CN110252353B - BiOI/Bi/TiO of ternary heterostructure2Composite photocatalytic material and preparation and application thereof - Google Patents
BiOI/Bi/TiO of ternary heterostructure2Composite photocatalytic material and preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 109
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- 239000002135 nanosheet Substances 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 23
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- 230000007547 defect Effects 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
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- 229910052740 iodine Inorganic materials 0.000 claims abstract description 8
- 239000011630 iodine Substances 0.000 claims abstract description 8
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- 238000001354 calcination Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
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- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
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- 239000003054 catalyst Substances 0.000 claims description 5
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- 238000001782 photodegradation Methods 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
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- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- LGPJVNLAZILZGQ-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCC[N+](C)(C)C LGPJVNLAZILZGQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
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- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a BiOI/Bi/TiO of a ternary heterostructure2Composite photocatalytic material, TiO2In order to expose the nano-sheet structure of the {001} crystal face and the {101} crystal face at the same time, oxygen vacancy and unsaturated Ti exist on the surface3+A defect site; the particle size of the BiOI is about 50-200 nm, and the BiOI is uniformly dispersed in the TiO2{001} crystal face; sandwiching metallic Bi particles between BiOI and TiO2Interface between the contacts. The preparation method comprises the following steps: firstly, preparing a crystal face which simultaneously exposes {001} and {101} crystal faces, and the surface of the crystal face has oxygen vacancy and unsaturated Ti3+TiO of defect sites2Nanosheets; then adding TiO2Adding the nanosheets and the bismuth source into the dispersed organic solution, dripping the organic solution containing the iodine source under vigorous stirring, and continuing stirring; transferring the mixture into a stainless steel high-pressure reaction kettle, and reacting for 12-36 h at the temperature of 140-170 ℃; cooling to room temperature, filtering, washing and vacuum drying. According to the invention, by TiO2The strong interaction between the metal Bi and the BiOI enhances the dispersibility of the BiOI, and the metal Bi is formed in situ between contact interfaces, so that the photon yield can be improved, and photo-generated electrons and holes have stronger redox capability and better catalytic activity.
Description
Technical Field
The invention belongs to the field of visible light photocatalytic materials, and particularly relates to a BiOI/Bi/TiO of a ternary heterostructure2A composite photocatalytic material and a preparation method and application thereof.
Background
Two-dimensional TiO co-exposing {001} and {101} crystal planes2The nanosheets have become TiO due to their unique photoproduction electron-hole pair separation capabilities2The research focus in the field of photocatalysis. However, TiO2Is a wide band gap (-3.2 eV) n-type semiconductor and can only be excited by ultraviolet light. In order to improve the light response capability in the visible light region, an effective method is to use TiO2A heterostructure catalyst is formed by recombination with a narrow bandgap semiconductor. Previously reported TiO2Among the basic heterostructure catalysts, metal-mediated heterojunctions (MMHs) are receiving much attention due to their high optical quantum yields. However, the preparation process of the metal-mediated heterostructure is relatively complex, and the metal involved is usually noble metal Au, Ag, Pd. The non-noble metal is used for replacing noble metal, and the development of the MMHs photocatalyst has important significance and is a current development trend.
BiOI is a narrow band gap (1.94eV) p-type semiconductor which can be excited by visible light, and the unique anisotropic layer structure is favorable for electron transport, so that the BiOI/TiO is constructed 2Suitable candidate materials for anisotropic heterostructures. However, in the actual preparation process, the BiOI is easy to agglomerate and grow into micron-sized independent microspheres, and the contact area of the heterojunction interface is greatly reduced. Furthermore, the quantum efficiency of BiOI is low due to electron-vacancyThe slow bulk transport of the hole counterparts results from the rapid recombination of the photogenerated carriers. By reducing the particle size of the BiOI, the particle size of the BiOI is improved2The dispersity of the nanosheets is realized, and the metal with a low Fermi level is introduced into a heterojunction interface to serve as a transmission medium of a photon-generated carrier, so that the defects are hopefully solved.
Disclosure of Invention
The invention aims to provide a simple and feasible BiOI/Bi/TiO with a ternary heterostructure2The preparation method and application of the composite photocatalytic material, and the BiOI/Bi/TiO with the ternary heterostructure synthesized by the method in one step2The composite photocatalytic material uses metal Bi to replace noble metals (Au, Ag, Pt and the like) as metal mediation to modulate the transfer path of photo-generated electrons and holes of the composite material and improve the separation efficiency of photo-generated electron hole pairs; the oxidation-reduction potential of the semiconductor material is adjusted, and the oxidation-reduction capability of the composite material is improved, so that the problems in the prior art are solved.
BiOI/Bi/TiO of ternary heterostructure2Composite photocatalytic material, TiO2In order to expose the nano-sheet structure of the {001} crystal face and the {101} crystal face at the same time, oxygen vacancy and unsaturated Ti exist on the surface3+A defect site; BiOI is uniformly dispersed in TiO2{001} crystal face; sandwiching metallic Bi particles between BiOI and TiO2Interface between the contacts. Based on TiO2Abundant oxygen vacancies and unsaturated Ti exist on the crystal face of the nano-sheet {001}3+Defect sites, which may be provided by TiO2And the BiOI, and the metal Bi is formed in situ between the contact interfaces. Titanium dioxide is made into a nano sheet, the exposed {001} high-energy surface defects are more, and in addition, the {001} crystal surface and the {101} crystal surface can form a surface heterojunction. Ti3+Is induced by oxygen vacancy, oxygen vacancy appears, oxygen atom is removed to leave two electrons, and the electrons are transferred to two adjacent Ti4+Into two Ti3+。 Ti3+Electrons can be given to play a role in reduction.
Further, the BiOI/Bi/TiO of the ternary heterostructure2The composite photocatalytic material simultaneously has BiOI, Bi and TiO2Three kinds of mattersAnd (4) phase(s).
The BiOI/Bi/TiO of the ternary heterostructure2The preparation method of the composite photocatalytic material mainly comprises the following steps:
(1) prepared TiO 2The nano sheet simultaneously exposes crystal faces of {001} and {101} and oxygen vacancy and unsaturated Ti exist on the surface3+A defect site;
(2) at the temperature of 26-28 ℃, TiO obtained in the step (1) is treated2Dispersing the nanosheets and the bismuth source in an organic solution, dropwise adding the organic solution containing the iodine source under vigorous stirring, and continuously stirring for 60-90 min; the stirring speed is 500-600 r/min
(3) Transferring the suspension obtained in the step (2) into a stainless steel high-pressure reaction kettle, controlling the temperature to be 140-170 ℃, and reacting for 12-36 h;
(4) cooling to room temperature, filtering to obtain a solid product, fully washing the product, and then drying in vacuum at 50-90 ℃ for 8-24 h; the washing is carried out by washing with absolute ethyl alcohol for 3-5 times and then with deionized water for 3-5 times.
Further, the TiO in the step (1)2The preparation of the nano sheet mainly comprises the following steps:
(S1) dropwise adding a morphology directing agent HF aqueous solution into a titanium source under the condition of violent stirring at 26-28 ℃, and keeping violent stirring for 60-120 min; the stirring speed is 500-1000 r/min;
(S2) transferring the mixed solution obtained in the step (S1) into a stainless steel high-pressure reaction kettle, controlling the temperature to be 180-240 ℃, and reacting for 12-36 hours;
(S3) cooling to room temperature, filtering to obtain a solid product, fully washing the product, and drying in vacuum at 50-90 ℃ for 8-24 h to obtain primary TiO with the surface containing F 2Nanosheets; washing is to wash the mixture for 3 to 5 times by using absolute ethyl alcohol and then wash the mixture for 3 to 5 times by using deionized water;
(S4) subjecting the F-containing primary TiO obtained in the step (S3) to2And placing the nanosheets in a tubular furnace, calcining and defluorinating at the temperature of 500-600 ℃, wherein the calcining atmosphere is air, inert or reducing atmosphere, and the calcining time is 2-4 h. The calcining atmosphere is air, helium, argon,One or more of nitrogen and hydrogen.
Further, the organic solvent comprises one or more of ethylene glycol, ethylene glycol monomethyl ether and glycerol; the bismuth source comprises one or more of bismuth nitrate pentahydrate, bismuth oxycarbonate and bismuth sulfate; the iodine source comprises one or more of potassium iodide, sodium iodide, and cetyltrimethylammonium iodide.
Further, the molar ratio of the bismuth source to the iodine source is 1: 1.
further, the HF and H2The volume ratio of O to the titanium source is 3: 2: 25.
further, the titanium source is one or more of tetrabutyl titanate, titanium tetrachloride and titanium isopropoxide.
The BiOI/Bi/TiO of the ternary heterostructure2The application of the composite photocatalytic material is characterized in that the composite photocatalytic material can be used as a catalyst for photodegradation of organic dye
Compared with the prior art, the invention is based on TiO 2Abundant oxygen vacancies and unsaturated Ti exist on the crystal face of the nano-sheet {001}3+Defect sites, using TiO2The strong interaction between the surface defect sites and the BiOI enhances the dispersibility of the BiOI and improves the dispersion in the BiOI and TiO2And metal Bi is formed in situ between the contact interfaces of the nano sheets. According to the invention, the metal Bi particles generated in situ are mediated by metal Bi instead of noble metals (Au, Ag, Pt and the like) as metals, so that the cost of introducing the metal in the middle layer is reduced, the transfer path of photo-generated electrons and holes of the composite material is modulated, and the separation efficiency of photo-generated electron-hole pairs is improved; the oxidation-reduction potential of the semiconductor material is adjusted, and the oxidation-reduction capability of the composite material is improved. The invention adopts a solvothermal synthesis method to construct the BiOI/Bi/TiO with a ternary heterostructure in one step2A composite photocatalytic material; the prepared composite material has the advantages of being different from the traditional BiOI/TiO2The electron transfer path of the binary heterostructure conforms to a Z-scheme electron transmission mechanism, can improve the light quantum yield of the material, and enables photoproduction electrons and holes to have stronger redox capability; compared with BiOI/TiO2The binary heterostructure has higher catalytic activity.
Drawings
FIG. 1 shows (a) TiO prepared in example 1, example 2 and example 3 2NBs、(b)TiO2MSs、 (c)TiO2NSs-a、(d)0.20BiOI/TiO2NBs、(e)0.20BiOI/TiO2MSs and (f)0.20BiOI/Bi/TiO2An X-ray powder diffraction spectrum of the NSs-a sample;
FIG. 2 shows (a) TiO fractions of samples obtained in example 1, example 2 and example 32NBs、(b)0.20 BiOI/TiO2NBs、(c)TiO2MSs、(d)0.20BiOI/TiO2MSs、(e)TiO2NSs-a, and (f)0.20BiOI/Bi/TiO2NSs-a field emission scanning electron microscope image;
FIG. 3 is a graph of the UV-visible diffuse reflectance spectra of samples made in example 1, example 2 and example 3;
FIG. 4 is a graph of the photocatalytic activity of samples prepared in example 1, example 2 and example 3;
FIG. 5 is a photoluminescence spectrum of samples prepared in example 1, example 2 and example 3;
FIGS. 6 (a) and (b) are 0.20BiOI/Bi/TiO samples obtained in example 12A transmission electron microscope image of the NSs-a ternary composite semiconductor photocatalytic material;
FIG. 7 is a 0.20BiOI/Bi/TiO scale obtained in example 12An X-ray photoelectron spectrum of the NSs-a ternary composite semiconductor photocatalytic material;
FIG. 8 is a 0.20BiOI/Bi/TiO scale obtained in example 12And (3) a free radical capture experimental activity diagram of the NSs-a ternary composite semiconductor photocatalytic material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
BiOI/Bi/TiO with molar ratio of Bi to Ti of 0.20:12A nano-sheet (calcined under air atmosphere) ternary composite semiconductor photocatalytic material.
(1) Mixing 9mL of HF (40 wt%) with 6mL of deionized water at 28 ℃, dropwise adding the mixture into 25mL of tetrabutyl titanate under the condition of vigorous stirring (500-1000 r/s), and keeping vigorous stirring for 60 min;
(2) transferring the suspension obtained in the step (1) into a 100mL stainless steel high-pressure reaction kettle, and reacting for 24h at 240 ℃;
(3) cooling to room temperature, filtering and collecting a solid product, washing with deionized water and absolute ethyl alcohol for 3-5 times respectively, and vacuum drying at 80 ℃ for 12 hours to obtain primary TiO with the surface containing F2A nanosheet;
(4) subjecting the primary TiO with the surface containing F obtained in the step (3)2Placing the nano-sheets in a tubular furnace for calcination and defluorination, and calcining for 2h at 500 ℃ in air atmosphere to obtain Ti with rich oxygen vacancies and unsaturated Ti on the surface3+TiO of defect sites2Nanosheets.
(5) 2mmol of TiO obtained in step (4) at 28 deg.C2Nanosheets and 0.4mmol Bi (NO)3)3·5H2Dispersing O in 20mL of glycol, dropwise adding a mixed solution of 20mL of glycol and 0.4mmol of KI under the condition of vigorous stirring (500-1000 r/s), and continuously stirring for 60 min;
(6) transferring the suspension obtained in the step (5) into a 100mL stainless steel high-pressure reaction kettle, and reacting for 24h at 160 ℃;
(7) and cooling to room temperature, filtering to obtain a solid product, washing with deionized water and absolute ethyl alcohol for 3-5 times respectively, and vacuum-drying at 80 ℃ for 12 hours. The resulting sample was named 0.20BiOI/Bi/TiO 2NSs-a。
0.20BiOI/Bi/TiO2The XRD spectrum of NSs-a is shown as f in figure 1, and the characteristic peaks appearing at 25.3 degrees, 37.8 degrees and 48.04 degrees are attributed to anatase phase TiO2The characteristic peaks appearing at 29.3 ° and 31.6 ° of (101), (004), and (200) planes of (b) are assigned to the (012) and (110) planes of the BiOI. The characteristic peak appearing at 27.1 ℃ is ascribed to the (012) face of metallic Bi, which indicates successful construction of BiOI/Bi/TiO2NSs-a ternary heterostructure. It is noted that d and e are BiOI/TiO, respectively2NBs and BiOI/TiO2XRD pattern of MSs, where no Bi metal is found, indicates two-dimensional TiO2Oxygen vacancy and unsaturated Ti unique to nanosheet surface3+The defect sites induce metallic Bi formation.
0.20BiOI/Bi/TiO2SEM spectra of NSs-a are shown in (c) and (d) of FIG. 2, and raw TiO2NSs-a simultaneously exposes two upper square 001 surfaces and eight surrounding 101 surfaces, and the surfaces are smooth and the edges and corners are clear; after loading BiOI, TiO2Many small particles (as indicated by circles in the figure) are grown on the NSs-a {001} plane, which is confirmed by TEM as BiOI, which has a particle size of only several tens of nanometers.
0.20BiOI/Bi/TiO2TEM spectra of NSs-a are shown in FIGS. 6(a) and 6(b), TiO2The spacing of the lattice fringes of NSs-a and BiOI is 0.355nm and 0.285nm, respectively, and the lattice fringes of metal Bi is 0.330 nm, which appear in BiOI and TiO 2Between the lattice fringes of NSs-a, the TiO is illustrated2NSs-a, BiOI and metal Bi exist in the composite material at the same time, and the metal Bi is included in the BiOI and the TiO2NSs-a.
0.20BiOI/Bi/TiO2XPS spectrum of NSs-a is shown in FIG. 7, and peaks at 457.5eV and 457.9eV are Ti in FIG. 7(a) and FIG. 7(b)3+The peak appearing at 531.8eV is a characteristic peak of oxygen vacancy in FIG. 7(d), indicating that TiO2Oxygen vacancy and unsaturated Ti exist on the surface of NSs-a3+A defect site. No characteristic peak of metal Bi was detected in FIGS. 7(e) and 7(f), since XPS detection is limited to a region of several nanometers in depth on the surface of the sample, and the surface layer does not have the characteristic peak of metal Bi, indicating that metal Bi is located in BiOI and TiO2Between the interlayers of NSs-a.
0.20BiOI/Bi/TiO2The UV-vis spectrum of NSs-a is shown in FIG. 3, which shows strong response to light in the range of 400-650nm, and still has response to light with wavelength longer than 650nm, compared with 0.20BiOI/TiO2NBs and 0.20BiOI/TiO2MSs exhibit better visible light absorption.
0.20BiOI/Bi/TiO2The photocatalytic activity of NSs-a is shown in FIG. 4, 0.20BiOI/Bi/TiO2NSs-a shows the optimal catalytic activity in the light degradation RhB reaction, and the degradation rate reaches 97.27 percent after 4 hours of illumination, which is obviously higher than 0.20BiOI/TiO 286.38% and 0.20BiOI/TiO of NBs286.60% of MSs.
0.20BiOI/Bi/TiO2The PL spectrum of NSs-a is shown in FIG. 5, 0.20BiOI/Bi/TiO2NSs-a has an emission intensity of less than 0.20BiOI/TiO2NBs-a and 0.20BiOI/TiO2MSs, description of BiOI/Bi/TiO2The ternary heterostructure can effectively inhibit photon-generated carrier recombination.
Example 2
TiO is prepared by the method reported in the literature2Nano belt, then 0.20BiOI/TiO is prepared2A nano-band binary composite semiconductor photocatalyst material.
(1) Under the condition of magnetic stirring (500-600 r/s) at 28 ℃, 0.4g of Degussa P25 is dispersed in 60mL of NaOH (10M) aqueous solution, and the mixture is magnetically stirred for 60 min;
(2) transferring the suspension obtained in the step (1) into a 100mL stainless steel high-pressure reaction kettle, and reacting for 72h at 180 ℃;
(3) and filtering and collecting solid precipitates, and washing the solid precipitates for 3-5 times by using deionized water and absolute ethyl alcohol respectively. The obtained solid precipitate is dispersed in 50mL of HCl (0.1M) aqueous solution again and stands for 48 h;
(4) filtering and collecting solid precipitate, washing with deionized water and absolute ethyl alcohol for 3-5 times respectively, vacuum drying at 80 ℃ for 12h, and calcining at 600 ℃ for 2h by using a muffle furnace to obtain TiO2A nanoribbon;
(5) 2mmol of TiO obtained in step (4) at 28 deg.C 2Nanobelt and 0.4mmol Bi (NO)3)3·5H2Dispersing O in 20mL of glycol, dropwise adding a mixed solution of 20mL of glycol and 0.4mmol of KI under the condition of vigorous stirring (500-1000 r/s), and continuously stirring for 60 min;
(6) transferring the suspension obtained in the step (5) into a 100mL stainless steel high-pressure reaction kettle, and reacting for 24h at 160 ℃;
(7) and cooling to room temperature, filtering to obtain a solid product, washing with deionized water and absolute ethyl alcohol for 3-5 times respectively, and vacuum-drying at 80 ℃ for 12 hours. The resulting sample was named 0.20BiOI/TiO2NBs
0.20BiOI/TiO2The XRD pattern of NBs is shown in FIG. 1, and the characteristic peaks appearing at 25.3 °, 37.8 ° and 48.04 ° are attributed to anatase phaseTiO2The characteristic peaks appearing at 29.3 ° and 31.6 ° are assigned to the (012) and (110) planes of the BiOI, and the peaks appearing at 44.3 ° can be assigned to the TiO2(B) This is due to incomplete crystallization during recrystallization. No diffraction peaks characteristic of metal Bi are present, indicating that the sample is BiOI/TiO only2NBs binary heterostructures.
0.20BiOI/TiO2SEM of NBs is shown in FIG. 2, in FIG. 2(a), pristine TiO2NBs have smooth and flat surfaces, generally 1-3 microns in length, varying widths of 50-300nm, and thicknesses of 25-40 nm; in FIG. 2(b), after supporting BiOI, TiO 2Growing a layer of BiOI thin slice with uneven size on the surface of the NBs.
0.20BiOI/TiO2The UV-vis profile of NBs is shown in FIG. 3, which shows a strong response between 400-650nm, but is weaker than 0.20BiOI/Bi/TiO2NSs-a, having no absorptive capacity for light having a wavelength greater than 650 nm.
0.20BiOI/TiO2The photocatalytic activity of NBs is shown in FIG. 4, 0.20BiOI/TiO2The degradation rate of NBs is 86.38%, which is lower than 0.20BiOI/Bi/TiO297.27% of NSs-a.
0.20BiOI/TiO2The PL spectrum of NBs is shown in FIG. 5, 0.20BiOI/TiO2NBs have the highest emission intensity and the most easily recombined photogenerated carriers.
Example 3
TiO preparation by methods reported in the literature2Preparing BiOI/TiO by using micron balls2A micron-sphere binary composite semiconductor photocatalyst material.
(1) 0.33mL of concentrated sulfuric acid (98%) and 0.3mL of H under the condition of magnetic stirring (500-600 r/s) at 28 DEG C2O, mixing, dropwise adding into a mixed solution of 15mL of tetrabutyl titanate and 75mL of absolute ethyl alcohol, and continuing to stir for 30min by magnetic force;
(2) transferring the suspension obtained in the step (1) into a 100mL stainless steel high-pressure reaction kettle, and reacting for 4h at 180 ℃;
(3) filtering to collect solid precipitate, washing with deionized water and anhydrous ethanol for 3-5 times, vacuum drying at 80 deg.C for 12 hr, and washing with horseCalcining the mixture for 2 hours at 600 ℃ in a muffle furnace to obtain TiO 2Micro-balls;
(4) 2mmol of TiO obtained in step (3) at 28 deg.C2Microspheres and 0.4mmol Bi (NO)3)3·5H2Dispersing O in 20mL of glycol, dropwise adding a mixed solution of 20mL of glycol and 0.4mmol of KI under the condition of vigorous stirring (500-1000 r/s), and continuously stirring for 60 min;
(5) transferring the suspension obtained in the step (4) into a 100mL stainless steel high-pressure reaction kettle, and reacting for 24h at 160 ℃;
(6) and cooling to room temperature, filtering to obtain a solid product, washing with deionized water and absolute ethyl alcohol for 3-5 times respectively, and vacuum-drying at 80 ℃ for 12 hours. The resulting sample was named 0.20BiOI/TiO2MSs
0.20BiOI/TiO2The XRD pattern of MSs is shown in figure 1, and the characteristic peaks appearing at 25.3 degrees, 37.8 degrees and 48.04 degrees are attributed to anatase phase TiO2The characteristic peaks appearing at 29.3 ° and 31.6 ° are assigned to the (012) and (110) planes of the BiOI. No diffraction peaks characteristic of metal Bi are present, indicating that the sample is BiOI/TiO only2An MSs binary heterostructure.
0.20BiOI/TiO2SEM of MSs is shown in FIG. 2, in FIG. 2(e), the original TiO2NBs 3-4 microns in diameter, composed of many fine TiO2The surface of the nano rod is provided with a plurality of pores and is relatively flat; in FIG. 2(f), after supporting BiOI, TiO2A layer of BiOI grows out of the MSs, the surface becomes very rough, and the pores are further enlarged.
0.20BiOI/TiO2The UV-vis profile of MSs is shown in FIG. 3, which shows a strong response between 400-650nm, but weaker than 0.20BiOI/Bi/TiO2NSs-a and 0.20BiOI/TiO2NBs, no absorption capability for light having a wavelength greater than 650 nm.
0.20BiOI/TiO2The photocatalytic activity of MSs is shown in FIG. 4, 0.20BiOI/TiO2The degradation rate of NBs is 86.60%, which is lower than 0.20BiOI/Bi/TiO297.27% of NSs-a.
0.20BiOI/TiO2The PL spectrum of MSs is shown in FIG. 5, 0.20BiOI/TiO2The emission intensity of NBs is higher than 0.20BiOI/Bi/TiO2NSs-a, the recombination capability of photogenerated carriers is stronger than 0.20BiOI/Bi/TiO2 NSs-a。
Example 4
The photodegradation rhodamine B is taken as a probe to carry out a cyclic experiment to probe the prepared 0.20BiOI/Bi/TiO2Photocatalytic activity of NSs-a. As shown in FIG. 4, the original BiOI and TiO2The catalytic effect of NSs-a is not ideal, only 65.52% and 51.84%. After loading BiOI, 0.20BiOI/Bi/TiO2The photodegradation efficiency of NSs-a is obviously higher than 0.20BiOI/TiO2NBs and 0.20BiOI/TiO2MSs, reaching 97.27%, indicating a ternary heterostructure BiOI/Bi/TiO2The catalytic activity of the composite photocatalytic material is superior to that of BiOI/TiO2A binary heterostructure.
Example 5
The benzoquinone, the isopropanol and the EDTA-2Na are respectively O2-OH and h+Investigating BiOI/Bi/TiO2An electron transmission mechanism of the nano-sheet ternary composite semiconductor photocatalytic material. As shown in FIG. 8, in FIGS. 8(a) and 8(b), the addition of EDTA-2Na resulted in the formation of the original BiOI and TiO 2The catalytic efficiency of NSs-a is greatly reduced, while the addition of benzoquinone and isopropanol to the original BiOI and TiO2The catalytic efficiency of NSs-a has little influence, which shows that+Is the main reactant species, O2-And OH plays little role due to BiOI and TiO2Is located below O2/·O2-Redox potential (-0.28 eV). In FIG. 8(c), the addition of benzoquinone greatly reduced by 0.20BiOI/Bi/TiO2Catalytic efficiency of NSs-a, whereas OH and h+The effect on catalytic efficiency is also enhanced, indicating that O2-Become the main reactive species due to BiOI/Bi/TiO2After the NSs-a heterostructure is formed, the valence band bending phenomenon, the conduction band and TiO of the BiOI occur2The valence band of NSs-a rises and falls respectively, and the oxidation-reduction potential of the conduction band of BiOI is more negative than that of O2/·O2-Has an oxidation-reduction potential of (-0.28eV), in which metal Bi plays a role in mediating electron transport, and TiO is formed after the catalyst is excited by light2On the conduction band of NSs-aThe photoproduction electrons are transferred to the valence band of the BiOI through the metal Bi to be compounded with the holes, and finally the electrons are enriched on the conduction band of the BiOI and adsorb O2Formation of O2-The holes are concentrated in TiO2On the valence band of NSs-a,. OH and h+The oxidizing ability of (a) is enhanced.
Example 6
The procedure of example 1 was followed to produce molar ratios of Bi to Ti of 0.10:1 and 0.30: 1 BiOI/Bi/TiO 2The ternary composite semiconductor photocatalytic material prepared by calcining the nanosheet (calcined under air atmosphere) was tested for degradation rate, and the results are shown in table 1. It can be seen from Table 1 that the highest degradation rate is obtained when the molar ratio of Bi to Ti is 0.20.
TABLE 1 BiOI/Bi/TiO with different Bi: Ti molar ratios2Comparison of degradation rates of nanosheets
Claims (9)
1. BiOI/Bi/TiO of ternary heterostructure2The composite photocatalytic material is characterized in that TiO2In order to expose the nano-sheet structure of the { 001 } crystal face and the { 101 } crystal face at the same time, oxygen vacancy and unsaturated Ti exist on the surface3+A defect site; BiOI is uniformly dispersed in TiO2{ 001 } crystal face; sandwiching metallic Bi particles between BiOI and TiO2Interface between the contacts;
the preparation method mainly comprises the following steps:
(1) prepared TiO2The nano sheet simultaneously exposes crystal faces of { 001 } and { 101 } and oxygen vacancy and unsaturated Ti exist on the surface3+A defect site;
(2) at the temperature of 26-28 ℃, the TiO obtained in the step (1) is treated2Dispersing the nanosheets and the bismuth source in an organic solution, dropwise adding the organic solution containing the iodine source under vigorous stirring, and continuously stirring for 60-90 min;
(3) transferring the suspension obtained in the step (2) into a stainless steel high-pressure reaction kettle, controlling the temperature to be 140-170 ℃, and reacting for 12-36 h;
(4) And cooling to room temperature, filtering to obtain a solid product, fully washing the product, and drying in vacuum at 50-90 ℃ for 8-24 h.
2. BiOI/Bi/TiO of the ternary heterostructure of claim 12The composite photocatalytic material is characterized in that the BiOI/Bi/TiO of the ternary heterostructure2The composite photocatalytic material simultaneously has BiOI, Bi and TiO2Three phases.
3. BiOI/Bi/TiO of the ternary heterostructure of claim 1 or 22The preparation method of the composite photocatalytic material is characterized by mainly comprising the following steps:
(1) prepared TiO2The nano sheet simultaneously exposes crystal faces of { 001 } and { 101 } and oxygen vacancy and unsaturated Ti exist on the surface3+A defect site;
(2) at the temperature of 26-28 ℃, the TiO obtained in the step (1) is treated2Dispersing the nanosheets and the bismuth source in an organic solution, dropwise adding the organic solution containing the iodine source under vigorous stirring, and continuously stirring for 60-90 min;
(3) transferring the suspension obtained in the step (2) into a stainless steel high-pressure reaction kettle, controlling the temperature to be 140-170 ℃, and reacting for 12-36 h;
(4) and cooling to room temperature, filtering to obtain a solid product, fully washing the product, and drying in vacuum at 50-90 ℃ for 8-24 h.
4. The method according to claim 3, wherein the TiO in the step (1) is2The preparation of the nano sheet mainly comprises the following steps:
(S1) dropwise adding a morphology directing agent HF aqueous solution into a titanium source under the condition of violent stirring at 26-28 ℃, and keeping violent stirring for 60-120 min;
(S2) transferring the mixed solution obtained in the step (S1) into a stainless steel high-pressure reaction kettle, controlling the temperature to be 180-240 ℃, and reacting for 12-36 hours;
(S3) cooling to room temperature, filtering to obtain a solid product, fully washing the product, and drying in vacuum at 50-90 ℃ for 8-24 h to obtain primary TiO with the surface containing F2A nanosheet;
(S4) subjecting the F-containing primary TiO obtained in the step (S3) to2And placing the nanosheets in a tubular furnace, calcining and defluorinating at the temperature of 500-600 ℃, wherein the calcining atmosphere is air, inert or reducing atmosphere, and the calcining time is 2-4 h.
5. The preparation method according to claim 3, wherein the organic solvent comprises one or more of ethylene glycol, ethylene glycol monomethyl ether, and glycerol; the bismuth source comprises one or more of bismuth nitrate pentahydrate, bismuth oxycarbonate and bismuth sulfate; the iodine source comprises one or more of potassium iodide, sodium iodide, and cetyltrimethylammonium iodide.
6. The method according to claim 3, wherein the molar ratio of the bismuth source to the iodine source is 1: 1.
7. the method according to claim 4, wherein the HF and the H are selected from the group consisting of2The volume ratio of the O to the titanium source is 3: 2: 25.
8. the preparation method according to claim 4, wherein the titanium source is one or more of tetrabutyl titanate, titanium tetrachloride and titanium isopropoxide.
9. BiOI/Bi/TiO of the ternary heterostructure of claim 1 or 22The application of the composite photocatalytic material is characterized in that the composite photocatalytic material is used as a catalyst for photodegradation of organic dyes.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785280A (en) * | 2015-04-14 | 2015-07-22 | 济南大学 | Flaky titanium dioxide/bismuth oxybromide composite photocatalyst and preparation method thereof |
| CN104874811A (en) * | 2015-05-22 | 2015-09-02 | 武汉工程大学 | Preparing method of simple substance bismuth/bismuth compound nanocomposite with oxygen vacancies |
| CN109550509A (en) * | 2018-12-11 | 2019-04-02 | 常州大学 | A kind of preparation method of Bi/BiOBr/RGO composite photo-catalyst and products thereof and application |
| CN109550513A (en) * | 2017-09-27 | 2019-04-02 | 天津大学 | A kind of preparation method and application of the titania nanotube heterojunction material of compound bismuth oxygen bromine |
-
2019
- 2019-07-02 CN CN201910588774.3A patent/CN110252353B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785280A (en) * | 2015-04-14 | 2015-07-22 | 济南大学 | Flaky titanium dioxide/bismuth oxybromide composite photocatalyst and preparation method thereof |
| CN104874811A (en) * | 2015-05-22 | 2015-09-02 | 武汉工程大学 | Preparing method of simple substance bismuth/bismuth compound nanocomposite with oxygen vacancies |
| CN109550513A (en) * | 2017-09-27 | 2019-04-02 | 天津大学 | A kind of preparation method and application of the titania nanotube heterojunction material of compound bismuth oxygen bromine |
| CN109550509A (en) * | 2018-12-11 | 2019-04-02 | 常州大学 | A kind of preparation method of Bi/BiOBr/RGO composite photo-catalyst and products thereof and application |
Non-Patent Citations (2)
| Title |
|---|
| Improved solar-driven photocatalytic performance of BiOI decorated TiO2 benefiting from the separation properties of photo-induced charge carriers;Jianzhang Li等;《Solid State Sciences》;20151224;第52卷;第106-111页 * |
| Photocatalytic Reduction of CO2 in Isopropanol on Bi2S3 Quantum Dots/TiO2 Nanosheets with Exposed {001} Facets;Yuwen Wang等;《J. Nanosci. Nanotechnol.》;20171231;第17卷(第3期);第1863-1869页 * |
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