CN116251608A - ZnO/Bi/BiOBr photocatalyst capable of efficiently degrading organic dye and simultaneously producing hydrogen and preparation method thereof - Google Patents
ZnO/Bi/BiOBr photocatalyst capable of efficiently degrading organic dye and simultaneously producing hydrogen and preparation method thereof Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 25
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000000593 degrading effect Effects 0.000 title claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 title description 2
- 238000006731 degradation reaction Methods 0.000 claims abstract description 27
- 230000015556 catabolic process Effects 0.000 claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 241001506047 Tremella Species 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 97
- 239000011787 zinc oxide Substances 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 20
- 229940043267 rhodamine b Drugs 0.000 claims description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
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- 239000002243 precursor Substances 0.000 claims description 12
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- 229940012189 methyl orange Drugs 0.000 claims description 7
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 7
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
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- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000011068 loading method Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract 1
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- 238000007146 photocatalysis Methods 0.000 description 7
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- 239000011701 zinc Substances 0.000 description 3
- -1 Bi(NO 3 ) 3 ·5H 2 O Chemical compound 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
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- B01J35/39—
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
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- 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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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
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Abstract
The invention relates to a ZnO/Bi/BiOBr photocatalyst capable of degrading dye and simultaneously producing hydrogen and a preparation method thereof, belonging to the technical fields of nano material preparation, environmental management, new energy and the like. The tremella ZnO/Bi/BiOBr photocatalyst is prepared. h is a + OH and dye molecules are gathered on porous ZnO to promote dye degradation to occur on ZnO, while electrons are gathered on BiOBr to promote photolysis of water to produce hydrogen, thereby realizing simultaneous production of photodegraded dyeHydrogen. Completely degrading RhB in 2 min under visible light; degradation was completed in 120 min under the sun. 1674.4. Mu. Mol.g in RhB solution without methanol sacrificial agent under visible light ‑1 ·h ‑1 Hydrogen production efficiency of (a). The preparation material has excellent performance, good appearance, simple and easy preparation method, mass production and wide application prospect in the field of photocatalytic materials.
Description
Technical Field
The invention relates to the technical fields of nano material preparation, environmental management, new energy sources and the like, in particular to a ZnO/Bi/BiOBr photocatalyst capable of efficiently degrading organic dye and simultaneously producing hydrogen and a preparation method thereof.
Background
The environmental and energy problems are two major problems to be faced by human beings, so that the problems are more and more emphasized, and the application of the photocatalysis technology in the fields of environmental treatment and clean energy provides new hopes for solving the two major problems, and the photocatalysis technology becomes a hot research hot spot in recent years. The development of photocatalysis technology and corresponding novel catalysts is still the main development direction of catalysis technology. Due to the continuous innovation of the photocatalysis technology, the degradation of organic pollutants and the water decomposition and hydrogen production by solar energy drive are one of the hottest topics at present. However, in the field of photocatalysis, the utilization rate of solar energy still does not achieve an ideal effect. The key of solving the problem is that: 1) The light absorption range is widened, and the separation efficiency and the photocatalytic activity of photo-generated electrons and holes are improved; 2) Searching for a quick and effective method for preparing the photocatalyst; 3) A photocatalyst capable of being repeatedly used and maintaining good circulation stability is developed. According to the existing theory that,the photodegradation and photodecomposition of water are in competition, and both consume active radicals (including O - ，·O 2- ，·O 2 - ，e - ，h + And OH, etc.), this must be eliminated. The concept of using organic molecules with electron donor properties as sacrificial agents for producing hydrogen by photolytic water has been proposed in the past, but so far, the more successful research effort has been mainly focused on typical electron donor organics such as carboxylic acids and alcohols. For relatively difficult degradation, research on hydrogen production in the degradation process of organic dyes with more serious water damage is relatively dispersed, and a theoretical system of a system is not formed to support the development in the direction. If multiple functions such as photocatalysis, adsorption degradation and photodecomposition of water of dye can be realized, hydrogen energy can be generated while sewage treatment is realized, the current situation that only money is burned and profit is not achieved in the sewage treatment process is changed, the cost is further saved, and secondary pollution is avoided. Has wide application prospect in the industries of sewage treatment, pesticide removal and degradation, and the like in the industries of printing and dyeing, pharmacy, petrochemical industry, papermaking, publishing, and the like.
In recent years, the novel photocatalyst bismuth oxyhalide (bisx, x=cl, br, I) has received close attention from a large number of researchers because of its suitable bandgap, low cost, and layered structure. The crystal structure of BiOX is composed of double X － Layer [ Bi ] 2 O 2 ］ 2+ The layers are alternately arranged along the c-axis, and the special lamellar structure ensures that the BiOX has excellent degradation performance and good photocatalytic activity. As a V-VI-VII ternary oxide semiconductor, the BiOX nanomaterial has the advantages of high catalytic activity, simple preparation process, low environmental toxicity, good stability, faster electron-hole separation rate, more active sites and the like, and is widely researched in the aspects of environmental management and energy conversion. Although the bisox photocatalyst exhibits excellent performance in photocatalytic reactions, its photocatalytic efficiency has yet to be improved. In order to further improve the photocatalytic performance of the BiOX photocatalyst, the requirements of practical application under sunlight are met, and the process still needs to be continuedImproving the light absorption capacity, the separation and transportation efficiency of the photo-generated carriers and the exposure of the active sites. The BiOCl band gap is the widest in BiOX photocatalysts containing different halogen elements, and has the highest response under ultraviolet light, and is even better than the traditional photocatalysts; the BiOI band gap is narrowest; the BiOBr band gap is between the two, and the best photocatalytic performance is achieved under full spectrum irradiation. In addition, the higher valence band position of the bilbr, compared to conventional catalysts, suggests a broader light absorption and a higher oxidation capacity.
ZnO is used as a traditional photocatalyst, has the advantages of no toxicity, low cost, easy preparation, high catalytic activity and the like, and is used as a direct wide band gap n-type semiconductor (Eg=3.27 eV), the exciton binding energy is up to 60 meV, hole-electron pairs can be generated when ultraviolet light with the wavelength of 386 nm is irradiated, and the photo-generated holes and H 2 O、OH - The reaction generates strong oxidizing OH which can degrade pollutants into H without selectivity at normal temperature 2 O、CO 2 And some inorganic ions, so that the catalyst has better application in the photocatalysis direction. However, znO has certain disadvantages, on the one hand, the optical response of ZnO is mainly in the uv region; on the other hand, the recombination rate of ZnO electron-hole pairs is high. In order to solve the problems and improve the activity of the catalyst, methods such as morphology modulation, heterojunction construction, noble metal doping and the like are generally adopted. The BiOBr serving as a novel photocatalyst has wider light absorption and higher oxidizing capability, is suitable for constructing a heterojunction with the traditional photocatalyst ZnO, utilizes reduced Bi simple substances to replace noble metals (Ag, au, pt and the like) in construction, exerts the plasma resonance (SPR) effect, constructs a typical Z-type heterojunction, effectively avoids the recombination of electrons and holes, enhances the absorbing capability of visible light, and can effectively improve the photocatalytic performance.
The invention discloses a ZnO/Bi/BiOBr photocatalyst capable of efficiently degrading organic dye and producing hydrogen, which is characterized in that Cetyl Trimethyl Ammonium Bromide (CTAB) is adopted as a bromine source of BiOBr, ethylene glycol is adopted as a reducing agent generated by Bi quantum dots, the prepared ZnO/Bi/BiOBr photocatalyst presents tremella shape, needle-shaped BiOBr is distributed among sheet layers of tremella structure, and the BiOBr tableThe quantum dots with the surface uniformly dispersed with simple substance Bi form a typical Z-shaped heterojunction structure to promote the separation of photo-generated electrons and holes, and the holes are gathered on ZnO phase and OH - The reaction generates OH, the ZnO phase surface has a porous structure, the adsorption of dye molecules on the ZnO phase surface is promoted, the degradation of dye molecules mainly occurs on the ZnO surface, electrons mainly gather on the BiOBr phase, and then the photodecomposition of water and hydrogen mainly occur on the BiOBr phase, so that the photodecomposition of water and hydrogen is realized, the degradation rate of rhodamine B (RhB) in 8 min is up to 98.62%, when the pH value of the RhB solution is 5, the degradation rate of RhB in 2 min is up to 97.7%, the degradation rates of Methylene Blue (MB) and Methyl Orange (MO) in 20 min are respectively up to 94.6% and 96.7%, in addition, the degradation rate of RhB in 120 min is up to 94.12% under the irradiation of sunlight, the catalyst can realize the photocatalytic hydrogen production under the irradiation of visible light, and the hydrogen production efficiency in the presence of a methanol sacrificial agent is up to 1.2 mu mol.g -1 ·h -1 More prominently, the catalyst can realize 1674.4 mu mol.g in RhB solution under the irradiation of visible light without adding methanol sacrificial agent -1 ·h -1 The hydrogen production efficiency of the catalyst realizes the high-efficiency hydrogen production while the RhB is degraded.
The photocatalyst designed by the invention is realized by the following steps: the template method is adopted to firstly synthesize ordered porous ZnO as a precursor, which is the precondition for obtaining the tremella material, and ZnO nano powder with other structures is adopted as the precursor after exploration, so that the material with the morphology can not be obtained; cetyl Trimethyl Ammonium Bromide (CTAB) is adopted as a bromine source of BiOBr, and other salts with similar functions are selected as the bromine source, so that tremella morphology of the invention can not be obtained; ethylene glycol is used as a reducing agent for constructing Bi quantum dots, is also a necessary condition for synthesizing the catalyst, and is reduced by other reducing agents, so that the photocatalytic performance is not excellent; in addition, parameters such as material consumption, hydrothermal reaction temperature, hydrothermal time and the like also directly influence the structure and photocatalytic performance of the prepared material, and the method has the advantages of abundant resources, low raw materials, simple operation in the synthesis process and high efficiency, and comprises the following specific steps:
synthesis of pure zinc oxide ordered mesoporous material precursor by soft template method
CTAB was used as a template for synthesis of porous ZnO precursor, zinc acetate dihydrate (Zn (CH) 3 COO) 2 ﹒2H 2 O) as zinc source, the specific synthesis steps are as follows:
(1) Accurately weighing 0.5-6. 6 g of cetyltrimethylammonium bromide (CTAB), dissolving in 250-1500mL of deionized water, and uniformly stirring on a magnetic stirrer at 50-180 ℃;
(2) Slowly adding 0.5-5g Zn (CH) 3 COO) 2 ﹒2H 2 O, continuing to stir until the materials are uniform;
(3) Slowly adding lithium hydroxide to adjust the pH to be alkaline;
(4) Continuing stirring the mixture at 50-180deg.C for 1-12 h;
(5) The resulting mixed solution was filtered and the product was dried at 60 ℃ for 24 h;
(6) Calcining the dried powdery product at 450-800 ℃ to obtain the ordered mesoporous zinc oxide precursor by 1-24 h. Synthesis of (II) Z-type ZnO/Bi/BiOBr composite photocatalyst
(1) Accurately weighing 0.2-4 g zinc oxide, dissolving in 10-500 mL ethylene glycol, and stirring at normal temperature;
(2) Slowly adding 0.5-5g Bi (NO) 3 ) 3 ·5H 2 O, continuing to stir evenly;
(3) Adding 0.5-10 g CTAB, and continuously stirring uniformly;
(4) Putting the mixed solution into a reaction kettle, heating the mixed solution in an oven at 100-180 ℃ for 2-24 h, taking out the mixed solution, and naturally cooling the mixed solution to room temperature;
(5) Filtering the obtained mixed solution, and drying the filtered product in a drying oven at 60 ℃ for one day to obtain the ZnO/Bi/BiOBr composite photocatalyst with the Z-type heterostructure.
Drawings
FIG. 1 is an SEM photograph of a tremella-like ZnO/Bi/BiOBr ternary composite material;
FIG. 2 is a TEM photograph of a tremella ZnO/Bi/BiOBr ternary composite material;
FIG. 3 is an XRD spectrum of a tremella ZnO/Bi/BiOBr ternary composite material;
fig. 4 is a degradation rate curve of the tremella ZnO/Bi/bio-br ternary composite material photodegradation organic pollutant RhB, MB, MO and the solar degradation RhB, which is also used as a summary drawing.
Description of the embodiments
CTAB (cetyltrimethylammonium bromide), naOH, zn (CH) 3 COO) 2 ·2H 2 O，LiOH， Bi(NO 3 ) 3 ·5H 2 O, ethylene glycol are all commercial analytically pure products and are self-made by a deionized water laboratory; the glassware and equipment used was the equipment and equipment commonly used in the laboratory.
Examples
The CTAB of 1 g is weighed and dissolved in 480 mL water and stirred evenly at 80 ℃; adding 4.92 g zinc acetate dihydrate, continuously stirring until the mixture is uniform, slowly adding lithium hydroxide, and simultaneously testing the pH by using pH test paper until the solution is slightly alkaline; the mixture was stirred at 80 ℃ for 2 h to obtain a mixed solution, which was filtered, and the filtered product was dried in a dry box at 60 ℃ for one day; placing the dried powdery product into a crucible, and calcining 4 h in a muffle furnace at 500 ℃; and taking out the product to obtain the ordered mesoporous ZnO precursor material.
Accurately weighing 0.2 g of the prepared porous zinc oxide precursor by an analytical balance, dispersing the porous zinc oxide precursor in ethylene glycol, and uniformly stirring at normal temperature; slowly adding Bi (NO) into the above-mentioned turbid liquid 3 ) 3 ·5H 2 O and CTAB, stirring 1 h; transferring the mixed solution obtained after stirring into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and preserving heat at 180 ℃ for 24 h; and (3) waiting for the reaction kettle to naturally cool to room temperature, filtering the obtained mixed solution, and drying the filtered product in a drying oven at 60 ℃ for one day to obtain the tremella ternary ZnO/Bi/BiOBr composite material.
The scanning electron microscope photograph of the tremella ternary ZnO/Bi/BiOBr composite material is shown in figure 1, and the prepared material is formed by 100+/-10 nm thin and multi-fold flat petals, has a diameter of about 7+/-1 mu m and is similar to the irregular shape of tremella, the specific surface area of the prepared material is greatly improved, and a large number of active sites are exposed; FIG. 2 is a TEM image of a tremella ternary ZnO/Bi/BiOBr composite material, and it can be seen that a large number of needle-shaped BiOBr exist on a prepared material flap, and Bi quantum dots are distributed on the surface of the BiOBr needle; the X-ray diffraction analysis result of the tremella ternary ZnO/Bi/BiOBr composite material is shown in figure 3, and by comparing the X-ray diffraction analysis result with a standard card, the prepared material is mainly in tetragonal phase BiOBr and hexagonal phase ZnO structures, and meanwhile, obvious single Bi sign diffraction peaks appear; FIG. 4 is a degradation rate curve of the tremella ternary ZnO/Bi/BiOBr composite material as a catalyst for degradation RhB, MB, MO and the degradation of RhB by sunlight, and as can be seen from the graph (a), after the catalyst reaches the adsorption equilibrium in the dark treatment, the degradation rate of RhB reaches 98.62% in 8 min of illumination; as can be seen from the graphs (b, c), after the catalyst reached adsorption equilibrium, the degradation rates of MB and MO reached 94.6% and 96.7% respectively in 20 min; the catalyst also has degradation performance on pollutants under sunlight, and as can be seen from a graph (d), the degradation rate of tremella ternary ZnO/Bi/BiOBr on RhB under sunlight reaches 94.12%, so that the tremella ternary ZnO/Bi/BiOBr composite material has a large application prospect in the field of photodegradation of pollutants.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention, as will be apparent to those skilled in the art, without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (2)
1. A ZnO/Bi/BiOBr photocatalyst capable of efficiently degrading organic dye and simultaneously producing hydrogen is characterized in that Cetyl Trimethyl Ammonium Bromide (CTAB) is adopted as a bromine source of BiOBr, ethylene glycol is adopted as a reducing agent generated by Bi quantum dots, the prepared ZnO/Bi/BiOBr photocatalyst presents tremella-like morphology, needle-like BiOBr is distributed among sheet layers of the tremella structure, and quantum dots of simple substance Bi are uniformly dispersed on the surface of the BiOBr, a typical Z-type heterojunction structure is constructed, separation of photo-generated electrons and holes is promoted, and the holes are gathered on ZnO phase and OH - The reaction generates OH, the ZnO phase surface has a porous structure, the adsorption of dye molecules on the ZnO phase surface is promoted, the degradation of dye molecules mainly occurs on the ZnO surface, electrons mainly gather on the BiOBr phase, and then the photodecomposition of water and hydrogen mainly occur on the BiOBr phase, so that the photodecomposition of water and hydrogen is realized, the degradation rate of rhodamine B (RhB) in 8 min is up to 98.62%, when the pH value of the RhB solution is 5, the degradation rate of RhB in 2 min is up to 97.7%, the degradation rates of Methylene Blue (MB) and Methyl Orange (MO) in 20 min are respectively up to 94.6% and 96.7%, in addition, the degradation rate of RhB in 120 min is up to 94.12% under the irradiation of sunlight, the catalyst can realize the photocatalytic hydrogen production under the irradiation of visible light, and the hydrogen production efficiency in the presence of a methanol sacrificial agent is up to 1.2 mu mol.g -1 ·h -1 More prominently, the catalyst can realize 1674.4 mu mol.g in RhB solution under the irradiation of visible light without adding methanol sacrificial agent -1 ·h -1 The hydrogen production efficiency of the catalyst realizes the high-efficiency hydrogen production while the RhB is degraded.
2. A preparation method of a ZnO/Bi/BiOBr photocatalyst capable of efficiently degrading an organic dye and simultaneously producing hydrogen as claimed in claim 1 is characterized in that a template method is adopted to synthesize ordered porous ZnO as a precursor, the ZnO nano powder with other structures is used as a precursor, the material with the morphology cannot be obtained through exploration, cetyl Trimethyl Ammonium Bromide (CTAB) is used as a bromine source of BiOBr, other salts with similar functions are selected as bromine sources, the tremella morphology of the invention cannot be obtained, in addition, the reducing agent is a big bright point of the invention, other reducing agents are adopted for reduction, the photocatalytic performance is not excellent, in addition, the material consumption, the hydrothermal reaction temperature, the hydrothermal time and other parameters directly influence the structure and the photocatalytic performance of the prepared material, the method has the advantages of abundant resources, low price of raw materials, simple operation of the synthesis process and high efficiency, and the specific steps of the method are as follows: (1) Method for synthesizing pure zinc oxide ordered mesoporous material precursor by soft template methodAccurately weighing 0.5-6 g of cetyltrimethylammonium bromide (CTAB) by an analytical balance, dissolving in 250-1500mL of deionized water, uniformly stirring on a magnetic stirrer, slowly adding 0.5-5g of zinc acetate dihydrate, continuously stirring to be uniform at 50-180 ℃, slowly adding lithium hydroxide to adjust pH to be alkaline, continuously stirring the mixture at 50-180 ℃ for 1-12 h, filtering the obtained mixed solution, filtering out a product, drying at 60 ℃ for 24 h, calcining the dried powdery product at 450-800 ℃ for 1-24 h to obtain an ordered mesoporous zinc oxide precursor; (2) The synthesis of the Z-type ZnO/Bi/BiOBr composite photocatalyst accurately weighs 0.2-4 g zinc oxide dissolved in 10-500 mL glycol, and is stirred uniformly at normal temperature, and 0.5-5g Bi (NO) is slowly added 3 ) 3 ·5H 2 And (3) continuously stirring uniformly O, adding 0.5-10 g of CTAB, continuously stirring uniformly, loading the mixed solution into a reaction kettle, heating in an oven at 100-180 ℃ for 2-24 h, taking out, naturally cooling to room temperature, filtering the obtained mixed solution, and drying the filtered product in a drying oven at 60 ℃ for one day to obtain the ZnO/Bi/BiOBr composite photocatalyst with the Z-type heterostructure.
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