CN115672302A - Three-dimensional foam graphene-TiO 2 -silver nanowire composite material and preparation method and application thereof - Google Patents
Three-dimensional foam graphene-TiO 2 -silver nanowire composite material and preparation method and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention provides three-dimensional foam graphene-TiO 2 -a method for preparing a silver nanowire composite, the method comprising the steps of: s1, mixing butyl titanate and hydrofluoric acid, reacting for 10-20 h at 150-250 ℃ after ultrasonic treatment, cleaning reaction products, and calcining for 2-5 h at 400-600 ℃ in Ar gas to obtain TiO with exposed (001) crystal face 2 Nanosheets; s2, (1) dispersing graphene oxide in water, and carrying out ultrasonic treatment; (2) Adding hydrazine hydrate into the solution obtained in the step (1), and then adding the titanium dioxide nanosheets and the silver nanowires; (3) reacting for 1-6 h at 130-250 ℃ after uniform dispersion; (4) And (4) carbonizing the reaction product obtained in the step (3), and calcining for 2-5 h at 400-600 ℃ in Ar gas to obtain the composite material. The invention also provides the composite material prepared by the method and application thereof. The invention relates to three-dimensional foam graphene-TiO 2 The silver nanowire composite material has good catalytic activity, catalytic stability and antibacterial performance, and has good application prospects in the fields of sewage treatment and the like.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to three-dimensional foam graphene-TiO 2 -silver nanowire composite material and preparation method and application thereof.
Background
At present, the main methods for sewage treatment comprise a physical method, a chemical method, a biological method and the like, but the methods generally have high treatment cost, long period, high treatment difficulty on toxic and harmful substances which are difficult to biodegrade, low degradation efficiency and incapability of thoroughly solving the pollution problem. The photocatalytic oxidation technology directly utilizes sunlight, has the advantages of simplicity, practicability, economy, mild reaction conditions, no secondary pollution and the like, and is paid attention by researchers in various countries in recent years. In the research of photocatalytic degradation of organic pollutants, the development of efficient and stable photocatalysts is urgent.
TiO 2 The advantages of no toxicity, stable property, chemical and photo corrosion resistance, no secondary pollution and the like are used as the most important advantagesThe potential semiconductor photocatalytic material is widely concerned by researchers at home and abroad. In practical application of TiO 2 In the process of photocatalyst, some key technical problems still exist to restrict the industrial application of the technology. The main points are as follows: 1) TiO2 2 The material property of (2) belongs to one of semiconductors (n type), has larger band gap energy, can effectively stimulate valence band electron to transit to a conduction band under the induction of ultraviolet light with the wavelength of less than 387nm to generate an electron-hole pair, and has the utilization rate of visible light of only 3 to 5 percent; 2) TiO2 2 The generated photon-generated carriers in the photocatalysis process have high recombination rate and low quantum efficiency, so that the treatment effect of industrial wastewater and domestic wastewater with high pollution concentration and large yield is difficult to meet; 3) In TiO 2 TiO is used in the process of photocatalytic treatment of organic wastewater 2 The photocatalyst is mostly in powder form, which is easy to increase the recovery difficulty and causes the problems of secondary pollution and the like.
In order to overcome the above problems, the prior art has developed nanostructured catalyst supports such as carbon materials (activated carbon, carbon nanotubes and graphene), metals and conductive polymers to maximize the electroactive surface area of the catalyst and to improve its catalytic activity and durability. But existing TiO 2 The electron transport rate and photocatalytic efficiency and stability of the photocatalyst are still further improved.
Disclosure of Invention
Based on the above, the invention aims to provide three-dimensional foam graphene-TiO 2 The silver nanowire composite material and the preparation method and application thereof have the advantages of high catalytic effect, good antibacterial property, stable catalytic performance and reusability.
In order to achieve the purpose, the invention adopts the following technical scheme.
A method of preparing a photocatalytic composite material, the method comprising the steps of: s1, mixing butyl titanate and hydrofluoric acid, reacting for 10-20 h at 150-250 ℃ after ultrasonic treatment, cleaning reaction products, and calcining for 2-5 h at 400-600 ℃ in Ar gas to obtain TiO with exposed (001) crystal face 2 Nanosheets; s2, (1) dispersing graphene oxide in water, and performing ultrasonic treatmentProcessing; (2) Adding hydrazine hydrate into the solution obtained in the step (1), and then adding the titanium dioxide nanosheet and the silver nanowire; (3) reacting for 1-6 h at 130-250 ℃ after uniform dispersion; (4) And (4) carbonizing the reaction product obtained in the step (3), and calcining for 2-5 h at 400-600 ℃ in Ar gas to obtain the photocatalytic composite material.
In some embodiments, the mass ratio of the silver nanowires, the titanium dioxide nanosheets, and the graphene oxide is (0.05-0.2): (0.5-4): 1.
in some embodiments, the silver nanowires have a diameter of 20 to 40nm and a length of 20 to 50 μm.
In some embodiments, the volume ratio of the butyl titanate to the hydrofluoric acid is (4-6): 1; preferably, the volume ratio of the butyl titanate to the hydrofluoric acid is 5:1.
in some embodiments, the butyl titanate and the hydrofluoric acid are mixed in step S1, and reacted for 15-20 h at 200-250 ℃ after ultrasonic treatment.
In some embodiments, the step (3) is performed for 3 to 6 hours at 130 to 200 ℃ after the uniform dispersion.
The invention also provides the photocatalytic composite material prepared by the preparation method.
The invention also provides application of the photocatalytic composite material prepared by the preparation method in treating water pollution, preparing hydrogen, oxidizing and reducing carbon dioxide and promoting photochemical reaction.
The invention also provides application of the photocatalytic composite material prepared by the preparation method in inhibiting bacterial growth.
The invention also provides a photocatalytic preparation or a bacteriostatic preparation, and the preparation comprises the photocatalytic composite material prepared by the preparation method.
The invention provides a photocatalytic composite material which is prepared from graphene oxide and TiO with an exposed (001) crystal face 2 The nano-sheet and the silver nano-wire are used as raw materials, and the three-dimensional foam graphene-TiO is prepared by reacting the 3 raw materials according to a proper proportion under a specific condition 2 -silver nanowire composite:
(1) The three-dimensional foam graphene can avoid stacked graphene nanosheets, effectively keep the huge specific surface area of the graphene nanosheets, reduce reflected incident light to the maximum extent and improve the utilization rate of light; the structure has rich macroporosity and multidimensional electron transmission ways, can effectively reduce the recombination of photo-generated electron-hole pairs, and improves the electron transmission rate, thereby improving the photocatalysis efficiency;
(2) Silver has good antibacterial, optical and catalytic properties. Ag not only can transfer photoproduced electrons to reduce the recombination rate of photoproduced electron-hole pairs, but also greatly improves TiO due to Local Surface Plasmon Resonance (LSPR) 2 The visible light utilization rate of the photocatalyst is high, silver nanoparticles are easy to agglomerate and cannot be uniformly dispersed in the three-dimensional foam graphene, so that the practical application of Ag is limited, and therefore the problem of agglomeration of the silver nanoparticles is solved by preparing the three-dimensional foam graphene-titanium dioxide-silver nanowire composite material from the dispersed nano silver wires, and the photocatalytic efficiency is improved.
(3) Selecting TiO with exposed (001) crystal face 2 Compared with crystal face (101) with more stable thermodynamics, the crystal face (001) of the nano-sheet has higher efficiency in the aspect of dissociative adsorption of reactant molecules, and the defect density of the single crystal structure of the nano-sheet is low, so that the recombination rate of photo-generated electron hole pairs at the crystal boundary and the crystal defect can be reduced, and the photocatalysis efficiency can be improved.
In addition, the photocatalytic composite material has stable catalytic performance, and the degradation rate of methylene blue after repeated use for 5 times is over 97 percent; and the antibacterial property of the antibacterial agent is further improved. Therefore, the photocatalytic composite material is very suitable for sewage treatment, hydrogen preparation, carbon dioxide oxidation reduction, photochemical reaction promotion and bacterial growth inhibition, and has a wide application prospect.
Drawings
Fig. 1 is a graph of photocatalytic degradation of methylene blue.
Detailed Description
Experimental procedures according to the invention, in which no particular conditions are specified in the following examples, are generally carried out under conventional conditions, or under conditions recommended by the manufacturer. The various chemicals used in the examples are commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to only those steps or modules listed, but may alternatively include other steps not listed or inherent to such process, method, article, or device.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The following description will be given with reference to specific examples.
Example 1
This example 1 provides a photocatalytic composite material (named AgNWs-TiO) 2 nanosheets-Graphene-1), the preparation steps of the photocatalytic composite material are as follows:
s1, synthesizing TiO with exposed (001) crystal face 2 Nanosheet: after 25ml of butyl titanate and 5ml of hydrofluoric acid are added into a Teflon beaker for ultrasound, the mixture is transferred into a reaction container with a Teflon substrate and then placed into an oven to be set at 200 ℃ for reaction for 18h. After the reaction is finished, the synthesized TiO2 nanosheet is washed for 3 times by ethanol and then calcined for 3 hours at 550 ℃ in Ar gas.
S2, preparing a three-dimensional foam graphene/titanium dioxide/silver nanowire composite material: (1) Dispersing graphene oxide in pure water, and performing ultrasonic treatment for 70s; (2) 1ml of hydrazine hydrate is added to the reaction mixture,adding titanium dioxide nanosheets and silver nanowires (AgNWs) into the graphene oxide dispersion liquid according to a certain proportion; agNWs, tiO 2 The mass ratio of the nanosheets to the graphene oxide is 0.15; (3) After uniform dispersion, putting the mixture into an oven for hydrothermal reaction, and reacting for 4 hours at 160 ℃; (4) Finally, carbonizing the obtained product, and calcining the product for 3 hours at 550 ℃ in Ar gas to prepare the AgNWs-TiO 2 nanosheets-Graphene-1 photocatalytic composite materials.
The silver nanowires are prepared by synthesizing pvp-wrapped silver nanowires (with the average diameter of 25nm and the length of 30 microns) by adopting a polyol reduction method, adding acetone into a reaction mixture after the reaction is finished, circularly cleaning for 3 times, and dispersing purified silver nanowires in pure water.
Example 2
This example 1 provides a photocatalytic composite material (named AgNWs-TiO) 2 nanosheets-Graphene-2); the preparation method of the photocatalytic composite material is substantially the same as that of the photocatalytic composite material in the example 1, except that AgNWs and TiO are used in the step (2) 2 The mass ratio of the nanosheets to the graphene oxide is as follows: 0.09:0.8:1.
Example 3
This example 1 provides a photocatalytic composite material (named AgNWs-TiO) 2 nanosheets-Graphene-3); the preparation method of the photocatalytic composite material is substantially the same as that of the photocatalytic composite material in the example 1, except that AgNWs and TiO are used in the step (2) 2 The mass ratio of the nanosheets to the graphene oxide is as follows: 0.12:3.2:1.
Comparative example 1
The comparative example provides a nano-silver/Graphene/nano-titanium dioxide composite material (named as Ag-Ti-Graphene), which is prepared by a one-step hydrothermal method and comprises the following preparation steps:
1. firstly, dispersing a certain amount of graphene oxide in distilled water, and performing ultrasonic dispersion for 0.5h to prepare a graphene oxide suspension with the concentration of 0.002 g/L;
2. dissolving a certain amount of silver nitrate in distilled water to obtain a water solution with silver ion concentration of 0.001 mol/L;
3. dissolving a certain amount of butyl titanate in ethanol to obtain an ethanol solution containing titanium ions with the concentration of 0.0125 mol/L;
4. mixing and uniformly dispersing the graphene oxide dispersion liquid, the aqueous solution containing silver ions and the ethanol solution containing titanium ions;
5. and transferring the solution into a hydrothermal reaction kettle, keeping the temperature at 180 ℃ for 4 hours, cooling, washing the prepared sample with distilled water for 5 times, finally washing with absolute ethyl alcohol once to remove impurities and unreacted ions, and drying in vacuum at 60 ℃ to constant weight to obtain the composite material.
Comparative example 2
This comparative example provides a graphene/titanium dioxide composite (named TiO) 2 nanosheets-Graphene) the composite material was prepared as follows:
1. synthesis of TiO with exposed (001) Crystal face 2 Nanosheet: after 25ml of butyl titanate and 5ml of hydrofluoric acid are added into a Teflon beaker for ultrasound, the mixture is transferred into a reaction container with a Teflon substrate and then placed into an oven to be set at 200 ℃ for reaction for 18h. Synthesizing TiO after the reaction is finished 2 And washing the nanosheets with ethanol for 3 times, and calcining the nanosheets in Ar gas at 550 ℃ for 3 hours.
2. Preparing a graphene/titanium dioxide composite material: (1) Dispersing graphene oxide in pure water, and performing ultrasonic treatment for 70s; (2) Adding 1ml of hydrazine hydrate, and adding titanium dioxide nanosheets into the graphene oxide dispersion liquid; tiO2 2 The mass ratio of the nano sheets to the graphene oxide is 2:1; (3) After uniform dispersion, putting the mixture into an oven for hydrothermal reaction, and reacting for 4 hours at 160 ℃; (4) And finally, carbonizing the obtained product, and calcining the product for 3 hours at 550 ℃ in Ar gas to obtain the composite material.
Comparative example 3
This comparative example provides a TiO having an exposed (001) crystal face 2 Nanosheet (denominated TiO) 2 nanosheets) prepared by the following steps:
TiO with exposed (001) crystal face 2 Nanosheet: adding 25ml of butyl titanate and 5ml of hydrofluoric acid into a Teflon beaker for ultrasound, transferring the mixture into a reaction container with a Teflon substrate, then putting the reaction container into an oven, setting the temperature at 200 ℃ and reacting for 18 hours; reaction ofAfter the completion of the synthesis of TiO 2 And washing the nanosheets with ethanol for 3 times, and calcining the nanosheets in Ar gas at 550 ℃ for 3 hours.
The photocatalytic activity of the materials prepared in examples 1 to 3 and comparative examples 1 to 3 above was evaluated by degradation of (10 mg/L) MB by the following specific method:
20mg of the materials prepared in the examples 1 to 3 and the comparative examples 1 to 3 are respectively added into 20mL of 10mg/LMB dye solution, are subjected to ultrasonic dispersion for 5min in a dark place, are magnetically stirred for 30min in a dark room to achieve adsorption-desorption balance, are subjected to photocatalytic reaction by taking a 500W xenon lamp as a light source, are sampled every 30min, are subjected to centrifugal separation, and are taken out, and the absorbance of the supernatant is measured at the position with the maximum absorption wavelength of 554nm of the solution. The group of MB dye solutions without added photocatalytic material served as a blank.
As shown in FIG. 1, the photocatalytic composite materials of the present invention (examples 1 to 3) exhibited the best catalytic performance, degrading about 99.5% of MB, which is significantly better than the materials of comparative examples 1 to 3 (comparative examples 1 to 3). Illustrating the three-dimensional foam graphene-TiO of the present invention 2 The catalytic efficiency of the silver nanowire composite material is higher. In FIG. 1, C 0 Represents the initial concentration of the MB dye solution, and C represents the concentration of the MB dye solution after the photocatalytic degradation of the photo-composite material.
To evaluate the catalytic stability of the inventive nanocomposites, a repeated use experiment was performed with the photocatalytic composite material in example 1 as an example: the photocatalytic composite material in example 1 is used for catalyzing the degradation of the MB dye solution, and the photocatalytic composite material is reused for 5 times. The degradation rate was calculated using the following formula: (C) 0 -C t )/C 0 X 100; wherein, C 0 Represents the initial concentration of the MB dye solution, C t Represents the concentration of the MB dye solution after the catalytic degradation of the photo-composite.
The results are shown in Table 1:
table 1 example 1 removal efficiency of photocatalytic composite material for reuse of MB
The results show that after the photocatalytic composite material is repeatedly used for 5 times, the degradation rate of the photocatalytic composite material in the embodiment 1 to MB is over 97 percent, and the photocatalytic composite material has stable performance and good reusability.
In order to evaluate the antibacterial performance of the optical composite material of the present invention, an escherichia coli antibacterial experiment was performed using the photocatalytic composite material of example 1 as an example, wherein silver nanowires (named AgNWs) were used as comparative example 4, and the silver nanowires (average diameter 25nm, length 30 μm) were synthesized by a polyol reduction method to wrap pvp. The specific method comprises the following steps:
(1) Taking the materials in the example 1 and the comparative examples 1-4 respectively to prepare aqueous solutions with the concentration of 1 g/L; (2) Taking Escherichia coli, and preparing bacteria with concentration of 10 -6 Bacterial liquid of each ml; (3) Respectively and uniformly mixing the aqueous solution and the bacterial liquid prepared by the materials in the example 1 and the comparative examples 1-4, adding 1mL of mixed solution into 10mL of liquid culture medium, uniformly mixing, and then pouring into a culture dish to serve as 5 experimental groups; (4) Adding 1mL of sterilized water into 10mL of liquid culture medium, mixing uniformly, and pouring into a culture dish as a control group; (5) The 5 experimental group plates and the control group plates are inversely placed in a biochemical incubator and are cultured for 24 hours at 37 ℃, the number of bacteria is counted respectively, and the bacteriostasis rate is calculated according to the following formula:
bacteriostasis rate = (number of bacteria in control group-number of bacteria in experimental group)/number of bacteria in control group x 100%. The results are shown in table 2:
TABLE 2 antimicrobial Rate of the different samples
| Group of | Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Antibacterial rate of Escherichia coli | 99.60％ | 96％ | 76％ | 16％ | 93％ |
As can be seen from Table 2, the three-dimensional foam graphene-TiO of the invention 2 The-silver nanowire composite also had excellent antibacterial properties, superior to the materials and AgNWs in comparative examples 1-3, due to the three-dimensional foamy graphene-TiO 2 The silver nanowire composite material has ultrahigh surface area and can adsorb and gather escherichia coli on the surface of the composite material, so that the interaction efficiency of bacteria and active bactericidal components is enhanced. The three-dimensional foam graphene-TiO 2 The excellent antibacterial performance of the silver nanowire composite material enables the silver nanowire composite material to have great advantages in sewage treatment.
In summary, the three-dimensional foam graphene-TiO 2 nano-sheet is prepared by taking graphene oxide, tiO2 nano-sheet and silver nano-wire as raw materials and reacting the 3 raw materials according to a proper proportion under a specific condition 2 The silver nanowire composite material has good catalytic activity, catalytic stability and antibacterial performance, and has good application prospects in the fields of sewage treatment and the like.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered as being described in the present specification.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a photocatalytic composite material is characterized by comprising the following steps: s1, mixing butyl titanate and hydrofluoric acid, reacting for 10-20 h at 150-250 ℃ after ultrasonic treatment, cleaning reaction products, and calcining for 2-5 h at 400-600 ℃ in Ar gas to obtain TiO with exposed (001) crystal face 2 Nanosheets; s2, (1) dispersing graphene oxide in water, and carrying out ultrasonic treatment; (2) Adding hydrazine hydrate into the solution obtained in the step (1), and then adding the titanium dioxide nanosheets and the silver nanowires; (3) reacting for 1-6 h at 130-250 ℃ after uniform dispersion; (4) And (4) carbonizing the reaction product obtained in the step (3), and calcining for 2-5 h at 400-600 ℃ in Ar gas to obtain the photocatalytic composite material.
2. The preparation method of the photocatalytic composite material as set forth in claim 1, wherein the mass ratio of the silver nanowires, the titanium dioxide nanosheets and the graphene oxide is (0.05-0.2): (0.5-4): 1.
3. the method of preparing a photocatalytic composite material as set forth in claim 1, wherein the silver nanowires have a diameter of 20 to 40nm and a length of 20 to 50 μm.
4. The method for preparing a photocatalytic composite material as set forth in claim 1, wherein the volume ratio of the butyl titanate to the hydrofluoric acid is (4 to 6): 1.
5. the method for preparing a photocatalytic composite material as set forth in claim 1, wherein in step S1, butyl titanate and hydrofluoric acid are mixed, and reacted at 200 to 250 ℃ for 15 to 20 hours after ultrasonic treatment.
6. The method for preparing a photocatalytic composite material as set forth in claim 1, wherein the step (3) is carried out by uniformly dispersing and then reacting at 130 to 200 ℃ for 3 to 6 hours.
7. A photocatalytic composite material produced by the production method as set forth in any one of claims 1 to 6.
8. Use of the photocatalytic composite material prepared by the preparation method according to any one of claims 1 to 6 for treating water pollution, producing hydrogen, redox carbon dioxide, and promoting photochemical reaction.
9. Use of a photocatalytic composite material prepared by the preparation method according to any one of claims 1 to 6 for inhibiting bacterial growth.
10. A photocatalytic or bacteriostatic formulation comprising the photocatalytic composite material prepared by the preparation method according to any one of claims 1 to 6.
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