CN111905807A - High instantaneous photocurrent nanometer TiO2Polyaniline/graphene composite material and preparation method thereof - Google Patents
High instantaneous photocurrent nanometer TiO2Polyaniline/graphene composite material and preparation method thereof Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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Abstract
The invention discloses a high instantaneous photocurrent nano TiO2The preparation method of the polyaniline/graphene composite material comprises the following steps: s1, mixing graphene dispersion liquid, aniline and H2SO4Uniformly mixing the aqueous solution, stirring in an ice bath for reaction, filtering, washing a filter cake, and drying to obtain a polyaniline/graphene material; s2, mixing a titanium source, ethanol and the polyaniline/graphene material uniformly, adding water, mixing uniformly, heating, keeping the temperature, and centrifuging to obtain a precipitate; adding the precipitate into HCl aqueous solution, mixing uniformly, carrying out hydrothermal reaction, then centrifuging,washing, precipitating and drying to obtain high instantaneous light current nano TiO2Polyaniline/graphene composite material. The invention discloses a high instantaneous photocurrent nano TiO2The polyaniline/graphene composite material is prepared according to the method. The spectral response range of the invention can be expanded to visible light, and the synergistic effect of the graphene, the polyaniline and the titanium dioxide effectively prevents the recombination of electron holes.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to high instantaneous photocurrent nano TiO2Polyaniline/graphene composite material and preparation method thereof.
Background
With the sustainable development of society, industrial pollution has become a big problem in human society. Water pollution is the most serious, especially non-biodegradable organic pollutants, and poses a serious threat to ecological safety. These organic contaminants have a complex chemical structure and are not easily removed from water. Once contaminants enter the food chain, everyone's health is compromised. Therefore, many scientists are working to find a low cost, high efficiency technique. Among many cleaning techniques, photocatalysts that utilize solar energy to degrade contaminants may be preferred.
Cheap nontoxic TiO2Is a widely used photocatalyst. TiO 22The band gap of (A) is 3.2-3.1 eV. Under uv light, the electron-hole pairs are more active. Thus, TiO2The photocatalytic activity under ultraviolet light is remarkable. But not under visible light. To make full use of sunlight, TiO is required2And (4) carrying out modification.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides a high instantaneous photocurrent nano TiO2The invention relates to a polyaniline/graphene composite material and a preparation method thereof, the spectral response range of the invention can be expanded to visible light, the electron hole recombination is effectively prevented by the synergistic effect of graphene, polyaniline and titanium dioxide, and the invention is a photocatalyst with great potential.
The invention provides a high instantaneous photocurrent nano TiO2The preparation method of the polyaniline/graphene composite material comprises the following steps:
s1, mixing graphene dispersion liquid, aniline and H2SO4Mixing the water solution, stirring in ice bath for reaction, filtering, washing the filter cake, and drying to obtainPolyaniline/graphene materials;
s2, mixing a titanium source, ethanol and the polyaniline/graphene material uniformly, adding water, mixing uniformly, heating, keeping the temperature, and centrifuging to obtain a precipitate; adding the precipitate into HCl aqueous solution, mixing uniformly, carrying out hydrothermal reaction, centrifuging, washing the precipitate, and drying to obtain the high instantaneous photocurrent nano TiO2Polyaniline/graphene composite material.
Preferably, in S2, the titanium source is butyl titanate.
Preferably, in S2, the nano TiO2TiO in/polyaniline/graphene composite material2And the weight ratio of the polyaniline/graphene material is 10-200: 1.
Preferably, TiO2And the polyaniline/graphene material may be in a weight ratio of 10:1, 50:1, 100:1, or 200: 1.
Preferably, in S2, the temperature is raised to 70-75 ℃ and the temperature is kept for 30 min.
Preferably, in S2, the temperature of the hydrothermal reaction is 175-185 ℃ and the time is 16 h.
Preferably, in S1, the molar ratio of graphene to aniline is 1: 6.
Preferably, in S1, the reaction is stirred in an ice bath for 5-6 h.
Preferably, in S1, the solvent of the graphene dispersion liquid is a mixed solution of isopropanol and water, wherein the volume ratio of isopropanol to water is 1: 5.
Preferably, in S1, the concentration of the aqueous sulfuric acid solution is 1 mol/L.
Preferably, in S2, the concentration of the aqueous HCl solution is 1 mol/L.
Preferably, in S2, the volume ratio of ethanol to water is 1: 1.5.
The graphene can be prepared according to conventional preparation methods in the field, and can also be obtained from the market.
The water is deionized water.
Not specifying the above H2SO4The amounts of the aqueous solution, ethanol, aqueous HCl solution, and the like are determined according to the particular operation.
The invention also provides a high instantaneous photocurrent sodiumTiO rice2Polyaniline/graphene composite material, according to the high instantaneous photocurrent nano TiO2The polyaniline/graphene composite material is prepared by a preparation method.
The catalytic principle of the present invention is shown in fig. 1, and fig. 1 is a catalytic structure of the present invention. As can be seen from fig. 1: nano TiO 22When the/polyaniline/graphene composite material is irradiated by visible light, TiO is2H in the valence band+Will be separated; h+Transferring the energy level to the HOMO energy level of PANI (polyaniline), and dispersing the energy level on the surface of graphene; e.g. of the type-Shift the LUMO level from PANI to lower TiO2Conduction band and graphene surface. The presence of polyaniline/graphene reduces the amount of pure TiO2The band gap of the organic electroluminescent material improves the efficiency of electron hole separation; more importantly, it prevents electron-hole pair recombination and generates more hydroxyl radicals.
Has the advantages that:
the invention adopts conductive polymers polyaniline and graphene to nano TiO2Carrying out treatment; firstly preparing polyaniline/graphene material, and then preparing nano TiO with titanium source by adopting hydrothermal method2Polyaniline/graphene composite material; the method not only avoids high-temperature sintering, but also ensures that the nano particles grow uniformly in the composite material; introducing graphene into polyaniline and nano TiO2After the system is adopted, the spectral response range of the composite material can be expanded to visible light; the holes generated on the valence band of titanium dioxide are transferred to the homogeneous level of polyaniline, and at the same time, the photoelectrons generated on the LUMO level of polyaniline are transferred to TiO2The separation of electron-hole pairs is realized on the conduction band of the organic electroluminescent device; the synergistic effect of the graphene, the polyaniline and the titanium dioxide effectively prevents the recombination of electron holes; nano TiO 22The band gap of the polyaniline/graphene composite material is reduced to 2.30ev, which is less than that of most TiO2The forbidden band width of the catalyst; at the same time, nano TiO2The instantaneous photocurrent of the polyaniline/graphene composite material is nano TiO 26 times of the total weight of the composition; nano TiO 22The/polyaniline/graphene composite material is a photocatalyst with great potential.
Drawings
FIG. 1 is a catalytic structure of the present invention.
FIG. 2 is an XRD pattern of products obtained in examples 1 to 4 and comparative examples 1 to 3, wherein 1 to 4 correspond to examples 1 to 4, TiO, respectively2Per PANI is comparative example 1, TiO2Comparative example 2, TiO, Graphene2Comparative example 3.
FIG. 3 is a FT-IR spectrum of products obtained in examples 1 to 4 and comparative examples 1 to 3, wherein 1 to 4 correspond to examples 1 to 4, TiO respectively2Per PANI is comparative example 1, TiO2Comparative example 2, TiO, Graphene2Comparative example 3.
FIG. 4 shows the preparation of nano TiO in example 22And (3) TEM images of the/polyaniline/graphene composite material, wherein a, b and c are TEM images with different amplified sizes.
FIG. 5 shows the preparation of nano TiO in examples 1-42TEM image of/polyaniline/graphene composite material, wherein a is example 1, b is example 2, c is example 3, and d is example 4.
FIG. 6 shows that the nano TiO prepared in example 22EDS diagram of/polyaniline/graphene composite material.
FIG. 7 shows that the nano TiO prepared in example 22The X-ray photoelectron spectrum of the/polyaniline/graphene composite material is shown in the specification, wherein a is a spectrum of C1s, O1s, N1s and Ti 2p, b is a spectrum of C1s, C is a spectrum of O1s, d is a spectrum of N1s, and e is a spectrum of Ti 2 p.
FIG. 8 is UV-VIS absorption spectra of the products of examples 1-3 and comparative example 3, where a is the UV-vis absorption spectrum, b is the UV-vis DRS spectrum, 1 is example 1, 2 is example 2, 3 is example 3, TiO2Comparative example 3.
FIG. 9 is a luminescence spectrum of the products of example 2 and comparative example 3, in which a is a photoluminescence spectrum and b is a transient photocurrent response graph, TiO2Comparative example 3, TiO2Example 2 is/PANI/graphene.
FIG. 10 is a graph showing the result of degradation of rhodamine B under visible light, wherein a is the absorbance of rhodamine B under different illumination times, the left graph in a is an overall graph, and the right graph in a is an enlarged graph; and B is an absorbance standard curve of rhodamine B solutions with different concentrations.
FIG. 11 is a graph showing the results of degradation of rhodamine B by the products of examples 1-4 under visible light, where a is example 1, B is example 2, c is example 3, and d is example 4.
FIG. 12 is a graph showing the results of degradation of rhodamine B under visible light for the products of examples 1-4 and comparative examples 1-3, wherein 1 is example 1, 2 is example 2, 3 is example 3, 4 is example 4, TiO2Per PANI is comparative example 1, TiO2Comparative example 2, TiO graphene2For comparative example 3, blank is without addition of a photocatalyst.
FIG. 13 is a graph showing the results of degradation of rhodamine B under visible light when the products of examples 2-3 are added in amounts of 100mg, where a is example 2 and B is example 3.
FIG. 14 shows the degradation result of the product of example 2 on rhodamine B under different conditions, wherein a is the recycling times, B is the pH, c is the temperature, and d is the concentration of rhodamine B.
FIG. 15 shows the degradation results of the product of example 2 on methylene blue and methyl orange, wherein MB is methylene blue, MO is methyl orange, and the concentrations of the methylene blue and the methyl orange are 10 mg/L.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
High instantaneous photocurrent nanometer TiO2The preparation method of the polyaniline/graphene composite material comprises the following steps:
s1, adding graphene into a mixed solution of isopropanol and water in a volume ratio of 1:5, and performing ultrasonic treatment for 30min to uniformly disperse the graphene to obtain a graphene dispersion liquid;
adding graphene dispersion and aniline into 200ml of H with the concentration of 1mol/L in ice bath2SO4Stirring in an aqueous solution in an ice bath for 6 hours, filtering, washing a filter cake, and drying to obtain a polyaniline/graphene material, wherein the molar ratio of graphene to aniline is 1: 6;
s2, adding butyl titanate and polyaniline/graphene materials into 10ml of ethanol, mixing uniformly, adding 15ml of water, mixing uniformly, and putting into a water bath at 75 ℃ for heat preservationCentrifuging at 8000rpm for 2min for 30min to obtain precipitate, and washing with water; adding the precipitate into 50ml of HCl aqueous solution with the concentration of 1mol/L, uniformly mixing to obtain milky liquid, transferring the milky liquid into an oven with the temperature of 180 ℃, preserving the temperature for 16 hours, cooling to the room temperature, centrifuging, washing the precipitate, and drying to obtain the high instantaneous photocurrent nano TiO2Polyaniline/graphene composite material, wherein, TiO2And the weight ratio of polyaniline/graphene material is 200: 1.
Example 2
TiO2And polyaniline/graphene material weight ratio of 100:1, otherwise the same as example 1.
Example 3
TiO2And polyaniline/graphene material weight ratio of 50:1, otherwise the same as example 1.
Example 4
TiO2And polyaniline/graphene material in a weight ratio of 10:1, otherwise as in example 1.
Comparative example 1
The preparation method of the binary product of the nano titanium dioxide and the polyaniline comprises the following specific steps: the operation of S2 in example 1 was otherwise the same as that of example 1, except that polyaniline/graphene material was replaced with polyaniline.
Comparative example 2
The preparation method of the binary product of the nano titanium dioxide and the graphene comprises the following specific steps: the procedure of S2 in example 1 was otherwise the same as that for the case where the polyaniline/graphene material was replaced with pure graphene.
Comparative example 3
The preparation method of the pure nano titanium dioxide comprises the following specific steps: the procedure of S2 in example 1 was otherwise the same as that for the case of no polyaniline/graphene material.
The results of the tests performed in examples 1 to 4 and comparative examples 1 to 3 are shown in FIGS. 2 to 15,
FIG. 2 is an XRD pattern of products obtained in examples 1 to 4 and comparative examples 1 to 3, wherein 1 to 4 correspond to examples 1 to 4, TiO, respectively2Per PANI is comparative example 1, TiO2Comparative example 2, TiO, Graphene2Comparative example 3.
As can be seen from fig. 2: pure TiO 22 θ of 27.44 °, 36.07 °, 41.236 characteristic peaks such as degree, 54.35 degree, 56.64 degree and 68.97 degree, which respectively correspond to rutile TiO 26 crystal planes of (110), (101), (111), (211), (220) and (301); 2 θ, 25.31 ° and 47.9 ° also exist, corresponding to anatase TiO2(101) And (200) a crystal plane; it can be seen that TiO2The crystal form of anatase type and rutile type are shared;
from TiO2The XRD pattern of the/Graphene (namely the product of the comparative example 2) shows that the addition of the Graphene greatly reduces the intensity of the diffraction peak of the rutile type and also improves the intensity of the diffraction peak of the anatase type; from the XRD patterns of the products of examples 1-4, it can be seen that when TiO is used2When the three substances of polyaniline and graphene are combined, the intensity of a diffraction peak tends to be stable; however, when the anatase peak is obscured by polyaniline/graphene, the activity of the complex decreases; in addition, polyaniline has no distinct peak indicating that polyaniline is amorphous.
FIG. 3 is a FT-IR spectrum of products obtained in examples 1 to 4 and comparative examples 1 to 3, wherein 1 to 4 correspond to examples 1 to 4, TiO respectively2Per PANI is comparative example 1, TiO2Comparative example 2, TiO, Graphene2Comparative example 3.
As can be seen from fig. 3: and TiO2As can be seen by comparing the FT-IR spectra of (A) 425cm-1～609cm-1Has an absorption peak of 425cm, which is a vibration peak of the Ti-O bond-1Is located at 609cm of the swelling vibration peak of the Ti-O-Ti bond-1Is the expansion vibration peak of Ti-O bond; 1400cm-1The weak peak is the absorption peak of Ti-OH, 1640cm-1The absorption peak is a characteristic peak of O-H bond bending vibration of adsorbed water; the presence of these peaks demonstrates TiO2Is present.
FIG. 4 shows the preparation of nano TiO in example 22And (3) TEM images of the/polyaniline/graphene composite material, wherein a, b and c are TEM images with different amplified sizes.
As can be seen in fig. 4 a-c: TiO 22The distribution in the composite material is uniform and closely related, and the agglomeration phenomenon is improved; the flake graphene has larger specific surface area, and is beneficial to polyaniline and TiO2When loaded in graphene, polyaniline is in an obvious rod shape,and TiO 22Then attached to the surface of polyaniline; increased TiO at about 0.35nm2The lattice spacing of the nanocrystals corresponds to the (101) crystal plane, and the results are consistent with those of the XRD pattern of fig. 2.
FIG. 5 shows the preparation of nano TiO in examples 1-42TEM image of/polyaniline/graphene composite material, wherein a is example 1, b is example 2, c is example 3, and d is example 4.
As can be seen from fig. 5: TiO 22The particles are distributed relatively dispersed, only a few of which are agglomerated, showing an ultra-high specific surface area; nano TiO 22When the weight ratio of polyaniline/graphene material is different, the dispersibility and uniformity of the composite material are different, and the nano TiO prepared in example 22The polyaniline/graphene composite material has better dispersibility and uniformity; the flake graphene is attached to the surface of polyaniline and is coated with a large amount of nano TiO2Surrounding; the addition of the graphene greatly improves the synergistic performance of the composite material.
FIG. 6 shows that the nano TiO prepared in example 22EDS diagram of/polyaniline/graphene composite material.
From FIG. 6, it can be calculated that the nano TiO prepared in example 22The mass ratio of C, O, N, Ti elements in the polyaniline/graphene composite material is shown in table 1.
TABLE 1 nanometer TiO2Mass ratio of C, O, N, Ti elements in polyaniline/graphene composite material
FIG. 7 shows that the nano TiO prepared in example 22The X-ray photoelectron spectrum of the/polyaniline/graphene composite material is shown in the specification, wherein a is a spectrum of C1s, O1s, N1s and Ti 2p, b is a spectrum of C1s, C is a spectrum of O1s, d is a spectrum of N1s, and e is a spectrum of Ti 2 p.
The measured spectrum in FIG. 7a shows peaks for C1s, O1s, N1s and Ti 2p, which confirms that the nano TiO is2Forming a polyaniline/graphene composite material;
c1s light shown in FIG. 7bThe spectrum shows that the five binding peaks are attributed to C-C/C ═ C bonds and C-N bonds of hydroxyl groups in polyaniline/graphene+Epoxy groups of C-O, surface O-C-OH groups and O-C ═ O bonds;
the O1s spectrum shown in fig. 7C shows that O1s has four binding energy peaks at 529.5eV, 531eV, 532eV and 529.9eV, representing Ti-O, C ═ O, C-H/C-O-C and-COOH bonds, respectively;
the N1s spectrum shown in fig. 7d indicates an energy spectrum of N1s with three binding peaks at 398.7eV, 399.6eV and 400.49eV, corresponding to ═ N-、-NH+and-N+Of a positively charged group of+And N-Proves that the polyaniline and the graphene pass through cation N (-N)+And N-) Partially hydrogen bonded;
the Ti 2p spectrum shown in FIG. 7e shows that the binding energy of Ti 2p3/2 is 446.08eV and that of Ti 2p1/2 is 458.68 eV.
FIG. 8 is UV-VIS absorption spectra of the products of examples 1-3 and comparative example 3, where a is the UV-vis absorption spectrum, b is the UV-vis DRS spectrum, 1 is example 1, 2 is example 2, 3 is example 3, TiO2Comparative example 3.
As can be seen from FIG. 8b, from the tangent of the wavelength axis to (AHV)1/2 and (HV), the forbidden band widths are obtained, 2.69eV for example 1, 2.30eV for example 2, 2.6eV for example 3, and nano TiO2Is 2.96 ev; polyaniline and graphene can reduce nano TiO2A band gap of polyaniline/graphene; 2.3eV less than most TiO2Forbidden band width of catalyst[1](ii) a Smaller energy gaps mean a wider photoresponse range and more electron-hole pairs, and the large surface areas of graphene and polyaniline extend the lifetime of electron-hole pairs.
FIG. 9 is a luminescence spectrum of the products of example 2 and comparative example 3, in which a is a photoluminescence spectrum and b is a transient photocurrent response graph, TiO2Comparative example 3, TiO2Example 2 is/PANI/graphene.
Photoluminescence spectroscopy can be used to measure electron recombination efficiency, as can be seen in FIG. 9a, nano TiO2The fluorescence intensity of the polyaniline/graphene composite material is obviously weakIn the presence of nano TiO2(ii) a This indicates that polyaniline/graphene promotes H+From TiO2The valence band is transferred to the HOMO level of polyaniline and provides a larger reaction area; FIG. 9b shows nano TiO2And nano TiO2The transient photocurrent response of the polyaniline/graphene composite material is generated by switching on and off a light source at a voltage of 1V under visible light, and the nano TiO is used for preparing the polyaniline/graphene composite material2The instantaneous current of the polyaniline/graphene composite material is nano TiO2And 6 times of that of the polyaniline and the graphene, the separation efficiency of electron holes can be effectively improved, and the service life of excited electrons can be prolonged.
In order to verify whether RhB (rhodamine B) can be degraded under visible light, 60ml of 10mg/L RhB solution is placed in a reflux cup and is kept at a constant temperature, the radiation is carried out for 90min, samples are taken every 30min, the absorbance is measured, the obtained result is shown in figure 10, the figure 10 is a result graph of the degradation of the rhodamine B under the visible light, wherein a is the absorbance of the rhodamine B under different illumination time, the left graph in a is an overall graph, and the right graph in a is an enlarged graph; and B is an absorbance standard curve of rhodamine B solutions with different concentrations.
As shown in FIG. 10a, the absorption peak of the original solution after 90min of illumination is 554nm, and the absorbance of the original solution has no obvious change, which indicates that rhodamine B is not degraded after 90min of illumination by visible light.
50mg of each of the products of examples 1 to 4 was taken, and each of the products was added to 60ml of a 20mg/L RhB solution, which was irradiated with a 300W visible xenon lamp, and samples were taken every 10min to measure the change in absorbance. The results are shown in FIG. 11, and FIG. 11 is a graph showing the results of degradation of rhodamine B by the products of examples 1-4 under visible light, wherein a is example 1, B is example 2, c is example 3, and d is example 4.
As can be seen from fig. 11: the product of example 1 degraded RhB to 94.5% within 1.5h and colorless within 2 h; with the increase of the content of polyaniline/graphene in the products of examples 2 and 3, not only the adsorption capacity is increased, but also RhB can be rapidly degraded into colorless within 1h, and the efficiency of the product of example 2 is the highest, which indicates that the combination of various substances in the product of example 2 is better; as shown in FIG. 11d, when polyaniline/graphene is in excess, it is added to nano TiO2Exposed crystal formThe surface has adverse effect, the degradation effect is greatly reduced, the degradation rate is 52.3 percent within 3 hours, and in the degradation process, because the nano TiO is used2The structure changes, and the UV-vis absorption peak keeps blue-shifting.
FIG. 12 is a graph showing the results of degradation of rhodamine B under visible light for the products of examples 1-4 and comparative examples 1-3, wherein 1 is example 1, 2 is example 2, 3 is example 3, 4 is example 4, TiO2Per PANI is comparative example 1, TiO2Comparative example 2, TiO graphene2For comparative example 3, blank is without addition of a photocatalyst.
As can be seen from fig. 12: the addition amount of the products of examples 1-4 and comparative examples 1-3 is 50mg, and under the irradiation of a 300W visible xenon lamp, pure nano TiO2Degrading by 33 percent within 90min, and preliminarily overcoming TiO2The disadvantage of no light response under visible light; TiO within 90-120min2/PANI and TiO2The degradation rate of the/graphene binary composite material on RhB can reach more than 90%, and the degradation speed of the products of the examples 2 and 3 is superior to that of other examples and comparative examples.
FIG. 13 is a graph showing the results of degradation of rhodamine B under visible light when the products of examples 2-3 are added in amounts of 100mg, where a is example 2 and B is example 3.
As can be seen from fig. 13: under the irradiation of a 300W visible xenon lamp, when the addition amount is 100mg, the product of the example 2 degrades RhB to about 95% within 30min, and the photodegradation efficiency is remarkably improved; when the addition amount of the product in the embodiment 3 is 100mg, the degradation effect is reduced, and the degradation rate only reaches 93% after illumination for 90 min; the example 2 product has a flat baseline compared to the ascending baseline in the example 3 product, because of the nano-TiO2Perfect semiconductor relation exists between the polyaniline and excessive graphene, and the bond strengthens nano TiO2The semiconductor properties of (1).
The degradation capability of the product of example 2 on rhodamine B under different recycling times, pH, temperature and rhodamine B concentration is considered, and the result is shown in FIG. 14, wherein FIG. 14 is the degradation result of the product of example 2 on rhodamine B under different conditions, wherein a is the recycling times, B is the pH, c is the temperature and d is the rhodamine B concentration.
As can be seen from FIG. 14, the product of example 2 is cycled for 5 times under visible light, and after 50min of each cycle, the 5 th degradation rate is 91.6%; the degradation effect is best when the PH is 7; when the temperature is 40 ℃, the photocatalytic activity is strongest; fig. 14d is a graph of degradation rates for RhB solutions at different concentrations.
FIG. 15 shows the degradation results of the product of example 2 on methylene blue and methyl orange, wherein MB is methylene blue, MO is methyl orange, and the concentrations of the methylene blue and the methyl orange are 10 mg/L.
As can be seen from FIG. 15, the product of example 2 also has significant degradation effect on other dyes, and the adsorption capacity is very small in the dark adsorption process; after 1h of visible light irradiation, MB is degraded to be colorless after 90min, and the degradation rate is 97.7%; MO degrades relatively slowly, degrades 66.3% after 1h, and degrades 98.2% after 90 min; it can be seen that the high degradation rate of the product of example 2 is common and can degrade a variety of anionic and cationic dyes.
In conclusion, the nano TiO provided by the invention2The/polyphenyl alkene/graphene composite material has an obvious photocatalysis effect under visible light, wherein, when the addition amount of 100mg is added, RhB (rhodamine B) can be degraded by 95% within 30min, after 5 times of circulation, the degradation rate of RhB can reach 92.6% within 50min, and the recovery and utilization value is very high; furthermore, MB (methylene blue) and MO (methyl orange) were degraded by 97% in 90 minutes, respectively.
Interestingly, nano TiO2(2.96ev) is compounded with polyphenyl alkene/graphene to obtain nano TiO2The band gap of the/polyphenyl alkene/graphene composite material is reduced to 2.30 ev. 2.3eV less than most TiO2Forbidden band width of composite catalyst[1]While, nano TiO2The instantaneous photocurrent of the/polyphenyl alkene/graphene composite material is nano TiO 26 times of that of nano TiO2The/polyphenyl alkene/graphene composite material is a photocatalyst with great potential.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
The cited documents are:
[1]X.F.Song,J.T.Qin,T.T.Li,G.Liu,X.X.Xia,Y.S.Li,Y.Liu,Efficient construction and enriched selective adsorption-photocatalytic activity of PVA/PANI/TiO2 recyclable hydrogel by electron beam radiation.Journal of Applied Polymer Science,(2019).16
Claims (10)
1. high instantaneous photocurrent nanometer TiO2The preparation method of the polyaniline/graphene composite material is characterized by comprising the following steps:
s1, mixing graphene dispersion liquid, aniline and H2SO4Uniformly mixing the aqueous solution, stirring in an ice bath for reaction, filtering, washing a filter cake, and drying to obtain a polyaniline/graphene material;
s2, mixing a titanium source, ethanol and the polyaniline/graphene material uniformly, adding water, mixing uniformly, heating, keeping the temperature, and centrifuging to obtain a precipitate; adding the precipitate into HCl aqueous solution, mixing uniformly, carrying out hydrothermal reaction, centrifuging, washing the precipitate, and drying to obtain the high instantaneous photocurrent nano TiO2Polyaniline/graphene composite material.
2. The high transient photocurrent nano-TiO of claim 12The preparation method of the/polyaniline/graphene composite material is characterized in that in S2, a titanium source is butyl titanate.
3. The highly transient photocurrent nano-TiO of claim 1 or 22The preparation method of the polyaniline/graphene composite material is characterized in that in S2, nano TiO is used2TiO in/polyaniline/graphene composite material2And the weight ratio of the polyaniline/graphene material is 10-200: 1.
4. The highly transient photocurrent in the form of nano-TiO as claimed in any one of claims 1 to 32Preparation method of/polyaniline/graphene composite materialCharacterized in that in S2, the temperature is raised to 70-75 ℃ and the temperature is preserved for 30 min.
5. The highly transient photocurrent in the form of nano-TiO of any of claims 1 to 42The preparation method of the polyaniline/graphene composite material is characterized in that in S2, the temperature of hydrothermal reaction is 175-185 ℃, and the time is 16 h.
6. The highly transient photocurrent in the form of nano-TiO of any of claims 1 to 52The preparation method of the polyaniline/graphene composite material is characterized in that in S1, the molar ratio of graphene to aniline is 1: 6.
7. The highly transient photocurrent in the form of nano-TiO of any of claims 1 to 62The preparation method of the/polyaniline/graphene composite material is characterized in that in S1, stirring and reacting for 5-6h in an ice bath.
8. The highly transient photocurrent in the form of nano-TiO of any one of claims 1 to 72The preparation method of the polyaniline/graphene composite material is characterized in that in S1, a solvent of a graphene dispersion liquid is a mixed solution of isopropanol and water, wherein the volume ratio of the isopropanol to the water is 1: 5; preferably, in S1, the concentration of the aqueous sulfuric acid solution is 1 mol/L.
9. The highly transient photocurrent in the form of nano-TiO of any one of claims 1 to 82The preparation method of the polyaniline/graphene composite material is characterized in that in S2, the concentration of HCl aqueous solution is 1 mol/L; preferably, in S2, the volume ratio of ethanol to water is 1: 1.5.
10. High instantaneous photocurrent nanometer TiO2Polyaniline/graphene composite material, characterized in that the high transient photocurrent nano TiO material according to any one of claims 1 to 92The polyaniline/graphene composite material is prepared by a preparation method.
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