CN105772096A - Nano composite material applied in solar potocatalysis and preparation method thereof - Google Patents
Nano composite material applied in solar potocatalysis and preparation method thereof Download PDFInfo
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- CN105772096A CN105772096A CN201610009703.XA CN201610009703A CN105772096A CN 105772096 A CN105772096 A CN 105772096A CN 201610009703 A CN201610009703 A CN 201610009703A CN 105772096 A CN105772096 A CN 105772096A
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- 239000000463 material Substances 0.000 title claims abstract description 28
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 229920002521 macromolecule Polymers 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- OCVXSFKKWXMYPF-UHFFFAOYSA-N 2-chloroimidazole Chemical class ClC1=NC=CN1 OCVXSFKKWXMYPF-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- -1 propenylmethyl chloro imidazoles Chemical class 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000011435 rock Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 208000035126 Facies Diseases 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000009881 electrostatic interaction Effects 0.000 abstract description 2
- 238000004945 emulsification Methods 0.000 abstract description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000002159 nanocrystal Substances 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910003145 α-Fe2O3 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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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- B01J35/39—
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- General Health & Medical Sciences (AREA)
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- Optics & Photonics (AREA)
- Electromagnetism (AREA)
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Abstract
The invention discloses a full-spectrum absorption nano composite material capable of being applied in solar photocatalysis and a preparation method thereof, wherein the nano composite material has relatively high catalytic efficiency. A positively and negatively charged adsorption method is adopted, a positively charged amphiphilic polymer and a negatively charged graphene oxide are combined through an electrostatic interaction, and an amphiphilic GO/polymer complex is obtained; moreover, by a method of ultrasonic emulsification, the complex is used for wrapping hydrophobic Cu7S4 nano-crystals to obtain a Cu7S4@GO nano composite material which is the nano composite material applied in solar photocatalysis. The nano composite material containing 3-5 mg of Cu7S4 has the photocatalysis effect as high as 94.7% under irradiation of 1 W/cm<2> of simulated sunlight, and has relatively high application prospect.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, particularly to the full spectral absorption of one, there is high light and urge
Change the Cu of efficiency7S4@GO nano-complex, can apply to solar radiation photocatalytic degradation Organic substance.
Technical background
Owing to quasiconductor is an efficient photocatalyst that solar energy can be converted into chemical energy, therefore,
The design of semiconductor light-catalyst material, synthesize and apply to cause and pay close attention to widely.People explore substantial amounts of
Quasiconductor.Such as conventional N-type semiconductor TiO2, owing to having bigger band gap, can only absorb occupy whole
The ultraviolet light of sunlight 5%.Furthermore α-Fe2O3Though there being relatively small band gap can utilize visible ray, but
The ability of transmission electronics is poor.And Si, the GaN etc. with good electron transmission performance have more weak catalysis energy
Power.
The most important condition of photocatalyst can produce electron hole pair exactly and have preferable electron transfer mediator,
Stop the quick combination in electronics and hole.Accordingly, it would be desirable to the design light of rationality urges structure and the composition of agent.By
In well designing and control metal and the interface of material with carbon element and Graphene and derivant graphene oxide thereof, tool
Having preferable electric conductivity and mechanicalness, this makes graphite alkenes material be referred to as good electron transmission bridge.Therefore,
Development can produce quasiconductor and the nano composite structure of the Graphene that can transmit electronics of electron hole pair, is
Sunlight directly utilizes the important need with catalytic field.
Summary of the invention
The present invention is converted into chemical energy demand for meeting solar energy, is specifically designed a kind of full spectral absorption and has and compare
The Cu of high light conversion efficiency7S4Nano composite material, can apply to photocatalysis.
The present invention uses the method for positive and negative electro-adsorption, is led to electronegative graphene oxide by the macromolecule of positively charged
Cross electrostatic interaction to combine, obtain the GO/polymer complex of amphiphilic, and by the method for ultrasonic emulsification, utilize
Complex is by hydrophobic Cu7S4Nanocrystalline cladding, obtains Cu7S4@GO nano composite material, is and is applied to
The nano composite material of sunlight catalytic.
The preparation method of a kind of nano composite material being applied to sunlight catalytic of the present invention, it specifically walks
Rapid as follows:
A. the amphiphilic macromolecule of 10-30mg positively charged is dispersed in 1-5mL chloroform, is then added to 3-8mL
DMSO in, mixing；It is subsequently added the graphene oxide solution that concentration is 3-8mg/mL, wherein oxygen
Functionalized graphene addition is 10-20mg, rocks vibration mix homogeneously；
B. adding ethanol in the mixed liquor of step a precipitate and be centrifuged, the dispersion of precipitation 0.5-2mL chloroform obtains function
Macromolecule-graphene oxide complex the dispersion liquid changed；
C. by scattered for organic facies Cu7S4Nano-particle joins in the dispersion liquid that step b obtains, Cu7S4Nano-particle
Content is 2-10mg, in the NaOH solution of the 0.3-1mM then proceeding to 10mL, at power is
100-500W ultrasonic under obtain stable emulsion；
DEG C d.30-60 the organic solvent during stirring evaporates the emulsion of step c at, 5000-15000 rev/min of centrifugal 5-20min
Obtain being applied to the nano composite material of sunlight catalytic, be finally re-dispersed in deionized water.
The amphiphilic macromolecule of described positively charged is polystyrene-methacrylic acid-propenylmethyl chloro imidazoles, its
Middle propenylmethyl chloro imidazoles mass content is 5-8%, and methacrylic acid mass content is 2-5%.
The amphiphilic macromolecule of described positively charged is polystyrene-methacrylic acid-acrylamide, wherein metering system
Acid mass content is 2-5%, and acrylamide mass content is 5-8%.
The amphiphilic macromolecule molecular weight ranges of described positively charged is 5000-10000.
By the organic application of catalytic degradation under sunlight conditions of the above-mentioned nano composite material prepared.
Beneficial effects of the present invention: the present invention is prepared for a kind of full spectral absorption and can apply to sunlight catalytic
Nano composite material, this composite has higher catalytic efficiency.Wherein contain 3-5mg Cu7S4Nanometer multiple
Condensation material is at simulated solar irradiation 1W/cm2Irradiation under, photocatalysis effect is up to 94.7%, has higher application
Prospect.
Accompanying drawing explanation
The Electronic Speculum figure of the nano composite material being applied to sunlight catalytic of Fig. 1: embodiment 1 preparation.
Prepared by Fig. 2: embodiment 1 is applied to the nano composite material of sunlight catalytic and the amphiphilic macromolecule of positively charged
The degradation curve contrast of polystyrene-methacrylic acid-propenylmethyl chloro imidazoles photocatalytic degradation rhodamine B
Figure.
Detailed description of the invention
Embodiment 1
A. by 10mg polystyrene-methacrylic acid-propenylmethyl chloro imidazoles (molecular weight 6000, acrylic first
Base chloro imidazoles mass content is 5%, and methacrylic acid mass content is 5%) it is dispersed in 1mL chloroform,
It is then added in the DMSO of 3mL, mixing；It is subsequently added the graphite oxide that concentration is 5mg/mL
Alkene solution, wherein graphene oxide addition is 20mg, rocks vibration 1 minute；
B. adding ethanol in the mixed liquor of step a precipitate and be centrifuged, the dispersion of precipitation 0.6mL chloroform obtains functionalization
Macromolecule-graphene oxide complex dispersion liquid；
C. by scattered for the chloroform of 0.4mL Cu7S4Nano-particle joins in the dispersion liquid that step b obtains, Cu7S4
Nano-particle content is 3.2mg, in the NaOH solution of the 1mM then proceeding to 10mL, at power
For 300W ultrasonic under obtain stable emulsion；
DEG C d.50 the chloroform during stirring evaporates the emulsion of step c at, 7000 revs/min of centrifugal 10min obtain being applied to too
The light-catalysed nano composite material of sun, is finally re-dispersed in deionized water.
The nano composite material being applied to sunlight catalytic of above-mentioned preparation is carried out photocatalytic degradation rhodamine B, instead
Answer condition: optical power density is 1W/cm2, nano composite material concentration is 7.5mg/mL, rhodamine B concentration
For 10ppm, degraded cumulative volume is 2mL.
Be not added with nano composite material light degradation rhodamine B solution for contrast, result is as shown in Figure 2.
Claims (4)
1. the preparation method of the nano composite material being applied to sunlight catalytic, it is characterised in that it is concrete
Step is as follows:
A. the amphiphilic macromolecule of 10-30mg positively charged is dispersed in 1-5mL chloroform, is then added to 3-8mL
DMSO in, mixing；It is subsequently added the graphene oxide solution that concentration is 3-8mg/mL, wherein aoxidizes
Graphene addition is 10-20mg, rocks vibration mix homogeneously；
B. adding ethanol in the mixed liquor of step a precipitate and be centrifuged, the dispersion of precipitation 0.5-2mL chloroform obtains function
Macromolecule-graphene oxide complex the dispersion liquid changed；
C. by scattered for organic facies Cu7S4Nano-particle joins in the dispersion liquid that step b obtains, Cu7S4Nano-particle
Content is 2-10mg, in the NaOH solution of the 0.3-1mM then proceeding to 10mL, at power is
100-500W ultrasonic under obtain stable emulsion；
DEG C d.30-60 the organic solvent during stirring evaporates the emulsion of step c at, 5000-15000 rev/min of centrifugal 5-20min
Obtain being applied to the nano composite material of sunlight catalytic, be finally re-dispersed in deionized water.
Preparation method the most according to claim 1, it is characterised in that the amphiphilic high score of described positively charged
Son is polystyrene-methacrylic acid-propenylmethyl chloro imidazoles, and wherein propenylmethyl chloro imidazoles quality contains
Amount is 5-8%, and methacrylic acid mass content is 2-5%.
Preparation method the most according to claim 1, it is characterised in that the amphiphilic high score of described positively charged
Son is polystyrene-methacrylic acid-acrylamide, and wherein methacrylic acid mass content is 2-5%, acryloyl
Amine mass content is 5-8%.
4. the nano composite material prepared according to the arbitrary described method of claim 1-3 is under sunlight conditions
The organic application of catalytic degradation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610009703.XA CN105772096A (en) | 2016-01-07 | 2016-01-07 | Nano composite material applied in solar potocatalysis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610009703.XA CN105772096A (en) | 2016-01-07 | 2016-01-07 | Nano composite material applied in solar potocatalysis and preparation method thereof |
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| CN201610009703.XA Pending CN105772096A (en) | 2016-01-07 | 2016-01-07 | Nano composite material applied in solar potocatalysis and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108831748A (en) * | 2018-06-27 | 2018-11-16 | 安徽大学 | A kind of nitrogen-doped graphene modification four vulcanization seven bronze medals/copper sulfide composite material and preparation methods and application down |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010061212A1 (en) * | 2008-11-25 | 2010-06-03 | Johnson Matthey Plc | Reduced copper sulphide sorbent for removing heavy metals |
| CN104258909A (en) * | 2014-08-01 | 2015-01-07 | 曲阜师范大学 | Fe3O4-poly-dopamine-Au nano-composite material as well as preparation method and application thereof |
-
2016
- 2016-01-07 CN CN201610009703.XA patent/CN105772096A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010061212A1 (en) * | 2008-11-25 | 2010-06-03 | Johnson Matthey Plc | Reduced copper sulphide sorbent for removing heavy metals |
| CN104258909A (en) * | 2014-08-01 | 2015-01-07 | 曲阜师范大学 | Fe3O4-poly-dopamine-Au nano-composite material as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| HONGLI CHEN ET AL.: "Cu2-xS/graphene oxide nanocomposites for efficient photocatalysis driven by real sunlight", 《RSC ADVANCES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108831748A (en) * | 2018-06-27 | 2018-11-16 | 安徽大学 | A kind of nitrogen-doped graphene modification four vulcanization seven bronze medals/copper sulfide composite material and preparation methods and application down |
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Application publication date: 20160720 |