CN112275306A - Simple calcination method for preparing BaTiO3/g-C3N4Method for preparing composite photocatalyst - Google Patents
Simple calcination method for preparing BaTiO3/g-C3N4Method for preparing composite photocatalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to a simple calcination method for preparing BaTiO3/g‑C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg‑g‑C3N4+mBaTiO3) Less than or equal to 25 percent by changing BaTiO3Preparing BaTiO by simple calcination method according to weight fraction3/g‑C3N4Composite photocatalyst, product BaTiO3/g‑C3N4The composite photocatalyst has a fiber-sheet composite structure, and system experiments prove that when mg-BaTiO3/(mg‑g‑C3N4+mBaTiO3) 20% of the photocatalystExhibit high photocatalytic activity and stability; the invention has the advantages that: in g-C3N4And BaTiO3The type II heterojunction is constructed between the two layers, so that the separation of photon-generated carriers is promoted, the redox capability is enhanced, a higher BET specific surface area is provided, and active sites are increased.
Description
[ technical field ]: the invention belongs to the field of composite photocatalysts, and particularly relates to a method for preparing BaTiO by adopting a simple calcination method3/g-C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg-g-C3N4+mBaTiO3)≤25％。
[ technical background ]: photocatalysis, an environmentally benign process for converting light energy into chemical energy, is generally considered to be a promising method for hydrogen evolution, contaminant degradation and carbon dioxide reduction. Meanwhile, photoelectrocatalysis, as another way of using solar energy, plays an increasingly important role in pollutant degradation and water decomposition. Electrocatalysis, can promote the performance and deliverable gravimetric energy and power of fuel cells. Optimization of catalytic performance depends on the composition and structure of the catalyst, so development of a catalyst with the appropriate composition is a critical step. Despite the natural advantages of metallic materials as catalysts, such as high efficiency, excellent selectivity and easy recovery, the expense, scarcity or bioaccumulation of metals makes their use on a large scale impossible. Therefore, the exploration of metal-free catalytic materials is crucial to achieving a major breakthrough and overcoming the serious challenges in catalysis.
In recent years, graphite phase carbon nitride (g-C)3N4) The visible light activity of the compound, the simple synthesis of low-cost materials, the chemical stability and the unique layered structureHas attracted global attention. Many effective methods have been applied to modify pristine bulk g-C3N4For example, into nanosheets (XU J, ZHANG L, SHI R, et al chemical evolution of a graphic carbon nitride for an electronic society of Photocatalysis [ J]Journal of Materials Chemistry a, 2013, 1 (46): 14766. ion 14772.), structural defect engineering (CHEN P-W, LI K, YU Y-X, et al cobalt-doped graphical carbon nitride photocatalysts with high actiVity for hydrogen evolution J]Applied Surface Science, 2017, 392: 608-615), surface property modification (Chengzhua-graphene oxide and g-C)3N4Modified plate film preparation conditions and anti-pollution performance research [ D]Guangdong university of industry, 2018), crystal structure optimization (Lijia graphite phase carbon nitride (g-C)3N4) Structural regulation and photocatalytic hydrogen production enhancement mechanism research [ D]University of western marble, 2019.), nanostructure architecture (ZHEN D, HUANG C, WANG X.post-annealing repaired Hollow Carbon nitrides for Hydrogen photodynamics [ J]Nanoscale, 2014, 7.) and heterostructure formation (JI C, DU C, STEINKRUGER JD, et al, in-situ thermal characterization of CdS/g-C3N4 nanocomposites for enhanced photocatalytic water splitting[J]Materials Letters, 2019, 240: 128-131.). At present, high purity g-C3N4The photocatalyst still has the scientific problems of low separation efficiency, weak oxidation reduction capability, low specific surface area and the like of the photo-generated charge carrier. Especially g-C3N4How the photocatalyst can provide more active sites and therefore, a certain technical bottleneck still exists for improving the photocatalytic activity.
Of interest is barium titanate (BaTiO)3BT) was first discovered to appear as a stacked capacitor, and has attracted a great deal of attention in the scientific community due to its high dielectric constant, low dielectric loss, and environmental friendliness. In recent years, with the development of technology, barium titanate is used as a photocatalytic semiconductor material due to its characteristic ferroelectric properties. As early as 2009, Liu and Ren were considered BaTiO-based3Potential of the material of (1) in the Piezoelectric field (LIU W, REN X. Large Piezoelectric Eff)ect in Pb-Free Ceramics[J]Physical Review Letters, 2009, 103: 257602.). With TiO2Different, perovskite type BaTiO3Undergoes a structural transition at the curie temperature, which results in a spontaneous ferroelectric polarization due to low conductivity, a temperature stable structure of the polar crystalline class. In detail, BaTiO when cooled at ambient pressure3A series of first order phase changes occur: cubic (space group Pm3m) → tetragonal (space group P4mm) → orthorhombic (space group Amm2) → rhombohedral (space group R3 m). This transition results in spontaneous polarization parallel to the edges of the crystal unit (quadrilateral) and subsequent reorientation along the face-diagonal (rhombus) and body-diagonal (rhombus). The piezoelectric properties strongly depend on the degree of spontaneous polarization.
Based on the consideration, the invention provides a method for preparing BaTiO by adopting a simple calcination method3/g-C3N4A method for preparing a composite photocatalyst mainly by using BaTiO3And g-C3N4The recombination forms a heterojunction structure, thereby solving the problem of g-C3N4The problem that the self photogenerated carrier recombination rate is too fast is solved, the specific surface area of the material is increased through controlling the shape, so that more active sites are increased, and the improvement on the g-C is realized3N4The catalytic activity of the photocatalyst has very important practical significance, and simultaneously provides solid theoretical basis and practical experience for the general application of the material in wider fields.
[ summary of the invention ]: the invention provides a simple calcination method for preparing BaTiO3/g-C3N4The method of compounding the photocatalyst is characterized in that the method adjusts BaTiO3Preparation of a composition having different BaTiO3Weight fraction of composite material, mg-g-C3N4+mBaTiO3Is 500mg, forms a fiber-sheet composite structure under specific conditions, and is prepared by subjecting BaTiO3/g-C3N4The composite photocatalyst is subjected to high-power transmission mirror HRTEM and ultraviolet-visible diffuse reflection spectrum analysis to explain BaTiO3/g-C3N4The photocatalytic activity mechanism and the optical absorption property of the composite photocatalyst; through a large number of experiments determineBaTiO with high photocatalytic activity and stability prepared by optimum raw material proportion and process parameters3/g-C3N4A composite photocatalyst is provided.
[ technical solution of the present invention ]: simple calcination method for preparing BaTiO3/g-C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg-g-C3N4+mBaTiO3) Less than or equal to 25 percent, to analyze pure melamine, tetrabutyl titanate Ti (OC) with the concentration of 98 percent4H9)4Solution, analytically pure barium acetate (CH)3COO)2Ba. Glacial acetic acid with the concentration of 36 percent is taken as a raw material, analytically pure polyvinylpyrrolidone (PVP) and absolute ethyl alcohol are taken as a dispersing agent and a solvent, and a simple calcination method is used for preparing BaTiO3/g-C3N4Composite photocatalyst, wherein 5 percent is less than or equal to mg-BaTiO3/(mg-g-C3N4+mBaTiO3) Less than or equal to 25 percent, and the technical scheme is as follows:
firstly, accurately weighing 0.000-20.000 g of analytically pure melamine at room temperature of 25 ℃, placing the melamine in a semi-closed alumina crucible in air atmosphere, placing the crucible and a muffle furnace with the heating rate of 3 ℃/min, heating to 500-600 ℃, preserving heat for 0.0-5.0 h, then cooling to room temperature of 25 ℃ along with the furnace, grinding the obtained block clockwise for 5-20 min by using an agate mortar to obtain uniform light yellow powder, placing the obtained light yellow powder into absolute ethyl alcohol for 10-50 min by ultrasound, then placing the light yellow powder into a blast drying oven with the heating rate of 5 ℃/min, heating to 50-100 ℃ for drying, and keeping the temperature for 6.0-30.0 h to obtain g-C used for experiments3N4Powder;
secondly, grinding the block g-C by using an agate mortar3N4Putting the mixture into a semi-closed alumina crucible, putting the semi-closed alumina crucible and the crucible into a muffle furnace with the heating rate of 5 ℃/min, heating to 100-550 ℃, preserving heat for 1.0-5.0 h, and carrying out secondary calcination to obtain the stripped g-C3N4(CN) nanosheets;
thirdly, preparing BaTiO by electrostatic spinning method3Fiber, 0.000-5.000 g of analytically pure PVP is added at a rate of 0.500-2.000 g/minStirring for 1.0-5.0 h in 0.000-5.000 mL of absolute ethanol to obtain solution A, and adding 98% tetrabutyl titanate Ti (OC) in 0.000-5.000 mL4H9)4Slowly adding the solution into 1.000-5.000 mL of absolute ethyl alcohol at a speed of 0.500-2.000 mL/min, stirring at a speed of 100-500 r/min for 0.0-5.0 h to obtain a solution B, slowly adding the solution B into the solution A at a speed of 0.500-2.000 mL/min, stirring at a speed of 100-500 r/min for 0.0-5.0 h to form a solution C, and adding 0.000-5.000 g of analytically pure barium acetate (CH)3COO)2Adding Ba into 5.000-10.000 mL of 10-50% glacial acetic acid solution at the speed of 0.500-2.000 mL/min until the Ba is completely dissolved to obtain solution D, slowly adding the solution D into the solution C at the speed of 0.500-2.000 mL/min, stirring at the speed of 100-500 r/min for 1.0-5.0 h to obtain precursor solution, performing a spinning process by using a spinning machine with the voltage of 15kV, the pipe diameter of 15mm and the speed of 1mL/h, allowing the obtained precursor solution to fall to a receiving plate under the action of a high-voltage electric field, wherein the length and width of the receiving plate are 40cm and 50cm, the material is a wood plate adhered with aluminum foil paper, the solution is 5-30 cm away from the receiving plate, drawing the precursor solution into fibers in the process to obtain criss-cross superfine composite fiber non-woven fabric, carefully taking down the fibers, and drying the non-woven fabric in a drying box at the temperature of 50-100 ℃ for 12.0-72.0 h, the heating rate is 5 ℃/min, and BaTiO is obtained after drying3/BaCO3Putting the composite fiber into a muffle furnace with the heating rate of 3 ℃/min again, heating to 500-1000 ℃ for calcining, and keeping the temperature for 1.0-5.0 h to finally obtain pure BaTiO3Fibers;
fourthly, weighing the g-C prepared in the second step at the room temperature of 25 DEG C3N40.200-0.500 g and 0.005-0.300 g BaTiO prepared in the third step3Grinding the mixture in an agate mortar for 20-50 min in a clockwise mode, then placing the mixture in a muffle furnace at the temperature of 200-500 ℃, heating the mixture at the rate of 3 ℃/min for 1.0-5.0 h to obtain BaTiO3/g-C3N4A composite photocatalyst is provided.
The simple calcination method is used for preparing BaTiO3/g-C3N4The method for preparing the composite photocatalyst adopts a simple calcination method at the temperature of 200-500 DEG CThe temperature rise rate is 3-5 ℃/min for 1.0-5.0 h, the operation of preparing the product is simpler, the product can be prepared in large quantities at one time, and mg-BaTiO is changed3/(mg-g-C3N4+mBaTiO3) The value of (A) is accurately controlled to form BaTiO3/g-C3N4The composite photocatalyst is added in an amount selected according to requirements, and the product performance is regulated and controlled.
Advantages and achievements of the present invention: the invention has the following advantages and beneficial effects: (1) successfully prepare BaTiO by a simple calcination method3/g-C3N4The g-C of the composite photocatalyst can be found by the representation of the microstructure and the composition3N4Nanosheet and BaTiO3The composite photocatalyst in a sheet-fiber combination shape is formed on the fiber; (2) in g-C3N4And BaTiO3A II-type heterojunction is constructed between the two, so that the separation of a photon-generated carrier is promoted, the redox capability is enhanced, a higher BET specific surface area is provided, and an active site is increased, so that the photocatalytic activity of the composite photocatalyst is enhanced, (2) the CNBT20 composite photocatalyst shows excellent photocatalytic activity for degrading rhodamine B (RhB) and tetracycline TC under LED white light, the degradation rate of RhB reaches 99.5%, the degradation rate of TC reaches 82.4%, and simultaneously, the kinetic constants are g-C3N48.75 times and 5.77 times of the nanosheets, the CNBT20 composite material is excellent in cycling stability, and the crystal structure is unchanged after five cycles; (3) a mechanism based on photo-generated carrier transfer in a photocatalytic degradation process is provided; (4) the CNBT20 composite photocatalyst has very important practical significance on the catalytic activity of the photocatalyst, and simultaneously provides a solid theoretical basis and practical experience for the general application of the materials in wider fields. (5) The preparation method provided by the invention has the characteristics of simple operation and high reaction efficiency, and the material can be widely applied to the fields of energy storage and conversion, catalytic degradation, environmental remediation and the like, and has bright market prospect and development potential.
[ description of the drawings ]
FIG. 1 shows BaTiO3/BaCO3XRD pattern of composite fiber calcined at 850 ℃ for 2h。
FIG. 2 shows BaTiO3/BaCO3The XRD pattern of the composite fiber after being calcined at 950 ℃ for 2 h.
FIG. 3 shows CN and BaTiO3And an XRD (X-ray diffraction) pattern of the CNBT composite photocatalyst.
FIG. 4 is an SEM picture of CN.
FIG. 5 shows BaTiO3SEM pictures of (d).
Fig. 6 is an SEM picture and EDS spectrum of the CNBT20 composite photocatalyst.
FIG. 7 is a TEM picture of CN.
FIG. 8 shows BaTiO3TEM pictures of (a).
Fig. 9 is a TEM picture of CNBT20 composite photocatalyst.
Fig. 10 is an HRTEM picture of CNBT 20.
FIG. 11 shows CN and BaTiO3And FT-IR spectrum of CNBT composite photocatalyst.
FIG. 12 shows CN and BaTiO3And ultraviolet-visible diffuse reflection spectrum of the CNBT composite photocatalyst.
FIG. 13 shows CN and BaTiO3And a Tauc plot of the CNBT composite photocatalyst.
FIG. 14 shows photoluminescence spectra of CN and CNBT composite photocatalysts.
FIG. 15 shows CN and BaTiO3And CNBT 20N2Adsorption and desorption isotherms.
FIG. 16 shows CN and BaTiO3And photocurrent response of CNBT 20.
FIG. 17 shows CN and BaTiO3And EIS nyquist plot of CNBT 20.
FIG. 18 shows CN and BaTiO3And a rate chart of degradation of RhB by the CNBT composite photocatalyst.
FIG. 19 shows CN and BaTiO3And a dynamic fitting graph of the CNBT composite photocatalyst on the RhB photocatalytic degradation.
FIG. 20 is a graph of the cycling stability of CNBT20 samples for degradation of RhB.
Fig. 21 is an XRD pattern before and after RhB degradation cycle for CNBT20 sample.
FIG. 22 shows CN and BaTiO3And a rate graph of degradation TC of the CNBT composite photocatalyst.
FIG. 23 shows CN and BaTiO3And a dynamic fitting graph of the CNBT composite photocatalyst on TC photocatalytic degradation.
FIG. 24 is a graph of the cycling stability of the degradation of TC in the CNBT20 sample.
Fig. 25 is an XRD pattern before and after the degradation TC cycle of the CNBT20 sample.
Fig. 26 is a graph of the effect of reactive species on the degradation of TC by CNBT 20.
FIG. 27 is a graph of the effect of reactive species on the degradation of RhB by CNBT 20.
FIG. 28 is a Mott-Schottky curve of CN.
FIG. 29 is BaTiO3The Mott-Schottky curve of (1).
Fig. 30 is a mechanism of photocatalytic degradation.
FIG. 31 is BaTiO3/g-C3N4A preparation process of the composite photocatalyst.
[ detailed description ] embodiments
In order to more clearly illustrate the advantages of this patent, the following embodiments and effects of the present invention are further illustrated with reference to the following examples, and fig. 1: BaTiO 23/BaCO3XRD pattern of composite fiber calcined at 850 ℃ for 2.0h, fig. 2: BaTiO 23/BaCO3XRD pattern of composite fiber calcined at 950 ℃ for 2.0h, fig. 3: CN, BaTiO3And XRD spectrum of the CNBT composite photocatalyst, and figure 4: SEM picture of CN, fig. 5: BaTiO 23SEM picture of (a), fig. 6: SEM picture and EDS spectrum of CNBT20 composite photocatalyst, fig. 7: TEM picture of CN, fig. 8: BaTiO 23TEM picture of (a), fig. 9: TEM images of CNBT20 composite photocatalyst, fig. 10: HRTEM picture of CNBT20, fig. 11: CN, BaTiO3And FT-IR spectrum of CNBT composite photocatalyst, FIG. 12: CN, BaTiO3And the ultraviolet-visible diffuse reflectance spectrum of the CNBT composite photocatalyst, fig. 13: CN, BaTiO3And Tauc plot of CNBT composite photocatalyst, fig. 14: photoluminescence spectra of the CN and CNBT composite photocatalyst, fig. 15: CN, BaTiO3And CNBT 20N2Adsorption-desorption isotherms, fig. 16: CN, BaTiO3And photocurrent response graph of CNBT20, fig. 17: CN, BaTiO3And E of CNBT20IS nyquist plot, fig. 18: CN, BaTiO3And a graph of the rate of degradation of RhB by the CNBT composite photocatalyst, fig. 19: CN, BaTiO3And a dynamic fitting graph of the CNBT composite photocatalyst on RhB photocatalytic degradation, and the graph is shown in FIG. 20: cyclic stability profile of CNBT20 sample degrading RhB, fig. 21: XRD patterns before and after RhB degradation cycle of CNBT20 sample, fig. 22: CN, BaTiO3And a graph of the degradation rate of the CNBT composite photocatalyst to TC, and the graph of FIG. 23: CN, BaTiO3And a kinetic fitting graph of the CNBT composite photocatalyst on TC photocatalytic degradation, and FIG. 24: cyclic stability plot of CNBT20 sample degradation TC, fig. 25: XRD patterns before and after TC cycle degradation of CNBT20 sample, fig. 26: graph of effect of reactive species on degradation of TC by CNBT20, fig. 27: effect of reactive species on RhB degradation by CNBT20, fig. 28: Mott-Schottky curve of CN, fig. 29: BaTiO 23The Mott-Schottky curve of (1), FIG. 30 shows the mechanism of photocatalytic degradation, and FIG. 31: BaTiO 23/g-C3N4The preparation process of the composite photocatalyst is used for illustrating different BaTiO3The influence of the weight fraction on the structure of the composite photocatalyst and the performance of products; it is understood that not all embodiments described herein, but all other embodiments available to those of ordinary skill in the art based on the embodiments of the present invention, are within the scope of the present invention.
Example 1: mg-BaTiO of sample 13/(mg-g-C3N4+mBaTiO3) BaTiO 5%3/g-C3N4Preparation of composite photocatalyst (CNBT5)
Weighing 10.000g of melamine (analytically pure) at room temperature of 25 ℃, placing the melamine (analytically pure) in a semi-closed alumina crucible in an air atmosphere, placing the crucible and a muffle furnace with the heating rate of 3 ℃/min, heating to 550 ℃, preserving heat for 4.0h, cooling to room temperature of 25 ℃ along with the furnace, grinding the obtained block clockwise for 10min by using an agate mortar to obtain uniform light yellow powder, placing the obtained light yellow powder into absolute ethyl alcohol for ultrasonic treatment for 30min, then placing the powder into a blast drying oven with the heating rate of 5 ℃/min, heating to 60 ℃, drying for constant temperature of 12.0h, and obtaining g-C used for experiments3N4Powder; will be ground by agate mortarMilled Block g-C3N4Placing into a semi-closed alumina crucible, placing into a muffle furnace with a heating rate of 5 deg.C/min together with the crucible, heating to 500 deg.C, maintaining for 2.0 hr, and calcining to obtain peeled g-C3N4(CN) nanosheets; preparing BaTiO by electrostatic spinning method3Fiber, 0.600g PVP (analytical grade) was added to 4.000mL absolute ethanol at 0.6g/min and stirred for 2.0h to give solution A, 1.680mL tetrabutyl titanate Ti (OC)4H9)4The solution (98% strength) was slowly added to 2.000mL of absolute ethanol at a rate of 1mL/min and stirred at a rate of 400r/min for 1.0h to give solution B, solution B was slowly added to solution A at a rate of 1mL/min and stirred at a rate of 400r/min for 0.5h to form solution C, and 1.264g of barium acetate (CH)3COO)2Adding Ba (analytically pure) into 8.000mL of 36% glacial acetic acid solution at the speed of 1mL/min until the Ba is completely dissolved to obtain a solution D, slowly adding the solution D into the solution C at the speed of 1mL/min, stirring for 2.0h at the speed of 400r/min to obtain a precursor solution, performing a spinning process by using a spinning machine with the voltage of 15kV, the pipe diameter of 15mm and the speed of 1mL/h, allowing the obtained precursor solution to fall to a receiving plate (the length multiplied by the width is 40cm multiplied by 50cm, the material is a wood plate adhered with aluminum foil paper, and the height of the solution from the receiving plate is 5-30 cm) under the action of a high-voltage electric field, drawing the precursor solution into fibers in the process to obtain longitudinally and transversely staggered superfine composite fiber non-woven fabric, carefully taking down the fibers, drying the wood plate in a blast drying oven at 60 ℃ for 48.0h at the heating rate of 5 ℃/min, drying to obtain BaTiO3/BaCO3The composite fiber is put into a muffle furnace with the heating rate of 3 ℃/min again to be heated to 950 ℃ for calcination, and the heat is preserved for 2.0h to finally obtain pure BaTiO3Fibers; 0.475g of the g-C prepared above was weighed at 25 ℃ at room temperature3N4And 0.025g of BaTiO3Grinding clockwise in agate mortar for 30min, and heat treating the mixture in muffle furnace at 300 deg.c and 3 deg.c/min for 2.0 hr to obtain BaTiO of sample 13/g-C3N4The composite photocatalyst CNBT 5.
The characteristic peaks shown in the XRD pattern (FIG. 3) of sample 1 can be seen, and the sample is1 the composite photocatalyst comprises CN and BaTiO respectively3The advantage of physical recombination can exert the respective photocatalytic performance of the characteristic peak; CN, BaTiO in sample 13SEM images (FIGS. 4 and 5) of the obtained material show that CN has a two-dimensional layered structure, the surface of each layer has wrinkles, the thickness of each layer is about 1 to 20nm, and BaTiO is obtained3The fiber is of a staggered rod-shaped fiber structure, the diameter is about 50-20nm, and the fiber is partially broken due to higher calcination temperature; CN, BaTiO in sample 13TEM images of (FIG. 7 and FIG. 8) show CN, BaTiO3The morphologies of (a) are 2D nanosheet and fiber, respectively, which correspond to the image of SEM; the FT-IR spectrum of sample 1 (FIG. 11) shows that for the composite of sample 1, it has CN and BaTiO, respectively3Can sufficiently define CN and BaTiO3Are successfully combined together; the visible light absorption performance of the sample 1 is shown in the chart CN and BaTiO3And the ultraviolet-visible diffuse reflectance spectrum of the CNBT composite photocatalyst (shown in figure 12), wherein the absorption sideband of the sample 1 is between CN and BaTiO3And closer to the absorption threshold of CN; the photoluminescence spectrum (fig. 14) of sample 1 shows that, for pure CN, it has a higher PL emission peak intensity, which indicates that the recombination rate of its photo-generated electron-hole pairs is very fast according to the nature of PL emission, and that the PL emission intensity is significantly reduced for the CNBT5 composite photocatalyst of sample 1, which indicates that after the two substances are recombined together, the photo-generated electron-hole separation efficiency of the composite photocatalyst is improved due to the formation of a heterojunction structure; the rate graph (FIG. 18) of sample 1 for degrading rhodamine B (RhB 5mg/L) dye shows that the composite photocatalyst of sample 1 exhibits a ratio of CN to BaTiO3The photocatalytic activity is higher, for the CNBT heterojunction structure, the improvement of the photocatalytic activity is attributed to the existence of the heterojunction structure, the existence of the heterojunction structure improves the separation efficiency of photo-generated electron-hole pairs, and the BET specific surface area of the composite material of the sample 1 is increased, so that more active points are provided, and the photocatalytic activity is improved; CN, BaTiO3And the kinetic fitting graph (FIG. 19) of the CNBT composite photocatalyst on the catalytic degradation of RhB shows that the slope generationThe kinetic constants (k) for degradation of RhB in sample 1 are shown, with the kinetic constant of 0.02062min for sample 1-1Again, it was demonstrated that the construction of the heterojunction structure can enhance photocatalytic activity; the rate of Tetracycline (TC) degradation plot (FIG. 22) for sample 1 shows that sample 1 exhibits a ratio of CN and BaTiO under white light illumination3Higher photocatalysis performance; CN, BaTiO3And the fitted kinetic graph (FIG. 23) of the CNBT composite photocatalyst on the photocatalytic degradation of TC shows that the kinetic constant of degrading TC of the sample 1 is 0.03252min-1(ii) a CN and BaTiO of sample 13The Mott-Schottky (FIG. 28 and FIG. 29) curve of (A) determines the flat band potential (E) of the photocatalystfb) Due to CN and BaTiO3All slopes of (a) are positive, indicating that they are both n-type semiconductors, EfbThe value of (A) can be determined by the intersection of the slope with the x-axis, CN and BaTiO3E of (A)VB1.63V and 2.39V, respectively, the mechanism of photocatalytic degradation of sample 1 (FIG. 30) is shown in BaTiO3And a heterojunction is formed between the photocatalyst and CN, so that the separation efficiency of a photon-generated carrier can be improved, and the photocatalytic activity of the composite photocatalyst for degrading RhB/TC is enhanced.
Example 2: mg-BaTiO of sample 23/(mg-g-C3N4+mBaTiO3) 10% BaTiO3/g-C3N4Preparation of composite photocatalyst (CNBT10)
Weighing 10.000g of melamine (analytically pure) at room temperature of 25 ℃, placing the melamine (analytically pure) in a semi-closed alumina crucible in an air atmosphere, placing the crucible and a muffle furnace with the heating rate of 3 ℃/min, heating to 550 ℃, preserving heat for 4.0h, cooling to room temperature of 25 ℃ along with the furnace, grinding the obtained block clockwise for 10min by using an agate mortar to obtain uniform light yellow powder, placing the obtained light yellow powder into absolute ethyl alcohol for ultrasonic treatment for 30min, then placing the powder into a blast drying oven with the heating rate of 5 ℃/min, heating to 60 ℃, drying for constant temperature of 12.0h, and obtaining g-C used for experiments3N4Powder; grinding the block g-C with agate mortar3N4Placing into a semi-closed alumina crucible, placing into a muffle furnace with a heating rate of 5 deg.C/min together with the crucible, heating to 500 deg.C, and maintainingThe temperature is 2.0h for secondary calcination to obtain stripped g-C3N4(CN) nanosheets; preparing BaTiO by electrostatic spinning method3Fiber, 0.600g PVP (analytical grade) was added to 4mL absolute ethanol at 0.6g/min and stirred for 2.0h to give solution A, 1.680mL tetrabutyl titanate Ti (OC)4H9)4The solution (98% strength) was slowly added to 2mL of absolute ethanol at a rate of 1mL/min and stirred at a rate of 400r/min for 1.0h to give solution B, solution B was slowly added to solution A at a rate of 1mL/min and stirred at a rate of 400r/min for 0.5h to form solution C, and 1.264g of barium acetate (CH)3COO)2Adding Ba (analytically pure) into 8.000mL of 36% glacial acetic acid solution at the speed of 1mL/min until the Ba is completely dissolved to obtain a solution D, slowly adding the solution D into the solution C at the speed of 1mL/min, stirring for 2.0h at the speed of 400r/min to obtain a precursor solution, performing a spinning process by using a spinning machine with the voltage of 15kV, the pipe diameter of 15mm and the speed of 1mL/h, allowing the obtained precursor solution to fall to a receiving plate (the length multiplied by the width is 40cm multiplied by 50cm, the material is a wood plate adhered with aluminum foil paper, and the height of the solution from the receiving plate is 5-30 cm) under the action of a high-voltage electric field, drawing the precursor solution into fibers in the process to obtain longitudinally and transversely staggered superfine composite fiber non-woven fabric, carefully taking down the fibers, drying the wood plate in a blast drying oven at 60 ℃ for 48.0h at the heating rate of 5 ℃/min, drying to obtain BaTiO3/BaCO3The composite fiber is put into a muffle furnace with the heating rate of 3 ℃/min again to be heated to 950 ℃ for calcination, and the heat is preserved for 2.0h to finally obtain pure BaTiO3Fibers; 0.450g of the g-C prepared above was weighed at 25 ℃ at room temperature3N4And 0.050g of BaTiO3Grinding clockwise in agate mortar for 30min, and heat treating the mixture in muffle furnace at 300 deg.C and heating rate of 3 deg.C/min for 2.0h to obtain BaTiO of sample 23/g-C3N4The composite photocatalyst CNBT 10.
As can be seen from the characteristic peaks shown in the XRD pattern (FIG. 3) of sample 2, the composite photocatalyst of sample 2 has CN and BaTiO respectively3The advantage of physical recombination can exert the respective photocatalytic performance of the characteristic peak; CN, BaTiO in sample 23SEM images (FIGS. 4 and 5) of the obtained material show that CN has a two-dimensional layered structure, the surface of each layer has wrinkles, the thickness of each layer is about 1 to 20nm, and BaTiO is obtained3The fiber is of a staggered rod-shaped fiber structure, the diameter is about 50-20nm, and the fiber is partially broken due to higher calcination temperature; CN, BaTiO in sample 23TEM images of (FIG. 7 and FIG. 8) show CN, BaTiO3The morphologies of (a) are 2D nanosheet and fiber, respectively, which correspond to the image of SEM; the FT-IR spectrum of sample 2 (FIG. 11) shows that for the composite of sample 2, it has CN and BaTiO, respectively3Can sufficiently define CN and BaTiO3Are successfully combined together; the visible light absorption performance of sample 2 is shown in the figure CN and BaTiO3And the ultraviolet-visible diffuse reflectance spectrum of the CNBT composite photocatalyst (shown in figure 12), wherein the absorption sideband of the sample 2 is between CN and BaTiO3And closer to the absorption threshold of CN; the photoluminescence spectrum of sample 2 (fig. 14) shows that, for pure CN, it has a higher PL emission peak intensity, which indicates that the recombination rate of its photo-generated electron-hole pairs is very fast according to the nature of PL emission, and that the PL emission intensity is significantly reduced for the CNBT5 composite photocatalyst of sample 2, which indicates that after the two substances are recombined together, the photo-generated electron-hole separation efficiency of the composite photocatalyst is improved due to the formation of a heterojunction structure; the rate graph (FIG. 18) of sample 2 for degrading rhodamine B (RhB 5mg/L) dye shows that the composite photocatalyst of sample 2 exhibits a ratio of CN to BaTiO3The photocatalytic activity is higher, for the CNBT heterojunction structure, the improvement of the photocatalytic activity is attributed to the existence of the heterojunction structure, the existence of the heterojunction structure improves the separation efficiency of photo-generated electron-hole pairs, and the BET specific surface area of the composite material of the sample 2 is increased, so that more active points are provided, and the photocatalytic activity is improved; CN, BaTiO3And a dynamic fitting graph (figure 19) of the CNBT composite photocatalyst on RhB photocatalytic degradation shows that the slope represents a dynamic constant (k) of sample 2 for degrading RhB, and the dynamic constant of sample 2 is 0.02069min-1Again, it was demonstrated that the construction of the heterojunction structure can enhance photocatalytic activity; sample (I)2 (fig. 22) shows that sample 2 exhibits a ratio of CN to BaTiO under white light illumination3Higher photocatalysis performance; CN, BaTiO3And a kinetic fitting graph (figure 23) of the CNBT composite photocatalyst on the photocatalytic degradation of the TC shows that the kinetic constant of the degradation TC of the sample 2 is 0.05333min-1(ii) a CN and BaTiO of sample 23The Mott-Schottky (FIG. 28 and FIG. 29) curve of (A) determines the flat band potential (E) of the photocatalystfb) Due to CN and BaTiO3All slopes of (a) are positive, indicating that they are both n-type semiconductors, EfbThe value of (A) can be determined by the intersection of the slope with the x-axis, CN and BaTiO3E of (A)VB1.63V and 2.39V, respectively, the mechanism of photocatalytic degradation of sample 2 (FIG. 30) is shown in BaTiO3And a heterojunction is formed between the photocatalyst and CN, so that the separation efficiency of a photon-generated carrier can be improved, and the photocatalytic activity of the composite photocatalyst for degrading RhB/TC is enhanced.
Example 3: mg-BaTiO of sample 33/(mg-g-C3N4+mBaTiO3) 15% of BaTiO3/g-C3N4Preparation of composite photocatalyst (CNBT15)
Weighing 10.000g of melamine (analytically pure) at room temperature of 25 ℃, placing the melamine (analytically pure) in a semi-closed alumina crucible in an air atmosphere, placing the crucible and a muffle furnace with the heating rate of 3 ℃/min, heating to 550 ℃, preserving heat for 4.0h, cooling to room temperature of 25 ℃ along with the furnace, grinding the obtained block clockwise for 10min by using an agate mortar to obtain uniform light yellow powder, placing the obtained light yellow powder into absolute ethyl alcohol for ultrasonic treatment for 30min, then placing the powder into a blast drying oven with the heating rate of 5 ℃/min, heating to 60 ℃, drying for constant temperature of 12.0h, and obtaining g-C used for experiments3N4Powder; grinding the block g-C with agate mortar3N4Placing into a semi-closed alumina crucible, placing into a muffle furnace with a heating rate of 5 deg.C/min together with the crucible, heating to 500 deg.C, maintaining for 2.0 hr, and calcining to obtain peeled g-C3N4(CN) nanosheets; preparing BaTiO by electrostatic spinning method3Fibers, 0.600g PVP (analytical grade) at 0.6Adding into 4.000mL of absolute ethanol at a rate of g/min, stirring for 2.0h to obtain solution A, and adding 1.680mL of tetrabutyl titanate Ti (OC)4H9)4The solution (98% strength) was slowly added to 2.000mL of absolute ethanol at a rate of 1mL/min and stirred at a rate of 400r/min for 1.0h to give solution B, solution B was slowly added to solution A at a rate of 1mL/min and stirred at a rate of 400r/min for 0.5h to form solution C, and 1.264g of barium acetate (CH)3COO)2Adding Ba (analytically pure) into 8.000mL of 36% glacial acetic acid solution at the speed of 1mL/min until the Ba is completely dissolved to obtain a solution D, slowly adding the solution D into the solution C at the speed of 1mL/min, stirring for 2.0h at the speed of 400r/min to obtain a precursor solution, performing a spinning process by using a spinning machine with the voltage of 15kV, the pipe diameter of 15mm and the speed of 1mL/h, allowing the obtained precursor solution to fall to a receiving plate (the length multiplied by the width is 40cm multiplied by 50cm, the material is a wood plate adhered with aluminum foil paper, and the height of the solution from the receiving plate is 5-30 cm) under the action of a high-voltage electric field, drawing the precursor solution into fibers in the process to obtain longitudinally and transversely staggered superfine composite fiber non-woven fabric, carefully taking down the fibers, drying the wood plate in a blast drying oven at 60 ℃ for 48.0h at the heating rate of 5 ℃/min, drying to obtain BaTiO3/BaCO3The composite fiber is put into a muffle furnace with the heating rate of 3 ℃/min again to be heated to 950 ℃ for calcination, and the heat is preserved for 2.0h to finally obtain pure BaTiO3Fibers; 0.425g of g-C prepared above were weighed at 25 ℃ at room temperature3N4And 0.075g of BaTiO3Grinding clockwise in agate mortar for 30min, and heat treating the mixture in muffle furnace at 300 deg.c and 3 deg.c/min for 2.0 hr to obtain BaTiO of sample 33/g-C3N4The composite photocatalyst CNBT 15.
As can be seen from the characteristic peaks shown in the XRD pattern (FIG. 3) of sample 3, the composite photocatalyst of sample 3 has CN and BaTiO respectively3The advantage of physical recombination can exert the respective photocatalytic performance of the characteristic peak; CN, BaTiO in sample 33SEM images (FIGS. 4 and 5) of the obtained material show that CN has a two-dimensional layered structure, the surface of each layer has wrinkles, the thickness of each layer is about 1 to 20nm, and BaTiO is obtained3The fiber is of a staggered rod-shaped fiber structure, the diameter is about 50-20nm, and the fiber is partially broken due to higher calcination temperature; CN, BaTiO in sample 33TEM images of (FIG. 7 and FIG. 8) show CN, BaTiO3The morphologies of (a) are 2D nanosheet and fiber, respectively, which correspond to the image of SEM; the FT-IR spectrum of sample 3 (FIG. 11) shows that for the composite of sample 3, it has CN and BaTiO, respectively3Can sufficiently define CN and BaTiO3Are successfully combined together; the visible light absorption performance of sample 3 is shown in the figure CN and BaTiO3And the ultraviolet-visible diffuse reflectance spectrum of the CNBT composite photocatalyst (shown in figure 12), wherein the absorption sideband of sample 3 is between CN and BaTiO3And closer to the absorption threshold of CN; the photoluminescence spectrum of sample 3 (fig. 14) shows that, for pure CN, it has a higher PL emission peak intensity, which indicates that the recombination rate of its photo-generated electron-hole pairs is very fast according to the nature of PL emission, and that the PL emission intensity is significantly reduced for the CNBT5 composite photocatalyst of sample 3, which indicates that after the two substances are recombined together, the photo-generated electron-hole separation efficiency of the composite photocatalyst is improved due to the formation of a heterojunction structure; the rate graph (FIG. 18) of sample 3 for degrading rhodamine B (RhB 5mg/L) dye shows that the composite photocatalyst of sample 3 exhibits a ratio of CN to BaTiO3Higher photocatalytic activity, for the CNBT heterojunction structure, the improvement of the photocatalytic activity is attributed to the existence of the heterojunction structure, which improves the separation efficiency of photo-generated electron-hole pairs, on the one hand, and the increase of the BET specific surface area of the composite material of the sample 3 provides more active points so as to improve the photocatalytic activity; CN, BaTiO3And a dynamic fitting graph (figure 19) of the CNBT composite photocatalyst on RhB photocatalytic degradation shows that the slope represents a dynamic constant (k) of sample 3 for degrading RhB, and the dynamic constant of sample 3 is 0.03646min-1Again, it was demonstrated that the construction of the heterojunction structure can enhance photocatalytic activity; the rate of Tetracycline (TC) degradation plot (FIG. 22) for sample 3 shows that sample 3 exhibits a ratio of CN and BaTiO under white light illumination3Higher photocatalysis performance; CN, BaTiO3And a dynamic fitting graph (figure 23) of the CNBT composite photocatalyst on the photocatalytic degradation of the TC shows that the kinetic constant of the degradation TC of the sample 3 is 0.05735min-1(ii) a CN and BaTiO of sample 33The Mott-Schottky (FIG. 28 and FIG. 29) curve of (A) determines the flat band potential (E) of the photocatalystfb) Due to CN and BaTiO3All slopes of (a) are positive, indicating that they are both n-type semiconductors, EfbThe value of (A) can be determined by the intersection of the slope with the x-axis, CN and BaTiO3E of (A)VB1.63V and 2.39V, respectively, the mechanism of photocatalytic degradation of sample 3 (FIG. 30) is shown in BaTiO3And a heterojunction is formed between the photocatalyst and CN, so that the separation efficiency of a photon-generated carrier can be improved, and the photocatalytic activity of the composite photocatalyst for degrading RhB/TC is enhanced.
Example 4: mg-BaTiO of sample 43/(mg-g-C3N4+mBaTiO3) 20% of BaTiO3/g-C3N4Preparation of composite photocatalyst (CNBT20)
Weighing 10.000g of melamine (analytically pure) at room temperature of 25 ℃, placing the melamine (analytically pure) in a semi-closed alumina crucible in an air atmosphere, placing the crucible and a muffle furnace with the heating rate of 3 ℃/min, heating to 550 ℃, preserving heat for 4.0h, cooling to room temperature of 25 ℃ along with the furnace, grinding the obtained block clockwise for 10min by using an agate mortar to obtain uniform light yellow powder, placing the obtained light yellow powder into absolute ethyl alcohol for ultrasonic treatment for 30min, then placing the powder into a blast drying oven with the heating rate of 5 ℃/min, heating to 60 ℃, drying for constant temperature of 12.0h, and obtaining g-C used for experiments3N4Powder; grinding the block g-C with agate mortar3N4Placing into a semi-closed alumina crucible, placing into a muffle furnace with a heating rate of 5 deg.C/min together with the crucible, heating to 500 deg.C, maintaining for 2.0 hr, and calcining to obtain peeled g-C3N4(CN) nanosheets; preparing BaTiO by electrostatic spinning method3Fiber, 0.600g PVP (analytical grade) was added to 4.000mL absolute ethanol at 0.600g/min and stirred for 2.0h to give solution A, 1.680mL tetrabutyl titanate Ti (OC)4H9)4The solution (concentration 98%) is prepared bySlowly adding 1mL/min into 2.000mL anhydrous ethanol, stirring at 400r/min for 1.0h to obtain solution B, slowly adding solution B into solution A at 1mL/min, stirring at 400r/min for 0.5h to obtain solution C, and adding 1.264g barium acetate (CH)3COO)2Adding Ba (analytically pure) into 8.000mL of 36% glacial acetic acid solution at the speed of 1mL/min until the Ba is completely dissolved to obtain a solution D, slowly adding the solution D into the solution C at the speed of 1mL/min, stirring for 2.0h at the speed of 400r/min to obtain a precursor solution, performing a spinning process by using a spinning machine with the voltage of 15kV, the pipe diameter of 15mm and the speed of 1mL/h, allowing the obtained precursor solution to fall to a receiving plate (the length multiplied by the width is 40cm multiplied by 50cm, the material is a wood plate adhered with aluminum foil paper, and the height of the solution from the receiving plate is 5-30 cm) under the action of a high-voltage electric field, drawing the precursor solution into fibers in the process to obtain longitudinally and transversely staggered superfine composite fiber non-woven fabric, carefully taking down the fibers, drying the wood plate in a blast drying oven at 60 ℃ for 48.0h at the heating rate of 5 ℃/min, drying to obtain BaTiO3/BaCO3The composite fiber is put into a muffle furnace with the heating rate of 3 ℃/min again to be heated to 950 ℃ for calcination, and the heat is preserved for 2.0h to finally obtain pure BaTiO3Fibers; 0.400g of the g-C prepared above was weighed at 25 ℃ at room temperature3N4And 0.100g of BaTiO3Grinding clockwise in agate mortar for 30min, and heat treating the mixture in muffle furnace at 300 deg.c and 3 deg.c/min for 2.0 hr to obtain BaTiO of sample 43/g-C3N4The composite photocatalyst CNBT 20.
As can be seen from the characteristic peaks shown in the XRD pattern (FIG. 3) of sample 4, the composite photocatalyst of sample 4 has CN and BaTiO respectively3The advantage of physical recombination can exert the respective photocatalytic performance of the characteristic peak; SEM image and EDS spectrum (FIG. 6) of sample 4 can show that after grinding and calcining, CN nanosheets and BaTiO3The fibers are tightly bound together and the EDS spectrum of FIG. 6 shows that the selected regions contain CN and BaTiO3The two materials can be preliminarily judged to be compounded together; TEM image of sample 4 (FIG. 9) shows the morphology of CNBT20 as a fiber-sheet composite junctionStructuring; HRTEM image (FIG. 10) of sample 4 was observed to show lattice fringes, which were analyzed to find that the lattice fringes at 0.284nm and 0.325nm correspond to BaTiO, respectively3(101) And CN (002) crystal face, which is consistent with the analysis result of XRD, indicating that BaTiO3And CN are physically compounded, which is beneficial to exerting the photocatalytic activity of the sample; the FT-IR spectrum of sample 4 (FIG. 11) shows that for the composite of sample 4, it has CN and BaTiO, respectively3Can sufficiently define CN and BaTiO3Are successfully combined together; the visible light absorption performance of sample 4 is shown in the chart CN and BaTiO3And the ultraviolet-visible diffuse reflectance spectrum of the CNBT composite photocatalyst (shown in figure 12), wherein the absorption sideband of the sample 4 is between CN and BaTiO3And closer to the absorption threshold of CN; tauc plot (FIG. 13) for sample 4, calculated band gaps Eg for CN, CdS and CNBT20 of 2.76eV, 2.81eV and 3.25eV, respectively; the photoluminescence spectrum of sample 4 (fig. 14) shows that, for pure CN, it has a higher PL emission peak intensity, which indicates that the recombination rate of its photo-generated electron-hole pairs is very fast according to the nature of PL emission, and that the PL emission intensity is significantly reduced for the CNBT5 composite photocatalyst of sample 4, which indicates that after the two substances are recombined together, the photo-generated electron-hole separation efficiency of the composite photocatalyst is improved due to the formation of a heterojunction structure; n of sample 42As can be seen from the adsorption-desorption test result chart (FIG. 15), CN and BaTiO3And CNBT20 all have H3Calculating typical IV isotherms of the hysteresis loop to obtain CN and BaTiO3And the BET specific surface areas of CNBT20 were 16.37m2/g，26.09m2G and 33.08m2(ii)/g; the photocurrent response plot (FIG. 16) for sample 4 shows the interaction with CN and BaTiO3Compared with the electrode, the CNBT20 electrode of the sample 4 has excellent transient photocurrent response, CN and BaTiO3And the photocurrent densities of the CNBT20 electrodes were 0.088 muA/cm2、0.036μA/cm2And 0.517. mu.A/cm2The current density of the CNBT20 electrode is 5.9 times that of the CN electrode and is BaTiO314.4 times of the electrode; the arc radius of the EIS Nyquist plot (FIG. 17) for sample 4 reflects the semiconductor photo-generated electron-hole pairsThe separation condition of (2) proves that the separation and transmission of the photo-generated electrons and holes of the CNBT20 composite photocatalyst of the sample 4 are more effective; the rate plot (FIG. 18) of rhodamine B (RhB 5mg/L) dye degradation for sample 4 shows that the composite photocatalyst of sample 4 exhibits a ratio of CN to BaTiO3The photocatalytic activity is higher, for the CNBT heterojunction structure, the improvement of the photocatalytic activity is attributed to the existence of the heterojunction structure, the existence of the heterojunction structure improves the separation efficiency of photo-generated electron-hole pairs, and the BET specific surface area of the composite material of the sample 4 is increased, so that more active points are provided, and the photocatalytic activity is improved; CN, BaTiO3And a dynamic fitting graph (figure 19) of the CNBT composite photocatalyst on RhB photocatalytic degradation shows that the slope represents a dynamic constant (k) of sample 4 for degrading RhB, and the dynamic constant of sample 4 is 0.06312min-1It is confirmed again that the structure of the heterojunction structure can enhance the photocatalytic activity, and the CNBT20 composite photocatalyst of sample 4 is a material for effectively degrading organic pollutants in water; the cycle stability chart of sample 4 for RhB degradation shows that the degradation rate is not significantly reduced after five cycles of RhB degradation; XRD (X-ray diffraction) patterns of the sample 4 before and after RhB degradation cycle show that the phase structure is not obviously changed before and after the cycle, which shows that the CNBT20 composite material has excellent stability; the rate of Tetracycline (TC) degradation plot (FIG. 22) for sample 4 shows that sample 4 exhibits a ratio of CN and BaTiO under white light illumination3The photocatalysis performance is higher, and after the illumination reaction for 90min, the degradation rate of the photocatalyst on RhB reaches 82.4 percent; CN, BaTiO3And the dynamic fitting graph (figure 23) of the CNBT composite photocatalyst on the TC photocatalytic degradation shows that the dynamic constant of degrading TC of the sample 4 is 0.07136min-1The k value is 5.77 times of CN, which indicates that the CNBT20 composite photocatalyst of the sample 4 is a material for effectively degrading antibiotics in water; the cycling stability plot (fig. 24) of sample 4 for degradation of TC shows that there is no significant decrease in degradation rate over five cycles of TC degradation; the XRD patterns (fig. 25) before and after the degradation TC cycle of the sample 4 show that the phase structure is not significantly changed before and after the cycle, indicating that the CNBT20 composite material has excellent stability; the effect of the reactive species on the degradation of TC and RhB by CNBT20 of sample 4 (FIGS. 26 and 27) is shown in FIG.As shown, disodium ethylenediaminetetraacetate (EDTA-2Na), Isopropanol (IPA) and p-Benzoquinone (BQ) are used to quench hole radicals (h) respectively+) Hydroxyl radical (. OH) and superoxide radical (. O)2-) When EDTA-2Na and BQ are added into a sample, the degradation rate of RhB and TC is obviously reduced; in addition, when the IPA scavenger is added, the degradation rates of RhB and TC are not changed, so that the active species for photocatalytic degradation of RhB and TC of the CNBT composite photocatalyst are the same, namely O2-And h+(ii) a CN and BaTiO of sample 43The Mott-Schottky (FIG. 28 and FIG. 29) curve of (A) determines the flat band potential (E) of the photocatalystfb) Due to CN and BaTiO3All slopes of (a) are positive, indicating that they are both n-type semiconductors, EfbThe value of (A) can be determined by the intersection of the slope with the x-axis, CN and BaTiO3E of (A)VB1.63V and 2.39V, respectively, the mechanism of photocatalytic degradation of sample 4 (FIG. 30) is shown in BaTiO3And a heterojunction is formed between the photocatalyst and CN, so that the separation efficiency of a photon-generated carrier can be improved, and the photocatalytic activity of the composite photocatalyst for degrading RhB/TC is enhanced.
Example 5: mg-BaTiO of sample 53/(mg-g-C3N4+mBaTiO3) 25% BaTiO3/g-C3N4Preparation of composite photocatalyst (CNBT25)
Weighing 10.000g of melamine (analytically pure) at room temperature of 25 ℃, placing the melamine (analytically pure) in a semi-closed alumina crucible in an air atmosphere, placing the crucible and a muffle furnace with the heating rate of 3 ℃/min, heating to 550 ℃, preserving heat for 4.0h, cooling to room temperature of 25 ℃ along with the furnace, grinding the obtained block clockwise for 10min by using an agate mortar to obtain uniform light yellow powder, placing the obtained light yellow powder into absolute ethyl alcohol for ultrasonic treatment for 30min, then placing the powder into a blast drying oven with the heating rate of 5 ℃/min, heating to 60 ℃, drying for constant temperature of 12.0h, and obtaining g-C used for experiments3N4Powder; grinding the block g-C with agate mortar3N4Placing into a semi-closed alumina crucible, placing into a muffle furnace with a heating rate of 5 deg.C/min together with the crucible, heating to 500 deg.C, and maintaining the temperature2.0h for a second calcination to give exfoliated g-C3N4(CN) nanosheets; preparing BaTiO by electrostatic spinning method3Fiber, 0.600g PVP (analytical grade) was added to 4.000mL absolute ethanol at 0.6g/min and stirred for 2.0h to give solution A, 1.680mL tetrabutyl titanate Ti (OC)4H9)4The solution (98% strength) was slowly added to 2.000mL of absolute ethanol at a rate of 1mL/min and stirred at a rate of 400r/min for 1.0h to give solution B, solution B was slowly added to solution A at a rate of 1mL/min and stirred at a rate of 400r/min for 0.5h to form solution C, and 1.264g of barium acetate (CH)3COO)2Adding Ba (analytically pure) into 8.000mL of 36% glacial acetic acid solution at the speed of 1mL/min until the Ba is completely dissolved to obtain a solution D, slowly adding the solution D into the solution C at the speed of 1mL/min, stirring for 2.0h at the speed of 400r/min to obtain a precursor solution, performing a spinning process by using a spinning machine with the voltage of 15kV, the pipe diameter of 15mm and the speed of 1mL/h, allowing the obtained precursor solution to fall to a receiving plate (the length multiplied by the width is 40cm multiplied by 50cm, the material is a wood plate adhered with aluminum foil paper, and the height of the solution from the receiving plate is 5-30 cm) under the action of a high-voltage electric field, drawing the precursor solution into fibers in the process to obtain longitudinally and transversely staggered superfine composite fiber non-woven fabric, carefully taking down the fibers, drying the wood plate in a blast drying oven at 60 ℃ for 48.0h at the heating rate of 5 ℃/min, drying to obtain BaTiO3/BaCO3The composite fiber is put into a muffle furnace with the heating rate of 3 ℃/min again to be heated to 950 ℃ for calcination, and the heat is preserved for 2.0h to finally obtain pure BaTiO3Fibers; 0.375g of the g-C prepared above was weighed at 25 ℃ at room temperature3N4And 0.125g of BaTiO3Grinding clockwise in agate mortar for 30min, and heat treating the mixture in muffle furnace at 300 deg.c and 3 deg.c/min for 2.0 hr to obtain BaTiO sample 53/g-C3N4The composite photocatalyst CNBT 25.
As can be seen from the characteristic peaks shown in the XRD pattern (FIG. 3) of the sample 5, the sample 5 composite photocatalyst has CN and BaTiO respectively3The advantage of physical recombination can exert the respective photocatalytic performance of the characteristic peak; CN, BaTiO in sample 53SEM images (FIGS. 4 and 5) of the obtained material show that CN has a two-dimensional layered structure, the surface of each layer has wrinkles, the thickness of each layer is about 1 to 20nm, and BaTiO is obtained3The fiber is of a staggered rod-shaped fiber structure, the diameter is about 50-20nm, and the fiber is partially broken due to higher calcination temperature; CN, BaTiO in sample 53TEM images of (FIG. 7 and FIG. 8) show CN, BaTiO3The morphologies of (a) are 2D nanosheet and fiber, respectively, which correspond to the image of SEM; the FT-IR spectrum of sample 5 (FIG. 11) shows that for the composite of sample 5, it has CN and BaTiO, respectively3Can sufficiently define CN and BaTiO3Are successfully combined together; the visible light absorption performance of sample 5 is shown in the chart CN and BaTiO3And the ultraviolet-visible diffuse reflectance spectrum of the CNBT composite photocatalyst (shown in figure 12), wherein the absorption sideband of the sample 5 is between CN and BaTiO3And closer to the absorption threshold of CN; the photoluminescence spectrum of sample 5 (fig. 14) shows that, for pure CN, it has a higher PL emission peak intensity, which indicates that the recombination rate of its photo-generated electron-hole pairs is very fast according to the nature of PL emission, and that the PL emission intensity is significantly reduced for the CNBT5 composite photocatalyst of sample 5, which indicates that after the two substances are recombined together, the photo-generated electron-hole separation efficiency of the composite photocatalyst is improved due to the formation of a heterojunction structure; the plot of the rate of degradation of rhodamine B (RhB 5mg/L) dye for sample 5 (FIG. 18) shows that the composite photocatalyst for sample 5 exhibits a ratio to CN and BaTiO3The photocatalytic activity is higher, for the CNBT heterojunction structure, the improvement of the photocatalytic activity is attributed to the existence of the heterojunction structure, the existence of the heterojunction structure improves the separation efficiency of photo-generated electron-hole pairs, and the BET specific surface area of the composite material of the sample 5 is increased, so that more active points are provided, and the photocatalytic activity is improved; CN, BaTiO3And the dynamic fitting graph (figure 19) of the CNBT composite photocatalyst on RhB photocatalytic degradation shows that the slope represents the dynamic constant (k) of sample 5 for degrading RhB, and the dynamic constant of sample 5 is 0.03311min-1Again, it was demonstrated that the construction of the heterojunction structure can enhance photocatalytic activity;the rate of Tetracycline (TC) degradation plot (FIG. 22) for sample 5 shows that sample 5 exhibits a ratio of CN and BaTiO under white light illumination3Higher photocatalysis performance; CN, BaTiO3And a dynamic fitting graph (figure 23) of the CNBT composite photocatalyst on the photocatalytic degradation of the TC shows that the kinetic constant of the degradation TC of the sample 5 is 0.05837min-1(ii) a CN and BaTiO of sample 53The Mott-Schottky (FIG. 28 and FIG. 29) curve of (A) determines the flat band potential (E) of the photocatalystfb) Due to CN and BaTiO3All slopes of (a) are positive, indicating that they are both n-type semiconductors, EfbThe value of (A) can be determined by the intersection of the slope with the x-axis, CN and BaTiO3E of (A)VB1.63V and 2.39V, respectively, the mechanism of photocatalytic degradation of sample 5 (FIG. 30) is shown in BaTiO3And a heterojunction is formed between the photocatalyst and CN, so that the separation efficiency of a photon-generated carrier can be improved, and the photocatalytic activity of the composite photocatalyst for degrading RhB/TC is enhanced.
FIG. 31 shows BaTiO of the present work3/g-C3N4Preparation process of composite photocatalyst, and preparation method of composite photocatalyst with different BaTiO3Weight fraction of composite material, mg-g-C3N4+mBaTiO3The total mass of (A) is 500 mg; wherein in mg-BaTiO3/(mg-g-C3N4+mBaTiO3) Five samples of different fractions were obtained at 5%, 10%, 15%, 20% and 25%, defined as CNBT5, CNBT10, CNBT15, CNBT20, CNBT25, respectively.
FIG. 1 shows BaTiO3/BaCO3The XRD pattern of the composite fiber calcined at 850 ℃ for 2.0h, and figure 2 is BaTiO3/BaCO3Calcining the composite fiber at 950 ℃ for 2.0h, and preparing BaTiO by the work3The fiber adopts an electrostatic spinning method, and the prepared fiber is BaTiO due to the PVP contained in the precursor3/BaCO3Composite fiber, and what is needed is pure BaTiO3Fibers, therefore, BaCO must be eliminated3Impurities; by observing BaTiO3/BaCO3The Thermogravimetric (TG) curve of the composite fiber found BaCO3Impurities at around 900 deg.C, for verification, BaCO at 900 deg.C3Decomposition occurs and is differentBaTiO at calcination temperature3/BaCO3XRD pattern analysis of the composite fiber; it can be seen from the figure that BaCO can still be seen in the diffractogram when the calcination temperature is 850 deg.C3Characteristic peaks of impurities, and when the calcination temperature is raised to 950 ℃, only BaTiO can be seen in the diffraction pattern3Characteristic peak of indicating BaCO during calcination3Complete decomposition, therefore pure BaTiO used in the experiment3The fiber calcination temperature was 950 ℃.
By controlling BaTiO3Weight fraction, preparation of BaTiO3/g-C3N4Composite photocatalyst, mg-BaTiO3/(mg-g-C3N4+m BaTiO3) When the content of the compound photocatalyst is 20%, the target product is in a sheet-fiber combination state, the CNBT20 compound photocatalyst shows excellent photocatalytic activity for degrading rhodamine B (RhB) and TC under LED white light, the degradation rate of RhB reaches 99.5%, and the degradation rate of TC reaches 82.4%; while the kinetic constants are g-C3N48.75 and 5.77 times that of the nanoplatelets; the CNBT20 composite material was excellent in cycle stability and the crystal structure was unchanged after five cycles; experiments have confirmed that h+And O2-Is the main active species in the degradation process; the excellent photocatalytic activity of the CNBT20 composite material is mainly due to the fact that the photocatalytic activity of the CNBT20 composite material is improved in g-C3N4And BaTiO3A II-type heterojunction is constructed between the two layers, so that the separation of photon-generated carriers is promoted and the redox capability is enhanced; and secondly, a higher BET specific surface area is provided, active point sites are increased, so that the photocatalytic activity of the composite photocatalyst is enhanced, and a mechanism based on photo-generated carrier transfer in a photocatalytic degradation process is provided.
Claims (10)
1. Simple calcination method for preparing BaTiO3/g-C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg-g-C3N4+mBaTiO3) Less than or equal to 25 percent, to analyze pure melamine, tetrabutyl titanate Ti (OC) with the concentration of 98 percent4H9)4Solution, analytically pure barium acetate (CH)3COO)2Ba. The concentration is 36%The glacial acetic acid is taken as a raw material, analytically pure polyvinylpyrrolidone (PVP) and absolute ethyl alcohol are taken as a dispersing agent and a solvent, and a simple calcination method is adopted to prepare BaTiO3/g-C3N4Composite photocatalyst, wherein 5 percent is less than or equal to mg-BaTiO3/(mg-g-C3N4+mBaTiO3) Less than or equal to 25 percent, and the technical scheme is as follows:
firstly, accurately weighing 0.000-20.000 g of analytically pure melamine at room temperature of 25 ℃, placing the melamine in a semi-closed alumina crucible in air atmosphere, placing the crucible and a muffle furnace with the heating rate of 3 ℃/min, heating to 500-600 ℃, preserving heat for 0.0-5.0 h, then cooling to room temperature of 25 ℃ along with the furnace, grinding the obtained block clockwise for 5-20 min by using an agate mortar to obtain uniform light yellow powder, placing the obtained light yellow powder into absolute ethyl alcohol for 10-50 min by ultrasound, then placing the light yellow powder into a blast drying oven with the heating rate of 5 ℃/min, heating to 50-100 ℃ for drying, and keeping the temperature for 6.0-30.0 h to obtain g-C used for experiments3N4Powder;
secondly, grinding the block g-C obtained in the first step by using an agate mortar3N4Putting the mixture into a semi-closed alumina crucible, putting the semi-closed alumina crucible and the crucible into a muffle furnace with the heating rate of 5 ℃/min, heating to 100-550 ℃, preserving heat for 1.0-5.0 h, and carrying out secondary calcination to obtain the stripped g-C3N4(CN) nanosheets;
thirdly, preparing BaTiO by electrostatic spinning method3A fiber, adding 0.000-5.000 g of analytically pure PVP into 0.000-5.000 mL of absolute ethyl alcohol at the speed of 0.500-2.000 g/min, stirring for 1.0-5.0 h to obtain a solution A, and adding 0.000-5.000 mL of 98% tetrabutyl titanate Ti (OC) with the concentration of 0.000-5.000 mL4H9)4Slowly adding the solution into 1.000-5.000 mL of absolute ethyl alcohol at a speed of 0.500-2.000 mL/min, stirring at a speed of 100-500 r/min for 0.0-5.0 h to obtain a solution B, slowly adding the solution B into the solution A at a speed of 0.500-2.000 mL/min, stirring at a speed of 100-500 r/min for 0.0-5.0 h to form a solution C, and adding 0.000-5.000 g of analytically pure barium acetate (CH)3COO)2Ba is added into 5.000-10.000 mL of 10-50% glacial acetic acid solution at a rate of 0.500-2.000 mL/minSlowly adding the solution D into the solution C at the speed of 0.500-2.000 mL/min, stirring at the speed of 100-500 r/min for 1.0-5.0 h to obtain a precursor solution, performing a spinning process by using a spinning machine with the voltage of 15kV, the pipe diameter of 15mm and the speed of 1mL/h, allowing the obtained precursor solution to fall to a receiving plate under the action of a high-voltage electric field, wherein the length x width of the receiving plate is 40cm x 50cm, the material is a wood plate adhered with aluminum foil paper, the height of the solution from the receiving plate is 5-30 cm, drawing the precursor solution into fibers in the process to obtain the criss-cross composite fiber non-woven fabric, carefully taking down the fibers, drying in an ultrafine drying oven at the temperature of 50-100 ℃ for 12.0-72.0 h, and increasing the temperature at the speed of 5 ℃/min to obtain BaTiO after drying3/BaCO3Putting the composite fiber into a muffle furnace with the heating rate of 3 ℃/min again, heating to 500-1000 ℃ for calcining, and keeping the temperature for 1.0-5.0 h to finally obtain pure BaTiO3Fibers;
fourthly, weighing the g-C prepared in the second step at the room temperature of 25 DEG C3N40.200-0.500 g and 0.005-0.300 g BaTiO prepared in the third step3Grinding the mixture in an agate mortar for 20-50 min in a clockwise mode, then placing the mixture in a muffle furnace at the temperature of 200-500 ℃, heating the mixture at the rate of 3 ℃/min for 1.0-5.0 h to obtain BaTiO3/g-C3N4A composite photocatalyst is provided.
2. Preparation of BaTiO by a simple calcination method according to claim 13/g-C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg-g-C3N4+mBaTiO3) Less than or equal to 25 percent, a simple calcination method is adopted for processing for 1.0 to 5.0 hours at the temperature of 200 to 500 ℃, the heating rate is 3 to 5 ℃/min, the operation of preparing the product is simpler, the mass preparation can be realized at one time, and the mg-BaTiO is changed3/(mg-g-C3N4+mBaTiO3) The value of (A) is accurately controlled to form BaTiO3/g-C3N4The composite photocatalyst is added in an amount selected according to requirements, and the product performance is regulated and controlled.
3. Preparation of BaTiO by a simple calcination method according to claim 13/g-C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg-g-C3N4+mBaTiO3) Not more than 25 percent, and is characterized in that XRD diffraction analysis is carried out on the sample to prove that the sample composite photocatalyst respectively has CN and BaTiO3CN nanosheet has two characteristic peaks at θ 13.1 ° and 2 θ 27.2 °, corresponding to (100) and (002) crystal planes, respectively, the first characteristic peak (100) corresponding to the tri-triazine unit structure filling motif; the latter (002) characteristic peak is related to the deposition of CN, the phase structure of CN before and after thermal stripping is not changed, and BaTiO3Fibres, BaTiO prepared3Is a high-purity perovskite structure; to CN, BaTiO3And mg-BaTiO3/(mg-g-C3N4+mBaTiO3) SEM analysis of 20% composite photocatalyst CNBT20, the prepared CN had a two-dimensional layered structure, the surface of each layer had wrinkles, the thickness of each layer was about 1-20nm, and BaTiO was prepared3The diameter of the fiber is about 50-20nm, the fiber is partially broken due to the higher calcining temperature, and after grinding and calcining, the CNBT20 is formed by CN nano-sheets and BaTiO3The fibers are tightly combined together, and the CNBT20 contains CN and BaTiO by X-ray energy spectrum EDS analysis3The two materials are compounded together.
4. Preparation of BaTiO by a simple calcination method according to claim 13/g-C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg-g-C3N4+mBaTiO3) Less than or equal to 25 percent, and is characterized in that for CN and BaTiO3And CNBT20, CN and BaTiO were found by TEM analysis3And the shapes of the CNBT20 are respectively 2D nano-sheet, fiber and fiber-sheet composite, which correspond to the SEM image, and show that the prepared fiber-sheet composite structure is observed by observing the HRTEM image of the CNBT20 to see lattice fringes, and 0.28 of the crystal lattice fringes is found by analysisLattice fringes of 4nm and 0.325nm correspond to BaTiO, respectively3(101) And CN (002) crystal face, indicating BaTiO3And CN are physically compounded, which is beneficial to exerting the respective photocatalytic activity of the CN and the CN.
5. Preparation of BaTiO by a simple calcination method according to claim 13/g-C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg-g-C3N4+mBaTiO3) Less than or equal to 25 percent, characterized in that the sample is subjected to surface functional group analysis and Fourier infrared spectrum FT-IR spectrum test, for CN nano-sheets, at 812cm-1Is a characteristic vibration peak of the tri-triazine ring unit, 1200-1700cm-1The absorption peak at (A) is an aromatic ring C-N tensile vibration mode, 3000--1-NH of aromatic ring defect site2Or stretching vibration mode of-NH group for BaTiO3628cm for fibre-1The nearby peak corresponds to Ti-O stretching vibration for 1380cm-1The characteristic peak near corresponds to Ba-Ti-O stretching vibration and is in 3441cm-1And 1637cm-1Characteristic peaks indicate water molecule-OH tensile and flexural vibration modes, which have CN and BaTiO, respectively, for CNBT composites3Can sufficiently define CN and BaTiO3Are successfully combined together.
6. Preparation of BaTiO by a simple calcination method according to claim 13/g-C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg-g-C3N4+mBaTiO3) Less than or equal to 25 percent, and is characterized in that the visible light absorption performance is characterized by an ultraviolet-visible diffuse reflection spectrum UV-vis DRS spectrum, CN and BaTiO3Has absorption sidebands of 487nm and 403nm respectively, and shows that the CN has visible light response capability, can utilize part of visible light, and has BaTiO3It has no visible light response capability, and for CNBT composite material, its absorption sideband is between CN and BaTiO3And closer to the absorption threshold of CN, ofBy using Tauc plot for CN, BaTiO3And the forbidden band width Eg of CNBT20, the prepared samples are direct band gap semiconductors, the calculated band gap Eg values of CN, CdS and CNBT20 are 2.76eV, 2.81eV and 3.25eV respectively, and the result is mutually verified with the spectrum of UV-vis DRS.
7. Preparation of BaTiO by a simple calcination method according to claim 13/g-C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg-g-C3N4+mBaTiO3) Less than or equal to 25 percent, and is characterized in that all samples are excited by light with the wavelength of 380nm, a wide and strong emission peak appears near 460nm, the emission peak has higher PL emission peak intensity for pure CN, the recombination rate of the photo-generated electron-hole pair is very fast according to the nature of PL emission, the PL emission intensity is obviously reduced for CNBT composite photocatalyst, the photo-generated electron-hole separation efficiency of the composite photocatalyst is improved due to the formation of a heterojunction structure after the two substances are compounded together, wherein the PL emission intensity of the CNBT20 composite photocatalyst reaches the lowest, and when BaTiO is BaTiO3The PL emission intensity was somewhat lowered by adding more than 20 wt% mainly due to excessive BaTiO3The fibers inhibit the photocatalytic activity of CN itself, and thus, BaTiO is suitable3The introduction of the compound material has an effect of improving the separation efficiency of the photon-generated carriers, and meanwhile, the improvement of the separation efficiency of the photon-generated carriers is one of the reasons for improving the photocatalytic activity of the compound material.
8. Preparation of BaTiO by a simple calcination method according to claim 13/g-C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg-g-C3N4+mBaTiO3) Not more than 25%, characterized in that N is applied to the sample2Adsorption-desorption test, CN, BaTiO3And CNBT20 all have H3Calculating typical IV isotherms of the hysteresis loop to obtain CN and BaTiO3And the BET specific surface areas of CNBT20 were 16.37m2/g、26.09m2G and 33.08m2The BET specific surface area of CNBT20 is slightly increased compared to the pure catalyst, so the size of BET specific surface area is also an important factor affecting the photocatalytic performance, since the large BET specific surface area provides more active sites, thereby enhancing its photocatalytic activity.
9. Preparation of BaTiO by a simple calcination method according to claim 13/g-C3N4A method for preparing a composite photocatalyst, wherein the content of mg-BaTiO is less than or equal to 5%3/(mg-g-C3N4+mBaTiO3) Less than or equal to 25 percent, and is characterized by performing photocurrent response and electrochemical impedance EIS analysis, CN and BaTiO3And the intensity of photocurrent of the CNBT20 electrode remained stable in five on/off light periods, and the CN and BaTiO3Compared with the electrode, the CNBT20 electrode has excellent transient photocurrent response, CN and BaTiO3And the photocurrent densities of the CNBT20 electrodes were 0.088 muA/cm2、0.036μA/cm2And 0.517. mu.A/cm2The current density of the CNBT20 electrode is 5.9 times that of the CN electrode and is BaTiO314.4 times of the electrode, so the separation and transmission of the photogenerated electrons and holes of the CNBT20 composite photocatalyst are more effective because of the existence of CN and BaTiO3A heterojunction structure is constructed between the two layers so as to promote the separation and transfer of photon-generated carriers; for CN, BaTiO3And EIS Nyquist plot of CNBT20, the arc radius of the EIS Nyquist plot can also reflect the separation condition of semiconductor photo-generated electron-hole pairs, generally, the smaller arc radius represents the effective separation of the photo-generated electron-hole pairs, and the separation and transmission of photo-generated electrons and holes of the CNBT20 composite photocatalyst are verified to be more effective, and the result and the results of PL spectrum and photocurrent response spectrum both show that the separation efficiency of photo-generated carriers is improved, so that the improvement of the separation efficiency of the photo-generated carriers is an influence factor for enhancing the photocatalytic degradation activity of the photo-generated carriers.
10. Preparation of BaTiO by a simple calcination method according to claim 13/g-C3N4Method for preparing composite photocatalystWherein 5 percent is less than or equal to mg-BaTiO3/(mg-g-C3N4+mBaTiO3) Less than or equal to 25 percent, and is characterized in that tetracycline TC of 20mg/L and rhodamine B RhB dye of 5mg/L are used as degradation products to detect reactive species, disodium ethylene diamine tetraacetic acid EDTA-2Na, isopropanol IPA and p-benzoquinone BQ are respectively used for quenching cavity free radicals h+OH and superoxide radical O2-When EDTA-2Na and BQ are added into a sample, the degradation rate of RhB and TC is obviously reduced; in addition, when the IPA scavenger is added, the degradation rates of RhB and TC are not changed, so that the active species for photocatalytic degradation of RhB and TC of the CNBT composite photocatalyst are the same, namely O2-And h+(ii) a Determination of the flat band potential E of a photocatalyst using the Mott-Schottky curvefbCN and BaTiO3All slopes of (A) are positive, indicating that they are all n-type semiconductors, EfbThe value of (A) can be determined by the intersection of the slope with the x-axis, g-C relative to Ag/AgCl3N4And E of PIfbAre respectively-1.13V and-0.86V, CN and BaTiO3E of (A)VB1.63V and 2.39V respectively; the sample heterojunction structure is shown to be a staggered II-type heterojunction through reactive species, and for the heterojunction, under the condition of LED white light irradiation, photo-generated electrons e-And a cavity h+With CN and BaTiO3Separating e in CB of CN-Transfer to BaTiO3And BaTiO 2, and3h of VB+Transferring to VB of CN to reduce the separation of photo-generated electrons and holes, thereby improving the photo-catalytic activity of the photo-generated electrons; then, in BaTiO3/g-C3N4At the interface of the catalyst, an oxygen reduction reaction is carried out on the BaTiO3And a heterojunction is formed between the photocatalyst and CN, so that the separation efficiency of a photon-generated carrier can be improved, and the photocatalytic activity of the composite photocatalyst for degrading RhB/TC is enhanced.
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