CN110354893B - CuOXPreparation method of/OMS-2 catalyst and application of catalyst in degradation of organic pollutants - Google Patents

Abstract

The invention discloses a preparation method of a Cu-loaded OMS-2 catalyst and application thereof in degrading organic pollutants. The CuO_Xthe/OMS-2 catalyst is prepared by adding copper nitrate solution into OMS-2, performing ultrasonic treatment, stirring, distilling under reduced pressure, drying, and calcining. The prepared catalyst can act on peroxymonosulfate to generate a sulfuric acid free radical with strong oxidizing property as an active substance, oxidize, decolor and degrade organic dye, can catalyze and degrade nitro compounds under the action of sodium borohydride, and can be recycled after reaction. The preparation method of the catalyst is simple, the obtained catalyst can continuously and efficiently catalyze and activate the peroxymonosulfate to degrade organic pollutants for many times at room temperature, can be recycled and reused after reaction, can greatly reduce the industrial cost, accords with the green production principle, and has great application prospect in the field of degrading organic wastewater.

Description

CuOXPreparation method of/OMS-2 catalyst and application of catalyst in degradation of organic pollutants

Technical Field

The invention relates to a CuO_XPreparation of OMS-2 catalyst and application thereof in degrading organic pollutants, belonging to the technical field of organic wastewater treatment.

Background

Oxides of manganese are a class of relatively potential heterogeneous catalysts, including MnO, Mn₂O₃、MnO₂And Mn₃O₄And the like, have applications in a variety of oxidation-reduction reactions. Recent research results indicate that oxides of manganese can be used to activate persulfates, e.g., Sapura et al examined MnO, Mn₂O₃And Mn₃O₄The degradation of phenol wastewater by the system consisting of persulfate and hydrogen sulfate, and the discovery of Mn₂O₃Has higher activity than other manganese oxide catalysts (Applied Catalysis B: Environmental,2013,142-143, 729-735). However, the existing manganese catalyst has the disadvantages of complex preparation process, unsatisfactory catalytic activity, large oxidant consumption and high wastewater treatment cost. While manganese oxide octahedral molecular sieve (OMS-2) belongs to alpha-MnO₂Is a novel material similar to a zeolite molecular sieve tunnel structure, and Mn exists in crystal lattices²⁺、Mn³⁺And Mn⁴⁺Has mild surface acidity and good oxidation-reduction property, and becomes a new research hotspot after the zeolite-type tetrahedral molecular sieve.

On the other hand, the protection of environmental water resources is a focus of global attention at present, and with the rapid development of modern economy, high-concentration organic wastewater poses a threat to precious water resources. Advanced oxidation technology is a dyeing wastewater treatment technology which has attracted much attention in recent years, because hydroxyl radicals (OH) with strong oxidizing property can be generated in the reaction process, and OH and various organic pollutants undergo oxidation reaction until the OH is degraded into harmless substances or intermediate products which are easy to biodegrade. In recent years, based on sulfate radicals (SO)₄ ^-·) The research of degrading the organic matters which are difficult to degrade in the wastewater by the advanced oxidation method is developed. Sulfate radicals can be generated by decomposing persulfate through high-temperature pyrolysis, photocatalysis, catalysis of transition metal and other modes, however, the energy consumption of the thermal activation persulfate technology is high, and the technical conditions of the photoactivation persulfate technology are harsh. The transition metal persulfate activation technology has low requirement on equipment, low energy consumption and more economical and practical, and common metal ions comprise Fe²⁺、Co²⁺、Mn²⁺、 Ni²⁺、Ce³⁺And Ag⁺And the like. The invention adopts CuO_XOMS-2 as a persulfate activating catalyst was found to be very highThe performance of catalytic degradation of pollutants.

Disclosure of Invention

The invention provides a CuO_XA method for preparing an OMS-2 catalyst and its use for degrading organic pollutants.

The CuO of the present invention_Xthe/OMS-2 catalyst is prepared by taking OMS-2 and copper nitrate as raw materials and performing ultrasonic treatment, reduced pressure distillation, drying and calcination. The catalytic performance test shows that the catalyst can better degrade organic pollutants.

The specific technical scheme is as follows:

CuO (copper oxide)_XPreparation method of/OMS-2 catalyst:

step 1, respectively weighing OMS-2 and copper nitrate and adding water;

2, performing ultrasonic treatment at the temperature of 20-35 ℃ for 2-4h, and stirring for 15-24 h;

step 3, carrying out reduced pressure distillation at 70-100 ℃ for 1-3h, and drying at 100-120 ℃ for 3-5 h;

step 4, calcining at the temperature of 300-400 ℃ for 1-3h to prepare the CuO_XAn OMS-2 catalyst.

The technical scheme of the invention is applied to catalyzing PMS to generate sulfate radicals to degrade organic pollutants. CuO (copper oxide)_XThe reaction mechanism of PMS to generate sulfate radical catalyzed by OMS-2 is as follows: CuO in the presence of PMS_XLower valence Cu in OMS-2⁺、Mn²⁺Or Mn³⁺Is oxidized into Cu²⁺、Mn⁴⁺The concomitant formation of sulfate radicals and hydroxyl radicals. Sulfate radicals are more oxidizing than hydroxyl radicals, and thus can efficiently degrade organic pollutants. The reaction mechanism is as follows:

the CuO_XThe method for catalyzing PMS to generate sulfate radicals to degrade organic pollutants by using the OMS-2 catalyst comprises the following steps:

step 1: adding PMS solution into the organic pollutant solution cuvette;

step 2: recording the absorption peak value of the organic pollutants at the moment by testing;

and step 3: rapid addition of CuO_XOMS-2, measuring the peak pattern of the ultraviolet-visible absorption spectrum of the organic pollutants by using an ultraviolet-visible spectrophotometer.

The CuO_XThe mass of the/OMS-2 catalyst in the reaction system is 5-15 mg.

The CuO_Xthe/OMS-2 catalyst has good catalytic degradation effect, is simple to operate, has no pollution, and accords with the principle of green chemistry.

CuO_Xthe/OMS-2 catalyst is a solid catalyst, can be repeatedly used in the catalytic process, has excellent catalytic effect on various organic pollutants, is small in dosage, can save cost, has better catalytic effect after being added with copper, and has good application prospect in the field of degrading organic pollutants.

Drawings

FIG. 1 is CuO prepared in example 1 of the present invention_XCharacteristic electron microscopy scan of/OMS-2.

FIG. 2 is CuO prepared in example 1 of the present invention_XXPS pattern for/OMS-2, A is the XPS pattern for copper detection and B is the XPS pattern for Mn detection.

FIG. 3 is CuO prepared in example 2 of the present invention_XThe UV-visible absorption spectrum of Acid Orange 7 degraded by sulfate radicals generated by catalyzing PMS by OMS-2.

FIG. 4 is CuO prepared in example 3 of the present invention_XThe UV-visible light absorption spectrum of the Methylene Blue is degraded by sulfate radicals generated by catalyzing PMS by OMS-2.

FIG. 5 is CuO prepared in example 4 of the present invention_XThe UV-visible absorption spectrogram of Reactive Blue 19 degraded by sulfate radicals generated by catalyzing PMS by OMS-2.

FIG. 6 is CuO prepared in example 5 of the present invention_XThe ultraviolet and visible light absorption spectrogram of the Reactive Red 2 degraded by sulfate radicals generated by catalyzing PMS by OMS-2.

FIG. 7 is CuO prepared in example 6 of the present invention_XOMS-2 catalysis PMS generation sulfate radical degradation Rhodamine B ultraviolet-visible absorption spectrum.

FIG. 8 is CuO prepared in example 7 of the present invention_XUV-visible light absorption spectrogram of/OMS-2 catalytic degradation p-nitrophenol.

FIG. 9 is CuO prepared in example 8 of the present invention_XUltraviolet and visible light absorption spectrogram of 2, 4-dinitrophenol catalytically degraded by/OMS-2.

FIG. 10 is CuO prepared in example 9 of the present invention_XThe ultraviolet and visible light absorption spectrogram of the 4-nitrobenzene diazonium tetrafluoroborate catalyzed and degraded by OMS-2.

FIG. 11 is CuO prepared in example 10 of the present invention_XDegradation time chart of 10 times of repeated cycles of the/OMS-2 catalytic degradation of p-nitrophenol.

FIG. 12 is CuO prepared in example 11 of the present invention_XDegradation time profile for 10 repeated cycles of OMS-2 catalyzed degradation of Rhodamine B.

Detailed Description

Example 1

To a 50ml round bottom flask was added OMS-2(2g), Cu (NO)₃)₂(0.15g dissolved in 10ml of water), then adding 10ml of water, carrying out ultrasonic treatment at room temperature for 3h, then continuing stirring at room temperature for 20h, carrying out reduced pressure distillation at 80 ℃ for 2h to obtain black powder, then drying the black powder at 110 ℃ for 4h, drying, and calcining at 350 ℃ for 2h to obtain the product.

FIG. 1 is CuO of example 1_XCharacteristic electron microscopy scan of/OMS-2 catalyst. The rod-like substance in the figure is CuO_XAn OMS-2 catalyst.

FIG. 2 is CuO of example 1_XXPS diagram of the/OMS-2 catalyst, from which CuO can be seen_Xthe/OMS-2 catalyst contains Cu (II), Cu (0) and Mn²⁺、Mn³⁺、Mn⁴⁺。

Example 2

CuO prepared by the invention_XApplication of/OMS-2 in catalyzing PMS to generate sulfate radicals to degrade Acid Orange 7.

CuO_XThe OMS-2 catalyzes PMS to generate sulfate radicals to degrade Acid Orange 7, namely the reaction mechanism exists in PMSBelow, CuO_XLower valence Cu in OMS-2⁺、Mn²⁺Or Mn³⁺Is oxidized into Cu²⁺、Mn⁴⁺Simultaneously, sulfate radicals and hydroxyl radicals with strong oxidizing property are generated, thereby degrading Acid Orange 7.

The CuO_XThe steps of the reaction of catalyzing PMS to generate sulfate radicals to degrade Acid Orange 7 by OMS-2 are as follows:

step 1: adding Acid Orange 7 solution into a cuvette, and adding PMS solution;

step 2: the test records the absorption peak value of Acid Orange 7 at the moment;

and step 3: rapid reaction of CuO_Xthe/OMS-2 catalyst was added to a cuvette and the peak pattern of the Acid Orange 7 UV-VIS absorption spectrum was measured with a UV-VIS spectrophotometer.

CuO described in step 3_XThe mass of the/OMS-2 catalyst is 5-15 mg.

FIG. 3 is CuO prepared by the present invention_XThe OMS-2 can generate sulfate radicals to degrade the ultraviolet and visible light absorption spectrogram of Acid Orange 7 in catalyzing PMS, the catalytic effect can be realized by detecting the characteristic peak of the Acid Orange 7 at the wavelength of 484nm through an ultraviolet-visible light photometer, and the termination of the reaction can be judged through the reduction of the absorbance of the Acid Orange 7 at the wavelength of 484 nm.

Example 3

CuO prepared by the invention_XApplication of/OMS-2 in catalyzing PMS to generate sulfate radicals to degrade Methylene Blue.

CuO_XThe reaction mechanism of degrading methyl Blue by catalyzing PMS to generate sulfate radicals by OMS-2, namely CuO in the presence of PMS_XLower valence Cu in OMS-2⁺、Mn²⁺Or Mn³⁺Is oxidized into Cu²⁺、 Mn⁴⁺Simultaneously, sulfate radicals and hydroxyl radicals with strong oxidizing property are generated, thereby degrading Methylene Blue.

The CuO_XThe method for catalyzing PMS to generate sulfate radicals to degrade Methylene Blue by using OMS-2 comprises the following steps:

step 1: adding a Methylene Blue solution into a cuvette, and adding a PMS solution;

step 2: recording the absorption peak value of the Methylene Blue at the moment by testing;

and step 3: rapid reaction of CuO_Xthe/OMS-2 catalyst was added to a cuvette and the peak pattern of the absorption spectrum of Methylene Blue in UV-visible light was measured with a UV-visible spectrophotometer.

CuO described in step 3_XThe mass of the/OMS-2 catalyst is 5-15 mg.

FIG. 4 is CuO prepared by the present invention_XThe OMS-2 can generate sulfate radicals in the catalytic PMS to degrade an ultraviolet-visible light absorption spectrogram of the Methylene Blue, the catalytic effect can be realized by detecting a characteristic peak of the Methylene Blue at the wavelength of 664nm by an ultraviolet-visible light photometer, and the termination of the reaction can be judged by the reduction of the absorbance of the Methylene Blue at the wavelength of 664 nm.

Example 4

CuO prepared by the invention_XApplication of/OMS-2 in catalyzing PMS to generate sulfate radicals to degrade Reactive Blue 19.

CuO_XThe reaction mechanism that the OMS-2 catalyzes PMS to generate sulfate radical to degrade Reactive Blue 19 is that CuO exists in the PMS_XLower valence Cu in OMS-2⁺、Mn²⁺Or Mn³⁺Is oxidized into Cu²⁺、 Mn⁴⁺Simultaneously, sulfate radicals and hydroxyl radicals with strong oxidizing property are generated, thereby degrading Reactive Blue 19.

The CuO_XThe reaction of OMS-2 for catalyzing PMS to generate sulfate radicals to degrade Reactive Blue 19 comprises the following steps:

step 1: adding Reactive Blue 19 solution into a cuvette, and adding PMS solution;

step 2: the test records the absorption peak value of Reactive Blue 19 at the moment;

and step 3: rapid reaction of CuO_Xthe/OMS-2 catalyst was added to the cuvette and the peak pattern of the Reactive Blue 19 UV-visible absorption spectrum was measured with a UV-visible spectrophotometer.

CuO described in step 3_XThe mass of the/OMS-2 catalyst is5-15mg。

FIG. 5 is CuO prepared by the present invention_XThe OMS-2 can generate sulfate radicals to degrade an ultraviolet and visible light absorption spectrogram of Reactive Blue 19 in the presence of catalytic PMS, the catalytic effect can be realized by detecting a characteristic peak of the Reactive Blue 19 at the wavelength of 593nm through an ultraviolet-visible light photometer, and the termination of the reaction can be judged by reducing the absorbance of the Reactive Blue 19 at the wavelength of 593 nm.

Example 5

CuO prepared by the invention_XApplication of/OMS-2 in catalyzing PMS to generate sulfate radicals to degrade Reactive Red 2.

CuO_XThe reaction mechanism that the OMS-2 catalyzes PMS to generate sulfate radicals to degrade Reactive Red 2 is that CuO exists in the presence of PMS_XLower valence Cu in OMS-2⁺、Mn²⁺Or Mn³⁺Is oxidized into Cu²⁺、Mn⁴⁺Simultaneously, sulfate radicals and hydroxyl radicals with strong oxidizing property are generated, thereby degrading Reactive Red 2.

The CuO_XThe reaction of OMS-2 for catalyzing PMS to generate sulfate radicals to degrade Reactive Red 2 comprises the following steps:

step 1: adding the Reactive Red 2 solution into a cuvette, and adding a PMS solution;

step 2: recording the absorption peak value of Reactive Red 2 at the moment by testing;

and step 3: rapid reaction of CuO_Xthe/OMS-2 catalyst is added into a cuvette, and the peak type of the Reactive Red 2 ultraviolet-visible light absorption spectrogram is measured by an ultraviolet-visible light photometer.

CuO described in step 3_XThe mass of the/OMS-2 catalyst is 5-15 mg.

FIG. 6 is CuO prepared by the present invention_XThe ultraviolet and visible light absorption spectrogram of the/OMS-2 for degrading Reactive Red 2 by generating sulfate radicals in the catalytic PMS can detect the characteristic peak of the Reactive Red 2 at the wavelength of 538nm through an ultraviolet-visible light photometer, and the termination of the reaction can be judged by the reduction of the absorbance of the Reactive Red 2 at the wavelength of 538 nm.

Example 6

CuO prepared by the invention_XApplication of/OMS-2 in catalyzing PMS to generate sulfate radicals to degrade Rhodamine B.

CuO_XThe reaction mechanism of degrading Rhodamine B by catalyzing PMS to generate sulfate radicals by OMS-2, namely CuO in the presence of PMS_XLower valence Cu in OMS-2⁺、Mn²⁺Or Mn³⁺Is oxidized into Cu²⁺、Mn⁴⁺Simultaneously, strong oxidizing sulfate radicals and hydroxyl radicals are generated, so that Rhodamine B is degraded.

The CuO_XThe steps of the reaction of OMS-2 in catalyzing PMS to generate sulfate radicals to degrade Rhodamine B are as follows:

step 1: adding the Rhodamine B solution into a cuvette, and adding PMS solution;

step 2: recording the absorption peak value of Rhodamine B at the moment by the test;

and step 3: rapid reaction of CuO_Xthe/OMS-2 catalyst was added to a cuvette and the peak pattern of the Rhodamine B UV-VIS absorption spectrum was measured using a UV-VIS spectrophotometer.

CuO described in step 3_XThe mass of the/OMS-2 catalyst is 5-15 mg.

FIG. 7 is CuO prepared by the present invention_XThe catalysis effect can be detected by an ultraviolet-visible light photometer at 556nm through a characteristic peak of Rhodamine B, and the termination of the reaction can be judged through the reduction of the absorbance of the Rhodamine B at 556 nm.

Example 7

CuO obtained in example 1 of the present invention was used_XThe application of the/OMS-2 catalyst in the reaction of catalytic degradation of p-nitrophenol and sodium borohydride.

CuO_XThe mechanism for catalyzing and degrading the p-nitrophenol by the/OMS-2 catalyst is as follows: firstly, sodium borohydride is hydrolyzed and decomposed to generate B (OH)₄ ^-And active hydrogen, and then transferring the active hydrogen to CuO_XThe catalyst is/OMS-2, and is adsorbed on the surface of the catalyst; finally, the active hydrogen on the surface of the catalyst reacts with p-nitrophenolP-aminophenol should be produced.

The CuO_XThe method for catalyzing the reaction of p-nitrophenol and sodium borohydride by using the OMS-2 catalyst comprises the following steps:

step 1: dissolving p-nitrophenol in deionized water, and performing ultrasonic treatment until the p-nitrophenol is dissolved to prepare a solution with the concentration of 2.5 multiplied by 10^{- 4}mmol/ml solution;

step 2: reacting NaBH₄Dissolving in deionized water to obtain a solution with a concentration of 2.5 × 10^-2mmol/ml solution;

and step 3: taking 1mL of the p-nitrophenol solution obtained in the step 1 to a cuvette, and adding NaBH obtained in the step 2₄1ml of the solution is mixed evenly

And 4, step 4: mixing CuO_Xthe/OMS-2 catalyst is quickly added into a reaction system, and an ultraviolet-visible light photometer is used for measuring the peak type of a p-nitrophenol ultraviolet visible light absorption spectrogram.

The CuO_XThe mass of the/OMS-2 catalyst in the reaction system is 5-15 mg.

Fig. 8 is an ultraviolet-visible light absorption spectrum diagram of catalytic degradation of p-nitrophenol by the catalyst prepared by the invention, the catalytic effect can be detected by an ultraviolet-visible light photometer at wavelengths of 400nm and 300nm to obtain characteristic peaks of p-nitrophenol and p-aminophenol, and the termination of the reaction can be judged by the decrease of the absorbance of p-nitrophenol at the wavelength of 400nm and the increase of the absorbance of p-aminophenol at the wavelength of 300 nm.

Example 8

CuO obtained in example 1 of the present invention was used_XThe application of the/OMS-2 catalyst in the catalytic degradation of 2, 4-dinitrophenol and sodium borohydride reaction.

CuO_XThe mechanism of the 2, 4-dinitrophenol catalytic degradation by the/OMS-2 catalyst is as follows: firstly, sodium borohydride is hydrolyzed and decomposed to generate B (OH)₄ ^-And active hydrogen, and then transferring the active hydrogen to CuO_XThe catalyst is/OMS-2, and is adsorbed on the surface of the catalyst; finally, the process is carried out in a batch,active hydrogen on the surface of the catalyst reacts with 2, 4-dinitrophenol to generate 2, 4-diaminophenol.

The CuO_XThe steps of the OMS-2 catalyst in catalyzing the reaction of 2, 4-dinitrophenol and sodium borohydride are as follows:

step 1: dissolving 2, 4-dinitrophenol in deionized water, and performing ultrasonic treatment until the solution is dissolved to prepare the solution with the concentration of 2.5 multiplied by 10^-4mmol/ml solution;

step 2: reacting NaBH₄Dissolving in deionized water to obtain a solution with a concentration of 2.5 × 10^-2mmol/ml solution;

and step 3: taking 1mL of the 2, 4-dinitrophenol solution obtained in the step 1 to a cuvette, and adding NaBH obtained in the step 2₄1ml of the solution is mixed evenly

And 4, step 4: mixing CuO_Xthe/OMS-2 catalyst is quickly added into the reaction system, and the peak type of the ultraviolet-visible light absorption spectrogram of the 2, 4-dinitrophenol is measured by an ultraviolet-visible light photometer.

The CuO_XThe mass of the/OMS-2 catalyst in the reaction system is 5-15 mg.

FIG. 9 is an ultraviolet-visible light absorption spectrum of 2, 4-dinitrophenol catalytically degraded by the catalyst prepared by the present invention, the catalytic effect can be detected by an ultraviolet-visible light photometer at the wavelengths of 440nm and 360nm for 2, 4-dinitrophenol, at 300nm for the characteristic peak of p-aminophenol, and the termination of the reaction can be judged by the decrease of the absorbance of 2, 4-dinitrophenol at the wavelengths of 440nm and 360nm and the increase of the absorbance of 2, 4-diaminophenol at 300 nm.

Example 9

CuO obtained in example 1 of the present invention was used_XThe application of the/OMS-2 catalyst in the catalytic degradation of 4-nitrobenzene diazonium tetrafluoroborate and sodium borohydride reaction.

CuO_XThe mechanism of the catalytic degradation of the 4-nitrobenzene diazonium tetrafluoroborate by the catalyst/OMS-2 is as follows: firstly, sodium borohydride is hydrolyzed and decomposed to generate B (OH)₄ ^-And active hydrogen, and then transferring the active hydrogen to CuO_XThe catalyst is/OMS-2, and is adsorbed on the surface of the catalyst; finally, the active hydrogen on the surface of the catalyst reacts with the 4-nitrobenzene diazonium tetrafluoroborate to generate the 4-aminobenzene diazonium tetrafluoroborate.

The CuO_XThe method for catalyzing the reaction of 4-nitrobenzene diazonium tetrafluoroborate and sodium borohydride by using the OMS-2 catalyst comprises the following steps:

step 1: dissolving 4-nitrobenzene diazonium tetrafluoroborate in deionized water, performing ultrasonic treatment until the solution is dissolved, and preparing the solution with the concentration of 2.5 multiplied by 10^-4mmol/ml solution;

step 2: reacting NaBH₄Dissolving in deionized water to obtain a solution with a concentration of 2.5 × 10^-2mmol/ml solution;

and step 3: taking 1mL of the 4-nitrobenzene diazonium tetrafluoroborate solution obtained in the step 1 into a cuvette, and adding NaBH obtained in the step 2₄1ml of the solution is mixed evenly

And 4, step 4: mixing CuO_Xthe/OMS-2 catalyst is quickly added into a reaction system, and an ultraviolet-visible light photometer is used for measuring the peak type of the ultraviolet-visible light absorption spectrogram of the 4-nitrobenzene diazo tetrafluoroborate.

The CuO_XThe mass of the/OMS-2 catalyst in the reaction system is 5-15 mg.

FIG. 10 is an ultraviolet-visible light absorption spectrum diagram of the novel catalyst prepared by the invention for catalytic degradation of 4-nitrophenyldiazonium tetrafluoroborate, the catalytic effect can be detected by an ultraviolet-visible light photometer at a wavelength of 400nm, and the termination of the reaction can be judged by the decrease of the absorbance of the 4-nitrophenyldiazonium tetrafluoroborate at the wavelength of 400 nm.

Example 10

CuO obtained in example 1 of the present invention was used_XThe application of the/OMS-2 catalyst in the reaction of catalytic degradation of p-nitrophenol and sodium borohydride is repeated for 10 times.

CuO_XThe mechanism for catalyzing and degrading the p-nitrophenol by the/OMS-2 catalyst is as follows: firstly, sodium borohydride is hydrolyzed and decomposed to generate B (OH)₄ ^-And active hydrogen, and then transferring the active hydrogen to CuO_XThe catalyst is/OMS-2, and is adsorbed on the surface of the catalyst; finally, active hydrogen on the surface of the catalyst reacts with p-nitrophenol to generate p-aminophenol.

The CuO_XThe method for catalyzing the reaction of p-nitrophenol and sodium borohydride by using the OMS-2 catalyst comprises the following steps:

step 1: dissolving p-nitrophenol in deionized water, and performing ultrasonic treatment until the p-nitrophenol is dissolved to prepare a solution with the concentration of 2.5 multiplied by 10^{- 4}mmol/ml solution;

step 2: reacting NaBH₄Dissolving in deionized water to obtain a solution with a concentration of 2.5 × 10^-2mmol/ml solution;

and step 3: taking 1mL of the p-nitrophenol solution obtained in the step 1 to a cuvette, and adding NaBH obtained in the step 2₄1ml of the solution is mixed evenly

And 4, step 4: mixing CuO_Xthe/OMS-2 catalyst is quickly added into a reaction system, and an ultraviolet-visible light photometer is used for measuring the peak type of a p-nitrophenol ultraviolet visible light absorption spectrogram.

And 5: mixing CuO_XThe step 1 to the step 4 are repeated by filtering, washing and drying the/OMS-2 catalyst, and the circulation is carried out for 10 times. The CuO_XThe mass of the/OMS-2 catalyst in the reaction system is 5-15 mg.

Fig. 11 is a graph of degradation time of p-nitrophenol in the catalytic degradation of the catalyst prepared by the invention in 10 times of repeated cycles, the catalytic effect can be represented by the ratio of absorbance before and after degradation and time, the ratio of absorbance before and after degradation is 0, which indicates complete degradation, and the shorter the time, the better the degradation effect.

Example 11

CuO prepared by the invention_XApplication of/OMS-2 in catalyzing PMS to generate sulfate radicals to degrade Rhodamine B.

CuO_XThe reaction mechanism of degrading Rhodamine B by catalyzing PMS to generate sulfate radicals by OMS-2, namely CuO in the presence of PMS_XLower valence Cu in OMS-2⁺、Mn²⁺Or Mn³⁺Is oxidized into Cu²⁺、Mn⁴⁺Simultaneously, strong oxidizing sulfate radicals and hydroxyl radicals are generated, so that Rhodamine B is degraded.

The CuO_XThe steps of the reaction of OMS-2 in catalyzing PMS to generate sulfate radicals to degrade Rhodamine B are as follows:

step 1: adding the Rhodamine B solution into a cuvette, and adding PMS solution;

step 2: recording the absorption peak value of Rhodamine B at the moment by the test;

and step 3: rapid reaction of CuO_Xthe/OMS-2 catalyst was added to a cuvette and the peak pattern of the Rhodamine B UV-VIS absorption spectrum was measured using a UV-VIS spectrophotometer.

And 4, step 4: mixing CuO_XThe step 1 to the step 4 are repeated by filtering, washing and drying the/OMS-2 catalyst, and the circulation is carried out for 10 times.

CuO described in step 3_XThe mass of the/OMS-2 catalyst is 5-15 mg.

FIG. 12 is a graph of the degradation time of Rhodamine B catalyzed and degraded by the catalyst prepared by the present invention after 10 times of repeated cycles, the catalytic effect can be expressed by the ratio of absorbance before and after degradation and the time, the ratio of absorbance before and after degradation is 0, which indicates complete degradation, and the shorter the time, the better the degradation effect.

Claims (3)

1. CuO (copper oxide)_XThe application of the/OMS-2 catalyst in the reaction of catalytic degradation of p-nitrophenol and sodium borohydride is characterized by comprising the following steps:

step 1: dissolving p-nitrophenol in deionized water, and performing ultrasonic treatment until the p-nitrophenol is dissolved to prepare a solution with the concentration of 2.5 multiplied by 10^-4mmol/ml solution;

step 2: reacting NaBH₄Dissolving in deionized water to obtain a solution with a concentration of 2.5 × 10^-2mmol/ml solution;

and step 3: putting 1mL of the p-nitrophenol solution obtained in the step 1 into a cuvette, adding 1mL of the NaBH4 solution obtained in the step 2, and uniformly mixing;

and 4, step 4: mixing CuO_XThe OMS-2 catalyst is quickly added into a reaction system, and an ultraviolet-visible light photometer is used for measuring the peak type of a p-nitrophenol ultraviolet visible light absorption spectrogram;

CuO_Xthe preparation method of the/OMS-2 catalyst comprises the following steps: a50 ml round bottom flask was charged with 2g of OMS-2, 0.15g of Cu (NO)₃)₂Dissolving in 10ml of water to obtain a solution, adding 10ml of water, performing ultrasonic treatment at room temperature for 3h, stirring at room temperature for 20h, performing reduced pressure distillation at 80 ℃ for 2h to obtain black powder, drying the black powder at 110 ℃ for 4h, drying, and calcining at 350 ℃ for 2h to obtain the product.

2. CuO (copper oxide)_XThe application of the/OMS-2 catalyst in the catalytic degradation of 2, 4-dinitrophenol and sodium borohydride reaction is characterized by comprising the following steps:

step 1: dissolving 2, 4-dinitrophenol in deionized water, and performing ultrasonic treatment until the solution is dissolved to prepare the solution with the concentration of 2.5 multiplied by 10^{- 4}mmol/ml solution;

step 2: reacting NaBH₄Dissolving in deionized water to obtain a solution with a concentration of 2.5 × 10^-2mmol/ml solution;

and step 3: putting 1mL of the 2, 4-dinitrophenol solution obtained in the step 1 into a cuvette, adding 1mL of the NaBH4 solution obtained in the step 2, and uniformly mixing;

and 4, step 4: mixing CuO_XThe OMS-2 catalyst is quickly added into a reaction system, and an ultraviolet-visible light spectrophotometer is used for measuring the peak type of the ultraviolet-visible light absorption spectrogram of the 2, 4-dinitrophenol;

CuO_Xthe preparation method of the/OMS-2 catalyst comprises the following steps: a50 ml round bottom flask was charged with 2g of OMS-2, 0.15g of Cu (NO)₃)₂Dissolving in 10ml water to obtain solution, adding 10ml water, performing ultrasonic treatment at room temperature for 3 hr, stirring at room temperature for 20 hr, distilling at 80 deg.C under reduced pressure for 2 hr to obtain black powder, drying at 110 deg.C for 4 hr, drying, and calcining at 350 deg.C for 2 hr to obtain the final productA compound (I) is provided.

3. CuO (copper oxide)_XThe application of the/OMS-2 catalyst in the catalytic degradation of 4-nitrobenzene diazonium tetrafluoroborate and sodium borohydride reaction is characterized by comprising the following steps:

step 1: dissolving 4-nitrobenzene diazonium tetrafluoroborate in deionized water, performing ultrasonic treatment until the solution is dissolved, and preparing the solution with the concentration of 2.5 multiplied by 10^-4mmol/ml solution;

step 2: reacting NaBH₄Dissolving in deionized water to obtain a solution with a concentration of 2.5 × 10^-2mmol/ml solution;

and step 3: taking 1mL of the 4-nitrobenzene diazonium tetrafluoroborate solution in the step 1 into a cuvette, adding 1mL of the NaBH4 solution in the step 2, and uniformly mixing;

and 4, step 4: mixing CuO_XThe OMS-2 catalyst is quickly added into a reaction system, and an ultraviolet-visible light photometer is used for measuring the peak type of the ultraviolet-visible light absorption spectrogram of the 4-nitrobenzene diazonium tetrafluoroborate;

CuO_Xthe preparation method of the/OMS-2 catalyst comprises the following steps: a50 ml round bottom flask was charged with 2g of OMS-2, 0.15g of Cu (NO)₃)₂Dissolving in 10ml of water to obtain a solution, adding 10ml of water, performing ultrasonic treatment at room temperature for 3h, stirring at room temperature for 20h, performing reduced pressure distillation at 80 ℃ for 2h to obtain black powder, drying the black powder at 110 ℃ for 4h, drying, and calcining at 350 ℃ for 2h to obtain the product.

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