CN105642295B - A kind of porous composite photo-catalyst and its application - Google Patents
A kind of porous composite photo-catalyst and its application Download PDFInfo
- Publication number
- CN105642295B CN105642295B CN201610043794.9A CN201610043794A CN105642295B CN 105642295 B CN105642295 B CN 105642295B CN 201610043794 A CN201610043794 A CN 201610043794A CN 105642295 B CN105642295 B CN 105642295B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- pollen pini
- composite photo
- znco
- porous composite
- 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.)
- Expired - Fee Related
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 229910001676 gahnite Inorganic materials 0.000 claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 19
- 229910003119 ZnCo2O4 Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 150000003751 zinc Chemical class 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 159000000013 aluminium salts Chemical class 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 239000006193 liquid solution Substances 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000000975 dye Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 229920002994 synthetic fiber Polymers 0.000 abstract description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
-
- B01J35/39—
-
- B01J35/613—
-
- B01J35/635—
-
- B01J35/647—
-
- 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
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a kind of porous composite photo-catalyst and its applications.The present invention prepares the photochemical catalyst ZnCo of porous structure using completely new technique using pollen pini as innovative raw material2O4/ZnO/ZnAl2O4.The preparation method of the product of the invention is simple, efficient, at low cost, easy to operate, pollution is small.The catalyst of preparation under classifying porous structure, excellent absorption property and simulated solar irradiation to organic pollution with good catalytic degradation activity, there is higher catalytic activity to organic dyestuff in sewage, degradation rate can reach 88% in 120min.The style and type of abundant porous photocatalytic agent synthetic material are brought newer theory by the proposition of this method to the preparation of photochemical catalyst.
Description
Technical field
Micro-nano composite photo-catalyst in terms of the present invention relates to a kind of sewage disposal, and in particular to a kind of pollen pini is made a living
The ZnCo of object template2O4/ZnO/ZnAl2O4Composite photo-catalyst and its application in terms of photocatalysis degradation organic contaminant.
Background technology
Energy shortage and environmental pollution are two main problems that entire human society is faced, and make full use of nature
Green energy resource becomes the key to solve the problem.Solar energy, should due to the advantages that its is inexhaustible, clean pollution-free, renewable
It is fully utilized to reduce dependence of the mankind to other non-renewable energy resources.The conversion application of solar energy is mainly big comprising four
Aspect is respectively：Solar cell, photocatalytic water, photoreduction carbon dioxide and photocatalysis degradation organic contaminant.Wherein, light
Catalysis technique due to not generating secondary pollution, can fully degraded organic pollution become research hotspot in recent years.Traditional
TiO2Photochemical catalyst is due to its wider energy gap（Eg=3.2 eV）Ultraviolet light can only be responded（About the 5% of sunlight）.For
Realize making full use of for solar energy, structure has low energy gap width structure, and the photochemical catalyst for being capable of responding to visible light has weight
Want meaning.
The ZnCo of spinel structure2O4Not only there is higher catalytic activity, good chemical stability, preparation condition
It is simple mild, and relatively narrow energy gap make its can with responding to visible light, so as to effectively improve the efficiency of light energy utilization.But
ZnCo2O4The specific surface area of nano-powder is smaller, it is easy reunite, photo-generate electron-hole recombination rate it is fast.Biological mould in nature
Plate can assign prepared photochemical catalyst porous structure, so as to improve its catalytic activity.In addition, stratiform double-layered hydroxides
（Layer double hydroxides, LDHs）Special lamellar structure imparts it and is widely applied range, such as absorption,
Photocatalysis, ultracapacitor etc..Moreover, the metal ion of each layer of LDHs is all atom level dispersion, LDHs and semiconductor are answered
It closes, heat-treated products can realize that atom level is compound with semiconductor, so as to fulfill efficiently separating for photo-generate electron-hole, into one
Step improves the photocatalytic activity of semiconductor.
Invention content
For problems of the prior art, the present invention provides a kind of porous composite photo-catalyst and its applications.This
Invention is prepared for ZnAl double-layered hydroxides using pollen template using hydro-thermal method（ZnAl-LDHs）/ZnCo2O4, then pass through
Subsequent calcination handles to have obtained ZnCo2O4/ZnO/ZnAl2O4Composite photo-catalyst, the catalyst remain the shape of pollen template
Looks, porous structure are conducive to improve photocatalysis efficiency.In addition, ZnCo2O4、ZnO、ZnAl2O4Three realizes answering for atomic size
It closes, is efficiently separated photo-generate electron-hole, so as to effectively improve the efficiency of light energy utilization and photocatalysis efficiency.
The present invention uses following technical scheme：
A kind of porous composite photo-catalyst, which is characterized in that it is prepared by following methods：
（1）Pretreatment：Pollen pini is put into absolute ethyl alcohol, magnetic agitation, which is impregnated, removes impurity, will then by filtering
The pollen pini of gained is placed in drying in drying box, obtains pretreatment pollen pini；
（2）Dipping and heat treatment：Soluble zinc salt and cobalt salt are made into a concentration of 0.05mol/L's according to certain mol proportion
Precursor solution A；Pretreated pollen pini is put into precursor solution A and is sufficiently impregnated, is placed in drying box after filtering
It is dry；The pollen pini after impregnation drying is taken, is warming up to 700 DEG C in air, calcines 1h, last cooled to room temperature is made
Remain the ZnCo of pollen template pattern2O4Photochemical catalyst；
（3）The urea of the soluble zinc salt of certain mol proportion, aluminium salt and 0.024mol-0.043mol are dissolved in 40mL distillations
In water, it is made into mixed solution B；Then by step（2）The sample 0.4g ultrasonic disperses of gained are used in combination in above-mentioned mixed solution B
Mixed liquor is transferred to appropriate pH by lye；
（4）By step（3）Mixture be transferred to 50mL the reaction kettle of polytetrafluoroethyllining lining in, carry out hydro-thermal it is anti-
Should, after reaction, gained is precipitated and is filtered, washed respectively for several times with distilled water and absolute ethyl alcohol, be finally putting into drying box into
Row drying；
（5）Take step（4）It is warming up to 700 DEG C by dried sediment in air, and 2h is calcined in heat preservation, last cold
But to room temperature, ZnCo is obtained2O4/ZnO/ZnAl2O4Composite photo-catalyst.
The step（1）The mass volume ratio of middle pollen pini and absolute ethyl alcohol is 1:10, soaking time 12h, dry temperature
Spend is 40 DEG C.
The step（2）Middle soluble zinc salt and cobalt salt are respectively zinc nitrate and cobalt nitrate, molar ratio 1:4；Dipping
When, the mass volume ratio of pollen pini and precursor solution is 1:10, dip time 5h.
The step（3）Middle soluble zinc salt and aluminium salt are respectively zinc nitrate and aluminum nitrate, and molar ratio is（1~3）：1,
Lye used is ammonium hydroxide, and it is 8.5 to adjust to pH.
The step（4）The temperature of middle hydro-thermal reaction is 120 DEG C, time 10h, and drying temperature is 60 DEG C.
The application of above-mentioned porous composite catalyst, which is characterized in that waste water from dyestuff is handled available for catalytic degradation, to dirt
Organic dyestuff has higher catalytic activity in water, and degradation rate can reach 88% in 120min.
The beneficial effects of the invention are as follows：The present invention is prepared using pollen pini as innovative raw material using completely new technique
The photochemical catalyst of porous structure.The preparation method of the product of the invention is simple, efficient, at low cost, easy to operate, pollution is small.It prepares
Catalyst under classifying porous structure, excellent absorption property and simulated solar irradiation to organic pollution with good
Catalytic degradation activity.The it is proposed of this method is by the style and type of abundant porous photocatalytic agent synthetic material, to photochemical catalyst
Preparation brings newer theory.
Description of the drawings
Fig. 1 is different embodiment photochemical catalysts under visible light to Congo red degradation figure.
Fig. 2 is the XRD spectrum of the made photochemical catalysts of embodiment 1-3 in the present invention.
Fig. 3 is that the SEM of biological template pollen pini used and made photochemical catalyst in the present invention schemes, and in figure, (a)-(b) is pine
The low high power SEM figures of pollen；(c)-(d) is ZnCo made from embodiment 12O4The low high power SEM figures of photochemical catalyst, illustration is corresponding
EDS power spectrums；(e)-(g) is ZnCo made from embodiment 32O4/ZnO/ZnAl2O4The low high power SEM figures of composite photo-catalyst；
(h) it is the EDS power spectrums of corresponding embodiment 3.
Fig. 4 is the N that photochemical catalyst is made in the embodiment of the present invention 32Adsorption/desorption curve and respective aperture distribution curve.In figure
(a) it is ZnCo2O4/ZnO/ZnAl2O4The N of composite photo-catalyst2Adsorption/desorption curve, (b) are corresponding pore size distribution curve.
Specific embodiment
With reference to embodiments, the forgoing and additional technical features and advantages are described in more detail.
Embodiment 1
A kind of porous composite photo-catalyst, preparation method are as follows：
（1）10g pollen pinis are immersed in 100 mL absolute ethyl alcohols, 12 h of magnetic agitation, remove the impurity in pollen pini,
40 DEG C of 10 h of drying of drying box are put into after filtering, complete the pretreatment of pollen pini；
（2）According to Zn2+With Co3+Molar ratio is 1：4 compound concentrations are the precursor solution A of 0.05mol/L；5g is taken to locate in advance
Pollen pini after reason is put into the precursor solution A of the above-mentioned preparations of 50 mL, 5 h is impregnated, by the pollen pini mistake after impregnation
Filter, is put into 50 DEG C of 8 h of drying of drying box.Pollen pini after drying is put into corundum crucible, is placed in Muffle furnace in air gas
700 DEG C are warming up under atmosphere, then heat preservation 1 h of calcining is down to room temperature in a manner of natural cooling, obtains ZnCo2O4Photochemical catalyst.
（3）1.62 mmol zinc nitrates, 1.62 mmol aluminum nitrates and 0.024 mol urea are added to the distillation of 40 mL
Mixed solution B is made into water, weighs 0.4 g ZnCo obtained2O4Photochemical catalyst is placed in above-mentioned mixed solution B, and uses ammonium hydroxide
The pH of mixed solution is adjusted to 8.5 or so, then by 30 min of mixed solution ultrasonic disperse, makes ZnCo2O4Photochemical catalyst with it is molten
Liquid is sufficiently mixed.
（4）Mixed solution after ultrasonic disperse is transferred in the reaction kettle of the polytetrafluoroethyllining lining of 50mL, at 120 DEG C
Lower reaction 10h after reaction, gained is precipitated and is filtered, washed respectively for several times with distilled water and absolute ethyl alcohol, until filtrate pH
It is 7, is subsequently placed into 60 DEG C of 6 h of drying of drying box.
（5）Finally dried sediment is put into corundum crucible, is placed in Muffle furnace and is warming up in air atmosphere
700 DEG C, heat preservation calcining 2h is finally cooled to room temperature, takes out sample, classifying porous ZnCo is made2O4/ZnO/ZnAl2O4Light is urged
Agent.
Embodiment 2
A kind of porous composite photo-catalyst, preparation method are as follows：
（1）10g pollen pinis are immersed in 100 mL absolute ethyl alcohols, 12 h of magnetic agitation, remove the impurity in pollen pini,
40 DEG C of 10 h of drying of drying box are put into after filtering, complete the pretreatment of pollen pini；
（2）According to Zn2+With Co3+Molar ratio is the precursor solution A that 1/4 compound concentration is 0.05mol/L；5g is taken to locate in advance
Pollen pini after reason is put into the precursor solution A of the above-mentioned preparations of 50 mL, 5 h is impregnated, by the pollen pini mistake after impregnation
Filter, is put into 50 DEG C of 8 h of drying of drying box.Pollen pini after drying is put into corundum crucible, is placed in Muffle furnace in air gas
700 DEG C are warming up under atmosphere, then heat preservation 1 h of calcining is down to room temperature in a manner of natural cooling, obtains ZnCo2O4Photochemical catalyst.
（3）3.24 mmol zinc nitrates, 1.62 mmol aluminum nitrates and 0.034 mol urea are added to the distillation of 40 mL
Mixed solution B is made into water, weighs 0.4 g ZnCo obtained2O4Photochemical catalyst is placed in above-mentioned mixed solution B, and uses ammonium hydroxide
The pH of mixed solution is adjusted to 8.5 or so, then by 30 min of mixed solution ultrasonic disperse, makes ZnCo2O4Photochemical catalyst with it is molten
Liquid is sufficiently mixed.
（4）Mixed solution after ultrasonic disperse is transferred in the reaction kettle of the polytetrafluoroethyllining lining of 50mL, at 120 DEG C
Lower reaction 10h after reaction, gained is precipitated and is filtered, washed respectively for several times with distilled water and absolute ethyl alcohol, until filtrate pH
It is 7, is subsequently placed into 60 DEG C of 6 h of drying of drying box.
（5）Finally dried sediment is put into corundum crucible, is placed in Muffle furnace and is warming up in air atmosphere
700 DEG C, heat preservation calcining 2h is finally cooled to room temperature, takes out sample, classifying porous ZnCo is made2O4/ZnO/ZnAl2O4Light is urged
Agent.
Embodiment 3
A kind of porous composite photo-catalyst, preparation method are as follows：
（1）10g pollen pinis are immersed in 100 mL absolute ethyl alcohols, 12 h of magnetic agitation, remove the impurity in pollen pini,
40 DEG C of 10 h of drying of drying box are put into after filtering, complete the pretreatment of pollen pini；
（2）According to Zn2+With Co3+Molar ratio is the precursor solution A that 1/4 compound concentration is 0.05mol/L；5g is taken to locate in advance
Pollen pini after reason is put into the precursor solution A of the above-mentioned preparations of 50 mL, 5 h is impregnated, by the pollen pini mistake after impregnation
Filter, is put into 50 DEG C of 8 h of drying of drying box.Pollen pini after drying is put into corundum crucible, is placed in Muffle furnace in air gas
700 DEG C are warming up under atmosphere, then heat preservation 1 h of calcining is down to room temperature in a manner of natural cooling, obtains ZnCo2O4Photochemical catalyst.
（3）4.86 mmol zinc nitrates, 1.62 mmol aluminum nitrates and 0.043 mol urea are added to the distillation of 40 mL
Mixed solution B is made into water, weighs 0.4 g ZnCo obtained2O4Photochemical catalyst is placed in above-mentioned mixed solution B, and uses ammonium hydroxide
The pH of mixed solution is adjusted to 8.5 or so, then by 30 min of mixed solution ultrasonic disperse, makes ZnCo2O4Photochemical catalyst with it is molten
Liquid is sufficiently mixed.
（4）Mixed solution after ultrasonic disperse is transferred in the reaction kettle of the polytetrafluoroethyllining lining of 50mL, at 120 DEG C
Lower reaction 10h after reaction, gained is precipitated and is filtered, washed respectively for several times with distilled water and absolute ethyl alcohol, until filtrate pH
It is 7, is subsequently placed into 60 DEG C of 6 h of drying of drying box.
（5）Finally dried sediment is put into corundum crucible, is placed in Muffle furnace and is warming up in air atmosphere
700 DEG C, heat preservation calcining 2h is finally cooled to room temperature, takes out sample, classifying porous ZnCo is made2O4/ZnO/ZnAl2O4Light is urged
Agent.
Test case
Photochemical catalyst is being simulated too in the analogies verification present invention using Congo red solution as dirty organic pollutants
Catalytic effect under sunlight, method are：50mg photochemical catalysts are put into the Congo red solution of 80mL 100mg/L, first black
30min is placed under dark situation, until adsorption equilibrium.After the completion of absorption, light-catalyzed reaction, photocatalysis are carried out under the irradiation of 500W xenon lamps
In the process, the Congo red solution of 5mL is taken out as sample every 10min, 3min is centrifuged under 4000 r/min, with light splitting light
Degree measurement tries the absorbance of Congo red solution under different catalysis times and is converted into concentration, to characterize degradation effect, concrete outcome
See Fig. 1.As seen from Figure 1, there is efficient catalysis to Congo red under visible light using the photochemical catalyst prepared by the invention
Effect.All kinds of catalyst are followed successively by the catalytic efficiency of congo red from high to low：Embodiment 3>Embodiment 2>Embodiment 1.
The especially degradation rate in 120min of embodiment 3 reaches more than 88%.Illustrate photochemical catalyst produced by the present invention to Congo red in sewage
Dyestuff has higher catalytic activity, the efficient process available for waste water from dyestuff.
The present invention also has detected the ZnCo of the made loads of the ZnAl-CLDH with different Zn/Al ratios of embodiment 1-32O4
The XRD diffracting spectrums of composite photo-catalyst.As a result see Fig. 2.By the XRD spectrum of Fig. 2 as it can be seen that in addition to ZnCo2O4Feature spread out
It penetrates outside peak, also ZnO and ZnAl2O4Diffraction maximum, and with the increase of Zn/Al ratios, ZnO and ZnAl2O4Diffraction maximum it is more next
It is more apparent.
Divide in addition, the present invention has done original pollen pini template and synthesized photochemical catalyst the corresponding power spectrum of SEM scanner unis
Analysis, is shown in Fig. 3.As seen from Figure 3, the porous microsphere structure that pollen pini is made of two parts of ontology and air bag, microsphere diameter are about
40 μm, as shown in Fig. 3 (a), (b), this structure provides feasibility for the preparation of porous photocatalytic agent.It can by Fig. 3 (c), (d)
To see the ZnCo that pollen pini is utilized to be prepared as biological template2O4Photochemical catalyst remains the microscopic appearance of pollen pini.By power spectrum point
Analysis shows that prepared sample mainly contains tetra- kinds of elements of Zn, Co, O, C, with reference to XRD analysis, show using pollen pini template into
Work(prepares ZnCo2O4.By Fig. 3 (e), (f), (g) it can be seen that ZnCo2O4/ZnO/ZnAl2O4Composite photo-catalyst equally retains
The micro-sphere structure of pollen pini, and in ZnCo2O4The microsphere surface successful growth substance of lamellar.By Fig. 3 (h) energy spectrum analysis
It understands that sample mainly contains five kinds of elements of Zn, Al, Co, O, C, with reference to XRD analysis, shows successfully to prepare using pollen pini template
Go out ZnCo2O4/ZnO/ZnAl2O4Composite photo-catalyst.
The present invention has studied the ZnCo prepared by embodiment 32O4/ZnO/ZnAl2O4The N of composite photo-catalyst2Adsorption/desorption
Curve and pore-size distribution are studied, and the results are shown in Figure 4.By Fig. 4 (a) it can be seen that ZnCo2O4/ZnO/ZnAl2O4It is compound
The N of photochemical catalyst2There are apparent hysteresis loops in higher-pressure region for adsorption/desorption curve, belong to V-type thermoisopleth, show exist in sample
It is a certain number of mesoporous；Pore size distribution curve in Fig. 4 (b) can be seen that other than mesoporous, and one is also included in sample
The macropore of fixed number amount illustrates to be successfully prepared the ZnCo containing the abundant mesoporous graded porous structure with macropore2O4/ZnO/
ZnAl2O4Composite photo-catalyst.The sample specific surface area is 48 m2/ g, total pore volume are 0.52 cm3/ g, average pore size are
43.75nm。
Claims (6)
1. a kind of porous composite photo-catalyst, which is characterized in that it is prepared by following methods：
（1）Pretreatment：Pollen pini is put into absolute ethyl alcohol, magnetic agitation, which is impregnated, removes impurity, then by filtering, by gained
Pollen pini be placed in drying box dry, obtain pretreatment pollen pini；
（2）Dipping and heat treatment：According to molar ratio it is 1 by soluble zinc salt and cobalt salt:Before 4 are made into a concentration of 0.05mol/L
Drive liquid solution A；Pretreated pollen pini is put into precursor solution A and is sufficiently impregnated, is placed in drying box and does after filtering
It is dry；The pollen pini after impregnation drying is taken, is warming up to 700 DEG C in air, calcines 1h, last cooled to room temperature is made and protects
The ZnCo of pollen template pattern is stayed2O4Photochemical catalyst；
（3）By soluble zinc salt and aluminium salt according to molar ratio（1~3）：The urea of 1 and 0.024mol-0.043mol is dissolved in 40mL steamings
In distilled water, it is made into mixed solution B；Then by step（2）The sample 0.4g ultrasonic disperses of gained in above-mentioned mixed solution B, and
Mixed liquor is transferred to appropriate pH with lye；
（4）By step（3）Mixture be transferred to 50mL the reaction kettle of polytetrafluoroethyllining lining in, carry out hydro-thermal reaction, instead
After answering, gained is precipitated and is filtered, washed respectively for several times with distilled water and absolute ethyl alcohol, be finally putting into drying box and done
It is dry；
（5）Take step（4）It, is warming up to 700 DEG C by dried sediment in air, and heat preservation calcining 2h is finally cooled to
Room temperature obtains ZnCo2O4/ZnO/ZnAl2O4Composite photo-catalyst.
2. porous composite photo-catalyst according to claim 1, which is characterized in that the step（1）Middle pollen pini and nothing
The mass volume ratio of water-ethanol is 1g:10ml, soaking time 12h, drying temperature are 40 DEG C.
3. porous composite photo-catalyst according to claim 1, which is characterized in that the step（2）Middle soluble zinc salt
It is respectively zinc nitrate and cobalt nitrate with cobalt salt；During dipping, the mass volume ratio of pollen pini and precursor solution is 1g:10ml, leaching
The stain time is 5h.
4. porous composite photo-catalyst according to claim 1, which is characterized in that the step（3）Middle soluble zinc salt
It is respectively zinc nitrate and aluminum nitrate with aluminium salt, lye used is ammonium hydroxide, and it is 8.5 to adjust to pH.
5. porous composite photo-catalyst according to claim 1, which is characterized in that the step（4）Middle hydro-thermal reaction
Temperature is 120 DEG C, time 10h, and drying temperature is 60 DEG C.
6. a kind of application of porous composite photo-catalyst described in claim 1, which is characterized in that contaminated for catalytic degradation processing
Expect waste water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610043794.9A CN105642295B (en) | 2016-01-22 | 2016-01-22 | A kind of porous composite photo-catalyst and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610043794.9A CN105642295B (en) | 2016-01-22 | 2016-01-22 | A kind of porous composite photo-catalyst and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105642295A CN105642295A (en) | 2016-06-08 |
| CN105642295B true CN105642295B (en) | 2018-06-29 |
Family
ID=56487789
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610043794.9A Expired - Fee Related CN105642295B (en) | 2016-01-22 | 2016-01-22 | A kind of porous composite photo-catalyst and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105642295B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108033493A (en) * | 2018-01-22 | 2018-05-15 | 中北大学 | Porous ZnCo2O4The synthetic method of nanometer sheet and pseudo-cubic micro nano structure |
| CN108864461B (en) * | 2018-07-03 | 2021-06-01 | 蔡菁菁 | Automobile glass material capable of efficiently adsorbing and degrading formaldehyde and preparation method thereof |
| CN109126802B (en) * | 2018-09-19 | 2021-02-09 | 山东科技大学 | Two-dimensional porous Co3O4Preparation method of-ZnO composite nanosheet |
| CN109052453B (en) * | 2018-10-25 | 2020-11-06 | 河南理工大学 | ZnCo2O4/ZnO heterostructure composite gas sensitive material and preparation method thereof |
| CN111644188A (en) * | 2020-02-29 | 2020-09-11 | 浙江工业大学 | ZnCo2O4/g-C3N4Composite material, preparation and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103101972A (en) * | 2012-12-04 | 2013-05-15 | 西安交通大学 | Preparation method of three-dimensional mesoporous titanium dioxide photocatalyst by means of biological template method |
| CN103101971A (en) * | 2011-11-11 | 2013-05-15 | 新疆大学 | Green biomimetic preparation method of titanium dioxide nano material |
| CN103420431A (en) * | 2013-07-31 | 2013-12-04 | 上海理工大学 | Preparation method ofzinc cobaltatenanometer material doped with zinc oxide |
-
2016
- 2016-01-22 CN CN201610043794.9A patent/CN105642295B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103101971A (en) * | 2011-11-11 | 2013-05-15 | 新疆大学 | Green biomimetic preparation method of titanium dioxide nano material |
| CN103101972A (en) * | 2012-12-04 | 2013-05-15 | 西安交通大学 | Preparation method of three-dimensional mesoporous titanium dioxide photocatalyst by means of biological template method |
| CN103420431A (en) * | 2013-07-31 | 2013-12-04 | 上海理工大学 | Preparation method ofzinc cobaltatenanometer material doped with zinc oxide |
Non-Patent Citations (2)
| Title |
|---|
| K. Thirunavukkarasu，et al..The role of surface Zn2+ ions in the transesterification of vegetable oils over ZnO supported on Al2O3 and Fe2O3†.《Catalysis Science ＆ Technology》.2014,851-860. * |
| Mixed valence Zn–Co-layered double hydroxides and their exfoliated nanosheets with electrode functionality;Myong A Woo，et al.;《Journal of Materials Chemistry》;20111231;第21卷;4286-4292 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105642295A (en) | 2016-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105642295B (en) | A kind of porous composite photo-catalyst and its application | |
| CN104128184B (en) | A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof | |
| CN106111174A (en) | G C3N4/ kaolinite composite photo-catalyst and preparation method thereof | |
| CN107159295A (en) | A kind of inverse opal materials derived of visible light photocatalytic degradation of organic pollutants and preparation method thereof | |
| CN107497456B (en) | Preparation method and application of layered bismuth oxychloride visible-light-driven photocatalyst | |
| CN106944074B (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| CN105148964B (en) | A kind of three-dimensional redox graphene Mn3O4/MnCO3Nano composite material and preparation method thereof | |
| CN106006720B (en) | One kind prepares SnS/SnS2The method of heterojunction material and application | |
| CN106622293B (en) | A kind of H-TiO2/CdS/Cu2-xThe preparation method of S nanobelt | |
| CN105642364A (en) | Compound photocatalyst and preparing method and application thereof | |
| CN107200350B (en) | TiO is prepared by template of corn stigma2The method of nano-tube array catalysis material | |
| CN104190406A (en) | C/Bi2MoO6 composite photocatalyst and preparation method thereof | |
| CN112844484B (en) | Boron nitride quantum dot/porous metal organic framework composite photocatalytic material and preparation method and application thereof | |
| CN112023972B (en) | Composite photocatalytic material and preparation method and application thereof | |
| CN103111313A (en) | Preparation method of burred BiOI/ZnO microspheres | |
| CN105642275A (en) | CeO2/Bi2WO6/MgAl-LDH composite photo-catalyst and preparation method and application thereof | |
| CN107442139A (en) | Sheet Z-type SnS for efficient degradation gentian violet2/Bi2MoO6The preparation method of heterojunction photocatalysis material | |
| CN105771962A (en) | Near-infrared response carbon quantum dots/Bi2MoO6 photocatalyst and preparing method thereof | |
| CN105664988B (en) | A kind of (BiO)2CO3/ C composite photo-catalysts and its application | |
| CN110479230A (en) | TiO2The carbon-based photo-thermal microreactor of self-supporting suspended biological matter and preparation method and application with photocatalytic activity of load | |
| CN107362792A (en) | A kind of preparation method of strontium titanates/niobic acid tin composite nano materials | |
| CN113976164A (en) | Preparation method of hydrogen-producing graphite-phase carbon nitride photocatalyst | |
| CN112892607A (en) | Stable ternary composite material for preparing hydrogen by photocatalytic water decomposition and preparation method thereof | |
| CN107597093A (en) | A kind of nano-particles self assemble Chinese herbaceous peony shape La3+Adulterate ZnO and its preparation method and application | |
| CN109126829A (en) | A kind of 3-D heterojunction structure CdS-MoS2The preparation method of composite granule |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180629 Termination date: 20210122 |