CN109622056A - A kind of composite efficient visible-light photocatalyst and its preparation method and application - Google Patents
A kind of composite efficient visible-light photocatalyst and its preparation method and application Download PDFInfo
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- CN109622056A CN109622056A CN201811630383.5A CN201811630383A CN109622056A CN 109622056 A CN109622056 A CN 109622056A CN 201811630383 A CN201811630383 A CN 201811630383A CN 109622056 A CN109622056 A CN 109622056A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 76
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 74
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 239000004964 aerogel Substances 0.000 claims abstract description 43
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 30
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 230000001699 photocatalysis Effects 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 3
- 239000000017 hydrogel Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 32
- 230000015556 catabolic process Effects 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 17
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229940126680 traditional chinese medicines Drugs 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- 150000003233 pyrroles Chemical class 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 206010011224 Cough Diseases 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004153 renaturation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 241000127225 Enceliopsis nudicaulis Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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Abstract
The invention belongs to catalyst technical fields, and in particular to a kind of composite efficient visible-light photocatalyst and its preparation method and application.Preparation method is the following steps are included: 1) to improve Hummers method preparation graphene oxide water solution；2) using methyl orange solution as template, potassium permanganate is that oxidant prepares nano-manganese dioxide modified polypyrrole pipe；3) nano-manganese dioxide modified polypyrrole pipe is mixed with graphene oxide solution and is uniformly dispersed, reacted in high pressure water heating kettle, manganese dioxide-polypyrrole graphene aerogel photochemical catalyst is made.The preparation method of provided composite efficient visible-light photocatalyst simple, efficient, low cost can be prepared active good through the invention, the high visible-light photocatalyst of stability, it is easy to industrialize, the problem of it is at high cost to solve traditional photochemical catalyst, poor repeatability.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of composite efficient visible-light photocatalyst and its preparation
Methods and applications.
Background technique
The environmental problem of China is increasingly serious now, and the existing processing method to organic wastewater exists to waste water requirement
A series of problems, such as height, cost is big.Photocatalytic degradation method, which handles waste water, has selectivity extensively, easy to use, low in cost etc. excellent
Point is the method for the following processing optimal prospect of waste water and gas.Traditional photochemical catalyst such as TiO2、ZrO2, ZnS, CdS ZnO or
BiVO4It is ultraviolet region etc. main light absorption area, but the ultraviolet light in sunlight is inhaled by atmosphere when reaching ground
Receipts reflect away major part, and the ultraviolet light content in practical earth's surface sunray leads to traditional photochemical catalyst luminous energy benefit less than 5%
It is low with rate.Traditional improved means include noble-metal-supported doping vario-property, and semiconductor material is compound etc..But these improvement costs are too
It is high, it is desirable that condition is harsh, can not large scale preparation production.Polypyrrole has characteristic of semiconductor organic polymer as a kind of, because
To be easily prepared, stability is good, environmentally friendly property and by the favor of researcher.Its forbidden bandwidth is moderate, rings to visible light
Should be good, it is a kind of photochemical catalyst of great potential.But since pure polypyrrole forbidden bandwidth is big, conductivity is small, and bad dispersibility is led
Cause its catalytic efficiency low, it is difficult to be applied individually to any photocatalysis field.
Manganese dioxide is a kind of large specific surface area, and electrochemical properties are stablized, low-cost electrochemical material, with poly- pyrrole
Doping is coughed up, on the one hand can be improved the dispersibility of polypyrrole, improves the adsorptivity of material；It can reduce the forbidden band of polypyrrole simultaneously
Width further widens its utilization rate to light source.
Graphene aerogel is a kind of with three-dimensional porous structure, bigger serface, the three-dimensional material of good conductivity.
It not only has the advantages that graphene absorption property is good, at the same three-dimensional porous structure enable its as carrier when good dispersion
Active component.Its higher conductivity can contain catalyst the electron-hole pair generated when light provocative reaction again
It is compound, improve the catalytic efficiency of catalyst.By the compound of graphene aerogel and polypyrrole and manganese dioxide, had
The visible-light photocatalyst of efficient degradation rate.
Summary of the invention
To solve the deficiencies in the prior art, the present invention provides a kind of high-efficient visible-light photocatalyst and preparation method thereof and
Using the response range that can solve traditional photochemical catalyst is small, problem at high cost.
Technical solution provided by the present invention is as follows:
A kind of efficient compound Visible Light Induced Photocatalytic catalyst, comprising:
Three-dimensional grapheme aeroge and the nano-manganese dioxide modified polypyrrole pipe being supported on graphene aerogel,
In, the general structure of the polypyrrole is as follows:
Wherein: A-Ion is oxidant anion, predominantly OH-Ion because use metallic salt as oxidant (such as
KMnO4) preparation PPy during, anion can also be used as dopant simultaneously, and form compound by electric charge transfer.
The chain structure of PPy is general Oxidation Doping structure at this time.
Above-mentioned composite efficient visible-light photocatalyst, the active component of photochemical catalyst are that nano-manganese dioxide is modified poly-
Pyrroles's pipe.
Above-mentioned composite efficient visible-light photocatalyst, the carrier of photochemical catalyst are three-dimensional structure graphene aerogel.
In Efficient non-metallic visible-light photocatalyst provided by the present invention, manganese dioxide modified polypyrrole pipe is with first
Base orange is template, and using potassium permanganate as oxidant, a step generates manganese dioxide-polypyrrole pipe of Nano grade.It prepares
Nano-manganese dioxide modified polypyrrole pipe disperses in graphene oxide solution, using high pressure hydro-thermal reaction, is formed and is uniformly divided
The manganese dioxide of cloth-polypyrrole graphene aerogel catalyst.Under light illumination, manganese dioxide modified polypyrrole pipe light excites,
Light induced electron and hole pair are generated by photoelectric effect, in graphene under conductivity improvement, light induced electron and hole are to answering
Conjunction rate reduces, and light induced electron can be transferred to catalyst surface faster, and further reaction generates hydroxyl radical free radical and other are strong
Oxide group carries out catalytic degradation to pollutant.
Based on the above-mentioned technical proposal, it may be implemented simple and convenient, inexpensive to prepare the high-efficient visible-light photocatalyst.
The present invention also provides a kind of preparation methods of high-efficient visible-light photocatalyst, comprising the following steps:
1) to improve Hummers method preparation graphene oxide water solution；
2) using methyl orange solution as template, potassium permanganate is that oxidant prepares nano-manganese dioxide modified polypyrrole pipe；
3) nano-manganese dioxide modified polypyrrole pipe is mixed with graphene oxide solution and is uniformly dispersed, in high pressure water heating kettle
Manganese dioxide-polypyrrole graphene aerogel photochemical catalyst is made in middle reaction.
A kind of preparation method of above-mentioned composite efficient visible-light photocatalyst, in the step 1), reaction temperature control
System is between 35 ± 5 DEG C, and after potassium permanganate adds, room temperature continues stirring oxidation 48-80h.
A kind of preparation method of above-mentioned composite efficient visible-light photocatalyst, in the step 1), graphene oxide
The concentration of aqueous solution is 2-10mg/ml.
A kind of preparation method of above-mentioned composite efficient visible-light photocatalyst, in the step 3), nanometer titanium dioxide
The quality of manganese modified polypyrrole pipe and the quality of graphene oxide water solution are mixed according to the ratio of mass ratio PPy:GO=2:1
It closes ultrasound to be allowed to be uniformly dispersed, forms stable glue.
A kind of preparation method of above-mentioned composite efficient visible-light photocatalyst in the step 3), uses self start type
Water heating kettle reacts 5h under 120 DEG C of environment, after gained hydrogel is dialysed in pure water, freeze-drying, can prepare obtain it is compound
Type manganese dioxide-polypyrrole graphene aerogel photochemical catalyst.
A kind of preparation method of above-mentioned composite efficient visible-light photocatalyst, in the step 2), potassium permanganate drop
After adding, sustained response 18-24h under agitation after being added dropwise.
A kind of preparation method of above-mentioned composite efficient visible-light photocatalyst, in the step 2), pyrroles and methyl
Orange solution is first mixed, and liquor potassic permanganate is added, and wherein liquor potassic permanganate need to be slowly dropped into, and rate of addition is
1.5-3s/ drop.
A kind of preparation method of above-mentioned composite efficient visible-light photocatalyst, in the step 3), graphene oxide
Solution is mixed with the hygrometric state ultrasonic disperse of nano-manganese dioxide modified polypyrrole pipe, makes active component uniform load in graphene gas
On gel.
The preparation method of the high-efficient visible-light photocatalyst provided through the invention can system simple, efficiently, inexpensive
It is standby to obtain stable high-efficient visible-light photocatalyst.
The present invention also provides the preparation methods of provided high-efficient visible-light photocatalyst according to the present invention to be prepared
High-efficient visible-light photocatalyst.
The present invention also provides application of the high-efficient visible-light photocatalyst provided by the present invention in light-catalyzed reaction.
The beneficial effects of the present invention are: high-efficient visible-light photocatalyst provided by the present invention is convenient using recycling, can
The light-exposed lower ability with efficient catalytic degradation multiple pollutant；High-efficient visible-light photocatalyst property provided by the present invention is steady
It is fixed, it is reproducible, it can be used repeatedly；The present invention is using methyl orange as template, and using potassium permanganate as oxidant, a step is generated
The manganese dioxide of Nano grade-polypyrrole pipe, preparation method is simple, at low cost；Degradation rate of the present invention is fast, in 30 minutes,
It can degrade substantially completely.
Detailed description of the invention
Fig. 1 is compound manganese dioxide-polypyrrole graphene aerogel photocatalysis obtained in the preparation process of embodiment 4
The SEM comparison diagram of agent and blank graphene aerogel.
In Fig. 1, a, b figure are compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst, and c, d figure are blank
Graphene aerogel.
Fig. 2 is degradation weight of the obtained compound manganese dioxide-polypyrrole graphene aerogel of embodiment 4 to methylene blue
Renaturation experimental performance figure.
Fig. 3 is that compound manganese dioxide-polypyrrole graphene aerogel that embodiment 4 obtains compares the poly- pyrrole of traditional tubulose
Cough up the catalytic kinetics datagram with the degradation 25mg/L methylene blue of blank graphene aerogel.
Fig. 4 is compound manganese dioxide-polypyrrole graphene aerogel that embodiment 4, embodiment 5 and embodiment 6 obtain
Different degradation times methylene blue residual concentration figure.
Specific embodiment
The principles and features of the present invention are described below, and illustrated embodiment is served only for explaining the present invention, is not intended to
It limits the scope of the invention.
Embodiment 1
A kind of efficient compound Visible Light Induced Photocatalytic catalyst, comprising:
Three-dimensional grapheme aeroge and the nano-manganese dioxide modified polypyrrole pipe being supported on graphene aerogel,
In, the general structure of the polypyrrole is as follows:
Wherein:
A-Ion is oxidant anion, predominantly OH-Ion, because using metallic salt as oxidant (such as KMnO4)
During preparing PPy, anion can also be used as dopant simultaneously, and form compound by electric charge transfer.PPy at this time
Chain structure be general Oxidation Doping structure.
1) to improve Hummers method preparation graphene oxide water solution；
2) using methyl orange solution as template, potassium permanganate is that oxidant prepares nano-manganese dioxide modified polypyrrole pipe；
3) nano-manganese dioxide modified polypyrrole pipe is mixed with graphene oxide solution and is uniformly dispersed, in high pressure water heating kettle
Manganese dioxide-polypyrrole graphene aerogel photochemical catalyst is made in middle reaction.
Preferably, in step 1), reaction temperature is controlled between 35 ± 5 DEG C, and after potassium permanganate adds, room temperature continues to stir
Mix oxidation 72h.
Preferably, in step 1), the concentration of graphene oxide water solution is 5mg/ml.
Preferably, in step 2), pyrroles and methyl orange solution are first mixed, and add liquor potassic permanganate,
Middle liquor potassic permanganate need to be slowly dropped into, and rate of addition is 2s/ drop.Sustained response is for 24 hours under agitation after being added dropwise.
Preferably, in step 3), the quality of nano-manganese dioxide modified polypyrrole pipe and the matter of graphene oxide water solution
Amount carries out mixing ultrasound according to the ratio of mass ratio PPy:GO=2:1 and is allowed to be uniformly dispersed, and forms stable glue.
Preferably, in step 3), after determining the product yield in step 2), after step 2) completes reaction, product is washed
After the completion of washing, filtering, without drying, it is added in graphene oxide solution directly under hygrometric state, to improve its degree of scatter.
Preferably, in step 3), 5h is reacted under 120 DEG C of environment using self start type water heating kettle, gained hydrogel is in pure water
After middle dialysis, freeze-drying can prepare and obtain compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst.
Embodiment 2
The preparation of compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst
One, prepare graphene oxide using improvement Hummers method: at 35 ± 5 DEG C, potassium permanganate adds for temperature control in reaction
It adds and is carried out again in next step after Oxidation at room temperature 48h after finishing.After reaction completion, product dilute hydrochloric acid and deionized water wash three times,
It is made into the solution of 2mg/mL；
Two, methyl orange is formulated as to the solution of 5mmol/L, 175 μ L pyrrole monomers are added in every 20ml methyl orange solution, stir
After mixing 30min, 10ml 0.0675g/ml liquor potassic permanganate is added with the speed of 1.5s/ drop, is stirred to react 18h after dripping.
Filter after the completion and be washed with water to filtrate be it is colourless, drain；
Three, 43ml graphene oxide solution is taken, the nano-manganese dioxide modified polypyrrole pipe drained but do not dried is added,
Ultrasonic disperse 2h, is put into hydrothermal reaction kettle, and 5h is reacted at 120 DEG C, takes out aeroge after the completion, is placed in 200ml pure water thoroughly
2h is analysed, is freeze-dried after taking-up, obtains compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst 1.
Embodiment 3
The preparation of compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst
One, prepare graphene oxide using improvement Hummers method: at 35 ± 5 DEG C, potassium permanganate adds for temperature control in reaction
It adds and is carried out again in next step after Oxidation at room temperature 80h after finishing.After reaction completion, product dilute hydrochloric acid and deionized water wash three times,
It is made into the solution of 10mg/mL；
Two, methyl orange is formulated as to the solution of 5mmol/L, 175 μ L pyrrole monomers are added in every 20ml methyl orange solution, stir
After mixing 30min, 10ml 0.0675g/ml liquor potassic permanganate is added with the speed of 3s/ drop, is stirred to react 20h after dripping.It is complete
At it is rear suction filtration and be washed with water to filtrate be it is colourless, drain；
Three, 43ml graphene oxide solution is taken, the nano-manganese dioxide modified polypyrrole pipe drained but do not dried is added,
Ultrasonic disperse 2h, is put into hydrothermal reaction kettle, and 5h is reacted at 120 DEG C, takes out aeroge after the completion, is placed in 200ml pure water thoroughly
2h is analysed, is freeze-dried after taking-up, obtains compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst 1.
Embodiment 4
The preparation of compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst 1
One, prepare graphene oxide using improvement Hummers method: at 35 ± 5 DEG C, potassium permanganate adds for temperature control in reaction
It adds and is carried out again in next step after Oxidation at room temperature 72h after finishing.After reaction completion, product dilute hydrochloric acid and deionized water wash three times,
It is made into the solution of 5mg/mL；
Two, methyl orange is formulated as to the solution of 5mmol/L, 175 μ L pyrrole monomers are added in every 20ml methyl orange solution, stir
After mixing 30min, 10ml 0.0675g/ml liquor potassic permanganate is added with the speed of 2s/ drop, is stirred to react for 24 hours after dripping.It is complete
At it is rear suction filtration and be washed with water to filtrate be it is colourless, drain；
Three, 43ml graphene oxide solution is taken, the nano-manganese dioxide modified polypyrrole pipe drained but do not dried is added,
Ultrasonic disperse 2h, is put into hydrothermal reaction kettle, and 5h is reacted at 120 DEG C, takes out aeroge after the completion, is placed in 200ml pure water thoroughly
2h is analysed, is freeze-dried after taking-up, obtains compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst 1.
Embodiment 5
The preparation of compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst 2
The present embodiment from the addition concentration of liquor potassic permanganate becomes in step 2 unlike specific embodiment 4
0.135g/ml, other are identical as specific embodiment 4.
Embodiment 6
The preparation of compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst 3
The present embodiment from the additive amount of graphene oxide solution becomes 21ml in step 3 unlike specific embodiment 4,
Other are identical as specific embodiment 4.
Embodiment 7
The preparation of compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst 4
The present embodiment becomes from the oxidization time unlike specific embodiment 4 in step 1 in graphene oxide preparation
For 24 hours, other are identical as specific embodiment 4.
Embodiment 8
The preparation of compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst 5
The present embodiment from hydrothermal reaction condition becomes 150 DEG C in step 3 unlike specific embodiment 4, other with it is specific
Embodiment 4 is identical.
The photochemical catalyst that embodiment 5 is prepared obtains compared with catalyst with embodiment 4, the loading capacity mistake of manganese dioxide
It is more, lead to that the reduction of catalyst surface polypyrrole pipe carrying capacity is made, catalytic performance reduces.The photochemical catalyst that embodiment 6 is prepared
It is obtained compared with catalyst with embodiment 4, the manganese dioxide loaded on graphene aerogel-polypyrrole amount is excessive, causes to lead
Cause Catalyst Adsorption less able, activity reduces；The photochemical catalyst that implementation 7 is prepared is compared with embodiment 4 obtains catalyst
Compared with, it is subsequent to prepare stable graphene oxide water solution since the oxidization time of graphene oxide is short, affect subsequent urge
The quality of agent；The photochemical catalyst that embodiment 8 is prepared obtains compared with catalyst with embodiment 4, and aeroge volume is reduced,
Porous structure is reduced, and is declined with the contact area of pollutant, activity reduces.Fig. 4 obtains for embodiment 4, embodiment 5 and embodiment 6
The methylene blue residual concentration figure of the different degradation times of compound manganese dioxide-polypyrrole graphene aerogel arrived.Due to
Compound manganese dioxide-polypyrrole graphene aerogel performance prepared by embodiment 7 and embodiment 8 is too poor, does not meet and does light and urge
The condition of agent, so without corresponding data.It can be seen from the figure that photocatalyst for degrading effect made from embodiment 4 is best,
Embodiment 6 is taken second place, and the degradation effect of embodiment 5 is worst, is hardly degraded.
Fig. 1 is compound manganese dioxide-polypyrrole graphene aerogel photocatalysis obtained in the preparation process of embodiment 4
The SEM comparison diagram of agent and blank graphene aerogel, it can be seen that tubulose polypyrrole successfully loads (such as on graphene aerogel
B figure), the manganese dioxide particle (such as a figure) that can be observed on tubulose polypyrrole is further amplified, it was demonstrated that the catalyst is multiple really
Mould assembly manganese dioxide-polypyrrole graphene aerogel.
Fig. 2 is degradation weight of the obtained compound manganese dioxide-polypyrrole graphene aerogel of embodiment 4 to methylene blue
Renaturation experimental performance figure is made according to the data of table 1.Sample is put into methylene blue solution, in different times point test
Methylene blue concentration in solution, takes out after 45 minutes, then the sample after drying is continued to throw by eccentric cleaning and low temperature drying
Enter in next group of methylene blue solution, it should be noted that experiment condition such as illumination, methylene blue concentration, catalyst and methylene
Blue amount ratio etc. is identical as first group, and (since catalyst centrifugal drying process has a small amount of loss, each more youngster is with more
The quality for mending loss, new catalyst is not added), it is so repeated four times, i.e., same four methylene blues of sample degradation
Solution, it is intermediate only sample to be centrifugated out, it then cleans, low temperature drying can be degraded next time.As can be seen that
The stability and repeatability of catalyst are preferable, may be reused, and in four degradations, the degradable time is both less than 50 points
Clock, and each degradation time difference amplitude is no more than 15min.
Fig. 3 is that compound manganese dioxide-polypyrrole graphene aerogel that embodiment 4 obtains compares the poly- pyrrole of traditional tubulose
Cough up the catalytic kinetics datagram with the degradation 25mg/L methylene blue of blank graphene aerogel.Be 20mg catalyst in figure,
The degradation catalytic kinetics datagram of polypyrrole pipe and blank graphene aerogel to 20ml 20mg/L methylene blue.From figure
It can be seen that degradation rate (the K=6.820h of composite catalyst-1) it is much larger than polypyrrole pipe (K=0.57h-1) and blank stone
Black alkene aeroge (K=0.144h-1) degradation rate, 32 minutes i.e. can reach it is degradable.
Embodiment 9 improves Hummers method
Experiment reagent:
Graphite powder (325 mesh, Aladdin)；Potassium nitrate (AR grades of traditional Chinese medicines)；The concentrated sulfuric acid (AR grades of traditional Chinese medicines)；Potassium permanganate (traditional Chinese medicines
AR grades)；Hydrochloric acid (AR grades of traditional Chinese medicines)；Pure water (UP grades)；30% hydrogen peroxide (traditional Chinese medicines)
Experimental facilities:
Beaker；Blender；Bag filter；
Experimental procedure:
1. taking graphite powder, potassium nitrate and the concentrated sulfuric acid, 0.75g potassium nitrate, the 50mL concentrated sulfuric acid, stirring are added in every 1g graphite powder
Mix 30min.
2. being slowly added to 5g potassium permanganate into mixed solution under stirring, addition rate cannot be below 1h and add,
It keeps temperature of reaction system in 35 ± 5 DEG C simultaneously, keeps thermotonus for a period of time after adding potassium permanganate.
3. after the reaction was completed, being stirred at room temperature 3 days, complete subsequent oxidation sufficiently.
4. 30ml hydrogen peroxide is slowly added dropwise into the solution after stirring 3 days under stirring, until solution is golden yellow,
Supernatant is removed after standing.
5. being cleaned with the hydrochloric acid of 100ml 3mol/L to solution lower layer；Mixing removes supernatant, cleaning three after standing
It is secondary.
6. being cleaned using UP water to lower layer's solution, mixing removes supernatant after standing, cleaning is three times.It is molten to collect lower layer
Liquid.
7. the preparation of graphene oxide solution: determining the solid content of high concentration graphene oxide solution, be then diluted to one
Determine concentration.
The methylene blue concentration of different time in 4 repeated experiments of photochemical catalyst made from 1 embodiment 4 of table
| Time (h) | 0.00 | 0.13 | 0.40 | 0.53 | 1.00 | 1.17 | 1.33 | 1.50 | 1.67 | 2.00 | 2.17 | 2.33 | 2.50 | 2.67 | 2.80 | 3.00 | 3.17 | 3.33 | 3.50 | 3.67 |
| Concentration (mg/L) | 25.0 | 7.43 | 1.64 | 0.79 | 25 | 10.89 | 5.95 | 2.34 | 0.51 | 25 | 13.67 | 6.80 | 3.33 | 1.01 | 0.20 | 25.0 | 15.33 | 6.72 | 2.01 | 0.60 |
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of composite efficient visible-light photocatalyst characterized by comprising
Three-dimensional grapheme aeroge and the nano-manganese dioxide modified polypyrrole pipe being supported on graphene aerogel, it is described to change
The general structure of property tubulose polypyrrole is as follows:
Wherein: A-Ion is oxidant anion.
2. composite efficient visible-light photocatalyst according to claim 1, it is characterised in that: the work of the photochemical catalyst
Property group is divided into nano-manganese dioxide modified polypyrrole pipe.
3. composite efficient visible-light photocatalyst according to claim 1, it is characterised in that: the load of the photochemical catalyst
Body is three-dimensional structure graphene aerogel.
4. a kind of preparation method of composite efficient visible-light photocatalyst, which comprises the following steps:
1) to improve Hummers method preparation graphene oxide water solution；
2) using methyl orange solution as template, potassium permanganate is that oxidant prepares nano-manganese dioxide modified polypyrrole pipe；
3) nano-manganese dioxide modified polypyrrole pipe is mixed with graphene oxide solution and is uniformly dispersed, it is anti-in high pressure water heating kettle
It answers, manganese dioxide-polypyrrole graphene aerogel photochemical catalyst, i.e., compound visible-light photocatalyst is made.
5. a kind of preparation method of composite efficient visible-light photocatalyst according to claim 4, it is characterised in that: institute
It states in step 1), reaction temperature controls between 35 ± 5 DEG C, and after potassium permanganate adds, room temperature continues stirring oxidation 48-80h.
6. a kind of preparation method of composite efficient visible-light photocatalyst according to claim 4, it is characterised in that: institute
It states in step 1), the concentration of graphene oxide water solution is 2-10mg/ml.
7. a kind of preparation method of composite efficient visible-light photocatalyst according to claim 4, it is characterised in that: institute
It states in step 3), the quality of nano-manganese dioxide modified polypyrrole pipe and the quality of graphene oxide water solution are according to mass ratio
The ratio of PPy:GO=2:1 carries out mixing ultrasound and is allowed to be uniformly dispersed, and forms stable glue.
8. a kind of preparation method of composite efficient visible-light photocatalyst according to claim 4, it is characterised in that: institute
It states in step 3), reacts 5h under 120 DEG C of environment using self start type water heating kettle, after gained hydrogel is dialysed in pure water, freezing
It is dry, it can prepare and obtain compound manganese dioxide-polypyrrole graphene aerogel photochemical catalyst.
9. being prepared into according to a kind of described in any item preparation methods of composite efficient visible-light photocatalyst of claim 4-8
The composite efficient visible-light photocatalyst arrived.
10. a kind of composite efficient visible-light photocatalyst according to claim 1-8 is in visible light photocatalysis
Application in reaction.
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| CN105070527A (en) * | 2015-08-27 | 2015-11-18 | 桂林理工大学 | Preparation method of graphene/polypyrrole/manganese-dioxide three-element composite electrode material |
| WO2016080910A1 (en) * | 2014-11-17 | 2016-05-26 | Nanyang Technological University | A composite material and method of preparation thereof |
| CN205412672U (en) * | 2015-11-30 | 2016-08-03 | 广东美的制冷设备有限公司 | Air purification device and air conditioner |
| CN106531472A (en) * | 2016-11-29 | 2017-03-22 | 桂林理工大学 | Preparation method of polypyrrole/graphene/ manganese oxide composite materials |
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| WO2016080910A1 (en) * | 2014-11-17 | 2016-05-26 | Nanyang Technological University | A composite material and method of preparation thereof |
| CN105070527A (en) * | 2015-08-27 | 2015-11-18 | 桂林理工大学 | Preparation method of graphene/polypyrrole/manganese-dioxide three-element composite electrode material |
| CN205412672U (en) * | 2015-11-30 | 2016-08-03 | 广东美的制冷设备有限公司 | Air purification device and air conditioner |
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