CN108620060A - A kind of bismuth molybdate graphene aerogel compound and preparation method thereof - Google Patents
A kind of bismuth molybdate graphene aerogel compound and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- 239000004964 aerogel Substances 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910002900 Bi2MoO6 Inorganic materials 0.000 claims abstract description 50
- 239000002131 composite material Substances 0.000 claims abstract description 44
- 230000015556 catabolic process Effects 0.000 claims abstract description 37
- 238000006731 degradation reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000004108 freeze drying Methods 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000017 hydrogel Substances 0.000 claims description 11
- 238000002604 ultrasonography Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000003344 environmental pollutant Substances 0.000 claims description 9
- 231100000719 pollutant Toxicity 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000019766 L-Lysine Nutrition 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 claims description 6
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 6
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 6
- 239000012456 homogeneous solution Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- -1 graphite Alkene Chemical class 0.000 claims description 5
- 239000004472 Lysine Substances 0.000 claims description 3
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000007246 mechanism Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- WPLOVIFNBMNBPD-ATHMIXSHSA-N subtilin Chemical compound CC1SCC(NC2=O)C(=O)NC(CC(N)=O)C(=O)NC(C(=O)NC(CCCCN)C(=O)NC(C(C)CC)C(=O)NC(=C)C(=O)NC(CCCCN)C(O)=O)CSC(C)C2NC(=O)C(CC(C)C)NC(=O)C1NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C1NC(=O)C(=C/C)/NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)CNC(=O)C(NC(=O)C(NC(=O)C2NC(=O)CNC(=O)C3CCCN3C(=O)C(NC(=O)C3NC(=O)C(CC(C)C)NC(=O)C(=C)NC(=O)C(CCC(O)=O)NC(=O)C(NC(=O)C(CCCCN)NC(=O)C(N)CC=4C5=CC=CC=C5NC=4)CSC3)C(C)SC2)C(C)C)C(C)SC1)CC1=CC=CC=C1 WPLOVIFNBMNBPD-ATHMIXSHSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- XWNOTOKFKBDMAP-UHFFFAOYSA-N [Bi].[N+](=O)(O)[O-] Chemical compound [Bi].[N+](=O)(O)[O-] XWNOTOKFKBDMAP-UHFFFAOYSA-N 0.000 abstract 1
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentoxide Inorganic materials [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 abstract 1
- 230000036571 hydration Effects 0.000 abstract 1
- 238000006703 hydration reaction Methods 0.000 abstract 1
- 238000001782 photodegradation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 150000008545 L-lysines Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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Abstract
The invention discloses a kind of bismuth molybdate graphene aerogel compounds and preparation method thereof, belong to the technical field of photochemical catalyst preparation.The present invention uses graphene oxide for raw material, and Bi is prepared with four hydration ammonium heptamolybdates and anhydrous nitric acid bismuth2MoO6Raw material finally obtain 3D Bi through solvent heat and freeze-drying process2MoO6/ redox graphene aerogel-containing composite materials.The 3D Bi of synthesis2MoO6The electron hole pair longer life expectancy of/redox graphene aerogel-containing composite materials, adsorption capacity to organic pollution and also enhances the absorbability of visible light so as to organic pollution catalytic degradation activity higher under visible light.3D Bi2MoO6/ redox graphene aerogel-containing composite materials photodegradation rate is Bi2MoO62.1 times, be 2.46 times of redox graphene aeroge, have higher actual application value.
Description
Technical field
The present invention relates to a kind of bismuth molybdate graphene aerogel compounds and preparation method thereof, belong to photochemical catalyst preparation
Technical field.
Background technology
Currently, with the rapid development of industry, problem of environmental pollution especially organic pollution problem getting worse.Generally
For, absorption is to solve one of the important method of organic pollution.The oxygen reduction of three-dimensional porous structure in numerous sorbing materials
Graphite alkene aeroge (GA), easy to operate since it is at low cost, the advantages that surface area is big, and open bore is big, thus to having
Adsorption rate very high (Acs Applied Materials＆Interfaces, 2012,4 (8), the pp 4373-of machine pollutant
4379).Although redox graphene aeroge is considered as a kind of sorbing material of effective processing organic pollution, have
Malicious organic pollution is only aggregated together, rather than is degraded to innocuous substance by GA, and subsequent processing may cause secondary pollution.
In addition, GA sorbing materials are difficult to regenerate, and need to handle to discharge pollutant when reaching its saturation.Therefore, GA is based on to inhale
All disadvantages mentioned above of enclosure material, it should develop the pollutant in a kind of degradable GA sorbing materials of new method.
In recent years, three-dimensional porous structure GA is combined the semiconductor/GA composite materials being prepared into semiconductor light-catalyst, no
It can only solve the problems, such as that the regeneration of GA sorbing material adsorption capacity finite sums is difficult, and adsorption capacity and powdery light can be increased
The dispersion degree of catalyst.In addition, semiconductor light-catalyst can be evenly distributed in the frame of three-dimensional structure GA, greatly reduce
The aggregation of powdered photochemical catalyst, and show more active sites.Due to low-density characteristic, 3D porous structures are partly led
Body/GA composite materials can be floated on easily in contaminant water, considerably increase three-dimensional structure semiconductor/GA composite photo-catalysts with
Contact surface between visible light.Including TiO therefore,2/ GA compounds, SnO2/ GA compounds and Cu2The mixing of O/GA compounds half
Conductor shows promising application in organic pollution processing.
Bismuthino semiconductor causes the extensive pass of research circle due to its significant photocatalysis performance as novel photocatalyst
Note.Bismuth molybdate (Bi2MoO6) it is used as n-type semiconductor, Eg is about 2.6eV, has good photocatalysis performance under visible light.
In recent years, flower shape Bi2MoO6Hollow ball, (Journal of Materials Chemistry, 2011,21,887-892) Er3 +The Bi of doping2MoO6Equal researchs all show Bi2MoO6Excellent photocatalytic activity (Applied Catalysis B:
Environmental110,2011,221–230).Although Bi2MoO6There is certain application prospect, but its in photocatalysis field
Specific surface area is low, it is seen that light absorption is low, and photogenerated charge carriers are quickly compound, hinders its practical application.Therefore, Bi is improved2MoO6
Visible absorption speed and photogenerated charge carriers it is quickly compound, to promote Bi2MoO6Photocatalysis effect in practical applications
Fruit.
Invention content
First purpose of the invention is to provide a kind of 3D Bi of high catalytic degradation activity2MoO6/ redox graphene gas
The preparation method of gel composite, the method are as follows：
(1) by graphene oxide (GO) suspension ultrasound 1-3 hours to form homogeneous solution；
(2) by Bi (NO3)3.5H2O and (NH4)6Mo7O24.4H2O is dissolved in deionized water, ultrasonic 1-2h (being known as A liquid), will
The GO solution and L-lysine prepared, which is added drop-wise to stir 1-2 hours in solution A, obtains mixed liquor；
(3) mixed liquor is transferred in the high-pressure hydrothermal reaction kettle containing polytetrafluoroethyllining lining, and added at 12-160 DEG C
It is 8-16 hours hot；After being cooled to room temperature, (3D) Bi is obtained2MoO6/ redox graphene hydrogel composites；
(4) after being immersed in deionized water and absolute ethyl alcohol for several times, gained compound is freeze-dried；It obtains
Bi2MoO6/ redox graphene aeroge (BMO/GA) composite material.
In an embodiment of the present invention, in the step (1) graphene oxide (GO) suspension a concentration of 1.5-
2.5mg/mL。
In an embodiment of the present invention, A liquid Bi (NO in the step (2)3)3.5H2A concentration of 10-30mg/ of O
Ml, (NH4)6Mo7O24.4H2A concentration of 5.0-30mg/mL of O.
In an embodiment of the present invention, the volume ratio of GO solution and solution A is 0.5-1.5 in the step (2)：1.
In an embodiment of the present invention, in the step (2) in mixed liquor L-lysine final concentration of 2.0-
4.0mg/mL。
In an embodiment of the present invention, freeze-drying refers to freezing to do at -40 to -50 DEG C in the step (4)
It is 20-30 hours dry.
In an embodiment of the present invention, (3D) Bi in the step (4)2MoO6/ redox graphene hydrogel
Compound is that have the 3D of three-dimensional structure independently mesoporous product
In an embodiment of the present invention, the Bi2MoO6/ redox graphene hydrogel composites are in mechanism of degradation
Application on pollutant.
Second purpose of the invention is to provide a kind of 3D Bi2MoO6The organic dirt of/redox graphene aeroge light degradation
Contaminate object method, the method the specific steps are：By 3D Bi2MoO6/ redox graphene aerogel-containing composite materials have been added to
In machine pollutant solution, 40-80min is stirred in dark, then carries out photocatalytic degradation experiment, light degradation time under visible light
Continue 80-100min.
The technological merit of the present invention：Bi2MoO6/ graphene aerogel compound is by solvent heat one-step synthesis method, then through cold
Freeze and be dried, method is simple；Pass through Bi2MoO6And the synergistic effect that graphene is compound, reduce Bi2MoO6Band gap, improve
Its adsorption capacity to organic pollution, enhances the utilization rate to visible light, reduces the compound of photo-generate electron-hole pair
Rate extends the service life of carrier；Bi simultaneously2MoO6Nanometer sheet is equably upper equal in the hole of redox graphene aeroge
Even attachment improves the chemical action between graphene, and to greatly improve compound, in visible light region, degradation has
The ability of machine pollutant.The results show that it is characterized in that comparing Bi2MoO6With redox graphene aeroge, 3D
Bi2MoO6210% and 246% has been respectively increased in the photocatalytic activity of/redox graphene aerogel-containing composite materials, to methylene
The removal rate of base indigo plant is 98.3%.
Description of the drawings
Degradation figure of Fig. 1 different catalysts to methylene blue：(a) redox graphene aeroge；(b)Bi2MoO6；
(c)Bi2MoO6/ redox graphene aerogel-containing composite materials.
The 3D Bi of Fig. 2 difference GA mass ratioes2MoO6Drop of/redox graphene the aerogel-containing composite materials to methylene blue
Xie Tu：(a) redox graphene aeroge；(b)Bi2MoO6；(c) Bi containing 5%GA2MoO6/ GA compounds；(d) contain 15%
The Bi of GA2MoO6/ GA compounds；(e) Bi containing 10%GA2MoO6/ GA compounds.
The UV-vis of Fig. 3 different catalysts schemes：(a)GA；(b) Bi containing 15%GA2MoO6/ GA compounds；(c) contain 10%
The Bi of GA2MoO6/ GA compounds；(d) Bi containing 5%GA2MoO6/ GA compounds；(e)Bi2MoO6。
Specific implementation mode
Following example can make those skilled in the art be fully understood by the present invention, but not limit this hair in any way
It is bright.
Embodiment 1：The preparation of redox graphene aeroge (GA) and light degradation pollutant
(1) synthesis of redox graphene aeroge (GA)：At room temperature, by 10mL GO (2mg/mL) suspension ultrasound 1
Hour is to form homogeneous solution.Then 0.04g L-lysines will be added in the GO solution prepared with vigorous stirring and stirs
1 hour.Later, it transfers the solution into and is transferred in high-pressure hydrothermal reaction kettles of the 50mL containing polytetrafluoroethyllining lining, and at 160 DEG C
Lower heating 10 hours.After being cooled to room temperature, 3D redox graphene hydrogels are obtained, are immersed in deionized water and anhydrous
In ethyl alcohol for several times after, gained compound is further freeze-dried 24 hours at -50 DEG C.Finally, reduction-oxidation graphite is obtained
The independent mesoporous products of the 3D of alkene aeroge (GA)；
(2) redox graphene aeroge (GA) light degradation organic pollution：By redox graphene aeroge
(GA) be added in the aqueous solution of methylene blue of a concentration of 10mg/L of 60mL, 60min stirred in dark, then under visible light into
Row photocatalytic degradation is tested, and the light degradation time continues 100min, pipettes 3mL solution per 20min in the process.As a result such as Fig. 2 (a) and
Shown in Fig. 3 (a), in the removal rate of methylene blue be 39.9%.
Embodiment 2：Pure Bi2MoO6Preparation and light degradation pollutant
(1) pure Bi2MoO6Synthesis：At room temperature, by the Bi (NO of 0.15g3)3.5H2O and 0.025g (NH4)6Mo7O24.4H2O
It is dissolved in 10mL deionized waters, at room temperature ultrasound 1h (being known as A liquid), then 0.04g L-lysines is added dropwise with vigorous stirring
It is stirred 1 hour in solution A.Later, it transfers the solution into and is transferred to high pressure hydro-thermal reactions of the 50mL containing polytetrafluoroethyllining lining
In kettle, and heated 10 hours at 160 DEG C.After being cooled to room temperature, after being immersed in deionized water and absolute ethyl alcohol for several times,
Products therefrom is further freeze-dried 24 hours at -50 DEG C.Finally, pure Bi is obtained2MoO6；
Pure Bi2MoO6Light degradation organic pollution：By pure Bi2MoO6It is added to the methylene blue of a concentration of 10mg/L of 60mL
In aqueous solution, 60min is stirred in dark, then carries out photocatalytic degradation experiment under visible light, the light degradation time continues
100min pipettes 3mL solution per 20min in the process.As a result as shown in Fig. 2 (b) and Fig. 3 (e), for the removal rate of methylene blue
It is 46.8%.
Embodiment 3：3D Bi2MoO6/ redox graphene aerogel-containing composite materials synthesize and light degradation organic pollution
(1)Bi2MoO6The synthesis of/redox graphene aerogel-containing composite materials：At room temperature, by 10mL GO (2.0mg/mL)
Suspension ultrasound 1 hour to form homogeneous solution.Meanwhile by the Bi (NO of 0.15g3)3.5H2O and 0.025g (NH4)6Mo7O24.4H2O is dissolved in 10mL deionized waters, at room temperature ultrasound 1h (be known as A liquid), then will be prepared with vigorous stirring
GO solution and 0.04g L-lysines are added drop-wise in solution A and stir 1 hour.Later, it transfers the solution into and is transferred to 50mL containing poly-
In the high-pressure hydrothermal reaction kettle of tetrafluoroethene liner, and heated 10 hours at 160 DEG C.After being cooled to room temperature, obtain three-dimensional
(3D)Bi2MoO6/ redox graphene hydrogel composites will after being immersed in deionized water and absolute ethyl alcohol for several times
Gained compound is further freeze-dried 24 hours at -50 DEG C.Finally, the Bi of mass fraction containing GA 10% is obtained2MoO6/ stone
The independent mesoporous products of the 3D of black alkene aeroge (BMO/GA) composite material；
(2)3D Bi2MoO6/ redox graphene aerogel-containing composite materials light degradation organic pollution：GA mass point will be contained
The 3D Bi of number 10%2MoO6/ redox graphene aerogel-containing composite materials are added to the methylene blue of a concentration of 10mg/L of 60mL
In aqueous solution, 60min is stirred in dark, then carries out photocatalytic degradation experiment under visible light, the light degradation time continues
100min pipettes 3mL solution per 20min in the process.To Bi2MoO6With redox graphene aeroge in the same way into
Row light degradation is tested, and carrying out absorbance to gained sample liquid measures to calculate degradation effect.As a result as shown in Fig. 2 (e) and Fig. 3 (c),
The results show that Bi2MoO6/ redox graphene aerogel-containing composite materials are 98.3% to the removal rate of methylene blue, are compared
Bi2MoO6210% and 246% has been respectively increased with the photocatalytic activity of redox graphene aeroge.
Embodiment 4：3D Bi2MoO6/ redox graphene aerogel-containing composite materials synthesize and light degradation organic pollution
(1)Bi2MoO6The synthesis of/redox graphene aerogel-containing composite materials：At room temperature, 10mL GO (2mg/mL) is outstanding
Supernatant liquid ultrasound 1 hour to form homogeneous solution.Meanwhile by the Bi (NO of 0.097g3)3.5H2O and 0.0162g (NH4)6Mo7O24.4H2O is dissolved in 10mL deionized waters, at room temperature ultrasound 1h (be known as A liquid), then will be prepared with vigorous stirring
GO solution and 0.04g L-lysines are added drop-wise in solution A and stir 1 hour.Later, it transfers the solution into and is transferred to 50mL containing poly-
In the high-pressure hydrothermal reaction kettle of tetrafluoroethene liner, and heated 10 hours at 160 DEG C.After being cooled to room temperature, obtain three-dimensional
(3D)Bi2MoO6/ redox graphene hydrogel composites will after being immersed in deionized water and absolute ethyl alcohol for several times
Gained compound is further freeze-dried 24 hours at -50 DEG C.Finally, the Bi that mass fraction containing GA is 15% is obtained2MoO6/
The independent mesoporous products of the 3D of redox graphene aeroge (BMO/GA) composite material；
(2)Bi2MoO6/ redox graphene aerogel-containing composite materials light degradation organic pollution：GA mass fractions, which will be contained, is
15% Bi2MoO6/ redox graphene aerogel-containing composite materials are added to the aqueous solution of methylene blue of a concentration of 10mg/L of 60mL
In, 60min is stirred in dark, then carries out photocatalytic degradation experiment under visible light, the light degradation time continues 100min, process
In pipette 3mL solution per 20min.To Bi2MoO6Light degradation survey is carried out in the same way with redox graphene aeroge
Examination carries out absorbance to gained sample liquid and measures to calculate degradation effect.As a result as shown in Fig. 2 (d) and Fig. 3 (b), the results show that
3D Bi2MoO6/ redox graphene aerogel-containing composite materials are 90.1% to the removal rate of methylene blue, compare Bi2MoO6With
192% and 225% has been respectively increased in the photocatalytic activity of redox graphene aeroge.
Embodiment 5：3D Bi2MoO6/ redox graphene aerogel-containing composite materials synthesize and light degradation organic pollution
(1)Bi2MoO6The synthesis of/redox graphene aerogel-containing composite materials：At room temperature, 10mL GO (2mg/mL) is outstanding
Supernatant liquid ultrasound 1 hour to form homogeneous solution.Meanwhile by the Bi (NO of 0.3g3)3.5H2O and 0.0545g (NH4)6Mo7O24.4H2O
Be dissolved in 10mL deionized waters, at room temperature ultrasound 1h (be known as A liquid), then with vigorous stirring by the GO solution prepared and
0.04g L-lysines are added drop-wise in solution A and stir 1 hour.Later, it transfers the solution into and is transferred to 50mL containing polytetrafluoroethylene (PTFE)
In the high-pressure hydrothermal reaction kettle of liner, and heated 10 hours at 160 DEG C.After being cooled to room temperature, three-dimensional (3D) Bi is obtained2MoO6/
Redox graphene hydrogel composites, after being immersed in deionized water and absolute ethyl alcohol for several times, by gained compound
Further it is freeze-dried 24 hours at -50 DEG C.Finally, the Bi of mass fraction containing GA 5% is obtained2MoO6/ redox graphene
The independent mesoporous products of the 3D of aeroge (BMO/GA) composite material；
(2)Bi2MoO6/ redox graphene aerogel-containing composite materials light degradation organic pollution：GA mass fractions will be contained
5% Bi2MoO6/ redox graphene aerogel-containing composite materials are added to the aqueous solution of methylene blue of a concentration of 10mg/L of 60mL
In, 60min is stirred in dark, then carries out photocatalytic degradation experiment under visible light, the light degradation time continues 100min, process
In pipette 3mL solution per 20min.To Bi2MoO6Light degradation survey is carried out in the same way with redox graphene aeroge
Examination carries out absorbance to gained sample liquid and measures to calculate degradation effect.As a result as shown in Fig. 2 (c) and Fig. 3 (d), the results show that
Bi2MoO6/ redox graphene aerogel-containing composite materials are 84.6% to the removal rate of methylene blue, compare Bi2MoO6And reduction
180% and 212% has been respectively increased in graphite oxide aerogel photocatalytic activity.
The result of embodiment 1-5 is as shown in Figures 2 and 3, according to the Bi of result GA2MoO6The degradation of/GA compounds
Rate is higher, and the percentage composition of GA has larger impact to the degradation efficiency of compound, wherein the Bi containing 10%GA2MoO6/ GA compounds
Degradation efficiency it is best.
Embodiment 7：3D Bi2MoO6/ redox graphene aerogel-containing composite materials reaction temperature and reaction time are to compound
The influence of object degradation efficiency
According to the technical solution of embodiment 6, change reaction temperature time prepared by compound, other reaction conditions and implementation
Example 6 is identical.Reaction time and temperature prepared by compound is that 11 hours, 110 DEG C of reactions are reacted in 140 DEG C of reactions for 13 hours, 120 DEG C
React 9 hours, respectively scheme 1, scheme 2, scheme 3 and scheme 4 within 12 hours, 130 DEG C.
Scheme 1, scheme 2, scheme 3 and scheme 4, result be respectively 65.7% to the removal rate of methylene blue, 54.2%,
61.9%, 42.6%, illustrate that this patent has peak optimization reaction time and temperature requirement, in the system of non-optimal reaction temperature and time
Under the conditions of standby, it is unable to reach this patent optimum efficiency.
Embodiment 8：3D Bi2MoO6When the reaction of/redox graphene aerogel-containing composite materials light degradation organic pollution
Between influence to degradation rate
According to the technical solution of embodiment 6, change degradable organic pollutant dark reaction time, other reaction conditions and reality
It is identical to apply example 6.The degradable organic pollutant dark reaction time is respectively 20min, 30min, 40min, 50min, respectively scheme,
Respectively scheme 1, scheme 2, scheme 3 and scheme 4.
Scheme 1, scheme 2, scheme 3 and scheme 4, result be respectively 28.3% to the removal rate of methylene blue, 37.2%,
69.1%, 77.3%, illustrate that this patent has best dark reaction time requirement, it, can not under the non-optimal dark reaction time
Reach this patent optimum efficiency.
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not limited to the present invention, any to be familiar with this skill
The people of art can do various change and modification, therefore the protection model of the present invention without departing from the spirit and scope of the present invention
Enclosing be subject to what claims were defined.
Claims (10)
1. a kind of 3D Bi of high catalytic degradation activity2MoO6The preparation method of/redox graphene aerogel-containing composite materials, it is special
Sign is that the method is as follows：
(1) by graphene oxide (GO) suspension ultrasound 1-3 hours to form homogeneous solution；
(2) by Bi (NO3)3.5H2O and (NH4)6Mo7O24.4H2O is dissolved in deionized water, and ultrasonic 1-2h (being known as A liquid) will prepare
Good GO solution and L-lysine, which is added drop-wise to stir 1-2 hours in solution A, obtains mixed liquor；
(3) mixed liquor is transferred in the high-pressure hydrothermal reaction kettle containing polytetrafluoroethyllining lining, and 8- is heated at 12-160 DEG C
16 hours；After being cooled to room temperature, (3D) Bi is obtained2MoO6/ redox graphene hydrogel composites；
(4) after being immersed in deionized water and absolute ethyl alcohol for several times, gained compound is freeze-dried；Obtain Bi2MoO6/
Redox graphene aeroge (BMO/GA) composite material.
2. method according to claim 1, which is characterized in that graphene oxide (GO) suspension is dense in the step (1)
Degree is 1.5-2.5mg/mL.
3. method according to claim 1, which is characterized in that A liquid Bi (NO in the step (2)3)3.5H2O's is a concentration of
10-30mg/ml, (NH4)6Mo7O24.4H2A concentration of 5.0-30mg/mL of O.
4. method according to claim 1, which is characterized in that the volume ratio of GO solution and solution A is in the step (2)
0.5-1.5:1。
5. method according to claim 1, which is characterized in that in the step (2) in mixed liquor L-lysine final concentration
For 2.0-4.0mg/mL.
6. method according to claim 1, which is characterized in that freeze-drying refers at -40 to -50 DEG C in the step (4)
Lower freeze-drying 20-30 hours.
7. method according to claim 1, which is characterized in that (3D) Bi in the step (4)2MoO6/ reduction-oxidation graphite
Alkene hydrogel composites are that have the 3D of three-dimensional structure independently mesoporous product.
8. the Bi that any the methods of claim 1-7 are prepared2MoO6/ redox graphene hydrogel composites.
9. Bi described in claim 82MoO6Application of/redox graphene the hydrogel composites on mechanism of degradation pollutant.
10. application according to claim 9, which is characterized in that tell that application is specially：By 3D Bi2MoO6/ oxygen reductions
Graphite alkene aerogel-containing composite materials are added in organic pollutant solution, stir 40-80min in dark, then under visible light
Photocatalytic degradation experiment is carried out, the light degradation time continues 80-100min.
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Application publication date: 20181009 |