CN111013630B - Heptamolybdate intercalated porous carbon nitride and preparation method and application thereof - Google Patents
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- B01J35/39—
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to heptamolybdate intercalated porous carbon nitride and a preparation method and application thereof, which comprises the step of carrying out thermal polymerization reaction by using dicyandiamide as a precursor, ammonium heptamolybdate tetrahydrate as a molybdenum source and urea as a pore-forming agent. The photocatalyst provided by the invention has strong response to visible light, high efficiency of degrading phenol pollutants and good recycling property, and the preparation process has the advantages of simple operation, mild reaction, environmental protection, low cost and the like, and shows wide application prospect in the field of environmental photocatalysis.
Description
Technical Field
The invention relates to the technical field of functional materials, in particular to heptamolybdate intercalated porous carbon nitride and a preparation method and application thereof.
Background
With the rapid development of the petrochemical industry, a large amount of phenolic substances are discharged into natural water bodies (such as surface water and underground water) by human beings, and the diversity, persistence, endocrine disruptions and acute toxicity of the phenolic substances seriously threaten the health of ecosystems and human bodies. Therefore, how to effectively remove the persistent phenolic compounds in the wastewater, reduce the pollution risk, and realize the recycling of water is a problem which needs to be solved at present. The traditional sewage treatment process, such as an adsorption method, an aerobic/anaerobic biological method, precipitation filtration, ion exchange and the like, can not effectively treat the pollutants, and has the defects of high cost, complex steps, easy generation of secondary pollution and the like. In recent years, due to environmental protection and the utilization of solar energy, heterogeneous photocatalytic oxidation has received extensive attention and research in the field of environmental purification.
Graphite phase carbon nitride (g-C)3N4) As a typical organic high polymer semiconductor, it can respond not only to visible light,Has good chemical stability and forms a highly delocalized pi conjugated structure. However, bulk phase g-C3N4The light absorption capability is weak, the photon-generated electrons and holes are easy to recombine, the service life of a current carrier is short, and the improvement of the utilization rate of visible light is always a challenging problem for research. Doping modification is often used to modulate g-C3N4The energy level structure enhances the surface oxidation reduction capability and promotes the separation and transmission of photo-generated electrons and holes, thereby improving the photodegradation efficiency. Compared with non-metal elements such as oxygen, chlorine, bromine and the like, the valence-variable transition metal such as molybdenum and the like can not only adjust energy bands, but also serve as an active center to accelerate the transmission of electrons of a photocatalytic system through redox circulation, so that the industrial practicability of the catalyst is increased. Therefore, a suitable doping modification method is searched for, and novel efficient g-C is developed3N4Base catalysts have become a new challenge in the field of environmental cleanup.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a heptamolybdate intercalated porous carbon nitride (Mo-UCN) visible-light-driven photocatalyst (used for efficiently removing phenolic pollutants) and a preparation method and application thereof.
One of the purposes of the invention is to provide a preparation method of a heptamolybdate intercalated carbon nitride material, which comprises the step of carrying out thermal polymerization reaction by using dicyandiamide as a precursor, ammonium heptamolybdate tetrahydrate as a molybdenum source and urea as a pore-forming agent.
According to some preferred embodiments of the present invention, the method comprises the steps of:
step 1), mixing dicyandiamide, urea and ammonium heptamolybdate tetrahydrate, and stirring at a certain temperature to obtain a solid mixture;
and 2), grinding the solid mixture obtained in the step 1), and then carrying out thermal polymerization reaction to obtain the catalyst.
According to some preferred embodiments of the invention, in the step 1), the mass of the dicyandiamide and the urea is 1 (0.1-10), and preferably 1 (0.2-3).
According to some preferred embodiments of the present invention, in step 1), the mass ratio of dicyandiamide to ammonium heptamolybdate tetrahydrate is 1 (0.001-0.1), preferably 1 (0.003-0.02).
According to some preferred embodiments of the present invention, in step 1), dicyandiamide and urea are dissolved in a solvent, the temperature is adjusted to 30-90 ℃, preferably 80 ℃, after stirring in a thermostatic water bath for 10-60 min, preferably 30min, ammonium heptamolybdate tetrahydrate is added, the temperature is maintained at 30-90 ℃, preferably 80 ℃, and stirring is continued until the solvent is evaporated to dryness, so as to obtain a premix.
According to some preferred embodiments of the present invention, in step 1), the solvent is an organic solvent or water, preferably water.
According to some preferred embodiments of the present invention, in step 2), the thermal polymerization conditions: the roasting temperature is 450-600 ℃, preferably 550 ℃, and the heating speed is 1-5 ℃ per min-1Preferably 2 ℃ min-1The roasting atmosphere is air, and the roasting time is 1-4 hours, preferably 3 hours.
The invention also aims to provide a heptamolybdate intercalated carbon nitride material prepared by the method.
The Mo-UCN visible light catalyst for efficiently removing phenolic pollutants provided by the invention is formed by connecting a two-dimensional layered structure g-C by heptamolybdate intercalation bonds3N4The structure is simple, and the photocatalytic activity and stability are excellent.
According to some preferred embodiments of the present invention, the carbon nitride is composed of graphite-phase carbon nitride having a heptamolybdate intercalated bonded two-dimensional layered structure.
The invention further aims to provide an application of the heptamolybdate intercalated carbon nitride material or the heptamolybdate intercalated carbon nitride material prepared by the method as a photocatalyst in visible light-catalyzed efficient degradation of environmental pollutants, preferably phenolic pollutants.
The method synthesizes the heptamolybdate intercalated porous carbon nitride catalyst by taking dicyandiamide as a precursor, ammonium heptamolybdate tetrahydrate as a molybdenum source and urea as a pore-forming agent through a high-temperature roasting method. In the process of constant-temperature water bath, heptamolybdate ions and dicyandiamide form a surface coordination structure to carry out molecular self-assembly, so that the transition metal is stably complexed in g-C3N4Between layers of (a). Because the method has simple operation and is reverseThe reaction condition is mild, and the raw materials are cheap and easy to obtain, so the method is suitable for large-scale production and practical application.
The invention has the beneficial effects that:
(1) the thermal polymerization preparation method of the heptamolybdate intercalated porous carbon nitride provided by the invention can be completed only by taking dicyandiamide, ammonium heptamolybdate tetrahydrate and urea as raw materials and roasting at high temperature in air. The method has the advantages of easily available raw materials, mild reaction conditions, low production cost, simple operation, capability of obtaining the material with high-efficiency activity of removing the difficultly degraded phenols by only one-step reaction, good recycling property and suitability for industrial popularization.
(2) The heptamolybdate intercalated porous carbon nitride prepared by the method is in a porous curled layered structure, and heptamolybdate bonds with two-dimensional layered carbon nitride in layers, so that effective adsorption is formed on phenolic pollutants, the mass transfer process of a catalytic system is promoted, and the heptamolybdate intercalated porous carbon nitride has high-efficiency photocatalytic degradation capability.
Drawings
FIG. 1 is a characterization map of 0.8 wt% Mo-UCN-2 prepared in example 1 of the present invention; wherein, a) is a Scanning Electron Microscope (SEM) picture, and b) is a Transmission Electron Microscope (TEM) picture.
FIG. 2 illustrates two Mo-UCN models prepared in example 1 of the present invention by DFT structure optimization; wherein a) is heptamolybdate horizontal intercalation g-C3N4Structure, b) is heptamolybdate vertical intercalation g-C3N4Structure (brown, blue, red, white are C, N, O, Mo atoms, respectively).
FIG. 3 is a graph showing the photodegradation performance of 0.8 wt% Mo-UCN-0.2-3 against BPA prepared in example 1 of the present invention.
FIG. 4 is a graph of the photodegradation performance of 0.3-2 wt% Mo-UCN-2 on BPA prepared in example 1 of the present invention.
FIG. 5 is an activity spectrum of 0.8 wt% Mo-UCN-2 cyclic photodegradation BPA prepared in example 1 of this invention.
FIG. 6 is an IR spectrum of 0.8 wt% Mo-UCN-2 prepared in inventive example 1 before and after cyclic degradation of BPA.
FIG. 7 is a graph of the photodegradation efficiencies of 0.8 wt% Mo-UCN-2 for different phenolic contaminants prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. The technical solution of the present invention is not limited to the following specific embodiments, and includes any combination of the specific embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
In the present invention, the specific techniques or conditions not specified in the examples are performed according to the techniques or conditions described in the literature in the art or according to the product specification. The instruments and the like are conventional products which are purchased by normal distributors and are not indicated by manufacturers. The chemical raw materials used in the invention can be conveniently bought in domestic chemical product markets.
Example 1
The preparation method of the two-dimensional porous layered Mo-UCN comprises the following specific steps:
(1) weighing 5g of dicyandiamide and 1-15 g of urea, adding the dicyandiamide and the urea into 40mL of water, placing the mixture into a water bath kettle with the constant temperature of 80 ℃, and magnetically stirring until the dicyandiamide and the urea are completely dissolved. Weighing a proper amount of ammonium heptamolybdate tetrahydrate (0.015-0.1 g) and adding the ammonium heptamolybdate tetrahydrate into the solution, and continuously stirring until the water is completely evaporated to obtain a solid mixture;
(2) grinding the solid mixture obtained in the step (1) into powder, placing the powder into a 50mL ceramic crucible, continuously roasting the powder at 550 ℃ for 3h in a muffle furnace (the heating rate is 2 ℃/min), naturally cooling the powder to normal temperature to obtain a product catalyst, namely x wt% Mo-UCN-y, wherein x represents the mass ratio of ammonium heptamolybdate tetrahydrate to dicyandiamide (0.3-2): 1, y represents the mass ratio of the preferable urea to the dicyandiamide (0.2-3): 1. the resulting Mo-UCN was a two-dimensional material, wherein SEM and TEM of 0.8 wt% Mo-UCN-2 are shown in FIGS. 1a and 1b, forming a porous, curled lamellar structure.
Example 2
The visible light degradation effect of the two-dimensional porous layered Mo-UCN prepared in the example 1 on BPA is detected, and the specific operation is as follows:
(1) 50mL of BPA solution (10 mg. L) was added to a 100mL beaker in this order-1) And 50mg of catalyst;
(2) magnetically stirring the suspension for 30min under dark condition to achieve adsorption-desorption balance;
(3) then in visible light (wavelength lambda)>420nm, light intensity of 20mw cm-2) Under irradiation, a catalytic reaction is carried out. Samples were taken at regular intervals and passed through a 0.45 μm filter to obtain a clear solution, and changes in the concentration of BPA in the solution were measured by high performance liquid chromatography.
FIG. 3 is a graph of the photodegradation efficiency of 0.8 wt% Mo-UCN-0.2-3 to BPA prepared with different amounts of pore-forming agent, and FIG. 4 is a graph of the photodegradation efficiency of 0.3-4 wt% Mo-UCN-2 to BPA prepared with different contents of molybdenum source; as can be seen from FIGS. 3 and 4, 0.8 wt% Mo-UCN-2 has the best catalytic activity, and the BPA removal rate reaches 95% after 30min of photoreaction.
Example 3
The stability and recycling effect of the two-dimensional porous layered Mo-UCN prepared in example 1 were examined, and the test was performed using 0.8 wt% Mo-UCN-2 having the best catalytic activity as a target sample, and the specific operations were as follows:
(1) to a 100mL beaker were added 50mg of 0.8 wt% Mo-UCN-2 catalyst and 50mL of BPA solution (10 mg. L.) in that order-1)；
(2) Magnetically stirring the suspension for 30min under dark condition to achieve adsorption-desorption balance;
(3) then in visible light (wavelength lambda)>420nm, light intensity of 20mw cm-2) Under irradiation, a catalytic reaction is carried out. Samples were taken at regular intervals and passed through a 0.45 μm filter to obtain a clear solution, and changes in the concentration of BPA in the solution were measured by high performance liquid chromatography.
(4) And (3) after the photocatalytic reaction, passing the residual suspension through a 0.45-micrometer filter membrane, washing and drying to obtain the residual catalyst, and continuously repeating the steps (1) to (4) for 5 times of cycle tests.
FIG. 5 is an activity diagram of 0.8 wt% Mo-UCN-2 cycle photodegradation BPA; as shown in FIG. 5, after 5 cycles of testing, BPA removal was nearly unchanged and still reached 97%. FIG. 6 is an infrared spectrum of 0.8 wt% Mo-UCN-2 solid powder before and after photodegradation of BPA; as can be seen from FIG. 6, the characteristic peak of 0.8 wt% Mo-UCN-2 before and after cyclic degradation of BPA is unchanged with g-C3N4The typical two-dimensional layered structure shows excellent stability and has practical application prospect.
Example 4
The broad spectrum of the two-dimensional porous layered Mo-UCN prepared in example 1 for removing phenolic pollutants was examined, specifically as follows:
(1) 50mL of 2, 4-dichlorophenol (2,4-DCP), 2,4, 6-trichlorophenol (2,4,6-TCP), 4-chlorophenol (4-CP), 2-chlorophenol (2-CP), and a phenol (phenol) solution (10 mg. L.) were added to a 100mL beaker in this order-1) And 50mg of catalyst;
(2) magnetically stirring the suspension for 30min under dark condition to achieve adsorption-desorption balance;
(3) then in visible light (wavelength lambda)>420nm, light intensity of 20mw cm-2) Under irradiation, a catalytic reaction is carried out. Samples were taken at regular intervals and passed through a 0.45 μm filter to obtain a clear solution, and the change in the concentration of contaminants in the solution was determined by high performance liquid chromatography.
FIG. 7 is a graph of photodegradation performance of 0.8 wt% Mo-UCN-2 for different phenolic contaminants; as can be seen from FIG. 7, after 60min of photoreaction, the removal rates of 2,4-DCP, 2,4,6-TCP, 4-CP, 2-CP and phenol reached 99%, 100%, 94%, 92% and 89%, indicating that 0.8 wt% Mo-UCN-2 has broad spectrum for visible light catalytic degradation of phenolic pollutants.
Comparative example 1
The method of example 1 was used except that urea and ammonium heptamolybdate tetrahydrate were not added to provide a pure Carbon Nitride (CN) catalyst with a BPA removal of only 13%.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (2)
1. The application of the heptamolybdate intercalated carbon nitride material as a photocatalyst in efficiently degrading phenolic pollutants by visible light is characterized in that the heptamolybdate intercalated carbon nitride material consists of graphite-phase carbon nitride with a heptamolybdate intercalated bond two-dimensional layered structure; the preparation method of the heptamolybdate intercalated carbon nitride material comprises the following steps:
1) mixing dicyandiamide, urea and ammonium heptamolybdate tetrahydrate, and stirring at a certain temperature to obtain a solid mixture;
2) grinding the solid mixture obtained in the step 1), and then carrying out thermal polymerization reaction to obtain the catalyst;
in the step 1), dissolving dicyandiamide and urea in a solvent, adjusting the temperature to 80 ℃, stirring in a constant-temperature water bath for 30min, adding ammonium heptamolybdate tetrahydrate, keeping the temperature at 80 ℃, and continuing stirring until the solvent is evaporated to dryness to obtain a premix; in the step 1), the solvent is water; in step 2), the thermal polymerization conditions: the roasting temperature is 550 ℃, and the temperature rising speed is 2 ℃ for min-1The roasting atmosphere is air, and the roasting time is 3 hours;
performing thermal polymerization reaction by using dicyandiamide as a precursor, ammonium heptamolybdate tetrahydrate as a molybdenum source and urea as a pore-forming agent; the mass ratio of the dicyandiamide to the urea is 1:2, and the mass ratio of the dicyandiamide to the ammonium heptamolybdate tetrahydrate is 1: 0.008.
2. A heptamolybdate intercalated carbon nitride material prepared by the preparation method in the application of claim 1, and consisting of graphite-phase carbon nitride with a heptamolybdate intercalated and bonded two-dimensional layered structure.
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| CN108273540A (en) * | 2018-02-13 | 2018-07-13 | 西安理工大学 | A kind of Mo doped graphites phase carbon nitride nanometer sheet powder and preparation method thereof |
| CN109174148A (en) * | 2018-08-10 | 2019-01-11 | 广州大学 | A kind of catalyst and preparation method thereof of catalysis oxidation toluene synthesizing benzaldehyde |
| CN110302824A (en) * | 2019-08-06 | 2019-10-08 | 辽宁大学 | Molybdenum doping graphite phase carbon nitride catalyst and its preparation method and application |
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| CN108273540A (en) * | 2018-02-13 | 2018-07-13 | 西安理工大学 | A kind of Mo doped graphites phase carbon nitride nanometer sheet powder and preparation method thereof |
| CN109174148A (en) * | 2018-08-10 | 2019-01-11 | 广州大学 | A kind of catalyst and preparation method thereof of catalysis oxidation toluene synthesizing benzaldehyde |
| CN110302824A (en) * | 2019-08-06 | 2019-10-08 | 辽宁大学 | Molybdenum doping graphite phase carbon nitride catalyst and its preparation method and application |
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