CN111790388B - Photocatalyst and preparation method and application thereof - Google Patents
Photocatalyst and preparation method and application thereof Download PDFInfo
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- CN111790388B CN111790388B CN202010545444.9A CN202010545444A CN111790388B CN 111790388 B CN111790388 B CN 111790388B CN 202010545444 A CN202010545444 A CN 202010545444A CN 111790388 B CN111790388 B CN 111790388B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 241000627951 Osteobrama cotio Species 0.000 claims abstract description 21
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 21
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 9
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 3
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 25
- 239000003446 ligand Substances 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229940011182 cobalt acetate Drugs 0.000 claims description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000004408 titanium dioxide Substances 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000003115 biocidal effect Effects 0.000 description 6
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229910010378 TiMOF Inorganic materials 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012984 antibiotic solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229960003405 ciprofloxacin Drugs 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000004298 light response Effects 0.000 description 3
- 150000002843 nonmetals Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000007547 defect Effects 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
- 229910052719 titanium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a photocatalyst and a preparation method thereofThe method and the application belong to the technical field of photocatalysis. The invention converts NH into 2 Dipping and depositing MIL-125(Ti) in a cobalt ion solution, and then calcining to prepare sponge solid CoTiO 3 /C‑TiO 2 The type II heterojunction photocatalyst not only has very large specific surface area and can provide more reaction active sites for catalytic reaction, but also introduces a carbon source to enhance the light absorption of the carbon source, so that CoTiO 3 /TiO 2 The photoproduction charge transfer type is changed from I type to II type, so that the composition of photoproduction charge is effectively inhibited, and the photocatalytic degradation activity of titanium dioxide is greatly improved. The preparation method of the photocatalyst is simple, the obtained photocatalyst has a novel structure, shows high-efficiency photocatalytic activity and good stability for resisting degradation of antibiotics under the action of visible light, and greatly improves the actual application prospect of the titanium dioxide photocatalyst.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and relates to a photocatalyst, and a preparation method and application thereof.
Background
With the rapid development of drugs in the past decades, antibiotics have been widely used and even abused in human and animal therapy. Since antibiotics are resistant to biological degradation and have a relatively stable chemical structure, conventional wastewater treatment techniques cannot effectively remove the antibiotics contained therein. Today, antibiotics are largely left in different environments, such as rivers, groundwater, soil, and even food on our tables. Research has shown that even trace concentrations (ng/L) of antibiotic residues can lead to the production of antibiotic-resistant bacteria, thereby posing a threat to human health. Therefore, it is necessary to find an effective method for completely removing the antibiotic residues in the wastewater.
Photocatalysis technology has received increasing attention in the field of antibiotic wastewater purification because of its high efficiency and long lasting stability and oxidizing ability. Among the known photocatalysts, titanium dioxide (TiO) 2 ) It has been extensively studied by researchers because of its non-toxicity, long-term stability and strong oxidizing power. But TiO is not limited to 2 There are two key issues: light absorption rangeThe narrow enclosure and the fast recombination rate of photo-generated electron-hole pairs seriously hinder the TiO 2 The practical production application of the method. Therefore, it is necessary to use TiO 2 Modification treatment is performed to solve the above-mentioned disadvantages.
An effective way for inhibiting the recombination of photogenerated electron-hole pairs is improved by constructing a heterojunction and a built-in electric field on a heterojunction interface. In recent years, TiO 2 With titanium-based perovskite oxides (ATiO) 3 ) (in particular, ATiO with visible light response) 3 ) Formed TiO 2 Heterojunction photocatalysts have attracted considerable attention because of their good photocatalytic activity for the degradation of toxic pollutants and the decomposition of water. ATiO reported so far 3 /TiO 2 The visible light response range of the heterojunction photocatalyst is narrow, and the visible light response capability is completely dependent on the ATO 3 . Therefore, a novel highly efficient wide absorbance ATiO was developed 3 /TiO 2 Heterojunction photocatalysts have important significance.
On the other hand, the non-metallic material doped with N, C, S, P is extended TiO 2 The method is simple and effective in photoresponse, reduces the recombination of photon-generated carriers and endows the photo-generated carriers with excellent photocatalytic activity. However, conventional non-metal doped TiO 2 The preparation method has obvious defects such as the need of adding an organic source and the aggregation of organic components. Therefore, a novel environment-friendly CoTiO was developed 3 Non-metal doped TiO 2 Composite materials are highly desirable.
Disclosure of Invention
In order to solve the defects and shortcomings in the prior art, the invention aims to provide a photocatalyst and a preparation method and application thereof.
In a first aspect, the present invention provides a method for preparing a photocatalyst, comprising the steps of: reacting NH 2 Dipping and depositing MIL-125(Ti) in a cobalt ion solution, and then calcining to obtain the photocatalyst.
The photocatalyst prepared by the preparation method is sponge solid CoTiO 3 /C-TiO 2 The type II heterojunction photocatalyst greatly improves the photocatalytic degradation activity of titanium dioxide. In the process of calcinationIn process, NH 2 MIL-125(Ti) is used as a sacrificial template of a sponge three-dimensional structure, so that the specific surface area of the photocatalyst is increased, more reaction active sites are provided for catalytic reaction, and a required carbon source is provided for the heterojunction photocatalyst, so that the photoresponse range is widened to 800 nm; by reaction on TiO 2 The introduction of carbon source enhances CoTiO 3 /C-TiO 2 Can also make CoTiO 3 /TiO 2 The type of photo-generated charge transfer is changed from type I to type II. In type II heterojunctions, the photogenerated electrons and holes migrate to CoTiO, respectively 3 And TiO 2 The surface can effectively inhibit the recombination of photo-generated charges. Meanwhile, the photocatalyst prepared by the preparation method shows high-efficiency photocatalytic activity and good stability for resisting degradation of antibiotics under the action of visible light.
As a preferred embodiment of the preparation process of the present invention, the NH 2 -mass ratio of MIL-125(Ti) to cobalt ions in said cobalt ion solution is greater than 2.5.
As a preferred embodiment of the preparation process of the present invention, the NH 2 -mass ratio of MIL-125(Ti) to cobalt ions in said cobalt ion solution is NH 2 -MIL-125 (Ti): cobalt ion is 1 (0.001 to 0.4).
As a preferable embodiment of the preparation method, the mass ratio of the NH2-MIL-125(Ti) to the cobalt ions in the cobalt ion solution is NH 2 -MIL-125 (Ti): cobalt ion 1: 0.15.
In a preferred embodiment of the preparation method of the present invention, the cobalt source in the cobalt ion solution is at least one of cobalt acetate, cobalt nitrate and cobalt sulfate.
As a preferable embodiment of the preparation method, the calcination treatment method is to heat the mixture to 400-600 ℃ at a rate of 1-3 ℃/min, and then to carry out heat preservation calcination for 1-2 hours.
As a preferred embodiment of the preparation process according to the invention, the NH 2 -the preparation method of MIL-125(Ti) comprises the following steps: mixing the ligand solution and titanate for hydrothermal reaction, and after the reaction is finished, carrying out solid-liquid separation to obtain the NH 2 -MIL-125(Ti)。
As a preferable embodiment of the preparation method of the present invention, the ligand solute of the ligand solution is 2-aminoterephthalic acid, and the solvent is a mixed solution of methanol and N, N-dimethylformamide; the titanate is at least one of tetrabutyl titanate, tetraethyl titanate and tetraisopropyl titanate.
As a preferred embodiment of the preparation method of the present invention, the molar ratio of the ligand solute of the ligand solution to the titanate is the ligand solute: titanate 3: 1; the temperature of the hydrothermal reaction is 100-180 ℃, and the time is 36-72 hours.
In a second aspect, the present invention provides a photocatalyst prepared by the above preparation method.
In a third aspect, the invention also provides application of the photocatalyst in removing antibiotics in wastewater.
Compared with the prior art, the invention has the following advantages: the invention uses a one-step calcination method to calcine NH doped with cobalt ions 2 MIL-125(Ti), and a series of sponge solid CoTiO obtained by controlling the addition of cobalt ions 3 /C-TiO 2 The obtained photocatalyst not only has very large specific surface area and can provide more reaction active sites for catalytic reaction, but also introduces a carbon source to enhance the light absorption of the catalyst, so that the CoTiO has high light absorption 3 /TiO 2 The photoproduction charge transfer type is changed from I type to II type, so that the composition of photoproduction charge is effectively inhibited, and the photocatalytic degradation activity of titanium dioxide is greatly improved. The photocatalyst prepared by the invention has a novel structure, shows high-efficiency photocatalytic activity and good stability for degrading antibiotics under the action of visible light, is simple in preparation method, and greatly improves the actual application prospect of the titanium dioxide photocatalyst.
Drawings
FIG. 1 shows CoTiO produced by the method of the present invention 3 /C-TiO 2 A topography of the photocatalyst;
FIG. 2 is a graph of the degradation performance of ciprofloxacin antibiotic;
FIG. 3 is a graph showing the removal rate of organic carbon content of ciprofloxacin antibiotic.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention is further illustrated by the following examples. It is apparent that the following examples are only a part of the embodiments of the present invention, and not all of them. It should be understood that the embodiments of the present invention are only for illustrating the technical effects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
Example 1 is an embodiment of the method for preparing the photocatalyst of the present invention, and the method for preparing the photocatalyst of the present example comprises the following steps:
(1) firstly, 10mL of mixed solution (V) of N, N-dimethylformamide and methanol is prepared N, N-dimethylformamide :V Methanol Adding 3mmol of 2-amino terephthalic acid, fully stirring for dissolving, adding 1mmol of tetrabutyl titanate, stirring at room temperature for 30min, putting into a polytetrafluoroethylene reaction kettle, reacting at 150 ℃ for 36 hours, cooling to room temperature after the reaction is finished, cleaning for 3 times by using N, N-dimethylformamide and methanol respectively, and then centrifugally drying to obtain NH 2 -MIL-125(Ti) powder;
(2) 1g of NH prepared in step (1) 2 dispersing-MIL-125 (Ti) powder in 100mL of cobalt acetate solution with the concentration of 0.5mg/mL, stirring for 30min, filtering and washing with deionized water, drying to obtain Co-TiMOF, heating the Co-TiMOF to 550 ℃ at the heating rate of 2 ℃/min, and preserving heat for 2 hours to obtain sponge-like CoTiO 3 /C-TiO 2 -1 a photocatalyst.
Example 2
Example 2 is an embodiment of the preparation method of the photocatalyst of the present invention, the preparation method of the photocatalyst of this example is the same as the preparation method of example 1 except that the cobalt acetate solution is used in a concentration of 1 mg/mL; the obtained photocatalyst is CoTiO with a sponge solid shape 3 /C-TiO 2 -2 a photocatalyst.
Example 3
Example 3 is an embodiment of the method of preparing the photocatalyst of the present invention, which is a method of preparing the photocatalyst of this example except that cobalt acetate solution is usedThe preparation method is the same as the preparation method of the embodiment 1 except that the concentration is 1.5 mg/mL; the obtained photocatalyst is CoTiO with a sponge solid shape 3 /C-TiO 2 -3 a photocatalyst.
Example 4
Example 4 is an embodiment of the method for preparing the photocatalyst of the present invention, and the method for preparing the photocatalyst of this example is the same as the method for preparing example 1 except that the cobalt acetate solution is used in a concentration of 4 mg/mL; the obtained photocatalyst is CoTiO with a sponge solid shape 3 /C-TiO 2 -4 photocatalyst.
Example 5
Example 5 is an embodiment of the method for preparing the photocatalyst of the present invention, and the method for preparing the photocatalyst of the present example comprises the following steps:
(1) firstly, 10mL of mixed solution (V) of N, N-dimethylformamide and methanol is prepared N, N-dimethylformamide :V Methanol Adding 3mmol of 2-amino terephthalic acid, fully stirring for dissolving, adding 1mmol of tetrabutyl titanate, stirring at room temperature for 30min, putting into a polytetrafluoroethylene reaction kettle, reacting at 150 ℃ for 36 hours, cooling to room temperature after the reaction is finished, cleaning for 3 times by using N, N-dimethylformamide and methanol respectively, and then centrifugally drying to obtain NH 2 -MIL-125(Ti) powder;
(2) 1g of NH prepared in step (1) 2 dispersing-MIL-125 (Ti) powder in 100mL of cobalt acetate solution with the concentration of 0.01mg/mL, stirring for 30min, filtering and washing with deionized water, drying to obtain Co-TiMOF, heating the Co-TiMOF to 550 ℃ at the heating rate of 2 ℃/min, and preserving heat for 2 hours to obtain sponge-like CoTiO 3 /C-TiO 2 -5 a photocatalyst.
Comparative example 1
The comparative example provides a method for preparing a photocatalyst, comprising the steps of:
(1) firstly, 10mL of mixed solution (V) of N, N-dimethylformamide and methanol is prepared N, N-dimethylformamide :V Methanol 2-amino terephthalic acid (3 mmol) was added thereto, and after sufficiently stirring and dissolving, 1mmol of titanic acid was added theretoStirring tetrabutyl ester at room temperature for 30min, placing into a polytetrafluoroethylene reaction kettle, reacting at 150 deg.C for 36 hr, cooling to room temperature after reaction, cleaning with N, N-dimethylformamide and methanol for 3 times, and centrifuging and drying to obtain NH 2 -MIL-125(Ti) powder;
(2) NH prepared in the step (1) 2 Heating MIL-125(Ti) powder to 600 ℃ at a heating rate of 1 ℃/min, and then preserving heat for 1 hour to obtain sponge solid C-TiO 2 A photocatalyst.
Comparative example 2
The comparative example provides a method for preparing a photocatalyst, comprising the steps of:
(1) firstly, 10mL of mixed solution (V) of N, N-dimethylformamide and methanol is prepared N, N-dimethylformamide :V Methanol Adding 1mmol of tetrabutyl titanate, stirring at room temperature for 30min, putting the mixture into a polytetrafluoroethylene reaction kettle, reacting at 150 ℃ for 72 hours, cooling to room temperature after the reaction is finished, cleaning with N, N-dimethylformamide and methanol for 3 times respectively, and then centrifuging and drying to obtain TiO 2 Powder;
(2) 1g of TiO prepared in step (1) 2 Dispersing the powder in 100mL cobalt acetate solution with the concentration of 1.5mg/mL, stirring for 30min, filtering and washing with deionized water, and drying to obtain Co-TiO 2 Then adding Co-TiO 2 Heating to 400 ℃ at the heating rate of 3 ℃/min, and then preserving heat for 2 hours to obtain CoTiO 3 A photocatalyst.
Performance testing
The photocatalysts of the examples 1 to 4 and the comparative examples 1 to 2 are subjected to a photocatalytic effect test, and the specific test process is as follows: weighing 100mg of photocatalyst, adding into 150mL of ciprofloxacin antibiotic solution with concentration of 10mg/L, stirring in dark for 30min to achieve adsorption balance, irradiating with visible light by using a 300W xenon lamp to perform photocatalytic reaction, taking about 7mL of solution every 5min, centrifuging and filtering the catalyst, measuring the absorbance of the antibiotic solution in filtrate by using an ultraviolet-visible spectrophotometer, plotting by using time as an abscissa and using the concentration ratio of the antibiotic solution in the filtrate to the original concentration as an ordinate, and drawing by using the time as an abscissaThe experimental results of the catalytic effect are shown in FIG. 2, and the results show that the synthesized spongy CoTiO 3 /C-TiO 2 The photocatalytic degradation performance of the (X ═ 1,2,3,4) photocatalyst is better than that of the cobalt-titanium ore CoTiO 3 With C-TiO doped with non-metals 2 The photocatalytic degradation rate of the photocatalyst can reach 99% in 120 min. The total organic carbon content of the filtrate was analyzed by a total organic carbon content analyzer, and the results are shown in FIG. 3, which indicates that the synthesized spongy CoTiO 3 /C-TiO 2 The total organic carbon removal rate of the X-ray catalyst is higher than that of perovskite CoTiO 3 With C-TiO doped with non-metals 2 The removal rate of the photocatalyst can reach 76 percent at most.
The above examples and comparative examples are illustrated with cobalt acetate and tetrabutyl titanate as examples, and similar effects can be obtained by using other cobalt sources (e.g., cobalt nitrate, cobalt sulfate) and titanium sources (e.g., tetraethyl titanate, tetraisopropyl titanate) in the actual production process.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. A method for preparing a photocatalyst, comprising the steps of: reacting NH 2 Dipping and depositing MIL-125(Ti) in a cobalt ion solution, and then calcining to obtain the sponge solid CoTiO 3 /C-TiO 2 A type II heterojunction photocatalyst;
the calcining treatment method comprises the steps of heating to 400-600 ℃ at the speed of 1-3 ℃/min, and then carrying out heat preservation and calcination for 1-2 hours;
the NH 2 -the preparation method of MIL-125(Ti) comprises the following steps: mixing the ligand solution and titanate for hydrothermal reaction, and after the reaction is finished, carrying out solid-liquid separation to obtain the NH 2 -MIL-125(Ti)；
The ligand solute of the ligand solution is 2-amino terephthalic acid, and the solvent is a mixed solution of methanol and N, N-dimethylformamide; the titanate is at least one of tetrabutyl titanate, tetraethyl titanate and tetraisopropyl titanate.
2. The method of claim 1, wherein the NH is 2 -mass ratio of MIL-125(Ti) to cobalt ions in said cobalt ion solution is NH 2 -MIL-125 (Ti): cobalt ion is 1 (0.001-0.4).
3. The method of claim 2, wherein the NH is 2 -mass ratio of MIL-125(Ti) to cobalt ions in said cobalt ion solution is NH 2 -MIL-125 (Ti): cobalt ion 1: 0.15.
4. The method according to claim 1, wherein the cobalt source in the cobalt ion solution is at least one of cobalt acetate, cobalt nitrate, and cobalt sulfate.
5. The method of claim 1, wherein the ligand solution has a molar ratio of ligand solute to titanate of ligand solute: titanate 3: 1; the temperature of the hydrothermal reaction is 100-180 ℃, and the time is 36-72 hours.
6. A photocatalyst produced by the production method as set forth in any one of claims 1 to 5.
7. Use of the photocatalyst of claim 6 for the removal of antibiotics from wastewater.
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