CN108855099B - Preparation method of efficient three-dimensional layered double-metal hydroxide/graphene composite photocatalyst and photocatalyst thereof - Google Patents
Preparation method of efficient three-dimensional layered double-metal hydroxide/graphene composite photocatalyst and photocatalyst thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910000000 metal hydroxide Inorganic materials 0.000 title abstract 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 claims abstract description 92
- 229960003405 ciprofloxacin Drugs 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 37
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000006731 degradation reaction Methods 0.000 claims abstract description 24
- 230000001699 photocatalysis Effects 0.000 claims abstract description 24
- 230000015556 catabolic process Effects 0.000 claims abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 17
- 230000000593 degrading effect Effects 0.000 claims abstract description 16
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 229910000943 NiAl Inorganic materials 0.000 claims abstract description 10
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 35
- 239000002135 nanosheet Substances 0.000 abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 239000012266 salt solution Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 4
- 239000003242 anti bacterial agent Substances 0.000 abstract description 2
- 229940088710 antibiotic agent Drugs 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 7
- 230000006798 recombination Effects 0.000 description 5
- 150000004679 hydroxides Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- -1 salt ions Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000005264 electron capture Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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)
- 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 preparation method of an efficient three-dimensional layered double hydroxide/graphene composite photocatalyst and the photocatalyst thereof, wherein the preparation method comprises the steps of placing graphite oxide in a solvent for uniform dispersion; dropwise adding a mixed salt solution of nickel, aluminum and iron, and stirring; adding urea, stirring and reacting. According to the invention, graphene is used as a carrier of an LDH nanosheet to form the layered double-metal hydroxide/graphene composite photocatalyst with a three-dimensional structure. The load of the graphene not only inhibits the agglomeration of LDH nano sheets, but also promotes the separation of photogenerated electron-hole pairs in the LDH, thereby being better applied to the photocatalytic degradation of antibiotics. Three-dimensional NiAl prepared by the invention0.85Fe0.15LDH/RGO25The composite photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is found to be more than 93%.
Description
Technical Field
The invention belongs to the technical field of preparation of environmental materials, and particularly relates to a preparation method of an efficient three-dimensional layered double-metal hydroxide/graphene composite photocatalyst and the photocatalyst.
Background
semiconductor-mediated photocatalytic technology has attracted researchers' attention for its low energy consumption and environmental friendliness in order to effectively remove chemical contaminants (e.g., antibiotic residues) from water. To date, researchers have developed various photocatalysts for water pollution remediation, such as metal oxides, metal sulfides, layered double hydroxides, and the like, through the efforts of researchers. Among these photocatalysts, Layered Double Hydroxides (LDHs) are considered as promising photocatalytic materials due to their unique layered structure, tunable metal composition and intercalating anions.
However, single-layer LDHs have poor charge mobility and high surface charge density, which easily leads to rapid recombination of photo-generated electron-hole pairs and agglomeration of LDH nanosheets, thus hindering their photocatalytic activity and limiting their practical applications.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
the present invention has been made in view of the above-mentioned technical drawbacks.
Therefore, as one aspect of the present invention, the present invention overcomes the defects existing in the prior art, and provides a preparation method of a high-efficiency three-dimensional layered double hydroxide/graphene composite photocatalyst.
in order to solve the technical problems, the invention provides the following technical scheme: a preparation method of an efficient three-dimensional layered double hydroxide/graphene composite photocatalyst is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
Placing graphite oxide in a solvent for uniform dispersion;
Dropwise adding a mixed salt solution of nickel, aluminum and iron, and stirring;
adding urea, stirring and reacting.
as an optimal scheme of the preparation method of the efficient three-dimensional layered double hydroxide/graphene composite photocatalyst, the preparation method comprises the following steps: the method comprises the step of uniformly dispersing graphite oxide in a solvent, wherein the concentration of the prepared graphene oxide is 6.5-66.2 g/L.
as an optimal scheme of the preparation method of the efficient three-dimensional layered double hydroxide/graphene composite photocatalyst, the preparation method comprises the following steps: the solvent comprises one of water, ethanol, glycol or glycerol.
as an optimal scheme of the preparation method of the efficient three-dimensional layered double hydroxide/graphene composite photocatalyst, the preparation method comprises the following steps: the mixed salt solution of nickel, aluminum and iron comprises a mixed salt solution of nickel nitrate, aluminum nitrate and ferric nitrate, wherein the molar ratio of the nickel nitrate to the aluminum nitrate to the ferric nitrate is 2: (1-X): x, wherein X is 0-0.2.
as an optimal scheme of the preparation method of the efficient three-dimensional layered double hydroxide/graphene composite photocatalyst, the preparation method comprises the following steps: the molar ratio of nickel nitrate to urea was 2: 16.
As an optimal scheme of the preparation method of the efficient three-dimensional layered double hydroxide/graphene composite photocatalyst, the preparation method comprises the following steps: and dropwise adding a mixed salt solution of nickel, aluminum and iron, and stirring, wherein the stirring time is 3 h.
As an optimal scheme of the preparation method of the efficient three-dimensional layered double hydroxide/graphene composite photocatalyst, the preparation method comprises the following steps: and adding urea, stirring and reacting, wherein the stirring time is 1h, the reaction is carried out at the temperature of 100-140 ℃, and the reaction time is 12 h.
As an optimal scheme of the preparation method of the efficient three-dimensional layered double hydroxide/graphene composite photocatalyst, the preparation method comprises the following steps: also comprises the following steps of (1) preparing,
Filtering, washing and drying: after the reaction, filtering and washing the reaction product, and drying at 60-80 ℃ for 10-14 h.
as another aspect of the invention, the invention overcomes the defects in the prior art, and provides the three-dimensional layered double hydroxide/graphene composite photocatalyst prepared by the preparation method.
in order to solve the technical problems, the invention provides the following technical scheme: the three-dimensional layered double hydroxide/graphene composite photocatalyst prepared by the preparation method is characterized in that: the nanosheet of the layered double hydroxide vertically grows on the flaky graphene and forms a three-dimensional structure, and the mass ratio of the layered double hydroxide to the graphene is 100: 5-100: 35, the size of the nano sheet is 100-150 nm.
as a preferred scheme of the three-dimensional layered double hydroxide/graphene composite photocatalyst provided by the invention: the layered double hydroxide is NiAlFe LDH.
the invention has the beneficial effects that: according to the invention, graphene is used as a carrier of an LDH nanosheet to form the layered double-metal hydroxide/graphene composite photocatalyst with a three-dimensional structure. The load of the graphene not only inhibits the agglomeration of LDH nano sheets, but also promotes the separation of photogenerated electron-hole pairs in the LDH, thereby being better applied to the photocatalytic degradation of antibiotics. Three-dimensional NiAl prepared by the invention0.85Fe0.15LDH/RGO25the composite photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is found to be more than 93%.
drawings
in order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows NiAl1-XFeXDegradation patterns of the LDH composite photocatalyst correspond to those of comparative examples 1-4 and comparative examples 1-2 (X is 0-0.3).
FIG. 2 shows three-dimensional NiAl0.85Fe0.15LDH/RGOY(Y ═ 0 to 35 wt%) degradation patterns of the composite photocatalysts, corresponding to those of examples 1 to 4 and comparative example 5.
FIG. 3 shows the three-dimensional NiAl prepared in example 30.85Fe0.15LDH/RGO25SEM image of composite photocatalyst.
Detailed Description
in order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
in the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
example 1:
(1) Placing graphite oxide in a solvent, and uniformly dispersing by ultrasonic to prepare the graphite oxide with the concentration of 6.5 g/L;
(2) dissolving 2mmol of nickel nitrate, 0.85mmol of aluminum nitrate and 0.15mmol of ferric nitrate in a solvent, dropwise adding the solution into the solution obtained in the step (1), and continuously stirring the solution for 3 hours;
(3) dissolving 16mmol of urea in a solvent, adding the solution into the solution in the step (2), and continuously stirring for 1 h;
(4) Reacting the solution at 120 ℃ for 12 h;
(5) filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(6) The prepared three-dimensional NiAl0.85Fe0.15LDH/RGO5The composite photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is found to reach 66%.
Example 2:
(1) placing graphite oxide in a solvent, and uniformly dispersing by ultrasonic to prepare the graphite oxide with the concentration of 21.7 g/L;
(2) dissolving 2mmol of nickel nitrate, 0.85mmol of aluminum nitrate and 0.15mmol of ferric nitrate in a solvent, dropwise adding the solution into the solution obtained in the step (1), and continuously stirring the solution for 3 hours;
(3) Dissolving 16mmol of urea in a solvent, adding the solution into the solution in the step (2), and continuously stirring for 1 h;
(4) reacting the solution at 120 ℃ for 12 h;
(5) Filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(6) The prepared three-dimensional NiAl0.85Fe0.15LDH/RGO15The composite photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is found to reach 84%.
example 3:
(1) Placing graphite oxide in a solvent, and uniformly dispersing by ultrasonic to prepare the graphite oxide with the concentration of 40.9 g/L; the solvent can be water, ethanol, glycol or glycerol;
(2) dissolving 2mmol of nickel nitrate, 0.85mmol of aluminum nitrate and 0.15mmol of ferric nitrate in a solvent, dropwise adding the solution into the solution obtained in the step (1), and continuously stirring the solution for 3 hours;
(3) Dissolving 16mmol of urea in a solvent, adding the solution into the solution in the step (2), and continuously stirring for 1 h;
(4) reacting the solution at 120 ℃ for 12 h;
(5) filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(6) the prepared three-dimensional NiAl0.85Fe0.15LDH/RGO25the composite photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is found to be more than 93%.
Example 4:
(1) Placing graphite oxide in a solvent, and uniformly dispersing by ultrasonic to prepare the graphite oxide with the concentration of 66.2 g/L;
(2) Dissolving 2mmol of nickel nitrate, 0.85mmol of aluminum nitrate and 0.15mmol of ferric nitrate in a solvent, dropwise adding the solution into the solution obtained in the step (1), and continuously stirring the solution for 3 hours;
(3) Dissolving 16mmol of urea in a solvent, adding the solution into the solution in the step (2), and continuously stirring for 1 h;
(4) reacting the solution at 120 ℃ for 12 h;
(5) Filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(6) the prepared three-dimensional NiAl0.85Fe0.15LDH/RGO35the composite photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is found to reach 80%.
comparative example 1:
(1) Dissolving 2mmol of nickel nitrate and 1mmol of aluminum nitrate in a solvent, and continuously stirring for 10 min;
(2) Dissolving 16mmol of urea in a solvent, adding the solution into the solution (1), and continuously stirring for 1 h;
(3) Reacting the solution at 120 ℃ for 12 h;
(4) filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(5) the prepared NiAl LDH photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of the ciprofloxacin, and the degradation rate of the ciprofloxacin within 120min is found to reach 31%.
Comparative example 2:
(1) dissolving 2mmol of nickel nitrate, 0.85mmol of aluminum nitrate and 0.15mmol of ferric nitrate in a solvent, and continuously stirring for 10 min;
(2) dissolving 16mmol of urea in a solvent, adding the solution into the solution (1), and continuously stirring for 1 h;
(3) Reacting the solution at 120 ℃ for 12 h;
(4) filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(5) the prepared NiAl0.85Fe0.15the LDH photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is found to reach 54%.
Comparative example 3:
(1) Dissolving 2mmol of nickel nitrate, 0.95mmol of aluminum nitrate and 0.05mmol of ferric nitrate in a solvent, and continuously stirring for 10 min;
(2) Dissolving 16mmol of urea in a solvent, adding the solution into the solution (1), and continuously stirring for 1 h;
(3) reacting the solution at 120 ℃ for 12 h;
(4) Filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(5) the prepared NiAl0.95Fe0.05the LDH photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is found to reach 41%.
comparative example 4:
(1) Dissolving 2mmol of nickel nitrate and 1mmol of aluminum nitrate in a solvent, and continuously stirring for 10 min;
(2) Dissolving 16mmol of urea in a solvent, adding the solution into the solution (1), and continuously stirring for 1 h;
(3) Reacting the solution at 120 ℃ for 12 h;
(4) filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(5) the prepared NiAl LDH photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of the ciprofloxacin, and the degradation rate of the ciprofloxacin within 120min is found to reach 31%.
comparative example 5:
(1) Dissolving 2mmol of nickel chloride, 0.85mmol of aluminum chloride and 0.15mmol of ferric chloride in a solvent, and continuously stirring for 10 min;
(2) Dissolving 16mmol of urea in a solvent, adding the solution into the solution (1), and continuously stirring for 1 h;
(3) reacting the solution at 120 ℃ for 12 h;
(4) Filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(5) The prepared NiAl0.85Fe0.15The LDH photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is found to reach 52%.
comparative example 6:
(1) Dissolving 2mmol of nickel nitrate and 1mmol of ferric nitrate in a solvent, and continuously stirring for 10 min;
(2) dissolving 16mmol of urea in a solvent, adding the solution into the solution (1), and continuously stirring for 1 h;
(3) reacting the solution at 120 ℃ for 12 h;
(4) filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(5) The prepared NiFe LDH photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of the ciprofloxacin, and the degradation rate of the ciprofloxacin within 120min is found to reach 40%.
comparative example 7:
(1) Dissolving 2mmol of zinc nitrate, 0.85mmol of aluminum nitrate and 0.15mmol of ferric nitrate in a solvent, and continuously stirring for 10 min;
(2) dissolving 16mmol of urea in a solvent, adding the solution into the solution (1), and continuously stirring for 1 h;
(3) reacting the solution at 120 ℃ for 12 h;
(4) Filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(5) ZnAl to be prepared0.85Fe0.15the LDH photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is found to reach 45%.
comparative example 8:
(1) Dissolving 2mmol of nickel nitrate, 0.85mmol of aluminum nitrate and 0.15mmol of cerium nitrate in a solvent, and continuously stirring for 10 min;
(2) dissolving 16mmol of urea in a solvent, adding the solution into the solution (1), and continuously stirring for 1 h;
(3) Reacting the solution at 120 ℃ for 12 h;
(4) filtering and washing the reaction product, and drying at 60 ℃ for 12 hours;
(5) The prepared NiAl0.85Ce0.15The LDH photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is found to reach 47%.
FIG. 1 shows NiAl1-XFeXDegradation patterns of the LDH composite photocatalyst correspond to those of comparative examples 1-4 and comparative examples 1-2 (X is 0-0.3).
as can be seen from FIG. 1, when the molar content of Fe is increased from 0 to 0.15, the catalytic degradation effect of the photoreaction is better and better. When the molar content of Fe is 0.15, NiAl1-XFeXthe LDH complex has the best photocatalysis effect,
the CIP degradation rate is slightly higher than 50%. The root cause of this phenomenon is Fe3+the photo-generated electrons are captured as capture sites, the recombination of photo-generated electron-hole pairs is inhibited, and the service life of the photo-generated electron-hole pairs is prolonged, so that the performance of photo-catalytic degradation of CIP is further improved. However, when the Fe molar content is further increased from 0.15 to 0.2, the photocatalytic reaction effect is remarkably reduced, probably because of excessive Fe3+Easily becomes the recombination center of photogenerated electron-hole pairs. Thus, NiAl is obtained with a Fe molar content of about 0.151-XFeXThe LDH catalyst has the best CIP degrading capability and photocatalytic activity.
FIG. 2 shows three-dimensional NiAl0.85Fe0.15LDH/RGOY(Y ═ 0 to 35 wt%) degradation patterns of the composite photocatalysts, corresponding to those of examples 1 to 4 and comparative example 5. As shown in FIG. 2, when the RGO content reaches 25 wt%, the photocatalytic effect is the best, and the optimum degradation rate of CIP is about 93%. Due to the presence of RGO, not only aggregation of LDH nanosheets is inhibited, but recombination of photo-generated electron-hole pairs is also effectively hindered. The catalytic degradation effect of the photoreaction is better and better in the process that the RGO content is increased from 0 wt% to 25 wt%, and the reason for the phenomenon is that graphene is introduced into the composite, so that the separation efficiency of electron-hole pairs is improved. However, when the RGO content exceeds 25 wt%, the photocatalytic reaction effect is remarkably reduced by increasing the RGO content. This is probably due to the fact that too high a content of RGO would cover the NiAl0.85Fe0.15The LDH active site, thereby causing the degradation performance of photocatalysis, is not beneficial to the reaction. Therefore, NiAl obtained at an RGO content of 25 wt%0.85Fe0.15LDH/RGOYThe catalyst has the best photocatalytic activity.
FIG. 3 shows the three-dimensional NiAl prepared in example 30.85Fe0.15LDH/RGO25SEM image of composite photocatalyst. As is clear from FIG. 3, the slightly curved NiAl0.85Fe0.15most LDH nano-sheets vertically grow on the surface of RGO to form NiAl with a three-dimensional structure0.85Fe0.15LDH/RGO25the three-dimensional structure of the nano-composite is one of the key points for the composite to exert the activity.
the LDH size of the composite photocatalyst prepared by the invention is only 100-150nm, and the flake graphene is used as a carrier of the LDH nanosheet and vertically grows on the surface of the graphene to form a three-dimensional structure. The three-dimensional structure not only effectively inhibits the agglomeration of LDH nano-sheets, but also greatly improves the separation efficiency of electron-hole pairs in LDH, thereby greatly improving the photocatalytic degradation performance of the photocatalyst on ciprofloxacin.
The research of the invention finds that the raw materials of nickel nitrate, aluminum nitrate and ferric nitrate have mutual synergistic effect, the surface of graphene oxide has more oxygen-containing functions, and metal salt ions are anchored on the graphene oxide in advance during the preparation process of the group, so that the metal salt ions are uniformly distributed, the agglomeration of layered double hydroxides is effectively inhibited in the LDH forming process, and the separation of photo-generated electron-hole pairs of the layered double hydroxides is promoted. The invention takes Fe as an electron capture site by doping3+So as to inhibit the recombination of electron-hole pairs and the agglomeration of the supported RGO, thereby improving the photocatalytic performance of the supported RGO. The ratio of divalent metal ions to trivalent metal ions of the present invention is 2:1, because the proportion is too high or too low, the crystallinity of the LDH is reduced or impure LDH is formed, the size of the LDH prepared by the invention is uniform, the LDH/RGO shape obtained by the method is better, and the activity of the three-dimensional layered double-metal hydroxide/graphene composite photocatalyst prepared by the invention is obviously increased compared with the prior art.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (1)
1. A preparation method of an efficient three-dimensional layered double hydroxide/graphene composite photocatalyst is characterized by comprising the following steps:
(1) Placing graphite oxide in a solvent, and uniformly dispersing by ultrasonic to prepare a solution with the concentration of 40.9 g/L; the solvent is water, ethanol, glycol or glycerol;
(2) dissolving 2mmol of nickel nitrate, 0.85mmol of aluminum nitrate and 0.15mmol of ferric nitrate in a solvent, dropwise adding the solution prepared in the step (1), and continuously stirring for 3 hours;
(3) Dissolving 16mmol of urea in a solvent, adding the solution prepared in the step (2), and continuously stirring for 1 h;
(4) Reacting the solution prepared in the step (3) at 120 ℃ for 12 h;
(5) filtering and washing the reaction product prepared in the step (4), and drying at 60 ℃ for 12 h;
(6) Subjecting the three-dimensional NiAl prepared in the step (5) to0.85Fe0.15 LDH/RGO25the composite photocatalyst is used for degrading ciprofloxacin under visible light to measure the photocatalytic activity of ciprofloxacin, and the degradation rate of ciprofloxacin within 120min is over 93 percent.
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CN113979509B (en) * | 2021-11-05 | 2023-11-10 | 北京农学院 | Application of ultrathin sheet metal hydroxide in antibiotic degradation |
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