CN110813360A - Nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst and preparation method and application thereof - Google Patents
Nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN110813360A CN110813360A CN201911190784.8A CN201911190784A CN110813360A CN 110813360 A CN110813360 A CN 110813360A CN 201911190784 A CN201911190784 A CN 201911190784A CN 110813360 A CN110813360 A CN 110813360A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 102
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 25
- 239000010439 graphite Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000011593 sulfur Substances 0.000 title claims abstract description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 56
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst as well as a preparation method and application thereof, belonging to the technical field of semiconductor photocatalysts. The preparation method provided by the invention comprises the following steps: mixing black titanium dioxide, graphite-phase carbon nitride, thiourea, an N, N-dimethylformamide solution and an ethanol solution, and carrying out hydrothermal reaction to obtain the nitrogen-sulfur doped black titanium dioxide/graphite-phase carbon nitride composite photocatalyst. The composite photocatalyst prepared by the preparation method provided by the invention has the advantages of low recombination rate of photo-generated electrons-holes, high photon utilization rate, high generation and separation efficiency of photo-generated electron-hole pairs and good photocatalytic activity.
Description
Technical Field
The invention belongs to the technical field of semiconductor photocatalysts, and particularly relates to a nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst as well as a preparation method and application thereof.
Background
Titanium dioxide (TiO) as a typical semiconductor photocatalyst developed from early to present2) Has relatively excellent photocatalytic performance, low cost, easy preparation, no toxicity and harm to environment and stable chemical performance, and is used in traditional photocatalysisThe field is widely applied. However, in practical application, the pure phase titanium dioxide has a large self band gap (about 3.2eV), a low quantum effect, a narrow spectral response range, and the application is limited due to the defect that the pure phase titanium dioxide can only be excited by ultraviolet light. Therefore, people modify the titanium dioxide by doping non-metallic elements and compounding with other semiconductors so as to reduce the band gap energy of the titanium dioxide, increase the adsorption capacity of the catalyst on pollutants, reduce the recombination of internal photoproduction electrons and holes, improve the utilization rate of the material on sunlight and improve the catalytic performance of the titanium dioxide.
In the field of photocatalysis in recent years, graphite-phase carbon nitride (g-C)3N4) The photocatalyst has the advantages of no toxicity, low cost, environmental friendliness, stable chemical performance and the like, and is widely applied to the field of photocatalysis. g-C3N4As a semiconductor polymer material, the material has a graphite-like layered structure and a unique electronic structure, has the advantages of good thermal stability, strong mechanical properties, acid and alkali resistance and the like, and is widely applied to the fields of photocatalysis and the like. However, g-C3N4The pi-pi conjugated electron structure in the structure leads the photogenerated electron-hole recombination rate to be fast, has stronger fluorescence effect and lower solar energy utilization efficiency, and limits the g-C3N4Development and application as photocatalytic materials.
Disclosure of Invention
In view of the above, the invention aims to provide a nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst, and a preparation method and application thereof. The composite photocatalyst prepared by the invention has the advantages of low photogenerated electron-hole recombination rate, high photon utilization rate, high photogenerated electron-hole pair generation and separation efficiency and good photocatalytic activity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst, which comprises the following steps:
mixing black titanium dioxide, graphite-phase carbon nitride, thiourea, an N, N-dimethylformamide solution and an ethanol solution, and carrying out hydrothermal reaction to obtain the nitrogen-sulfur doped black titanium dioxide/graphite-phase carbon nitride composite photocatalyst.
Preferably, the black titanium dioxide is prepared by the following steps:
under the protective atmosphere, mixing titanium dioxide and sodium borohydride, and carrying out reduction reaction to obtain black titanium dioxide.
Preferably, the mass ratio of the titanium dioxide to the sodium borohydride is 1: 1-4: 1.
Preferably, the temperature of the reduction reaction is 200-500 ℃ and the time is 1-3 h.
Preferably, the mass ratio of the black titanium dioxide, the graphite-phase carbon nitride, the thiourea and the N, N-dimethylformamide solution is (30-80): 15: 48: 8.
preferably, the temperature of the hydrothermal reaction is 120-200 ℃ and the time is 8-12 h.
Preferably, the graphite phase carbon nitride is prepared by a method comprising the following steps:
and calcining the melamine to obtain the graphite-phase carbon nitride.
Preferably, the calcining comprises a first calcining and a second calcining in sequence;
the temperature of the first calcination and the temperature of the second calcination are independently 500-550 ℃, the heat preservation time is independently 2-4 h, and the temperature rise rate of the temperature rise to the first calcination temperature and the second calcination temperature is independently 2.5-5 ℃/min.
The invention also provides the nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst prepared by the preparation method in the technical scheme, wherein the doping quality of the sulfur element and the nitrogen element is independently less than 1% of the quality of the black titanium dioxide.
The invention also provides application of the nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst in the technical scheme in the field of sewage treatment of refractory organic pollutants.
The invention provides a preparation method of a nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst, which comprises the following steps: mixing black titanium dioxide, graphite-phase carbon nitride, thiourea, an N, N-dimethylformamide solution and an ethanol solution, and carrying out hydrothermal reaction to obtain the nitrogen-sulfur doped black titanium dioxide/graphite-phase carbon nitride composite photocatalyst. The black titanium dioxide adopted by the invention has the characteristic of small band gap; the band gap of the black titanium dioxide is further adjusted by doping N and S elements simultaneously, so that the response range of the black titanium dioxide to visible light is widened, the recombination rate of photo-generated electron-hole pairs is reduced, and the utilization rate of photons is improved; meanwhile, black titanium dioxide is compounded with graphite-phase carbon nitride with a narrow band gap, and the constructed heterojunction structure can remarkably enhance and accelerate the electron transfer rate, and improve the generation and separation efficiency of photo-generated electron-hole pairs, so that the performance of the composite photocatalyst is improved. The example results show that compared with titanium dioxide P25, BT and NS-BT, the CN/NS-BT prepared by the invention has the optimal degradation capacity, the degradation of rhodamine B reaches more than 90% in two hours, and the CN/NS-BT prepared by the invention keeps the degradation efficiency of the material about 90% after three groups of cycles without obvious reduction, which indicates that CN/NS-BT has stronger photocatalytic cycle stability.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a diagram of a reaction apparatus for photocatalytic performance test;
FIG. 2 is an X-ray diffraction pattern of BT, NS-BT and CN/NS-BT from example 1;
FIG. 3 shows BT, graphite phase carbon nitride (g-C)3N4) NS-BT and CN/NS-BT from example 1;
FIG. 4 is a micrograph of NS-BT and CN/NS-BT obtained in example 1, wherein (a) is a SEM of NS-BT, (b) is a SEM of CN/NS-BT, (c) is a TEM of CN/NS-BT, and (d) is a TEM of CN/NS-BT;
FIG. 5 is an element distribution diagram of CN/NS-BT obtained in example 1;
FIG. 6 is an X-ray photoelectron spectrum of CN/NS-BT obtained in example 1, wherein (a) is a full spectrum and (b) is an XPS plot of Ti 2 p;
FIG. 7 is a graph showing the photocatalytic degradation of rhodamine B by titanium dioxide P25, BT, NS-BT and CN/NS-BT prepared in example 1 under visible light;
FIG. 8 is a graph of the solid UV-VIS diffuse reflectance absorption spectra of titanium dioxide P25, BT, NS-BT and CN/NS-BT from example 1;
FIG. 9 is a band gap energy spectrum of titanium dioxide P25, BT, NS-BT and CN/NS-BT obtained in example 1;
FIG. 10 is a graph of photoluminescence spectra of BT, NS-BT and CN/NS-BT obtained in example 1;
FIG. 11 is a chart showing the stability of the CN/NS-BT cyclically photocatalytic degradation rhodamine B prepared in example 1;
FIG. 12 shows the result of the degradation of rhodamine B by BT and CN/NS-BT under visible light under different preparation conditions, wherein 12a is titanium dioxide P25 and NaBH in different proportions4The test result of the degradation performance of the prepared BT, 12b is the test result of the degradation performance of the prepared BT at different reduction reaction temperatures, and 12C is the test result of BT and g-C in different proportions3N4And 12d is a test result of the degradation performance of the prepared CN/NS-BT, and the test result of the degradation performance of the prepared BT at different hydrothermal reaction temperatures.
Detailed Description
The invention provides a preparation method of a nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst, which comprises the following steps:
mixing black titanium dioxide (BT) and graphite-phase carbon nitride (g-C)3N4) Mixing thiourea, a N, N-dimethylformamide solution (DMF solution) and an ethanol solution, and carrying out hydrothermal reaction to obtain the nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst (CN/NS-BT).
In the present invention, the black titanium dioxide is preferably prepared by the steps comprising: under the protective atmosphere, mixing titanium dioxide and sodium borohydride, and carrying out reduction reaction to obtain black titanium dioxide.
In the invention, the mass ratio of the titanium dioxide to the sodium borohydride is preferably 1:1 to 4:1, more preferably 1:1 to 3:1, and even more preferably 2: 1. In the invention, the titanium dioxide is preferably titanium dioxide P25, and the titanium dioxide P25 is preferably a mixture comprising 20% rutile and 80% titanium dioxide by mass. The specific source of the sodium borohydride is not particularly limited in the invention, and the sodium borohydride can be prepared from conventional commercial products in the field. In the present invention, the mixing is preferably carried out in a mortar, and the mixing is preferably carried out by grinding.
In the present invention, the protective atmosphere is preferably nitrogen. In the invention, the reduction reaction is preferably carried out in a tubular furnace, the temperature of the reduction reaction is preferably 200-500 ℃, more preferably 300 ℃, and the time is preferably 1-3 hours, more preferably 2 hours. According to the invention, titanium dioxide and sodium borohydride with specific dosage ratio are adopted to carry out reduction reaction under the condition of specific reduction reaction parameters, and the reduction reaction is fully generated by regulating and controlling the reaction temperature, so that the catalytic performance of black titanium dioxide is improved to the greatest extent. And a defect state is introduced into titanium dioxide molecules, and the band gap of the black titanium dioxide is reduced by constructing oxygen vacancies.
After the reduction reaction is completed, the present invention preferably washes the resulting reduction reaction product three times each in ethanol and deionization in sequence. The specific operation mode of the washing is not particularly limited in the present invention, and a washing mode known to those skilled in the art may be adopted. The invention effectively removes Na by washing+And compound impurities thereof.
In the present invention, the graphite-phase carbon nitride is preferably prepared by a method comprising the steps of: and calcining the melamine to obtain the graphite-phase carbon nitride. In the present invention, the melamine is preferably purchased from the Shanghai pharmaceutical group chemical reagent. In the present invention, the calcination is preferably carried out in a muffle furnace. In the invention, the calcination sequentially preferably comprises a first calcination and a second calcination, wherein the temperature of the first calcination is preferably 500-550 ℃, and more preferably 550 ℃; the time is preferably 2 to 4 hours, more preferably 4 hours, and the temperature rise rate for raising the temperature to the first calcination temperature is preferably 2.5 to 5 ℃/min, more preferably 2.5 ℃/min. After the first calcination is completed, the present invention preferably grinds the product obtained after the first calcination, and then performs the second calcination. The particle size of the product after grinding is not particularly limited in the present invention until the product has no granular feel. In the invention, the temperature of the second calcination is 500-550 ℃, more preferably 500 ℃, the time is preferably 2-4 h, more preferably 2h, and the heating rate for heating to the second calcination temperature is preferably 2.5-5 ℃/min, more preferably 5 ℃/min. According to the invention, a mode of combining twice calcination and grinding is adopted, and the calcined product obtained by once calcination is ground and then is calcined for the second time, so that the photocatalytic performance of the photocatalyst product is effectively improved.
In the invention, the mass ratio of the black titanium dioxide, the graphite-phase carbon nitride, the thiourea and the N, N-dimethylformamide in the N, N-dimethylformamide solution is preferably (30-80): 15: 48: more preferably (40 to 60): 15: 48: 8, more preferably 50: 15: 48: 8. in the present invention, the thiourea is preferably purchased from national chemical group ltd. In the present invention, the mass concentration of the N, N-dimethylformamide solution is preferably 99.8%, and N, N-dimethylformamide in the N, N-dimethylformamide solution is preferably purchased from a beijing chemical plant. In the present invention, the ethanol solution preferably has a mass concentration of 99.8%, and the absolute ethanol in the ethanol solution is preferably purchased from Beijing chemical plant.
In the present invention, the black titanium dioxide (BT), graphite phase carbon nitride (g-C)3N4) The thiourea, the N, N-dimethylformamide solution (DMF solution) and the ethanol solution are preferably mixed in this order by subjecting the thiourea and the DMF solution to ultrasonic treatment for 10min, followed by first mixing, and then second mixing with the ethanol solution, the black titanium dioxide and the graphite-phase carbon nitride. In the present invention, the first mixing means is preferably magnetic stirring. The time and the rotating speed of the magnetic stirring are not specially limited, and the solution can be stirred to be clear. In the present invention, the second mixing mode is preferably magnetic stirring, and the magnetic stirring is performedThe time of (3) is preferably 60 min. The magnetic stirring speed is not specially limited, and the materials can be uniformly mixed.
In the invention, the hydrothermal reaction is preferably carried out in a high-pressure reaction kettle, the temperature of the hydrothermal reaction is preferably 120-200 ℃, more preferably 180 ℃, and the time is preferably 10-12 h, more preferably 10 h.
After the hydrothermal reaction is completed, the present invention preferably washes the obtained hydrothermal reaction product in deionized water and ethanol three times each in turn. The specific operation mode of the washing is not particularly limited in the present invention, and a washing mode known to those skilled in the art may be adopted. After washing is finished, the obtained washing product is preferably dried, the drying is preferably carried out in a vacuum drying oven, the drying temperature is preferably 80-120 ℃, and the drying time is preferably 10-12 hours. According to the invention, through carrying out hydrothermal reaction under specific conditions and regulating and controlling the temperature and reaction time of the hydrothermal reaction, the material can be compounded and doped to the greatest extent, and meanwhile, the doped N and S elements can further adjust the band gap of black titanium dioxide, so that the response range of the titanium dioxide to visible light is widened, the recombination rate of photo-generated electron-hole pairs is reduced, and the utilization rate of photons is improved; meanwhile, titanium dioxide is compounded with graphite-phase carbon nitride with a narrow band gap, and the electron transfer rate can be obviously increased and accelerated by constructing a heterojunction structure, so that the generation and separation efficiency of photo-generated electron-hole pairs is improved, and the performance of the composite photocatalyst is improved.
The invention also provides the nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst prepared by the preparation method in the technical scheme, wherein the doping quality of the sulfur element and the nitrogen element is independently less than 1% of the quality of the black titanium dioxide. In the invention, the main doping positions of nitrogen and sulfur elements are positioned on the surface and the interface of the black titanium dioxide to provide chemical reaction active sites, thereby improving the visible light response capability of the titanium dioxide.
The invention also provides application of the nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst in the technical scheme in the field of sewage treatment of refractory organic pollutants.
In the invention, the nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst is preferably used for treating sewage containing rhodamine B, methyl orange, methylene blue or phenol organic pollutants, and in order to illustrate that the nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst prepared by the invention can be used for treating sewage containing refractory organic pollutants, the nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst is further preferably used for treating sewage containing rhodamine B organic pollutants in the embodiment of the invention.
The nitrogen-sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst provided by the present invention, the preparation method and the application thereof are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Table 1 shows the instruments and their types used in the examples of the present invention.
Table 1 shows the instruments and their types used in the examples of the present invention
| Name of instrument | Model or number | Manufacturer of the product |
| X-ray diffractometer | D8Advance | Bruker, Germany |
| Digital display constant temperature magnetic stirrer | 85-2 | Instrument factory in south of the Yangtze river of gold jar city |
| Xenon lamp light source | PLS-SXE30 | Beijing Poffei Tech technologies Co Ltd |
| Ultraviolet visible spectrophotometer | UV-2550 | Shimadzu Japan Ltd |
| Fluorescence spectrophotometer | LS55 | PerkinElmer Instrument Co., Ltd, UK |
| Fourier infrared spectrometer | SpectrumOne | PerkinElmer Instrument Co., Ltd, UK |
| Scanning electron microscope | Hitachi,SU8010 | Japan Electron optics Co Ltd |
| Transmission electron microscope | JEM-2100F | Japan Electron optics Co Ltd |
Example 1
1) Weighing titanium dioxide P25 and NaBH according to the mass ratio of 2:14Mixing the two materials, grinding in a mortar, placing the ground mixture in a tube furnace, keeping the temperature at 300 ℃ for 2h in nitrogen atmosphere to obtain defective black titanium dioxide, and washing the product with ethanol and deionized water for three times to remove Na+And compound impurities thereof.
2) Putting melamine into a ceramic crucible with a cover, putting a sample into a muffle furnace, calcining for 4 hours at 550 ℃, and raising the temperature at 2.5 ℃ per minute-1A yellow, lumpy solid was obtained and ground well to a powder; the obtained yellow powder is spread in a square magnetic boat and is placed in a muffle furnace to be calcined for 2 hours at 500 ℃ to obtain light yellow powder.
3) Dissolving 48mg of thiourea in 8mL of DMF solution, carrying out ultrasonic treatment for 10min, putting the solution into a magnetic stirrer, and fully stirring until the solution is clear; slowly adding 20mL of ethanol solution into the solution prepared in the previous step, adding 50mg of BT (black titanium dioxide) and 15mg of graphite-phase carbon nitride into the mixed solution, stirring for 60min, placing the uniformly stirred suspension into a high-pressure reaction kettle, carrying out hydrothermal reaction for 10h at 180 ℃, washing the obtained sample with deionized water and ethanol for three times respectively, placing the precipitate into a vacuum drying oven, and drying for 12h at 80 ℃ to obtain gray black powder, namely the nitrogen-sulfur doped black titanium dioxide/graphite-phase carbon nitride composite photocatalyst (CN/NS-BT).
Comparative example 1
Dissolving 48mg of thiourea in 8mL of DMF solution, carrying out ultrasonic treatment for 10min, putting the solution into a magnetic stirrer, and fully stirring until the solution is clear. Slowly adding 20mL of ethanol solution into the solution prepared in the last step, adding 50mg of BT into the mixed solution, stirring for 30min, placing the uniformly stirred suspension into a 40mL high-pressure reaction kettle, carrying out hydrothermal reaction for 10h at 180 ℃, washing the obtained sample with deionized water and ethanol for three times respectively, placing the precipitate into a vacuum drying oven, and drying for 12h at 80 ℃ to obtain black powder, namely the nitrogen-sulfur element doped black titanium dioxide (NS-BT).
Photocatalytic Performance test
FIG. 1 is a diagram of a reaction apparatus for photocatalytic performance test. The light source adopts a 300W xenon lamp, is arranged above the reaction container, and light rays directly irradiate the reaction solution. The ultraviolet light (λ >400nm) is filtered out at the light source using a filter. The reaction vessel is placed on a magnetic stirrer to be stirred at normal temperature, and the circulating water is kept to be cooled.
In this experiment, 20mg of photocatalyst was dispersed into 60mL of RhB solution. The suspension was moved to the dark under magnetic stirring for 30 minutes before irradiation with visible light to ensure that the adsorption/desorption equilibrium was established. The reaction suspension was then irradiated under visible light for 2 hours, at constant time intervals (30 minutes), in 4mL samples of solution and centrifuged to separate the catalyst. The maximum absorption wavelength (554nm) of the RhB concentration of the sample was analyzed by a UV-vis spectrophotometer.
FIG. 2 is an X-ray diffraction pattern of BT, NS-BT and CN/NS-BT obtained in example 1. As can be seen from the figure, BT shows typical anatase diffraction peaks, and the characteristic peaks at 25.3 °, 37.8 °, 48.1 °, 54.1 °, 54.9 °, 62.7 °, 68.9 °, 70.2 ° and 75.1 ° correspond to the anatase (101), (004), (200), (105), (211), (204), (116) and (220) crystal planes, respectively. After N, S element doping and graphite phase carbon nitride adding, because the content is small and the diffraction intensity is weak, no corresponding obvious characteristic peak is observed, no influence is generated on the diffraction peak of titanium dioxide, and the titanium dioxide is still the main material and is not influenced.
FIG. 3 shows BT, graphite phase carbon nitride (g-C)3N4) NS-BT and CN/NS-BT from example 1, the internal bonding structure of the material was further explored. As can be seen from the figure, the titanium dioxide is 500-750 cm-1Is due to the stretching of the Ti-O bond and the elastic vibration of the Ti-O-Ti bond. For pure g-C3N4In particular 1250 to 1641cm-1The series of absorption peaks occurring in the range is attributed to the typical stretching pattern of the C, N heterocyclic ring (C-N and C ═ N), and at 817cm-1The sharp absorption peak at (A) can then be attributed to the typical vibration mode of the triazine ring, from which g-C can also be demonstrated3N4The partial structure of (a) consists of triazine units. The change in the absorption peaks of NS-BT compared to titania was attributed to the presence of Ti-O-S, Ti-S, Ti-O-Ti and O-Ti-N bonds, indicating successful doping of the N, S elements. The CN/NS-BT composite material shows a more obvious characteristic absorption peak, g-C, compared with titanium dioxide3N4At 1641cm-1、1412cm-1And 1250cm-1The characteristic absorption peak still exists, and the complete retention of the structure is proved. In the range of 3000-3500 cm-1The peaks in the range correspond to surface adsorbed water and hydroxyl groups.
FIG. 4 is a micrograph of NS-BT and CN/NS-BT obtained in example 1, wherein (a) is a SEM of NS-BT, (b) is a SEM of CN/NS-BT, (c) is a TEM of CN/NS-BT, and (d) is a TEM of CN/NS-BT, wherein the morphology of CN/NS-BT is mainly formed by the accumulation of nanoparticles, and the CN/NS-BT is further observed by a TEM and has a particle size within 10nm, and the crystal lattice structure is further studied by a high-resolution projection electron microscope (HRTEM), and 0.35nm of crystal lattice fringes corresponding to the (101) crystal plane of titanium dioxide are observed, and the amorphous region is the structure of graphite-phase carbonitride.
FIG. 5 is an elemental mapping of CN/NS-BT obtained in example 1, where it can be observed that Ti, O, N, S, C elements appear for the synthesized sample, where Ti and O are the main elements, which confirms the successful recombination of CN/NS-BT. The content of N and S elements is less due to doping.
FIG. 6 shows X-ray photoelectron spectroscopy spectra of CN/NS-BT obtained in example 1, wherein (a) is a full spectrum and (b) is a XPS spectrum of Ti 2p, which was characterized by X-ray photoelectron spectroscopy (XPS) measurement in order to further analyze the bonding structure of elements of the material. As can be seen from the full spectrum of FIG. 6(a), obvious peaks of Ti 2p, O1S, N1S, S2 p and C1S appear, and the result confirms the synthesis of the composite photocatalyst CN/NS-BT. Simultaneously, the Ti 2p is subjected to Gaussian fitting, as shown in FIG. 6(b), and is divided into four fitting peaks corresponding to Ti respectively corresponding to 464.11eV, 463.54eV, 458.43eV and 457.84eV 4+2p1/2，Ti 3+2p1/2，Ti 4+2p3/2，Ti 3+2p3/2This structure confirmed Ti3+The presence of O vacancies was confirmed, indicating TiO2Reduction reaction occurs, which also corresponds to the bonding structure of black titanium dioxide, proving the successful preparation of the material.
FIG. 7 is a graph showing the photocatalytic degradation of titanium dioxide P25, BT, NS-BT, CN/NS-BT obtained in example 1 to rhodamine B under visible light, for the sake of TableCharacterizing the photocatalytic activity of the prepared sample by exposing the sample to visible light (lambda)>400nm) and a degradation test of a rhodamine B (RhB) solution is carried out, and the degradation capability of industrial titanium dioxide P25 under the illumination condition of 120min is very weak, the photocatalytic activity is basically absent under the visible light, and the degradation degree is only within 5 percent within two hours; compared with the titanium dioxide P25, the BT has the advantages that the band gap is adjusted due to the existence of oxygen vacancies, the degradation capability is obviously enhanced, the degradation capability is further improved after N, S element doping, and the degradation degree of the BT with the oxygen vacancies can reach 30-40% within two hours; after N, S element doping is carried out on BT, the photocatalytic activity of NS-BT is further improved under visible light, and the photodegradation degree of NS-BT can reach 50-60% within two hours; the CN/NS-BT prepared in the example 1 has optimal degradation capacity, and the degradation of rhodamine B in two hours reaches over 90 percent, which is attributed to TiO after compounding2A heterostructure is formed with CN, the generation and separation of photo-generated electrons and holes are accelerated, the carrier transmission rate is obviously enhanced, meanwhile, the band gap of the catalyst is narrowed, the visible light response range is obviously enhanced, and the photocatalytic activity is greatly improved.
FIG. 8 is a solid UV-visible diffuse reflection absorption spectrum of titanium dioxide P25, BT, NS-BT and CN/NS-BT obtained in example 1, and FIG. 9 is a band gap energy spectrum of titanium dioxide P25, BT, NS-BT and CN/NS-BT obtained in example 1, by further investigating the optical properties of the materials by performing solid UV-visible diffuse reflection absorption spectrum tests on four groups of samples of P25, BT, NS-BT and CN/NS-BT, it can be seen that the prepared BT, NS-BT and CN/NS-BT has gradually increased visible response range and red shift of absorption edge compared with titanium dioxide P25, and the band gap energy spectrum converted by Kubelka-Munk function shows that BT, NS-BT and CN/NS-BT have gradually narrowed band gap compared with titanium dioxide P25, therefore under the light excitation condition, the transport of photogenerated carriers occurs more easily, so the catalytic performance is improved accordingly.
FIG. 10 is a photoluminescence spectrum of BT, NS-BT and CN/NS-BT obtained in example 1, and the prepared BT, NS-BT and CN/NS-BT samples are subjected to photoluminescence spectrum tests, and the absorption peak intensities are known, and the lower the absorption peak intensities are, the lower the recombination rate of photo-generated carriers is, so that CN/NS-BT can be seen to have the lowest recombination rate of photo-generated electrons and holes, which also proves the best catalytic performance.
FIG. 11 is a chart of stability tests of CN/NS-BT degrading rhodamine B by cyclic photocatalysis prepared in example 1. In order to study the cycling stability of the catalyst, three sets of cycling degradation stability tests were performed on CN/NS-BT, as shown in fig. 11, it can be seen that the degradation efficiency of the material remained around 90% after three sets of cycling, and no significant decrease occurred, which confirms the strong photocatalytic cycling stability of the material.
Example 2
Titanium dioxide P25 and NaBH in different proportions4Effect on the degradation Properties of the prepared BT
Titanium dioxide P25 with NaBH4Respectively mixing the materials according to the mass ratio of 1:1, 2:1 and 3:1, fully grinding the mixture in a mortar, placing the ground mixture in a tube furnace, and keeping the temperature at 300 ℃ for 2 hours in a nitrogen atmosphere to obtain the defective BT1 (P25: NaBH)4＝1:1)、BT2(P25：NaBH42:1) and BT3 (P25: NaBH43:1), the product was washed three times with ethanol and deionized water to remove Na, respectively+And compound impurities thereof.
The degradation degree of the obtained products BT 1-BT 3 to rhodamine B is tested under the condition of visible light irradiation, and the test results are shown in figure 12 a.
FIG. 12a shows different ratios of titanium dioxide P25 and NaBH4The test result of the degradation performance of the prepared BT shows that the degradation capacities of BT 1-BT 3 are all within the range of 30-40%, and the prepared BT has the strongest catalytic degradation performance when the mass ratio is 2:1, which indicates that titanium dioxide P25 and NaBH are4The different proportions of the components have important influence on the degradation performance of the prepared BT, and further have important influence on the degradation performance of CN/NS-BT.
Example 3
Effect of different reduction reaction temperatures on the degradation Properties of the prepared BT
Titanium dioxide P25 with NaBH4Mixing the materials according to the mass ratio of 2:1, putting the mixture into a mortar for full grinding, putting the ground mixture into a tube furnace, preserving the heat for 2 hours at 200 ℃, 300 and 400 ℃ under the nitrogen atmosphere to obtain BT4(200 ℃), BT5(300 ℃) and BT6(400 ℃) in defect states, and washing the products with ethanol and deionized water for three times to remove Na+And compound impurities thereof.
The degradation degree of the obtained products BT 4-BT 6 to rhodamine B is tested under the condition of visible light irradiation, and the test results are shown in figure 12B.
FIG. 12b shows the test results of the degradation performance of the prepared BT at different reduction reaction temperatures, and it can be seen from the graph that the degradation capacities of BT 4-BT 6 are all within the range of 30% -40%, and it can be seen that the prepared BT has the strongest catalytic degradation performance when the reaction temperature is 300 ℃, which indicates that different reduction reaction temperatures have important influence on the degradation performance of the prepared BT, and further have important influence on the degradation performance of CN/NS-BT.
Example 4
BT and g-C with different proportions3N4Effect on the degradation Properties of the prepared CN/NS-BT
Dissolving 48mg of thiourea in 8mL of DMF solution, carrying out ultrasonic treatment for 10min, putting the solution into a magnetic stirrer, and fully stirring until the solution is clear; slowly adding 20mL of ethanol solution into the solution prepared in the previous step, and adding the BT and g-C prepared in the example 1 into the mixed solution3N4Wherein BT and g-C3N4The mass ratio of (A) to (B) is respectively 80: 15. 50: 15 and 30: 15 at the hydrothermal reaction temperature of 180 ℃ for 10h, washing the obtained sample with deionized water and ethanol for three times respectively, placing the precipitate in a vacuum drying oven, and drying at 80 ℃ for 12h to obtain the product CN/NS-BT1 (BT: g-C)3N4＝80：15)、CN/NS-BT2(BT：g-C3N450: 15) and CN/NS-BT1 (BT: g-C3N4＝30：15)。
The degradation degree of the obtained products CN/NS-BT 1-CN/NS-BT 3 to rhodamine B is tested under the condition of visible light irradiation, and the test results are shown in figure 12 c.
FIG. 12C shows BT and g-C in different ratios3N4As a result of the degradation performance test of the prepared CN/NS-BT, it can be seen from the figure that the degradation capacities of CN/NS-BT 1-CN/NS-BT 3 are all in the range of 85% -98%, and it can be seen that BT and g-C are present3N4The mass ratio of (A) to (B) is respectively 50: 15 hours, the prepared CN/NS-BT has the strongest catalytic degradation performance, which indicates that BT and g-C with different proportions3N4Has important influence on the degradation performance of the prepared CN/NS-BT.
Example 5
Effect of different hydrothermal reaction temperatures on the degradation Properties of the obtained CN/NS-BT
Dissolving 48mg of thiourea in 8mL of DMF solution, carrying out ultrasonic treatment for 10min, putting the solution into a magnetic stirrer, and fully stirring until the solution is clear; slowly adding 20mL of ethanol solution into the solution prepared in the previous step, and adding the BT and g-C prepared in the example 1 into the mixed solution3N4Wherein BT and g-C3N4The mass ratio of (A) to (B) is 50: 15 at the hydrothermal reaction temperature of 120, 150 and 180 ℃ for 10 hours, washing the obtained sample with deionized water and ethanol three times respectively, placing the precipitate in a vacuum drying oven, and drying at 80 ℃ for 12 hours to obtain products CN/NS-BT4(120 ℃), CN/NS-BT5(150 ℃) and CN/NS-BT6(180 ℃).
The degradation degree of the obtained products CN/NS-BT 4-CN/NS-BT 6 to rhodamine B is tested under the condition of visible light irradiation, and the test results are shown in figure 12 d.
FIG. 12d is a result of testing the degradation performance of the prepared CN/NS-BT at different hydrothermal reaction temperatures, and it can be seen from the graph that the degradation capacities of CN/NS-BT 4-CN/NS-BT 6 are all in the range of 85% -98%, and that the prepared CN/NS-BT has the strongest catalytic degradation performance when the hydrothermal reaction temperature is 180 ℃, which indicates that different hydrothermal reaction temperatures have important influence on the degradation performance of the prepared CN/NS-BT.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a nitrogen and sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst is characterized by comprising the following steps:
mixing black titanium dioxide, graphite-phase carbon nitride, thiourea, an N, N-dimethylformamide solution and an ethanol solution, and carrying out hydrothermal reaction to obtain the nitrogen-sulfur doped black titanium dioxide/graphite-phase carbon nitride composite photocatalyst.
2. The production method according to claim 1, wherein the black titanium dioxide is produced by a process comprising:
under the protective atmosphere, mixing titanium dioxide and sodium borohydride, and carrying out reduction reaction to obtain black titanium dioxide.
3. The preparation method according to claim 2, wherein the mass ratio of the titanium dioxide to the sodium borohydride is 1: 1-4: 1.
4. The preparation method according to claim 2, wherein the temperature of the reduction reaction is 200 to 500 ℃ and the time is 1 to 3 hours.
5. The preparation method according to claim 1, wherein the mass ratio of the black titanium dioxide to the graphite-phase carbon nitride to the N, N-dimethylformamide in the N, N-dimethylformamide solution is (30-80): 15: 48: 8.
6. the preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 120 to 200 ℃ for 8 to 12 hours.
7. The method of claim 1, wherein the graphite phase carbon nitride is prepared by a method comprising:
and calcining the melamine to obtain the graphite-phase carbon nitride.
8. The production method according to claim 7, characterized in that the calcination includes a first calcination and a second calcination in this order;
the temperature of the first calcination and the temperature of the second calcination are independently 500-550 ℃, the heat preservation time is independently 2-4 h, and the temperature rise rate of the temperature rise to the first calcination temperature and the second calcination temperature is independently 2.5-5 ℃/min.
9. The nitrogen-sulfur doped black titanium dioxide/graphite-phase carbon nitride composite photocatalyst prepared by the preparation method of any one of claims 1 to 8, wherein the doping amounts of sulfur and nitrogen are independently less than 1% of the mass of black titanium dioxide.
10. The use of the nitrogen-sulfur doped black titanium dioxide/graphite phase carbon nitride composite photocatalyst of claim 9 in the field of wastewater treatment containing refractory organic pollutants.
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|---|---|---|---|---|
| CN112657533A (en) * | 2021-01-11 | 2021-04-16 | 北京理工大学 | Carbon-nitrogen-sulfur co-doped heterojunction photocatalyst and preparation method and application thereof |
| CN112853257A (en) * | 2020-12-31 | 2021-05-28 | 中国建筑材料科学研究总院有限公司 | Black sulfur-doped titanium dioxide film and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179344A (en) * | 2016-06-25 | 2016-12-07 | 河南工业大学 | A kind of indoor air purification agent of efficient white light catalysis and preparation method thereof |
| CN106861744A (en) * | 2017-01-23 | 2017-06-20 | 吉林大学 | A kind of nitrogen sulphur is co-doped with the one-step method for synthesizing of titanium dioxide/graphene quantum dot heterostructures |
-
2019
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106179344A (en) * | 2016-06-25 | 2016-12-07 | 河南工业大学 | A kind of indoor air purification agent of efficient white light catalysis and preparation method thereof |
| CN106861744A (en) * | 2017-01-23 | 2017-06-20 | 吉林大学 | A kind of nitrogen sulphur is co-doped with the one-step method for synthesizing of titanium dioxide/graphene quantum dot heterostructures |
Non-Patent Citations (1)
| Title |
|---|
| SOUMYASHREE PANY等: "A facile in situ approach to fabricate N,S-TiO2/g-C3N4 nanocomposite with excellent activity for visible light induced water splitting for hydrogen evolution", 《PHYS. CHEM. CHEM. PHYS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112853257A (en) * | 2020-12-31 | 2021-05-28 | 中国建筑材料科学研究总院有限公司 | Black sulfur-doped titanium dioxide film and preparation method and application thereof |
| CN112853257B (en) * | 2020-12-31 | 2022-06-28 | 中国建筑材料科学研究总院有限公司 | Black sulfur-doped titanium dioxide film and preparation method and application thereof |
| CN112657533A (en) * | 2021-01-11 | 2021-04-16 | 北京理工大学 | Carbon-nitrogen-sulfur co-doped heterojunction photocatalyst and preparation method and application thereof |
| CN112657533B (en) * | 2021-01-11 | 2023-07-04 | 北京理工大学 | Carbon-nitrogen-sulfur co-doped heterojunction photocatalyst and preparation method and application thereof |
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