CN114100662A - 3D flower-shaped Z-shaped heterojunction catalyst and preparation method and application thereof - Google Patents
3D flower-shaped Z-shaped heterojunction catalyst and preparation method and application thereof Download PDFInfo
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- CN114100662A CN114100662A CN202111446842.6A CN202111446842A CN114100662A CN 114100662 A CN114100662 A CN 114100662A CN 202111446842 A CN202111446842 A CN 202111446842A CN 114100662 A CN114100662 A CN 114100662A
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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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- B01J37/08—Heat treatment
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F2101/305—Endocrine disruptive 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
- C02F2101/345—Phenols
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a 3D flower-shaped Z-shaped heterojunction catalyst, a preparation method and application thereof, wherein the catalyst is prepared by doping g-C with oxygen3N4(O‑g‑C3N4) As a carrier, O-g-C3N4Having a two-dimensional nano-platelet structure, MoS2As a photocatalytically active component, MoS2Having a three-dimensional flower-like nanostructure, MoS2Uniformly dispersed on the surface of the carrier. The invention successfully prepares the 3D/2D MoS by adopting a solvothermal method2/O‑g‑C3N4Composite material, and 2D MoS2Comparative 3D MoS2The composite material has larger specific surface area, thereby exposing more reactive active sites, being mainly applied to degradation of endocrine disruptors in sewage, solving the problem of environmental pollution caused by other methods such as a template agent or a dipping-vulcanizing method and the like at present and meeting conditions, and providing a new approach for a green, safe and low-cost synthesis technology.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, relates to a functional catalyst for photocatalytic degradation of endocrine disruptors, and a preparation method and application thereof, and particularly relates to 3D flower-shaped MoS2/O-g-C3N4A Z-type heterojunction catalyst, a preparation method and application thereof.
Background
Among the various pollutions, the pollution of water resources which human beings rely on for survival is the most serious. Among them, the main industries causing the problem of water pollution to be aggravated are printing and dyeing wastewater and medical wastewater. According to incomplete statistics, the discharge amount of the medical wastewater of China only reaches 20 hundred million tons per year currently, and the discharge amount is the fifth of the discharge amount of the industrial wastewater of China. Endocrine disruptors in medical waste water can be transferred to the environment through plastics and are increasingly detected in aqueous environments, posing a serious threat to the ecological environment. Bisphenol A (BPA), also known as bisphenol propane, is a low toxicity compound and is an important raw material for producing polycarbonate, epoxy resin, phenolic resin, polysulfone and special materials. Because of its light weight, colorless and good toughness, it is widely used to make food and beverage containers such as notebook, mobile phone and milk bottle. However, numerous studies have demonstrated that BPA has endocrine disrupting effects, can be transported to the environment through plastics, and that increasing amounts of BPA are detected in water bodies, posing a serious threat to ecosystem.
Currently, various removal techniques, such as chemical reactions, biodegradation, and physical adsorption, are studied. Among them, photocatalytic degradation is considered as an effective method for removing phenolic pollutants in water. The photocatalysis technology is to convert low-density solar energy into high-density chemical energy, can directly utilize the solar energy to degrade and mineralize various organic pollutants in water and air, and has the advantages of mild reaction condition and no pollutionDyeing, low cost and the like. However, the fast recombination of photo-generated electrons-holes and the narrow range of photo-response in photocatalysts are currently major concerns. Therefore, the development of efficient photocatalysts is the focus and core of photocatalytic scientific research at present. Graphite phase carbon nitride (g-C)3N4) Since 2009, the semiconductor material is discovered to be used for photocatalytic hydrogen production as an n-type non-metal semiconductor material, the semiconductor material is gradually a research hotspot in the field of photocatalysis. The unique semiconductor energy band structure and good chemical stability of the semiconductor energy band structure are widely applied to the fields of photocatalytic hydrogen evolution, photocatalytic degradation, carbon dioxide reduction and the like. However, the currently synthesized g-C3N4The defects of small specific surface area, over-high photon-generated carrier recombination rate and the like still exist, and the photocatalytic activity is low. The modification method comprises element doping, heterojunction structure construction with other semiconductors and microstructure construction. In the modification methods, the porous structure can provide a large specific surface area and a channel for easy diffusion of a photon-generated carrier, so that light capture is improved, the mass transfer process is accelerated, and more active sites are provided for a photocatalytic reaction. In addition, doping with non-metallic elements is achieved by varying g-C3N4The chemical property, band gap reduction and electronic structure adjustment of the organic electroluminescent material can further effectively improve the g-C3N4Photocatalytic performance.
MoS2The semiconductor is an n-type semiconductor, the band gap is only 1.2-1.9 eV, and the semiconductor has a large specific surface area and excellent photoelectric properties. Simultaneous MoS2As a cocatalyst, more reactive active sites can be provided, the charge transfer resistance is reduced, and the photocatalytic performance is improved. Most of the reported MoS2/g-C3N4The composites are synthesized by a complex dip-cure process or other complex conditions, however, the composites prepared using this process, 2D MoS due to van der Waals interactions2Stacking or agglomeration is prone to occur and the process is also particularly complex. Numerous studies have demonstrated that 3D flower-like MoS, consisting of a suitable amount of nanosheets2It may inhibit stacking and agglomeration of sheets, expose more reactive sites, increase the specific surface area of catalyst, shorten charge transmission path and raise the interfaceTransfer efficiency, and stronger photoactivity.
Disclosure of Invention
The invention aims to provide a 3D flower-shaped Z-shaped heterojunction catalyst, and a preparation method and application thereof, and the 3D/2D MoS is successfully prepared by adopting a solvothermal method2/O-g-C3N4Composite material, and 2D MoS2Compare 3D MoS2The composite material has larger specific surface area, thereby exposing more reactive active sites, being mainly applied to degradation of endocrine disruptors in sewage, solving the problem of environmental pollution caused by other methods such as a template agent or a dipping-vulcanizing method and the like at present and meeting conditions, and providing a new approach for a green, safe and low-cost synthesis technology.
The purpose of the invention is realized by the following technical scheme:
A3D flower-shaped Z-shaped heterojunction catalyst is prepared by doping g-C with oxygen3N4(O-g-C3N4) As a carrier, O-g-C3N4Having a two-dimensional nano-platelet structure, MoS2As a photocatalytically active component, MoS2Having a three-dimensional flower-like nanostructure, MoS2Uniformly dispersed on the surface of the carrier, O-g-C3N4And MoS2Is 0.5: 0.1 to 0.3.
The preparation method of the 3D flower-shaped Z-shaped heterojunction catalyst comprises the step of carrying out solvothermal method on MoS2Is added to O-g-C3N4The method comprises the following steps:
step one, weighing O-g-C3N4Adding MoS thereto2Dispersing the mixture in an ethylene glycol solution, performing ultrasonic treatment for 0.5-1.5 h, and then putting the mixture into a magnetic stirrer to be stirred until the mixture is dissolved, wherein:
step two, transferring the solution obtained in the step one to a polytetrafluoroethylene reaction kettle, and reacting for 20-30 hours at 190-200 ℃;
step three, alternately washing the reaction product obtained in the step two by using absolute ethyl alcohol and deionized water, and then drying the reaction product in a forced air drying oven at the temperature of 60-80 ℃ to obtain MoS2/O-g-C3N4A catalyst.
The 3D flower-shaped Z-shaped heterojunction catalyst can be applied to photocatalytic degradation of bisphenol A (BPA), and the specific method comprises the following steps: mixing a to-be-degraded product and a catalyst, carrying out photocatalytic reaction after adsorption balance is achieved under a dark reaction condition, completing a degradation process, and carrying out solid-liquid separation on a reaction liquid obtained in the degradation process to obtain a degradation liquid and the used catalyst; and (4) filtering the degradation liquid by using a filter membrane, and then measuring the degradation content in a high performance liquid chromatography. Wherein: the degradation product is endocrine disruptor bisphenol A, the concentration of the degradation product is 30ppm, the addition amount of the degradation product is 50mL, and the addition amount of the catalyst is 0.05 g.
The invention also provides a circulation experiment of the catalyst, which comprises the following steps: and washing the used catalyst obtained after solid-liquid separation with ethanol, and drying at 80 ℃ for 6h to obtain the catalyst for the next step of photocatalytic degradation circulation.
Compared with the prior art, the invention has the following advantages:
1. the invention adds ammonium oxalate into precursor, and the ammonium oxalate and urea are synthesized into oxygen-doped modified g-C by a thermal polymerization method3N4Oxygen doping will replace g-C3N4At the position of N, creating N vacancies, resulting in energy level defects, by changing g-C3N4The chemical property, the band gap reduction and the electronic structure adjustment of the catalyst effectively improve the visible light response range of the catalyst and enhance the photocatalytic activity of the catalyst.
2. O-g-C in the invention3N4The construction of the porous structure of the catalyst can provide a large specific surface area and a channel for easy diffusion of a photon-generated carrier, thereby improving light capture, accelerating the mass transfer process and providing more active sites for photocatalytic reaction.
3. 3D flower-like MoS of the invention2/O-g-C3N4Z-type heterojunction catalyst with O-g-C3N4As a carrier, MoS2As the photocatalytic active component, the active component is a 3D flower-like structure, and compared with the 2D shape, the 3D flower-like structure can increase the specific surface area of the catalyst, namely the mass transfer of the bisphenol A can be accelerated through physical adsorption. At the same time, O-g-C3N4And MoS2The close contact and mutual synergistic effect between the interfaces effectively enhance the photocatalytic performance of the catalyst.
4、O-g-C3N4And MoS2The formation of Z-type heterojunction between the two layers effectively improves the effective separation of photo-generated electrons and holes, enhances the redox capability of the electrons and the holes and plays an effective role in the degradation of bisphenol A. The construction of the heterojunction effectively solves the problem of g-C3N4The self photogenerated carriers are quickly recombined.
5. 3D flower-shaped MoS2/O-g-C3N4The Z-type heterojunction catalyst can be applied to photocatalytic degradation of bisphenol A, has low application and operation requirements, mild reaction conditions and environmental friendliness, can be separated from degradation liquid by centrifugation after the degradation process is finished, and has a good circulation effect.
6. The preparation method of the catalyst provided by the invention is simple and convenient, has low process operation requirement required by application, and meets the requirement of industrial production.
Drawings
FIG. 1 is an oxygen-doped g-C prepared in example 13N4Scanning electron microscope photographs of (a);
FIG. 2 is the MoS prepared in example 22Scanning electron micrographs of the catalyst;
FIG. 3 is the MoS prepared in example 32/O-g-C3N4Scanning electron micrographs of the catalyst;
FIG. 4 is pure g-C prepared in comparative example 13N4Scanning electron micrographs of the catalyst;
FIG. 5 shows O-g-C prepared in examples 1 to 53N4Carrier, MoS2And MoS of different loading capacity2/O-g-C3N4Catalysts (0.1, 0.2 and 0.3%) and pure g-C prepared in comparative example 13N4XRD pattern of the catalyst;
FIG. 6 shows O-g-C prepared in examples 1 to 53N4Carrier, MoS2And do notMoS with same load capacity2/O-g-C3N4Catalysts (0.1, 0.2 and 0.3%) and pure g-C prepared in comparative example 13N4A photocatalytic degradation profile of the catalyst;
FIG. 7 shows O-g-C prepared in examples 1 to 53N4Carrier, MoS2And MoS of different loading capacity2/O-g-C3N4Catalysts (0.1, 0.2 and 0.3%) and pure g-C prepared in comparative example 13N4A photocatalytic degradation kinetic curve graph of the catalyst;
FIG. 8 is a graph of a photocatalytic degradation cycle experiment for example 4;
FIG. 9 is a possible degradation pathway for BPA from example 4;
FIG. 10 is a graph showing the effect on the rate of photodegradation of BPA by the addition of different radical scavengers in example 4;
FIG. 11 is a extrapolation of the chart for the photocatalytic degradation of BPA of example 4.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
Example 1:
weighing 10g of urea and 1g of oxygen source (ammonium oxalate) and dissolving in deionized water, carrying out ultrasonic treatment for 30min, then placing in a magnetic stirrer, stirring at 80 ℃ until the water is evaporated to dryness, transferring the obtained solid into a crucible, placing in a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, and keeping at the temperature for 2h to obtain yellow powder which is oxygen-doped graphite-phase carbon nitride nanosheet and is marked as O-g-C3N4。
Example 2:
weighing 2.1g molybdenum source (sodium molybdate) by using an analytical balance, putting the molybdenum source (sodium molybdate) into a beaker, adding 3.8g sulfur source (thiourea) into the beaker, adding 30mL deionized water, vigorously stirring at normal temperature for 1h, putting the mixture into a 50mL polytetrafluoroethylene reaction kettle, reacting at 200 ℃ for 24h, alternately washing the mixture by using absolute ethyl alcohol and deionized water, and putting the mixture into a forced air drying device to dry the mixtureOven drying at 60 deg.C to obtain black powder of molybdenum disulfide, and adding MoS2And (4) showing.
Example 3:
weighing 0.5g O-g-C3N4To this was added 0.1g of MoS2Dispersing the mixture in 25mL of glycol solution and carrying out ultrasonic treatment for 1h, then putting the mixture into a magnetic stirrer to be stirred until the mixture is dissolved, transferring the obtained solution into a 50mL polytetrafluoroethylene reaction kettle, reacting for 24h at 200 ℃, and carrying out cross washing by using absolute ethyl alcohol and deionized water. Drying at 60 deg.C in a forced air drying oven to obtain MoS based on the carrier2MoS with 0.1% of load2/O-g-C3N4A catalyst.
Example 4:
this example differs from example 3 in that: MoS2Was added in an amount of 0.2g, and the MoS of the obtained catalyst2The loading was 0.2%.
Example 5:
this example differs from example 3 in that: MoS2Was added in an amount of 0.3g, and the MoS of the obtained catalyst2The loading was 0.3%.
Comparative example 1:
the present comparative example differs from example 1 in that: pure g-C is obtained without adding ammonium oxalate3N4A catalyst.
FIG. 1 is O-g-C prepared in example 13N4Scanning Electron microscopy of the support, from FIG. 1 it can be seen that O-g-C3N4The carrier is of a skeleton structure and is provided with a large number of holes, and the hole structure can shorten the diffusion and migration distance of photo-generated charges from a bulk phase to the surface, so that the recombination of the photo-generated charges in the carrier is inhibited.
FIG. 2 is the MoS prepared in example 22Scanning electron micrograph of catalyst, pure MoS can be obtained from FIG. 22Presents a three-dimensional flower-shaped nano structure, the nano flower structure is formed by self-assembling thin nano sheets with the thickness of about 10nm, the ultrathin nano sheets have the characteristic of forming a loose porous structure by self-assembling, and the previous pure MoS is avoided2The disordered stacking characteristic of the bulk structure, and the ultrathin nanosheet structure can expose moreThe edges of the sheet layer have more reactive active sites, so that the specific surface area of the catalyst is enhanced, and the diffusion path of reactive molecules and surface charges is shortened.
FIG. 3 is the MoS prepared in example 32/O-g-C3N4Scanning electron micrograph of Z-type heterojunction catalyst, MOS prepared in comparative example 22The scanning electron microscope image of the catalyst can show that the catalyst is similar to MoS2In contrast, 0.2% MoS2/O-g-C3N4The surface of the composite material has a nano-sheet structure and is smooth, probably due to O-g-C3N4Attachment of nanosheet structure to MoS2Flower-like structure surface. 3D MoS2And 2D O-g-C3N4The close contact of the interface is favorable for MoS2And O-g-C3N4The electron migration between the porous nano structure and the porous nano structure is helpful to enhance the photocatalytic activity of the porous nano structure.
FIG. 4 is g-C prepared in comparative example 13N4Scanning Electron microscopy of the catalyst, pure g-C3N4Is in a nano sheet structure and contains a small amount of pore structures. With pure g-C3N4In contrast, O-g-C in example 13N4Has a large amount of pore structure, which is formed by ammonium oxalate [ (NH) in the pyrolysis process4)2C2O4]Decomposed released gas (NH)3、H2O, CO and CO2) And the result is that. The porous structure is O-g-C3N4The catalyst provides a higher specific surface area and a larger pore volume, exposing more active sites, thereby enhancing the photocatalytic activity of the catalyst.
To further verify the effect of pore structure on surface area and MoS2The addition amount of (A) is compared with the surface area inhibition effect, and N is carried out on the catalysts prepared in examples 1-5 and comparative example 12Adsorption test, the specific surface area and pore volume changes obtained are shown in the table below. As can be seen from the data in Table 1, with g-C3N4In contrast, O-g-C3N4The specific surface area of the catalyst is increased, and the specific surface area is increased along with MoS2Increase in load, MoS2/O-g-C3N4Specific surface area of catalystA tendency of increasing first and then decreasing was exhibited, and an inflection point appeared at a load amount of 0.2%.
TABLE 1
FIG. 5 shows O-g-C prepared in examples 1 to 53N4Carrier, MoS2And MoS of different loading capacity2/O-g-C3N4Catalysts (0.1, 0.2 and 0.3%) and pure g-C prepared in comparative example 13N4XRD pattern of the catalyst. g-C3N4There are two distinct diffraction peaks at 12.7 ° and 27.5 °, corresponding to the (100) and (002) crystal planes, respectively. The weaker characteristic peak at 12.7 ° corresponds to the in-plane stacking of the triazine ring structure, and the strong diffraction peak at 27.5 ° corresponds to the interlayer stacking of the aromatic material. With pure g-C3N4In contrast, O-g-C3N4The (002) crystal plane diffraction peak of (A) is shifted toward a low angle [ as shown in the inset of FIG. 5]The larger the interlayer spacing after O doping. For pure MoS2All diffraction peaks conform to MoS22H-MoS being hexagonal2. As can be seen from the figure, with MoS2The increase in the amount added, the diffraction peak intensities at 12.7 ° and 27.5 ° gradually decreased, which is probably due to MoS2Nanosheets and O-g-C3N4The nano-sheet forms a heterojunction structure. From MoS2/O-g-C3N4The composite material can be seen in an XRD pattern with O-g-C3N4And MoS2Characteristic peak of (D), indicating MoS2Successful incorporation into O-g-C3N4And (4) nano-chips.
Example 6:
adding 0.03g of bisphenol A into deionized water to prepare a bisphenol A solution with the concentration of 30ppm, and adding 50mL of bisphenol A solution and 0.05g of O-g-C prepared in examples 1-5 into a reactor3N4Carrier, MoS2And MoS of different loading capacity2/O-g-C3N4Catalysts (0.1, 0.2 and 0.3%) and pure g-C prepared in comparative example 13N4Catalyst ofIrradiating the sample for 1h by using a 500W xenon lamp as a light source, taking out the sample once every 10min, separating and filtering the sample, testing the concentration of bisphenol A in the solution by using high performance liquid chromatography, and calculating the degradation rate:
in the formula: c0Is the initial concentration of BPA before reaction, mol/L; ctThe concentration of BPA after photocatalytic tmin, mol/L.
The data degradation results are shown in fig. 6, and the relevant data are shown in table 2. From the degradation results, O-g-C3N4The improvement of the photocatalytic performance is probably due to the fact that the O doping increases the specific surface area of the catalyst and increases the reaction active sites. 0.2% MoS2/O-g-C3N4The degradation effect of the composite material is obviously enhanced within 60min, the degradation rate reaches 92.6 percent and probably is mainly attributed to 0.2 percent of MoS2/O-g-C3N4The photoresponse range is widened, the catalyst is moved to the long wavelength, visible light can be better utilized, and the formation of a heterojunction can also be used for effectively separating photon-generated electrons from holes and reducing photon-generated carrier recombination. However, regardless of MoS2The supported amount is increased or decreased, and the photocatalytic effect is lower than 0.2 percent MoS2/O-g-C3N4Composite material, probably due to 0.1% MoS2/O-g-C3N4And 0.3% MoS2/O-g-C3N4The excess reactive sites on the surface are caused as recombination centers of photogenerated carriers. O-g-C3N4And MoS2The close contact of the interfaces can shorten the transmission distance of electrons between the two interfaces, thereby effectively inhibiting the recombination of photon-generated carriers.
TABLE 2
The corresponding kinetic constants were calculated by fitting the degradation experiment:
-ln(Ct/C0)＝kt；
wherein, Ct: BPA concentration at time t, C0: initial concentration, k: a rate constant.
The data degradation kinetics results are shown in fig. 7, and it can be seen from the degradation kinetics results that all samples degrade BPA following the first order reaction kinetics. 0.2% MoS2/O-g-C3N4The reaction rate of the composite material is optimal and is pure g-C3N4、O-g-C3N4And MoS215.2, 2.9 and 1.9 times. The results prove that element doping and the heterojunction structure have a synergistic effect, and the synergistic effect can further improve the photocatalytic activity and promote the separation of photoinduced carriers.
Example 7:
the catalyst reacted in example 6 was washed with absolute ethanol and dried at 80 ℃ for 6 hours to obtain the photocatalyst to be recycled in the next step, and the operation of example 6 was continued and repeated 5 times.
The cyclic degradation results are shown in fig. 8, and cyclic tests show that the degradation rate of BPA can reach 85% after 5 cycles under the same conditions. The degradation rate is reduced due to some losses in the washing and drying process after the photocatalytic reaction, while stirring also removes a small amount of MoS2/O-g-C3N4Powder, but after 3 cycles, the catalyst activity remained relatively stable, indicating 0.2% MoS synthesized2/O-g-C3N4Has certain stability and recyclability.
To explore further 0.2% MoS2/O-g-C3N4The reaction mechanism for degrading BPA is that the intermediate is analyzed by LC-MS, and the intermediate product of BPA degradation is detected and identified, as shown in FIG. 9. The active oxidizing radicals can degrade the BPA molecule by two possible mechanisms, namely, the cleavage and hydroxylation of C-C bonds. Based on previous studies and established intermediates, two possible BPA degradation pathways have been proposed. Route 1: the hydroxylation process of BPA on the benzene ring of its molecule results in BPA dihydroxylated P1 (wt: 259). The OH group on the dihydroxylated BPA molecule mayFor further oxidation to tetracarbonyl BPA [ P2 (wt:255)]The tetracarbonylated BPA was further oxidized to (2E,4Z) -3- (2- (3, 4-dioxan-1, 5-ethen-1-yl)) hex-2, 4-dienedioic acid P3 (wt: 287). Route 2: the reactive species attack the electron-rich C-C bond associated with the phenyl group of BPA, generating isopropylphenol P4 (wt:135) upon cleavage of the C-C bond mechanism. Thus, further oxidation of isopropenylphenol produced 1- (2, 4-dihydroxyphenyl) ketene P5 (wt: 149). Thereafter, all of these aromatic compounds undergo complex hydroxylation, dehydroxylation, oxidation, and ring-opening reactions leading to the formation of small molecules, such as acetic acid P6 (wt:60), etc., and finally, mineralization of BPA and its products leading to CO2And H2And forming O.
In order to examine the effect of active substances in photocatalysis, different quenchers were added to the photocatalytic reaction system. Selecting Isopropanol (IPA) as a scavenger of hydroxyl free radical (. OH), and p-Benzoquinone (BQ) as a superoxide free radical (. O)2 -) The scavenger of (a) is disodium ethylenediaminetetraacetate (EDTA-2Na) as a cavity (h)+) The scavenger of (2), potassium bromate (KBrO)3) As electrons (e)-) The scavenger of (1). As shown in fig. 10, to 0.2% MoS2/O-g-C3N4When BQ and EDTA-2Na are added into the reaction solution, the degradation efficiency of BPA is remarkably reduced from 93 percent to 36 percent and 53 percent respectively, which shows that O2 -And h+Is the main active substance. Adding KBrO3After addition of IPA, the degradation of BPA slightly decreased, indicating that e-And OH are negligible.
Calculation from the above results and radical Capture experiments for 0.2% MoS2/O-g-C3N4The photocatalytic mechanism of the composite material was investigated, and the results are shown in fig. 11. First, O-g-C is presumed3N4And MoS2Between following the conventional type II charge separation path, e-From O-g-C3N4Migration of CB to MoS2CB, h of+From MoS2VB of (a) to O-g-C3N4VB of (2). For MoS2In terms of CB potential (-0.06eV) to O2/·O2 -Correction (-0.33 eV); thus, MoS2E on CB-Can not remove O2Reduction to O2 -. At the same time, O-g-C3N4(+1.32eV) potential ratio of VB to OH-OH (+1.99eV) is more negative, indicating O-g-C3N4H on VB+OH cannot be generated. This is inconsistent with the free radical capture experiment. Based on the above analysis, the migration path of photo-induced carriers cannot follow the conventional type II heterojunction. Based on O-g-C3N4And MoS2The existence of strong electrostatic attraction and energy band potential, and the direct Z-shaped heterojunction migration path for photo-induced carrier separation is provided. O-g-C3N4Nanosheet and MoS2After nanoflower electrostatic bonding, MoS2E-on CB reacts rapidly with O-g-C under the action of built-in electric field3N4H at VB+The combination effectively prolongs the service life of the photo-generated electron-hole pairs. Then, O-g-C3N4Has a CB potential of (-1.13eV) to O2/. O2 -More negative, therefore, O-g-C3N4E of-O adsorbed to photocatalytic surfaces2Reaction to form O2 -. Then, O2Decomposition into OH radicals and H2O2。0.2％MoS2/O-g-C3N4Medium MoS2VB in (a) cannot generate OH radicals, therefore h+It is possible to directly photodegrade BPA to CO2And H2O。0.2％MoS2/O-g-C3N4The Z-type heterojunction of (a) can be h+Remain in MoS2In the corrected VB potential energy, e-Remaining in O-g-C3N4More negative CB potential. Therefore, they have strong oxidizing and reducing abilities and can effectively degrade BPA. Therefore, the Z-type heterojunction can effectively promote the separation of photoinduced carriers and prevent the occurrence of photo-corrosion.
In conclusion, the invention adopts the solvothermal method to prepare the 3D/2D MoS2/O-g-C3N4Composite material, and 2D MoS2Compare 3D MoS2Has a larger specific surface area, thereby exposing more reactive sites. O-g-C3N4By the pair g-C3N4Modifying to replace the position of N with O atom to generate energy level defect and solve g-C3N4The self-quantization efficiency is low. At the same time, MoS2And O-g-C3N4The close contact of the interfaces and the mutual synergistic effect obviously enhance the active sites of the photocatalytic reaction and the absorption capacity of visible light, and effectively improve the separation of photon-generated carriers. According to LC-MS and radical trapping experiments, 0.2% MoS was proposed2/O-g-C3N4A possible photocatalytic degradation mechanism for degrading BPA by the heterojunction composite material provides a new method for preparing the high-efficiency heterojunction photocatalyst.
Claims (9)
1. A3D flower-shaped Z-shaped heterojunction catalyst is characterized in that the catalyst is O-g-C with a two-dimensional nano sheet structure3N4As a carrier, O-g-C3N4MoS with three-dimensional flower-like nanostructures2As a photocatalytically active component, MoS2Uniformly dispersed on the surface of the carrier, O-g-C3N4And MoS2Is 0.5: 0.1 to 0.3.
2. 3D flower-like Z-type heterojunction catalyst according to claim 1, characterized in that said O-g-C3N4And MoS2Is 0.5: 0.1.
3. 3D flower-like Z-type heterojunction catalyst according to claim 1, characterized in that said O-g-C3N4And MoS2Is 0.5: 0.2.
4. 3D flower-like Z-type heterojunction catalyst according to claim 1, characterized in that said O-g-C3N4And MoS2Is 0.5: 0.3.
5. a method for preparing a 3D flower-like Z-type heterojunction catalyst as claimed in any of claims 1 to 4, characterized in that the method comprises the following steps:
step one, weighing O-g-C3N4Adding MoS thereto2Dispersing the mixture in an ethylene glycol solution, performing ultrasonic treatment for 0.5-1.5 h, and then putting the mixture into a magnetic stirrer to stir until the mixture is dissolved:
step two, transferring the solution obtained in the step one to a polytetrafluoroethylene reaction kettle for reaction;
step three, alternately washing the reaction product obtained in the step two by using absolute ethyl alcohol and deionized water, and then putting the reaction product into a forced air drying oven for drying to obtain MoS2/O-g-C3N4A catalyst.
6. The preparation method of the 3D flower-shaped Z-shaped heterojunction catalyst according to claim 5, wherein the reaction temperature is 190-200 ℃ and the reaction time is 20-30 h.
7. The method for preparing a 3D flower-shaped Z-shaped heterojunction catalyst according to claim 5, wherein the drying temperature is 60-80 ℃.
8. Use of the 3D flower-like Z-heterojunction catalyst of any of claims 1 to 4 for photocatalytic degradation of bisphenol a.
9. The application of the 3D flower-shaped Z-shaped heterojunction catalyst in the photocatalytic degradation of bisphenol A according to claim 8 is characterized in that the application method comprises the following steps: after mixing the degradation product and the catalyst, carrying out photocatalytic reaction after reaching adsorption balance under the dark reaction condition, and finishing the degradation process, wherein: the degradation product is endocrine disruptor bisphenol A, the concentration of the degradation product is 30ppm, the addition amount of the degradation product is 50mL, and the addition amount of the catalyst is 0.05 g.
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