CN103157462A - Preparation method and application of novel manganese-tungstate photocatalyst - Google Patents
Preparation method and application of novel manganese-tungstate photocatalyst Download PDFInfo
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- CN103157462A CN103157462A CN2013100850482A CN201310085048A CN103157462A CN 103157462 A CN103157462 A CN 103157462A CN 2013100850482 A CN2013100850482 A CN 2013100850482A CN 201310085048 A CN201310085048 A CN 201310085048A CN 103157462 A CN103157462 A CN 103157462A
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- wolframic acid
- photocatalyst
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000011941 photocatalyst Substances 0.000 title abstract description 8
- CRLHSBRULQUYOK-UHFFFAOYSA-N dioxido(dioxo)tungsten;manganese(2+) Chemical compound [Mn+2].[O-][W]([O-])(=O)=O CRLHSBRULQUYOK-UHFFFAOYSA-N 0.000 title abstract 2
- 239000002253 acid Substances 0.000 claims description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005352 clarification Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000703 high-speed centrifugation Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000017105 transposition Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 239000002060 nanoflake Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
- 230000002673 intoxicating effect Effects 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a novel manganese-tungstate photocatalyst. The nanoscale photocatalyst in a three-dimensional hierarchical structure is synthesized ultrasonically. The photocatalyst is intact in crystal form and simple and controllable in preparation process, has high thermal stability and good photocatalytic degradation activity and can be synthesized in a short time. The special three-dimensional hierarchical structure of the photocatalyst is beneficial to the recycling of the photocatalyst.
Description
[technical field]
The present invention relates to a kind of preparation method of nano-scale photocatalyst.
[background technology]
Problem of environmental pollution has become the serious hindrance of present restriction social development.Especially the organic pollution in trade effluent such as polycyclic aromatic hydrocarbon, phenols, chlorobenzene class etc., be difficult to carry out biodegradation, has bioaccumulation and extremely strong intoxicating, and the harm of ecological environment is difficult to estimate.Utilizing photocatalytic degradation to react to process organic pollution in waste water, is an effective way of pollution control of water.This novel pollution control technology have degraded thoroughly, the advantage such as energy consumption is low, easy and simple to handle, degradation condition is gentle, under photochemical catalyst auxiliary, organic pollution can be converted into fully inorganic molecules, satisfy the sewage drainage standard that day by day improves.
Recent study person has attempted preparing the multiple light catalyst organic pollution in waste water has been carried out the light degradation experiment, and result of study confirms multiple nano-scale photocatalyst such as TiO with photocatalytic oxidation
2, ZnO, CdS etc., can play excellent catalytic performance to organic degradation process.Therefore have direct relation between the PhotoelectrocatalytiPerformance Performance of sodium meter level photochemical catalyst and its particle diameter and structure, adopt the structure of suitable synthetic method regulation and control end product and pattern to become one of the study hotspot in nanometer synthetic field.The report demonstration simple nanostructured of tungstates such as nano particle, nanometer rods, nanometer sheet etc. can effectively prepare by softening method, yet the preparation of the especially three-dimensional graded structure of graded structure report but seldom.The composition machine unit of three-dimensional graded structure remains in the nanoscale scope, has high photocatalysis efficiency, and its larger size is conducive to the recycling of photochemical catalyst simultaneously.Therefore, the photochemical catalyst of the three-dimensional graded structure of preparation is applied for it and is had realistic meaning.
The preparation method who the purpose of this invention is to provide the wolframic acid manganese photochemical catalyst that a kind of preparation flow is simply controlled, heat endurance is high.The petal-shaped structure of the pattern of this type of catalyst for being combined into by different level by nano flake, this type of photochemical catalyst has good Photocatalytic activity, and its special three-dimensional graded structure also is conducive to the recycling process of photochemical catalyst.
[summary of the invention]
The invention provides a kind of preparation process simply controlled, have three-dimensional graduation petal-shaped structure, a wolframic acid manganese photochemical catalyst that photocatalysis performance is good.
Wolframic acid manganese photochemical catalyst in the present invention prepares by following steps:
---a is to containing 1.0mmol MnCl
24H
2Add 1g PEG2000 in the 50ml aqueous solution of O, vigorous stirring is until obtain the evenly solution of clarification;
---b adds 50ml to contain 1.0mmol Na in solution
2WO
42H
2The O aqueous solution;
---c enters ultrasonic half an hour in ultrasonic grinder (being set to ultrasonic 5 seconds, intermittently 15 seconds) with the solution transposition, utilizes cooling system that system temperature is remained on below 323K in building-up process;
---d is precipitated the reactant liquor high speed centrifugation, utilizes absolute ethyl alcohol and deionized water washing and precipitating repeatedly, and drying is 4 hours under 60 ℃, can get wolframic acid manganese sample.
The present invention utilizes ultrasonic method to synthesize wolframic acid manganese photochemical catalyst.When reactant liquor is subject to high-intensity ultrasonic irradiation, can form air pocket in solution when low pressure, then air pocket subsides when high pressure.The energy that air pocket discharges can significantly improve reaction rate, can guarantee that the product that obtains has good degree of crystallinity, can effectively control particle diameter and the decentralization of nano particle again simultaneously.
The X-ray diffraction spectrogram shows that the product that obtains is monoclinic system huebnerite structure, the crystal formation of sample is good, the energy that this explanation ultrasonic procedure provides can guarantee the complete of sample crystal formation under lower reaction temperature condition, hyperacoustic utilization is Reaction time shorten effectively, course of reaction is simply controlled, and the higher-energy that the while ultrasonic wave provides also is conducive to the generation of special appearance.
Utilize SEM we can to observe wolframic acid manganese sample topography fairly regular, show as the petal-shaped that is combined into by different level by the multi-disc nano flake, the sample topography homogeneous is not found other pattern.The petal-shaped structure is the sandwich construction that is combined together to form by a lot of two-dimensional slice.The diameter of these thin slices is at 200-400nm, and thickness is 10-30nm, adopts the mode of Bian-Bian combination to form flower-like structure.This graduate petal-shaped structure still can keep its structural integrity through long-time ultrasonic in solution, can destroyedly not become the nanometer sheet of dispersion.
Utilizing the synthetic wolframic acid manganese sample of this kind ultrasonic method to have special three-dimensional graduation petal-shaped structure, is the local superenergy that provides due to supersonic source on the one hand, and adding of surfactant polyethylene is also most important to the generation of this kind pattern.Peg molecule is adsorbed on wolframic acid manganese particle surface and has formed the hydrophilic diaphragm of the large molecule of one deck in course of reaction; its strand is longer; the sterically hindered effect of diaphragm that forms is larger; simultaneously the long-chain hydrocarbon of peg molecule has certain stabilization to wolframic acid manganese side, so formed the sandwich construction of sheet under ul-trasonic irradiation.
The petal-shaped structure that this type of three-dimensional graduate wolframic acid manganese nanostructured is combined into by different level by many nano flakes consists of, specific area with superelevation, the adsorbance of its surface dye is higher in the light degradation process, increase its surperficial light induced electron/hole and the interactional probability of dye molecule, thereby had higher photocatalytic activity.The light degradation experiment shows that this type of wolframic acid manganese sample has the more excellent photocatalytic activity of wolframic acid bismuth sample, effectively rhodamine B degradation dyestuff.Have simultaneously good heat endurance, repeatedly recovery and ultrasonic dispersion process still can not destroyed its three-dimensional graded structure, and photocatalysis performance is also without obviously decay.
Advantage of the present invention and effect:
1, the present invention utilizes ultrasonic method to synthesize wolframic acid manganese photochemical catalyst, has the simple controlled advantage of short, reaction condition of reaction time, and the product for preparing has higher specific area, good degree of crystallinity and special three-dimensional graduation petal-shaped structure.
2, the present invention utilize preparation wolframic acid manganese as photochemical catalyst, effectively the aqueous solution of rhodamine B degradation dyestuff, still can effectively keep its three-dimensional graded structure in removal process.
[description of drawings]
Fig. 1, MnWO
4The stereoscan photograph of sample;
The absorption spectrum of Fig. 2, the rhodamine B aqueous solution is trend (illustration is for estimating the photocatalysis performance curve of the prepared wolframic acid manganese photochemical catalyst of the present invention as contaminant water system model with the rhodamine B aqueous solution) over time.
[specific embodiment]
To containing 1.0mmol MnCl
24H
2Add 1g PEG2000 in the 50ml aqueous solution of O, vigorous stirring is until obtain the evenly solution of clarification; Add 50ml to contain 1.0mmol Na in solution
2WO
42H
2The O aqueous solution; The solution transposition is entered ultrasonic half an hour in ultrasonic grinder (being set to ultrasonic 5 seconds, intermittently 15 seconds), utilize cooling system that system temperature is remained on below 323K in building-up process; The reactant liquor high speed centrifugation is precipitated, utilizes absolute ethyl alcohol and deionized water washing and precipitating repeatedly, drying is 4 hours under 60 ℃, can get wolframic acid manganese sample.
Claims (1)
1. wolframic acid manganese photochemical catalyst is characterized in that this photochemical catalyst prepares by following steps:
---a is to containing 1.0mmol MnCl
24H
2Add 1g PEG2000 in the 50ml aqueous solution of O, vigorous stirring is until obtain the evenly solution of clarification;
---b adds 50ml to contain 1.0mmol Na in solution
2WO
42H
2The O aqueous solution;
---c enters ultrasonic half an hour in ultrasonic grinder (being set to ultrasonic 5 seconds, intermittently 15 seconds) with the solution transposition, utilizes cooling system that system temperature is remained on below 323K in building-up process;
---d is precipitated the reactant liquor high speed centrifugation, utilizes absolute ethyl alcohol and deionized water washing and precipitating repeatedly, and drying is 4 hours under 60 ℃, can get wolframic acid manganese sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100850482A CN103157462A (en) | 2013-03-05 | 2013-03-05 | Preparation method and application of novel manganese-tungstate photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100850482A CN103157462A (en) | 2013-03-05 | 2013-03-05 | Preparation method and application of novel manganese-tungstate photocatalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103157462A true CN103157462A (en) | 2013-06-19 |
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ID=48581298
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100850482A Pending CN103157462A (en) | 2013-03-05 | 2013-03-05 | Preparation method and application of novel manganese-tungstate photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103157462A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457657A (en) * | 2015-12-16 | 2016-04-06 | 江苏大学 | Method for preparing CdS/MnWO4 heterojunction compound photo-catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528514A (en) * | 2003-10-10 | 2004-09-15 | 广西大学 | Preparation of tungstate phatocatalyst and use of catalytic degradation of molasses alcohol waste water thereof |
| WO2011149996A2 (en) * | 2010-05-24 | 2011-12-01 | Siluria Technologies, Inc. | Nanowire catalysts |
| CN102372305A (en) * | 2010-08-13 | 2012-03-14 | 范晓星 | Mesoporous tungstate photocatalysis material and preparation method thereof |
-
2013
- 2013-03-05 CN CN2013100850482A patent/CN103157462A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528514A (en) * | 2003-10-10 | 2004-09-15 | 广西大学 | Preparation of tungstate phatocatalyst and use of catalytic degradation of molasses alcohol waste water thereof |
| WO2011149996A2 (en) * | 2010-05-24 | 2011-12-01 | Siluria Technologies, Inc. | Nanowire catalysts |
| CN102372305A (en) * | 2010-08-13 | 2012-03-14 | 范晓星 | Mesoporous tungstate photocatalysis material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| H.Y. HE等: "Photodegradation of methyl orange aqueous on MnWO4 powder under different light resources and initial pH", 《DESALINATION》 * |
| 郭金学等: "纳米钨酸锰的超声合成及其性质研究", 《青岛科技大学学报(自然科学版)》 * |
| 陈菲: "纳米钨酸锰和氧化铈的超声合成及其性质研究", 《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 |
|---|---|---|---|---|
| CN105457657A (en) * | 2015-12-16 | 2016-04-06 | 江苏大学 | Method for preparing CdS/MnWO4 heterojunction compound photo-catalyst |
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Application publication date: 20130619 |