CN114931936A - 1T-MoS 2 /TiO 2 Preparation and application of/rGO composite photocatalytic material - Google Patents

1T-MoS 2 /TiO 2 Preparation and application of/rGO composite photocatalytic material Download PDF

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CN114931936A
CN114931936A CN202210544754.8A CN202210544754A CN114931936A CN 114931936 A CN114931936 A CN 114931936A CN 202210544754 A CN202210544754 A CN 202210544754A CN 114931936 A CN114931936 A CN 114931936A
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rgo
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CN114931936B (en
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段涛
吴林珍
李依林
李蕊
孟旗
刘睿熹
粟阳藩
何攀
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Southwest University of Science and Technology
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Abstract

The invention discloses a macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material comprises the following steps: dispersing a titanium source in a hydrofluoric acid solution, and synthesizing a titanium dioxide nanosheet with thin-layer characteristics by adopting a hydrothermal method; adding titanium dioxide nanosheets into a mixed solution containing a molybdenum source and a sulfur source, uniformly dispersing, growing metal phase molybdenum disulfide on the surfaces of the titanium dioxide nanosheets in situ by a hydrothermal method, and washing and drying to obtain a solid binary composite material 1T-MoS 2 /TiO 2 (ii) a Mixing binary composite material 1T-MoS 2 /TiO 2 Uniformly dispersing the graphene oxide in a graphene oxide aqueous solution, transferring the graphene oxide aqueous solution to a high-pressure reaction kettle, and carrying out hydrothermal treatment to obtain macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO hydrogel; subjecting macroscopic three-dimensional 1T-MoS 2 /TiO 2 Freezing and drying the rGO hydrogel after cyclic dialysis to obtain macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO composite material. 1T-MoS of the invention 2 /TiO 2 the/rGO material has higher removal rate for organic matters and U (VI) in simulated nuclear waste liquid and shows good circulation stability.

Description

1T-MoS 2 /TiO 2 Preparation and application of/rGO composite photocatalytic material
Technical Field
The invention relates to a macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 Preparation and application of/rGO composite photocatalytic material.
Background
Titanium dioxide has been widely used as a photocatalytic material which has been most widely studied in photocatalytic technologies for various applications. The band gap width of the anatase phase titanium dioxide at normal temperature is 3.2eV, the responsive light wavelength range is limited to an ultraviolet region, but the ultraviolet region only accounts for 3% -5% of the whole solar spectrum range. The method for increasing the photo-excitation charge transfer path and the separation efficiency of the photocatalytic material by constructing the heterojunction is an effective means for improving the photocatalytic efficiency. From this point of view, through a certain construction mode, titanium dioxide and other materials (conductors such as metal phase molybdenum disulfide, reduced graphene oxide, noble metal platinum and the like, semiconductors such as carbon nitride, cadmium sulfide, graphene oxide and the like) can be involved in constructing the heterojunction photocatalytic material, so that the photocatalytic efficiency is improved.
Molybdenum disulfide (2H-MoS) with semiconductor characteristic as common stable state of molybdenum disulfide 2 ) And a metal phase molybdenum disulfide (1T-MoS) having conductive properties 2 ). Compared with the 2H phase, the 1T phase molybdenum disulfide has more abundant edge active sites, and the balance of Fermi energy level of the 1T phase molybdenum disulfide and titanium dioxide to form a heterojunction photocatalytic material is favorable for photo-generated electrons of the titanium dioxide which are excited by light and jump to a conduction band to be transferred to 1T-MoS 2 The energy level of the catalyst is higher, so that the space separation of electrons and holes generated by light excitation is realized, and the recombination probability of carriers on the surface of the catalyst is effectively reduced. The heterojunction composite material expands the response range of the catalytic material to visible light, and the rich active sites on the surface of the molybdenum disulfide are not only beneficial to the adsorption performance of the material to a substrate, but also beneficial to the oxidation-reduction reaction of the material and the contacted substrate on more active sites, thereby achieving the purpose of catalytic removal.
Based on the above-mentioned teaching, the photocatalytic technology at present is rapidly developed, and the photocatalytic material in powder still has a serious examination that is difficult to recycle. According to the invention, a cross-linked structure with rich pore channels formed by graphene oxide is used as a support structure and a heterojunction composite material formed by a conductor material and titanium dioxide and molybdenum disulfide to construct a macroscopic three-dimensional heterojunction composite photocatalytic material. The invention lays a foundation for constructing a macroscopic and efficient multi-element composite material combining adsorption, catalysis and environmental pollution remediation.
Disclosure of Invention
The preparation method of the invention aims to overcome the defects of the powder photocatalytic material, and the preparation method of the invention adopts graphene aerogel as a carrier, titanium dioxide material as a main catalyst and molybdenum disulfide as a cocatalyst to prepare the powder photocatalytic material by a hydrothermal methodMacroscopically efficient three-dimensional 1T-MoS 2 /TiO 2 the/rGO composite photocatalytic material. The method can be used in the fields of uranium reduction removal, organic matter degradation and the like in strong acid, high salt and multi-nuclide environments.
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the purpose of the invention, a macroscopic three-dimensional 1T-MoS for photocatalysis is provided 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material comprises the following steps:
step one, dispersing a titanium source in a hydrofluoric acid solution, and synthesizing a titanium dioxide nanosheet with a thin-layer characteristic by adopting a hydrothermal method;
step two, adding the titanium dioxide nanosheets into a mixed solution containing a molybdenum source and a sulfur source, uniformly dispersing, growing metal phase molybdenum disulfide on the surfaces of the titanium dioxide nanosheets in situ by a hydrothermal method, and washing and drying the solid to obtain the binary composite material 1T-MoS 2 /TiO 2 ；
Step three, mixing the binary composite material 1T-MoS 2 /TiO 2 Uniformly dispersing the graphene oxide in a graphene oxide aqueous solution, transferring the graphene oxide aqueous solution to a high-pressure reaction kettle, and carrying out hydrothermal treatment to obtain macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO hydrogel;
step four, performing macroscopic three-dimensional 1T-MoS 2 /TiO 2 Freezing and drying the rGO hydrogel after cyclic dialysis to obtain macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO composite material.
Preferably, in the step one, the titanium source is any one of titanium tetrachloride, tetrabutyl titanate and titanium dioxide P25, the titanium source is added in a titanium source solution mode, the concentration of the titanium source solution is 98 wt%, the concentration of the hydrofluoric acid solution is more than or equal to 40 wt%, and the volume ratio of the titanium source solution to the hydrofluoric acid solution is 15-30: 2-4; the temperature of the hydrothermal method is 160-220 ℃, and the duration is 10-24 h; in the first step, a hydrothermal method is followed by washing and drying, the washing method is any one of suction filtration washing, centrifugal washing and ultrasonic sedimentation washing, and the drying method is any one of freeze drying, natural drying, constant-temperature drying and program variable-temperature drying.
Preferably, in the second step, the molybdenum source is any one of molybdenum trioxide, ammonium molybdate and ammonium molybdate tetrahydrate, and the sulfur source is one or a combination of thioacetamide and thiourea; the temperature of the hydrothermal method is 160-220 ℃, and the duration is 3-12 h; the mass ratio of the titanium dioxide nanosheet to the molybdenum source is 4-6: 1; the mass ratio of the titanium dioxide nanosheet to the sulfur source is 4-6: 1-3; in the second step, the washing method is any one of suction filtration washing, centrifugal washing and ultrasonic sedimentation washing, and the drying method is any one of freeze drying, natural drying, constant temperature drying and program variable temperature drying.
Preferably, in the third step, the graphene oxide aqueous solution is any one of a graphene aqueous solution prepared by a Hummers method, a graphene aqueous solution purchased directly, a single-layer graphene powder aqueous solution, and a single-layer graphene oxide powder aqueous solution.
Preferably, in the third step, a cross-linking agent is added into the graphene oxide aqueous solution to form hydrogel, wherein the cross-linking agent is one or a combination of a borax aqueous solution, a mint plant extract and a Lemongrass plant extract; the concentration of the graphene oxide aqueous solution is 5-15 mg/mL; the concentration of the cross-linking agent is 5-15 mg/mL; the volume ratio of the graphene oxide aqueous solution to the cross-linking agent is 4-6: 1; binary composite material 1T-MoS 2 /TiO 2 The mass volume ratio of the graphene oxide to the graphene oxide aqueous solution is 0.1-0.2 g: 4-6 mL; the temperature of the hydrothermal treatment is 120-180 ℃, and the duration time is 3-12 h.
Preferably, the process of step three is as follows: mixing binary composite material 1T-MoS 2 /TiO 2 Adding the graphene oxide aqueous solution and a cross-linking agent into a microwave and ultrasonic integrated reactor, simultaneously starting microwaves and ultrasonic waves, carrying out synergistic treatment for 60-90 min, transferring the obtained product into a high-pressure reaction kettle, carrying out hydrothermal treatment, and obtaining the macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO hydrogel; wherein the temperature of the synergistic treatment is 65-75 ℃, the microwave power is 800-1000W, the ultrasonic power is 600-800W, and the ultrasonic power isThe frequency is 35-45 KHz; the concentration of the graphene oxide aqueous solution is 5-15 mg/mL; the concentration of the cross-linking agent is 5-15 mg/mL; the cross-linking agent is one or more of borax water solution, herba Menthae plant extractive solution, and Ledum Palustre extractive solution; the volume ratio of the graphene oxide aqueous solution to the cross-linking agent is 4-6: 1; binary composite material 1T-MoS 2 /TiO 2 The mass volume ratio of the graphene oxide to the graphene oxide aqueous solution is 0.1-0.2 g: 4-6 mL; the temperature of the hydrothermal treatment is 120-180 ℃, and the duration time is 3-12 h.
Preferably, in the third step, the obtained macroscopic three-dimensional 1T-MoS 2 /TiO 2 Addition of supercritical CO into/rGO hydrogel 2 In the reaction device, CO of 10MPa is injected 2 Heating to 60-65 ℃, and then continuously injecting CO 2 Soaking and swelling the macroscopic three-dimensional 1T-MoS under the pressure of 15-25 MPa 2 /TiO 2 Releasing pressure for 1-2 h by using/rGO hydrogel to obtain pretreated macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO hydrogel.
Preferably, in the fourth step, deionized water or 0.5-5 wt% ethanol water is adopted for circulating dialysis, and circulating dialysis washing is performed for 5-10 times; in the fourth step, the process of freeze drying is as follows: precooling for 12h at-18 to-15 ℃, taking out, and freeze-drying for at least 48h at-60 to-40 ℃. The hydrogel is pre-frozen at low temperature so as to enable water in the reduced graphene oxide hydrogel to form ice crystals; under the condition of freeze drying, the water in the hydrogel is volatilized to finally form the aerogel.
The invention also provides the macroscopic three-dimensional 1T-MoS prepared by the preparation method 2 /TiO 2 The application of the/rGO composite material in radioactive wastewater treatment is to convert macroscopic three-dimensional 1T-MoS 2 /TiO 2 the/rGO composite material is added into the radioactive waste water containing uranium to perform photocatalytic reaction under the condition that a xenon lamp simulates sunlight, so that the photocatalytic reduction of hexavalent uranium in the radioactive waste water containing uranium is realized.
The invention also provides the macroscopic three-dimensional 1T-MoS prepared by the preparation method 2 /TiO 2 /rGO composite material in organic matter wastewater treatmentApplication of (1) to macroscopic three-dimensional 1T-MoS 2 /TiO 2 the/rGO composite material is added into organic wastewater to perform photocatalytic reaction under the condition that a xenon lamp simulates sunlight, so that the degradation of organic matters in the organic wastewater is realized.
The invention at least comprises the following beneficial effects:
(1) according to the invention, graphene oxide and plant extract are used as cross-linking agents, and a macroscopic three-dimensional reduced graphene oxide aerogel with a porous cross-linking structure is prepared by a hydrothermal method;
(2) by adopting the preparation method, the preparation steps are simple and efficient, the energy consumption is lower, no environmental pollution is caused, and the prepared multi-element composite photocatalytic material has excellent organic matter degradation performance and nuclide reduction performance;
(3) the macroscopic three-dimensional multi-element composite photocatalytic material prepared by the method can be used in the fields of organic matter treatment in common industrial sewage, reduction removal of U (VI) in simple nuclear waste liquid, nuclide adsorption reduction removal in complex environment and the like.
(4) The preparation method has simple and convenient operation process and convenient operation, and can realize the recycling of the catalytic material.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a macroscopic three-dimensional 1T-MoS prepared in example 1 of the present invention 2 /TiO 2 Physical map of/rGO composite;
FIG. 2 shows a macroscopic three-dimensional 1T-MoS prepared in example 1 of the present invention 2 /TiO 2 SEM image of/rGO composite;
FIG. 3 shows TiO (a) prepared in example 1 of the present invention 2 、(b)1T-MoS 2 、(c)1T-MoS 2 /TiO 2 X-ray diffraction (XRD) pattern of/rGO composite;
FIG. 4 shows macroscopic three-dimensional 1T-MoS prepared in examples 1 to 6 of the present invention 2 /TiO 2 the/rGO composite material is degraded in a photocatalytic way under a 300W xenon lamp light sourceDegradation rate of organic tannic acid;
FIG. 5 shows the macroscopically three-dimensional 1T-MoS prepared in examples 1, 7 and 9 of the present invention 2 /TiO 2 The degradation rate of the/rGO composite material in the light of a 300W xenon lamp for photocatalytic degradation of organic matter tannic acid;
FIG. 6 shows a macroscopic three-dimensional 1T-MoS prepared in example 1 of the present invention 2 /TiO 2 rGO composite material, TiO 2 And 1T-MoS 2 A dynamic curve of photocatalytic degradation of organic matter tannic acid under dark conditions and a 300W xenon lamp light source;
FIG. 7 shows macroscopic three-dimensional 1T-MoS prepared in examples 1 to 6 of the present invention 2 /TiO 2 The removal rate of U (VI) in simulated nuclear waste liquid is removed by photocatalytic reduction of the/rGO composite material under dark conditions and 300W xenon lamp illumination conditions;
FIG. 8 is a macroscopic three-dimensional 1T-MoS prepared in examples 1, 7 and 9 of the present invention 2 /TiO 2 The removal rate of U (VI) in the simulated nuclear waste liquid is removed by the aid of photocatalytic reduction of the/rGO composite material under dark conditions and 300W xenon lamp illumination conditions;
FIG. 9 shows a macroscopic three-dimensional 1T-MoS prepared in example 1 of the present invention 2 /TiO 2 rGO composite material, TiO 2 And 1T-MoS 2 And (3) carrying out photocatalytic reduction under dark conditions and a 300W xenon lamp light source to simulate the kinetic curve of U (VI) in the nuclear waste liquid.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material comprises the following steps:
step one, taking 20mL of n-butyl titanate solution (98 wt%) and 3.2mL of hydrofluoric acid solution (40 wt%), adding 50mL of polytetrafluorethyleneContinuously stirring and uniformly mixing the lining of the high-pressure reaction kettle with the vinyl fluoride lining to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, fully mixing and washing the obtained product by using 1% sodium hydroxide solution for the last time, and drying the obtained product at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets (TiO nanosheets) 2 ) Fig. 3 (a) is an XRD spectrum of the prepared anatase phase titanium dioxide;
step two, adding 0.5g of the obtained titanium dioxide nanosheet into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea into the deionized water, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain 1T-MoS 2 /TiO 2 A composite material;
taking 3.75mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35 KHz; 0.15g of the 1T-MoS obtained above was taken 2 /TiO 2 Adding the composite material into the mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at 180 ℃ for 6 hours to obtain reduced graphene oxide hydrogel;
step four, dialyzing the hydrogel by using an ethanol water solution with the concentration of 2 wt%, wherein the dialysis time is 4h, and repeating for 3 times; precooling for 12h at-17 ℃ after dialysis, taking out, and freeze-drying for 48h at-50 ℃ to obtain the macroscopic three-dimensional 1T-MoS 2 /TiO 2 /rGO aerogels.
FIG. 1 shows a macroscopic three-dimensional 1T-MoS prepared in example 1 of the present invention 2 /TiO 2 Physical map of/rGO composite;
FIG. 2 shows the 1T-MoS prepared in example 1 2 /TiO 2 SEM images of rGO aerogels; from the figure, it can be seen that the graphene aerogel has a uniformly distributed 3D layered porous skeleton, which can greatly increase the adsorption performance and the macrostructure support performance of the material.
FIG. 3 shows TiO (a) prepared in example 1 of the present invention 2 、(b)1T-MoS 2 、(c)1T-MoS 2 /TiO 2 X-ray diffraction (XRD) pattern of/rGO composite;
FIG. 4 shows macroscopic three-dimensional 1T-MoS prepared in examples 1 to 6 of the present invention 2 /TiO 2 An ultraviolet spectrophotometer curve of the rGO composite material for photocatalytic degradation of organic matter tannic acid under a 300W xenon lamp light source and a characteristic peak value change curve of the composite material for photocatalytic degradation of organic matter tannic acid under dark conditions and light conditions, wherein the composite material only has adsorption performance on the organic matter tannic acid under the dark conditions and reaches adsorption balance within 30 min;
FIG. 6 is a macroscopic three-dimensional 1T-MoS prepared in example 1 of the present invention 2 /TiO 2 rGO composite material, TiO 2 、1T-MoS 2 、1T-MoS 2 /TiO 2 The dynamic curve of photocatalytic degradation of organic matter tannic acid by rGO under dark conditions and a 300W xenon lamp light source;
FIG. 7 shows macroscopic three-dimensional 1T-MoS prepared in examples 1 to 6 of the present invention 2 /TiO 2 The removal rate of U (VI) in simulated nuclear waste liquid is removed by photocatalytic reduction of the/rGO composite material under dark conditions and 300W xenon lamp illumination conditions;
FIG. 9 shows a macroscopic three-dimensional 1T-MoS prepared in example 1 of the present invention 2 /TiO 2 rGO composite material, TiO 2 、1T-MoS 2 、1T-MoS 2 /TiO 2 The dynamic curve of U (VI) in the simulated nuclear waste liquid is subjected to photocatalytic reduction by the rGO under the dark condition and a 300W xenon lamp light source.
Example 2:
macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material comprises the following steps:
step one, adding 20mL of n-butyl titanate solution and 3.2mL of hydrofluoric acid solution into a lining of a high-pressure reaction kettle with a 50mL polytetrafluoroethylene lining, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, fully mixing and washing the obtained product by using 1% sodium hydroxide solution for the last time, and drying the obtained product at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
step two, adding 0.5g of the obtained titanium dioxide nanosheet into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea into the deionized water, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain 1T-MoS 2 /TiO 2 A composite material;
taking 4.5mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the power of the ultrasonic treatment is 800W, and the ultrasonic frequency is 35 KHz; 0.15g of the 1T-MoS obtained above was taken 2 /TiO 2 Adding the composite material into the mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 6 hours at the temperature of 180 ℃ to obtain reduced graphene oxide hydrogel;
step four, dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2%, wherein the dialysis time is 4h, and repeating for 3 times; precooling for 12h at-17 ℃ after dialysis, taking out, and freeze-drying for 48h at-50 ℃ to obtain the macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO aerogel.
Example 3:
macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material comprises the following steps:
step one, adding 20mL of n-butyl titanate solution and 3.2mL of hydrofluoric acid solution into a lining of a high-pressure reaction kettle with a 50mL polytetrafluoroethylene lining, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, fully mixing and washing the obtained product by using 1% sodium hydroxide solution for the last time, and drying the obtained product at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
step two, adding 0.5g of the obtained titanium dioxide nanosheet into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea into the deionized water, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain 1T-MoS 2 /TiO 2 A composite material;
taking 3mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35 KHz; 0.15g of the 1T-MoS obtained above was taken 2 /TiO 2 Adding the composite material into the mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at 180 ℃ for 6 hours to obtain reduced graphene oxide hydrogel;
step four, dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2%, wherein the dialysis time is 4h, and repeating for 3 times; precooling for 12h at-17 ℃ after dialysis, taking out, and freeze-drying for 48h at-50 ℃ to obtain the macroscopic three-dimensional 1T-MoS 2 /TiO 2 /rGO aerogels.
Example 4:
macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material comprises the following steps:
step one, adding 20mL of n-butyl titanate solution and 3.2mL of hydrofluoric acid solution into a lining of a high-pressure reaction kettle with a 50mL polytetrafluoroethylene lining, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, fully mixing and washing the obtained product by using 1% sodium hydroxide solution for the last time, and drying the obtained product at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
step two, adding 0.5g of the titanium dioxide nanosheet into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain 1T-MoS 2 /TiO 2 A composite material;
step three, taking 2.25mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35 KHz; 0.15g of the 1T-MoS obtained above was taken 2 /TiO 2 Adding the composite material into the mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 6 hours at the temperature of 180 ℃ to obtain reduced graphene oxide hydrogel;
step four, dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2%, wherein the dialysis time is 4 hours, and repeating for 3 times; precooling for 12h at-17 ℃ after dialysis, taking out, and freeze-drying for 48h at-50 ℃ to obtain macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO aerogel.
Example 5:
macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material comprises the following steps:
step one, adding 20mL of n-butyl titanate solution and 3.2mL of hydrofluoric acid solution into a lining of a high-pressure reaction kettle with a 50mL polytetrafluoroethylene lining, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing the white precipitate for 3-5 times by using deionized water and absolute ethyl alcohol, fully mixing and washing the white precipitate by using a 1% sodium hydroxide solution for the last time, and drying the washed solution at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
step two, adding 0.5g of the obtained titanium dioxide nanosheet into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea into the deionized water, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain 1T-MoS 2 /TiO 2 A composite material;
step three, taking 1.5mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35 KHz; 0.15g of the 1T-MoS obtained above was taken 2 /TiO 2 Adding the composite material into the mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 6 hours at the temperature of 180 ℃ to obtain reduced graphene oxide hydrogel;
step four, dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2%, wherein the dialysis time is 4 hours, and repeating for 3 times; precooling for 12h at-17 ℃ after dialysis, taking out, and freeze-drying for 48h at-50 ℃ to obtain the macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO aerogel.
Example 6:
macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material comprises the following steps:
step one, adding 20mL of n-butyl titanate solution and 3.2mL of hydrofluoric acid solution into a lining of a high-pressure reaction kettle with a 50mL polytetrafluoroethylene lining, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, fully mixing and washing the obtained product by using 1% sodium hydroxide solution for the last time, and drying the obtained product at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
step two, adding 0.5g of the obtained titanium dioxide nanosheet into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea into the deionized water, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain black precipitate, centrifugally washing the black precipitate for 3-5 times by using deionized water and absolute ethyl alcohol, and drying the washed black precipitate at the temperature of 80 ℃ to obtain 1T-MoS 2 /TiO 2 A composite material;
step three, taking 0.75mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the ultrasonic power is 800W, and the ultrasonic frequency is 35 KHz; 0.15g of the 1T-MoS obtained above was taken 2 /TiO 2 Adding the composite material into the mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 6 hours at the temperature of 180 ℃ to obtain reduced graphene oxide hydrogel;
step four, dialyzing the hydrogel by adopting an ethanol water solution with the concentration of 2%, wherein the dialysis time is 4h, and repeating for 3 times; precooling for 12h at-17 ℃ after dialysis, taking out, and freeze-drying for 48h at-50 ℃ to obtain macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO aerogel.
Example 7:
macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material comprises the following steps:
step one, adding 20mL of n-butyl titanate solution (98 wt%) and 3.2mL of hydrofluoric acid solution (40 wt%) into a lining of a high-pressure reaction kettle with a 50mL polytetrafluoroethylene lining, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, fully mixing and washing the obtained product by using 1% sodium hydroxide solution for the last time, and drying the obtained product at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
step two, adding 0.5g of the obtained titanium dioxide nanosheet into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea into the deionized water, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain 1T-MoS 2 /TiO 2 A composite material;
step three, 0.15g of the 1T-MoS obtained in the step 2 /TiO 2 Adding the composite material, 3.75mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract into a microwave and ultrasonic integrated reactor, simultaneously starting microwaves and ultrasonic waves, performing synergistic treatment for 60min, then transferring into a high-pressure reaction kettle, and reacting for 6 hours at the temperature of 180 ℃ to obtain reduced graphene oxide hydrogel; wherein the temperature of the synergistic treatment is 70 ℃, the microwave power is 1000W, the ultrasonic power is 800W, and the ultrasonic frequency is 35 KHz;
step four, dialyzing the hydrogel by using an ethanol water solution with the concentration of 2 wt%, wherein the dialysis time is 4h, and repeating for 3 times; precooling for 12h at-17 ℃ after dialysis, taking out, and freeze-drying for 48h at-50 ℃ to obtain the macroscopic three-dimensional 1T-MoS 2 /TiO 2 /rGO aerogels.
Example 8:
macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material comprises the following steps:
step one, adding 20mL of n-butyl titanate solution (98 wt%) and 3.2mL of hydrofluoric acid solution (40 wt%) into a lining of a high-pressure reaction kettle with a 50mL polytetrafluoroethylene lining, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, fully mixing and washing the obtained product by using 1% sodium hydroxide solution for the last time, and drying the obtained product at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
step two, adding 0.5g of the obtained titanium dioxide nanosheet into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea into the deionized water, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain 1T-MoS 2 /TiO 2 A composite material;
taking 3.75mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract, stirring, and performing ultrasonic treatment to obtain a mixed graphene oxide aqueous solution, wherein the power of the ultrasonic treatment is 800W, and the ultrasonic frequency is 35 KHz; 0.15g of the 1T-MoS obtained above was taken 2 /TiO 2 Adding the composite material into the mixed graphene oxide aqueous solution, continuously stirring to obtain a fully and uniformly mixed solution, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 6 hours at the temperature of 180 ℃ to obtain reduced graphene oxide hydrogel; adding the obtained reduced graphene oxide hydrogel into supercritical CO 2 In the reaction device, CO of 10MPa is injected 2 Heating to 60 deg.C, and continuously injecting CO 2 Until the pressure is 20MPa, soaking and swelling the macroscopic three-dimensional 1T-MoS 2 /TiO 2 Performing pressure relief on the rGO hydrogel for 1h to obtain a pretreated reduced graphene oxide hydrogel;
step four, dialyzing the pretreated reduced graphene oxide hydrogel by using an ethanol aqueous solution with the concentration of 2 wt%, wherein the dialysis time is 4h, and repeating for 3 times; pre-cooling at-17 deg.C for 12h after dialysis, taking out, and freeze-drying at-50 deg.C for 48h to obtain macroscopic extractVicat 1T-MoS 2 /TiO 2 a/rGO aerogel.
Example 9:
macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material comprises the following steps:
step one, adding 20mL of n-butyl titanate solution (98 wt%) and 3.2mL of hydrofluoric acid solution (40 wt%) into a lining of a high-pressure reaction kettle with a 50mL polytetrafluoroethylene lining, and continuously stirring and uniformly mixing to obtain a mixed solution; sealing the mixed solution in a high-pressure reaction kettle, reacting for 24 hours at the temperature of 200 ℃ to obtain white precipitate, centrifugally washing the white precipitate for 3-5 times by using deionized water and absolute ethyl alcohol, fully mixing and washing the white precipitate by using a 1% sodium hydroxide solution for the last time, and drying the washed solution at the temperature of 80 ℃ to obtain anatase-phase titanium dioxide nanosheets;
step two, adding 0.5g of the obtained titanium dioxide nanosheet into 75mL of deionized water, adding 0.1g of ammonium molybdate and 0.19g of thiourea into the deionized water, and continuously stirring to obtain a fully and uniformly mixed solution; transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at the temperature of 200 ℃ to obtain black precipitate, centrifugally washing for 3-5 times by using deionized water and absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain 1T-MoS 2 /TiO 2 A composite material;
step three, 0.15g of the 1T-MoS obtained in the step 2 /TiO 2 Adding the composite material, 3.75mL of 10mg/mL graphene oxide aqueous solution and 1mL of 10mg/mL mint plant extract into a microwave and ultrasonic integrated reactor, simultaneously starting microwaves and ultrasonic waves, performing synergistic treatment for 60min, then transferring into a high-pressure reaction kettle, and reacting for 6 hours at the temperature of 180 ℃ to obtain reduced graphene oxide hydrogel; adding the obtained reduced graphene oxide hydrogel into supercritical CO 2 In the reaction device, CO of 10MPa is injected 2 Heating to 60 deg.C, and continuously injecting CO 2 Until the pressure is 20MPa, soaking and swelling the macroscopic three-dimensional 1T-MoS 2 /TiO 2 Performing pressure relief on the rGO hydrogel for 1h to obtain a pretreated reduced graphene oxide hydrogel; wherein the temperature of the co-treatment isThe microwave power is 1000W, the ultrasonic power is 800W, and the ultrasonic frequency is 35KHz at 70 ℃;
step four, dialyzing the hydrogel by using an ethanol water solution with the concentration of 2 wt%, wherein the dialysis time is 4h, and repeating for 3 times; precooling for 12h at-17 ℃ after dialysis, taking out, and freeze-drying for 48h at-50 ℃ to obtain the macroscopic three-dimensional 1T-MoS 2 /TiO 2 /rGO aerogels.
FIG. 5 shows the macroscopically three-dimensional 1T-MoS prepared in examples 1, 7 and 9 of the present invention 2 /TiO 2 The degradation rate of the/rGO composite material for degrading the organic matter tannic acid through photocatalysis under a 300W xenon lamp light source; by CO-processing with microwaves and ultrasound, and by supercritical CO 2 Soaking and swelling to prepare the macroscopic three-dimensional 1T-MoS 2 /TiO 2 The degradation rate of the/rGO composite material to organic matter tannic acid is obviously improved;
FIG. 8 is a macroscopic three-dimensional 1T-MoS prepared in examples 1, 7 and 9 of the present invention 2 /TiO 2 The removal rate of U (VI) in simulated nuclear waste liquid is removed by photocatalytic reduction of the/rGO composite material under dark conditions and 300W xenon lamp illumination conditions; by using microwave and ultrasonic wave for CO-treatment, and by supercritical CO 2 Soaking and swelling to prepare the obtained macroscopic three-dimensional 1T-MoS 2 /TiO 2 The removal rate of the/rGO composite material to U (VI) in the simulated nuclear waste liquid is obviously improved.
The macroscopic three-dimensional 1T-MoS prepared in the examples was investigated by reductive removal of wastewater containing U (VI) 2 /TiO 2 Photocatalytic activity of/rGO aerogel composites; the dark reaction phase is represented by a time negative value, which indicates the adsorption capacity of the material for the target removal. The specific procedure of the catalytic experiment was as follows: 1T-MoS 2 /TiO 2 10mg of/rGO composite was added to 50mL of 10mg/L U (VI) solution; the solution was transferred to a photocatalytic reactor using a xenon lamp (300W, lambda)>365nm) for 60 min; at 20, 40, 60, 80, 100 and 120min, taking 5mL of reaction solution into a centrifuge tube, filtering and precipitating by using a filter head to obtain a clear solution, and measuring the uranium concentration of the solution by using ICP-OES; the specific process of the tannin degradation rate experiment is as follows: 1T-MoS 2 /TiO 2 Adding 10mg of/rGO composite material into 50mL of tannic acid solution with the concentration of 40 mg/L; the solution was transferred to a photocatalytic reactor using a xenon lamp (300W, lambda)>365nm) irradiating the solution for 120 min; at 20, 40, 60, 80, 100 and 120min, 5mL of the reaction solution is taken out of a centrifuge tube, a filter head is used for filtering and precipitating to obtain a clear solution, and the concentration of the residual tannic acid in the solution is measured by an ultraviolet spectrophotometer.
While embodiments of the invention have been described above, it is not intended to be limited to the details shown, described and illustrated herein, but is to be accorded the widest scope consistent with the principles and novel features herein disclosed, and to such extent that such modifications are readily available to those skilled in the art, and it is not intended to be limited to the details shown and described herein without departing from the general concept as defined by the appended claims and their equivalents.

Claims (10)

1. Macroscopic three-dimensional 1T-MoS for photocatalysis 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material is characterized by comprising the following steps:
step one, dispersing a titanium source in a hydrofluoric acid solution, and synthesizing a titanium dioxide nanosheet with a thin-layer characteristic by adopting a hydrothermal method;
step two, adding titanium dioxide nanosheets into a mixed solution containing a molybdenum source and a sulfur source, uniformly dispersing, growing metal phase molybdenum disulfide on the surfaces of the titanium dioxide nanosheets in situ by a hydrothermal method, and washing and drying the solid to obtain a binary composite material 1T-MoS 2 /TiO 2 ；
Step three, mixing the binary composite material 1T-MoS 2 /TiO 2 Uniformly dispersing the graphene oxide in a graphene oxide aqueous solution, transferring the graphene oxide aqueous solution to a high-pressure reaction kettle, and carrying out hydrothermal treatment to obtain macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO hydrogel;
step four, performing macroscopic three-dimensional 1T-MoS 2 /TiO 2 Freezing and drying the rGO hydrogel after cyclic dialysis to obtain macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO composite material.
2. Such as rightMacroscopic three-dimensional 1T-MoS for photocatalysis according to claim 1 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material is characterized in that in the first step, a titanium source is any one of titanium tetrachloride, tetrabutyl titanate and titanium dioxide P25, the titanium source is added in a titanium source solution mode, the concentration of the titanium source solution is 98 wt%, the concentration of a hydrofluoric acid solution is more than or equal to 40 wt%, and the volume ratio of the titanium source solution to the hydrofluoric acid solution is 15-30: 2-4; the temperature of the hydrothermal method is 160-220 ℃, and the duration is 10-24 h; in the first step, a hydrothermal method is followed by washing and drying, the washing method is any one of suction filtration washing, centrifugal washing and ultrasonic sedimentation washing, and the drying method is any one of freeze drying, natural drying, constant-temperature drying and program variable-temperature drying.
3. Macroscopic three-dimensional 1T-MoS for photocatalysis as claimed in claim 1 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material is characterized in that in the second step, the molybdenum source is any one of molybdenum trioxide, ammonium molybdate and ammonium molybdate tetrahydrate, and the sulfur source is one or the combination of thioacetamide and thiourea; the temperature of the hydrothermal method is 160-220 ℃, and the duration is 3-12 h; the mass ratio of the titanium dioxide nanosheets to the molybdenum source is 4-6: 1; the mass ratio of the titanium dioxide nanosheet to the sulfur source is 4-6: 1-3; in the second step, the washing method is any one of suction filtration washing, centrifugal washing and ultrasonic sedimentation washing, and the drying method is any one of freeze drying, natural drying, constant temperature drying and program variable temperature drying.
4. Macroscopic three-dimensional 1T-MoS for photocatalysis as claimed in claim 1 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material is characterized in that in the third step, the graphene oxide aqueous solution is any one of a graphene aqueous solution prepared by a Hummers method, a directly purchased graphene aqueous solution, a single-layer graphene powder aqueous solution and a single-layer graphene oxide powder aqueous solution.
5. Macroscopic three dimensional 1T-MoS for photocatalysis as claimed in claim 1 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material is characterized in that in the third step, a cross-linking agent is added into the graphene oxide aqueous solution to form hydrogel, wherein the cross-linking agent is one or a combination of more of a borax aqueous solution, a mint plant extracting solution and a Ledum palustre plant extracting solution; the concentration of the graphene oxide aqueous solution is 5-15 mg/mL; the concentration of the cross-linking agent is 5-15 mg/mL; the volume ratio of the graphene oxide aqueous solution to the cross-linking agent is 4-6: 1; binary composite material 1T-MoS 2 /TiO 2 The mass-to-volume ratio of the graphene oxide to the graphene oxide aqueous solution is 0.1-0.2 g: 4-6 mL; the temperature of the hydrothermal treatment is 120-180 ℃, and the duration time is 3-12 h.
6. Macroscopic three-dimensional 1T-MoS for photocatalysis as claimed in claim 1 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material is characterized by comprising the following steps: mixing binary composite material 1T-MoS 2 /TiO 2 Adding the graphene oxide aqueous solution and a cross-linking agent into a microwave and ultrasonic integrated reactor, simultaneously starting microwaves and ultrasonic waves, carrying out synergistic treatment for 60-90 min, transferring the obtained product into a high-pressure reaction kettle, carrying out hydrothermal treatment, and obtaining the macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO hydrogel; wherein the temperature of the synergistic treatment is 65-75 ℃, the microwave power is 800-1000W, the ultrasonic power is 600-800W, and the ultrasonic frequency is 35-45 KHz; the concentration of the graphene oxide aqueous solution is 5-15 mg/mL; the concentration of the cross-linking agent is 5-15 mg/mL; the cross-linking agent is one or more of borax water solution, herba Menthae plant extractive solution, and Ledum Palustre L plant extractive solution; the volume ratio of the graphene oxide aqueous solution to the cross-linking agent is 4-6: 1; binary composite material 1T-MoS 2 /TiO 2 The mass volume ratio of the graphene oxide to the graphene oxide aqueous solution is 0.1-0.2 g: 4-6 mL; the temperature of the hydrothermal treatment is 120-180 ℃, and the duration time is 3-12 h.
7. Macroscopic three-dimensional 1T-MoS for photocatalysis as claimed in claim 1 or 6 2 /TiO 2 /rGO complexThe preparation method of the composite photocatalytic material is characterized in that in the third step, the obtained macroscopic three-dimensional 1T-MoS 2 /TiO 2 Addition of supercritical CO into/rGO hydrogel 2 In the reaction device, CO of 10MPa is injected 2 Heating to 60-65 ℃, and then continuously injecting CO 2 Soaking and swelling to macroscopic three-dimensional 1T-MoS under the pressure of 15-25 MPa 2 /TiO 2 Releasing pressure for 1-2 h by using/rGO hydrogel to obtain pretreated macroscopic three-dimensional 1T-MoS 2 /TiO 2 a/rGO hydrogel.
8. Macroscopic three dimensional 1T-MoS for photocatalysis as claimed in claim 1 2 /TiO 2 The preparation method of the/rGO composite photocatalytic material is characterized in that in the fourth step, deionized water or 0.5-5 wt% ethanol water solution is adopted for circulating dialysis, and circulating dialysis washing is carried out for 5-10 times; in the fourth step, the freeze drying process comprises the following steps: precooling for 12h at-18 to-15 ℃, taking out, and freeze-drying for at least 48h at-60 to-40 ℃.
9. Macroscopic three-dimensional 1T-MoS prepared by the preparation method of claim 1 2 /TiO 2 The application of the/rGO composite photocatalytic material in radioactive wastewater treatment is characterized in that the macroscopic three-dimensional 1T-MoS 2 /TiO 2 the/rGO composite material is added into the radioactive waste water containing uranium to perform photocatalytic reaction under the condition that a xenon lamp simulates sunlight, so that the photocatalytic reduction of hexavalent uranium in the radioactive waste water containing uranium is realized.
10. Macroscopic three-dimensional 1T-MoS prepared by the preparation method of claim 1 2 /TiO 2 The application of the/rGO composite photocatalytic material in organic matter wastewater treatment is characterized in that macroscopic three-dimensional 1T-MoS is adopted 2 /TiO 2 the/rGO composite material is added into organic wastewater to perform photocatalytic reaction under the condition that a xenon lamp simulates sunlight, so that the degradation of organic matters in the organic wastewater is realized.
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