CN105727963A - Fe and Cu co-doped nano-sized ZnO photocatalyst and preparation method thereof - Google Patents
Fe and Cu co-doped nano-sized ZnO photocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN105727963A CN105727963A CN201610239671.2A CN201610239671A CN105727963A CN 105727963 A CN105727963 A CN 105727963A CN 201610239671 A CN201610239671 A CN 201610239671A CN 105727963 A CN105727963 A CN 105727963A
- Authority
- CN
- China
- Prior art keywords
- doped nano
- photocatalyst
- preparation
- zno photocatalyst
- nano zno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 43
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 title abstract 5
- 239000010949 copper Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011701 zinc Substances 0.000 claims abstract description 14
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000012153 distilled water Substances 0.000 claims abstract description 9
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 46
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- -1 iron ion Chemical class 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910016411 CuxO Inorganic materials 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 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 abstract description 15
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 15
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 2
- 150000001879 copper Chemical class 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 244000283207 Indigofera tinctoria Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a Fe and Cu co-doped nano-sized ZnO photocatalyst and a preparation method thereof.The general formula of the photocatalyst is Zn[0.98-x]Fe0.02CuxO, wherein x ranges from 0.01 to 0.05.The preparation method of the photocatalyst comprises the following steps that 1, a zinc salt, a ferric salt and a copper salt are dissolved in distilled water, and a uniformly mixed solution is obtained, wherein the mixing amount of ferric ions is 2 mol%, and the mixing amount of the copper ions is 1-5 mol%; 2, the pH value of the mixed solution is adjusted till the mixed solution is neutral, and stirring is conducted to enable the mixed solution to form gel; 3, the gel is dried and calcined, and the Fe and Cu co-doped nano-sized ZnO photocatalyst is obtained.The Fe and Cu co-doped nano-sized ZnO photocatalyst can significantly promote the photocatalytic performance of ZnO, and when the Fe and Cu co-doped nano-sized ZnO photocatalyst is used for catalytically degrading methylene blue, the degradation rate within 60 min can reach 99.5%.
Description
Technical field
The present invention relates to a kind of nano ZnO photocatalyst and preparation method thereof, be specifically related to a kind of Fe, Cu codope and receive
Rice ZnO photocatalyst and preparation method thereof.
Background technology
Water is one of essential condition of life on earth existence, and the normal productive life of the mankind and the existence of other life are required for big
The source of clean water of amount.Along with the size of population increases and family, the unreasonable discharge of industrial wastewater, water pollution problems has become
For the focus paid close attention to both at home and abroad.Therefore, how to process increasing productive life sewage, and make it again become clean
Water has become as research worker urgent problem.Photocatalysis is a kind of novel sewage disposal technology, has efficiently,
Energy consumption of reaction is low, and secondary pollution is little, and operating cost is low and simple operation and other advantages, is widely studied and applied.
ZnO is as a kind of excellent semiconductor light-catalyst, and the energy gap under room temperature reaches 3.37eV, and has higher
Exciton bind energy (60meV), due to its have photocatalytic activity height, chemical stability preparation good, easy, to human body
Harmless, cheap, use safety etc. advantage and interested to researchers.Under the irradiation of light, ZnO produces after exciting
Electron-hole pair has oxidation, the ability of reduction, is progressively degraded, finally after making Organic substance generation redox reaction
It is completely oxidized to environment amenable CO2、H2O and nontoxic inorganic molecules.But, ZnO is in photocatalytic applications
In there is the problems such as the separation efficiency in photoresponse narrow range, electronics and hole is low, so that its catalytic performance is limited.
Research finds, passes through Fe3+、Cu2+、Ni2+And Mn2+Deng transition metal ions, the doping of ZnO photocatalyst is changed
Property, thus it is possible to vary the band-gap energy of ZnO, generation impurity energy level and lattice defect, improve photo-quantum efficiency and oxidoreduction
Ability, thus improve photocatalytic activity.Additionally, transition metal ions and Zn in ZnO crystal2+Atomic radius difference
Not quite, it is easy to doping enters in ZnO lattice, therefore using doped transition metal ions modification is to improve ZnO photocatalysis
The conventional means of performance.But, great majority research at present is just for the impact of single-element doping, about two kinds of transition gold
The report belonging to elements compounding doping ZnO material is actually rare.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide a kind of Fe, Cu that can be effectively improved photocatalytic activity and is co-doped with
Miscellaneous nano ZnO photocatalyst, the second object of the present invention is to provide the preparation method of this catalyst.
Technical scheme: Fe, Cu co-doped nano ZnO photocatalyst of the present invention, uses formula Zn0.98-xFe0.02CuxO
Representing, wherein, x is 0.01～0.05.This photocatalyst can be obviously improved the photocatalysis performance of ZnO, uses it for
Catalytic degradation methylene blue, the degradation rate in 60min is 68%～99.5%.
Preferably, x is 0.01～0.02.Now, the photocatalysis performance of this photocatalyst is the strongest, for catalytic degradation methylene
During base indigo plant, the degradation rate in 60min is 92%～99.5%.
The preparation method of Fe, Cu co-doped nano ZnO photocatalyst of the present invention, comprises the steps:
(1) zinc salt and iron salt, mantoquita are dissolved in distilled water and get a uniform mixture, wherein, iron ion volume
For 2mol%, copper ion volume is 1～5mol%；
(2) regulate the pH value of mixed solution, until this mixed solution is neutrality, stirs, form it into gel；
(3) by this gel drying, calcining, Fe, Cu co-doped nano ZnO photocatalyst is obtained.
In above-mentioned steps (2), adding the pH value of citric acid regulation mixed solution, the citric acid of addition is total with metal ion
The mol ratio of amount is (15～20): (11～15).
Concrete, in step (2), after mixed solution is stirred 3～5h under the water bath of 60～80 DEG C, form gel.
In above-mentioned steps (3), gel is dried at 60～100 DEG C 12～24h.
Further, in step (3), after gel drying, at 450～650 DEG C, calcine 2～4h.
Preferably, in step (1), zinc salt is zinc acetate, zinc sulfate, zinc nitrate or zinc chloride；Iron salt is ferric nitrate
Or iron chloride；Mantoquita is copper acetate, copper sulfate, copper nitrate or copper chloride.
Beneficial effect: compared with prior art, it is an advantage of the current invention that: (1) present invention uses Fe, Cu to be co-doped with receiving
Rice ZnO, it is possible to significantly improve the photocatalysis performance of nano-ZnO, when using it for catalytic degradation methylene blue, 60min
Interior degradation rate is up to 99.5%；(2) present invention utilizes sol-gal process to prepare Fe, Cu co-doped nano ZnO light to urge
Agent, the method is easy and simple to handle, be easily achieved industrialization, can be that large-scale production nano composite material provides one conscientiously
Feasible approach.
Accompanying drawing explanation
Fig. 1 is the TEM figure of the photocatalyst that embodiment 1 prepares；
Fig. 2 is the XRD diffraction pattern of the photocatalyst of different Fe, Cu dopings that embodiment 4 prepares；
Fig. 3 is the effect of the photocatalyst photocatalytic degradation methylene blue of different Fe, Cu dopings that embodiment 4 prepares
Figure；
Fig. 4 is Zn0.97Fe0.02Cu0.01During O photocatalyst catalytic degradation methylene blue, methylene blue is with the suction of degradation time
Receive spectrum.
Detailed description of the invention
Below in conjunction with the accompanying drawings technical scheme is described further.
Embodiment 1
(1) 2.13g zinc acetate, 0.0808g ferric nitrate and 0.02g copper acetate are dissolved in 100mL distilled water stirring
Get a uniform mixture；
(2) it is added dropwise in mixed solution after 2.956g citric acid 100mL distilled water stirring and dissolving, will mixing
Solution regulation is to neutral；
(3) above-mentioned mixed liquor is formed under 70 DEG C of water bath gel after mechanical agitation 4h；
(4) gel is dried in drying baker 24h at 60 DEG C；
(5) at 500 DEG C, calcine 2h after being ground by desciccate, obtain Zn0.97Fe0.02Cu0.01O photocatalyst.
Fig. 1 is the TEM figure of the photocatalyst that the present embodiment prepares, and as shown in Figure 1, the photocatalyst pattern of preparation is
Spherical, size is more uniform, and particle diameter is about 20nm.
Embodiment 2
(1) 1.5499g zinc sulfate, 0.05406 iron chloride and 0.0319g copper sulfate are dissolved in 100mL distilled water
Stirring gets a uniform mixture；
(2) it is added dropwise in mixed solution after 2.865g citric acid 100mL distilled water stirring and dissolving, will mixing
Solution regulation is to neutral；
(3) above-mentioned mixed liquor is formed under 80 DEG C of water bath gel after mechanical agitation 5h；
(4) gel is dried in drying baker 18h at 100 DEG C；
(5) at 650 DEG C, calcine 3h after being ground by desciccate, obtain Zn0.96Fe0.02Cu0.02O photocatalyst.
Embodiment 3
(1) 2.5745g zinc nitrate, 0.0808g ferric nitrate and 0.051g copper chloride are dissolved in 100mL distilled water
Stirring gets a uniform mixture；
(2) it is added dropwise in mixed solution after 2.1014g citric acid 100mL distilled water stirring and dissolving, will be mixed
Close solution regulation to neutral；
(3) above-mentioned mixed liquor is formed under 60 DEG C of water bath gel after mechanical agitation 3h；
(4) gel is dried in drying baker 12h at 80 DEG C；
(5) at 450 DEG C, calcine 4h after being ground by desciccate, obtain Zn0.95Fe0.02Cu0.03O photocatalyst.
Embodiment 4
With reference to embodiment 1, arranging 5 groups of parallel laboratory tests, difference is, the doping of Fe and Cu:
First group: iron ion volume is 2mol%, copper ion volume is 1mol%, prepares Zn0.97Fe0.02Cu0.01O light is urged
Agent；
Second group: iron ion volume is 2mol%, copper ion volume is 2mol%, prepares Zn0.96Fe0.02Cu0.02O light is urged
Agent；
3rd group: iron ion volume is 2mol%, copper ion volume is 3mol%, prepares Zn0.95Fe0.02Cu0.03O light is urged
Agent；
4th group: iron ion volume is 2mol%, copper ion volume is 4mol%, prepares Zn0.94Fe0.02Cu0.04O light is urged
Agent；
5th group: iron ion volume is 2mol%, copper ion volume is 5mol%, prepares Zn0.93Fe0.02Cu0.05O light is urged
Agent.
As shown in Figure 2, the angle of diffraction 2 θ is at 31.8 °, 34.4 °, 36.3 °, 47.6 °, 56.7 °, 62.9 °, 66.4 °
Etc., respectively with (100), (002), (101) of ZnO, (102), (110), (103), the feature diffraction of (220) crystal face
Peak is consistent, mates (No.36-1451) with the JCPDS card of ZnO, and diffraction peak-to-peak type is relatively more sharp-pointed, does not occur it
The characteristic peak of his material, shows that Fe, Cu codope sample of preparation is hexagonal wurtzite structure ZnO.Additionally, with
The increase of doping, the intensity of diffraction maximum gradually weakens, and diffraction maximum gradually to wide-angle offset, this show Fe,
Cu ion comes in ZnO lattice.
Weigh the photocatalyst Zn that the above-mentioned 5 groups of experiments of 50mg prepare0.98-xFe0.02CuxO (wherein, 0.01≤x≤0.05) puts into
In the test tube of 50mL, it is subsequently adding the methylene blue solution (10mg/L) prepared, the ultrasonic 30min of lucifuge, then places
Under the mercury lamp of 500W, every 15min samples, with UV725 type visible spectrophotometer in methylene blue absorption maximum
Its absorbance is surveyed at wavelength 664nm.
The photodegradation rate D of methylene blue solution is calculated as follows:
C0: initial absorbance；Ct: it is absorbance during t in the time.Experimental results such as Fig. 3.
From the figure 3, it may be seen that when the doping of iron ion is 2mol%, when the doping of copper ion is 1～5mol%, prepare
Fe, Cu co-doped nano ZnO photocatalyst have excellence photocatalysis performance, the degraded of methylene blue in 60min
Rate is 68%～99.5%；Simultaneously it can be seen that increase with the doping of copper ion, the catalytic performance of the photocatalyst prepared
It is gradually reduced, but when the doping of copper ion increases to 5mol%, uses prepared photocatalyst for degrading methylene blue,
In 60min, the degradation rate of methylene blue still has 68%.
The doping of iron ion keeps constant, when the doping of copper ion is 1～2mol%, and urging of prepared photocatalyst
Changing performance the strongest, in 60min, the degradation rate of methylene blue is 92%～99.5%；Wherein, the doping of copper ion is 1mol%
Time, the degradation rate of methylene blue is maximum, and in 60min, maximum material removal rate is up to 99.5%, now, and can be more by Fig. 4
Intuitively arriving, after degraded 60min, methylene blue solution has decoloured completely.
Claims (10)
1. Fe, Cu co-doped nano ZnO photocatalyst, it is characterised in that described photocatalyst formula
Zn0.98-xFe0.02CuxO represents, wherein, x is 0.01～0.05.
Fe, Cu co-doped nano ZnO photocatalyst the most according to claim 1, it is characterised in that x is
0.01～0.02.
The preparation method of Fe, Cu co-doped nano ZnO photocatalyst the most according to claim 1, its feature
It is, comprises the steps:
(1) zinc salt and iron salt, mantoquita are dissolved in distilled water and get a uniform mixture, wherein, iron ion volume
For 2mol%, copper ion volume is 1～5mol%；
(2) regulate the pH value of mixed solution, until this mixed solution is neutrality, stirs, form it into gel；
(3) by this gel drying, calcining, Fe, Cu co-doped nano ZnO photocatalyst is obtained.
The preparation method of Fe, Cu co-doped nano ZnO photocatalyst the most according to claim 3, its feature
It is, in step (2), adds the pH value of citric acid regulation mixed solution, the citric acid of addition and metal ion total amount
Mol ratio be (15～20): (11～15).
The preparation method of Fe, Cu co-doped nano ZnO photocatalyst the most according to claim 3, its feature
Being, in step (2), described mixed solution forms gel after stirring 3～5h under the water bath of 60～80 DEG C.
The preparation method of Fe, Cu co-doped nano ZnO photocatalyst the most according to claim 3, its feature
Being, in step (3), described gel is dried 12～24h at 60～100 DEG C.
The preparation method of Fe, Cu co-doped nano ZnO photocatalyst the most according to claim 3, its feature
It is, in step (3), after described gel drying, at 450～650 DEG C, calcines 2～4h.
The preparation method of Fe, Cu co-doped nano ZnO photocatalyst the most according to claim 3, its feature
Being, in step (1), described zinc salt is zinc acetate, zinc sulfate, zinc nitrate or zinc chloride.
The preparation method of Fe, Cu co-doped nano ZnO photocatalyst the most according to claim 3, its feature
Being, in step (1), described iron salt is ferric nitrate or iron chloride.
The preparation method of Fe, Cu co-doped nano ZnO photocatalyst the most according to claim 3, its feature
Being, in step (1), described mantoquita is copper acetate, copper sulfate, copper nitrate or copper chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610239671.2A CN105727963B (en) | 2016-04-18 | 2016-04-18 | A kind of Fe, Cu co-doped nano ZnO photocatalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610239671.2A CN105727963B (en) | 2016-04-18 | 2016-04-18 | A kind of Fe, Cu co-doped nano ZnO photocatalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105727963A true CN105727963A (en) | 2016-07-06 |
| CN105727963B CN105727963B (en) | 2018-05-18 |
Family
ID=56255705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610239671.2A Active CN105727963B (en) | 2016-04-18 | 2016-04-18 | A kind of Fe, Cu co-doped nano ZnO photocatalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105727963B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107570161A (en) * | 2017-10-23 | 2018-01-12 | 烟台智本知识产权运营管理有限公司 | A kind of preparation method of the ZnO photocatalyst of Co doping |
| CN107626315A (en) * | 2017-10-23 | 2018-01-26 | 烟台智本知识产权运营管理有限公司 | A kind of preparation method of the ZnO photocatalyst of Fe doping |
| CN107754803A (en) * | 2017-10-23 | 2018-03-06 | 烟台智本知识产权运营管理有限公司 | A kind of preparation method of the ZnO photocatalyst of Fe and Co doping |
| CN107774280A (en) * | 2017-10-23 | 2018-03-09 | 烟台智本知识产权运营管理有限公司 | A kind of preparation method of the ZnO photocatalyst of Fe and Mn doping |
| CN107824195A (en) * | 2017-10-23 | 2018-03-23 | 烟台智本知识产权运营管理有限公司 | A kind of preparation method of the ZnO photocatalyst of Co and Mn doping |
| CN108620086A (en) * | 2018-04-04 | 2018-10-09 | 菏泽学院 | The preparation method of novel flakes Zn-Cu-W photochemical catalysts |
| CN109225259A (en) * | 2018-11-15 | 2019-01-18 | 西南民族大学 | Copper silver co-doped nano zinc oxide and preparation method thereof as photochemical catalyst |
| CN109675591A (en) * | 2018-12-17 | 2019-04-26 | 深圳信息职业技术学院 | A kind of preparation method and applications of Fe (II) and/or Cu (II) modified photocatalytic material |
| US20190344245A1 (en) * | 2018-05-11 | 2019-11-14 | Jiangxi University Of Science & Technology | Method of preparing large-size high-porosity fe-doped photocatalytic porous magnetic microspheres and uses thereof |
| CN110759489A (en) * | 2019-11-15 | 2020-02-07 | 盐城工学院 | Electricity-zero-valent iron system for accelerating removal of sulfide in sewage pipeline |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103252251A (en) * | 2013-05-22 | 2013-08-21 | 江南大学 | Preparation method of co-doped ZnO nano material |
| CN104128211A (en) * | 2014-07-30 | 2014-11-05 | 河北大学 | Multiple metal ion doped nano ZnO transparent photocatalyst emulsion and preparation method thereof |
-
2016
- 2016-04-18 CN CN201610239671.2A patent/CN105727963B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103252251A (en) * | 2013-05-22 | 2013-08-21 | 江南大学 | Preparation method of co-doped ZnO nano material |
| CN104128211A (en) * | 2014-07-30 | 2014-11-05 | 河北大学 | Multiple metal ion doped nano ZnO transparent photocatalyst emulsion and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 丁艳等: "M2+（M=Cu、Cd、Ag、Fe）掺杂氧化锌纳米粉晶的抗菌性能", 《无机化学学报》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107570161A (en) * | 2017-10-23 | 2018-01-12 | 烟台智本知识产权运营管理有限公司 | A kind of preparation method of the ZnO photocatalyst of Co doping |
| CN107626315A (en) * | 2017-10-23 | 2018-01-26 | 烟台智本知识产权运营管理有限公司 | A kind of preparation method of the ZnO photocatalyst of Fe doping |
| CN107754803A (en) * | 2017-10-23 | 2018-03-06 | 烟台智本知识产权运营管理有限公司 | A kind of preparation method of the ZnO photocatalyst of Fe and Co doping |
| CN107774280A (en) * | 2017-10-23 | 2018-03-09 | 烟台智本知识产权运营管理有限公司 | A kind of preparation method of the ZnO photocatalyst of Fe and Mn doping |
| CN107824195A (en) * | 2017-10-23 | 2018-03-23 | 烟台智本知识产权运营管理有限公司 | A kind of preparation method of the ZnO photocatalyst of Co and Mn doping |
| CN108620086A (en) * | 2018-04-04 | 2018-10-09 | 菏泽学院 | The preparation method of novel flakes Zn-Cu-W photochemical catalysts |
| US20190344245A1 (en) * | 2018-05-11 | 2019-11-14 | Jiangxi University Of Science & Technology | Method of preparing large-size high-porosity fe-doped photocatalytic porous magnetic microspheres and uses thereof |
| US10933406B2 (en) * | 2018-05-11 | 2021-03-02 | Jiangxi University Of Science & Technology | Method of preparing large-size high-porosity Fe-doped photocatalytic porous magnetic microspheres and uses thereof |
| CN109225259A (en) * | 2018-11-15 | 2019-01-18 | 西南民族大学 | Copper silver co-doped nano zinc oxide and preparation method thereof as photochemical catalyst |
| CN109675591A (en) * | 2018-12-17 | 2019-04-26 | 深圳信息职业技术学院 | A kind of preparation method and applications of Fe (II) and/or Cu (II) modified photocatalytic material |
| CN110759489A (en) * | 2019-11-15 | 2020-02-07 | 盐城工学院 | Electricity-zero-valent iron system for accelerating removal of sulfide in sewage pipeline |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105727963B (en) | 2018-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105727963A (en) | Fe and Cu co-doped nano-sized ZnO photocatalyst and preparation method thereof | |
| CN101653728B (en) | Preparation method and application thereof for zinc ferrite/titanium dioxide nano compounded visible light photocatalyst | |
| CN101947454B (en) | Transitional metal-doped zinc oxide mesoporous material with visible light catalytic activity and preparation method thereof | |
| Zhang et al. | Construction of Pt-decorated g-C3N4/Bi2WO6 Z-scheme composite with superior solar photocatalytic activity toward rhodamine B degradation | |
| CN103861575A (en) | Method for preparing doped-modified TiO2/graphene composite material | |
| Ri et al. | The synthesis of a Bi 2 MoO 6/Bi 4 V 2 O 11 heterojunction photocatalyst with enhanced visible-light-driven photocatalytic activity | |
| CN109395761B (en) | Nitrogen-doped BiOIO3Preparation method and application of photocatalyst | |
| CN109939643A (en) | α-Fe2O3Adulterate the preparation method and applications of charcoal | |
| CN103240073B (en) | Zn<2+>-doped BiVO4 visible-light-driven photocatalyst and preparation method thereof | |
| CN107175099A (en) | A kind of V ion dopings BiNb5O14Photochemical catalyst and its preparation method and application | |
| CN109261172A (en) | A kind of preparation method and purposes of bismuth oxyiodide/bismuth oxybromide heterojunction photocatalyst | |
| CN104707635B (en) | A kind of high activity phosphorus doping bismuth vanadate photocatalyst and preparation method and application | |
| CN110465303A (en) | A kind of LaNiO of calcium analysis3The preparation method and application of perovskite type photocatalyst | |
| CN104971761A (en) | Nitrogen/sulfur-doped bismuth oxyhalide visible light catalysis material and preparation method thereof | |
| CN103372424B (en) | A kind of synthetic method of high activity N-F codope pucherite visible-light photocatalysis material | |
| Chen et al. | Co/S co-doped Mn3O4-based sulfur-oxide nano-flakes catalyst for highly efficient catalytic reduction of organics and hexavalent chromium pollutants | |
| CN100460067C (en) | Composite bismuth vanadium photocatalyst supported by nickel oxide and preparation method thereof | |
| CN107349943A (en) | The preparation method of bismuth stannate/silver-colored silver chlorate plasma nano composite photocatalyst material | |
| Dos Santos et al. | Investigation of the photocatalytic and optical properties of the SrMoO4/g-C3N4 heterostructure obtained via sonochemical synthesis with temperature control | |
| Prabhavathy et al. | Visible light-induced Silver and Lanthanum co-doped BiVO4 nanoparticles for photocatalytic dye degradation of organic pollutants | |
| CN112142097A (en) | Cadmium stannate trihydrate, and preparation method and application thereof | |
| CN101708454B (en) | Flaky Mg-Al composite oxide for loading ZnO nano particles as well as preparation and application thereof | |
| CN113441142B (en) | Preparation method and application of oxygen vacancy-rich graphene-loaded porous nano ferroelectric oxide catalyst | |
| Qu et al. | A new visible-light-induced Z-scheme photocatalytic system: Er3+: Y3Al5O12/(MoS2/NiGa2O4)-(BiVO4/PdS) for refractory pollutant degradation with simultaneous hydrogen evolution | |
| CN102500406B (en) | Iron, nitrogen and fluoride co-doped titanium dioxide (TiO2) photocatalyst and application thereof in degrading organic pollutants in visible light |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |