CN107442142A - AgBr/ZVO catalyst and its preparation method and purposes with visible light catalysis activity - Google Patents
AgBr/ZVO catalyst and its preparation method and purposes with visible light catalysis activity Download PDFInfo
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- CN107442142A CN107442142A CN201710795072.3A CN201710795072A CN107442142A CN 107442142 A CN107442142 A CN 107442142A CN 201710795072 A CN201710795072 A CN 201710795072A CN 107442142 A CN107442142 A CN 107442142A
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- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000000694 effects Effects 0.000 title abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 47
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 35
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- 229910019501 NaVO3 Inorganic materials 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 5
- 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 description 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004042 decolorization Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001125671 Eretmochelys imbricata Species 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- -1 zinc vanadic acid salt Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- 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—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- 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
Abstract
The invention belongs to photocatalysis field, and in particular to a kind of AgBr/Zn3(OH)2V2O7·2H2O composite catalysts and preparation method thereof, this method use pyrovanadic acid zinc (Zn3(OH)2V2O7·2H2O, write a Chinese character in simplified form into ZVO) method of compound narrow band gap silver bromide (AgBr), the AgBr/ZVO composite catalysts of different quality ratio are prepared for by hydro-thermal and two steps of precipitation.The composite catalyst improves the visible light catalysis activity of pyrovanadic acid zinc to a certain extent, further improves photocatalysis efficiency.The invention discloses its preparation method.
Description
Technical field
The present invention relates to the composite catalyst with visible light catalysis activity, more particularly to AgBr/ZVO composite catalysts.
Background technology
As industrial technology is fast-developing, global environmental pollution and shortage of resources problem are increasingly serious.Physical absorption, change
Learn oxidation, these traditional pollutant abatement technologies such as biodegradation often because energy consumption is excessive, cost is too high, be also easy to produce secondary pollution with
And reason can not meet the needs of current to contaminant degradation is not thorough etc..Therefore, there is an urgent need to find or develop by people
A kind of green, the technology of energy-conservation solve resource and environment two fold problem simultaneously.Photocatalysis technology is a kind of in the energy and environment neck
There is the green technology of important application prospect in domain simultaneously, and research and develop becomes the field with preparing efficient visible light catalytic material
Study hotspot.
1972, two scientists of Fujishima and Honda study first found N-type semiconductor TiO2Electrode is ultraviolet
Under light can photodissociation aquatic products hydrogen, started multiphase photocatalysis research New Times and this new field of conductor photocatalysis.
1976, Carey etc. utilized TiO2The chlorine being stripped of under ultraviolet light in Polychlorinated biphenyls, that has widened photocatalysis technology applies model
Enclose, a new approaches are provided for the oxidation Decomposition of organic matter.This series of final extensive concern for causing people of discovery,
Application study of the photocatalysis technology in fields such as environment also develops rapidly.
The pyrovanadic acid zinc vanadic acid salt type material important as one of which, there is special porous framework structure, be a kind of
Potential catalysis material.But pyrovanadic acid zinc is due to greater band gap, relatively low to sun light utilization efficiency, limit in practice should
With, and the research being modified at present to its visible light catalytic is also fewer.Silver bromide is as a kind of semiconductor of narrow band gap, in theory
With very high Photocatalytic oxidation activity.Therefore, the present invention is compound by silver bromide and pyrovanadic acid zinc, and the light for improving pyrovanadic acid zinc is urged
Change activity, prepare the composite catalyst of novel visible response.
The content of the invention
It is an object of the invention to provide the good AgBr/ZVO composite catalysts of a kind of high catalytic activity and chemical stability and
Preparation method and use.
Technical scheme is as follows：
A kind of AgBr/ZVO composite catalysts, it is characterized in that preparing the compound difference of pyrovanadic acid zinc using hydro-thermal and two steps of precipitation
Ratio AgBr composite catalyst, described AgBr and ZVO mass ratioes are 0.01: 1-1.5: 1.
A kind of preparation method of above-mentioned AgBr/ZVO catalyst, it is characterized in that comprising the following steps：
Step 1, by Zn: V=3: 2 the ratio between the amount of material, weigh a certain amount of Zn (NO3)2·6H2O and NaVO3·2H2O
It is dissolved in respectively in distilled water, by NaVO3After solution ultrasonic disperse, Zn (NO are slowly added to while stirring3)2In solution, continue magnetic force
Stirring obtains precursor liquid；
Step 2, the pH to 6-10 with gained precursor liquid in concentrated ammonia liquor regulating step 1, stir, are transferred to reactor
In, good seal；
Step 3, by precursor liquid in step 2 reactor at 70-160 DEG C hydro-thermal 2-20h；
Step 4, after step 3 reactor naturally cools to room temperature, filtering, with distillation water washing, drying, produce pyrovanadic acid
Zinc；
Step 5, take pyrovanadic acid zinc in step 4 to add in distilled water, magnetic agitation carried out after ultrasonic disperse, thereto by
It is added dropwise to the AgNO that concentration is 0.01mol/L3Solution, lucifuge stirring；
Step 6, it is added dropwise in mixed liquor into step 5 and AgNO3The isometric 0.01mol/L NaBr solution of solution,
Continue lucifuge stirring；
Step 7, after step 6 reaction terminate after, sediment is filtered, with distillation water washing, drying, produce AgBr/ZVO and answer
Close catalyst.
Application of the above-mentioned AgBr/ZVO composite catalysts in photocatalytic degradation organic matter.
The present invention proposes one kind with Zn (NO3)2·6H2O、NaVO3·2H2O、AgNO3It is that AgBr/ is made in raw material with NaBr
ZVO composite photo-catalysts and its simple synthetic method.
The Photocatalytic Degradation Property of AgBr/ZVO catalysis materials is by sunlight color dysprosium lamp photocatalytic degradation methylene blue
Solution is characterized.Specific experiment process is as follows：1.0g/L AgBr/ZVO catalyst is added to 10mg/L methylene blue
In solution, Photoreactor is placed in dark absorption 30min to reach the balance of the adsorption-desorption between catalyst and dye molecule.It is dark to inhale
After attached end, dysprosium lamp is opened, reactor is moved to the underface of light source, fixed light source and about 15 centimetres of distance for reacting liquid level,
Visible light catalytic reaction is carried out under magnetic stirring condition, 4mL samples are taken every 20min, it is purple after 0.22 μm of water system filter filters
Outer visible spectrophotometer determines filtrate absorbance at 664nm.
The structure characterization methods of AgBr/ZVO catalysis materials：With the crystal knot of X-ray diffraction (XRD) spectrum analysis sample
Structure and crystallization situation, size, pattern and distribution of particle etc. are analyzed with SEM (SEM), with ultraviolet spectrometer point
Analyse the light absorbs situation of material.
The beneficial effects of the present invention are：The invention provides a kind of preparation method, prepared by hydro-thermal and precipitation two-step method
AgBr/ZVO composite catalysts, prepared catalyst improve the visible light catalysis activity of pyrovanadic acid zinc, show efficient light
Catalytic degradation performance, this is provided necessarily for developing the new Treatment process of poisonous, harmful organic dyestuff in environmental improvement
Theoretical foundation and application instruct.
Brief description of the drawings
Under the conditions of Fig. 1 is precursor liquid PH=10 in embodiment 1, hydro-thermal time 10h, AgBr compositely proportional is 0.05, AgBr/
XRD spectrums of the ZVO under different hydrothermal temperatures.
Fig. 2 is that different AgBr are answered in embodiment 1 under the conditions of precursor liquid PH=10, hydro-thermal time 10h, 120 DEG C of hydrothermal temperature
AgBr/ZVO XRD spectrum under composition and division in a proportion example.
Jiao prepared under the conditions of Fig. 3 is precursor liquid pH=10 in embodiment 1,120 DEG C of hydrothermal temperature, hydro-thermal time are 10h
Zinc vanadate, composite catalyst that 0.20 AgBr prepares is compounded with this basis and independent AgBr ultraviolet-visible overflows
Reflect (UV-vis DRS).
Fig. 4 (a), (b) are precursor liquid pH=10,120 DEG C of hydrothermal temperature, hydro-thermal time pyrovanadic acid when being 10h, 20h respectively
The pattern SEM figures of zinc.
Fig. 5 is precursor liquid pH=10,120 DEG C of hydrothermal temperature, hydro-thermal time are that 10h, AgBr compositely proportional are 0.05,0.20
AgBr/ZVO composite catalysts pattern SEM figure.
Embodiment
With reference to embodiment, the present invention will be further described in detail, but this explanation will not be formed to the present invention's
Limitation.
Embodiment 1：
The preparation process of AgBr/ZVO composite catalysts is as follows：
Step 1, by Zn: V=3: 2 (mol ratios), weigh a certain amount of Zn (NO3)2·6H2O and NaVO3·2H2O difference is molten
In distilled water, by NaVO3After solution ultrasonic disperse, Zn (NO are slowly added to while stirring3)2In solution, continue magnetic agitation and obtain
To precursor liquid；
Step 2, the pH to 6-10 (specific PH is 6,8,10) with gained precursor liquid in concentrated ammonia liquor regulating step 1, stirring is equal
It is even, it is transferred in reactor, good seal；
Step 3, by precursor liquid in step 2 reactor 70-160 DEG C (actual temp is 70 DEG C respectively, 90 DEG C, 120 DEG C,
140 DEG C, 160 DEG C) under hydro-thermal 2-20h (specific time distinguish 2h, 10h, 20h)；
Step 4, after step 3 reactor naturally cools to room temperature, filtering, with distillation water washing for several times, drying, produce Jiao
Zinc vanadate；
Step 5, take the pyrovanadic acid zinc in a certain amount of step 4 to add in distilled water, magnetic force is carried out after ultrasonic disperse 10min and is stirred
Mix, the 0.01mol/L AgNO of certain volume are added dropwise thereto3Solution, lucifuge stirring；
Step 6, it is added dropwise in mixed liquor into step 5 and AgNO3The isometric 0.01mol/L NaBr solution of solution,
Continue lucifuge stirring；
Step 7, after step 6 reaction terminate after, sediment is filtered, with distillation water washing for several times, drying, produce AgBr/
The mass ratio of ZVO composite catalysts, wherein AgBr and pyrovanadic acid zinc for 0.01: 1-1.5: 1 (AgBr compositely proportionals difference 0.01,
0.05、0.20、1.00、1.50)。
Under the conditions of Fig. 1 is precursor liquid PH=10, hydro-thermal time 10h, AgBr compositely proportional is 0.05, AgBr/ZVO is in difference
XRD spectrum under hydrothermal temperature.As seen from the figure, in all samples existing hexagonal crystal system pyrovanadic acid zinc characteristic diffraction peak, in 2 θ
To have also appeared AgBr diffraction maximum at 26.7 °, 31.0 °, 44.4 °, 55.1 °, 64.6 ° and 73.4 °, illustrate that AgBr is loaded to
On pyrovanadic acid zinc.In addition, with the raising of hydrothermal temperature, the diffraction peak heights of composite catalyst also increase, and illustrate composite catalyzing
The crystal formation of agent gradually improves；But after hydrothermal temperature is more than 120 DEG C, the diffraction peak heights of composite catalyst no longer raise, explanation
When hydrothermal temperature reaches 120 DEG C, the crystal formation of the catalyst has tended to be intact, continues to improve hydrothermal temperature, its crystal formation is influenceed
Less.
Under the conditions of Fig. 2 is precursor liquid PH=10, hydro-thermal time 10h, 120 DEG C of hydrothermal temperature, under different AgBr compositely proportionals
AgBr/ZVO XRD spectrum.As shown in Figure 2, have the characteristic diffraction peak of pyrovanadic acid zinc in composite catalyst, and 26.7 °,
AgBr diffraction maximum at 31.0 °, 44.4 °, 55.1 °, 64.6 ° and 73.4 ° be present, illustrate that AgBr has been supported on pyrovanadic acid zinc
On.With the increase of AgBr compositely proportionals, the intensity of AgBr diffraction maximum also strengthens therewith in composite catalyst, correspondingly pyrovanadium
The diffraction peak intensity of sour zinc gradually weakens.
Fig. 3 is AgBr, pyrovanadic acid zinc, AgBr/ZVO UV-Vis DRS (UV-vis DRS), as seen from the figure, Jiao
The photo-absorption region of Zinc vanadate is narrower, and to visible absorption very little, it is about 382nm to absorb band edge；AgBr is more than 380nm in wavelength
Visible region have stronger absorption, its absorb band edge be about 502nm；And composite catalyst in wavelength except being less than 380nm
Ultraviolet region have outside stronger absorption, also have certain absorption between 380-460nm to wavelength, its absorb band edge compared to list
There is obvious red shift in body pyrovanadic acid zinc, and it is 405nm that it, which absorbs band edge, illustrates that the compound of AgBr effectively extends pyrovanadic acid zinc
Light absorption wavelength scope.After AgBr and pyrovanadic acid zinc are compound so that the band gap of pyrovanadic acid zinc narrows, to visible absorption ability
Become strong.
Fig. 4 (a), (b) are precursor liquid pH=10,120 DEG C of hydrothermal temperature, hydro-thermal time pyrovanadic acid when being 10h, 20h respectively
The pattern SEM figures of zinc.As seen from the figure, when the hydro-thermal time is 10h, pyrovanadic acid zinc is in relatively regular hexagon, and about 3 μm of the length of side is thick
About 0.5 μm, and surface is still attached with less particle；When hydro-thermal time lengthening is to 20h, pyrovanadic acid zinc is in irregular thin slice
Shape, particle diameter have increased, but thickness is thinning, and surface polishes.
Fig. 5 is precursor liquid pH=10,120 DEG C of hydrothermal temperature, hydro-thermal time are that 10h, AgBr compositely proportional are 0.05,0.20
When AgBr/ZVO composite catalysts pattern SEM figures, by figure it can be seen that after adding AgBr, ZVO pattern is not sent out substantially
Changing, AgBr particles are attached to pyrovanadic acid zinc surface.
Embodiment 2：
In order to examine influence of the precursor liquid pH value to AgBr/ZVO visible light activities, hydrothermal temperature be 120 DEG C, hydro-thermal when
Between when being that 10h, AgBr compositely proportional is 0.05, AgBr/ZVO composite catalysts are prepared under different precursor liquid pH value conditions.
As a result show, when precursor liquid pH value is 10, AgBr/ZVO to the percent of decolourization highest of methylene blue, precursor liquid pH for it is acid when,
Decolorizing effect is poor.When precursor liquid pH is 6, AgBr/ZVO is 54.9% to the percent of decolourization of methylene blue；It is 8 in precursor liquid pH
When, AgBr/ZVO is 65.5% to the percent of decolourization of methylene blue；When precursor liquid pH is 10, AgBr/ZVO takes off to methylene blue
Color rate is 71.8%.In general, AgBr/ZVO decoloring ability is gradual with the increase of synthetic catalyst precursor liquid pH value
Enhancing.Therefore, in the preparation process of AgBr/ZVO photochemical catalysts, optimal precursor liquid pH value is 10.
Embodiment 3：
In order to examine influence of the hydrothermal temperature to AgBr/ZVO visible light activities, in precursor liquid PH=10, hydro-thermal time
When 10h, AgBr compositely proportional are 0.05, AgBr/ZVO composite catalysts are prepared under different hydrothermal temperatures.In hydrothermal temperature
For 70 DEG C, 90 DEG C, 120 DEG C, 140 DEG C, 160 DEG C when, AgBr/ZVO is 61.9% to the percent of decolourization of methylene blue, 64.3%,
71.8%th, 70.6%, 70.9%.As a result show, when hydrothermal temperature is 120 DEG C, the percent of decolourization highest of methylene blue.With reference to not
XRD spectrum with the composite catalyst prepared under hydrothermal temperature understands, the crystal formation of catalyst with the raising of hydrothermal temperature and by
Gradual change is good, can improve the photocatalytic activity of catalyst to a certain extent；But with the increase of crystallinity, the particle diameter of catalyst is past
Toward that can become larger, cause its specific surface area to reduce, thus be unfavorable for the absorption to target contaminant, and then influence pollutant
Final degradation effect.Therefore, in the preparation process of AgBr/ZVO composite catalysts, optimal hydrothermal temperature is 120 DEG C.
Embodiment 4：
In order to examine the hydro-thermal time to AgBr/ZVO activity influence, precursor liquid PH=10,120 DEG C of hydrothermal temperature,
When AgBr compositely proportional is 0.05, AgBr/ZVO composite catalysts are prepared under not the same hydro-thermal time.As a result show, in water
When the hot time is 2h, 10h, 20h when, AgBr/ZVO is 56.5%, 71.8%, 58% to the percent of decolourization of methylene blue.Reason can
Can be that during hydro-thermal time shorter (2h), catalyst is in bulk loosely, and now the specific surface area of catalyst is larger, but crystal formation
It is poor, cause its photocatalytic activity relatively low, the decolorizing effect to methylene blue is mainly as caused by absorption；The hydro-thermal time prolongs
When length is to 10h, the crystal formation of catalyst gradually improves, and photocatalytic activity is improved, and the composite catalyst prepared under the conditions of this is same
When with good absorption property and photocatalytic activity；When hydro-thermal time lengthening is to 20h, the influence improved to catalyst crystal formation is simultaneously
Less, catalyst particle size is made constantly to become big on the contrary, specific surface area is reduced, and surface-active point position is reduced, the absorption to methylene blue
Property reduce, eventually affect the decolorizing effect of pollutant.Therefore, in the preparation process of AgBr/ZVO composite catalysts, most preferably
The hydro-thermal time is 10h.
Embodiment 5：
In order to examine AgBr compositely proportionals to AgBr/ZVO activity influence, precursor liquid PH be 10, hydrothermal temperature 120
DEG C, the hydro-thermal time is when being 10h, prepare the AgBr/ZVO catalyst of different AgBr compositely proportionals.AgBr compositely proportionals be 0.01,
0.05th, 0.20,1.00,1.50 when, AgBr/ZVO is 34.3% to the percent of decolourization of methylene blue, 71.8%, 85.2%,
95.1%th, 94.9%.As a result show, after being compounded with AgBr, the photocatalytic activity of catalyst has compared to pyrovanadic acid zinc significantly to be carried
Height, and with the increase of AgBr compositely proportionals, photocatalytic activity is in rise trend；But when AgBr compositely proportional is more than 1.00
When, to improving the effect of photocatalytic activity and little.Consider the preparation cost of photocatalysis efficiency and catalyst, choose AgBr
Compositely proportional be 0.20, under the conditions of this after light reaction 120min, the Photocatalytic Decoloration rate of methylene blue has reached 85.2%, phase
220%, 40% has been respectively increased than pyrovanadic acid zinc and AgBr.
Claims (3)
1. a kind of AgBr/ZVO composite catalysts, it is characterized in that：The compound difference of pyrovanadic acid zinc is prepared using hydro-thermal and two steps of precipitation
Ratio AgBr composite catalyst, described AgBr and ZVO mass ratioes are 0.01: 1-1.5: 1.
A kind of 2. preparation method of the AgBr/ZVO catalyst described in claim 1, it is characterized in that comprising the following steps：
Step 1, by Zn: V=3: 2 the ratio between the amount of material, weigh a certain amount of Zn (NO3)2·6H2O and NaVO3·2H2O distinguishes
It is dissolved in distilled water, by NaVO3After solution ultrasonic disperse, Zn (NO are slowly added to while stirring3)2In solution, continue magnetic agitation
Obtain precursor liquid；
Step 2, the pH to 6-10 with gained precursor liquid in concentrated ammonia liquor regulating step 1, stir, are transferred in reactor, close
Seal；
Step 3, by precursor liquid in step 2 reactor at 70-160 DEG C hydro-thermal 2-20h；
Step 4, after step 3 reactor naturally cools to room temperature, filtering, with distillation water washing, drying, produce pyrovanadic acid zinc；
Step 5, take the pyrovanadic acid zinc in step 4 to add in distilled water, magnetic agitation is carried out after ultrasonic disperse, add dropwise thereto
Enter the AgNO that concentration is 0.01mol/L3Solution, lucifuge stirring；
Step 6, it is added dropwise in mixed liquor into step 5 and AgNO3The isometric 0.01mol/L NaBr solution of solution, continue
Lucifuge stirs；
Step 7, after step 6 reaction terminates, sediment is filtered, with distillation water washing, drying, produces that AgBr/ZVO is compound to be urged
Agent.
3. application of the AgBr/ZVO composite catalysts in photocatalytic degradation organic matter described in claim 1.
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| CN110479243A (en) * | 2019-09-03 | 2019-11-22 | 陕西科技大学 | A kind of flower-shaped Zn3(OH)2V2O7·2H2O photochemical catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391066A (en) * | 2016-09-14 | 2017-02-15 | 南京航空航天大学 | Composite light catalyst for quickly and efficiently degrading rhodamine B and preparation method of composite light catalyst |
-
2017
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|---|---|---|---|---|
| CN106391066A (en) * | 2016-09-14 | 2017-02-15 | 南京航空航天大学 | Composite light catalyst for quickly and efficiently degrading rhodamine B and preparation method of composite light catalyst |
Non-Patent Citations (2)
| Title |
|---|
| FANGFANG WANG ET AL.: "Synthesis of hexagonal Zn3(OH)2V2O7•2H2O nanoplates by a hydrothermal approach: Magnetic and photocatalytic properties", 《MATERIALS CHARACTERIZATION》 * |
| 王萌: "焦钒酸锌的制备及其光催化性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479243A (en) * | 2019-09-03 | 2019-11-22 | 陕西科技大学 | A kind of flower-shaped Zn3(OH)2V2O7·2H2O photochemical catalyst and preparation method thereof |
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