CN112076739A - Composite material for efficiently degrading organic dye in wastewater and preparation method thereof - Google Patents
Composite material for efficiently degrading organic dye in wastewater and preparation method thereof Download PDFInfo
- Publication number
- CN112076739A CN112076739A CN202010947736.5A CN202010947736A CN112076739A CN 112076739 A CN112076739 A CN 112076739A CN 202010947736 A CN202010947736 A CN 202010947736A CN 112076739 A CN112076739 A CN 112076739A
- Authority
- CN
- China
- Prior art keywords
- tio
- composite material
- zno
- wastewater
- organic dye
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000002351 wastewater Substances 0.000 title claims abstract description 16
- 230000000593 degrading effect Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 239000004005 microsphere Substances 0.000 claims description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000011806 microball Substances 0.000 claims description 5
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 24
- 239000002245 particle Substances 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 241000257465 Echinoidea Species 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 241000258149 Hemicentrotus Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003256 environmental substance Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 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
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a composite material for efficiently degrading organic dye in wastewater and a preparation method thereof, wherein the composite material is echinoid TiO2ZnO nanoparticles are uniformly loaded on the surface of the micron sphere, and TiO2And forms a heterojunction with ZnO. TiO of the invention2the/ZnO composite material can efficiently degrade organic dyes in wastewater, is non-toxic and environment-friendly, has large particles, is easy to separate from water, does not cause secondary pollution, and can be widely applied to treatment of organic dye wastewater.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a composite material for efficiently degrading organic dyes in wastewater and a preparation method thereof.
Background
Organic dyes are widely applied to the fields of leather, cosmetics, printing and dyeing and the like, and about 12 percent of the dyes are released into the environment in the production and use processes and easily enter water bodies. Most dyes are stable and difficult to be naturally degraded, and the ecological balance and the biological health are seriously influenced. The advanced oxidation technology is one of the important methods for treating organic dye wastewater, can generate strong oxidizing substances such as hydroxyl radicals and the like, and can degrade macromolecular organic substances which are difficult to biodegrade into small molecular substances or inorganic substances which are easy to biodegrade by destroying chromophoric groups through physical and chemical actions by utilizing the high chemical activity and non-selectivity of the strong oxidizing substances. At present, the advanced oxidation technology mainly comprises the following steps: fenton method, ozone oxidation method, wet oxidation method, ultrasonic oxidation method, photocatalytic oxidation method, supercritical water oxidation method, low temperature plasma technology, etc.
Compared with other advanced oxidation technologies, the photocatalysis technology is an efficient and safe environment-friendly environmental purification technology, and has the advantages of simple operation, low energy consumption and no secondary pollution. Various photocatalysts for contaminant degradation have been developed, such as TiO with good photocatalytic activity2、ZnO、CeO2、CdS、BiVO4And NiO, etc. TiO compared with other photocatalysts2It is attracting attention because of its non-toxicity, high chemical stability, low cost and strong light responsiveness. TiO 22Mainly comprises three crystal forms, namely anatase, rutile and brookite, wherein anatase phase TiO2The photocatalytic performance of (2) is optimal. TiO in general2The smaller the particle size of the nano particles, the larger the specific surface area, and the more active sites, the more favorable the photocatalytic reaction. But the particle size is too small, and the catalyst is not easy to separate from the water body. Therefore, researchers increase the specific surface area of the nano structure through three-dimensional layering, such as self-assembly structures like sea urchins, flowers and trees, and the like, so that better photocatalytic performance is obtained.
The recombination of photogenerated electrons and holes is an important factor limiting the photocatalytic performance (Journal of Environmental Chemical Engineering,7(3), (2019) 103096). Researchers throughA large number of experimental studies have found that TiO2With other semiconductors (e.g. ZnO, CdS, WO)3Etc.) coupling to construct a heterojunction structure is an effective method to hinder rapid charge recombination. Wherein, ZnO has valence band and conduction band ratio TiO2Is more negative in the valence and conduction bands, which contributes to ZnO/TiO2Separation of photogenerated electrons and holes in the heterojunction. And against CdS, WO3In other words, ZnO has the advantage of being non-toxic. Thus, the construction of TiO2The composite structure with ZnO improves the photocatalysis performance, and has important research value.
Disclosure of Invention
Based on the problems of the prior art, the invention aims to provide TiO for efficiently degrading organic dye in wastewater2the/ZnO composite material and the preparation method thereof solve the problems of poor degradation effect, complex technology, difficult separation from water and the like of the existing catalyst.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a composite material for efficiently degrading organic dye in wastewater is characterized in that: the composite material is sea urchin-shaped TiO2ZnO nanoparticles are uniformly loaded on the surface of the micron sphere, and TiO2And forms a heterojunction with ZnO. Wherein, the TiO is2The microspheres are anatase phases, and the ZnO nanoparticles are wurtzite crystal phases.
The preparation method of the composite material comprises the following steps:
step 1, mixing and uniformly stirring deionized water, diethylene glycol, titanium potassium oxalate and urea, then transferring the mixture to a reaction kettle for hydrothermal reaction at 190 ℃ for 10-12h, centrifuging, washing and drying the obtained product, then placing the product in a muffle furnace, heating to 500-550 ℃, and carrying out heat preservation and calcination for 1-2 h to obtain echinoid TiO2Micro-balls;
Further, in the step 1, the dosage ratio of the deionized water, the diethylene glycol, the potassium titanium oxalate and the urea is 20 mL: 50-70 mL: 0.6-1.0 g: 2.2-2.6 g.
Further, in step 2, the concentration of the aqueous solution of hexamethylenetetramine is 0.05mol/L, and the aqueous solution of zinc nitrate, hexamethylenetetramine, deionized water and sea urchin-like TiO are added2The dosage ratio of the micro-spheres is 40 mg: 5-15 mL: 50-70 mL: 0.1-0.3 g.
Further, in the step 1, the temperature rise rate is 5-10 ℃/min.
In step 2 of the preparation method of the present invention, hexamethylenetetramine functions to hydrolyze at a high temperature to generate hydroxyl, and then reacts with zinc ions to form zinc hydroxide, and finally ZnO is formed.
Compared with the prior art, the invention has the beneficial effects that:
1. TiO of the invention2the/ZnO composite material can efficiently degrade organic dyes in wastewater, is non-toxic and environment-friendly, has large particles, is easy to separate from water, does not cause secondary pollution, can be widely applied to the treatment of organic dye wastewater, overcomes the defects of high degradation cost, complex degradation process and the like of the existing catalyst, and has important social benefits and good application prospects.
2. The composite material prepared by the invention is sea urchin-shaped TiO2ZnO nanoparticles are uniformly loaded on the surface of the microspheres, the particles are large, the specific surface area is large, the external burr-shaped appearance can provide more active sites for photodegradable organic dyes, and meanwhile, TiO nanoparticles are uniformly loaded on the surface of the microspheres2And ZnO form a heterojunction, thereby prolonging the service life of a photon-generated carrier and reducing the recombination of the photon-generated carrier, so that the composite material has excellent photocatalytic performance.
3. According to the invention, a large number of experiments are carried out to screen suitable raw materials and suitable preparation parameters, and a simple two-step hydrothermal method is adopted to mix ZnO and TiO2Compounding to prepare sea urchin-shaped TiO2The micron spheres are attached with ZnO nanoparticles on the surfaces, and the method is simple and easy to implement.
Drawings
FIG. 1 shows TiO obtained in example 1 of the present invention2SEM picture (FIG. 1(a)), EDS picture (FIG. 1(b)) and EDS element general spectrum (FIG. 1(c)) of/ZnO composite material;
FIG. 2 shows TiO obtained in example 1 of the present invention2XPS diagram of/ZnO composite material, wherein FIG. 2(a) is XPS spectrum of composite material, FIG. 2(b-d) is position of Ti2p, O1s, Zn2p peak with high resolution;
FIG. 3 shows TiO obtained in example 1 of the present invention2ZnO composite material and pure urchin-shaped TiO2XRD pattern of microspheres;
FIG. 4 shows TiO in example 1 of the present invention2/ZnO composite material (TZ) and TiO2ZnO mixture (PMTZ) and pure echinoid TiO2The degradation effect of the microspheres on the organic dye (methyl orange) changes along with the illumination time.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. The following disclosure is merely exemplary and illustrative of the inventive concept, and those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
The experimental reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
This example prepares TiO for efficient degradation of organic dyes in wastewater as follows2The ZnO composite material:
step 1, adding 20mL of deionized water, 60mL of diethylene glycol, 0.8g of potassium titanium oxalate and 2.4g of urea into a 100mL beaker, uniformly stirring by magnetic force, then transferring the mixture into a reaction kettle for hydrothermal reaction at 180 ℃ for 12 hours, sequentially washing the obtained product by centrifugation, deionized water and absolute ethyl alcohol, drying the product at 60 ℃ overnight, then placing the product in a muffle furnace, and raising the temperature at 5 ℃/minHeating to 500 deg.C at a certain rate, and calcining for 1 hr to obtain sea urchin-shaped TiO2Micro-balls;
FIG. 1 shows TiO obtained in this example2SEM picture (FIG. 1(a)), EDS picture (FIG. 1(b)) and EDS element summary spectrum (FIG. 1(c)) of/ZnO composite material. As shown in FIG. 1(a), the prepared TiO2The sea urchin sphere is about 1.5 mu m in diameter, and a plurality of burrs are distributed on the outer part of the sea urchin sphere, so that more active sites can be provided for photodegradation of organic dyes, and the degradation rate is improved. From FIG. 1(b) TiO2The element distribution of the/ZnO composite material shows that Zn is uniformly distributed in TiO2Surface, this example demonstrates the successful synthesis of TiO2/ZnO composite, TiO2Forming a heterojunction with ZnO, thereby increasing the lifetime of the photogenerated carriers and reducing the recombination of the photogenerated carriers. The elemental summary spectrum of FIG. 1(c) gives the Zn, Ti and O contents in the composite material, and it can be seen that the composite material is TiO2Mainly comprises the following steps.
FIG. 2 shows TiO obtained in this example2XPS plot of the/ZnO composite. The XPS spectrum of the composite material shown in fig. 2(a) shows characteristic peaks of C1s, Ti2p, O1s and Zn2p, which further indicates that the composite material contains Ti, Zn and O elements, and the presence of C element is due to contamination of C element in the XPS test system, thereby indicating that the example has successfully prepared TiO2A/ZnO composite material. FIG. 2(b-d) shows the positions of the peaks of Ti2p, O1s, and Zn2p with high resolution. FIG. 2(b) shows TiO2Respectively located at 458.6eV (Ti2 p)3/2) And 464.3eV (Ti2 p)1/2). FIG. 2(c) shows two characteristic peaks of ZnO, respectively located at 1022.7eV (Zn2 p)3/2) And 1045.9eV (Zn 2)p1/2). FIG. 2(d) shows the characteristic peak of O at 530.1eV for TiO2Or lattice oxygen in ZnO.
FIG. 3 shows TiO obtained in this example2the/ZnO composite material (TZ in the figure) and the urchin-shaped TiO obtained in the step 12XRD pattern of microspheres. The elongated spike appearing at 25.3 ° in the graph corresponds to anatase TiO2The peak appearing at 31.9 degrees is the (100) plane of the wurtzite crystalline phase ZnO. Pure TiO2And TiO2the/ZnO composite material detects the following crystal faces: 25.3 ° (101), 37.8 ° (004), 48.0 ° (200), 54.0 ° (105), 55.1 ° (211), with anatase TiO2The standard card (JCPDS card No. 73-1764) is consistent with that of the present example, which shows that TiO is obtained in this example2TiO in/ZnO composite material2Has good anatase crystalline phase. At the same time, 31.9 ° (100), 34.7 ° (002) crystallographic planes were also detected in the composite material, which is consistent with the standard card for wurtzite crystalline phase ZnO { JCPDS card No.36-1451}, wherein the 36.2 ° (101) and 56.4 ° (110) crystallographic planes of wurtzite crystalline phase ZnO coincide with the 37.8 ° and 55.1 ° crystallographic phases of anatase in the figure.
This example also prepared TiO for comparison of degradation efficiency2A mixture of/ZnO and/or PMTZ, prepared by mixing 16.4mg of Hemicentrotus TiO2Grinding the micro-spheres and 3.6mg of ZnO nano-particles for 10min to ensure that the micro-spheres and the ZnO nano-particles are physically and uniformly mixed to obtain the nano-particles.
The TiO obtained in this example2/ZnO composite material and echinoid TiO2Micro-sphere, TiO2Pure TiO is researched by taking methyl orange as a target dye pollutant by taking a ZnO mixture (PMTZ) as a photocatalyst2、TiO2/ZnO mixture and TiO2The degradation effect of the/ZnO composite material is measured by adopting an ultraviolet visible spectrophotometer to measure the change of the dye concentration before and after ultraviolet irradiation: preparing 20mg/L methyl orange aqueous solution in a 50mL beaker, then weighing 20mg of photocatalyst, mixing the photocatalyst into the methyl orange aqueous solution, magnetically stirring for 1h under dark condition before illumination to achieve the adsorption-desorption balance of the organic dye and the photocatalyst, and then using a xenon lamp light source provided with an ultraviolet filter with the central wavelength of 365nm as an ultraviolet light source to irradiate the solution for 4h while continuously stirring the solution. Every otherA1 mL sample was taken at 0.5h and the photocatalyst was filtered off, and then the change in dye concentration was measured using an ultraviolet-visible spectrophotometer.
FIG. 4 is TiO2/ZnO composite Material, TiO2ZnO mixture and pure echinoid TiO2The degradation effect of the microspheres on the organic dye (methyl orange) changes along with the illumination time, and the result shows that the TiO is added2/ZnO composite Material, TiO2ZnO mixture and pure echinoid TiO2The concentrations of the methyl orange solution with the microspheres as the photocatalyst after 4 hours of illumination are respectively 0.769mg/L, 5.484mg/L and 6.009mg/L, and the degradation rates of the methyl orange solution with the microspheres as the photocatalyst are respectively 96.2%, 72.6% and 69.9% according to calculation. It can be seen that this example successfully produced TiO2the/ZnO composite material has higher degradation effect on methyl orange due to the sea urchin-shaped appearance of the composite material providing more active sites for photocatalytic reaction, and compared with simple physical mixing, ZnO and TiO in the composite material2The formed heterojunction can prolong the service life of a photon-generated carrier and reduce the recombination of the photon-generated carrier, thereby synergistically promoting the degradation effect.
The present invention is not limited to the above exemplary embodiments, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A composite material for efficiently degrading organic dye in wastewater is characterized in that: the composite material is sea urchin-shaped TiO2ZnO nanoparticles are uniformly loaded on the surface of the micron sphere, and TiO2And forms a heterojunction with ZnO.
2. The composite material of claim 1, wherein: the TiO is2The microspheres are anatase phases, and the ZnO nanoparticles are wurtzite crystal phases.
3. A method for preparing a composite material according to claim 1 or 2, comprising the steps of:
step 1, mixing and uniformly stirring deionized water, diethylene glycol, titanium potassium oxalate and urea, then transferring the mixture to a reaction kettle for hydrothermal reaction at 190 ℃ for 10-12h, centrifuging, washing and drying the obtained product, then placing the product in a muffle furnace, heating to 500-550 ℃, and carrying out heat preservation and calcination for 1-2 h to obtain echinoid TiO2Micro-balls;
step 2, mixing and uniformly stirring zinc nitrate, a hexamethylenetetramine aqueous solution and deionized water, and then adding the echinoid TiO prepared in the step 12The micro-balls are continuously stirred evenly and then transferred into a reaction kettle to react for 2 to 3 hours at the temperature of between 90 and 100 ℃, and the obtained product is centrifuged, washed and dried to obtain TiO for efficiently degrading organic dye in wastewater2A/ZnO composite material.
4. The production method according to claim 3, characterized in that: in the step 1, the dosage ratio of deionized water, diethylene glycol, potassium titanium oxalate and urea is 20 mL: 50-70 mL: 0.6-1.0 g: 2.2-2.6 g.
5. The production method according to claim 3, characterized in that: in step 2, the concentration of the aqueous solution of the hexamethylenetetramine is 0.05mol/L, and the aqueous solution of the zinc nitrate and the hexamethylenetetramine, the deionized water and the echinoid TiO are added2The dosage ratio of the micro-spheres is 40 mg: 5-15 mL: 50-70 mL: 0.1-0.3 g.
6. The production method according to claim 3, characterized in that: in the step 1, the heating rate is 5-10 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010947736.5A CN112076739A (en) | 2020-09-10 | 2020-09-10 | Composite material for efficiently degrading organic dye in wastewater and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010947736.5A CN112076739A (en) | 2020-09-10 | 2020-09-10 | Composite material for efficiently degrading organic dye in wastewater and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112076739A true CN112076739A (en) | 2020-12-15 |
Family
ID=73736336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010947736.5A Pending CN112076739A (en) | 2020-09-10 | 2020-09-10 | Composite material for efficiently degrading organic dye in wastewater and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112076739A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113083276A (en) * | 2021-03-11 | 2021-07-09 | 浙江理工大学 | Titanium dioxide/zinc oxide heterojunction material with dendritic structure and preparation method thereof |
| US11969710B1 (en) | 2023-07-05 | 2024-04-30 | King Faisal University | Lu2O3@ZnO nanocomposites for photodegradation of textile wastewater dyes |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009023854A (en) * | 2007-07-17 | 2009-02-05 | National Institute Of Advanced Industrial & Technology | Epitaxial nano tio2 particle coating and method for preparing the same |
| CN101648148A (en) * | 2009-09-23 | 2010-02-17 | 合肥工业大学 | Preparation method of nanometer photocatalyst film for degrading organic matter in waste water |
| CN105645459A (en) * | 2016-01-15 | 2016-06-08 | 长沙理工大学 | Surface modified urchin-shaped ZnO/TiO2 composite material and preparation method thereof |
| CN106902801A (en) * | 2017-02-22 | 2017-06-30 | 浙江大学 | A kind of nanoscale sea urchin shape TiO2/ ZnO photocatalyst and preparation method thereof |
| CN108722466A (en) * | 2018-06-05 | 2018-11-02 | 青岛科技大学 | A kind of g-C3N4The preparation method of/ZnO compound hollow microballoons |
| CN110280231A (en) * | 2019-08-01 | 2019-09-27 | 山东大学 | A kind of secondary structure TiO2Optical fiber catalysis material of load and the preparation method and application thereof |
-
2020
- 2020-09-10 CN CN202010947736.5A patent/CN112076739A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009023854A (en) * | 2007-07-17 | 2009-02-05 | National Institute Of Advanced Industrial & Technology | Epitaxial nano tio2 particle coating and method for preparing the same |
| CN101648148A (en) * | 2009-09-23 | 2010-02-17 | 合肥工业大学 | Preparation method of nanometer photocatalyst film for degrading organic matter in waste water |
| CN105645459A (en) * | 2016-01-15 | 2016-06-08 | 长沙理工大学 | Surface modified urchin-shaped ZnO/TiO2 composite material and preparation method thereof |
| CN106902801A (en) * | 2017-02-22 | 2017-06-30 | 浙江大学 | A kind of nanoscale sea urchin shape TiO2/ ZnO photocatalyst and preparation method thereof |
| CN108722466A (en) * | 2018-06-05 | 2018-11-02 | 青岛科技大学 | A kind of g-C3N4The preparation method of/ZnO compound hollow microballoons |
| CN110280231A (en) * | 2019-08-01 | 2019-09-27 | 山东大学 | A kind of secondary structure TiO2Optical fiber catalysis material of load and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHENG, PENGFEI ET AL.,: ""High specific surface area urchin-like hierarchical ZnO-TiO2 architectures: Hydrothermal synthesis and photocatalytic properties"", 《MATERIALS LETTERS》 * |
| YU, XIN ET AL.,: ""One-step synthesis of ultrathin nanobelts-assembled urchin-like anatase TiO2 nanostructures for highly efficient photocatalysis"", 《CRYSTENGCOMM》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113083276A (en) * | 2021-03-11 | 2021-07-09 | 浙江理工大学 | Titanium dioxide/zinc oxide heterojunction material with dendritic structure and preparation method thereof |
| CN113083276B (en) * | 2021-03-11 | 2023-02-28 | 浙江理工大学 | Titanium dioxide/zinc oxide heterojunction material with dendritic structure and preparation method thereof |
| US11969710B1 (en) | 2023-07-05 | 2024-04-30 | King Faisal University | Lu2O3@ZnO nanocomposites for photodegradation of textile wastewater dyes |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lum et al. | Ash based nanocomposites for photocatalytic degradation of textile dye pollutants: a review | |
| Habib et al. | Synthesis and characterization of ZnO-TiO 2 nanocomposites and their application as photocatalysts | |
| CN102580742B (en) | Activated carbon-loaded cuprous oxide photocatalyst and preparation method thereof | |
| Sherly et al. | Microwave assisted combustion synthesis of coupled ZnO–ZrO2 nanoparticles and their role in the photocatalytic degradation of 2, 4-dichlorophenol | |
| Gan et al. | The fabrication of bio-renewable and recyclable cellulose based carbon microspheres incorporated by CoFe2O4 and the photocatalytic properties | |
| Mardikar et al. | Sunlight driven highly efficient degradation of methylene blue by CuO-ZnO nanoflowers | |
| Baeissa | Photocatalytic degradation of methylene blue dye under visible light irradiation using In/ZnO nanocomposite | |
| Mohammadi et al. | Photocatalytic degradation of aqueous ammonia by using TiO2ZnO/LECA hybrid photocatalyst | |
| Prabha et al. | Photodegradation of phenol by zinc oxide, titania and zinc oxide–titania composites: nanoparticle synthesis, characterization and comparative photocatalytic efficiencies | |
| Zangeneh et al. | Photomineralization of recalcitrant wastewaters by a novel magnetically recyclable boron doped-TiO2-SiO2 cobalt ferrite nanocomposite as a visible-driven heterogeneous photocatalyst | |
| Li et al. | Photocatalytic degradation of methyl orange in a sparged tube reactor with TiO2-coated activated carbon composites | |
| Bayat et al. | A magnetic ZnFe2O4/ZnO/perlite nanocomposite for photocatalytic degradation of organic pollutants under LED visible light irradiation | |
| CN101972645B (en) | Preparation method of visible light response type semiconductor photocatalyst bismuth vanadate | |
| Adhikari et al. | Visible light assisted improved photocatalytic activity of combustion synthesized spongy-ZnO towards dye degradation and bacterial inactivation | |
| CN103599802A (en) | Preparation method of silver phosphate/graphene nanocomposite | |
| Pouretedal et al. | Photodegradation study of congo red, methyl orange, methyl red and methylene blue under simulated solar irradiation catalyzed by ZnS/CdS nanocomposite | |
| Kitchamsetti et al. | Bimetallic MOF derived ZnCo2O4 nanocages as a novel class of high performance photocatalyst for the removal of organic pollutants | |
| Shokri et al. | Photocatalytic degradation of ceftriaxone in aqueous solutions by immobilized TiO2 and ZnO nanoparticles: Investigating operational parameters | |
| Eskikaya et al. | Photocatalytic activity of calcined chicken eggshells for Safranin and Reactive Red 180 decolorization | |
| Alsulmi et al. | Rational engineering of S-scheme CeO2/g-C3N4 heterojunctions for effective photocatalytic destruction of rhodamine B dye under natural solar radiations | |
| CN112076739A (en) | Composite material for efficiently degrading organic dye in wastewater and preparation method thereof | |
| Abumousa | MgO@ ZrO2@ g-C3N4 composite for efficient photodegradation of alizarin red dye | |
| Wang et al. | Preparation of g-C3N4/diatomite composite with improved visible light photocatalytic activity | |
| Liu et al. | Hollow microsphere TiO2/ZnO p–n heterojuction with high photocatalytic performance for 2, 4-dinitropheno mineralization | |
| Mensah et al. | Enhanced photocatalytic degradation of dyes using a novel waste toner-based TiO2/Fe2O3@ nanographite nanohybrid: a sustainable approach |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201215 |