CN110170328B - Preparation method and application of cobalt manganate/N-doped graphene composite catalyst - Google Patents
Preparation method and application of cobalt manganate/N-doped graphene composite catalyst Download PDFInfo
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- CN110170328B CN110170328B CN201910162260.1A CN201910162260A CN110170328B CN 110170328 B CN110170328 B CN 110170328B CN 201910162260 A CN201910162260 A CN 201910162260A CN 110170328 B CN110170328 B CN 110170328B
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention provides a preparation method and application of a cobalt manganate/N-doped graphene composite catalyst for activating persulfate, which comprises the following steps: s1, selecting raw materials, S2, preparing cobalt manganate, and S3, compounding to obtain a dry cobalt manganate/N-doped graphene complex; s4, calcining to obtain the cobalt manganate/N-doped graphene composite catalyst, reducing the preparation cost of the cobalt manganate/N-doped graphene composite catalyst by modifying the preparation process of the cobalt manganate/N-doped graphene composite catalyst, promoting the composite catalyst to be suitable for industrial large-scale production, and effectively removing pollutants in water by aiming at the application of the N-doped graphene modification treatment to the composite catalyst in the aspect of water treatment.
Description
Technical Field
The invention relates to the field of graphene, in particular to a preparation method and application of a cobalt manganate/N-doped graphene composite catalyst for activating persulfate.
Background
The traditional water treatment technology is difficult to effectively remove novel pollutants in water, and the advanced oxidation technology has the characteristics of high efficiency, thoroughness and economy for removing the organic pollutants, so that the advanced oxidation technology is widely applied to the field of water treatment. In recent years, advanced oxidation technologies based on persulfate activation have attracted attention because of their strong oxidizing power and degradation efficiency. Nanocarbons (such as Carbon Nanotubes (CNTs), graphene Oxide (GO)), metal-based catalysts are used for persulfate activation, and metal oxide composites can further improve their catalytic activity. Oxidation processes based on metal and non-metal composites do not require energy supply and can avoid potential secondary contamination of the metal catalyst. Therefore, the composition of metal oxide and carbon material is a promising material. In the former report, the composite material is prepared on the basis of graphene oxide. There are no documents and patent reports on the removal of pollutants in water by activating persulfate through a cobalt manganate/N-doped graphene composite catalyst prepared by taking graphene (N-doped graphene) as a raw material and oxidizing the persulfate.
Disclosure of Invention
Technical problems to be solved
In view of the above, the present invention aims to provide a preparation method of a cobalt manganate/N-doped graphene composite catalyst, which reduces the preparation cost by modifying the preparation process of the cobalt manganate/N-doped graphene composite catalyst, so as to enable the composite catalyst to adapt to industrial mass production, and can effectively remove pollutants in water by applying the composite catalyst to water treatment by means of N-doped graphene modification treatment. .
(II) technical scheme
In order to solve the technical problems, an object of the present invention is to provide a method for preparing a cobalt manganate/N-doped graphene composite catalyst, comprising the steps of:
s1, selecting raw materials, namely cobalt nitrate, manganese nitrate, citric acid, ultrapure water, N-doped graphene and ethanol;
s2, preparing cobalt manganate, namely preparing dry cobalt manganate by adopting a gel method, then calcining for 2 hours in a muffle furnace at 500 ℃ and at a heating rate of 10 ℃/min to obtain the cobalt manganate;
s3, compounding, namely dispersing the cobalt manganate and the N-doped graphene obtained in the step S2 in ethanol according to a mass ratio of 1:1, performing ultrasonic treatment for 30min, uniformly mixing, performing suction filtration, washing with water, and finally performing vacuum drying at 50-60 ℃ for 12-24h to obtain a dried cobalt manganate/N-doped graphene composite;
and S4, calcining, namely placing the cobalt manganate/N-doped graphene complex obtained in the step S3 into a tubular furnace under the inert atmosphere, controlling the temperature to be 400-800 ℃ for calcining, controlling the heating rate to be 10-15 ℃/min, keeping the temperature for 60-180min, and cooling to room temperature under the inert atmosphere to obtain the persulfate-activated cobalt manganate/N-doped graphene composite catalyst.
Preferably, in the technical scheme, the mass ratio of cobalt manganate to N-doped graphene is = (1:1).
Preferably, in the technical scheme, the N-doped graphene is commercial graphene and is prepared by a reduction oxidation method, and the nitrogen content is 5-10%.
In the technical scheme, the temperature in the S4 step is preferably controlled at 400 ℃, or 500 ℃, or 600 ℃, or 700 ℃ or 800 ℃.
According to the technical scheme, the temperature rise rate in the step S4 is preferably 10 ℃/min, and the temperature is kept for 120min.
In the technical scheme, the drying time in the step S4 is preferably 24h.
The invention also provides application of the cobalt manganate/N-doped graphene composite catalyst and an application method thereof.
The cobalt azomanganate/N-doped graphene composite catalyst prepared by the method is applied to removal of pollutants in water.
The prepared cobalt azomanganate/N-doped graphene composite catalyst can remove the following pollutants in water:
antiseptic Ethylparaben (EP),
Sunscreen 2-phenylbenzimidazole-5-sulfonic acid (PBSA),
Dye rhodamine B,
Methyl orange
One or more of them mixed together.
The application method of the prepared cobalt manganate/N-doped graphene composite catalyst in removing water pollution comprises the following steps of adding a certain amount of the prepared cobalt manganate/N-doped graphene composite catalyst into sewage to be treated, adding a certain amount of potassium hydrogen persulfate, and stirring/oscillating at normal temperature.
(III) advantageous effects
In the preparation method of the cobalt azomanganate/N-doped graphene composite catalyst provided by the invention, the CoMn is prepared by adopting industrial graphene through subsequent heat treatment 2 O 4 Compared with the prior experimental preparation method, the/N-rGO composite material is more suitable for industrial large-scale production, and meanwhile, the CoMn is obtained by the preparation method 2 O 4 the/N-rGO composite material has better application effect, namely the treatment effect is better than that of the monomers of the two.
The CoMn obtained by the preparation method provided by the invention 2 O 4 the/N-rGO composite material alsoCan be applied in water treatment to remove pollutants in sewage, particularly has high-efficiency effect on removing novel pollutants such as preservative Ethylparaben (EP), sun-screening agent PBSA and the like and conventional pollutants such as dye rhodamine B and methyl orange, and the CoMn is obtained by the preparation 2 O 4 the/N-rGO is a nano carbon composite material, is environment-friendly, has no secondary pollution caused by metal leaching in the removing process, and is CoMn 2 O 4 the/N-rGO is used as a catalyst in the water treatment process and is matched with potassium hydrogen Persulfate (PMS) as an oxidant, the adding amount is relatively small, and the cost for removing pollutants in water is effectively reduced.
Drawings
FIG. 1 is an XRD diffraction pattern of cobalt manganate/N-doped graphene prepared by the preparation method provided by the invention;
FIG. 2 is SEM and TEM images of the prepared cobalt manganate/N-doped graphene;
FIG. 3 is an EDX elemental analysis spectrum of the prepared cobalt manganate/N-doped graphene;
FIG. 4 is a graph showing the effect of cobalt manganate/N-doped graphene on removing the preservative Ethylparaben (EP);
FIG. 5 is a graph showing the effect of the prepared cobalt manganate/N-doped graphene on the removal of the sunscreen PBSA;
FIG. 6 is a graph showing the effect of cobalt manganate/N-doped graphene on removing dyes methyl orange and rhodamine B.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Dispersing a certain amount of cobalt manganate prepared by a gel method and N-doped graphene in ethanol, uniformly mixing under an ultrasonic condition, filtering, washing with water, drying in a vacuum drying oven at 50 ℃ for 24 hours, and finally calcining in a tubular furnace under nitrogen atmosphere at different temperatures (400 ℃, 500 ℃, 600, 700 ℃ and 800 ℃) respectively. The calcination time is different (30 min, 60min, 90 min, 120min and 240 min), and the heating rate is selected to be 10, 12 and 15 ℃/min for carrying out a plurality of tests. And cooling to room temperature in an inert atmosphere (nitrogen can be selected) to obtain the cobalt manganate/N-doped graphene composite material.
Example 1
A certain amount of cobalt manganate prepared by a gel method and N-doped graphene are dispersed in ethanol, and are uniformly mixed under the ultrasonic condition, filtered and washed, and then are dried for 24 hours in a vacuum drying oven at 50 ℃, and finally are calcined for 2 hours at 500 ℃ in a tubular furnace under nitrogen atmosphere, wherein the heating rate is selected to be 10 ℃/min for multiple tests. And cooling to room temperature in a nitrogen atmosphere to obtain the cobalt manganate/N-doped graphene composite material.
Morphological analysis of the samples was performed using Quanta400FEG Scanning Electron Microscope (SEM) (FEI, USA) and JEM-2100F High Resolution Transmission Electron Microscope (HRTEM) (japanese JEOL), respectively, for the test samples. X-ray diffraction (XRD) spectra were recorded using a D8-X-ray diffractometer (Bruker, germany).
Wherein, FIG. 1 is XRD diffraction spectrum of cobalt manganate/N-doped graphene prepared by the preparation method provided by the invention, coMn 2 O 4 The XRD pattern of the compound has diffraction peaks at 18.2 degrees, 29.3 degrees, 31.2 degrees, 32.8 degrees, 36.3 degrees, 38.7 degrees, 44.7 degrees, 51.8 degrees, 54.3 degrees, 56.5 degrees, 59.0 degrees, 60.6 degrees, 65.1 degrees and 74.9 degrees, and the compound is the same as CoMn 2 O 4 The standard cards of (a) are consistent, and the situation of cobalt manganate, N-doped graphene, cobalt manganate/N-doped graphene can be compared by means of fig. 1, which illustrates that after recombination no significant shift of diffraction peaks is found, which means that the doping process does not significantly destroy the respective crystal structure.
FIG. 2 shows SEM electron micrographs that a large amount of cobalt manganate (CoMn) is loaded on graphene sheets (N-rGO) 2 O 4 ) Nanoparticles, coMn 2 O 4 The presence of (b) did not damage the N-rGO. Furthermore, from the figure, no isolated CoMn was observed 2 O 4 Particles outside of N-rGO, indicating CoMn 2 O 4 Binding to N-rGO is better. At the same time, the composite material as a whole takes on a corrugated and stacked layer morphology. The above features and the corrugated sheet morphology are further revealed by TEM.
Fig. 3 is an EDX elemental analysis spectrogram of cobalt manganate/N-doped graphene prepared by the preparation method provided by the invention, which shows that the composite catalyst contains elements of C, N, O, co, and Mn.
Example 2
Test samples prepared in example 1 were subjected to an experiment for degrading the preservative Ethylparaben (EP). Wherein CoMn 2 O 4 The mass ratio of/N-rGO to PMS =1: (3-10).
CoMn was selected in example 2 2 O 4 The mass ratio of/N-rGO to PMS =1:5. namely:
adding CoMn of 50 mg/L into EP solution of 10 mg/L 2 O 4 PMS/N-rGO and 250 mg/L, sampled at intervals and filtered to remove CoMn 2 O 4 and/N-rGO, adding methanol to terminate the reaction, and analyzing the EP concentration change of the reaction solution by HPLC.
As a comparison, coMn was added separately 2 O 4 And N-rGO is used as a catalyst, and other conditions are the same as above.
As shown in FIG. 4, coMn alone was used in the same amount of catalyst and oxidant 2 O 4 When N-rGO is used as a catalyst, PMS can not be effectively activated to remove EP; use of CoMn in degradation process 2 O 4 The degradation rate is slower; when N-rGO is used, the rate of degradation starts fast and the rate of subsequent degradation is also slower. While using a composite catalyst CoMn 2 O 4 the/N-rGO can remove 98.82% of EP after 45 min.
Example 3
The test samples prepared in example 1 were subjected to the sunscreen removal PBSA test. Wherein CoMn 2 O 4 The mass ratio of/N-rGO to PMS =1: (3-10).
CoMn was selected in example 2 2 O 4 The mass ratio of/N-rGO to PMS =1:5. namely:
to a 5 mg/L PBSA solution was added 50 mg/L CoMn 2 O 4 PMS/N-rGO and 250 mg/L, sampled at intervals and filtered to remove CoMn 2 O 4 /N-IrGO，The reaction was terminated by adding methanol, and the reaction solution was analyzed for changes in PBSA concentration by HPLC.
As a comparison, coMn was added separately 2 O 4 And N-rGO is used as a catalyst, and other conditions are the same as above.
As shown in FIG. 5, coMn was used in the same amount of catalyst and oxidant 2 O 4 The PBSA of 86.00% can be removed after 45min in the case of/N-rGO; while CoMn alone is used 2 O 4 In the process, the removal rate after 45min is only 35.35 percent; when N-rGO is used alone, the catalytic degradation effect is not obvious and can not be sustained.
Example 4
The test sample prepared in example 1 was subjected to an experiment for removing dyes Methyl Orange (Methyl Orange) and Rhodamine B (Rhodamine B). Wherein CoMn 2 O 4 The mass ratio of/N-rGO to PMS =1: (3-10).
CoMn was selected in example 2 2 O 4 The mass ratio of/N-rGO to PMS =1:5. namely:
adding CoMn of 50 mg/L into 100 mg/L methyl orange solution 2 O 4 PMS/N-rGO and 250 mg/L, sampled at intervals and filtered to remove CoMn 2 O 4 And adopting a spectrophotometer to measure the absorbance of the solution and analyze the concentration change of the methyl orange in the reaction solution. Adding CoMn of 50 mg/L into 50 mg/L rhodamine B solution 2 O 4 Per time interval, samples were taken from the/N-rGO and 500 mg/L PMS, and the CoMn was removed by filtration 2 O 4 And adopting a spectrophotometer to measure the absorbance of the solution and analyze the concentration change of the rhodamine B in the reaction solution. As shown in FIG. 6, the removal rates of methyl orange and rhodamine B after 20min are 98.35% and 99.09%, respectively.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (6)
1. The application of the cobalt manganate/N-doped graphene composite catalyst in removing pollutants in water is characterized in that:
the preparation method of the cobalt manganate/N-doped graphene composite catalyst comprises the following steps:
s1, selecting raw materials, namely cobalt nitrate, manganese nitrate, citric acid, ultrapure water, N-doped graphene and ethanol;
s2, preparing cobalt manganate, namely preparing dry cobalt manganate by adopting a gel method, then calcining for 2 hours in a muffle furnace at 500 ℃ and at a heating rate of 10 ℃/min to obtain the cobalt manganate;
s3, compounding, namely dispersing the cobalt manganate and the N-doped graphene obtained in the step S2 in ethanol according to a mass ratio of 1:1, performing ultrasonic treatment for 30min, uniformly mixing, performing suction filtration, washing with water, and finally performing vacuum drying at 50-60 ℃ for 12-24h to obtain a dried cobalt manganate/N-doped graphene composite;
s4, calcining, namely placing the cobalt manganate/N-doped graphene complex obtained in the step S3 into a tubular furnace under the inert atmosphere, controlling the temperature to be 400-800 ℃ for calcining, controlling the heating rate to be 10-15 ℃/min, keeping the temperature for 60-180min, and cooling to room temperature under the inert atmosphere to obtain a persulfate-activated cobalt manganate/N-doped graphene composite catalyst;
the contaminants in the water include: one or more of antiseptic Ethylparaben (EP), sunscreen agent 2-phenylbenzimidazole-5-sulfonic acid (PBSA), and dye rhodamine B;
the N-doped graphene is commercial graphene and is prepared by a reduction oxidation method, and the nitrogen content is 5-10%.
2. The application of the cobalt manganate/N-doped graphene composite catalyst in removing pollutants in water as claimed in claim 1, wherein the temperature in the S4 step is controlled at 400 ℃ or 500 ℃ or 600 ℃ or 700 ℃ or 800 ℃.
3. The application of the cobalt manganate/N-doped graphene composite catalyst in removing pollutants in water as claimed in claim 2, wherein in the step S4, the temperature rise rate is 10 ℃/min, and the temperature is kept for 120min.
4. The application of the cobalt manganate/N-doped graphene composite catalyst in removing pollutants in water as claimed in claim 3, wherein the drying time in the S4 step is 24h.
5. The application of the cobalt manganate/N-doped graphene composite catalyst in removing pollutants in water as claimed in claim 1, wherein the application method comprises the following steps of adding a certain amount of the cobalt manganate/N-doped graphene composite catalyst prepared in claim 1 into the sewage to be treated, adding a certain amount of potassium hydrogen persulfate, and stirring/oscillating at normal temperature.
6. The application of the cobalt manganate/N-doped graphene composite catalyst in removing pollutants in water as claimed in claim 5, wherein the mass ratio of the cobalt manganate/N-doped graphene composite catalyst to potassium hydrogen persulfate is =1: (3-10).
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