CN110102282A - A kind of cerium dopping photocatalyst of zinc oxide and preparation method thereof - Google Patents
A kind of cerium dopping photocatalyst of zinc oxide and preparation method thereof Download PDFInfo
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- CN110102282A CN110102282A CN201910422401.9A CN201910422401A CN110102282A CN 110102282 A CN110102282 A CN 110102282A CN 201910422401 A CN201910422401 A CN 201910422401A CN 110102282 A CN110102282 A CN 110102282A
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- zinc oxide
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 63
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 47
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 62
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 46
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical group [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 59
- 235000011164 potassium chloride Nutrition 0.000 claims description 30
- 239000001103 potassium chloride Substances 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 17
- 235000002639 sodium chloride Nutrition 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 28
- 230000015556 catabolic process Effects 0.000 abstract description 20
- 238000006731 degradation reaction Methods 0.000 abstract description 20
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000007146 photocatalysis Methods 0.000 abstract description 17
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 16
- 229940012189 methyl orange Drugs 0.000 abstract description 16
- 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 12
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000356 contaminant Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- 238000004140 cleaning Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000000703 Cerium Chemical class 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 2
- -1 Methyl Chemical group 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/13—Organo-metallic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Toxicology (AREA)
- Metallurgy (AREA)
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Abstract
The present invention provides a kind of preparation methods of cerium dopping photocatalyst of zinc oxide, comprising the following steps: using zinc as anode, inert electrode is cathode, to contain conductive salt, Ce3+Aqueous solution with 2-methylimidazole is that conduction liquid is electrolysed, and obtains Ce/ZIF-8；The Ce/ZIF-8 is roasted, cerium dopping photocatalyst of zinc oxide is obtained.The present invention is using Zn as anode, and under certain function of current, anodic solution, Zn occurs2+The ZIF-8 for generating and there is porous structure, Ce in solution are reacted with 2-methylimidazole into electrolyte3+It is carried in porous ZIF-8 structure, is fired, Ce/ZnO photochemical catalyst is made, is applied to photocatalysis degradation organic contaminant field, having a good application prospect has good degradation effect to methyl orange and methylene blue etc..
Description
Technical field
The present invention relates to photocatalyst technology field, in particular to a kind of cerium dopping photocatalyst of zinc oxide and its preparation side
Method.
Background technique
Photocatalysis degradation organic contaminant is a kind of novel one of wastewater treatment method, has degradation thoroughly, and green can
The features such as sustainable development, but catalyst the problems such as there are sun light utilization efficiency is low, and degradation efficiency is not high.
ZnO is a kind of common photochemical catalyst, and as n-type semiconductor, room temperature forbidden bandwidth is 3.37eV, in wave
Under the long ultraviolet light less than 387nm, it can excite and generate photo-generate electron-hole pair, so that generating has Strong oxdiative ability
Living radical (OH and O2 –), there is good degradation to organic pollutant.But ZnO forbidden bandwidth is big, can only inhale
Ultraviolet light is received, causes it low to the utilization rate of solar energy；And photo-generate electron-hole is compound to easily occurring, and it is living to reduce photocatalysis
Property.Rare earth element ce has special 4f electron structure, and Ce doping ZnO can inhibit the compound of photo-generate electron-hole, Ke Yigai
The activity of kind catalyst；In addition, rare earth element ce itself can absorb the electromagnetic radiation in Uv and visible light area, can be improved after doping
Utilization rate of the ZnO to sunlight.Preparation Ce doping ZnO catalyst mainly uses sol-gel method, chemical precipitation method, water at present
Thermal method etc., it is relatively fewer using electro-deposition method preparation Ce doping ZnO catalyst, this is because electrodeposition process is generally used for adulterating
Active component, and the metal cation adulterated generally passes through electrochemical reduction and is deposited on carrier surface；In addition, due to electro-deposition
The parameters such as deposition voltage, current density, solution composition have large effect to catalyst performance in the process, are difficult controllably to make
The standby high catalyst of catalytic degradation efficiency out.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of cerium dopping photocatalyst of zinc oxide and preparation method thereof, this hair
The cerium dopping photocatalyst of zinc oxide of bright preparation has excellent Photocatalytic Degradation Property, has to methyl orange and methylene blue excellent
Different photocatalytic degradation efficiency.
The present invention provides a kind of preparation methods of cerium dopping photocatalyst of zinc oxide, comprising the following steps:
Using zinc as anode, inert electrode is cathode, to contain conductive salt, Ce3+Aqueous solution with 2-methylimidazole is conduction
Liquid is electrolysed, and Ce/ZIF-8 is obtained；
The Ce/ZIF-8 is roasted, cerium dopping photocatalyst of zinc oxide is obtained.
Preferably, the molar ratio of the meltage of the zinc and 2-methylimidazole is 1:2~5.
Preferably, the Ce3+Molar ratio with the meltage of zinc is 0.1~10:1000.
Preferably, the inert electrode is graphite electrode or glass-carbon electrode.
Preferably, the conductive salt is potassium chloride, sodium chloride, potassium nitrate or sodium nitrate.
Preferably, the concentration of conductive salt is 0.001~2mol/L in the electrolyte.
Preferably, the current density of the electrolysis is 0.0005~0.07Acm-2。
Preferably, the temperature of the roasting is 450~700 DEG C, and the time is 2~4h.
The present invention also provides the cerium dopping photocatalyst of zinc oxide that the preparation method described in above scheme is prepared.
Preferably, cerium accounts for the 0.5~5% of catalyst gross mass in the cerium dopping photocatalyst of zinc oxide.
Advantageous effects: the present invention provides a kind of preparation method of cerium dopping photocatalyst of zinc oxide, including it is following
Step: using zinc as anode, inert electrode is cathode, to contain conductive salt, Ce3+With the aqueous solution of 2-methylimidazole be conduction liquid into
Row electrolysis, obtains Ce/ZIF-8；The Ce/ZIF-8 is roasted, cerium dopping photocatalyst of zinc oxide is obtained.The present invention with
Zn is anode, and under certain function of current, anodic solution, Zn occurs2+Reacting generation with 2-methylimidazole into electrolyte has
The ZIF-8 of porous structure, Ce in solution3+It is carried in porous ZIF-8 structure, is fired, Ce/ZnO photochemical catalyst is made, by it
Applied to photocatalysis degradation organic contaminant field, having a good application prospect to methyl orange and methylene blue etc., it is good to have
Degradation effect.Embodiment experimental data shows: illumination 30min under 500W xenon lamp, cerium dopping photocatalyst of zinc oxide is to methylene
The degradation rate of base indigo plant is up to 85%；Illumination 180min under 500W xenon lamp, degradation rate of the cerium dopping photocatalyst of zinc oxide to methyl orange
Up to 60%.
Detailed description of the invention:
Fig. 1 is the schematic diagram of the device of preparation method provided by the invention；
Fig. 2 is the XRD diagram of Ce/ZnO photochemical catalyst obtained in embodiment 1；
Fig. 3 is the SEM figure of Ce/ZnO photochemical catalyst obtained in embodiment 1；
Fig. 4 is that embodiment 6, embodiment 11, the cerium dopping photocatalyst of zinc oxide in embodiment 12 and embodiment 13 aoxidize
The curve of zinc photocatalyst for degrading methyl orange；
Fig. 5 is the curve of cerium dopping photocatalyst of zinc oxide the degradation methyl orange and methylene blue in embodiment 6.
Specific embodiment
The present invention provides a kind of preparation method of cerium dopping photocatalyst of zinc oxide, comprising the following steps:
Using zinc as anode, inert electrode is cathode, to contain conductive salt, Ce3+Aqueous solution with 2-methylimidazole is conduction
Liquid is electrolysed, and Ce/ZIF-8 is obtained；
The Ce/ZIF-8 is roasted, cerium dopping photocatalyst of zinc oxide is obtained.
For the present invention using zinc as anode, inert electrode is cathode, to contain conductive salt, Ce3+With the aqueous solution of 2-methylimidazole
It is electrolysed for conduction liquid, obtains Ce/ZIF-8.
In the present invention, the anode is preferably zinc metal sheet, and the thickness of the zinc metal sheet is preferably 0.05~1mm, and width is preferred
For 1~2cm.The present invention is not particularly limited the length of zinc metal sheet, selects its length according to the dosage of zinc metal sheet.
In the present invention, the meltage of the zinc and the molar ratio of 2-methylimidazole are preferably 1:2~5, more preferably 1:3
~4.
In the present invention, the Ce3+Molar ratio with the meltage of zinc is preferably 0.1~10:1000, further preferably
0.5~5:100, more preferably 2:100.In the present invention, the Ce3+It is preferred that being provided by cerous nitrate or cerous sulfate.
In the present invention, the inert electrode preferably includes graphite electrode or glass-carbon electrode or other is suitble to do electrode
Carbon material, more preferably graphite electrode.
In the present invention, the conductive salt is preferably potassium chloride, sodium chloride, potassium nitrate or sodium nitrate, more preferably chlorination
Potassium or sodium chloride.In the present invention, the concentration of conductive salt is preferably 0.001~2mol/L in the conduction liquid, further preferably
For 0.1~1mol/Lmol/L, more preferably 1mol/L.
In the present invention, the current density of the electrolysis is preferably 0.0005~0.07Acm-2, more preferably 0.02~
0.05A·cm-2。
It in the present invention, further preferably include being filtered to the electrolyte after electrolysis, being solid to filtering gained after the electrolysis
Body is successively washed and is dried in vacuo, and Ce/ZIF-8 is obtained.
The present invention is not particularly limited the method for filtering, selects filter method well known to those skilled in the art.
In the present invention, the washing is preferably that deionized water is washed to neutrality.The present invention is to vacuum drying method without spy
It is different to limit, select vacuum drying method well known to those skilled in the art.
The present invention is using Zn piece as anode, and under certain function of current, anodic solution, Zn occurs2+Into electrolyte and 2- first
The reaction of base imidazoles generates the ZIF-8 with porous structure, and ZIF-8 has cellular structure abundant, and cerium salt is adsorbed in solution
The surface ZIF-8 obtains Ce/ZIF-8 after filtration washing, and obtained Ce/ZIF-8 is roasted, and the cerium salt of load is through high temperature
Roasting is oxidized to CeO2, ZIF-8 obtains ZnO through high-temperature process, obtains cerium dopping photocatalyst of zinc oxide.
In the present invention, the temperature of the roasting is preferably 450~700 DEG C, further preferably 500~650 DEG C, more excellent
It is selected as 550~600 DEG C.
In the present invention, the Ce in the electrolyte3+It is carried in porous ZIF-8 structure, through high-temperature roasting, Ce/ is made
ZnO photocatalyst.
The present invention also provides the cerium dopping zinc oxide photocatalysis that the preparation method that above-mentioned technical proposal provides is prepared
Agent.In the present invention, cerium preferably accounts for the 0.5~5% of catalyst gross mass in the cerium dopping photocatalyst of zinc oxide, more preferably
It is 2~4%.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
Embodiment 1
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.025g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 1g is taken, anode will be done after the oxidation Membrane cleaning on Zn piece surface,
Graphite flake does cathode, connects device by Fig. 1, constant current is with 0.018Acm-2Current density is reacted to the dissolution of anode Zn piece and is reached
98%, power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；
Obtained Ce/ZIF-8 is risen to 500 DEG C of roasting 3h, obtained 0.5%Ce/ZnO after cooling in Muffle furnace with 5 DEG C/min heating rate
Photochemical catalyst (cerium account for Ce/ZnO photochemical catalyst gross mass 0.5%).
Fig. 2 is the XRD diagram of Ce/ZnO photochemical catalyst obtained in 1 in embodiment.As shown in Figure 2: this method is prepared
The ZnO catalyst material of Ce doping.
Fig. 3 is the SEM figure of Ce/ZnO photochemical catalyst obtained in 1 in embodiment.As shown in Figure 3: Ce/ZnO photochemical catalyst
Particle is more uniform.
Embodiment 2
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.1g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 1g is taken, anode, graphite flake are done in cleaning after removing Zn piece oxidation film
Cathode is done, connects device by Fig. 1, constant current is with 0.018Acm-2Current density is reacted to the dissolution of anode Zn piece up to 98%, is closed
Power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；It will be made
Ce/ZIF-8, with 5 DEG C/min heating rate, rises to 500 DEG C of roasting 3h, obtains 2%Ce/ZnO photocatalysis after cooling in Muffle furnace
Agent.
Embodiment 3
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.25g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 1g is taken, anode, graphite flake are done in cleaning after removing Zn piece oxidation film
Cathode is done, connects device by Fig. 1, constant current is with 0.018Acm-2Current density is reacted to the dissolution of anode Zn piece up to 98%, is closed
Power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；It will be made
Ce/ZIF-8, with 5 DEG C/min heating rate, rises to 500 DEG C of roasting 3h, obtains 5%Ce/ZnO photocatalysis after cooling in Muffle furnace
Agent.
Embodiment 4
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.025g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 0.5g is taken, sun is done in cleaning after removing Zn piece surface film oxide
Pole, graphite flake do cathode, connect device by Fig. 1, constant current is with 0.018 Acm-2Current density reacts molten to anode Zn piece
Solution closes power supply up to 98%, takes out electrolyte filtering, and obtained solid is washed with deionized to neutrality, dry, obtains Ce/
ZIF-8；Obtained Ce/ZIF-8 is risen to 500 DEG C of roasting 3h, obtained 1% after cooling in Muffle furnace with 5 DEG C/min heating rate
Ce/ZnO photochemical catalyst.
Embodiment 5
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.05g, 2-methylimidazole 6.0g, stirring and dissolving；Zn piece 1g is taken, except anode is done in cleaning after Zn piece oxidation film, graphite flake is done
Cathode connects device by Fig. 1, and constant current is with 0.018 Acm-2Current density is reacted to the dissolution of anode Zn piece up to 98%, is closed
Power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；It will be made
Ce/ZIF-8, with 5 DEG C/min heating rate, rises to 500 DEG C of roasting 3h, obtains 1%Ce/ZnO photocatalysis after cooling in Muffle furnace
Agent.
Embodiment 6
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.05g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 1g is taken, anode, graphite flake are done in cleaning after removing Zn piece oxidation film
Cathode is done, connects device by Fig. 1, constant current is with 0.018Acm-2Current density is reacted to the dissolution of anode Zn piece up to 98%, is closed
Power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；It will be made
Ce/ZIF-8, with 5 DEG C/min heating rate, rises to 600 DEG C of roasting 3h, obtains 1%Ce/ZnO photocatalysis after cooling in Muffle furnace
Agent.
Embodiment 7
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.025g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 1g is taken, except anode, graphite flake are done in cleaning after Zn piece oxidation film
Cathode is done, connects device by Fig. 1, constant current is with 0.018Acm-2Current density is reacted to the dissolution of anode Zn piece up to 98%, is closed
Power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；It will be made
Ce/ZIF-8, with 5 DEG C/min heating rate, rises to 700 DEG C of roasting 3h, obtains 0.5%Ce/ZnO photocatalysis after cooling in Muffle furnace
Agent.
Embodiment 8
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.025g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 1g is taken, anode, graphite are done in cleaning after removing Zn piece oxidation film
Piece does cathode, connects device by Fig. 1, constant current is with 0.018Acm-2Current density is reacted to the dissolution of anode Zn piece up to 98%,
Power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；It will be made
Ce/ZIF-8, with 5 DEG C/min heating rate, rises to 500 DEG C of roasting 2h, obtains 0.5%Ce/ZnO photocatalysis after cooling in Muffle furnace
Agent.
Embodiment 9
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.1g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 1g is taken, anode, graphite flake are done in cleaning after removing Zn piece oxidation film
Cathode is done, connects device by Fig. 1, constant current is with 0.036Acm-2Current density is reacted to the dissolution of anode Zn piece up to 98%, is closed
Power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；It will be made
Ce/ZIF-8, with 5 DEG C/min heating rate, rises to 500 DEG C of roasting 3h, obtains 2%Ce/ZnO photocatalysis after cooling in Muffle furnace
Agent.
Embodiment 10
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.1g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 1g is taken, anode, graphite flake are done in cleaning after removing Zn piece oxidation film
Cathode is done, connects device by Fig. 1, constant current is with 0.06Acm-2Current density is reacted to the dissolution of anode Zn piece up to 98%, is closed
Power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；It will be made
Ce/ZIF-8, with 5 DEG C/min heating rate, rises to 500 DEG C of roasting 3h, obtains 2%Ce/ZnO photocatalysis after cooling in Muffle furnace
Agent.
Embodiment 11
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.025g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 1g is taken, anode, graphite are done in cleaning after removing Zn piece oxidation film
Piece does cathode, connects device by Fig. 1, constant current is with 0.018Acm-2Current density is reacted to the dissolution of anode Zn piece up to 98%,
Power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；It will be made
Ce/ZIF-8, with 5 DEG C/min heating rate, rises to 600 DEG C of roasting 3h, obtains 0.5%Ce/ZnO photocatalysis after cooling in Muffle furnace
Agent.
Embodiment 12
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.10g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 1g is taken, anode, graphite flake are done in cleaning after removing Zn piece oxidation film
Cathode is done, connects device by Fig. 1, constant current is with 0.018Acm-2Current density is reacted to the dissolution of anode Zn piece up to 98%, is closed
Power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；It will be made
Ce/ZIF-8, with 5 DEG C/min heating rate, rises to 600 DEG C of roasting 3h, obtains 2%Ce/ZnO photocatalysis after cooling in Muffle furnace
Agent.
Embodiment 13
Ionized water 50mL is removed, it is 1.0molL that KCl, which is added, and is configured to concentration-1Ce (NO is added in KCl solution3)3·
6H2O 0.00g, 2-methylimidazole 3.8g, stirring and dissolving；Zn piece 1g is taken, anode, graphite flake are done in cleaning after removing Zn piece oxidation film
Cathode is done, connects device by Fig. 1, constant current is with 0.018Acm-2Current density is reacted to the dissolution of anode Zn piece up to 98%, is closed
Power supply is closed, electrolyte filtering is taken out, obtained solid is washed with deionized to neutrality, it is dry, obtain Ce/ZIF-8；It will be made
Ce/ZIF-8, with 5 DEG C/min heating rate, rises to 600 DEG C of roasting 3h, obtains ZnO photocatalyst after cooling in Muffle furnace.
Catalytic performance test carries out (by taking methyl orange as an example, other degradation product methods are referring to this method) by the following method:
Take 50mL 10mgL-1Methyl orange solution in the light reaction pipe equipped with 50mg catalyst, and be protected from light at 25 DEG C
It stirs 30min and carries out dark treatment, reach adsorption-desorption balance, then stirred under the irradiation of 500W xenon lamp with lasting magnetic force
Photocatalytic degradation experiment is carried out under conditions of mixing, the methyl orange solution after taking 2mL to react at regular intervals, by needle type filtration
The absorbance of solution is measured after device filtering under the maximum absorption wavelength (464nm) of methyl orange.Using formula: D=(1-C/
C0(wherein D is the degradation rate of methyl orange, C to) × 100%0For the initial concentration of methyl orange, C is the concentration of methyl orange after light reaction)
Calculate the degradation rate of methyl orange, and with C/C0Time mapping probes into different materials to methyl orange as the degradation of time is imitated
Rate.
Take 50mL 10mgL-1Methylene blue solution in the light reaction pipe equipped with 50mg catalyst, and kept away at 25 DEG C
Light stirs 30min and carries out dark treatment, reaches adsorption-desorption balance, then under the irradiation of 500 W xenon lamps and lasting magnetic force
Photocatalytic degradation experiment is carried out under conditions of stirring, the methylene blue solution after taking 2mL to react at regular intervals, by pin type
The absorbance of solution is measured after filter filtering under the maximum absorption wavelength (660nm) of methylene blue.Using formula: D
=(1-C/C0(wherein D is the degradation rate of methylene blue, C to) × 100%0For the initial concentration of methylene blue, C is Asia after light reaction
The concentration of methyl blue) calculate the degradation rate of methylene blue, and with C/C0Time mapping, probes into different materials to methylene
Indigo plant with the time degradation efficiency.
Fig. 4 is embodiment 6,13 gained of embodiment 11,12 gained cerium dopping photocatalyst of zinc oxide of embodiment and embodiment
Photocatalyst of zinc oxide declines the curve of solution methyl orange in above-mentioned illumination.As shown in Figure 4: the zinc oxide photocatalysis of different cerium contents
Agent all has certain photocatalysis performance, and wherein 1%Ce/ZnO performance is more excellent.
Fig. 5 is 6 gained cerium dopping photocatalyst of zinc oxide of embodiment in above-mentioned illumination decline solution methyl orange and methylene blue
Curve.As shown in Figure 5: cerium dopping photocatalyst of zinc oxide all has preferable catalytic degradation to methyl orange and methylene blue
Can, wherein the degradation rate to methylene blue is obviously very fast.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of cerium dopping photocatalyst of zinc oxide, comprising the following steps:
Using zinc as anode, inert electrode is cathode, to contain conductive salt, Ce3+With the aqueous solution of 2-methylimidazole be conduction liquid into
Row electrolysis, obtains Ce/ZIF-8；
The Ce/ZIF-8 is roasted, cerium dopping photocatalyst of zinc oxide is obtained.
2. preparation method according to claim 1, which is characterized in that the meltage of the zinc and mole of 2-methylimidazole
Than for 1:2~5.
3. preparation method according to claim 1, which is characterized in that the Ce3+Molar ratio with the meltage of zinc is 0.1
~10:1000.
4. preparation method according to claim 1, which is characterized in that the inert electrode is graphite electrode or glass carbon electricity
Pole.
5. preparation method according to claim 1, which is characterized in that the conductive salt is potassium chloride, sodium chloride, potassium nitrate
Or sodium nitrate.
6. preparation method according to claim 5, which is characterized in that the concentration of conductive salt is 0.001 in the electrolyte
~2mol/L.
7. preparation method according to claim 1, which is characterized in that the current density of the electrolysis be 0.0005~
0.07A·cm-2。
8. preparation method according to claim 1, which is characterized in that the temperature of the roasting is 450~700 DEG C, the time
For 2~4h.
9. the cerium dopping photocatalyst of zinc oxide that preparation method described in claim 1~8 any one is prepared.
10. cerium dopping photocatalyst of zinc oxide according to claim 9, which is characterized in that the cerium dopping zinc oxide light
Cerium in Catalysts accounts for the 0.5~5% of catalyst gross mass.
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| CN111068646A (en) * | 2019-12-18 | 2020-04-28 | 中国科学院青岛生物能源与过程研究所 | CO (carbon monoxide)2Preparation method of zinc-tin oxide catalyst for preparing formic acid by electrochemical reduction |
| CN111118532A (en) * | 2019-11-21 | 2020-05-08 | 华南师范大学 | Method for preparing zinc gluconate based on photo-enhanced fruit fuel cell |
| CN114574896A (en) * | 2022-03-18 | 2022-06-03 | 南京师范大学 | Carbon cloth loaded Ce-CoO oxygen evolution electrocatalyst and preparation method thereof |
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2019
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111118532A (en) * | 2019-11-21 | 2020-05-08 | 华南师范大学 | Method for preparing zinc gluconate based on photo-enhanced fruit fuel cell |
| CN111118532B (en) * | 2019-11-21 | 2021-12-10 | 华南师范大学 | Method for preparing zinc gluconate based on photo-enhanced fruit fuel cell |
| CN111068646A (en) * | 2019-12-18 | 2020-04-28 | 中国科学院青岛生物能源与过程研究所 | CO (carbon monoxide)2Preparation method of zinc-tin oxide catalyst for preparing formic acid by electrochemical reduction |
| CN111068646B (en) * | 2019-12-18 | 2022-08-16 | 中国科学院青岛生物能源与过程研究所 | CO (carbon monoxide) 2 Preparation method of zinc-tin oxide catalyst for preparing formic acid by electrochemical reduction |
| CN114574896A (en) * | 2022-03-18 | 2022-06-03 | 南京师范大学 | Carbon cloth loaded Ce-CoO oxygen evolution electrocatalyst and preparation method thereof |
| CN114574896B (en) * | 2022-03-18 | 2023-01-31 | 南京师范大学 | Carbon cloth loaded Ce-CoO oxygen evolution electrocatalyst and preparation method thereof |
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