CN110624595A - Calcium-indium-sulfur/titanium carbide photocatalytic composite material and preparation method thereof - Google Patents
Calcium-indium-sulfur/titanium carbide photocatalytic composite material and preparation method thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 Calcium-indium-sulfur Chemical compound 0.000 title description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title description 2
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 80
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 8
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims abstract description 8
- 239000002135 nanosheet Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 230000015556 catabolic process Effects 0.000 claims description 8
- 238000006731 degradation reaction Methods 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 239000000969 carrier Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 230000031700 light absorption Effects 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 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 description 16
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 16
- 239000011941 photocatalyst Substances 0.000 description 13
- 239000010936 titanium Substances 0.000 description 12
- 230000006798 recombination Effects 0.000 description 8
- 238000005215 recombination Methods 0.000 description 7
- 230000000593 degrading effect Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 229910009818 Ti3AlC2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a CaIn2S4/Ti3C2Photocatalytic composite material and preparation method thereof, and CaIn2S4/Ti3C2In the photocatalytic composite material, Ti3C2Is a two-dimensional organ-shaped structure, CaIn2S4Is a flower-shaped microsphere structure assembled by two-dimensional nano sheets, Ti3C2Distributed in CaIn2S4Around the flower-like microspheres. Two-dimensional layered Ti3C2Increased CaIn as cocatalyst2S4The light absorption and the transfer separation of the photogenerated carriers are realized, thereby improving the CaIn2S4Photocatalytic activity ofAnd (4) sex. CaIn of the invention2S4/Ti3C2The photocatalytic composite material can be used as a potential visible light catalytic material to effectively reduce carbon dioxide and degrade antibiotics. The preparation method is simple, mild in experimental conditions, simple to operate, low in cost, beneficial to large-scale production and has a certain application prospect.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and relates to CaIn2S4/Ti3C2A photocatalytic composite material and a preparation method thereof.
Background
In the world, the problems of energy shortage and environmental pollution are faced while the human society and economy develop at a high speed, the emission of a large amount of greenhouse gases, and the removal of dyes, heavy metal ions and antibiotics in wastewater become problems to be solved urgently. Among them, tetracycline antibiotics, the second major class of antibiotics currently produced and used globally, are widely used in the pharmaceutical industry, animal husbandry and aquaculture industry, and the large amount of discharged tetracycline has caused great harm to the ecosystem and human health. Therefore, the control and reduction of the residue of tetracycline hydrochloride in the environment is imminent.
Solar semiconductor photocatalysis technology is recognized as one of effective ways to solve environmental and energy problems at the same time, and is receiving attention. The metal sulfide has the advantages of narrow band gap, proper band edge potential and the like, and is considered as a potential photocatalytic material, such as CdS. However, CdS is easily corroded during a photocatalytic process and has poor photostability, so that its practical application is limited. In contrast, ternary chalcogenide AB2X4(A ═ Cu, Zn, Cd; B ═ In, Ga, Al; X ═ S, Se) has many advantages such as appropriate forbidden bandwidth, good photochemical stability and excellent optical properties, and is an ideal photocatalytic material, and attracts much attention.In particular, CaIn2S4Has good visible light absorption capacity and excellent photoelectric property, and is considered to be one of the choices of high-efficiency visible light photocatalyst. The patent (CN104971762A) discloses a visible light response type CaIn2S4The photocatalytic material has strong light absorption capacity and can effectively degrade organic dye under the irradiation of visible light. An article (International journal of Hydrogen Energy Volume 38, Issue 30,8October 2013, Pages 13153-2S4The hydrogen production efficiency of the photocatalyst reaches 30.92 mu mol g-1·h-1. However, the low solar energy utilization rate and the difficult separation of photon-generated carriers are key scientific problems, which limit the activity and practical application of the photocatalyst. Meanwhile, CaIn is concerned2S4Photocatalysts are used for reducing carbon dioxide and degrading antibiotics, and are rarely reported. The research of the photocatalyst with high efficiency and wide spectrum response is one of the key problems to be solved in the field of semiconductor photocatalysis, and is an urgent requirement for realizing the medium-and-long-term scientific and technical development planning of the country and promoting the development of the strategic emerging industry of the country.
The construction of semiconductor composite materials is an effective method for expanding light absorption and promoting the transfer and separation of photon-generated carriers. Two-dimensional layered Ti3C2A large number of coordination unsaturated surface atoms are exposed on the surface of the material, so that the material has high reactivity, more catalytic reaction active sites, excellent conductivity, high specific surface area and stability, can effectively solve the key scientific problem of difficult separation of photon-generated carriers when being used as a cocatalyst, and is favored by researchers in the field of photocatalysis (appl.Catal.B: environ.,2019,246, 12; adv.Funct.Mater.,2018,28, 1800136). Therefore, based on Ti3C2And CaIn2S4Construction of CaIn2S4/Ti3C2The photocatalytic composite material can expand the light absorption range and improve the photo-generated charge separation efficiency by utilizing the synergistic coupling effect of the photocatalytic composite material, so that the high-efficiency photocatalytic composite material is obtained.
Disclosure of Invention
The invention aims to solve the problems and provide a high-efficiency wide-spectrum response CaIn2S4/Ti3C2A photocatalytic composite material and a preparation method thereof. CaIn of the invention2S4/Ti3C2The photocatalytic composite material has good activity of degrading organic pollutants such as antibiotics and reducing carbon dioxide under the irradiation of visible light. The hydrothermal method adopted by the invention has the advantages of simple preparation method, convenient operation, low cost and the like, and is suitable for industrial production.
In order to achieve the purpose, the invention provides the technical scheme that: high-efficiency wide-spectrum response CaIn2S4/Ti3C2Photocatalytic composite material, said composite material having Ti3C2Dispersed in CaIn2S4Around flower-like microspheres, said Ti3C2Is a two-dimensional organ-shaped structure, the CaIn2S4Is a flower-shaped microsphere structure formed by self-assembling nano sheets.
In the above technical solution, preferably, the Ti3C2With CaIn2S4The mass ratio of (A) is 0.5-5%. With Ti3C2Increase in the ratio of (1), CaIn2S4/Ti3C2The light absorption properties of the photocatalytic composite material are enhanced, which facilitates the occurrence of photocatalytic reactions. In addition, when Ti3C2Is doped to pure CaIn2S4In the process, due to the proper electronic structure, photo-generated carriers in the photocatalysis process can be effectively transferred, so that the recombination of the photo-generated carriers is inhibited, and the CaIn is further improved2S4Photocatalytic activity of (1). However, when Ti is used3C2When the doping ratio of (A) exceeds an optimum value, Ti3C2The photocatalyst is taken as a recombination center to promote the recombination of photon-generated carriers, thereby reducing the photocatalytic activity. Therefore, the cocatalyst Ti in the composite photocatalytic material3C2The doping ratio of (a) will directly influence the photocatalytic activity. More preferably, the Ti is3C2With CaIn2S4The mass ratio of (B) is 3%.
The photocatalytic composite material disclosed by the invention has good visible light absorption, shows excellent photocatalytic activity when reducing carbon dioxide and degrading pollutants such as antibiotics, and can be used as a potential broad-spectrum response photocatalyst.
The invention also provides CaIn2S4/Ti3C2The preparation method of the photocatalytic composite material comprises the following steps:
first, Ti3A1C2Adding into HF acid, magnetically stirring at room temperature for etching, centrifuging, and vacuum drying to obtain accordion-shaped Ti3C2A material;
in a second step, a source of calcium, a source of indium and the Ti obtained3C2Dissolving in deionized water, and performing ultrasonic dispersion to obtain a uniform mixed solution A;
dissolving a sulfur source in deionized water, and performing ultrasonic stirring to obtain a solution B;
fourthly, dropwise adding the solution B into the solution A, uniformly stirring to obtain a mixed solution C, transferring the mixed solution C into a hydrothermal reaction kettle, reacting for 12-24 h at the constant temperature of 100-2S4/Ti3C2A photocatalytic composite material. In the above method, preferably, each 1g of Ti is3A1C220ml of HF acid with the mass fraction of 40 percent is needed; the molar ratio of the calcium source to the indium source to the sulfur source is 1:2: 4; the calcium source is at least one of calcium nitrate and calcium chloride; the indium source is at least one of indium nitrate and indium chloride; the sulfur source is at least one of flutolacetamide, thiourea and sulfur powder.
Preferably, in the solution A, the concentration of the calcium source is 0.05-0.2 mol/L; the concentration of the indium source is 0.1-0.4 mol/L; in the solution B, the concentration of the sulfur source is 0.2-0.8 mol/L.
The CaIn provided by the invention2S4/Ti3C2The photocatalytic composite material has the advantages of no toxicity, low cost and the like, has good activity of reducing carbon dioxide under the irradiation of visible light, and can also haveEffectively degrading pollutants such as antibiotics and the like. The preparation method is simple, mild in experimental conditions, simple to operate, low in cost, beneficial to large-scale production and has a certain application prospect.
Drawings
FIG. 1 shows CaIn synthesized in example 1 of the present invention2S4/Ti3C2X-ray diffraction pattern of (a).
FIG. 2 shows CaIn synthesized in example 1 of the present invention2S4/Ti3C2Scanning electron micrograph (c).
FIG. 3 shows CaIn synthesized in example 1 of the present invention2S4/Ti3C2Light absorption spectrum of (a).
FIG. 4 shows CaIn synthesized in example 1 of the present invention2S4/Ti3C2A photocurrent map of (a).
FIG. 5 shows CaIn synthesized in example 1 of the present invention2S4/Ti3C2Graph of efficiency of photocatalytic reduction of carbon dioxide.
FIG. 6 shows CaIn synthesized in example 1 of the present invention2S4/Ti3C2The efficiency chart of the photocatalytic degradation of tetracycline hydrochloride is shown.
Detailed Description
The technical scheme of the invention is further illustrated by the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, various changes or modifications may be made by one skilled in the art after reading the disclosure of the present invention, and equivalents may fall within the scope of the invention as defined by the claims appended hereto.
Example 1
1) Preparation of the photocatalyst
1g Ti3AlC2Slowly adding into 20mL HF solution with mass fraction of 40%, stirring at room temperature for 72h, cleaning, and vacuum drying to obtain organ-shaped Ti3C2A material.
Adding 2mmol of CaCl2·2H2O、4mmol InCl3·4H2O and Ti3C2(8,24 and 40mg) were added to 40ml of deionized water, respectively, and subjected to ultrasonic dispersion for 30 minutes to obtain a solution A. 8mmol of thioacetamide was added to 40ml of deionized water, and stirred for 30 minutes to obtain a B solution. And then, dropwise adding the solution B into the solution A, stirring for 60 minutes to form a uniformly dispersed mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 12 hours at a constant temperature of 160 ℃, cooling to room temperature, cleaning, and drying in vacuum to obtain CaIn2S4/Ti3C2A composite material. Addition of 8,24 and 40mg of Ti3C2Prepared CaIn2S4/Ti3C2The composite materials are respectively named CaIn2S4/Ti3C2-8，CaIn2S4/Ti3C2-24 and CaIn2S4/Ti3C2-40. In the absence of Ti3C2Under the conditions of (1), pure CaIn2S4Was synthesized in the same manner.
FIG. 1 shows CaIn2S4/Ti3C2X-ray diffraction pattern of the photocatalytic composite material. As shown in fig. 1, peaks at 27.4 °, 33.2 °, 43.5 °, and 47.7 ° correspond to CaIn, respectively2S4(311) Diffraction peaks of (400), (511), (440), indicating CaIn produced2S4Is a cubic phase.
FIG. 2 shows CaIn2S4/Ti3C2-40 scanning electron micrographs of the photocatalytic composite material. As can be seen from the figure, Ti3C2Is a two-dimensional organ-shaped structure, CaIn2S4Is a flower-like microsphere structure formed by self-assembling nano sheets, Ti3C2Distributed in CaIn2S4Around the flower-like microspheres.
FIG. 3 shows CaIn2S4/Ti3C2Ultraviolet-visible absorption spectrum of the photocatalytic composite material. As can be seen from the figure, CaIn2S4/Ti3C2The photocatalytic composite material has strong light absorption in both ultraviolet and visible light regions,can be used as a high-efficiency wide-spectrum response photocatalytic composite material.
FIG. 4 shows CaIn2S4/Ti3C2Photocurrent spectra of the photocatalytic composite material. As can be seen from the figure, CaIn2S4/Ti3C2The photocurrent intensity of the photocatalytic composite material is obviously higher than that of pure CaIn2S4And with Ti3C2Increase in the doping ratio, CaIn2S4/Ti3C2The photocurrent intensity of the photocatalytic composite material was enhanced, indicating that Ti was doped3C2The recombination of photogenerated carriers is suppressed. However, when Ti is used3C2When the doping ratio exceeds 3%, CaIn2S4/Ti3C2The photocurrent intensity of the photocatalytic composite material decreased, indicating excessive Ti3C2The recombination of photogenerated carriers is inhibited as recombination centers, which is disadvantageous for the progress of the photocatalytic reaction.
2) Photocatalytic experiment
Characterizing the prepared CaIn2S4/Ti3C2The photocatalytic activity of the photocatalytic composite material is realized when carbon dioxide is reduced and tetracycline hydrochloride is degraded.
The process of photocatalytic reduction of carbon dioxide: 10ml of water and prepared CaIn2S4/Ti3C2The photocatalytic composite material (100mg) is uniformly mixed to form a suspension, and the suspension is coated on ITO glass by a screen printing method to form a photocatalyst film. The catalyst film and 1g of sodium bicarbonate were simultaneously placed in a 100ml sealed glass reaction flask, evacuated and then 5ml of a sulfuric acid solution was added dropwise to the glass reaction flask in reaction with the sodium bicarbonate to generate carbon dioxide gas. And (4) turning on a xenon lamp light source to perform a photocatalytic reaction. The content of the product was analyzed on-line at intervals by gas chromatography, and its photocatalytic activity was shown in FIG. 5.
The process of degrading tetracycline hydrochloride by photocatalysis comprises the following steps: the prepared CaIn2S4/Ti3C2Adding 50mg/L tetracycline hydrochloride solution (1g/L) into the photocatalytic composite material50ml) was added, and under magnetic stirring, after a dark reaction for 30 minutes, a xenon lamp light source was turned on, and a visible light source having a cutoff wavelength of 420nm was placed when using a xenon lamp, to perform a photocatalytic reaction. A certain amount of tetracycline hydrochloride solution is taken at intervals, an ultraviolet-visible spectrophotometer is used for testing the absorption spectrum of the solution, and the degradation rate of the tetracycline hydrochloride can be calculated through the change of the intensity of an absorption peak. The photocatalytic activity is shown in FIG. 6.
FIG. 5 shows the synthesized CaIn2S4And CaIn2S4/Ti3C2The effect of photocatalytic reduction of carbon dioxide. As can be seen from the figure, the product methane content increases significantly with increasing light exposure time. CaIn2S4And CaIn2S4/Ti3C2The average yield of the product methane reaches 8 and 13 mu mol.h respectively-1·g-1. Thus, with pure CaIn2S4In contrast, CaIn2S4/Ti3C2The effect of photocatalytic reduction of carbon dioxide is obviously improved.
FIG. 6 shows the synthesized CaIn2S4And CaIn2S4/Ti3C2The efficiency graph of the photocatalytic degradation of tetracycline hydrochloride. As can be seen from the figure, the photocatalytic activity is significantly improved with the increase of the light irradiation time. Under the irradiation of visible light, CaIn2S4/Ti3C2The degradation rate of tetracycline hydrochloride reaches 92 percent. Thus, with pure CaIn2S4In contrast, CaIn2S4/Ti3C2The effect of degrading tetracycline hydrochloride by photocatalysis is obviously improved.
Further, CaIn of the present invention2S4/Ti3C2The photocatalytic composite material is not prepared from CaIn2S4And Ti3C2Simple mixing of the two materials, when the CaIn is mixed under the same conditions2S4And Ti3C2Mixing the two according to the mass ratio of 3 percent to obtain CaIn2S4/Ti3C2Wl mixtures, tested for photocatalytic degradation of tetracycline hydrochloride. CaIn2S4/Ti3C2The degradation rate of wl to tetracycline hydrochloride reaches 62%, which is obviously lower than that of CaIn synthesized by the hydrothermal method of the invention2S4/Ti3C2Photocatalytic composite materials, because the interface contact of the mixture resulting from physical mixing is poor, resulting in rapid recombination of photogenerated carriers. Compared with a direct physical mixing method, the composite photocatalyst prepared by the hydrothermal method has a good contact interface, which is beneficial to transfer and separation of photon-generated carriers and can effectively inhibit the recombination of the photon-generated carriers, thereby achieving the purpose of enhancing the photocatalytic performance.
Example 2
4mmol of CaCl2·2H2O、8mmol InCl3·4H2O and 24mg Ti3C2Adding the mixture into 40ml of deionized water, and carrying out ultrasonic dispersion for 30 minutes to obtain a solution A. 16mmol of thioacetamide was added to 40ml of deionized water and stirred for 30 minutes to obtain a B solution. And then, dropwise adding the solution B into the solution A, stirring for 60 minutes to form a uniformly dispersed mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 12 hours at a constant temperature of 120 ℃, cooling to room temperature, cleaning, and drying in vacuum to obtain CaIn2S4/Ti3C2A composite material.
The test method described in example 1 was used to test the degradation activity of the photocatalyst prepared in this example to tetracycline hydrochloride under visible light irradiation, and the degradation rate to tetracycline hydrochloride reached 90%.
Example 3
Adding 3mmol of CaCl2·2H2O、6mmol InCl3·4H2O and 40mg Ti3C2Adding the mixture into 40ml of deionized water, and carrying out ultrasonic dispersion for 30 minutes to obtain a solution A. 12mmol of thioacetamide was added to 40ml of deionized water, and stirred for 30 minutes to obtain a B solution. And then, dropwise adding the solution B into the solution A, stirring for 60 minutes to form a uniformly dispersed mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 12 hours at a constant temperature of 180 ℃, cooling to room temperature, washing, and drying in vacuum to obtain CaIn2S4/Ti3C2A composite material.
The photocatalyst prepared in this example was tested for reduction of carbon dioxide under visible light irradiation by the test method described in example 1, and the average yield of methane reached 15. mu. mol. h-1·g-1。
Example 4
2mmol of Ca (NO)3)2·4H2O、4mmol In(NO3)3·4.5H2O and 8mg Ti3C2Adding the mixture into 40ml of deionized water, and carrying out ultrasonic dispersion for 30 minutes to obtain a solution A. 8mmol of thiourea was added to 40ml of deionized water and stirred for 30 minutes to obtain a solution B. And then, dropwise adding the solution B into the solution A, stirring for 60 minutes to form a uniformly dispersed mixed solution, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 12 hours at a constant temperature of 120 ℃, cooling to room temperature, cleaning, and drying in vacuum to obtain CaIn2S4/Ti3C2A composite material.
The test method described in example 1 was used to test the degradation activity of the photocatalyst prepared in this example to tetracycline hydrochloride under visible light irradiation, and the degradation rate to tetracycline hydrochloride reached 97%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention, and is provided for illustration and description. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. CaIn2S4/Ti3C2A photocatalytic composite material, characterized in that Ti is contained in the photocatalytic composite material3C2Distributed in CaIn2S4Around flower-like microspheres, said Ti3C2Is an organ-shaped structure formed by stacking two-dimensional sheets, the CaIn2S4Is a flower-shaped microsphere structure formed by self-assembling nano sheets.
2. The CaIn of claim 12S4/Ti3C2Photocatalytic composite material, characterized in that Ti is contained in the material3C2With CaIn2S4The mass ratio is 0.5-5%.
3. CaIn2S4/Ti3C2The preparation method of the photocatalytic composite material is characterized by comprising the following steps: the preparation method comprises the following steps:
first, Ti3A1C2Adding into HF acid, magnetically stirring at room temperature for etching, centrifuging, and vacuum drying to obtain accordion-shaped Ti3C2A material;
in a second step, a source of calcium, a source of indium and the Ti obtained3C2Dissolving in deionized water, and performing ultrasonic dispersion to obtain a uniform mixed solution A;
dissolving a sulfur source in deionized water, and performing ultrasonic stirring to obtain a solution B;
fourthly, dropwise adding the solution B into the solution A, uniformly stirring to obtain a mixed solution C, transferring the mixed solution C into a hydrothermal reaction kettle, reacting for 12-24 h at the constant temperature of 100-2S4/Ti3C2A photocatalytic composite material.
4. The CaIn of claim 32S4/Ti3C2A process for the preparation of a photocatalytic composite material, characterized in that in the first step every 1g of Ti3A1C220ml of 40% HF acid are used.
5. The CaIn of claim 32S4/Ti3C2The preparation method of the photocatalytic composite material is characterized in thatThe molar ratio of the calcium source to the indium source to the sulfur source is 1:2: 4.
6. The CaIn of claim 32S4/Ti3C2The preparation method of the photocatalytic composite material is characterized in that the calcium source is at least one of calcium nitrate and calcium chloride, and the concentration of the calcium source in the solution A is 0.05-0.2 mol/L.
7. The CaIn of claim 32S4/Ti3C2The preparation method of the photocatalytic composite material is characterized in that the indium source is at least one of indium nitrate and indium chloride, and the concentration of the indium source in the solution A is 0.1-0.4 mol/L.
8. The CaIn according to claim 32S4/Ti3C2The preparation method of the photocatalytic composite material is characterized in that the sulfur source is at least one of dimethylacetamide, thiourea and sulfur powder, and the concentration of the sulfur source in the solution B is 0.2-0.8 mol/L.
9. CaIn2S4/Ti3C2Use of a photocatalytic composite material, characterized in that the composite material is capable of being used for photocatalytic reduction of carbon dioxide and degradation of antibiotics.
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