CN108855099A - A kind of preparation method and its photochemical catalyst of efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst - Google Patents
A kind of preparation method and its photochemical catalyst of efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst Download PDFInfo
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- CN108855099A CN108855099A CN201810802983.9A CN201810802983A CN108855099A CN 108855099 A CN108855099 A CN 108855099A CN 201810802983 A CN201810802983 A CN 201810802983A CN 108855099 A CN108855099 A CN 108855099A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 40
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000004411 aluminium Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 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 26
- 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 17
- 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 15
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- -1 graphite alkene Chemical class 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 abstract description 50
- 229960003405 ciprofloxacin Drugs 0.000 abstract description 25
- 230000015556 catabolic process Effects 0.000 abstract description 23
- 238000006731 degradation reaction Methods 0.000 abstract description 23
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 229910000943 NiAl Inorganic materials 0.000 abstract description 7
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 230000003115 biocidal effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 238000007146 photocatalysis Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 5
- 230000002045 lasting effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000007812 deficiency Effects 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000003839 salts Chemical class 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
- 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
- 230000002776 aggregation Effects 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 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 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 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
- 239000000203 mixture Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 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
- 238000003911 water pollution Methods 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
- B01J23/70—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
Landscapes
- 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 the preparation methods and its photochemical catalyst of a kind of efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst comprising, graphite oxide is placed in solvent and is uniformly dispersed；The mixing salt solution of nickel, aluminium, iron, stirring is added dropwise；Urea is added, stirring is reacted.The present invention forms layered double hydroxide/graphene composite photocatalyst of three-dimensional structure using graphene as the carrier of LDH nanometer sheet.The load of graphene not only inhibits the reunion of LDH nanometer sheet, but also promotes the separation of photo-generate electron-hole pair in LDH, to preferably be applied to the photocatalytic degradation of antibiotic.Three-dimensional NiAl prepared by the present invention0.85Fe0.15LDH/RGO25Composite photo-catalyst degrades Ciprofloxacin under visible light to survey its photocatalytic activity, and discovery Ciprofloxacin degradation rate in 120min reaches 93% or more.
Description
Technical field
The invention belongs to technical field of environmental material preparation, and in particular to a kind of efficient three-layer laminated bimetal hydroxide
Object/graphene composite photocatalyst preparation method and its photochemical catalyst.
Background technique
In order to effectively remove the chemical pollutant in water (such as antibiotic residues), semiconductor mediate photocatalysis technology by
It is low in its energy consumption, extensive concern that is environmentally friendly and causing researcher.Up to the present, researcher's exerting by researcher
Power develops the various photochemical catalysts for water pollution reparation, such as metal oxide, metal sulfide, layered bi-metal hydrogen-oxygen
Compound etc..In these photochemical catalysts, layered double hydroxide (LDH) is due to its unique layer structure, adjustable gold
Belong to composition and insertion anion and is considered as promising catalysis material.
However, single layer LDH has poor charge mobility and higher surface charge density, this is easy to cause photoproduction electric
The reunion of son-hole pair Quick Casting and LDH nanometer sheet limits its practical application to hinder its photocatalytic activity.
Summary of the invention
The purpose of this section is to summarize some aspects of the embodiment of the present invention and briefly introduce some preferable implementations
Example.It may do a little simplified or be omitted to avoid our department is made in this section and the description of the application and the title of the invention
Point, the purpose of abstract of description and denomination of invention it is fuzzy, and this simplification or omit and cannot be used for limiting the scope of the invention.
In view of above-mentioned technological deficiency, the present invention is proposed.
Therefore, as one aspect of the present invention, the present invention overcomes the deficiencies in the prior art, provides a kind of high
The preparation method of three-layer laminated double-metal hydroxide/graphene composite photocatalyst of effect.
In order to solve the above technical problems, the present invention provides following technical solutions：A kind of efficient three-layer laminated bimetallic
Hydroxide/graphene composite photocatalyst preparation method, it is characterised in that：Including,
Graphite oxide is placed in solvent and is uniformly dispersed；
The mixing salt solution of nickel, aluminium, iron, stirring is added dropwise；
Urea is added, stirring is reacted.
Preparation as efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst of the present invention
A kind of preferred embodiment of method：Described graphite oxide is placed in solvent is uniformly dispersed, the concentration including preparing graphene oxide
For 6.5~66.2g/L.
Preparation as efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst of the present invention
A kind of preferred embodiment of method：The solvent includes one of water, ethyl alcohol, ethylene glycol or glycerine.
Preparation as efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst of the present invention
A kind of preferred embodiment of method：The nickel, aluminium, iron mixing salt solution, including nickel nitrate, aluminum nitrate, ferric nitrate salt-mixture
Solution, the nickel nitrate, aluminum nitrate, ferric nitrate molar ratio be 2：(1-X)：X, wherein X is 0~0.2.
Preparation as efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst of the present invention
A kind of preferred embodiment of method：The molar ratio of nickel nitrate and urea is 2:16.
Preparation as efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst of the present invention
A kind of preferred embodiment of method：The mixing salt solution that nickel, aluminium, iron is added dropwise, stirring, wherein the stirring, time 3h.
Preparation as efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst of the present invention
A kind of preferred embodiment of method：The addition urea, stirring, is reacted, wherein the stirring, time 1h, the progress
Reaction, temperature are 100~140 DEG C, reaction time 12h.
Preparation as efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst of the present invention
A kind of preferred embodiment of method：Further include,
It is filtered, washed and dried：It is described reacted after, reaction product is filtered and washed, and at 60~80 DEG C
10~14h of lower drying.
As another aspect of the present invention, the present invention overcomes the deficiencies in the prior art, provides the preparation side
Three-layer laminated double-metal hydroxide/graphene composite photocatalyst made from method.
In order to solve the above technical problems, the present invention provides following technical solutions：Three-dimension layer made from the preparation method
Shape double-metal hydroxide/graphene composite photocatalyst, it is characterised in that：The nanometer sheet of layered double-metal hydroxide
Vertical-growth forms three-dimensional structure on flake graphite alkene, and the mass ratio of layered double hydroxide and graphene is
100：5~100：35, nanometer sheet is having a size of 100~150nm.
A kind of preferred side as three-layer laminated double-metal hydroxide/graphene composite photocatalyst of the present invention
Case：Layered double-metal hydroxide is NiAlFe LDH.
Beneficial effects of the present invention：The present invention forms the stratiform of three-dimensional structure using graphene as the carrier of LDH nanometer sheet
Double-metal hydroxide/graphene composite photocatalyst.The load of graphene not only inhibits the reunion of LDH nanometer sheet, but also
The separation of photo-generate electron-hole pair in LDH is promoted, to preferably be applied to the photocatalytic degradation of antibiotic.System of the present invention
Standby three-dimensional NiAl0.85Fe0.15LDH/RGO25It is living to survey its photocatalysis that composite photo-catalyst degrades Ciprofloxacin under visible light
Property, discovery Ciprofloxacin degradation rate in 120min reaches 93% or more.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill of field, without any creative labor, it can also be obtained according to these attached drawings other
Attached drawing.Wherein：
Fig. 1 is NiAl1-XFeXThe degradation figure of LDH composite photo-catalyst corresponds to comparative examples 1~4 and comparative example 1
~2 photochemical catalyst (X=0~0.3).
Fig. 2 is three-dimensional NiAl0.85Fe0.15LDH/RGOYThe degradation figure of (Y=0~35wt%) composite photo-catalyst, corresponds to
The composite photo-catalyst of Examples 1 to 4 and comparative example 5.
Fig. 3 is three-dimensional NiAl prepared by embodiment 30.85Fe0.15LDH/RGO25The SEM of composite photo-catalyst schemes.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, right combined with specific embodiments below
A specific embodiment of the invention is described in detail.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, but the present invention can be with
Implemented using other than the one described here other way, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by the specific embodiments disclosed below.
Secondly, " one embodiment " or " embodiment " referred to herein, which refers to, may be included at least one realization side of the invention
A particular feature, structure, or characteristic in formula." in one embodiment " that different places occur in the present specification not refers both to
The same embodiment, nor the individual or selective embodiment mutually exclusive with other embodiments.
Embodiment 1：
(1) that graphite oxide is placed in ultrasonic disperse in solvent is uniform, and being configured to concentration is 6.5g/L；
(2) 2mmol nickel nitrate, 0.85mmol aluminum nitrate and 0.15mmol ferric nitrate are dissolved in solvent, and added dropwise
Enter in (1), persistently stirs 3h；
(3) 16mmol urea is dissolved in solvent, and be added in (2), persistently stir 1h；
(4) above-mentioned solution is reacted into 12h at 120 DEG C；
(5) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(6) by prepared three-dimensional NiAl0.85Fe0.15LDH/RGO5Composite photo-catalyst degrade under visible light cyclopropyl sand
For star to survey its photocatalytic activity, discovery Ciprofloxacin degradation rate in 120min reaches 66%.
Embodiment 2：
(1) that graphite oxide is placed in ultrasonic disperse in solvent is uniform, and being configured to concentration is 21.7g/L；
(2) 2mmol nickel nitrate, 0.85mmol aluminum nitrate and 0.15mmol ferric nitrate are dissolved in solvent, and added dropwise
Enter in (1), persistently stirs 3h；
(3) 16mmol urea is dissolved in solvent, and be added in (2), persistently stir 1h；
(4) above-mentioned solution is reacted into 12h at 120 DEG C；
(5) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(6) by prepared three-dimensional NiAl0.85Fe0.15LDH/RGO15Composite photo-catalyst degrade under visible light cyclopropyl sand
For star to survey its photocatalytic activity, discovery Ciprofloxacin degradation rate in 120min reaches 84%.
Embodiment 3：
(1) that graphite oxide is placed in ultrasonic disperse in solvent is uniform, and being configured to concentration is 40.9g/L；Solvent can be water,
Ethyl alcohol, ethylene glycol or glycerine；
(2) 2mmol nickel nitrate, 0.85mmol aluminum nitrate and 0.15mmol ferric nitrate are dissolved in solvent, and added dropwise
Enter in (1), persistently stirs 3h；
(3) 16mmol urea is dissolved in solvent, and be added in (2), persistently stir 1h；
(4) above-mentioned solution is reacted into 12h at 120 DEG C；
(5) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(6) by prepared three-dimensional NiAl0.85Fe0.15LDH/RGO25Composite photo-catalyst degrade under visible light cyclopropyl sand
For star to survey its photocatalytic activity, discovery Ciprofloxacin degradation rate in 120min reaches 93% or more.
Embodiment 4：
(1) that graphite oxide is placed in ultrasonic disperse in solvent is uniform, and being configured to concentration is 66.2g/L；
(2) 2mmol nickel nitrate, 0.85mmol aluminum nitrate and 0.15mmol ferric nitrate are dissolved in solvent, and added dropwise
Enter in (1), persistently stirs 3h；
(3) 16mmol urea is dissolved in solvent, and be added in (2), persistently stir 1h；
(4) above-mentioned solution is reacted into 12h at 120 DEG C；
(5) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(6) by prepared three-dimensional NiAl0.85Fe0.15LDH/RGO35Composite photo-catalyst degrade under visible light cyclopropyl sand
For star to survey its photocatalytic activity, discovery Ciprofloxacin degradation rate in 120min reaches 80%.
Comparative example 1：
(1) 2mmol nickel nitrate, 1mmol aluminum nitrate are dissolved in solvent, persistently stir 10min；
(2) 16mmol urea is dissolved in solvent, and be added in (1), persistently stir 1h；
(3) above-mentioned solution is reacted into 12h at 120 DEG C；
(4) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(5) prepared NiAl LDH photochemical catalyst is degraded into Ciprofloxacin under visible light to survey its photocatalytic activity,
It was found that Ciprofloxacin degradation rate reaches 31% in 120min.
Comparative example 2：
(1) 2mmol nickel nitrate, 0.85mmol aluminum nitrate and 0.15mmol ferric nitrate are dissolved in solvent, it is lasting to stir
10min；
(2) 16mmol urea is dissolved in solvent, and be added in (1), persistently stir 1h；
(3) above-mentioned solution is reacted into 12h at 120 DEG C；
(4) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(5) by prepared NiAl0.85Fe0.15LDH photochemical catalyst degrades Ciprofloxacin under visible light to survey its photocatalysis
Activity, discovery Ciprofloxacin degradation rate in 120min reach 54%.
Comparative example 3：
(1) 2mmol nickel nitrate, 0.95mmol aluminum nitrate and 0.05mmol ferric nitrate are dissolved in solvent, it is lasting to stir
10min；
(2) 16mmol urea is dissolved in solvent, and be added in (1), persistently stir 1h；
(3) above-mentioned solution is reacted into 12h at 120 DEG C；
(4) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(5) by prepared NiAl0.95Fe0.05LDH photochemical catalyst degrades Ciprofloxacin under visible light to survey its photocatalysis
Activity, discovery Ciprofloxacin degradation rate in 120min reach 41%.
Comparative example 4：
(1) 2mmol nickel nitrate, 1mmol aluminum nitrate are dissolved in solvent, persistently stir 10min；
(2) 16mmol urea is dissolved in solvent, and be added in (1), persistently stir 1h；
(3) above-mentioned solution is reacted into 12h at 120 DEG C；
(4) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(5) prepared NiAl LDH photochemical catalyst is degraded into Ciprofloxacin under visible light to survey its photocatalytic activity,
It was found that Ciprofloxacin degradation rate reaches 31% in 120min.
Comparative example 5：
(1) 2mmol nickel chloride, 0.85mmol aluminium chloride and 0.15mmol iron chloride are dissolved in solvent, it is lasting to stir
10min；
(2) 16mmol urea is dissolved in solvent, and be added in (1), persistently stir 1h；
(3) above-mentioned solution is reacted into 12h at 120 DEG C；
(4) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(5) by prepared NiAl0.85Fe0.15LDH photochemical catalyst degrades Ciprofloxacin under visible light to survey its photocatalysis
Activity, discovery Ciprofloxacin degradation rate in 120min reach 52%.
Comparative example 6：
(1) 2mmol nickel nitrate, 1mmol ferric nitrate are dissolved in solvent, persistently stir 10min；
(2) 16mmol urea is dissolved in solvent, and be added in (1), persistently stir 1h；
(3) above-mentioned solution is reacted into 12h at 120 DEG C；
(4) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(5) prepared NiFe LDH photochemical catalyst is degraded into Ciprofloxacin under visible light to survey its photocatalytic activity,
It was found that Ciprofloxacin degradation rate reaches 40% in 120min.
Comparative example 7：
(1) 2mmol zinc nitrate, 0.85mmol aluminum nitrate and 0.15mmol ferric nitrate are dissolved in solvent, it is lasting to stir
10min；
(2) 16mmol urea is dissolved in solvent, and be added in (1), persistently stir 1h；
(3) above-mentioned solution is reacted into 12h at 120 DEG C；
(4) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(5) by prepared ZnAl0.85Fe0.15LDH photochemical catalyst degrades Ciprofloxacin under visible light to survey its photocatalysis
Activity, discovery Ciprofloxacin degradation rate in 120min reach 45%.
Comparative example 8：
(1) 2mmol nickel nitrate, 0.85mmol aluminum nitrate and 0.15mmol cerous nitrate are dissolved in solvent, it is lasting to stir
10min；
(2) 16mmol urea is dissolved in solvent, and be added in (1), persistently stir 1h；
(3) above-mentioned solution is reacted into 12h at 120 DEG C；
(4) reaction product is filtered and washed, and the dry 12h at 60 DEG C；
(5) by prepared NiAl0.85Ce0.15LDH photochemical catalyst degrades Ciprofloxacin under visible light to survey its photocatalysis
Activity, discovery Ciprofloxacin degradation rate in 120min reach 47%.
Fig. 1 is NiAl1-XFeXThe degradation figure of LDH composite photo-catalyst corresponds to comparative examples 1~4 and comparative example 1
~2 photochemical catalyst (X=0~0.3).
From fig. 1, it can be seen that the catalytic degradation effect of light reaction is become better and better when Fe molar content increases to 0.15 from 0.Work as Fe
When molar content is 0.15, NiAl1-XFeXThe photocatalysis effect of LDH compound is best,
The degradation rate of CIP is slightly above 50%.The basic reason for this phenomenon occur is Fe3+Light is captured as capture site
Raw electronics, it is suppressed that photo-generate electron-hole pair compound and the service life for extending them, to make its photocatalytic degradation CIP's
Performance is further promoted.But when Fe molar content is further increased from 0.15 to 0.2, light-catalyzed reaction effect
But obviously declined, this may be because of excessive Fe3+Readily become the complex centre of photo-generate electron-hole pairs.Therefore,
Fe molar content NiAl obtained when being about 0.151-XFeXThe ability photocatalytic activity of LDH catalyst degradation CIP is best.
Fig. 2 is three-dimensional NiAl0.85Fe0.15LDH/RGOYThe degradation figure of (Y=0~35wt%) composite photo-catalyst, corresponds to
The composite photo-catalyst of Examples 1 to 4 and comparative example 5.As shown in Fig. 2, when RGO content reaches 25wt%, photocatalysis effect
Be it is best, the best degradation rate of CIP is about 93%.Due to the presence of RGO, the aggregation of LDH nanometer sheet is not only inhibited, but also
Also effective ground resistance has hindered photo-generate electron-hole to reconfiguring.During RGO content increases to 25wt% from 0wt%, light
The catalytic degradation effect of reaction is become better and better, and the reason of this phenomenon occur is that graphene is introduced into compound, is improved
The separative efficiency of electron-hole pair.But after RGO content is more than 25wt%, continue to improve RGO content, light-catalyzed reaction
Effect is but obviously declined.This may be since the RGO of too high amount can cover NiAl0.85Fe0.15The active site of LDH, from
And Photocatalytic Degradation Property is caused to decline, it is unfavorable for the progress of reaction.So RGO content is obtained when being 25wt%
NiAl0.85Fe0.15LDH/RGOYCatalyst photocatalytic activity is best.
Fig. 3 is three-dimensional NiAl prepared by embodiment 30.85Fe0.15LDH/RGO25The SEM of composite photo-catalyst schemes.From Fig. 3
In it will be clear that slightly curved NiAl0.85Fe0.15LDH nanometer sheet in the surface RGO vertical-growth, forms three-dimensional knot mostly
The NiAl of structure0.85Fe0.15LDH/RGO25Nano-complex, this three-dimensional structure are that compound of the present invention plays its active key point
One of.
LDH size is only 100-150nm in composite photo-catalyst prepared by the present invention, and using flake graphite alkene as LDH
The carrier of nanometer sheet, upper vertical-growth, forms three-dimensional structure on the surface of graphene.This three-dimensional structure not only restrained effectively
The reunion of LDH nanometer sheet, and the separative efficiency of electron-hole pair in LDH is greatly improved, it is urged to substantially improve light
Photocatalytic Degradation Property of the agent to Ciprofloxacin.
Through the research of the invention finds that, mutually act synergistically between raw material nickel nitrate of the invention, aluminum nitrate and ferric nitrate, oxygen
Graphite alkene surface has more oxygen-containing function, and ionizable metal salt is anchored on graphene oxide in advance in the preparation for group, makes
Ionizable metal salt is evenly distributed, and leads to the reunion that restrained effectively layered double hydroxide during LDH formation,
And promote the separation of the photo-generate electron-hole pair of layered double hydroxide.The present invention is caught as electronics by doping and is grabbed
The Fe in site3+Inhibit the compound of electron hole pair, and load RGO inhibits its reunion, and then improves its photocatalysis performance.
The ratio of bivalent metal ion and trivalent metal ion of the invention is 2：1, all may this is because the ratio is too high or too low
Lead to the LDH that the crystallinity of LDH drops or low formation is impure, the LDH's that the present invention prepares is of uniform size, and side of the present invention
The LDH/RGO pattern that method obtains is more preferable, three-layer laminated double-metal hydroxide/graphene composite photocatalyst prepared by the present invention
Activity obviously increases compared with the prior art.
It should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable
Embodiment describes the invention in detail, those skilled in the art should understand that, it can be to technology of the invention
Scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered in this hair
In bright scope of the claims.
Claims (10)
1. a kind of preparation method of efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst, feature exist
In：Including,
Graphite oxide is placed in solvent and is uniformly dispersed；
The mixing salt solution of nickel, aluminium, iron, stirring is added dropwise；
Urea is added, stirring is reacted.
2. the preparation of efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst as described in claim 1
Method, it is characterised in that：Described graphite oxide is placed in solvent is uniformly dispersed, and the concentration including preparing graphene oxide is
6.5~66.2g/L.
3. the system of efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst as claimed in claim 1 or 2
Preparation Method, it is characterised in that：The solvent includes one of water, ethyl alcohol, ethylene glycol or glycerine.
4. the system of efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst as claimed in claim 1 or 2
Preparation Method, it is characterised in that：The nickel, aluminium, iron mixing salt solution, the salt-mixture including nickel nitrate, aluminum nitrate, ferric nitrate is molten
Liquid, the nickel nitrate, aluminum nitrate, ferric nitrate molar ratio be 2：(1-X)：X, wherein X is 0~0.2.
5. the preparation of efficient three-layer laminated double-metal hydroxide/graphene composite photocatalyst as claimed in claim 4
Method, it is characterised in that：The molar ratio of nickel nitrate and urea is 2:16.
6. efficient three-layer laminated double-metal hydroxide/graphene complex light as described in any in claim 1,2 or 4 is urged
The preparation method of agent, it is characterised in that：The mixing salt solution that nickel, aluminium, iron is added dropwise, stirring, wherein the stirring, when
Between be 3h.
7. efficient three-layer laminated double-metal hydroxide/graphene complex light as described in any in claim 1,2 or 4 is urged
The preparation method of agent, it is characterised in that：The addition urea, stirring, is reacted, wherein the stirring, time 1h,
Described to be reacted, temperature is 100~140 DEG C, reaction time 12h.
8. efficient three-layer laminated double-metal hydroxide/graphene complex light as described in any in claim 1,2 or 4 is urged
The preparation method of agent, it is characterised in that：Further include,
It is filtered, washed and dried：It is described reacted after, reaction product is filtered and washed, and at 60~80 DEG C do
Dry 10~14h.
9. three-layer laminated double-metal hydroxide/graphene complex light made from any preparation method of claim 1~8
Catalyst, it is characterised in that：The nanometer sheet vertical-growth of layered double-metal hydroxide is formed on flake graphite alkene
The mass ratio of three-dimensional structure, layered double hydroxide and graphene is 100：5~100：35, nanometer sheet having a size of 100~
150nm。
10. three-layer laminated double-metal hydroxide/graphene composite photocatalyst as claimed in claim 9, it is characterised in that：
Layered double-metal hydroxide is NiAlFe LDH.
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