CN115301225A - Preparation method and application of bismuth/titanium dioxide photocatalytic degradation material with hollow microsphere structure - Google Patents
Preparation method and application of bismuth/titanium dioxide photocatalytic degradation material with hollow microsphere structure Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 239000004005 microsphere Substances 0.000 title claims abstract description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 71
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title description 9
- 229940036359 bismuth oxide Drugs 0.000 title description 9
- 229910000416 bismuth oxide Inorganic materials 0.000 title description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 title description 8
- 230000001699 photocatalysis Effects 0.000 claims abstract description 41
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 23
- 229940012189 methyl orange Drugs 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001016 Ostwald ripening Methods 0.000 description 2
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
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- B01J35/39—
-
- B01J35/51—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses Bi-doped TiO with hollow microsphere morphology 2 A method for synthesizing a photocatalytic material. The material is TiO with a hollow microsphere shape structure 2 The bismuth-doped TiO is prepared by taking a semiconductor material as a precursor and adopting a dipping roasting method 2 A hollow microsphere structural material; the material has large surface area, can provide a large number of photocatalytic active sites and adsorb more organic matters such as methyl orange and the like in aqueous solutionContaminant, and at the same time, bi is doped to TiO 2 The light response range of the microsphere is widened to a visible light region, the energy required by the generation of oxygen vacancies on the surface of the microsphere is reduced, and therefore more photo-generated electrons are excited. Moreover, the Bi-doped TiO with the hollow microsphere shape prepared by the invention 2 The material is proved to have better Methyl Orange (MO) degradation effect. In addition, the preparation method has mild process conditions and low cost, is suitable for large-scale production and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of semiconductor photocatalytic materials, and particularly relates to a titanium dioxide composite material with a hollow microsphere structure, which can improve the activity of visible light photocatalytic degradation pollutants, and a preparation method and application thereof.
Background
With the rapid development of social economy, the problems of energy shortage, environmental pollution and the like are increasingly shown. As a new technology, the semiconductor photocatalysis technology not only can decompose water to produce hydrogen as clean energy by photocatalysis, but also can degrade pollutants by photocatalysis, and is more and more concerned by people. The synthesis method of the photocatalytic material is one of the key factors for determining the performance and application value of the photocatalytic material, and the photocatalytic material synthesized by different approaches has certain influence on the aspects of structure, morphology, size and the like, and the influence further causes the difference of the photocatalytic performance.
Ma et al prepared a visible light photocatalytic Bi-TiO 2 The material SBA-15 is subjected to research of light reduction RhB, and experimental results show that proper bismuth doping can enhance photocurrent through reduced electron-hole recombination and improve photocatalytic activity under visible light through reduction of band gap, but the prepared material does not produce a special shape structure, and the preparation process involves three steps of synthesis of SAB-15, tiO2/SAB-15 and Bi-TiO2/SBA-15, and is relatively complex and not suitable for industrial production; zeng et al devised an aqueous synthesis method to produce hollow nanospheres of tin 4+ doped anatase and rutile titanium dioxide with high homogeneity. By adjusting TiF 4 And SnF 4 To adjust the Sn content in the nanospheres. Analysis shows that as the doping concentration increases, sn 4+ Ions can be linearly incorporated into the titanium dioxide lattice with a phase transition from anatase to rutile, during which emphasis is placed on the role of the ostwald ripening mechanism, which is considered to be a simple template-free alternative to the preparation of hollow nanostructures, and they do not investigate their visible photocatalytic activity; in patent CN106395890A, sodium metavanadate, titanyl sulfate and urea are added in a one-step hydrothermal synthesis methodReacting the autoclave with water, cooling, filtering, washing and drying; the vanadium-doped titanium dioxide ultrathin hollow structure microspheres are obtained after calcination, and the advantages are that the materials are synthesized in one step, but the calcination temperature and time only give range values and are not accurate, and the photocatalytic performance test is not carried out; CN107308941A uses nickel nitrate as doping source and utilizes template method to obtain porous TiO 2 The doping amount of the hollow spheres and the nickel is respectively adjusted within the range of 0.1-5%, the synthesis steps are complicated, the photocatalytic performance test is not carried out, and the method is not suitable for industrial production.
In the present invention, we first propose to use TiO as the material 2 The hollow microspheres are used as precursors to prepare Bi-doped TiO with different concentrations by adopting a simple impregnation roasting method 2 A photocatalytic semiconductor material of hollow microspheres and application thereof in photocatalytic degradation of Methyl Orange (MO).
Disclosure of Invention
The invention aims to provide a preparation method of a bismuth-doped hollow microsphere morphology titanium dioxide nano material, which has the advantages of simple process, convenience in operation, suitability for large-scale production and the like. The synthesized titanium dioxide with the hollow microspherical morphology has higher activity in the aspect of photocatalytic degradation of methyl orange pollutants. Firstly, the titanium dioxide nano material with the hollow microspherical structure has larger surface area, can provide a large amount of photocatalytic reaction active sites and adsorb more organic pollutants in aqueous solution; second, doping of Bi by doping in TiO 2 Interstitial or substituted TiO in crystal lattice 2 Ti in the crystal 4+ Mixing TiO with 2 The range of the photo-response of (a) is widened to the visible region, so that more visible light can be absorbed and more photo-generated electrons can be excited. Meanwhile, the p track with spatial anisotropy and the hybridized s-p track can generate a high dispersion energy band structure, so that the mobility of a photon-generated carrier can be improved, and the separation and transfer of photon-generated charges in the photocatalysis process can be enhanced; finally, the metal doping also changes the original TiO 2 The recombination rate of electron and hole pairs is reduced, thereby enabling TiO to be formed 2 The hydroxyl free radical with strong oxidizability in the product can not be deactivated and improvedThe performance of photocatalysis is ensured, so that the high efficiency of the photocatalysis reaction is ensured.
In order to achieve the purpose, the invention adopts the following technical scheme:
Bi-TiO containing hollow microspherical morphology 2 The composite photocatalytic material is prepared through preparing semi-conductor titania material with hollow microsphere structure, soaking and roasting titania material to prepare different concentration dopings in the atomic ratio of R Bi ) Bi-TiO of (2) 2 The composite photocatalysis material has a hollow microspherical structure in the final shape.
The method comprises the following specific steps:
adding 0.01mol of Ti (SO) 4 ) 2 Adding into 150ml distilled water, and vigorously stirring with magnetic stirrer for 30 min; then 0.01mol of NH is added 4 F and 0.02mol of urea are stirred for 30min again; putting the mixed solution into a high-pressure kettle with 200ml of polytetrafluoroethylene as a lining, and carrying out hydrothermal treatment at 180 ℃ for 12 h; centrifuging the white precipitate, and washing with distilled water and ethanol; and drying the washed product in a vacuum oven at 80 ℃ for 6 hours to obtain the titanium dioxide with the hollow microsphere shape.
With the prepared TiO 2 The hollow microsphere is used as a precursor, and a dipping roasting method is adopted to prepare Bi-doped TiO 2 Hollow microspheres: dispersing 0.2g of titanium dioxide powder into 25ml of powder containing 2M HNO 3 Adding bismuth source Bi (NO) in an atomic ratio to the aqueous solution of (to improve the solubility of bismuth nitrate in water) 3 ) 3 (ii) a The mixed solution was stirred continuously vigorously at 90 ℃ until dried. The dried sample was then calcined in air at 500 ℃ for 3 hours. Bi and Ti (R) Bi ) Are 0, 0.1, 0.5 and 0.75 atoms, respectively. With R Bi The color of the calcined sample slightly changes from white to light yellow, namely the material is obtained. Then Bi (NO) 3 ) 3 Annealing at 500 ℃ for 3h in the air directly to prepare Bi for photocatalytic comparison 2 O 3 。
The invention claims a hollow microspherical structure semiconductor photocatalyst prepared by the method and application of the material as degradation Methyl Orange (MO).
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention prepares Bi-TiO with hollow microspherical structure 2 The photocatalyst method comprises two steps, firstly synthesizing titanium dioxide with a hollow microsphere morphology structure, then preparing the titanium dioxide photocatalyst with different concentrations of Bi doped hollow microsphere morphology by taking the titanium dioxide as a precursor and adopting an immersion roasting method. No organic or inorganic dissolution is added in the synthesis process, so that the idea of directly synthesizing the product and improving the photocatalytic hydrogen production activity can be popularized in the field of photocatalysis.
(2) The preparation method of the hollow microspherical bismuth/titanium dioxide photocatalyst has the characteristics of mild process conditions, simplicity and convenience in operation, suitability for large-scale production and the like.
(3) The Bi-TiO with hollow microspherical appearance prepared by the invention 2 The semiconductor material improves the activity of photocatalytic degradation of pollutants. First, bi-TiO of hollow microspherical structure 2 The semiconductor material has larger specific surface area, which is beneficial to exposing more photocatalytic active sites and adsorbing more organic pollutants such as methyl orange and the like in the aqueous solution; second, doping of Bi by doping in TiO 2 Interstitial or substituted TiO in crystal lattice 2 Ti in the crystal 4+ Adding TiO to 2 The range of photoresponse of (a) is broadened into the visible region so that more visible light can be absorbed and more photogenerated electrons can be excited. And the research finds that the original TiO is changed by metal doping 2 The recombination rate of electron and hole pairs is reduced, thereby enabling TiO to be formed 2 Hydroxyl free radicals with strong oxidizability cannot be inactivated, and the performance of photocatalysis is improved, so that the high efficiency of photocatalysis reaction is ensured; the specific principle is that under the irradiation condition of simulated sunlight, bi-TiO 2 The photocatalyst is excited by illumination to generate photoproduction electrons and holes, through the transmission action of current carriers, electrons on a valence band of the titanium dioxide photocatalyst migrate to a conduction band position, and the holes are remained at the valence band position, so that the photoproduction electrons and the holes are effectively separatedElectrons in the conduction band under the action of an electric field (e) - ) Can form superoxide radical (O) with some oxidizing substances 2- ) And hydroperoxy radical (. HO) radical 2 ) And holes (h) left in the valence band + ) Will also oxidize H 2 The O molecule generates a large amount of hydroxyl radicals (. OH) having strong activity and strong oxidizing property. The hydroxyl free radicals can react with pollutants in the sewage, and the reaction mechanism is mainly addition reaction or hydrogen substitution reaction with unsaturated double bonds and triple bonds of the hydroxyl free radicals. In photocatalytic degradation, strongly oxidizing hydroxyl radicals (. OH) and superoxide radicals (. O) 2- ) Can react with pollutants in the wastewater for oxidation and reduction, so that the pollutants are decomposed into non-toxic small molecular substances such as H which do not pollute the environment 2 O、CO 2 And the like. Because the titanium dioxide photocatalytic material is in a hollow microspherical shape, more specific surface area and active reaction sites can be provided in the reaction process, so that water molecules can be in full contact reaction with the titanium dioxide photocatalytic material, and the titanium dioxide photocatalytic material has considerable photocatalytic activity in the pollutant degradation process.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the photocatalyst system prepared in example 1;
FIG. 2 shows example 1, R Bi Bi-TiO of =0.5 2 Scanning Electron Microscope (SEM) images of the composite photocatalytic material;
FIG. 3 shows Bi-TiO prepared according to example 1 2 Ultraviolet-visible absorption spectrum of the photocatalyst system;
FIG. 4 shows the degradation efficiency of Methyl Orange (MO) by photocatalyst under visible light irradiation in example 1;
the specific implementation mode is as follows:
the technical solution of the present invention will be further described in detail with reference to specific examples. It should be understood that the examples are for the purpose of further illustrating the subject matter of the invention and should not be construed in any way as limiting the scope of the invention.
Example 1:
Bi-TiO 2 preparation of hollow microsphere morphology composite photocatalytic materialThe preparation method comprises the following steps:
1.1 adding 0.01mol of Ti (SO) 4 ) 2 Adding into 150ml distilled water, stirring vigorously with magnetic stirrer for 30min, adding 0.01mol NH 4 F and 0.02mol of urea are treated for 30min to prepare a mixed precursor solution;
1.2 putting the mixed solution into an autoclave with 200ml of polytetrafluoroethylene as a lining, carrying out hydrothermal treatment at 180 ℃ for 12h, carrying out centrifugal separation on white precipitates after the hydrothermal treatment, and washing with distilled water and ethanol;
1.3 drying the washed product in a vacuum oven at 80 ℃ for 6 hours, and grinding the dried product to obtain the titanium dioxide material with the hollow microsphere shape.
2.1 dispersing 0.2g of titanium dioxide powder into 25ml of 2M HNO 3 In an aqueous solution of (to improve the solubility of bismuth nitrate in water), and in an atomic ratio (R) Bi ) Adding Bi (NO) 3 ) 3 The mixed solution is stirred vigorously at 90 ℃ until being dried;
2.2 the dried sample is calcined in air at 500 ℃ for 3 hours to obtain the different R Bi The bismuth/titanium dioxide composite photocatalytic material. Bi and Ti (R) Bi ) Are 0, 0.1, 0.5 and 0.75 atoms, respectively. With R Bi The color of the calcined sample is slightly changed from white to light yellow;
2.3 adding Bi (NO) 3 ) 3 Directly annealing for 3 hours at 500 ℃ in the air to prepare Bi for photocatalytic comparison 2 O 3 。
In order to verify the performance improvement of the bismuth/titanium dioxide composite material relative to titanium dioxide, the material obtained in the above example 1 was subjected to an activity experiment of photocatalytic degradation of Methyl Orange (MO) aqueous solution, which specifically includes the following steps:
(1) 0.1g of Bi in TiO 2 The hollow microspheres are dispersed in the concentration of 4 multiplied by 10 -5 M in 25mL MO in water, placed in a 9.0cm petri dishThe preparation method comprises the following steps of (1) performing;
(2) Placing a 300W xenon lamp at a position 20cm away from the reaction solution as a visible light source to trigger the photocatalytic reaction;
(3) And (3) completely filtering ultraviolet light with the wavelength of less than 420nm by using an ultraviolet filter. The solution was allowed to reach adsorption-desorption equilibrium between the photocatalyst, MO and water for 30 minutes before irradiation with visible light. The MO concentration was measured with an ultraviolet-visible spectrophotometer (UV-2550, shimadzu, japan);
(4) After a period of irradiation with visible light (every 0.5 h), the reaction solution was taken out and the change in the concentration of MO was measured. Because the MO solution has low concentration, the photocatalytic decolorization process is a quasi-first-order reaction which can be expressed as ln (C) 0 /C) = kt, where k is the apparent rate constant, C 0 And C is the concentration of MO at t =0 and t = t, respectively.
From fig. 1, it can be seen that XRD patterns between 0.01 and 0.1 of Bi doping of the sample prepared in example 1 all show the crystal structure of titanium dioxide; the XRD spectrum peak doped above 0.1 corresponds to the crystal structure of bismuth oxide, which shows that the crystal structure of the material is changed along with the increase of the doping ratio.
FIG. 2 shows example 1, R Bi Bi-TiO of =0.5 2 Scanning Electron Microscope (SEM) images of the composite photocatalytic material; as can be seen, the bismuth/titanium dioxide composite photocatalyst with the hollow microsphere morphology is successfully prepared.
FIG. 3 shows Bi-TiO prepared according to example 1 2 The ultraviolet-visible absorption spectrum of the photocatalyst system; it can be seen that the absorption band edge red-shifted with the loading of bismuth oxide.
Fig. 4 shows the degradation efficiency of Methyl Orange (MO) on the photocatalysts with different atomic ratios in example 1, and it can be seen that the degradation efficiency of the composite material with all doping ratios is greatly improved compared with that of titanium dioxide, thus demonstrating the superiority of the material prepared by the present invention.
It should be noted that the above-described embodiments are intended to provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the invention in any way. Thus, it will be understood by those skilled in the art that the present invention may be modified and equivalents may be substituted; all technical solutions and modifications thereof which do not depart from the spirit and technical essence of the present invention should be covered by the scope of the present patent.
1.Ma,J.；Chu,J.；Qiang,L.S.；Xue,J.Q.Synthesis and structural characterization of novel visible photocatalyst Bi-TiO 2 /SBA-15and its photocatalytic performance.Rsc Adv.2012,2(9),3753-3758.
2.Li,J.；Zeng,H.C.Hollowing Sn-doped TiO 2 nanospheres via ostwald ripening.J. Am.Chem.Soc.2007,129(51),15839-47.
Claims (5)
1. Bi-TiO with hollow microspherical morphology structure prepared by taking titanium dioxide semiconductor material with hollow microspherical morphology as precursor and adopting dipping roasting method 2 The composite photocatalytic material is characterized in that the material is prepared by calcining a titanium dioxide precursor, wherein no organic or inorganic solvent is added in the synthesis process, and the material has a hollow microspherical structure.
2. The method for preparing the composite material according to claim 1, characterized by comprising the steps of:
adding 0.01mol of Ti (SO) 4 ) 2 Adding 150ml distilled water, and vigorously stirring with a magnetic stirrer for 30 min; then 0.01mol of NH is added 4 F and 0.02mol of urea are stirred for 30min again; putting the mixed solution into a high-pressure kettle with 200ml of polytetrafluoroethylene as a lining, and carrying out hydrothermal treatment at 180 ℃ for 12 hours; centrifuging the white precipitate, and washing with distilled water and ethanol; and drying the washed product in a vacuum oven at 80 ℃ for 6 hours, and grinding to obtain the titanium dioxide material with the hollow microsphere shape.
3. The method of claim 2, comprising the steps of:
dispersing 0.2g of the powder obtained in claim 2 into 25ml of a solution containing 2M HNO 3 In an aqueous solution of (to improve the solubility of bismuth nitrate in water), in an atomic ratio (R) Bi ) Adding Bi (NO) 3 ) 3 (ii) a The mixed solution is continuously stirred vigorously at 90 ℃ until being dried; the dried sample was then calcined in air at 500 ℃ for 3 hours; bi and Ti (R) Bi ) Are 0, 0.1, 0.5 and 0.75 atoms respectively, with R Bi The color of the calcined sample slightly changes from white to light yellow, namely the material is obtained.
4. Bi-TiO with hollow microspheroidal morphology prepared according to the process of claims 2-3 2 A composite photocatalyst.
5. The Bi-TiO compound of claim 4 having a hollow microspheroidal morphology 2 The application of the composite photocatalytic material is characterized in that the material is applied to the photodegradation of Methyl Orange (MO) as a photocatalyst.
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