CN109621957A - A kind of copper oxide nanometer particle catalyst and preparation method thereof for degrading nitrobenzene - Google Patents
A kind of copper oxide nanometer particle catalyst and preparation method thereof for degrading nitrobenzene Download PDFInfo
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- CN109621957A CN109621957A CN201811617171.3A CN201811617171A CN109621957A CN 109621957 A CN109621957 A CN 109621957A CN 201811617171 A CN201811617171 A CN 201811617171A CN 109621957 A CN109621957 A CN 109621957A
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- copper oxide
- nanometer particle
- oxide nanometer
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- nitrobenzene
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- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 title claims abstract description 138
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 63
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 63
- 239000002245 particle Substances 0.000 title claims abstract description 62
- 230000000593 degrading effect Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title claims description 27
- 239000010949 copper Substances 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000006385 ozonation reaction Methods 0.000 abstract description 8
- 229960000935 dehydrated alcohol Drugs 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- LYCAIKOWRPUZTN-NMQOAUCRSA-N 1,2-dideuteriooxyethane Chemical compound [2H]OCCO[2H] LYCAIKOWRPUZTN-NMQOAUCRSA-N 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 229960004643 cupric oxide Drugs 0.000 description 58
- 238000002474 experimental method Methods 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 238000010525 oxidative degradation reaction Methods 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/40—
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
A kind of copper oxide nanometer particle and preparation method thereof for degrading nitrobenzene, belongs to environment protecting nano material preparation technical field.It is that will be put into 5~10% sulfuric acid solution and dehydrated alcohol after each ultrasonic 1~4 hour to wash drying with a thickness of the Cu metal substrate of 0.1~5mm；Then hydro-thermal reaction is carried out, hydro-thermal reaction solution composition is naoh concentration 10%~30%, glycerol concentration 2~8%, ethylene glycol 2~8%；Hydrothermal temperature is 100~280 DEG C, and the hydro-thermal reaction time is 10~48h；After hydro-thermal reaction, by the pure water washing boiled of copper sheet, after it is dry in high pure nitrogen；Then above-mentioned copper sheet is placed in the oxygen containing 3000~9000ppm ozone, is gradually heated to 180~250 DEG C with 1~2 DEG C/min of rate, keeps 5~10h, last Temperature fall.Preparation step of the invention is simple, at low cost, can be widely applied to the fields such as photocatalysis or Catalytic Ozonation organic pollutant.
Description
Technical field
The invention belongs to environment protecting nano material preparation technical fields, and in particular to a kind of copper metal substrate (i.e. Cu piece) is in situ
The self-growing copper oxide nanometer particle catalyst and preparation method thereof for degrading nitrobenzene.
Background technique
CuO is a kind of widely used oxide, can be applied to power cell anode-cathode material, catalysis material, sensor film
Material, heterogeneous catalysis material, optical material, Meta Materials etc..Wherein nanometer CuO material has in environmental contaminants catalytic purification field
There is good application prospect.
Currently, the customary preparation methods of copper oxide nano material include solvent-thermal method, sol-gal process, the precipitation method, electrification
Method, hydro-thermal method, microwave method etc..Nitrobenzene is a kind of hypertoxic chemical substance for polluting environment, harm health, by U.S.EPA
It is classified as and answers one of 129 kinds of pollutants of priority acccess control, be also listed in 58 kinds of China and answer one of toxic chemical of priority control, nitre
Base benzene not only damages the fertility system of buck, simultaneously because its biodegradability is poor, more difficult harmless treatment.CuO receives
Rice grain can trigger ozone and generate more hydroxyl radical free radicals, so as to improve the degradation rate of p-nitrophenyl.
Present invention introduces novel, green Technology Ways to be prepared for the copper oxide nanometer particle catalysis for degrading nitrobenzene
Agent.
Summary of the invention
The object of the present invention is to provide a kind of for the copper oxide nanometer particle catalyst of degrading nitrobenzene and its preparation side
Method.Copper oxide nanometer particle of the present invention for degrading nitrobenzene is that growth in situ forms on Cu metal substrate, main
Wanting ingredient is CuO nano particle, and size is distributed in 14~253nm.
Copper oxide nanometer particle catalyst for degrading nitrobenzene of the invention, can be by adjusting pre-treatment, hydro-thermal
Reaction temperature and time, oxidizing reaction temperature and time etc. obtain the various sizes of cupric oxide nano for degrading nitrobenzene
Grain.The prepared copper oxide nanometer particle size for degrading nitrobenzene is distributed in 14~253nm (see Examples 1 to 4).
Copper oxide nanometer particle of the present invention for degrading nitrobenzene has a characteristic that regular shape, preparation
Raw material is cheap, and synthetic route is easy, and the degradation effect of p-nitrophenyl is obvious.
The Cu metal substrate, by weight percent 100% calculate, contain Cu>99.5%, 0<Sb<0.005%, 0<As<
0.005%, 0 < P < 0.005%, with a thickness of 0.1~5mm.
A kind of preparation method of copper oxide nanometer particle catalyst for degrading nitrobenzene of the present invention, step
It is as follows:
(1) sulfuric acid solution (quality of mass fraction 5~10% will be sequentially placed into a thickness of the Cu metal substrate of 0.1~5mm
The sulfuric acid solution of score 5~10% is formulated by the concentrated sulfuric acid) and dehydrated alcohol in respectively ultrasound 1~4 hour, washed after taking-up
It is dry；
(2) the Cu metal substrate that step (1) obtains is put into water in the mixed aqueous solution of sodium hydroxide, glycerol and ethylene glycol
Thermal response, sodium hydroxide mass fraction 10%~30% in mixed aqueous solution, qualities of glycerin score 2~8%, quality of glycol point
Number 2~8%, hydrothermal temperature are 100~280 DEG C, and the hydro-thermal reaction time is 10~48h；
(3) then dry in high pure nitrogen by the Cu metal substrate pure water washing boiled that step (2) obtains；
(4) the Cu metal substrate that step (3) obtains is placed in the oxygen containing 3000~9000ppm ozone, with 1~
2 DEG C/min of rate is gradually heated to 180~250 DEG C, keeps 5~10h, room temperature is finally naturally cooling to, thus in Cu metal
A kind of copper oxide nanometer particle catalyst for degrading nitrobenzene of the present invention is obtained on substrate.
In the experiment of copper oxide nanometer particle Catalytic Ozonation nitrobenzene, reaction vessel is continuously passed through 1.6mg/L ozone,
Maintaining reaction vessel temperature is 25 DEG C, and reacting solution pH value 6.8, copper oxide nanometer particle catalyst is (by nano particle from Cu
Being used after being removed on metal substrate) input amount is 450mg/L, the concentration of the nitro benzene aquatic solution of preparation is 30 μ g/L, and degradation is real
After testing beginning, nitrobenzene solution is flowed through repeatedly and (is stirred using magnetic stirrer) copper oxide nanometer particle surface and sufficiently connects with it
Touching, degradation experiment continue 25min.Residual nitrobenzene is measured by volumetric flask extraction after detection reaction, i.e., anti-
Solution to be measured is dissolved in surely in the volumetric flask that volume is 50m L after answering, and the benzene that 1m L is added extracts solution, and molten from extracting
The sample introduction solution for taking out 1 μ L in liquid with micro syringe, measures nitro in solution with the gas chromatograph equipped with ECD detector
The content of benzene, to obtain the Catalytic Ozonation rate of copper oxide nanometer particle p-nitrophenyl.Catalytic Ozonation rate is (i.e.
Abbreviation degradation rate)=(nitro phenenyl concentration after nitro phenenyl concentration-reaction before reacting)/nitro phenenyl concentration * 100% before reacting.
It, can be by adjusting pretreatment mode, the temperature of hydro-thermal reaction for the copper oxide nanometer particle of degrading nitrobenzene
The various sizes of cupric oxide nano for degrading nitrobenzene is obtained with time, the temperature and time of oxidation, heat gas etc.
Grain.
Copper oxide nanometer particle catalyst for degrading nitrobenzene of the invention has the advantage that preparation process is simple,
Raw material is easy to get, low in cost.The copper oxide nanometer particle for being used for degrading nitrobenzene, which will administer field in poisonous organic wastewater, to be had
There is biggish application prospect.
Detailed description of the invention
Fig. 1: the copper oxide nanometer particle catalyst schematic diagram for degrading nitrobenzene；
Fig. 2: the electronic energy spectrum of the copper oxide nanometer particle catalyst (corresponding to embodiment 1) for degrading nitrobenzene,
As can be seen from Figure, the component of the nano-particle material be Cu and O, be divided into CuO.The ingredient of remaining embodiment and implementation
Example 1 is similar, is also CuO.The electron spectrum peak of Cu appears near 1ev, 8ev, 9ev.
Fig. 3: copper oxide nanometer particle catalyst (corresponding to embodiment 1) surface for degrading nitrobenzene utilizes X-ray
The resulting Cu2p spectrogram of XPS Analysis instrument, gained combine energy data to select the combination energy (284.8eV) of C1s as ginseng
Than.From figure 3, it can be seen that can be the strong peak at 933.6eV in combination, the 2p of Cu can be attributed to3/2Peak, and include in figure
The apparent peak Shakeup (combination of the peak Shakeup can be located near 940.7eV), show to be tested is used for degrading nitrobenzene
The chemical state of copper is Cu in copper oxide nanometer particle2+, that is, also turn out that the ingredient of the nano-particle material is CuO.Remaining
The XPS figure of nano-particle material prepared by embodiment is similar to Example 1, that is, proves that the ingredient of the type nano granular material is
CuO。
Fig. 4: the X-ray diffractogram of the copper oxide nanometer particle catalyst (corresponding to embodiment 1) for degrading nitrobenzene,
It can be seen from the figure that all diffraction maximums of product can be demarcated as the CuO of monoclinic system, with standard diagram JCPDS 45-
0937 matches.The X-ray diffractogram of nano-particle material prepared by remaining embodiment is similar to Example 1, that is, proving should
Type nano granular material is monocline CuO structure.
Fig. 5: the electricity of the prepared copper oxide nanometer particle catalyst for degrading nitrobenzene under the conditions of differential responses
Mirror figure.Scheme a corresponding embodiment 1, the resulting copper oxide nanometer particle size for degrading nitrobenzene is mainly distributed on 14~
29nm；Scheme b corresponding embodiment 2, the resulting copper oxide nanometer particle size for degrading nitrobenzene is mainly distributed on 23~
42nm；Scheme c corresponding embodiment 3, the resulting copper oxide nanometer particle size for degrading nitrobenzene is mainly distributed on 28~
47nm；Scheme d corresponding embodiment 4, the resulting copper oxide nanometer particle size for degrading nitrobenzene is mainly distributed on 30~
53nm。
Specific embodiment
Embodiment 1: the preparation of the copper oxide nanometer particle catalyst for degrading nitrobenzene
(1) it will be put into a thickness of the Cu metal substrate of 0.1mm each super in the sulfuric acid solution and dehydrated alcohol of mass fraction 5%
Sound 1 hour, drying was washed afterwards；
(2) above-mentioned Cu metal substrate is subjected to hydro-thermal reaction, hydro-thermal reaction aqueous solution composition are as follows: sodium hydroxide mass fraction
10%%, qualities of glycerin score 2%, quality of glycol score 2%.Hydrothermal temperature is 100 DEG C, and the hydro-thermal reaction time is
10h；
(3) after hydro-thermal reaction, by the pure water washing boiled of copper sheet, after it is dry in high pure nitrogen.
(4) above-mentioned copper sheet is placed in the oxygen containing 3000ppm ozone, is gradually heated to 1 DEG C/min of rate
180 DEG C, 5h is kept, room temperature is finally naturally cooling to, to be obtained on Cu metal substrate of the present invention a kind of for dropping
Solve the copper oxide nanometer particle of nitrobenzene.
The copper oxide nanometer particle size for degrading nitrobenzene shown under electron microscope is mainly distributed on 14~29nm.
In copper oxide nanometer particle Catalytic Ozonation nitrobenzene experiment, used ozone concentration is 1.6mg/L,
Temperature is 25 DEG C, and the pH value of reaction solution is 6.8, and catalyst (i.e. copper oxide nanometer particle) input amount is 450mg/L, preparation
The concentration of nitrobenzene solution is 30 μ g/L, and after degradation experiment starts, nitrobenzene solution flows through copper oxide nanometer particle surface repeatedly
And come into full contact with it, degradation experiment continues 25min.Detection reaction after residual nitrobenzene be by volumetric flask extraction come
Measurement, from extraction solution with micro syringe take out 1 μ L sample introduction solution, with equipped with ECD detector gas chromatograph come
The content for measuring nitrobenzene in the sample introduction solution show that the catalysis of the copper oxide nanometer particle p-nitrophenyl is smelly by calculating
Oxidative degradation rate is 70.4%.
Embodiment 2: the preparation of the copper oxide nanometer particle catalyst for degrading nitrobenzene
(1) it will be put into 5% sulfuric acid solution and dehydrated alcohol each ultrasonic 4 hours with a thickness of the Cu metal substrate of 5mm, after
Wash drying；
(2) above-mentioned Cu metal substrate is subjected to hydro-thermal reaction, hydro-thermal reaction solution composition are as follows: naoh concentration 30%,
Glycerol concentration 8%, ethylene glycol 2%.Hydrothermal temperature is 280 DEG C, the hydro-thermal reaction time 40h；
(3) after hydro-thermal reaction, by the pure water washing boiled of copper sheet, after it is dry in high pure nitrogen.
(4) above-mentioned copper sheet is placed in the oxygen containing 5000ppm ozone, is gradually heated to 1 DEG C/min of rate
200 DEG C, 9h is kept, room temperature is finally naturally cooling to, to be obtained on Cu metal substrate of the present invention a kind of for dropping
Solve the copper oxide nanometer particle of nitrobenzene.
The copper oxide nanometer particle size for degrading nitrobenzene shown under electron microscope is mainly distributed on 23~42nm.
In copper oxide nanometer particle Catalytic Ozonation nitrobenzene experiment, used ozone concentration is 1.6mg/L,
Temperature is 25 DEG C, and the pH value of reaction solution is 6.8, and catalyst (i.e. copper oxide nanometer particle) input amount is 450mg/L, preparation
The concentration of nitrobenzene solution is 30 μ g/L, and after degradation experiment starts, nitrobenzene solution flows through copper oxide nanometer particle surface repeatedly
And come into full contact with it, degradation experiment continues 25min.Detection reaction after residual nitrobenzene be by volumetric flask extraction come
Measurement, from extraction solution with micro syringe take out 1 μ L sample introduction solution, with equipped with ECD detector gas chromatograph come
The content for measuring nitrobenzene in the sample introduction solution show that the catalysis of the copper oxide nanometer particle p-nitrophenyl is smelly by calculating
Oxidative degradation rate is 68.7%.
Embodiment 3: the preparation of the copper oxide nanometer particle catalyst for degrading nitrobenzene
(1) it will be put into 5% sulfuric acid solution and dehydrated alcohol each ultrasonic 4 hours with a thickness of the Cu metal substrate of 5mm, after
Wash drying；
(2) above-mentioned Cu metal substrate is subjected to hydro-thermal reaction, hydro-thermal reaction solution composition are as follows: naoh concentration 30%,
Glycerol concentration 8%, ethylene glycol 2%.Hydrothermal temperature is 280 DEG C, the hydro-thermal reaction time 36h；
(3) after hydro-thermal reaction, by the pure water washing boiled of copper sheet, after it is dry in high pure nitrogen.
(4) above-mentioned copper sheet is placed in the oxygen containing 5000ppm ozone, is gradually heated to 1 DEG C/min of rate
200 DEG C, 8h is kept, room temperature is finally naturally cooling to, to be obtained on Cu metal substrate of the present invention a kind of for dropping
Solve the copper oxide nanometer particle of nitrobenzene.
The copper oxide nanometer particle size for degrading nitrobenzene shown under electron microscope is mainly distributed on 28~47nm.
In copper oxide nanometer particle Catalytic Ozonation nitrobenzene experiment, used ozone concentration is 1.6mg/L,
Temperature is 25 DEG C, and the pH value of reaction solution is 6.8, and catalyst (i.e. copper oxide nanometer particle) input amount is 450mg/L, preparation
The concentration of nitrobenzene solution is 30 μ g/L, and after degradation experiment starts, nitrobenzene solution flows through copper oxide nanometer particle surface repeatedly
And come into full contact with it, degradation experiment continues 25min.Detection reaction after residual nitrobenzene be by volumetric flask extraction come
Measurement, from extraction solution with micro syringe take out 1 μ L sample introduction solution, with equipped with ECD detector gas chromatograph come
The content for measuring nitrobenzene in the sample introduction solution show that the catalysis of the copper oxide nanometer particle p-nitrophenyl is smelly by calculating
Oxidative degradation rate is 66.4%.
Embodiment 4: the preparation of the copper oxide nanometer particle catalyst for degrading nitrobenzene
(1) will to be put into each ultrasound 1-4 in 10% sulfuric acid solution and dehydrated alcohol with a thickness of the Cu metal substrate of 5mm small
When, drying is washed afterwards；
(2) above-mentioned Cu metal substrate is subjected to hydro-thermal reaction, hydro-thermal reaction solution composition are as follows: naoh concentration 30%,
Glycerol concentration 8%, ethylene glycol 8%.Hydrothermal temperature is 280 DEG C, the hydro-thermal reaction time 48h；
(3) after hydro-thermal reaction, by the pure water washing boiled of copper sheet, after it is dry in high pure nitrogen.
(4) above-mentioned copper sheet is placed in the oxygen containing 9000ppm ozone, is gradually heated to 1 DEG C/min of rate
250 DEG C, 10h is kept, room temperature is finally naturally cooling to, to be obtained on Cu metal substrate of the present invention a kind of for dropping
Solve the copper oxide nanometer particle of nitrobenzene.
The copper oxide nanometer particle size for degrading nitrobenzene shown under electron microscope is mainly distributed on 30~53nm.
In copper oxide nanometer particle Catalytic Ozonation nitrobenzene experiment, used ozone concentration is 1.6mg/L,
Temperature is 25 DEG C, and the pH value of reaction solution is 6.8, and catalyst (i.e. copper oxide nanometer particle) input amount is 450mg/L, preparation
The concentration of nitrobenzene solution is 30 μ g/L, and after degradation experiment starts, nitrobenzene solution flows through copper oxide nanometer particle surface repeatedly
And come into full contact with it, degradation experiment continues 25min.Detection reaction after residual nitrobenzene be by volumetric flask extraction come
Measurement, from extraction solution with micro syringe take out 1 μ L sample introduction solution, with equipped with ECD detector gas chromatograph come
The content for measuring nitrobenzene in the sample introduction solution show that the catalysis of the copper oxide nanometer particle p-nitrophenyl is smelly by calculating
Oxidative degradation rate is 60.7%.
The above is only the preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment,
All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
For those of ordinary skill, several improvements and modifications without departing from the principles of the present invention should be regarded as protection of the invention
Range.
Claims (4)
1. a kind of preparation method of the copper oxide nanometer particle catalyst for degrading nitrobenzene, its step are as follows:
(1) by the sulfuric acid solution for being sequentially placed into mass fraction 5~10% with a thickness of the Cu metal substrate of 0.1~5mm and anhydrous second
It is 1~4 hour ultrasonic respectively in alcohol, drying is washed after taking-up；
(2) that the Cu metal substrate that step (1) obtains is put into hydro-thermal in the mixed aqueous solution of sodium hydroxide, glycerol and ethylene glycol is anti-
It answers, sodium hydroxide mass fraction 10%~30% in mixed aqueous solution, qualities of glycerin score 2~8%, quality of glycol score 2
~8%, hydrothermal temperature is 100~280 DEG C, and the hydro-thermal reaction time is 10~48h；
(3) then dry in high pure nitrogen by the Cu metal substrate pure water washing boiled that step (2) obtains；
(4) the Cu metal substrate that step (3) obtains is placed in the oxygen containing 3000~9000ppm ozone, with 1~2 DEG C/
The rate of minute is gradually heated to 180~250 DEG C, keeps 5~10h, room temperature is finally naturally cooling to, thus in Cu metal substrate
On obtain the copper oxide nanometer particle catalyst for degrading nitrobenzene.
2. a kind of preparation method of the copper oxide nanometer particle catalyst for degrading nitrobenzene as described in claim 1,
Be characterized in that: the Cu metal substrate 100% calculates by weight percent, contains Cu>99.5%, 0<Sb<0.005%, 0<As
< 0.005%, 0 < P < 0.005%, with a thickness of 0.1~5mm.
3. a kind of copper oxide nanometer particle catalyst for degrading nitrobenzene, it is characterised in that: be by claims 1 or 2 institute
The method stated is prepared.
4. a kind of copper oxide nanometer particle catalyst for degrading nitrobenzene as claimed in claim 3, it is characterised in that: oxygen
Changing copper nano particles is that growth in situ forms on Cu metal substrate, and main component is CuO nano particle, size is distributed in 14~
253nm。
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102641736A (en) * | 2012-03-19 | 2012-08-22 | 中国科学院过程工程研究所 | Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof |
| CN107572577A (en) * | 2017-10-29 | 2018-01-12 | 王兴利 | A kind of copper oxide nanocrystal material available for degrading nitrobenzene and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102641736A (en) * | 2012-03-19 | 2012-08-22 | 中国科学院过程工程研究所 | Sea urchin shaped copper oxide catalyst, as well as preparation method and application thereof |
| CN107572577A (en) * | 2017-10-29 | 2018-01-12 | 王兴利 | A kind of copper oxide nanocrystal material available for degrading nitrobenzene and preparation method thereof |
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