CN104258876A - Silver micrometer line photocatalyst, and preparation method and application thereof - Google Patents
Silver micrometer line photocatalyst, and preparation method and application thereof Download PDFInfo
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- CN104258876A CN104258876A CN201410560441.7A CN201410560441A CN104258876A CN 104258876 A CN104258876 A CN 104258876A CN 201410560441 A CN201410560441 A CN 201410560441A CN 104258876 A CN104258876 A CN 104258876A
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- silver
- micro wire
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- copper
- photocatalyst
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 title abstract description 14
- 239000004332 silver Substances 0.000 title abstract description 14
- 239000011941 photocatalyst Substances 0.000 title abstract description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 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 22
- 229940043267 rhodamine b Drugs 0.000 description 21
- 239000000463 material Substances 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The invention provides a silver micrometer line photocatalyst, and a preparation method and application thereof. The photocatalyst is easy to prepare and beneficial to commercialized production. The method is simple to operate, and the photocatalyst prepared has high catalytic activity. The method comprises the steps of taking water as solvent at room temperature, sequentially feeding homemade a copper micrometer line, polyvinyl pyrrolidon and silver nitrate solution into the water in stirring condition, and preparing a silver micrometer line. The method is performed at the room temperature, heating is not required, and energy is saved. The method is simple and beneficial to mass preparation, and the photocatalyst can efficiently catalyze the decomposition of hydrogen peroxide, so that the oxygenolysis rate of hydrogen oxide for catalyzing organic pollutant, and the photocatalyst has high photocatalytic activity.
Description
technical field:
The present invention relates to a kind of silver-colored micro wire photochemical catalyst, also relate to the preparation method of this photochemical catalyst, belong to photocatalyst technology field.
background technology:
Environment and human survival closely related, environment has become the major issue that human social faces, and it is more and more urgent that the new and effective material of human research carrys out Environment control.The research and development of catalysis material has been subject to society and has paid much attention to, and development visible-light-responsive photocatalyst tool is of great significance.Japanese Scientists Fujishima in 1972 etc. find TiO
2monocrystalline electricity level can realize photochemical catalyzing (FujishimaA, 1972), finds nano-TiO again afterwards
2there is the ability of photocatalysis to degrade organic matter, and there is the outstanding advantage such as very high stability, nontoxic pollution-free, be extensively studied in photocatalysis field and utilize.But TiO
2energy gap be 3.2eV, the absorbing wavelength of its correspondence is 387.5nm, and light absorption is only confined to ultraviolet region.But this part light only accounts for and is irradiated to 5% of ground solar spectrum, lower solar energy utilization ratio limits the application of photochemical catalyst in the depollution of environment and new energy development etc.2010, a kind of visible-light photocatalyst-silver orthophosphate with strong oxidizing property of " nature " magazine ran.This Novel silver phosphate photocatalyst absorbing wavelength can be less than the sunshine of 520 nm, in multiple degradation of organic dyes experiment, showed extremely superior photocatalytic activity.According to experimental result such as investigation silver orthophosphate water decomposition performance under visible light illumination and coating decomposability etc., the visible ray photooxidation performance demonstrating silver orthophosphate is the decades of times of known photochemical catalyst at present.
Recent study finds, silver is of many uses, is a kind of important catalyst material.Liquid-phase precipitation method is easy and simple to handle, and the product simultaneously obtained has that higher chemical uniformity, grain graininess are comparatively thin, Size Distribution is narrower and has certain morphology controllable.Explore easy synthetic method, improve Ag photocatalysis property further, have very important meaning.
summary of the invention:
An object of the present invention is to provide a kind of Novel silver micro wire catalyst, this photochemical catalyst prepare simple, be beneficial to and commercially produce.
Another object of the present invention is to provide the preparation method of above-mentioned silver-colored micro wire catalyst, and this preparation method is easy to operate, can complete at ambient temperature, does not need heating, can economize energy.
Another object of the present invention is to provide the application of above-mentioned silver-colored micro wire catalyst in photocatalysis to degrade organic matter.
Concrete technical scheme of the present invention is as follows:
A preparation method for silver-colored micro wire photochemical catalyst, comprises the steps:
1) under stirring condition, copper micro wire is added to the water, bulking value (0.01-0.1) g/30ml of copper micro wire and water;
2) then add polyvinylpyrrolidone, ultrasonic oscillation 1-10min at 10-30 DEG C, make copper micro wire be dispersed in system, obtain copper dispersion liquid for subsequent use; In polyvinylpyrrolidone and step 1), the mass ratio of copper micro wire is 80:(3-8);
3) take silver nitrate, add water preparation (2-4) wt% liquor argenti nitratis ophthalmicus in another container;
4), when stirring, pour step 2 into by disposable for the liquor argenti nitratis ophthalmicus of step 3)) copper dispersion liquid in; Wherein, the volume ratio of liquor argenti nitratis ophthalmicus and copper dispersion liquid is 1:(2-5); When solution becomes black gray expandable, stop stirring;
5) centrifugal, wash 2-3 time respectively with deionized water and absolute ethyl alcohol;
6) at 55-80 DEG C of temperature, drying time is 3-5h, obtains silver-colored micro wire photochemical catalyst.
Silver-colored micro wire photochemical catalyst prepared by above-mentioned preparation method.
The present invention also provides this application of silver-colored micro wire photochemical catalyst in degradable organic pollutant.
This application is specially this application of silver-colored micron linear light in catalyzing hydrogen peroxide degradable organic pollutant.
the present invention compared to existing technology tool has the following advantages:
The preparation method of the present invention's silver micro wire is simple, can complete at ambient temperature, not need heating, can save
The about energy.
The present invention's silver micro wire preparation process is simple, cost is low, saves economical; And traditional Physical the elemental silver of bulk is become nano level silver ion, the expensive preparation cost of device therefor is high, and producing cost is expensive.Therefore, compared with physical method, there is obvious economic benefit.
Silver-colored micro wire provided by the invention, can the decomposition of efficient catalytic hydrogen peroxide, thus greatly accelerates the oxidation Decomposition speed of hydrogen peroxide catalyzed organic pollution.
accompanying drawing illustrates:
Fig. 1 is the XRD figure of silver-colored micro wire prepared by the embodiment of the present invention one.
Fig. 2 is the SEM figure that the silver-colored micro wire of the embodiment of the present invention one preparation expands 1200 times.
Fig. 3 is the SEM figure that the silver-colored micro wire of the embodiment of the present invention one preparation expands 3200 times.
Fig. 4 is the contrast test curve map of silver-colored catalysis rhodamine B degraded.
Wherein, C
0for the initial concentration of rhodamine B, C is the rhodamine B concentration value measured after adding silver-colored micro wire catalyzing hydrogen peroxide rhodamine B degradation a period of time, and t is the time.
detailed description of the invention:
The copper micro wire adopted in the present invention refers to the copper cash of Micro-scale length, and its preparation method is positive pentagonal prism shape copper micro wire in the application for a patent for invention of 201310505999.0 (publication date is on January 8th, 2014) with application number.
embodiment one:
Under room temperature, get the deionized water of 30mL, pour in container, add the copper micro wire of 0.05g under agitation, then 0.8g PVP K-30 (Chemical Reagent Co., Ltd., Sinopharm Group, lower same) is added, ultrasonic oscillation 10min at 25 DEG C, copper micro wire is dispersed in system uniformly, obtains solution A.
Take the AgNO of 0.3189
3(0.00187mol) in another container, add 10mL deionized water dissolving, stir, obtain uniform liquor argenti nitratis ophthalmicus, under stirring, pour in solution A by disposable for liquor argenti nitratis ophthalmicus, react under stirring, until the color of reaction system becomes black from redness, reaction terminates, and obtains reaction mixture solution.
After centrifugal treating, respectively wash 3 times with deionized water and absolute ethyl alcohol successively, under 60 DEG C of conditions, dry 7h, obtain silver-colored micro wire catalyst, be set to material 1.
As can be seen from the X-ray image K-M of Fig. 1 material 1, material 1 is silver-colored simple substance.
As can be seen from the electron microscope shape appearance figure of Fig. 2, Fig. 3 material 1, material 1 is silver-colored micro wire simple substance.
application Example
In Catalysis experiments, the organic absorption spectrum that is degraded uses ultraviolet one visible spectrophotometer to measure, according to Lambert mono-Beer law, according to the change of organic matter characteristic absorption peak intensity, can quantitatively calculate its change in concentration, when extinction material is identical, when cuvette thickness is identical, the change of the change secondary indication solution concentration of absorbance can be used, because rhodamine B has a characteristic absorption peak at 554nm place, so the change of absorbance can be utilized to weigh the change in concentration of rhodamine B in solution, calculate C/C
0, draw C/C
0relative to the curve of time, to characterize the activity of the catalyzing hydrogen peroxide degradable organic pollutant of catalyst, wherein C
0for the initial concentration of rhodamine B, C is the concentration value of the rhodamine B of measuring after adding the present invention's silver micron catalyzing hydrogen peroxide rhodamine B degradation a period of time, and t is the time.
concrete contrast experiment is as follows:
The application of silver-colored micron linear light of the present invention in catalyzing hydrogen peroxide degradable organic pollutant.
The material 1 embodiment 1 prepared and commercialization silver (Guangzhou Da Tian Silver Jewelry Co., Ltd filamentary silver) are as photocatalyst for degrading rhodamine B.
Prepare three groups of rhodamine B solution respectively: getting 10mL mass percentage concentration is 30% H
2o
2solution, 2mg rhodamine B, is first dissolved in rhodamine B in suitable quantity of water, then joins H
2o
2in solution, and be settled to 200mL with water, obtain rhodamine B solution.
Get first group of 200ml rhodamine B solution, add 0.1g photochemical catalyst, stir, then react under 400 1 700nm illumination, got 3mL reactant liquor every ten minutes, after centrifugation, get supernatant liquor, detect the concentration of rhodamine B with spectrophotometer, obtain the degradation curve of rhodamine B.
Second group of 200ml rhodamine B solution, does not add photochemical catalyst, and as in blank, other operating procedures are the same.
3rd group of 200ml rhodamine B solution, add the commercial silver of 0.1g as photochemical catalyst, other operating procedures are the same.The three suite lines obtained are as Fig. 4.
In Fig. 4, as can be seen from the degradation curve of three groups of rhodamine Bs, under the irradiation of visible ray (400 1 700nm), material 1 catalyzing hydrogen peroxide decomposition rate is very fast, so the degradation rate of rhodamine B is also very fast, be significantly higher than speed and the blank group of common commercial silver catalysis rhodamine B degraded.
Claims (4)
1. a preparation method for silver-colored micro wire photochemical catalyst, is characterized in that: the concrete steps of the method comprise:
1) under stirring condition, copper micro wire is added to the water, w/v (0.01-0.1) g/30ml of copper micro wire and water
2) then add polyvinylpyrrolidone, ultrasonic oscillation 1-10min at 10-30 DEG C, make copper micro wire be dispersed in system, obtain copper dispersion liquid for subsequent use; In polyvinylpyrrolidone and step 1), the mass ratio of copper micro wire is 80:(3-8);
3) take silver nitrate, add water preparation (2-4) wt% liquor argenti nitratis ophthalmicus in another container;
4), when stirring, pour step 2 into by disposable for the liquor argenti nitratis ophthalmicus of step 3)) copper dispersion liquid in; Wherein, the volume ratio of liquor argenti nitratis ophthalmicus and copper dispersion liquid is 1:(2-5); When solution becomes black gray expandable, stop stirring;
5) centrifugal, wash 2-3 time respectively with deionized water and absolute ethyl alcohol;
6) at 55-80 DEG C of temperature, drying time is 3-5h, obtains silver-colored micro wire photochemical catalyst.
2. the silver-colored micro wire photochemical catalyst prepared of preparation method described in claim 1.
3. the application of silver-colored micro wire photochemical catalyst in degradable organic pollutant described in claim 2.
4. application according to claim 3, is specially this application of silver-colored micron linear light in catalyzing hydrogen peroxide degradable organic pollutant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410560441.7A CN104258876B (en) | 2014-10-21 | 2014-10-21 | A kind of silver micro wire photocatalyst and its preparation method and application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410560441.7A CN104258876B (en) | 2014-10-21 | 2014-10-21 | A kind of silver micro wire photocatalyst and its preparation method and application |
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| Publication Number | Publication Date |
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| CN104258876A true CN104258876A (en) | 2015-01-07 |
| CN104258876B CN104258876B (en) | 2016-06-29 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004148305A (en) * | 2002-10-11 | 2004-05-27 | Osaka Gas Co Ltd | Photocatalyst and air cleaner using the same |
| CN103769165A (en) * | 2014-03-04 | 2014-05-07 | 南京信息工程大学 | Preparation method and application of surface-loaded linear silver photocatalyst |
| CN103816896A (en) * | 2014-03-06 | 2014-05-28 | 南京信息工程大学 | Preparation method and application of micrometer tubular silver simple substance |
-
2014
- 2014-10-21 CN CN201410560441.7A patent/CN104258876B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004148305A (en) * | 2002-10-11 | 2004-05-27 | Osaka Gas Co Ltd | Photocatalyst and air cleaner using the same |
| CN103769165A (en) * | 2014-03-04 | 2014-05-07 | 南京信息工程大学 | Preparation method and application of surface-loaded linear silver photocatalyst |
| CN103816896A (en) * | 2014-03-06 | 2014-05-28 | 南京信息工程大学 | Preparation method and application of micrometer tubular silver simple substance |
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| CN104258876B (en) | 2016-06-29 |
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Application publication date: 20150107 Assignee: Nanjing Qingyang Technology Co.,Ltd. Assignor: Nanjing University of Information Science and Technology Contract record no.: X2023320000240 Denomination of invention: A Silver Microwire Photocatalyst and Its Preparation Method and Application Granted publication date: 20160629 License type: Common License Record date: 20231121 |
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Application publication date: 20150107 Assignee: Fujian hefuyun Information Technology Co.,Ltd. Assignor: Nanjing University of Information Science and Technology Contract record no.: X2023980051730 Denomination of invention: A Silver Microwire Photocatalyst and Its Preparation Method and Application Granted publication date: 20160629 License type: Common License Record date: 20231212 |
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Application publication date: 20150107 Assignee: Nanjing Xinqihang Software Technology Co.,Ltd. Assignor: Nanjing University of Information Science and Technology Contract record no.: X2023980051736 Denomination of invention: A Silver Microwire Photocatalyst and Its Preparation Method and Application Granted publication date: 20160629 License type: Common License Record date: 20231213 |
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