CN113304767A - Magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst and preparation method and application thereof - Google Patents
Magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 76
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 75
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 67
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 41
- 239000010452 phosphate Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910016516 CuFe2O4 Inorganic materials 0.000 claims abstract description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 13
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 10
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- 238000003756 stirring Methods 0.000 claims description 24
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- 238000006243 chemical reaction Methods 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 239000012467 final product Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
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- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
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- 235000021317 phosphate Nutrition 0.000 description 25
- 239000000243 solution Substances 0.000 description 18
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- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
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- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 1
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- DDBMQDADIHOWIC-UHFFFAOYSA-N aclonifen Chemical compound C1=C([N+]([O-])=O)C(N)=C(Cl)C(OC=2C=CC=CC=2)=C1 DDBMQDADIHOWIC-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 208000020470 nervous system symptom Diseases 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
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- 231100000572 poisoning Toxicity 0.000 description 1
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- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
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- 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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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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Abstract
The invention discloses a magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst and a preparation method and application thereof, and belongs to the technical field of photocatalystsGraphite and CuFe2O4The preparation method of the catalyst comprises the steps of firstly preparing NrGO/CuFe2O4Then combining the magnetic nitrogen-doped reduced graphene/phosphate visible-light-induced photocatalyst with nitrate by adopting an in-situ coprecipitation method to obtain magnetic nitrogen-doped reduced graphene/phosphate visible-light-induced photocatalyst powder; the magnetic nitrogen-doped reduced graphene/phosphate visible-light-induced photocatalyst is applied to removal of 2,4-DCP in water. The magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst provided by the invention has the advantages of high magnetization intensity, strong electron conductivity, high catalytic activity, stable physicochemical property and good removal effect on refractory organic matters; the preparation method of the catalyst is simple, low in cost, easy to control the process and environment-friendly.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst and a preparation method and application thereof.
Background
Chlorophenols (CPCs) are a class of refractory organic pollutants and are widely applied to dyes in medicines, pesticides and industrial and agricultural production. Among various chlorophenol compounds, 2, 4-dichlorophenol (2,4-DCP) can be used for organic synthesis to prepare 2, 4-derivative bactericides, pesticide aclonifen (2,4-D) and the like, intermediates of ipara and medicine thiobis-dichlorophenol, and certain methyl compounds for preparing mothproof, anticorrosion and seed disinfection, and is widely applied to related industries such as chemical industry, agriculture and the like. It is highly corrosive and irritating to the eyes and skin. Anemia and various nervous system symptoms can be caused in severe cases of poisoning. And 2,4-DCP has anti-biodegradability in water due to the stable physicochemical structure of the DCP, and poses serious threats to aquatic organisms and human health. Therefore, in recent years, the removal of 2,4-DCP in water has been receiving more and more attention.
The traditional 2,4-DCP treatment process mainly comprises a flocculation method, an oxidation method, a biological method and the like; however, the use of conventional water treatment methods is limited due to the difficult biodegradability of 2,4-DCP itself, the limitation of membrane fouling, and the limitation of safety and economy. The visible light catalytic oxidation method is to directly utilize sunlight to excite a semiconductor system, generate various active species through a series of reactions, and generate physical and chemical reactions with pollutants adsorbed on the surface of the active species, so as to achieve the aim of removing organic matters through selective enrichment and oxidation; as a low-energy and high-efficiency treatment method, visible light photocatalysis is receiving more and more attention from people to remove 2,4-DCP in water.
The oxo acid catalyst has many advantages, such as stable structure (acid radical ions of sulfate, phosphate, etc.), and easy crystallization. Silver phosphate (Ag)3PO4) Has proper forbidden band width (2.36ev), obvious quantum efficiency (more than or equal to 90 percent) and higher surface energy, and is one of the most widely applied visible light catalysts. This makes the photocatalyst from H comparable to other visible light active photocatalysts2O to O2The oxidation potential of (a) is significantly enhanced. Has high photocatalytic degradation activity on various toxic pollutants under visible light. However, the use of phosphate in water treatment is limited by its photo-corrosiveness, poor electron transfer capability, poor surface adsorption, etc.
Therefore, against the above-mentioned drawbacks of phosphates, for Ag3PO4Certain modification is carried out to improve Ag3PO4The photoelectron conductivity of (1). The nitrogen-doped reduced graphene has high specific surface area and abundant functional groups, and can overcome Ag3PO4And (4) light corrosion. However, no catalyst for combining nitrogen-doped reduced graphene with phosphate exists at present.
In recent years, magnetic separation technology has been widely used in the field of water treatment, and is an efficient separation technology for separating different magnetic substances by the action of magnetic field force. Because the magnetic force of the magnetic substance in the magnetic field is many times larger than the gravity, the technology has the advantages of large treatment capacity, good solid-liquid separation effect, small occupied area and the like.
Disclosure of Invention
1. Technical problem to be solved
The invention aims to provide a magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst with high photocatalytic efficiency, to solve the problems in the prior art, and a preparation method and application of the photocatalyst in water treatment.
2. Technical scheme
In order to solve the problems, the invention adopts the following technical scheme:
a magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst has a structural formula as follows:
the invention also provides a preparation method of the magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst, and the preparation method of the magnetic nitrogen-doped reduced graphene/phosphate visible-light-induced photocatalyst comprises the following steps:
S1、NrGO/CuFe2O4the preparation of (1): dispersing 80-100 mg of nitrogen-doped reduced graphene oxide powder in 100mL of distilled water, and performing ultrasonic treatment to obtain a nitrogen-doped reduced graphene dispersion liquid; slowly adding Fe (NO) under stirring3)3·9H2O and Cu (NO)3)2·3H2O, after the metal salt is completely dissolved, heating the reaction mixture to 80 ℃, and then dropwise adding ammonia water until the pH value is 10; continuously stirring the reaction mixture for 3-5 hours to generate a precipitate; repeatedly washing the obtained precipitate with water, and drying to obtain NrGO/CuFe2O4；
S2, preparing a magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst: taking 100mg of NrGO/CuFe obtained in step S12O4Dispersing in 150-200 mL of deionized water, carrying out ultrasonic treatment, dropwise adding 12-16 mL of nitrate solution into the dispersion liquid, and continuously stirring for 6 hours; adding 10-15 mLNa into the reaction system2HPO4And continuously stirring the solution for 6h, centrifuging, collecting the final product, washing for multiple times, and drying overnight in vacuum to obtain the magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst powder.
Further, the preparation method of the nitrogen-doped reduced graphene oxide comprises the following steps:
s1-1, dissolving 300-400 mg of graphene in 100-150 mL of double distilled water, performing ultrasonic treatment, and stirring at a constant temperature until the liquid is transparent and clear to obtain a graphene dispersion liquid;
s1-2, adding 30-40 mu L of hydrazine hydrate into the dispersion liquid obtained in the step S1-1, then placing the dispersion liquid into a polytetrafluoroethylene-lined stainless steel autoclave, carrying out hydrothermal reaction for 20-24 h at 180-220 ℃, cooling to room temperature, separating, washing for multiple times, and drying for 4-8 h at 80 ℃ to obtain nitrogen-doped reduced graphene oxide (NrGO) powder.
Further, in step S1, Fe (NO)3)3·9H2The concentration of O is 0.07 mol.L-1，Cu(NO3)2·3H2The concentration of O is 0.035 mol.L-1The concentration of ammonia water is 0.5 to 1 mol.L-1Said Fe (NO)3)3·9H2O and Cu (NO)3)2·3H2The volume ratio of O is 1: 1.
Further, in step S2, the concentration of the nitrate solution was 100 mg/mL-1，Na2HPO4The concentration of the solution was 100 mg/mL-1。
Preferably, in step S2, the nitrate is AgNO3。
Preferably, the temperature rise rate of the calcination is 2-4 ℃ min-1。
Preferably, the frequency of the ultrasonic wave in the ultrasonic treatment is 60-90 MHz.
The invention also provides application of the magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst in removing 2,4-DCP in water, and the magnetic nitrogen-doped reduced graphene/phosphate visible photocatalyst is applied to removing 2,4-DCP in water.
3. Advantageous effects
(1) From the property measurements of the products in the examples, NrGO and CuFe2O4Tightly combined with phosphate; all elements in the magnetic nitrogen-doped reduced graphene/phosphate visible-light-induced photocatalyst exist and are uniformly distributed; the absorption spectrum of the obtained catalyst is expanded, and the band gap value is obviously reduced; the separation efficiency of photoproduction holes and electrons of the obtained catalyst is obviously improved; under the action of visible light, the photoelectric effect immediately occurs and reaches the maximum value instantly; the obtained catalyst is externally magnetizedThe magnetic field can be rapidly separated, and the magnetic field can be well dispersed after being removed; the photocatalytic degradation rate of the obtained catalyst is improved, and the photocatalytic efficiency is obviously improved; the degradation efficiency of the obtained catalyst after repeated cyclic utilization still reaches more than 88 percent, and the composition of the photocatalyst is not changed after repeated cycles. The magnetic nitrogen-doped reduced graphene/phosphate particle visible light photocatalyst provided by the invention has the advantages of high magnetization intensity, strong electron conductivity, high photocatalytic efficiency, good treatment effect on refractory organic pollutants 2,4-DCP, stable physicochemical property and high application value.
(2) The magnetic nitrogen-doped reduced graphene/phosphate particle visible-light-driven photocatalyst is synthesized by an in-situ co-precipitation method in two steps, so that the synthesis time is greatly saved, the operation steps are simplified, no pollutant is generated in the reaction process, and the photocatalyst provided by the invention is simple in preparation method, low in cost, easy to control in process and environment-friendly.
In conclusion, the magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst provided by the invention has the advantages of high magnetization intensity, strong electron conductivity, high catalytic activity, stable physicochemical property and good removal effect on refractory organic matters; the preparation method of the catalyst is simple, low in cost, easy to control the process and environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows Ag3PO4、CuFe2O4And Ag3PO4/NrGO/CuFe2O4An XRD pattern of (a);
in FIG. 2, (a) and (b) are Ag3PO4SEM images of (a), (c) and (d) are Ag3PO4/NrGO/CuFe2O4SEM image of (E)Is Ag3PO4/NrGO/CuFe2O4TEM image of (f) is high magnification Ag3PO4/NrGO/CuFe2O4A TEM image of (a);
FIG. 3 is Ag3PO4/NrGO/CuFe2O4Photoelectron Spectroscopy (XPS) spectrum of (a);
FIG. 4 shows Ag3PO4、CuFe2O4、Ag3PO4/CuFe2O4And Ag3PO4/NrGO/CuFe2O4Ultraviolet-visible spectrum of (a);
FIG. 5 shows Ag3PO4、CuFe2O4、Ag3PO4/CuFe2O4And Ag3PO4/NrGO/CuFe2O4A fluorescence spectrum of (a);
FIG. 6 shows Ag3PO4、CuFe2O4、Ag3PO4/CuFe2O4And Ag3PO4/NrGO/CuFe2O4A photocurrent map of;
FIG. 7 is CuFe2O4And Ag3PO4/NrGO/CuFe2O4The magnetization curve of (a);
in FIG. 8, (a) and (b) are Ag3PO4/NrGO/CuFe2O4Degradation curves for different concentrations of 2, 4-DCP;
in FIG. 9(a) is Ag3PO4/NrGO/CuFe2O4The column diagram of the efficiency of 1-5 repeated cycles of photocatalytic degradation of 2,4-DCP, and (b) is Ag3PO4/NrGO/CuFe2O4 the main processXRD patterns of the first and fifth cycles;
FIG. 10 shows Ag3PO4/NrGO/CuFe2O4Results in radical trapping experiments are shown schematically.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the specific material additions, material ratios, process conditions and results thereof described in the examples are illustrative only and should not be taken as limiting the invention as detailed in the claims.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
A preparation method of a magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst comprises the following steps:
(1) preparing a graphene dispersion liquid: dissolving 320mg of graphene in 120mL of double distilled water, performing ultrasonic treatment, and stirring for 2 hours at a constant temperature until the liquid is transparent and clear to obtain a graphene dispersion liquid, wherein the frequency of the ultrasonic wave is 75 MHz;
(2) preparation of nitrogen-doped reduced graphene oxide (NrGO): adding 32 mu L of hydrazine hydrate into the dispersion liquid obtained in the step (1), quickly placing the dispersion liquid into a polytetrafluoroethylene-lined stainless steel autoclave, performing hydrothermal reaction for 20 hours at 180 ℃, cooling to room temperature, separating, washing with deionized water and absolute ethyl alcohol respectively for three times, and then drying for 5 hours at 80 ℃ to obtain nitrogen-doped reduced graphene oxide (NrGO) powder;
(3) preparing a nitrogen-doped reduced graphene dispersion liquid: dispersing 100mg of the nitrogen-doped reduced graphene oxide (NrGO) powder synthesized in the step (2) in 100mL of double distilled water, and performing ultrasonic treatment for 2 hours to obtain a nitrogen-doped reduced graphene dispersion liquid;
(4)NrGO/CuFe2O4the preparation of (1): slowly adding Fe (NO) into the nitrogen-doped reduced graphene dispersion liquid obtained in the step (3) under the stirring condition3)3·9H2O(0.07mol·L-1) And Cu (NO)3)2·3H2O(0.035mol·L-1) 50mL each of the solutions, after the metal salt was completely dissolved, the reaction mixture was heated to 80 ℃ and then aqueous ammonia (0.5 mol. L) was added dropwise-1) Until the pH is 10; continuously stirring the reaction mixture for 4 hours to generate a precipitate; repeatedly washing the obtained precipitate with water for three times, and drying in an oven at 80 ℃ overnight to obtain NrGO/CuFe2O4；
(5)Ag3PO4/NrGO/CuFe2O4The preparation of (1): taking 100mg of NrGO/CuFe obtained in the step (4)2O4Dispersing in 160mL deionized water, after ultrasonic treatment, adding 12.2mL AgNO3Aqueous solution (100 mg. mL)-1) Dropwise adding the mixture into the dispersion liquid, and continuously stirring for 6 hours; 10mL of Na was added to the above reaction system2HPO4Solution (100 mg. mL)-1) Continuously stirring for 6h, centrifuging, collecting the final product, washing with deionized water and anhydrous ethanol for three times, and vacuum drying at 45 deg.C for 12h to obtain Ag3PO4/NrGO/CuFe2O4Visible light catalyst powder.
Ag obtained as above3PO4/NrGO/CuFe2O4The photocatalyst belongs to a magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst, and the structural formula of the magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst is as follows:
following the Ag obtained3PO4/NrGO/CuFe2O4And (3) carrying out performance detection analysis on the photocatalyst:
for Ag3PO4、CuFe2O4And Ag3PO4/NrGO/CuFe2O4The photocatalyst was subjected to X-ray diffraction (XRD), and as a result, as shown in FIG. 1, it was found from FIG. 1 that Ag was produced3PO4/NrGO/CuFe2O4The photocatalyst shows Ag3PO4And CuFe2O4All diffraction peaks of the nano material are due to Ag3PO4Strongly mask the diffraction peaks corresponding to NrGO.
Observation of Ag with Scanning Electron Microscope (SEM)3PO4、Ag3PO4/NrGO/CuFe2O4And observing Ag with Transmission Electron Microscope (TEM)3PO4/NrGO/CuFe2O4And high power Ag3PO4/NrGO/CuFe2O4As shown in FIG. 2, it can be seen from FIG. 2 that pure Ag3PO4The {111} crystal face is exposed, and the diameter is about 0.5 μm; prepared Ag3PO4Non-uniform distribution on the surface of the NrGO; CuFe2O4Nanoparticles in Ag3PO4And the surface of the NrGO compound is also distributed irregularly; further characterization of Ag by HR-TEM3PO4/NrGO/CuFe2O4Microstructure of photocatalyst, Ag3PO4{210} crystal plane of (B), interplanar spacing of 0.261nm, indicating NrGO and CuFe2O4With Ag3PO4The combination is tight.
Obtaining Ag3PO4/NrGO/CuFe2O4An X-ray photoelectron spectroscopy (XPS) spectrum of the photocatalyst is shown in FIG. 3, and it can be seen from FIG. 3 that Ag is obtained by analyzing the spectrum3PO4/NrGO/CuFe2O4All elements in the photocatalyst are present and uniformly distributed.
Obtaining Ag3PO4、CuFe2O4、Ag3PO4/CuFe2O4And Ag3PO4/NrGO/CuFe2O4The UV-visible spectrum of (A) is shown in FIG. 4, and it can be seen from FIG. 4 that the ratio is compared with that of Ag3PO4、CuFe2O4、Ag3PO4/CuFe2O4，Ag3PO4/NrGO/CuFe2O4The absorption spectrum of the crystal is expanded from 530nm to 670nm, and the band gap value is reduced from the original 2.34eV to 1.44 eV.
Obtaining Ag3PO4、CuFe2O4、Ag3PO4/CuFe2O4And Ag3PO4/NrGO/CuFe2O4As shown in FIG. 5, the fluorescence spectrum of the photocatalyst is shown in FIG. 5, and it can be seen from FIG. 5 that the photocatalyst Ag was compared with the photocatalyst Ag under the action of visible light3PO4、CuFe2O4And Ag3PO4/CuFe2O4，Ag3PO4/NrGO/CuFe2O4The response value of (A) is the lowest, which indicates that the separation efficiency of photogenerated holes and electrons is remarkably improved.
Obtaining Ag3PO4、CuFe2O4、Ag3PO4/CuFe2O4And Ag3PO4/NrGO/CuFe2O4As shown in fig. 6, as can be seen from fig. 6, the photocurrent spectrum of the photocatalyst shows that the photoelectric effect immediately occurs under the action of visible light and instantaneously reaches a maximum value.
Obtaining CuFe2O4And magnetic Ag3PO4/NrGO/CuFe2O4The hysteresis loop of the photocatalyst is shown in FIG. 7, and it can be seen from FIG. 7 that Ag is3PO4/NrGO/CuFe2O4The specific saturation magnetization of the photocatalyst reaches 47.6emu/g, and the photocatalyst has the characteristic of superparamagnetism, which indicates that Ag3PO4/NrGO/CuFe2O4The photocatalyst can be rapidly separated in an external magnetic field, and can be well dispersed after the magnetic field is removed.
Example 2
A preparation method of a magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst comprises the following steps:
(1) preparing a graphene dispersion liquid: dissolving 350mg of graphene in 130mL of double distilled water, performing ultrasonic treatment, and stirring for 2 hours at a constant temperature until the liquid is transparent and clear to obtain a graphene dispersion liquid, wherein the frequency of the ultrasonic wave is 60 MHz;
(2) preparation of nitrogen-doped reduced graphene oxide (NrGO): adding 36 mu L of hydrazine hydrate into the dispersion liquid obtained in the step (1), quickly placing the dispersion liquid into a polytetrafluoroethylene-lined stainless steel autoclave, performing hydrothermal reaction for 22h at 200 ℃, cooling to room temperature, separating, washing with deionized water and absolute ethyl alcohol respectively for three times, and drying at 80 ℃ for 6h to obtain nitrogen-doped reduced graphene oxide (NrGO) powder;
(3) preparing a nitrogen-doped reduced graphene dispersion liquid: dispersing 100mg of the nitrogen-doped reduced graphene oxide (NrGO) powder synthesized in the step (2) in 100mL of double distilled water, and performing ultrasonic treatment for 2 hours to obtain a nitrogen-doped reduced graphene dispersion liquid;
(4)NrGO/CuFe2O4the preparation of (1): slowly adding Fe (NO) into the nitrogen-doped reduced graphene dispersion liquid obtained in the step (3) under the stirring condition3)3·9H2O(0.07mol·L-1) And Cu (NO)3)2·3H2O(0.035mol·L-1) 80mL each of the solutions, after the metal salt was completely dissolved, the reaction mixture was heated to 80 ℃ and then aqueous ammonia (0.5 mol. L) was added dropwise-1) Until the pH is 10; continuously stirring the reaction mixture for 4 hours to generate a precipitate; repeatedly washing the obtained precipitate with water for three times, and drying in an oven at 80 ℃ overnight to obtain NrGO/CuFe2O4；
(5)Ag3PO4/NrGO/CuFe2O4The preparation of (1): taking 100mg of NrGO/CuFe obtained in the step (4)2O4Dispersing in 180mL deionized water, after ultrasonic treatment, adding 14.4mL AgNO3Aqueous solution (100 mg. mL)-1) Dropwise adding the mixture into the dispersion liquid, and continuously stirring for 6 hours; to the above reaction system was added 12mL of Na2HPO4Solution (100 mg. mL)-1) Continuously stirring for 6h, centrifuging, collecting the final product, washing with deionized water and anhydrous ethanol for three times, and vacuum drying at 50 deg.C for 12h to obtain Ag3PO4/NrGO/CuFe2O4Visible light catalyst powder.
Example 3
A preparation method of a magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst comprises the following steps:
(1) preparing a graphene dispersion liquid: dissolving 380mg of graphene in 150mL of double-distilled water, performing ultrasonic treatment, and stirring for 2 hours at a constant temperature until the liquid is transparent and clear to obtain a graphene dispersion liquid, wherein the frequency of the ultrasonic wave is 90 MHz;
(2) preparation of nitrogen-doped reduced graphene oxide (NrGO): adding 36 mu L of hydrazine hydrate into the dispersion liquid obtained in the step (1), quickly placing the dispersion liquid into a polytetrafluoroethylene-lined stainless steel autoclave, performing hydrothermal reaction for 24 hours at 220 ℃, cooling to room temperature, separating, washing with deionized water and absolute ethyl alcohol respectively for three times, and drying for 8 hours at 80 ℃ to obtain nitrogen-doped reduced graphene oxide (NrGO) powder;
(3) preparing a nitrogen-doped reduced graphene dispersion liquid: dispersing 80mg of the nitrogen-doped reduced graphene oxide (NrGO) powder synthesized in the step (2) in 100mL of double distilled water, and performing ultrasonic treatment for 2 hours to obtain a nitrogen-doped reduced graphene dispersion liquid;
(4)NrGO/CuFe2O4the preparation of (1): slowly adding Fe (NO) into the nitrogen-doped reduced graphene dispersion liquid obtained in the step (3) under the stirring condition3)3·9H2O(0.07mol·L-1) And Cu (NO)3)2·3H2O(0.035mol·L-1) 80mL each of the solutions, after the metal salt was completely dissolved, the reaction mixture was heated to 80 ℃ and then aqueous ammonia (1 mol. L) was added dropwise-1) Until the pH is 10; continuously stirring the reaction mixture for 4 hours to generate a precipitate; repeatedly washing the obtained precipitate with water for three times, and drying in an oven at 80 ℃ overnight to obtain NrGO/CuFe2O4；
(5)Ag3PO4/NrGO/CuFe2O4The preparation of (1): taking 100mg of NrGO/CuFe obtained in the step (4)2O4Dispersing in 200mL deionized water, after ultrasonic treatment, adding 15.8mL AgNO3Aqueous solution (100 mg. mL)-1) Dropwise adding the mixture into the dispersion liquid, and continuously stirring for 6 hours; to the above reaction system was added 14mL of Na2HPO4Solution (100 mg. mL)-1) Continuously stirring for 6h, centrifuging, collecting final product, washing with deionized water and anhydrous ethanol for three times, and vacuum drying at 50 deg.C for 14h to obtain the final productAg3PO4/NrGO/CuFe2O4Visible light catalyst powder.
Example 4
Magnetic Ag obtained in example 1 was used3PO4/NrGO/CuFe2O4The photocatalytic degradation test of 2,4-DCP by photocatalyst is carried out by using magnetic Ag3PO4/NrGO/CuFe2O4The photocatalyst degrades the target pollutant 2,4-DCP in the photocatalyst.
Wherein, magnetic Ag3PO4/NrGO/CuFe2O4The dosage of the photocatalyst is 25mg, the content of the prepared target pollutant 2,4-DCP is 15mg/L, the pH value of the solution is adjusted to 7.0, and the water temperature is controlled at 25 ℃. A250W xenon lamp (a filter lambda is less than or equal to 420nm) is used as a light source, sampling test is carried out every 10min, analysis is carried out by utilizing a high performance liquid chromatography (Shimadzu), a chromatographic column is an inverse phase column (Eclipse XDBC18, 4.6x150mm, 5 mu m), a degradation curve of Ag3PO4/NrGO/CuFe2O4 to 2,4-DCP is drawn, and the result is shown in figure 8 (a).
Comparative example 1
Magnetic Ag in example 43PO4/NrGO/CuFe2O4Photocatalyst is replaced by CuFe2O4Otherwise, as in example 4, the degradation curve was plotted, and the results are shown in FIG. 8 (a).
Comparative example 2
Magnetic Ag in example 43PO4/NrGO/CuFe2O4Photocatalyst is replaced by Ag3PO4Otherwise, as in example 4, the degradation curve was plotted, and the results are shown in FIG. 8 (a).
Comparative example 3
Magnetic Ag in example 43PO4/NrGO/CuFe2O4Photocatalyst is replaced by Ag3PO4/CuFe2O4Otherwise, as in example 4, the degradation curve was plotted, and the results are shown in FIG. 8 (a).
Example 5
This embodiment is different from embodiment 4 in that:
the content of the prepared target pollutant 2,4-DCP is 10mg/L, and the other steps are the same as the example 4. The degradation curves of Ag3PO4/NrGO/CuFe2O4 on 2,4-DCP are plotted, and the results are shown in FIG. 8 (b).
Comparative example 4
Magnetic Ag in example 53PO4/NrGO/CuFe2O4Photocatalyst is replaced by CuFe2O4Otherwise, as in example 5, a degradation curve was plotted, and the results are shown in FIG. 8 (b).
Comparative example 5
Magnetic Ag in example 53PO4/NrGO/CuFe2O4Photocatalyst is replaced by Ag3PO4Otherwise, as in example 5, a degradation curve was plotted, and the results are shown in FIG. 8 (b).
Comparative example 6
Magnetic Ag in example 53PO4/NrGO/CuFe2O4Photocatalyst is replaced by Ag3PO4/CuFe2O4Otherwise, as in example 5, a degradation curve was plotted, and the results are shown in FIG. 8 (b).
As can be seen from FIG. 8, magnetic Ag3PO4/NrGO/CuFe2O4The photocatalytic degradation rate of 2,4-DCP reaches 95.28% when the photocatalyst is subjected to visible light catalysis for 60 min; visible light catalysis for 60min, pure Ag3PO4And pure CuFe2O4The photodegradation efficiency of 2,4-DCP is 40.1% and 32.2% respectively; mixing with pure Ag after 60min visible light catalysis3PO4(k＝0.00747min-1) Compared with the modified magnetic Ag3PO4/NrGO/CuFe2O4(k-0.01978 min-1) the degradation efficiency is improved by about 2.58 times, and the magnetic Ag3PO4/NrGO/CuFe2O4The photocatalytic efficiency is obviously improved.
Example 6
Five equal parts of water containing 2,4-DCP with the same concentration are taken, and one part of the magnetic Ag prepared in the example 1 is added3PO4/NrGO/CuFe2O4The photocatalyst is used for degrading five parts of water to be treated one by one, and the degradation treatment is carried out every timeThe time is the same, and the Ag in each degradation treatment is calculated3PO4/NrGO/CuFe2O4The degradation efficiency of the photocatalyst was plotted in a bar graph, and as shown in FIG. 9(a), it was found from FIG. 9(a) that Ag was contained in the solution3PO4/NrGO/CuFe2O4The degradation efficiency of the photocatalyst gradually decreased with the increase of the number of cycles, and Ag in the fifth cycle3PO4/NrGO/CuFe2O4The efficiency of 2,4-DCP photocatalytic degradation of the photocatalyst still reaches more than 88 percent.
In addition, as can be seen from FIG. 9(b) by XRD analysis, Ag was obtained after five cycles3PO4/NrGO/CuFe2O4The composition of the photocatalyst is unchanged.
Example 7
Magnetic Ag by radical capture experiment3PO4/NrGO/CuFe2O4Further analysis of the mechanism of photocatalytic degradation of 2,4-DCP by photocatalyst, it can be seen from FIG. 10 that the order of the active species mainly contributing in the catalytic oxidation process is mainly OH-And secondly O2-。
According to the content, the magnetic nitrogen-doped reduced graphene/phosphate particle photocatalyst provided by the invention has the advantages of high magnetization intensity, strong electron conductivity, high catalytic activity, stable physicochemical property and good removal effect on refractory organic matters; the preparation method of the catalyst is simple, low in cost, easy to control the process and environment-friendly.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. The magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst is characterized by having a structural formula as follows:
2. the preparation method of the magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst according to claim 1, characterized by comprising the following steps:
S1、NrGO/CuFe2O4the preparation of (1): dispersing nitrogen-doped reduced graphene oxide powder in distilled water, wherein the mass ratio of the nitrogen-doped reduced graphene oxide powder to the distilled water is (0.08-0.1): 100, and performing ultrasonic treatment to obtain a nitrogen-doped reduced graphene dispersion liquid; slowly adding Fe (NO) under stirring3)3·9H2O and Cu (NO)3)2·3H2O solution of Fe (NO)3)3·9H2O solution, Cu (NO)3)2·3H2The volume ratio of the O solution to the distilled water is (50-80): (50-80): 100, after the metal salt is completely dissolved, heating the reaction mixture to 80 ℃, and then dropwise adding ammonia water until the pH value is 10; continuously stirring the reaction mixture for 3-5 hours to generate a precipitate; washing the obtained precipitate with water repeatedly, and drying to obtain NrGO/CuFe2O4；
S2, preparing a magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst: taking the NrGO/CuFe obtained in the step S12O4Dispersed in deionized water, the NrGO/CuFe2O4And deionized water, wherein the mass ratio of the nitrate solution to the deionized water is 0.1 (150-200), a nitrate solution is dropwise added into the dispersion liquid, the volume ratio of the nitrate solution to the deionized water is (12-16): 150-200, and the mixture is continuously stirred for 6 hours; adding Na into the reaction system2HPO4Solution of said Na2HPO4The volume ratio of the solution to the nitrate water solution is (10-15): 12-16), the continuous stirring is carried out for 6 hours, the final product is collected after the centrifugation, and the final product is obtained after the washing and the vacuum drying overnightMagnetic nitrogen-doped reduced graphene/phosphate visible-light-induced photocatalyst powder.
3. The method for preparing a magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst according to claim 2, wherein in step S1, the method for preparing nitrogen-doped reduced graphene oxide comprises the following steps:
s1-1, dissolving graphene in double distilled water, wherein the mass ratio of the graphene to the double distilled water is (0.3-0.4) to (100-150), performing ultrasonic treatment, and stirring at a constant temperature until the liquid is transparent and clear to obtain a graphene dispersion liquid;
s1-2, adding hydrazine hydrate into the dispersion liquid obtained in the step S1-1, wherein the volume ratio of the hydrazine hydrate to the double distilled water is (0.03-0.04): (100-150), placing the hydrazine hydrate and the double distilled water into a polytetrafluoroethylene-lined stainless steel autoclave, carrying out hydrothermal reaction for 20-24 h under the condition of keeping the temperature of 180-220 ℃, cooling to room temperature, separating, washing for multiple times, and drying for 4-8 h at the temperature of 80 ℃ to obtain the nitrogen-doped reduced graphene oxide powder.
4. The method for preparing the magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst according to claim 2, wherein in step S1, Fe (NO) is added3)3·9H2The concentration of O is 0.07 mol.L-1，Cu(NO3)2·3H2The concentration of O is 0.035 mol.L-1The concentration of ammonia water is 0.5 to 1 mol.L-1Said Fe (NO)3)3·9H2O and Cu (NO)3)2·3H2The volume ratio of O is 1: 1.
5. The method for preparing the magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst according to claim 2, wherein in step S2, the concentration of the nitrate solution is 100 mg-mL-1，Na2HPO4The concentration of the solution was 100 mg/mL-1。
6. A method as claimed in claim 2The preparation method of the magnetic nitrogen-doped reduced graphene/phosphate visible-light-driven photocatalyst is characterized in that in step S2, the nitrate is AgNO3。
7. The preparation method of the magnetic nitrogen-doped reduced graphene/phosphate visible-light-induced photocatalyst according to claim 2, wherein the frequency of ultrasonic waves in the ultrasonic treatment is 60-90 MHz.
8. The application method of the magnetic nitrogen-doped reduced graphene/phosphate visible-light-induced photocatalyst according to claim 1, wherein the magnetic nitrogen-doped reduced graphene/phosphate visible-light-induced photocatalyst is applied to removal of 2,4-DCP in water.
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