydrogen peroxide to oxidize dye wastewater.
When dye wastewater with pH=3.5 contains methyl orange with concentration of 20mg/L or active violet with concentration of 20mg/L, under the condition of room temperature, the hydrogen peroxide adding amount is 40mg/L, the catalyst adding amount is 1.0g/L, and MnCeO provided in examples 1, 6 and 7 is calculated by the dye wastewater x The metal oxide exhibits excellent methyl orange removal ability and active violet removal ability.
Claims (28)
1. MnCeO x A method for producing a metal oxide, wherein the method comprises:
1) Dissolving Mn salt and Ce salt which are precursors of metal oxide in water to obtain a mixture A, adding a precipitant solution into the mixture A, radiating for 13-17min by using low-frequency ultrasonic waves, and then carrying out catalytic oxidation to obtain a mixture B; the frequency of the low-frequency ultrasonic wave is 20kHz-48kHz;
2) Solid-liquid separation, drying and roasting of the mixture B to obtain the MnCeO x A metal oxide.
2. The preparation method according to claim 1, wherein the time of the low-frequency ultrasonic irradiation is 15min; the frequency of the low-frequency ultrasonic wave is 20-40 kHz.
3. The preparation method according to claim 1, wherein the concentration of the Mn salt in the mixture A is 0.1 to 0.4mol/L based on the volume of the mixture A; the concentration of Ce salt in the mixture A is 0.1-0.4mol/L.
4. A production method according to claim 1 or 3, wherein the molar ratio of Mn in the Mn salt to Ce in the Ce salt is 1:1.
5. The preparation method according to claim 1, wherein the Mn salt comprises a divalent Mn salt and KMnO 4 At least one of them.
6. The preparation method according to claim 5, wherein the divalent Mn salt is MnCl 2 。
7. The method of claim 1, wherein the Ce salt comprises CeCl 4 。
8. The method of claim 1, wherein the precipitant comprises at least one of NaOH and KOH.
9. The production method according to claim 1 or 8, wherein the concentration of the precipitant in the precipitant solution is 0.5 to 2 mol/L.
10. The preparation method according to claim 9, wherein the concentration of the precipitant in the precipitant solution is 1mol/L.
11. The preparation method according to claim 1 or 8, wherein the amount of the precipitant solution is such that the precipitant solution is added to mixture a until the pH of the mixture of both is 11.
12. The production method according to claim 1, wherein the mixture B is subjected to an aging treatment during which high-frequency ultrasonic radiation is continuously applied, before solid-liquid separation is performed; wherein the frequency of the high-frequency ultrasonic wave is 100-800kHz.
13. The preparation method according to claim 12, wherein the high-frequency ultrasonic irradiation is applied for 45min to 4h.
14. The preparation method according to claim 13, wherein the time for applying the high-frequency ultrasonic radiation is 45 minutes.
15. The preparation method according to claim 1, wherein the preparation method comprises the following specific steps:
1) Dissolving Mn salt and Ce salt which are precursors of metal oxide in water to obtain a mixture A, dropwise adding a precipitant solution into the mixture A until the pH value of the mixture A is 11, and then carrying out catalytic oxidation by using low-frequency ultrasonic radiation of 20kHz-40kHz for 15min to obtain a mixture B;
wherein the molar ratio of Mn in the Mn salt to Ce in the Ce salt is 1:1; the concentration of Mn salt in the mixture A is 0.1-0.4mol/L; the concentration of Ce salt in the mixture A is 0.1-0.4mol/L; the concentration of the precipitant in the precipitant solution is 1mol/L;
mn salt is MnCl 2 And KMnO 4 At least one of (a) and (b); ce salt is CeCl 4 The method comprises the steps of carrying out a first treatment on the surface of the The precipitant is NaOH;
2) Aging the mixture B for 45min, continuously applying high-frequency ultrasonic radiation of 100-800kHz during the aging treatment, and carrying out solid-liquid separation, drying and roasting on the aged mixture B to obtain the MnCeO x A metal oxide.
16. The production method according to claim 1 or 15, wherein MnCeO produced by controlling frequency of high-frequency ultrasonic waves is controlled when high-frequency ultrasonic radiation is applied x Average particle diameter of metal oxide:
when the frequency of high-frequency ultrasonic is controlled to be not lower than 100kHz, the prepared MnCeO x The average particle size of the metal oxide is not more than 420nm;
when the frequency of high-frequency ultrasonic is controlled to be not lower than 200kHz, the prepared MnCeO x The average particle size of the metal oxide is not more than 300nm;
when the frequency of high-frequency ultrasonic is controlled to be not lower than 300kHz, the prepared MnCeO x The average particle size of the metal oxide is not more than 270nm;
when the frequency of high-frequency ultrasonic is controlled to be not lower than 500kHz, the prepared MnCeO x The average particle size of the metal oxide is not more than 190nm;
when the frequency of high-frequency ultrasonic is controlled to be not lower than 800kHz, the prepared MnCeO x The average particle diameter of the metal oxide is not more than 90nm.
17. The production method according to claim 16, wherein MnCeO is produced when the frequency of the high-frequency ultrasonic wave is controlled to 100-200kHz x The average particle size of the metal oxide is 420nm-300nm; when the frequency of high-frequency ultrasonic wave is controlled between 200kHz and 300kHz, the prepared MnCeO x The average particle size of the metal oxide is 300nm-270nm; when the frequency of high-frequency ultrasonic wave is controlled between 300kHz and 500kHz, the prepared MnCeO x The average particle size of the metal oxide is 270nm-190nm; when the frequency of high-frequency ultrasonic wave is controlled between 500 and 800kHz, the prepared MnCeO x The average particle diameter of the metal oxide is 190nm-90nm.
18. The production method according to claim 17, wherein MnCeO is produced when the frequency of the high-frequency ultrasonic wave is controlled to 100kHz x The average particle size of the metal oxide is 420nm; when the frequency of high-frequency ultrasonic wave is controlled at 200kHz, the prepared MnCeO x The average particle diameter of the metal oxide is 300nm; when the frequency of high-frequency ultrasonic wave is controlled at 300kHz, the prepared MnCeO x The average particle diameter of the metal oxide is 270nm; when the frequency of high-frequency ultrasonic wave is controlled at 500kHz, the prepared MnCeO x The average particle diameter of the metal oxide is 190nm; when the frequency of high-frequency ultrasonic wave is controlled at 800kHz, the prepared MnCeO x The average particle diameter of the metal oxide was 90nm.
19. The production method according to claim 1 or 15, wherein the intensity of the low-frequency ultrasound is 3.0-12W/cm 2 。
20. The method of claim 19, wherein the low frequency ultrasound has an intensity of 3.0-8.0W/cm 2 。
21. The production method according to any one of claims 12 to 15, wherein the intensity of the high-frequency ultrasonic wave is 0.5 to 1.5W/cm 2 。
22. The production method according to claim 1 or 15, wherein the baking temperature is 500 ℃; the roasting time is 4-12h.
23. The MnCeOx metal oxide produced by the production method of claim 1 or 15, wherein the MnCeO x Ce of metal oxide 4+ With Ce 3+ The ratio of (C) to (C) is 3-4:1, mn 4+ With Mn 3+ The ratio of (2) is 1.7-2.4:1.
24. MnCeO according to claim 23 x A metal oxide, wherein the MnCeO x The average particle size of the metal oxide is not more than 420nm.
25. MnCeO according to claim 24 x A metal oxide, wherein the MnCeO x The average particle size of the metal oxide is not more than 300nm.
26. MnCeO according to claim 25 x A metal oxide, wherein the MnCeO x The average particle size of the metal oxide is not more than 270nm.
27. MnCeO according to claim 23 x A metal oxide, wherein the MnCeO x The average particle size of the metal oxide is not largeAt 190nm.
28. MnCeO according to claim 23 x A metal oxide, wherein the MnCeO x The average particle diameter of the metal oxide is not more than 90nm.
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