CN107983379A - A kind of ZnO/CoP compound nanometer photocatalysts and preparation method thereof - Google Patents
A kind of ZnO/CoP compound nanometer photocatalysts and preparation method thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 12
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- 239000011858 nanopowder Substances 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- 239000012153 distilled water Substances 0.000 claims description 28
- 238000007747 plating Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002114 nanocomposite Substances 0.000 claims description 15
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 14
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- 238000004090 dissolution Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 14
- 230000001235 sensitizing effect Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
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- 238000011068 loading method Methods 0.000 claims description 8
- 239000004471 Glycine Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical class [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 7
- 235000013904 zinc acetate Nutrition 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000008236 heating water Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000011943 nanocatalyst Substances 0.000 abstract description 2
- 238000007772 electroless plating Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
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- 238000000703 high-speed centrifugation Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
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- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
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- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical group [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to inorganic composite nano catalyst preparation technical field, is a kind of ZnO/CoP compound nanometer photocatalysts and its preparation process.The ZnO/CoP compound nanometer photocatalysts are prepared using the method for hydro-thermal method and electroless plating, the component of the catalyst contains ZnO nano powder and CoP nano particles.Diffusing reflection and absorption spectroanalysis find that the spectral response of the simple ZnO nano powder of composite material ratio at visible ray and near infrared region significantly increases.This method preparation process is succinct, and obtained composite photocatalyst material performance is stablized, cost-effective, suitable for mass production, available for photocatalysis pollution control of water field.
Description
Technical field
The invention belongs to inorganic composite nano catalysis material preparing technical field, and in particular to a kind of CoP nano particles are repaiied
Adorn composite nano-catalyst of ZnO nano powder and preparation method thereof.
Background technology
With the development of global industry, a large amount of organic pollutions are discharged into water, have threatened the health of the mankind, this
Kind situation causes scientist and widely pays close attention to.At present, the conventional semiconductors nano-crystalline photocatalysis agent using ZnO as representative receives
Extensive concern, since it has the advantages such as purification air, degradation of organic substances, antibacterial, automatically cleaning, and cost is low, photochemistry property
Matter is stable, non-secondary pollution, this has important meaning to solving the problems, such as that the great society such as current pollution control, energy-saving and emission-reduction is deeply concerned
Justice.
However, the energy gap (about 3.2~3.4eV) of ZnO is larger, can only have to the sunlight of wavelength ＜ 387nm
Effect absorbs, this part only accounts for solar spectrum gross energy less than 10%, and the visible ray of sunshine gross energy ＞ 90% is accounted for remaining
It can not but be utilized with infra-red radiation.Meanwhile the quantity of photogenerated charge separation state (electron-hole pair) of ZnO nano crystalline substance photochemical catalyst is easy to
It is compound, cause photo-quantum efficiency to reduce, usually not more than 10%.This 2 points overall effects for causing traditional ZnO photocatalysis technologies
Rate is very limited, significantly limit its popularization and application.
Low-gap semiconductor modification technique can effectively extend the spectral response range of semiconductor nano, improve photic electricity
The separated quantum yield of lotus, so as to optimize its photocatalysis efficiency.CoP is the narrow-band semiconductor of a kind of excellent performance, is had following
Feature：1) wider spectral response range, so as to have good absorbing ability；2) less electron recombination can and it is stronger
Electron donation, so as to improve the separation of charge ability at nanocrystalline interface, improves optical energy utilization efficiency；3) higher light is steady
Qualitative, chemical stability and heat endurance, ensure longer service life and complex environment adaptability.
These characteristics show that CoP is particularly well suited as the dressing agent of ZnO nano crystalline substance, for composite photocatalyst functional material
Preparation, be a kind of effective important method for improving photochemical catalyst.
The content of the invention
The object of the present invention is to provide a kind of ZnO/CoP compound nanometer photocatalysts and preparation method thereof.The present invention passes through
The mode of narrow-band semiconductor CoP modifications can solve photoelectricity existing for current ZnO-hole-recombination rate height, light to a certain extent
The problems such as quantum efficiency is low, improve the visible light-responded property and photocatalytic activity of ZnO.The preparation side of the composite photo-catalyst at the same time
Method is simple, and process conditions easy-regulating, cost is low, is easy to industrial production and popularization and application.
A kind of ZnO/CoP compound nanometer photocatalysts, the component of the compound nanometer photocatalyst contain ZnO nano powder and
CoP nano particles, the mass ratio of the CoP and ZnO are 1.0~5.0:100, there is composite nanostructure.
The CoP is supported on ZnO surfaces, and load capacity of the CoP on ZnO surfaces is 1%~5%.
The size of ZnO/CoP compound nanometer photocatalysts is between 200~400nm scopes.
A kind of preparation method of ZnO/CoP compound nanometer photocatalysts, includes the following steps：
(1) ZnO nano powder is prepared using hydro-thermal method
First, 0.5485~1.097g zinc acetates, 0.315~0.63g sodium hydroxides and 10~20mL water are taken, is placed in beaker
In, be vigorously stirred after 10min and be transferred in reaction kettle, heat 12~24h, by the solid powder obtained after reaction by water and
Ethanol washs repeatedly, and the solid powder after washing is obtained ZnO nano powder after temperature is 60~70 DEG C of 3~6h of heat drying
Body.
(2) sensitizing solution is prepared
Weigh 0.5~1g of stannous chloride dihydrate, ultrasonic dissolution in 2.5~5mL hydrochloric acid plus distilled water be settled to 0.5~
1L is made into sensitizing solution.
(3) activating solution is prepared
0.05~0.1g of palladium bichloride is weighed, ultrasonic dissolution is in 0.5~1mL hydrochloric acid plus distilled water is settled to 1L and is made into activation
Liquid.
(4) plating solution is prepared
Weigh 0.5945~1.189g of CoCL2 6H2O, 2.12~4.24g of sodium hypophosphite, glycine 1.126~
2.252g adds distilled water 80mL in container, until completely dissolved, adds sodium hydroxide solution, and it is 11 to adjust solution pH value,
And it is used as plating solution stand-by after being transferred to 100mL volumetric flasks.
(5) CoP loading ZnO nanocomposites are prepared
By the plating solution mixing that step (1) obtains ZnO nano powder and step (4) obtains, ultrasound, is stirred, after uniform, water-bath
60 DEG C of heating, reacts 3~5h.Obtained product is washed with distilled water and ethanol alternating centrifugal.Then under vacuum conditions, it is warm
Spend to dry 3~5h in 60~70 DEG C of temperature ranges, be dried, to ensure ZnO/CoP samples having obtained abundant drying.
As preference, a kind of preparation method of ZnO/CoP compound nanometer photocatalysts, includes the following steps：
(1) ZnO nano powder is prepared using hydro-thermal method
First, 1.097g zinc acetates are weighed and 0.63g sodium hydroxides are placed in beaker, 20mL water is added, is vigorously stirred
It is transferred to after 10min in reaction kettle, heats 24h, the solid powder obtained after reaction is washed repeatedly by water and ethanol, will
Solid powder after washing obtains ZnO nano-powders after temperature is 70 DEG C of heat drying 3h.
(2) sensitizing solution is prepared
Stannous chloride dihydrate 1g is weighed, ultrasonic dissolution is in 5mL hydrochloric acid plus distilled water is settled to 1L and is made into sensitizing solution.
(3) activating solution is prepared
Palladium bichloride 0.1g is weighed, ultrasonic dissolution is in 1mL hydrochloric acid plus distilled water is settled to 1L and is made into activating solution.
(4) plating solution is prepared
CoCL2 6H2O 1.189g, sodium hypophosphite 4.24g are weighed, glycine 2.252g adds distilled water in container
80mL, until completely dissolved, adds sodium hydroxide solution, and it is 11 to adjust solution ph, and is transferred to conduct after 100mL volumetric flasks
Plating solution is stand-by.
(5) CoP loading ZnO nanocomposites are prepared
By the plating solution mixing that step (1) obtains ZnO nano powder and step (4) obtains, ultrasound, is stirred, after uniform, water-bath
60 DEG C of heating, reacts 3h.Obtained product is washed with distilled water and ethanol alternating centrifugal.Then under vacuum conditions, in temperature
Spend for dry 3h in the range of 60~70 DEG C, ensure that ZnO/CoP samples are fully dried.
Advantageous effect of the invention：
A certain amount of ZnO nano powder, then the method by using chemical plating are prepared using hydro-thermal method, prepare CoP loads
ZnO nano composite material.Find the simple ZnO nano powder of composite material ratio visible using diffusing reflection and absorption spectroanalysis
Spectral response at light and near infrared region significantly increases.Since preparation process is succinct, obtained composite catalyzing material property is stablized,
It is cost-effective, it is suitable for mass producing, air and water pollution is administered available for photocatalysis.
Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is that ZnO the and ZnO/CoP samples prepared by embodiment 1 scheme the activity of photocatalytic degradation methylene blue.
Fig. 2 is the XRD spectra of the ZnO and ZnO/CoP composite materials prepared by embodiment 1.
Fig. 3 is UV-Vis DRS (UV-DRS) spectrum.
Fig. 4 is the XPS spectrum figure of ZnO/CoP nano composite photo-catalysts.
Fig. 5 is the scanning electron microscope (SEM) photograph of prepared ZnO nano powder and ZnO/CoP nano composite photo-catalysts.
Embodiment
Embodiment 1
A certain amount of ZnO nano powder, then the method by using chemical plating are prepared using hydro-thermal method, it is different to prepare CoP
The ZnO/CoP nanocomposites of load capacity.
First, by 1.097g zinc acetates, 0.63g sodium hydroxides and 20mL water, in beaker, 10min is vigorously stirred, it
After be transferred in reaction kettle, heat 24h, the solid powder obtained after reaction is washed repeatedly by water and ethanol, after washing
Solid powder temperature be 70 DEG C of 3~6h of heat drying after obtain ZnO nano powder.
Stannous chloride dihydrate 1g is weighed, ultrasonic dissolution is in 5mL hydrochloric acid plus distilled water is settled to 1L and is made into sensitizing solution.Weigh
Palladium bichloride 0.1g, ultrasonic dissolution is in 1mL hydrochloric acid plus distilled water is settled to 1L and is made into activating solution.CoCL2 6H2O 1.189g, it is secondary
Sodium phosphite 4.24g, glycine 2.252g, adds distilled water 80mL, waits to be completely dissolved, and adds sodium hydroxide solution, adjusts solution
PH value is 11, and is used as plating solution stand-by after being transferred to 100mL volumetric flasks.
Next, prepare 4.0wt%CoP loading ZnO nanocomposites.By the ZnO nano powder of 1.0g and 4.0mL
Plating solution mixes, ultrasound, stirring, and after uniform, 60 DEG C of heating water bath, reacts 5h.Obtained product distilled water and ethanol are replaced
Centrifuge washing, then under vacuum conditions, is dry 5h in 60~70 DEG C of temperature ranges in temperature, ensures ZnO/CoP (4wt%
CoP) sample is fully dried.
The photocatalytic activity of ZnO/CoP (4wt%CoP) photochemical catalyst of the present invention is by being catalyzed drop under simulated solar illumination
Solution organic dyestuff methylene blue is measured, specific as follows：
The ZnO/CoP photochemical catalysts for weighing 0.1g be added in 100mL methylene blue solutions (initial concentration 10mg/L,
Labeled as C0), magnetic agitation 0.5h reaches adsorption equilibrium in the dark, and opening power is 500W xenon lamps (analog solar spectrum).
Magnetic agitation is wherein kept during light-catalyzed reaction, and makes in reaction process using cooling cycle machine that the temperature remains within the normal range, is avoided
Heat affecting light-catalyzed reaction caused by illumination, samples for every 20~30 minutes, and sampling solution is through 8000rpm/min high speed centrifugations
After 20min, solution concentration (being labeled as C) is tested on ultraviolet-visible spectrophotometer, different illumination are obtained it is possible thereby to test
Photocatalysis Decomposition rate of the photochemical catalyst to organic dyestuff methylene blue solution under time.
It is work of the prepared ZnO and ZnO/CoP (4wt%CoP) samples to photocatalytic degradation methylene blue as shown in Figure 1
Property figure.The ZnO/CoP composite photo-catalysts prepared with this method, compared to pure ZnO nano powder, show under simulated solar irradiation
The photocatalytic activity of higher is gone out.And CoP, when 4wt% amounts load, ZnO/CoP composite material exhibits have gone out highest light and have urged
Change activity.
Fig. 2 compares for the XRD spectra of ZnO and ZnO/CoP compound nanometer photocatalysts material prepared by embodiment 1, can be with
Find out that the ZnO composite nano materials after 4wt%CoP modifications still maintain the crystal structure of ZnO.
Fig. 3 provides ZnO nano powder and ZnO/CoP (4wt%CoP) nano-photocatalyst prepared by embodiment 1 is compound
The uv-visible absorption spectra of material compares, it can be clearly seen that ZnO/CoP composite materials are in 400nm regions from Fig. 3
Absorbing ability it is very strong, and ungroomed ZnO does not absorb in the region.
Fig. 4 is the XPS spectrograms of ZnO/CoP (4wt%CoP) nano composite photo-catalyst prepared by embodiment 1, is represented
CoP nano particles have successfully been plated to the surface of ZnO nano powder.
ZnO/CoP (4wt%CoP) nano composite photocatalytic prepared by the ZnO nano powder and embodiment 1 that Fig. 5 is provided
The scanning electron microscope (SEM) photograph of agent, it can be seen that the pattern for the ZnO nano powder not being modified is nano particle, and particle diameter is in 200~400nm
There are the CoP nano particles of one layer of thin layer on scope, the ZnO of CoP modifications, surface, and particle diameter is in 200~400nm scopes.
Embodiment 2
A certain amount of ZnO nano powder prepared using hydro-thermal method, then the method by using chemical plating, prepare CoP not
With the ZnO/CoP nanocomposites of load capacity.
First, 1.097g zinc acetates, 0.63g sodium hydroxides and 20mL water are placed in beaker, are vigorously stirred 10min, it
After be transferred in reaction kettle, heat 24h, the solid powder obtained after reaction is washed repeatedly by water and ethanol, after washing
Solid powder temperature be 70 DEG C of 3~6h of heat drying after obtain ZnO nano powder.
Stannous chloride dihydrate 1g is weighed, ultrasonic dissolution is in 5mL hydrochloric acid plus distilled water is settled to 1L and is made into sensitizing solution.Weigh
Palladium bichloride 0.1g, ultrasonic dissolution is in 1mL hydrochloric acid plus distilled water is settled to 1L and is made into activating solution.Weigh CoCL2 6H2O
1.189g, sodium hypophosphite 4.24g, glycine 2.252g, adds distilled water 80mL, until completely dissolved, it is molten to add sodium hydroxide
Liquid, it is 11 to adjust solution ph, and is used as plating solution stand-by after being transferred to 100mL volumetric flasks.
Next, 1.0wt%CoP loading ZnO nanocomposites are prepared, by the ZnO nano powder of 1.0g and 1.0mL
Plating solution mixes, ultrasound, stirring, and after uniform, 60 DEG C of heating water bath, reacts 5h.Obtained product distilled water and ethanol are replaced
Centrifuge washing；Then under vacuum conditions, temperature is dry 5h in 70 DEG C of temperature ranges, is dried, ensures ZnO/CoP
(1wt%CoP) sample has obtained abundant drying.
The photocatalytic activity of ZnO/CoP (1wt%CoP) photochemical catalyst of the present invention is by being catalyzed drop under simulated solar illumination
Solution organic dyestuff methylene blue is measured, specific as follows：
The ZnO/CoP photochemical catalysts for weighing 0.1g be added in 100mL methylene blue solutions (initial concentration 10mg/L,
Labeled as C0), magnetic agitation 0.5h reaches adsorption equilibrium in the dark, and opening power is 500W xenon lamps (analog solar spectrum).
Magnetic agitation is wherein kept during light-catalyzed reaction, and makes in reaction process using cooling cycle machine that the temperature remains within the normal range, is avoided
Heat affecting light-catalyzed reaction caused by illumination, every 20~30min samplings, sampling solution is through 8000rpm/min high speed centrifugations
After 20min, solution concentration (being labeled as C) is tested on ultraviolet-visible spectrophotometer, different illumination are obtained it is possible thereby to test
Photocatalysis Decomposition rate of the photochemical catalyst to organic dyestuff methylene blue solution under time.
Fig. 1 is that prepared ZnO and ZnO/CoP (1wt%CoP) samples scheme the activity of photocatalytic degradation methylene blue.
The ZnO/CoP composite photo-catalysts prepared with this method, compared to pure ZnO nano powder, under simulated solar irradiation, its photocatalysis
Activity improves.
Embodiment 3
A certain amount of ZnO nano powder prepared using hydro-thermal method, then the method by using chemical plating, prepare CoP not
With the ZnO/CoP nanocomposites of load capacity.
First, by 1.097g zinc acetates, 0.63g sodium hydroxides and 20mL water, in beaker, 10min is vigorously stirred, it
After be transferred in reaction kettle, heat 24h, the solid powder obtained after reaction is washed repeatedly by water and ethanol, after washing
Solid powder temperature be 70 DEG C of 3~6h of heat drying after obtain ZnO nano powder.
Stannous chloride dihydrate 1g is weighed, ultrasonic dissolution is in 5mL hydrochloric acid plus distilled water is settled to 1L and is made into sensitizing solution.Weigh
Palladium bichloride 0.1g, ultrasonic dissolution is in 1mL hydrochloric acid plus distilled water is settled to 1L and is made into activating solution.Weigh CoCL2 6H2O
1.189g, sodium hypophosphite 4.24g, glycine 2.252g, adds distilled water 80mL until completely dissolved, and it is molten to add sodium hydroxide
Liquid, it is 11 to adjust solution ph, and is used as plating solution stand-by after being transferred to 100mL volumetric flasks.
Next, prepare 5.0wt%CoP loading ZnO nanocomposites.By the ZnO nano powder of 1.0g and 5.0mL
Plating solution mixes, ultrasound, stirring, and after uniform, 60 DEG C of heating water bath, reacts 5h.Obtained product distilled water and ethanol are replaced
Centrifuge washing.Then under vacuum conditions, temperature is dry 5h in 70 DEG C of temperature ranges, is dried, ensures ZnO/CoP
(1wt%CoP) sample has obtained abundant drying.
The photocatalytic activity of ZnO/CoP (5wt%CoP) photochemical catalyst of the present invention is by being catalyzed drop under simulated solar illumination
Solution organic dyestuff methylene blue is measured, specific as follows：
The ZnO/CoP photochemical catalysts for weighing 0.1g be added in 100mL methylene blue solutions (initial concentration 10mg/L,
Labeled as C0), magnetic agitation 0.5h reaches adsorption equilibrium in the dark, and opening power is 500W xenon lamps (analog solar spectrum),
Magnetic agitation is wherein kept during light-catalyzed reaction, and makes in reaction process using cooling cycle machine that the temperature remains within the normal range, is avoided
Heat affecting light-catalyzed reaction caused by illumination, every 20~30min samplings, sampling solution is through 8000rpm/min high speed centrifugations
After 20min, solution concentration (being labeled as C) is tested on ultraviolet-visible spectrophotometer, different illumination are obtained it is possible thereby to test
Photocatalysis Decomposition rate of the photochemical catalyst to organic dyestuff methylene blue solution under time.
Fig. 1 is that prepared ZnO and ZnO/CoP (5wt%CoP) samples scheme the activity of photocatalytic degradation methylene blue.
The ZnO/CoP composite photo-catalysts prepared with this method, compared to pure ZnO nano powder, under simulated solar irradiation, its photocatalysis
Activity improves, but its photocatalytic activity is slightly below ZnO/CoP (4wt%CoP).
Claims (5)
1. a kind of ZnO/CoP compound nanometer photocatalysts, it is characterised in that the component of the compound nanometer photocatalyst contains ZnO
The mass ratio of nano-powder and CoP nano particles, the CoP nano particles and ZnO nano powder is 1.0~5.0:100, have
Composite nanostructure.
2. a kind of ZnO/CoP compound nanometer photocatalysts according to claim 1, it is characterised in that described CoP nanometers
Particle loading is 1%~5% in the load capacity of ZnO nano powder surface in ZnO nano powder, CoP nano particles.
3. a kind of ZnO/CoP compound nanometer photocatalysts according to claim 1, it is characterised in that the ZnO/CoP is answered
The size of nano-photocatalyst is closed between 200~400nm scopes.
A kind of 4. method for preparing the ZnO/CoP compound nanometer photocatalysts as described in claims 1 to 3, it is characterised in that including
Following steps：
(1) ZnO nano powder is prepared using hydro-thermal method
First, 0.5485~1.097g zinc acetates, 0.315~0.63g sodium hydroxides and 10~20mL water are taken, is placed in beaker,
It is transferred to after being vigorously stirred 10min in reaction kettle, heats 12~24h, the solid powder obtained after reaction is passed through into water and ethanol
Wash repeatedly, by the solid powder after washing after temperature is 60~70 DEG C of 3~6h of heat drying, obtain ZnO nano powder.
(2) sensitizing solution is prepared
0.5~1g of stannous chloride dihydrate is weighed, ultrasonic dissolution adds distilled water to be settled to 0.5~1L and match somebody with somebody in 2.5~5mL hydrochloric acid
Into sensitizing solution.
(3) activating solution is prepared
0.05~0.1g of palladium bichloride is weighed, ultrasonic dissolution adds distilled water to be settled to 0.5~1L with surviving in 0.5~1mL hydrochloric acid
Change liquid.
(4) plating solution is prepared
Weigh 0.5945~1.189g of CoCL2 6H2O, 2.12~4.24g of sodium hypophosphite, 1.126~2.252g of glycine in
In container, add distilled water 80mL, until completely dissolved, add sodium hydroxide solution, it is 11 to adjust solution ph, and is transferred to
It is stand-by as plating solution after 100mL volumetric flasks.
(5) CoP loading ZnO nanocomposites are prepared
The mixing of plating solution that the ZnO nano powder and step (4) that step (1) is obtained obtain, ultrasound, after stirring evenly, water-bath adds
60 DEG C of heat, reacts 3~5h；Obtained product is washed with distilled water and ethanol alternating centrifugal.Then under vacuum conditions, temperature
For dry 3~5h in 60~70 DEG C of temperature ranges, ensure that ZnO/CoP samples are fully dried.
A kind of 5. method for preparing the ZnO/CoP compound nanometer photocatalysts as described in claims 1 to 3, it is characterised in that including
Following steps：
(1) ZnO nano powder is prepared using hydro-thermal method
First, 1.097g zinc acetates are weighed and 0.63g sodium hydroxides are placed in beaker, 20mL are added water to, after being vigorously stirred 10min
It is transferred in reaction kettle, heats 24h, the solid powder obtained after reaction is washed repeatedly by water and ethanol, after washing
Solid powder obtains ZnO nano powder under the conditions of temperature is 70 DEG C after heat drying 3h.
(2) sensitizing solution is prepared
Stannous chloride dihydrate 1g is weighed, ultrasonic dissolution is in 5mL hydrochloric acid plus distilled water is settled to 1L and is made into sensitizing solution.
(3) activating solution is prepared
Palladium bichloride 0.1g is weighed, ultrasonic dissolution is in 1mL hydrochloric acid plus distilled water is settled to 1L and is made into activating solution.
(4) plating solution is prepared
CoCL2 6H2O 1.189g is weighed, sodium hypophosphite 4.24g, glycine 2.252g add distilled water 80mL, treat in container
After being completely dissolved, sodium hydroxide solution is added, it is 11 to adjust solution ph, and is transferred in 100mL volumetric flasks and is treated as plating solution
With.
(5) CoP loading ZnO nanocomposites are prepared
The plating solution that step (1) obtains ZnO nano powder and step (4) obtains is mixed, ultrasound, stirring, uniformly after, heating water bath
60 DEG C, react 3h；Obtained product is washed with distilled water and ethanol alternating centrifugal.Then under vacuum conditions, it is in temperature
Dry 3h in the range of 60~70 DEG C, ensures that ZnO/CoP samples are fully dried.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108993573A (en) * | 2018-08-09 | 2018-12-14 | 沈阳师范大学 | Compound nanometer photocatalyst and preparation method |
| CN114097825A (en) * | 2021-12-16 | 2022-03-01 | 山东大学 | Quaternized chitosan coated Ag-loaded CoP nanoneedle and preparation method thereof |
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| CN102219254A (en) * | 2011-06-20 | 2011-10-19 | 厦门大学 | Preparation method of zinc oxide nanorod |
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| CN102219254A (en) * | 2011-06-20 | 2011-10-19 | 厦门大学 | Preparation method of zinc oxide nanorod |
| CN103170369A (en) * | 2013-02-28 | 2013-06-26 | 安徽大学 | Preparation method of zinc oxide/polyaniline composite photocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108993573A (en) * | 2018-08-09 | 2018-12-14 | 沈阳师范大学 | Compound nanometer photocatalyst and preparation method |
| CN114097825A (en) * | 2021-12-16 | 2022-03-01 | 山东大学 | Quaternized chitosan coated Ag-loaded CoP nanoneedle and preparation method thereof |
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Application publication date: 20180504 |