CN108283930B - Non-equal-ratio sulfur indium cadmium composite photocatalyst, preparation method and application - Google Patents
Non-equal-ratio sulfur indium cadmium composite photocatalyst, preparation method and application Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- FCNBPGQGSGENIO-UHFFFAOYSA-N cadmium;sulfanylideneindium Chemical compound [Cd].[In]=S FCNBPGQGSGENIO-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 85
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000000593 degrading effect Effects 0.000 claims abstract description 6
- 230000000694 effects Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 74
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000008367 deionised water Substances 0.000 claims description 36
- 229910021641 deionized water Inorganic materials 0.000 claims description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 32
- QOYRNHQSZSCVOW-UHFFFAOYSA-N cadmium nitrate tetrahydrate Chemical compound O.O.O.O.[Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QOYRNHQSZSCVOW-UHFFFAOYSA-N 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 23
- 239000005457 ice water Substances 0.000 claims description 23
- HVDZMISZAKTZFP-UHFFFAOYSA-N indium(3+) trinitrate trihydrate Chemical compound O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVDZMISZAKTZFP-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- 230000015556 catabolic process Effects 0.000 claims description 14
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 14
- 238000006731 degradation reaction Methods 0.000 claims description 14
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000003115 biocidal effect Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 description 22
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 10
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 229940088710 antibiotic agent Drugs 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 229960002180 tetracycline Drugs 0.000 description 2
- 229930101283 tetracycline Natural products 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 150000003522 tetracyclines Chemical class 0.000 description 2
- 229930182555 Penicillin Natural products 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [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
- 238000001514 detection method Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001937 non-anti-biotic effect Effects 0.000 description 1
- 150000002960 penicillins Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 150000007660 quinolones Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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Abstract
The invention relates to an unequal-ratio sulfur indium cadmium composite photocatalyst, a preparation method and application thereof, and belongs to the technical field of preparation of environment-friendly materials. The invention realizes the purpose of using Cd0.45In1.10S2.10the/CNTs nano composite material is used as a photocatalyst, a semiconductor is excited under visible light, CNTs (carbon nanotubes) serving as a loaded carbon material carrier are fully contacted with pollutant molecules, and special catalysis or conversion is realized through an interface interaction effect, so that surrounding oxygen and water molecules are excited into substances with strong oxidizing property, such as oxygen free radicals with strong oxidizing property, hydroxyl free radicals and the like, and the aim of degrading harmful organic substances in the environment is fulfilled. The method does not cause resource waste and secondary pollution, is simple and convenient to operate, and is a green, environment-friendly and efficient pollution treatment technology.
Description
Technical Field
The invention relates to an anisometric indium polysulfide compound Cd with a unique crystalline phase0.45In1.10S2.10Load onA preparation method and application of a composite photocatalyst of Carbon Nanotubes (CNTs) belong to the technical field of preparation of environment-friendly materials.
Background
The problem of organic pollutant pollution in water environment has become a hot problem of environmental pollution in the world today. With rapid progress of medical technology and biological science, the types of antibiotics are rapidly expanded, and are roughly divided into quinolones, sulfonamides, penicillins and the like, and finally the antibiotics are directly discharged into the environment in the form of raw medicines, so that extensive and uncontrollable non-point source pollution is formed, the influence is generated on microbial communities in water, high-grade organisms are influenced through the transmission effect of a food chain, and the balance of an ecological system is damaged, so that the antibiotics are remained and migrate in the environment and have potential hazards. According to the results of component analysis of 'scientific bulletin', 68 antibiotics are contained in Chinese surface water, the concentration is high, in addition, 90 non-antibiotic medicinal components are detected, the detection frequency is up to 100%, drinking water such as taking medicine also gives a serious warning to people, the problem of antibiotic water pollution seriously threatens the normal life of people, and a green effective method is required to be immediately taken for solving. The photocatalytic technology has come into existence as an environment-friendly technology, is efficient and convenient, and utilizes sunlight with low cost, so that the technology has wide attention of researchers at home and abroad in recent years.
Researchers are constantly exploring new high-efficiency semiconductor photocatalysts. Common metal oxide/sulfide semiconductor photocatalysts such as TiO2ZnO, CdS, etc. all have better performance, and some non-integral ratio multi-element polysulfide with unique crystal structure, such as Cd0.45In1.10S2.10And the like become hot spots for the research of the semiconductor photocatalyst due to more appropriate band gap and special appearance. Meanwhile, as a novel one-dimensional carbon nano material, Carbon Nanotubes (CNTs) have the advantages of light weight, rich surface active functional groups, excellent mechanical and electrochemical properties and the like, become a hotspot in the field of material research, and are an excellent carrier for synthesizing a supported composite photocatalyst. Thus passing throughThe preparation of the supported polysulfide composite photocatalyst with CNTs as a carrier for degrading and removing antibiotic organic pollutants in a water body has great research value.
Disclosure of Invention
The invention prepares Cd by combining a solvothermal method and an ice bath method0.45In1.10S2.10/CNTs composite photocatalyst.
The present invention achieves the above-described object by the following technical means.
Cd (cadmium)0.45In1.10S2.10The preparation method of the/CNTs composite material photocatalyst comprises the following steps:
(1)Cd0.45In1.10S2.10preparing a precursor:
adding Cd (NO)3)2·4H2O (cadmium nitrate tetrahydrate), In (NO)3)3·3H2O (indium nitrate trihydrate) and thiourea are put into a glass beaker, methanol is added to completely dissolve the O (indium nitrate trihydrate) and the thiourea, after the mixture is fully stirred by magnetic force, the mixture is transferred into a vacuum reaction kettle and put into a drying oven to be heated, the mixture is taken out after treatment and put into ice water to be cooled to 5 ℃ in an ice bath, filtered, washed by deionized water and ethanol for a plurality of times, and dried to obtain Cd0.45In1.10S2.10A precursor;
(2)Cd0.45In1.10S2.10preparation of a/CNTs composite material photocatalyst:
uniformly dispersing carbon nanotubes in deionized water to obtain carbon nanotube dispersion, and adding Cd (NO)3)2·4H2O (cadmium nitrate tetrahydrate), In (NO)3)3·3H2Putting O (indium nitrate trihydrate) and thiourea into a glass beaker, adding methanol to completely dissolve the O (indium nitrate trihydrate) and the thiourea, adding the prepared carbon nano tube dispersion liquid, stirring and ultrasonically mixing the mixture uniformly, then transferring the mixture into a vacuum reaction kettle, putting the vacuum reaction kettle into an oven to heat, taking the mixture out after treatment, putting the mixture into ice water to cool the mixture to 5 ℃, filtering the mixture, washing the mixture with deionized water and ethanol for a plurality of times, and drying the mixture to obtain Cd0.45In1.10S2.10/CNTs composite photocatalyst.
The molar ratio of the cadmium nitrate tetrahydrate, the indium nitrate trihydrate and the thiourea in the steps (1) and (2) is 1: 2.5: 4.
cd prepared in step (2)0.45In1.10S2.10And CNTs in a mass ratio of 5: 1.
in the steps (1) and (2), the temperature of the solvent heat treatment is 140-180 ℃; the time of solvent heat treatment is 6-12 h.
Cd of the invention0.45In1.10S2.10The morphology is a two-dimensional square sheet type structure, and the size is 200 and 500 nm; cd [ Cd ]0.45In1.10S2.10the/CNTs are two-dimensional square sheet-shaped loaded on a curved tubular structure.
In the technical scheme, the dosage of the methanol and the deionized water can ensure that the soluble solid is completely dissolved or uniformly dispersed.
Cd obtained by the above-mentioned preparation method0.45In1.10S2.10the/CNTs composite photocatalyst is applied to degrading tetracycline hydrochloride in antibiotic wastewater.
Tetracycline hydrochloride antibiotics were used as standard and purchased from Shanghai Shunbo bioengineering, Inc.
The invention has the beneficial effects that:
(1) the invention utilizes the unique crystal form and two-dimensional tetragonal structure of a non-integral polysulfide semiconductor Cd0.45In1.10S2.10, and greatly improves the efficiency of photodegradation of antibiotic pollutants by the Cd0.45In1.10S2.10/CNTs nano composite material through compounding with a novel one-dimensional carbon material carrier which has large specific surface area and excellent physicochemical properties. FIG. 1 shows the comparison between Cd0.45In1.10S2.10/CNTs and Cd0.45In1.10S2.10, and it can be seen that the photoresponse range of the composite photocatalyst is obviously widened after the CNTs are added, which has a certain relation with the excellent physicochemical properties of the CNTs.
(2) The invention prepares the green and environment-friendly Cd by a novel method combining a solvothermal method and an ice bath method0.45In1.10S2.10The CNTs composite photocatalyst and the aim of efficiently degrading the antibiotic wastewater are fulfilled.
(3) The invention realizes the purpose of using Cd0.45In1.10S2.10the/CNTs nano composite material is used as a photocatalyst, a semiconductor is excited under visible light, CNTs (carbon nanotubes) serving as a loaded carbon material carrier are fully contacted with pollutant molecules, and special catalysis or conversion is realized through an interface interaction effect, so that surrounding oxygen and water molecules are excited into substances with strong oxidizing property, such as oxygen free radicals with strong oxidizing property, hydroxyl free radicals and the like, and the aim of degrading harmful organic substances in the environment is fulfilled. The method does not cause resource waste and secondary pollution, is simple and convenient to operate, and is a green, environment-friendly and efficient pollution treatment technology.
Drawings
FIG. 1 shows Cd0.45In1.10S2.10UV-vis diagram of/CNTs composite photocatalyst.
FIG. 2 shows Cd0.45In1.10S2.10XRD pattern of/CNTs composite photocatalyst.
FIG. 3 shows Cd0.45In1.10S2.10TEM image of/CNTs composite photocatalyst.
Detailed Description
The invention is further illustrated by the following examples.
The difference of the implementation conditions of the examples can cause the doped composite photocatalytic material to generate different lattice structures and interface effects, thereby causing the difference of the degradation rate. The method is researched, and the optimal process parameters in the implementation process of the method are respectively as follows: cd (NO)3)2·4H2O0.308 g, In (NO)3)3·3H20.798g of O and 0.304g of thiourea, namely the molar ratio of the cadmium nitrate tetrahydrate to the indium nitrate trihydrate to the thiourea is 1: 2.5: 4, the optimal adding amount of the carbon nano tube is 0.08g, namely the prepared Cd0.45In1.10S2.10And CNTs in a mass ratio of 5: 1, Cd0.45In1.10S2.10The CNTs composite photocatalyst is heated for 8 hours at the optimal hydrothermal synthesis temperature of 160 ℃, and the optimal degradation effect can reach 93.78%.
Photocatalytic activity evaluation of the photocatalyst prepared in the present invention: in DW-Type 01 photochemical reaction apparatus (purchased from science and technology limited of Yangzhou university city), irradiating with visible light, adding 100m L tetracycline hydrochloride simulated wastewater into the reactor, measuring its initial value, adding the prepared photocatalyst, magnetically stirring, starting aeration device, introducing air to keep the catalyst in suspension or floating state, sampling and analyzing at 10min interval during the irradiation process, centrifuging, collecting supernatant, and purifying with lambda-gamma-maxAbsorbance was measured with a spectrophotometer at 357nm and by the formula: dr ═ 1-Ai/A0]× 100 the degradation rate is calculated by 100 percent, wherein A0Absorbance of the tetracycline solution to equilibrium for adsorption, AiThe absorbance of the tetracycline solution was determined for the timed samples.
Example 1:
(1)Cd0.45In1.10S2.10preparing a precursor:
0.308g Cd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.319g In (NO)3)3·3H2O and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, after the mixture is fully stirred by magnetic force, the mixture is transferred into a 100m L vacuum reaction kettle and put into a baking oven to be heated for 8 hours at 160 ℃, the mixture is taken out after treatment and put into ice water to be cooled to 5 ℃ in an ice bath, the filtration is carried out, deionized water and ethanol are used for washing for a plurality of times, and the Cd is obtained after drying0.45In1.10S2.10A precursor;
(2)Cd0.45In1.10S2.10preparation of a/CNTs composite material photocatalyst:
0.08g of carbon nanotubes was uniformly dispersed in 20m L of deionized water to obtain a carbon nanotube dispersion, and 0.308gCd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.319g In (NO)3)3·3H2O (indium nitrate trihydrate) and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, then the prepared carbon nano tube dispersion liquid is added, the mixture is stirred and ultrasonically mixed uniformly, then the mixture is transferred into a vacuum reaction kettle and put into an oven to be heated for 8 hours at 160 ℃, the vacuum reaction kettle is taken out after treatment and put into ice water to be cooled to 5 ℃, filtered and filtered, andwashing with deionized water and ethanol for several times and drying to obtain Cd0.45In1.10S2.10/CNTs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride reaches 61.25% within 60 min.
Example 2:
(1)Cd0.45In1.10S2.10preparing a precursor:
0.308g Cd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.638g In (NO)3)3·3H2O and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, after the mixture is fully stirred by magnetic force, the mixture is transferred into a 100m L vacuum reaction kettle and put into a baking oven to be heated for 8 hours at 160 ℃, the mixture is taken out after treatment and put into ice water to be cooled to 5 ℃ in an ice bath, the filtration is carried out, deionized water and ethanol are used for washing for a plurality of times, and the Cd is obtained after drying0.45In1.10S2.10A precursor;
(2)Cd0.45In1.10S2.10preparation of a/CNTs composite material photocatalyst:
0.08g of carbon nanotubes are uniformly dispersed in 20m L deionized water, and 0.308g of Cd (NO) is weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.638g In (NO)3)3·3H2O (indium nitrate trihydrate) and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, then the prepared carbon nano tube dispersion liquid is added, the mixture is stirred and ultrasonically mixed uniformly, then the mixture is transferred to a vacuum reaction kettle and put into an oven to be heated for 8 hours at 160 ℃, the treated mixture is taken out and put into ice water to be cooled to 5 ℃ in an ice bath, filtered, washed by deionized water and ethanol for a plurality of times and dried to obtain Cd0.45In1.10S2.10/CNTs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride reaches 78.99% within 60 min.
Example 3:
(1)Cd0.45In1.10S2.10preparing a precursor:
0.308g Cd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, after the mixture is fully stirred by magnetic force, the mixture is transferred into a 100m L vacuum reaction kettle and put into a baking oven to be heated for 8 hours at 160 ℃, the mixture is taken out after treatment and put into ice water to be cooled to 5 ℃ in an ice bath, the filtration is carried out, deionized water and ethanol are used for washing for a plurality of times, and the Cd is obtained after drying0.45In1.10S2.10A precursor;
(2)Cd0.45In1.10S2.10preparation of a/CNTs composite material photocatalyst:
0.08g of carbon nanotubes are uniformly dispersed in 20m L deionized water, and 0.308g of Cd (NO) is weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O (indium nitrate trihydrate) and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, then the prepared carbon nano tube dispersion liquid is added, the mixture is stirred and ultrasonically mixed uniformly, then the mixture is transferred to a vacuum reaction kettle and put into an oven to be heated for 8 hours at 160 ℃, the treated mixture is taken out and put into ice water to be cooled to 5 ℃ in an ice bath, filtered, washed by deionized water and ethanol for a plurality of times and dried to obtain Cd0.45In1.10S2.10/CNTs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride reaches 93.78% within 60 min.
Example 4:
(1)Cd0.45In1.10S2.10preparing a precursor:
0.308g Cd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate), 1.276g In (NO)3)3·3H2O and 0.304g of thiourea were put into a glass beaker, 50m of L m of methanol was added to completely dissolve the thiourea, and after the mixture was magnetically stirred sufficiently,transferring the mixture into a 100m L vacuum reaction kettle, heating in an oven at 160 ℃ for 8h, taking out after treatment, placing in ice water, cooling to 5 ℃ in an ice bath, filtering, washing with deionized water and ethanol for several times, and drying to obtain Cd0.45In1.10S2.10A precursor;
(2)Cd0.45In1.10S2.10preparation of a/CNTs composite material photocatalyst:
0.08g of carbon nanotubes are uniformly dispersed in 20m L deionized water, and 0.308g of Cd (NO) is weighed3)2·4H2O (cadmium nitrate tetrahydrate), 1.276g In (NO)3)3·3H2O (indium nitrate trihydrate) and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, then the prepared carbon nano tube dispersion liquid is added, the mixture is stirred and ultrasonically mixed uniformly, then the mixture is transferred to a vacuum reaction kettle and put into an oven to be heated for 8 hours at 160 ℃, the treated mixture is taken out and put into ice water to be cooled to 5 ℃ in an ice bath, filtered, washed by deionized water and ethanol for a plurality of times and dried to obtain Cd0.45In1.10S2.10/CNTs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride reaches 88.17% within 60 min.
Example 5:
(1)Cd0.45In1.10S2.10preparing a precursor:
0.308g Cd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, after the mixture is fully stirred by magnetic force, the mixture is transferred into a 100m L vacuum reaction kettle and put into a drying oven to be heated for 8 hours at 140 ℃, the mixture is taken out after treatment and put into ice water to be cooled to 5 ℃ in an ice bath, the filtration is carried out, deionized water and ethanol are used for washing for a plurality of times, and the Cd is obtained after drying0.45In1.10S2.10A precursor;
(2)Cd0.45In1.10S2.10/CNTs composite material photocatalysisPreparation of the agent:
0.08g of carbon nanotubes are uniformly dispersed in 20m L deionized water, and 0.308g of Cd (NO) is weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O (indium nitrate trihydrate) and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, then the prepared carbon nano tube dispersion liquid is added, the mixture is stirred and ultrasonically mixed uniformly, then the mixture is transferred to a vacuum reaction kettle and put into an oven to be heated for 8 hours at the temperature of 140 ℃, the treated mixture is taken out and put into ice water to be cooled to 5 ℃ in an ice bath, the filtered mixture is washed by deionized water and ethanol for a plurality of times and dried to obtain Cd0.45In1.10S2.10/CNTs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride reaches 63.57% within 60 min.
Example 6:
(1)Cd0.45In1.10S2.10preparing a precursor:
0.308g Cd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, after the mixture is fully stirred by magnetic force, the mixture is transferred into a 100m L vacuum reaction kettle and put into an oven to be heated for 8 hours at 180 ℃, the mixture is taken out after treatment and put into ice water to be cooled to 5 ℃ in an ice bath, the filtration is carried out, deionized water and ethanol are used for washing for a plurality of times, and the Cd is obtained after drying0.45In1.10S2.10A precursor;
(2)Cd0.45In1.10S2.10preparation of a/CNTs composite material photocatalyst:
0.08g of carbon nanotubes are uniformly dispersed in 20m L deionized water, and 0.308g of Cd (NO) is weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O (indium nitrate trihydrate) and 0.304g of thiourea were placed in a glass beaker, 50m of L m of methanol was added to dissolve completely, and the prepared carbon nanotubes were addedStirring and ultrasonically mixing the dispersion liquid uniformly, transferring the dispersion liquid to a vacuum reaction kettle, heating the dispersion liquid in an oven at 180 ℃ for 8 hours, taking the dispersion liquid out after treatment, placing the dispersion liquid in ice water, cooling the dispersion liquid to 5 ℃ in an ice bath, filtering the dispersion liquid, washing the dispersion liquid with deionized water and ethanol for a plurality of times, and drying the dispersion liquid to obtain Cd0.45In1.10S2.10/CNTs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride reaches 82.19% within 60 min.
Example 7:
(1)Cd0.45In1.10S2.10preparing a precursor:
0.308g Cd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate) 0.798g In (NO)3)3·3H2O and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, after the mixture is fully stirred by magnetic force, the mixture is transferred into a 100m L vacuum reaction kettle and put into a baking oven to be heated for 6 hours at 160 ℃, the mixture is taken out after treatment and put into ice water to be cooled to 5 ℃ in an ice bath, the filtration is carried out, deionized water and ethanol are used for washing for a plurality of times, and the Cd is obtained after drying0.45In1.10S2.10A precursor;
(2)Cd0.45In1.10S2.10preparation of a/CNTs composite material photocatalyst:
0.08g of carbon nanotubes are uniformly dispersed in 20m L deionized water, and 0.308g of Cd (NO) is weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O (indium nitrate trihydrate) and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, then the prepared carbon nano tube dispersion liquid is added, the mixture is stirred and ultrasonically mixed uniformly, then the mixture is transferred to a vacuum reaction kettle and put into an oven to be heated for 6 hours at 160 ℃, the treated mixture is taken out and put into ice water to be cooled to 5 ℃ in an ice bath, filtered, washed by deionized water and ethanol for a plurality of times and dried to obtain Cd0.45In1.10S2.10/CNTs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride reaches 78.69% within 60 min.
Example 8:
(1)Cd0.45In1.10S2.10preparing a precursor:
0.308g Cd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, after the mixture is fully stirred by magnetic force, the mixture is transferred into a 100m L vacuum reaction kettle and put into a baking oven to be heated for 12 hours at 160 ℃, the mixture is taken out after treatment and put into ice water to be cooled to 5 ℃ in an ice bath, the filtration is carried out, deionized water and ethanol are used for washing for a plurality of times, and the Cd is obtained after drying0.45In1.10S2.10A precursor;
(2)Cd0.45In1.10S2.10preparation of a/CNTs composite material photocatalyst:
0.08g of carbon nanotubes are uniformly dispersed in 20m L deionized water, and 0.308g of Cd (NO) is weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O (indium nitrate trihydrate) and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, then the prepared carbon nano tube dispersion liquid is added, the mixture is stirred and ultrasonically mixed uniformly, then the mixture is transferred to a vacuum reaction kettle and put into an oven to be heated at 160 ℃ for 12 hours, the treated mixture is taken out and put into ice water to be cooled to 5 ℃ in an ice bath, filtered, washed by deionized water and ethanol for a plurality of times and dried to obtain Cd0.45In1.10S2.10/CNTs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride reaches 79.28% within 60 min.
Example 9:
(1)Cd0.45In1.10S2.10preparing a precursor:
0.308g Cd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, after the mixture is fully stirred by magnetic force, the mixture is transferred into a 100m L vacuum reaction kettle and put into a baking oven to be heated for 8 hours at 160 ℃, the mixture is taken out after treatment and put into ice water to be cooled to 5 ℃ in an ice bath, the filtration is carried out, deionized water and ethanol are used for washing for a plurality of times, and the Cd is obtained after drying0.45In1.10S2.10A precursor;
(2)Cd0.45In1.10S2.10preparation of a/CNTs composite material photocatalyst:
0.04g of carbon nanotubes are uniformly dispersed in 20m L deionized water, and 0.308g of Cd (NO) is weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O (indium nitrate trihydrate) and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, then the prepared carbon nano tube dispersion liquid is added, the mixture is stirred and ultrasonically mixed uniformly, then the mixture is transferred to a vacuum reaction kettle and put into an oven to be heated for 8 hours at 160 ℃, the treated mixture is taken out and put into ice water to be cooled to 5 ℃ in an ice bath, filtered, washed by deionized water and ethanol for a plurality of times and dried to obtain Cd0.45In1.10S2.10/CNTs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride reaches 89.06% within 60 min.
Example 10:
(1)Cd0.45In1.10S2.10preparing a precursor:
0.308g Cd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O and 0.304g thiourea are put into a glass beaker, 50m L methanol is added to be completely dissolved, after the magnetic stirring is fully carried out, the mixture is transferred into a 100m L vacuum reaction kettle and put into a baking oven to be heated for 8 hours at 160 ℃, the mixture is taken out after the treatment and put into ice water to be cooled to 5 ℃ in an ice bath, the filtration is carried out, deionized water and ethanol are used for washing for a plurality of times, and the drying is carried out, namelyTo obtain Cd0.45In1.10S2.10A precursor;
(2)Cd0.45In1.10S2.10preparation of a/CNTs composite material photocatalyst:
0.16g of carbon nanotubes was uniformly dispersed in 20m L m deionized water, and 0.308g of Cd (NO) was weighed3)2·4H2O (cadmium nitrate tetrahydrate), 0.798g In (NO)3)3·3H2O (indium nitrate trihydrate) and 0.304g of thiourea are put into a glass beaker, 50m of L methanol is added to be completely dissolved, then the prepared carbon nano tube dispersion liquid is added, the mixture is stirred and ultrasonically mixed uniformly, then the mixture is transferred to a vacuum reaction kettle and put into an oven to be heated for 8 hours at 160 ℃, the treated mixture is taken out and put into ice water to be cooled to 5 ℃ in an ice bath, filtered, washed by deionized water and ethanol for a plurality of times and dried to obtain Cd0.45In1.10S2.10/CNTs composite photocatalyst.
(3) And (3) taking 0.08g of the sample in the step (2) to perform a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline hydrochloride reaches 90.10% within 60 min.
FIG. 1 shows Cd0.45In1.10S2.10UV-vis diagram of/CNTs composite photocatalyst, and Cd is shown in the diagram0.45In1.10S2.10Compared with the In not doped with Cd In photo-response capability of the/CNTs composite photocatalyst2S3Is greatly enhanced.
FIG. 2 shows Cd0.45In1.10S2.10XRD pattern of/CNTs composite photocatalyst, wherein Cd is clearly shown in the pattern0.45In1.10S2.10CNTs and In2S3Characteristic peak of (a);
FIG. 3 shows Cd0.45In1.10S2.10TEM image of/CNTs composite photocatalyst, from which Cd can be seen0.45In1.10S2.10The shape of the/CNTs is a two-dimensional square sheet-shaped load on a curved tubular structure, wherein Cd0.45In1.10S2.10The size is 200-500 nm.
Claims (7)
1. A kind ofThe equal-ratio sulfur indium cadmium composite photocatalyst is characterized by being prepared by the following method: uniformly dispersing carbon nanotubes in deionized water to obtain carbon nanotube dispersion, and adding Cd (NO)3)2·4H2O (cadmium nitrate tetrahydrate), In (NO)3)3·3H2Putting O (indium nitrate trihydrate) and thiourea into a glass beaker, adding methanol to completely dissolve the O (indium nitrate trihydrate) and the thiourea, adding the prepared carbon nano tube dispersion liquid, stirring and ultrasonically mixing the mixture uniformly, then transferring the mixture into a vacuum reaction kettle, putting the vacuum reaction kettle into an oven to heat, taking the mixture out after treatment, putting the mixture into ice water to cool the mixture to 5 ℃, filtering the mixture, washing the mixture with deionized water and ethanol for a plurality of times, and drying the mixture to obtain Cd0.45In1.10S2.10CNTs composite photocatalyst; controlling the molar ratio of cadmium nitrate tetrahydrate, indium nitrate trihydrate and thiourea and the adding amount of the carbon nano tube to obtain the Cd0.45In1.10S2.10And the mass ratio of the CNTs, the solvent thermal synthesis temperature and time, thereby obtaining the non-equal ratio sulfur indium cadmium composite photocatalyst with the optimal degradation effect.
2. The unequal-ratio cadmium indium sulfide composite photocatalyst as claimed in claim 1, wherein the molar ratio of cadmium nitrate tetrahydrate, indium nitrate trihydrate and thiourea is 1: 2.5: 4.
3. the unequal-ratio S, in and Cd composite photocatalyst as claimed in claim 1, wherein the prepared Cd0.45In1.10S2.10And CNTs in a mass ratio of 5: 1.
4. the composite photocatalyst of claim 1, wherein the temperature of the solvent heat treatment is 140 ℃ and 180 ℃; the time of solvent heat treatment is 6-12 h.
5. The anisometric cadmium indium sulfide composite photocatalyst as claimed in claim 4, wherein the temperature of the solvothermal treatment is 160 ℃; the time of solvent heat treatment is 8 h.
6. The unequal-ratio S, in and Cd composite photocatalyst as claimed in claim 1, wherein the Cd is Cd0.45In1.10S2.10The morphology is a two-dimensional square sheet type structure, and the size is 200 and 500 nm; cd [ Cd ]0.45In1.10S2.10the/CNTs are two-dimensional square sheet-shaped loaded on a curved tubular structure.
7. The use of the non-equal proportion S, in, Cd composite photocatalyst as claimed in claim 1, in visible light for degrading tetracycline hydrochloride in antibiotic wastewater.
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| CN102557002A (en) * | 2011-11-29 | 2012-07-11 | 上海师范大学 | Carbon nanotube/ternary chalcogenide semiconductor nano composite material and preparation method thereof |
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| CN102557002A (en) * | 2011-11-29 | 2012-07-11 | 上海师范大学 | Carbon nanotube/ternary chalcogenide semiconductor nano composite material and preparation method thereof |
| CN103316692A (en) * | 2013-06-24 | 2013-09-25 | 江苏大学 | Preparation method and application of CdS/CNTs composite photocatalyst |
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