CN110560104A - Ni2Preparation method and application of P/NiCo-LDH composite photocatalytic material - Google Patents
Ni2Preparation method and application of P/NiCo-LDH composite photocatalytic material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 93
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000004098 Tetracycline Substances 0.000 claims abstract description 19
- 229960002180 tetracycline Drugs 0.000 claims abstract description 19
- 229930101283 tetracycline Natural products 0.000 claims abstract description 19
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 19
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 21
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 20
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 238000006731 degradation reaction Methods 0.000 abstract description 20
- 230000015556 catabolic process Effects 0.000 abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000005447 environmental material Substances 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- -1 transition metal nickel phosphide Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 229940072172 tetracycline antibiotic Drugs 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 210000000936 intestine Anatomy 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- 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
- B01J23/755—Nickel
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/19—
-
- 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
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of environmental materials, and particularly relates to Ni2A preparation method and application of a P/NiCo-LDH composite photocatalytic material. The invention uses transition metal nickel phosphide as a promoter which can replace noble metal to carry out load modification on NiCo-LDH, and Ni is added in the process of synthesizing NiCo-LDH at low temperature2P mixed solution, and growing in situ to obtain Ni2P is loaded on NiCo-LDH to obtain Ni2P/NiCo-LDH composite photocatalytic material. The composite photocatalytic material prepared by the invention has simple and convenient preparation process and is similar to a pure NiCo-LDH catalytic materialCompared with the prior art, the tetracycline degradation agent has excellent degradation effect on tetracycline in a simulated degradation process.
Description
Technical Field
The invention belongs to the field of environmental materials, and particularly relates to Ni2A preparation method and application of a P/NiCo-LDH composite photocatalytic material.
background
Layered Double Hydroxides (LDH) are layered compounds formed by a brucite layer structure with positive charges and anions with negative charges filled between layers, are called layered double hydroxides, and are also called hydrotalcite-like compounds. LDH materials of different physical and chemical properties can be regulated by varying the metal ions and anions, due to the tunability of the metal elements and anions. The LDH material has good adsorption effect, specific surface area and abundant peak groups on the surface, and is often used as a carrier material and an adsorption material.
The modification of noble metals or rare earth metals generally shows good catalytic performance and stability, but the noble metals or rare earth metals are not beneficial to practical use due to the problems of price and content. Non-noble metals, such as phosphide, sulfide and alloy materials based on transition metals such as Fe, Co and Ni, all exhibit catalytic properties close to those of noble metals. Therefore, the development and utilization of transition metals instead of noble metals have great potential.
The tetracycline antibiotic as a broad-spectrum medicine can inhibit the multiplication of bacteria and play an important role in the treatment of bacterial infection diseases, but the tetracycline is difficult to be absorbed by intestines and stomach after entering a human body, and excessive tetracycline is discharged into a water body in the form of a parent compound. The abuse of the tetracycline in the aquaculture industry and the animal husbandry aggravates the pollution of the water environment, so that the research on the removal of the tetracycline in the water environment has important significance. Whether or not Ni can be constructed2The P-LDH composite material is used for removing tetracycline antibiotic pollution in the environment through photocatalysis, and no related research and report is found.
disclosure of Invention
In view of the above, the present invention is to provide Ni2The invention discloses a preparation method and application of a P/NiCo-LDH composite photocatalytic material, and researches Ni2P is taken as a promoter, the formation mechanism of the P in the aspect of modifying LDH photocatalytic materials and the advantage of the P in the aspect of photocatalytic performance are provided, and the Ni provided by the invention2P/NiCo-LDH composite photocatalytic material applied to antibiotics for treating wastewater pollutants, in particular to antibiotics for treating wastewater pollutantsA tetracycline.
The invention provides Ni2The preparation method of the P/NiCo-LDH composite photocatalytic material specifically comprises the following steps:
（1）Ni2Preparing a P precursor: dissolving nickel nitrate hexahydrate in deionized water, adding dilute ammonia water solution, stirring in water bath, reacting completely, centrifuging, washing precipitate, and drying to obtain Ni2p precursor;
（2）Ni2Preparation of P: sodium hypophosphite and Ni obtained in step (1)2Fully grinding and mixing the P precursor, reacting in a down-tube furnace under the protection of inert gas, washing and drying in vacuum to obtain Ni2P material, Ni2p material is added into water to be dispersed into Ni2P mixed liquor for standby;
（3）Ni2Preparing a P/NiCo-LDH composite photocatalytic material: dissolving nickel nitrate hexahydrate, cobalt nitrate hexahydrate and ammonium chloride in deionized water, stirring and mixing, dropwise adding a NaOH solution, and adding Ni prepared in the step (2)2Continuously stirring the P mixed solution for reaction, then centrifugally washing, and drying in vacuum to obtain Ni2P/NiCo-LDH。
preferably, the dosage ratio of the nickel nitrate hexahydrate, the deionized water and the ammonia water in the step (1) is 0.72 g: 72 ~ 108 mL: 75 mL.
Preferably, the temperature of the water bath in the step (1) is 70-90 ℃, the reaction time is 10-14 hours, and the temperature during drying is not more than 90 ℃.
Preferably, in step (2), sodium hypophosphite and Ni are added2The mass ratio of the P precursor is 20: 3; the inert gas is N2Or Ar;
Preferably, the temperature of the tubular furnace in the step (2) is 300 ℃, the calcining time is 5 h, the heating rate is 2 ℃/min, and the drying temperature is 60-70 ℃.
Preferably, Ni is as defined in step (2)2The concentration of the P mixed solution was 1 mg/mL.
preferably, in the step (3), the molar ratio of the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate and the ammonium chloride is 9: 6 ~ 9: 80, the molar ratio of the NaOH and the cobalt nitrate hexahydrate is 6: 11, the concentration of the NaOH solution is 0.08 mol/L,
Preferably, Ni is as defined in step (3)2the dosage ratio of the P mixed solution to the nickel nitrate hexahydrate is 2 ~ 8 mL: 0.90 mmol.
Preferably, the reaction temperature in the step (3) is 50-60 ℃, the reaction time is 10-14 hours, and the drying temperature is 60 ℃.
The invention also provides Ni prepared by the preparation method2The P/NiCo-LDH composite photocatalytic material is applied to the degradation of antibiotic wastewater, and is further applied to the degradation of tetracycline.
Compared with the prior art, the invention has the following beneficial effects:
The invention uses transition metal nickel phosphide as a promoter which can replace noble metal to carry out load modification on NiCo-LDH, and Ni is added in the process of synthesizing NiCo-LDH at low temperature2P mixed solution, and growing in situ to obtain Ni2P is loaded on NiCo-LDH to obtain Ni2P/NiCo-LDH composite photocatalytic material. XRD patterns in example 3 prove that the composite photocatalytic materials respectively contain Ni2Characteristic peaks of P and NiCo-LDH, TEM image shows that NiCo-LDH is a flower-like structure composed of sheets, Ni2P is loaded on the surface of NiCo-LDH in an irregular granular manner, the feasibility of the transition metal phosphide and the LDH material in the aspect of removing environmental pollutants by photocatalysis is researched, and an experimental basis and theoretical guidance are provided for researching the transition metal phosphide in the aspect of catalysis; the composite photocatalytic material prepared by the invention is simple and convenient in preparation process, and has excellent degradation effect on tetracycline in a simulated degradation process compared with a pure NiCo-LDH catalytic material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 shows Ni prepared in example 32A comparison graph of XRD patterns of the P/NiCo-LDH composite photocatalytic material and the pure NiCo-LDH catalytic material prepared in example 5 is shown;
FIG. 2 shows Ni prepared in example 32a TEM image of the P/NiCo-LDH composite photocatalytic material;
FIG. 3 shows Ni prepared in examples 1 to 4 of the present invention2And the P/NiCo-LDH composite photocatalytic material and the pure NiCo-LDH catalytic material prepared in the example 5 are compared with a tetracycline degradation curve.
Detailed Description
The invention is further illustrated by the following examples.
The reagents ethanol, sodium hydroxide, ammonia water and ammonium chloride used in the invention are purchased from national chemical reagent company Limited; nickel nitrate hexahydrate and cobalt nitrate hexahydrate were purchased from shanghai alatin reagent ltd; deionized water was prepared for the laboratory's deionized water system.
The photocatalytic activity of the composite catalytic material prepared in the invention is evaluated as follows: the method comprises the steps of irradiating in a photochemical reactor by a 300W xenon lamp, adding 100 mL of tetracycline simulation wastewater into a reactor, measuring an initial value, adding the prepared 10mg of composite catalytic material, magnetically stirring to keep the catalytic material in a suspended or floating state, carrying out dark adsorption for half an hour, sampling and analyzing at an interval of 15 min in the illumination process, carrying out centrifugal separation, taking supernatant, measuring absorbance by a spectrophotometer, and measuring the degradation rate. The formula of degradation rate: ƞ = [ (1-C)t/C0)]x100% where C0absorbance of the solution to equilibrium adsorption, CtThe absorbance of the solution was determined for a timed sample.
Example 1
（1）Ni2Preparing a P precursor: dissolving 0.72 g of nickel nitrate hexahydrate in 108mL of deionized water, dropwise adding 75 mL of 0.5mol/L dilute ammonia water solution, stirring in a water bath at 70 ℃, reacting for 10 hours, centrifuging to separate out precipitates, washing with deionized water and ethanol, and drying at 90 ℃ for later use;
（2）Ni2P preparation: 0.199 g of hypophosphorous acidSodium and 0.03 g of Ni prepared in step (1)2Fully grinding and mixing the P precursor, reacting in a tube furnace under the protection of Ar, calcining at 300 ℃ for 5 h to obtain black solid powder, washing, and vacuum drying at 70 ℃ to obtain Ni2P material, Ni2Adding P material into water to disperse into Ni with the concentration of 1 mg/mL2P mixed liquor for standby;
（3）Ni2Preparing a P/NiCo-LDH composite photocatalytic material: dissolving 0.90 mmol of nickel nitrate hexahydrate, 0.60 mmol of cobalt nitrate hexahydrate and 8.0 mmol of ammonium chloride in 40 mL of deionized water, stirring, then dropwise adding 20 mL of 0.5mol/L NaOH solution to promote reaction, continuously heating and stirring for reaction at the reaction temperature of 60 ℃, and adding 2 mL of Ni prepared in the step (2) after 2 hours2Continuously keeping the temperature of the P mixed solution, stirring and reacting for 10 hours, centrifuging, washing with deionized water and ethanol, and drying in vacuum to obtain Ni2P/NiCo-LDH composite photocatalytic material.
(4) Photocatalytic degradation test:
Taking Ni prepared in the step (3)2A P/NiCo-LDH composite photocatalytic material is subjected to a photocatalytic degradation test in a photochemical reactor, and the degradation rate of the photocatalytic material to tetracycline is measured to reach 31% within 90 min.
Example 2
（1）Ni2p precursor: dissolving 0.72 g of nickel nitrate hexahydrate in 72 mL of deionized water, dropwise adding 75.mL of 0.5mol/L dilute ammonia water solution, stirring in a water bath at 90 ℃, reacting for 12 hours, centrifuging to separate out solids, washing with deionized water and ethanol, and drying at 60 ℃ for later use;
（2）Ni2P preparation: 0.199 g of sodium hypophosphite and 0.03 g of Ni prepared in step (1)2P precursor is fully grinded and mixed in N2reacting in a tube furnace under protection, calcining at 300 ℃ for 5 h at the heating rate of 2 ℃/min to obtain black solid powder, washing, and vacuum drying at 60 ℃ to obtain Ni2P material, Ni2Adding P material into water to disperse into Ni with the concentration of 1 mg/mL2P mixed liquor for standby;
（3）Ni2P/NiCo-LDH complexesPreparing a composite photocatalytic material: dissolving 0.90 mmol of nickel nitrate hexahydrate, 0.90 mmol of cobalt nitrate hexahydrate and 8.0 mmol of ammonium chloride in 40 mL of deionized water, stirring, then dropwise adding 20 mL of 0.5mol/L NaOH solution to promote reaction, continuously heating and stirring for reaction at the reaction temperature of 60 ℃, and adding 4 mL of Ni prepared in the step (2) after 2 hours2Continuously keeping the temperature of the P mixed solution, stirring and reacting for 12 hours, centrifuging, washing with deionized water and ethanol, and drying in vacuum to obtain Ni2P/NiCo-LDH composite photocatalytic material.
(4) Photocatalytic degradation test:
Taking Ni prepared in the step (3)2A P/NiCo-LDH composite photocatalytic material is subjected to a photocatalytic degradation test in a photochemical reactor, and the degradation rate of the photocatalytic material to tetracycline is measured to reach 46% within 90 min.
Example 3
（1）Ni2P precursor: dissolving 0.72 g of nickel nitrate hexahydrate in 100 mL of deionized water, dropwise adding 75 mL of 0.5mol/L dilute ammonia water solution, stirring in a water bath at 80 ℃, reacting for 12 hours, centrifuging to separate out solids, washing with deionized water and ethanol, and drying at 60 ℃ for later use;
（2）Ni2P preparation: 0.199 g of sodium hypophosphite and 0.03 g of Ni prepared in step (1)2P precursor is fully grinded and mixed in N2Reacting in a tube furnace under protection, calcining at 300 ℃ for 5 h to obtain black solid powder, washing, and vacuum drying at 60 ℃ to obtain Ni2P material, Ni2adding P material into water to disperse into Ni with the concentration of 1 mg/mL2P mixed liquor for standby;
（3）Ni2Preparing a P/NiCo-LDH composite photocatalytic material: dissolving 0.90 mmol of nickel nitrate hexahydrate, 0.60 mmol of cobalt nitrate hexahydrate and 8.0 mmol of ammonium chloride in 40 mL of deionized water, stirring, then dropwise adding 20 mL of 0.5mol/L NaOH solution to promote reaction, continuously heating and stirring for reaction at the reaction temperature of 60 ℃, and adding 6mL of Ni prepared in the step (2) after 2 hours2P mixed solution, continuously keeping the temperature, stirring and reacting for 14 hours, centrifuging, washing with deionized water and ethanol, and drying in vacuumDrying to obtain Ni2P/NiCo-LDH composite photocatalytic material.
(4) Photocatalytic degradation test:
Taking Ni prepared in the step (3)2A P/NiCo-LDH composite photocatalytic material is subjected to a photocatalytic degradation test in a photochemical reactor, and the degradation rate of the photocatalytic material to tetracycline is measured to reach 42% within 90 min.
Example 4
（1）Ni2P precursor: dissolving 0.72 g of nickel nitrate hexahydrate in 100 mL of deionized water, dropwise adding 75 mL of 0.5mol/L dilute ammonia water solution, stirring in a water bath at 80 ℃, reacting for 14 hours, centrifuging to separate out solids, washing with deionized water and ethanol, and drying at 70 ℃ for later use;
（2）Ni2P preparation: 0.199 g of sodium hypophosphite and 0.03 g of Ni prepared in step (1)2Fully grinding and mixing the P precursor, introducing N2Reacting in a tube furnace under protection, calcining at 300 ℃ for 5 h to obtain black solid powder, washing, and vacuum drying at 60 ℃ to obtain Ni2P material, Ni2Adding P material into water to disperse into Ni with the concentration of 1 mg/mL2P mixed liquor for standby;
（3）Ni2preparing a P/NiCo-LDH composite photocatalytic material: dissolving 0.90 mmol of nickel nitrate hexahydrate, 0.70 mmol of cobalt nitrate hexahydrate and 8.0 mmol of ammonium chloride in 40 mL of deionized water, stirring, then dropwise adding 20 mL of 0.5mol/L NaOH solution to promote reaction, continuously heating and stirring for reaction at the reaction temperature of 60 ℃, and adding 8mL of Ni prepared in the step (2) after 2 hours2Continuously keeping the temperature of the P mixed solution, stirring and reacting for 11 hours, centrifuging, washing with deionized water and ethanol, and drying in vacuum at 60 ℃ to obtain Ni2P/NiCo-LDH composite photocatalytic material.
(4) photocatalytic degradation test:
Taking Ni prepared in the step (3)2A P/NiCo-LDH composite photocatalytic material is subjected to a photocatalytic degradation test in a photochemical reactor, and the degradation rate of the photocatalytic material to tetracycline is measured to reach 24% within 90 min.
Example 5: preparation of pure NiCo-LDH catalytic material
Dissolving 0.90 mmol of nickel nitrate hexahydrate, 0.60 mmol of cobalt nitrate hexahydrate and 8.0 mmol of ammonium chloride in 40 mL of deionized water, stirring, then dropwise adding 20 mL of 0.5mol/L NaOH solution, heating and stirring at 60 ℃ for 16 hours, centrifuging, washing with deionized water and ethanol, and drying in vacuum to obtain the pure NiCo-LDH catalytic material. The prepared pure NiCo-LDH catalytic material is placed in a photochemical reactor for a photocatalytic degradation test, and the degradation rate of the pure NiCo-LDH catalytic material to tetracycline is about 18% within 90 min.
FIG. 1 shows Ni prepared in example 32a comparison graph of XRD patterns of the P/NiCo-LDH composite photocatalytic material and the pure NiCo-LDH catalytic material prepared in example 5 is shown; in the figure, a is XRD of a pure NiCo-LDH catalytic material; b is Ni2an XRD (X-ray diffraction) pattern of the P/NiCo-LDH composite photocatalytic material; it can be seen that Ni is compared with the XRD pattern of the pure NiCo-LDH catalytic material2Besides the original NiCo-LDH characteristic peak, some new small peaks appear in the P/NiCo-LDH composite photocatalytic material map, and the new peaks belong to Ni by comparing with an XRD standard card2Diffraction Peak of P (PDF # 03-0953), indicating Ni produced2the P/NiCo-LDH composite photocatalytic material contains NiCo-LDH and Ni2P two materials.
FIG. 2 shows Ni prepared in example 32TEM image of P/NiCo-LDH composite photocatalytic material, it can be clearly seen from FIG. 2 that many small particles are combined with a flake-type flower-like material, wherein the small particles are Ni2P, the flake-type flower-like material is NiCo-LDH, and TEM images can show that the two materials are closely combined together.
FIG. 3 shows Ni prepared in examples 1 to 4 of the present invention2a graph comparing the degradation curves of the P/NiCo-LDH composite photocatalytic material and the pure NiCo-LDH catalytic material in example 5 to tetracycline; in the figure, LDH is pure NiCo-LDH catalytic material, and 1 is Ni prepared in example 12P/NiCo-LDH composite photocatalytic material, 2 is Ni prepared in example 22P/NiCo-LDH composite photocatalytic material, 3 is Ni prepared in example 32P/NiCo-LDH composite photocatalytic material, 4 is Ni prepared in example 42P/NiCo-LDH composite photocatalytic materialAnd (5) feeding. As can be seen from FIG. 3, the degradation rate of the pure NiCo-LDH catalytic material is about 18%, but Ni prepared in examples 1-42The degradation rate of the P/NiCo-LDH composite photocatalytic material is improved, and the degradation effect of the product obtained in example 2 is the best, which reaches 46 percent and is 2.6 times of the effect of the pure NiCo-LDH catalytic material, so that the Ni prepared by the method is proved2The P/NiCo-LDH composite photocatalytic material has more excellent tetracycline degradation effect.
while embodiments of the invention have been shown and described above, it is to be understood that the above embodiments are exemplary and not to be construed as limiting the invention, and that various embodiments or examples and features of various embodiments or examples described in this specification are capable of being combined and brought together by those skilled in the art without thereby conflicting with each other.
Claims (10)
1. Ni2The preparation method of the P/NiCo-LDH composite photocatalytic material is characterized by comprising the following steps of:
(1) Dissolving nickel nitrate hexahydrate in deionized water, adding dilute ammonia water solution, stirring in water bath, reacting completely, centrifuging, washing precipitate, and drying to obtain Ni2P precursor;
(2) Sodium hypophosphite and Ni obtained in step (1)2Fully grinding and mixing the P precursor, reacting in a down-tube furnace under the protection of inert gas, washing and drying in vacuum to obtain Ni2P material, Ni2P material is added into water to be dispersed into Ni2p mixed liquor for standby;
(3) dissolving nickel nitrate hexahydrate, cobalt nitrate hexahydrate and ammonium chloride in deionized water, stirring and mixing, dropwise adding a NaOH solution, and adding Ni prepared in the step (2)2continuously stirring the P mixed solution for reaction, then centrifugally washing, and drying in vacuum to obtain Ni2P/NiCo-LDH composite photocatalytic material.
2. the preparation method of the composite photocatalytic material as claimed in claim 1, wherein the dosage ratio of the nickel nitrate hexahydrate, the deionized water and the ammonia water in the step (1) is 0.72 g: 72 ~ 108 mL: 75 mL.
3. The method for preparing the composite photocatalytic material as claimed in claim 1, wherein the temperature of the water bath in the step (1) is 70-90 ℃, the stirring reaction time is 10-14 hours, and the drying temperature is not more than 90 ℃.
4. The method for preparing the composite photocatalytic material as claimed in claim 1, wherein the sodium hypophosphite and Ni in step (2)2The mass ratio of the P precursor is 20: 3; the inert gas is N2Or Ar.
5. The method for preparing the composite photocatalytic material as claimed in claim 1, wherein the temperature of the tubular furnace in the step (2) is 300 ℃, the calcination time is 5 hours, the heating rate is 2 ℃/min, and the drying temperature is 60-70 ℃.
6. The method for preparing a composite photocatalytic material according to claim 1, wherein the Ni in step (2)2The concentration of the P mixed solution was 1 mg/mL.
7. the preparation method of the composite photocatalytic material as claimed in claim 1, wherein the molar ratio of the nickel nitrate hexahydrate, the cobalt nitrate hexahydrate and the ammonium chloride in the step (3) is 9: 6 ~ 9: 80, the molar ratio of the NaOH and the cobalt nitrate hexahydrate is 6: 11, and the concentration of the NaOH solution is 0.08 mol/L.
8. the method for preparing a composite photocatalytic material according to claim 1, wherein the Ni in step (3)2the dosage ratio of the P mixed solution to the nickel nitrate hexahydrate is 2 ~ 8 mL: 0.90 mmol.
9. The method for preparing the composite photocatalytic material as claimed in claim 1, wherein the reaction temperature in the step (3) is 50-60 ℃, the reaction time is 10-14 hours, and the drying temperature is 60 ℃.
10. ni produced by the production method according ~ any one of claims 1 ~ 92The P/NiCo-LDH composite photocatalytic material is used for catalyzing and degrading tetracycline.
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