CN105170990B - Application of the Ni/Fe bimetallic face-centered cubic crystal nano particles in Polychlorinated biphenyls is removed - Google Patents
Application of the Ni/Fe bimetallic face-centered cubic crystal nano particles in Polychlorinated biphenyls is removed Download PDFInfo
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- CN105170990B CN105170990B CN201510435864.0A CN201510435864A CN105170990B CN 105170990 B CN105170990 B CN 105170990B CN 201510435864 A CN201510435864 A CN 201510435864A CN 105170990 B CN105170990 B CN 105170990B
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Abstract
The invention discloses application of the Ni/Fe bimetallic face-centered cubic crystal nano particles in Polychlorinated biphenyls is removed, using liquid phase reduction, using PVP as stabilizer, with NaBH4As reducing agent, substep adds ferrous ion and nickel ion is reduced, and the Ni/Fe duplex metal nano granules prepared are the face-centerd cubic structure of rule, and particle diameter distribution is uniform, and specific surface area is big, and stability is good, is not susceptible to polymerism.The nano particle prepared using technical solution of the present invention being capable of effectively catalytic degradation Polychlorinated biphenyls.
Description
The present patent application be parent application " Ni/Fe bimetallic face-centered cubic crystal nano particles and preparation method thereof and should
With " divisional application, parent application number be 201410008400.7, the applying date is on January 2nd, 2014.
Technical field
The invention belongs to technical field of nano material, more particularly, is related to a kind of face-centered cube nanocrystal
Grain, and in particular to one kind utilizes the Ni/Fe bimetallic center of area cubic crystals of liquid phase reduction preparation using PVP as macromolecular template
Application of the body nano particle in Polychlorinated biphenyls is removed.
Background technology
Polychlorinated biphenyls (Polychlorinated Biphenyls, abbreviation PCBs) is a kind of typical persistence in environment
Organic pollution.Since it has higher chemical inertness, heat endurance, anti-flammability, thermal conductivity and insulating properties, once extensive use
In fields such as power industry, Plastics Processing Industry, chemical industry and printings.Counted according to the World Health Organization (WHO), from eighties of last century
Since the twenties starts production, to the end of the eighties, the whole world produces about 2 × 10 altogether7T Industrial PC Bs, wherein about 31% discharge
Into environment.Since PCBs has bioaccumulation and " three cause " effect, can long-distance migration in the world, and
And in its migration, conversion process, amplification can be bioaccumulation, its concentration level may improve decades of times even hundreds of times, right
Ecological environment and health, which produce, greatly to threaten.United Nations Environment Programme is classified as 12 kinds that Global Priority controls and is held
One of long property toxic organic pollutant, and most industrial countries have stopped producing more chlorine after the 1970s
Biphenyl, but since its property is stablized, be not easy to degrade in the environment, pollution of the Polychlorinated biphenyls to environment will also continue to grow very much one section
Time.
In view of PCBs generalities present in water body, domestic and foreign scholars carry out for the degraded of PCBs in recent ten years
A series of research, research show that the committed step of PCBs degradeds is dechlorination reaction, and the method for use mainly has hydrogenization method, chlorine
Solution, reversion method and metal deoxidization etc..Wherein, it is current most active one using metal deoxidization processing Polychlorinated biphenyls
Item investigative technique, has very big potential, is considered as even abroad most to have one of method of application prospect.Zero-valent metal by
In with very strong reproducibility, and it is cheap and easy to get, therefore reducing agent can be used as, Polychlorinated biphenyls is sloughed chlorine atom, so as to reduce
The toxicity of Polychlorinated biphenyls.Common zero-valent metal has iron, aluminium, magnesium, zinc and tin etc., in numerous zero-valent metals using Zero-valent Iron and
The reduction of its compound removes the most study of halogenated organic and Polychlorinated biphenyls, and iron is safe from harm for environment, so
As more commonly used Polychlorinated biphenyls catalysis dechlorination method.
The content of the invention
It is double it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of Ni/Fe for degradation of polychlorinated biphenyl
The preparation method of metal face-centered cubic crystal nano particle, the preparation method is easy to operate, and reaction condition is gentle, and reaction process is easy
Control, it is environmentally friendly, and obtained reactor product is stablized, and is not susceptible to polymerism.
Ni/Fe bimetallic face-centered cubic crystal nano particles and preparation method thereof, are prepared as steps described below：
Step 1, the PVP of 4-5 mass parts is dissolved in deionized water, is fully mixed by magnetic agitation, obtain mass body
The PVP solution that product concentration is 8-10%；
Step 2, by FeSO4·7H2O dissolves in a solvent, to obtain ferrous solution, the solvent by PVP solution,
Deionized water and absolute ethyl alcohol composition, the volume ratio of the PVP solution, deionized water and absolute ethyl alcohol is 3：(9-10)：(8-
10), preferred volume ratio 3：9：8；Selection inert gas is passed through to go deoxygenation in solvent, wherein the inert gas for nitrogen or
Person's argon gas or helium, deoxygenation time are 20-30min；
Step 3, in the ferrous solution prepared to step 2, NaBH is added dropwise4Solution, wherein n (Fe2+) and n (BH4 —) rub
That ratio 1：2, to make reduction reaction fully carry out, preferably excessive NaBH4Solution, the NaBH4Solution is by NaBH4Powder is molten
In absolute ethyl alcohol and the mixed solution of deionized water, wherein the absolute ethyl alcohol and deionized water and volume ratio are 2：3；
Complete in 15-20min to be added dropwise, after completion of dropwise addition in the case where rotating speed is the mechanical agitation of 1500-2000r/min stirring 20-
30min；
Step 4, the zeroth order Fe nano particles obtained after the completion of step 3 washing is placed in absolute ethyl alcohol, and thereto
NiCl is added dropwise2·6H2O ethanol solutions, described be added dropwise is completed in 15-25min, in the machinery of 1000-1500r/min
It is sufficiently mixed under stirring condition, after titration, mixes 20-40min, the dosage of the nickel is ferrous iron (i.e. ferro element) matter
2%-the 5% of amount.
Step 5, after being mechanical agitation after completing above-mentioned preparation process, collected with magnetic method, obtained Ni/Fe is double
Metal nanoparticle is washed 3 times with absolute ethyl alcohol, obtains final product free from foreign meter.
Ni/Fe bimetallic face-centered cubic crystal nano particles answering in Polychlorinated biphenyls is removed according to above-mentioned technical proposal
With.
Realize following whole reaction process step by step in the inventive solutions：
Fe(H2O)6 2++2BH4 -→Fe↓+2Be(OH)3+7H2↑
Ni2++Fe0→Fe2++Ni↓
In this course, iron is firstly generated, then in addition element nickel, to be reacted with iron, due to elemental nickel
Additive amount is less and system is sufficiently mixed and is reacted under conditions of continued mechanical stirring, after drop reaction, i.e.,
The composite nanometer particle of nickel and iron can be formed.
In the inventive solutions, W metal plays catalyst, can accelerate the dechlorination efficiency of Zero-valent Iron, leads to
Often select Ni/Fe duplex metal nano granule degradation of polychlorinated biphenyl cheap and easy to get.The liquid phase reduction of selection have it is easy to operate,
The advantages that process control is strong, and cost is relatively low, usually selects sodium borohydride liquid phase reduction to prepare Ni/Fe bimetal nanos
Grain, but the nano particle prepared easily is reunited, and influences degradation efficiency, so adding stabilizer in liquid phase preparation process
PVP (K30), PVP (K30) can prevent the reunion of nano-particle, and the degradation process of bimetallic system will not be had an impact.
Compared with prior art, the advantages of the present invention are：
(1) consersion unit needed for the present invention is simple, equipment cost is relatively low.
(2) bimetallic preparation process controllability of the present invention is stronger, and easy to operate, reaction condition is gentle, for further industry
Metaplasia production offer is possible, and PVP (K30) is cheap and easy to get, is widely used in medicine and accurate chemical industry.
(3) the Ni/Fe bimetal nano face-centered cubic crystals specific grain surface product obtained by the present invention is big, it is dispersed and
It is not susceptible to polymerize, product structure is stablized, and observes by sweep electron microscope, the Ni/Fe bimetal nanos of generation
Grain is the face-centered cube of rule, and for particle diameter distribution uniform concentration between 50-150nm, specific surface area is 30-35m2/ g is right
The removal ability of Polychlorinated biphenyls is significantly larger than nano iron particles.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) of Ni/Fe bimetallic face-centered cubic crystal nano particles prepared by the present invention
Picture.
When Fig. 2 is that Ni/Fe bimetallic face-centered cubic crystals nano particle prepared by the present invention is used for PCB77 in degradation water,
Measure concentration C and initial concentration C0Ratio with the time (h) change curve.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment.
Embodiment 1
(1) 4gPVP (K30) is dissolved in deionized water, is fully mixed by magnetic agitation, be settled to 50ml, obtain matter
Measure the PVP solution that volumetric concentration is 8%.
(2) take the 7.5mlPVP solution as described in (1) to be dissolved in the mixed solution of deionized water and absolute ethyl alcohol, be transferred to
In there-necked flask, letting nitrogen in and deoxidizing 30min.The overall solution volume is 50ml, PVP solution 7.5ml, deionized water 22.5ml, ethanol
20ml, volume ratio 3:9:8.
(3) 0.417gFeSO is weighed4·7H2O powder is added in above-mentioned solution, in the mechanical agitation that rotating speed is 2000r/min
Under the conditions of mix 20min so that FeSO4·7H2O powder fully dissolves, at this time FeSO4·7H2The molar concentration of O is
0.03mol/L。
(4) NaBH is slowly added dropwise into there-necked flask4Solution, according to n (Fe2+) and n (BH4 —) ratio 1:2, NaBH4For
0.003mol, to make reduction reaction fully carry out, configures NaBH4Claim slightly excessive NaBH during solution4Powder, weighs 0.125g's
NaBH4Powder is dissolved in 4ml absolute ethyl alcohols and the mixed solution of 6ml deionized waters, and NaBH is obtained after stirring evenly4Solution,
20min completes to be added dropwise, and 30min is stirred in the case where rotating speed is the mechanical agitation of 2000r/min after completion of dropwise addition.
(5) after stirring, collected with magnetic method, obtained nano zero-valence Fe nano particles wash 4 with deoxidation distilled water
It is secondary, to remove remaining ion and compound in solution, to make washing thorough, when last time is washed, the ultrasonic disperse several seconds.Wash
After washing, 24ml absolute ethyl alcohols are added toward there-necked flask is interior.
(6) by NiCl2·6H2O powder is placed in absolute ethyl alcohol, and wherein the quality of elemental nickel is the 5% of element weight of iron,
By 36ml NiCl2·6H2O ethanol solutions are slowly dropped into above-mentioned solution, are added dropwise and are completed in 25min.In 1500r/min
Mechanical agitation under be sufficiently mixed, after titration, mix 20min, which is Fe and Ni2+Metal reduction reaction.
(7) after mechanical agitation, collected with magnetic method, obtained Ni/Fe duplex metal nano granules are washed with absolute ethyl alcohol
Wash 3 times, obtain final product free from foreign meter, be dried in vacuo, weigh, about 0.1g or so.
Embodiment 2
(1) 5gPVP (K30) is dissolved in deionized water, is fully mixed by magnetic agitation, be settled to 50ml, obtain matter
Measure the PVP solution that volumetric concentration is 10%.
(2) take the 7.5mlPVP solution as described in (1) to be dissolved in the mixed solution of deionized water and absolute ethyl alcohol, be transferred to
In there-necked flask, letting nitrogen in and deoxidizing 30min.The overall solution volume is 50ml, PVP solution 7.5ml, deionized water 22.5ml, ethanol
20ml, volume ratio 3:10:10.
(3) 0.417gFeSO is weighed4·7H2O powder is added in above-mentioned solution, in the mechanical agitation that rotating speed is 2000r/min
Under the conditions of mix 15min so that FeSO4·7H2O powder fully dissolves, at this time FeSO4·7H2The molar concentration of O is
0.03mol/L。
(4) NaBH is slowly added dropwise into there-necked flask4Solution, according to n (Fe2+) and n (BH4 —) ratio 1:2, NaBH4For
0.003mol, to make reduction reaction fully carry out, configures NaBH4Claim slightly excessive NaBH during solution4Powder, weighs 0.120g's
NaBH4Powder is dissolved in 4ml absolute ethyl alcohols and the mixed solution of 6ml deionized waters, and NaBH is obtained after stirring evenly4Solution,
Complete to be added dropwise in 20min, 30min is stirred in the case where rotating speed is the mechanical agitation of 2000r/min after completion of dropwise addition.
(5) after stirring, collected with magnetic method, obtained nano zero-valence Fe nano particles wash 4 with deoxidation distilled water
It is secondary, to remove remaining ion and compound in solution, to make washing thorough, when last time is washed, the ultrasonic disperse several seconds.Wash
After washing, 24ml absolute ethyl alcohols are added toward there-necked flask is interior.
(6) by NiCl2·6H2O powder is placed in absolute ethyl alcohol, and wherein the quality of elemental nickel is the 2% of element weight of iron,
By 36ml NiCl2·6H2O ethanol solutions are slowly dropped into above-mentioned solution, are added dropwise and are completed in 20min.In 1200r/min
Mechanical agitation under be sufficiently mixed, after titration, mix 30min, which is Fe and Ni2+Metal reduction reaction.
(7) after mechanical agitation, collected with magnetic method, obtained Ni/Fe duplex metal nano granules are washed with absolute ethyl alcohol
Wash 3 times, obtain final product free from foreign meter, be dried in vacuo, weigh, about 0.1g or so.
Embodiment 3
(1) 5gPVP (K30) is dissolved in deionized water, is fully mixed by magnetic agitation, be settled to 50ml, obtain matter
Measure the PVP solution that volumetric concentration is 10%.
(2) take the 7.5mlPVP solution as described in (1) to be dissolved in the mixed solution of deionized water and absolute ethyl alcohol, be transferred to
In there-necked flask, letting nitrogen in and deoxidizing 30min.The overall solution volume is 50ml, PVP solution 7.5ml, deionized water 22.5ml, ethanol
20ml, volume ratio 3:9:9.
(3) 0.417gFeSO is weighed4·7H2O powder is added in above-mentioned solution, in the mechanical agitation that rotating speed is 2000r/min
Under the conditions of mix 20min so that FeSO4·7H2O powder fully dissolves, at this time FeSO4·7H2The molar concentration of O is
0.03mol/L。
(4) NaBH is slowly added dropwise into there-necked flask4Solution, according to n (Fe2+) and n (BH4 —) ratio 1:2, NaBH4For
0.003mol, to make reduction reaction fully carry out, configures NaBH4Claim slightly excessive NaBH during solution4Powder, weighs 0.125g's
NaBH4Powder is dissolved in 4ml absolute ethyl alcohols and the mixed solution of 6ml deionized waters, and NaBH is obtained after stirring evenly4Solution,
20min or so completes to be added dropwise, and 30min is stirred in the case where rotating speed is the mechanical agitation of 2000r/min after completion of dropwise addition.
(5) after stirring, collected with magnetic method, obtained nano zero-valence Fe nano particles wash 4 with deoxidation distilled water
It is secondary, to remove remaining ion and compound in solution, to make washing thorough, when last time is washed, the ultrasonic disperse several seconds.Wash
After washing, 24ml absolute ethyl alcohols are added toward there-necked flask is interior.
(6) by NiCl2·6H2O powder is placed in absolute ethyl alcohol, and wherein the quality of elemental nickel is the 3% of element weight of iron,
By 36mlNiCl2·6H2O ethanol solutions are slowly dropped into above-mentioned solution, are added dropwise and are completed in 25min.In 1500r/min
Mechanical agitation under be sufficiently mixed, after titration, mix 40min, which is Fe and Ni2+Metal reduction reaction.
(7) after mechanical agitation, collected with magnetic method, obtained Ni/Fe duplex metal nano granules are washed with absolute ethyl alcohol
Wash 3 times, obtain final product free from foreign meter, be dried in vacuo, weigh, about 0.1g or so.
The static experiment of degraded PCB77 is carried out with the nano particle of above-mentioned preparation：By the PCB77 that 40ml concentration is 5mg/L
Solution is placed in conical flask, leads to 20-30min of nitrogen, removes the oxygen in PCB77 solution, adds the Ni/Fe of about 0.3g or so
Duplex metal nano granule, sealing, degradation reaction carry out under anaerobic.Conical flask is placed in constant temperature oscillation case, is maintained at
Carried out under 30 DEG C of constant temperatures.The 0h, 1h, 2h carried out respectively in reaction, 4h, 8h, 12h, 24h, 36h, 48h sampling, pass through GC-
ECD Instrument measurings obtain the concentration of the PCB77 of each sample point.The concentration of 0h is denoted as initial concentration C0, the concentration measured is denoted as
Concentration C is measured, degradation rate is calculated by the following formula, and degraded figure as shown in Figure 2, degradation rate can be realized substantially
More than 82%, it is preferably able to realize 89% degradation rate.
Exemplary description has been done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent substitution of creative work equal
Fall into protection scope of the present invention.
Claims (3)
- Application of the 1.Ni/Fe bimetallic face-centered cubic crystal nano particles in Polychlorinated biphenyls is removed, it is characterised in that described Ni/Fe bimetallic face-centered cubic crystal nano particle diameters, which are evenly distributed, to be concentrated between 50-150nm, specific surface area for 30- 35m2/ g, is prepared as steps described below：Step 1, the PVP of 4-5 mass parts is dissolved in deionized water, is fully mixed by magnetic agitation, it is dense to obtain quality volume Spend the PVP solution for 8-10%；Step 2, by FeSO4·7H2O dissolves in a solvent, to obtain ferrous solution, the solvent by PVP solution, go from Sub- water and absolute ethyl alcohol composition, the volume ratio of the PVP solution, deionized water and absolute ethyl alcohol is 3：(9-10)：(8-10)； Selection inert gas is passed through in solvent to go deoxygenation, and the deoxygenation time is 20-30min；Step 3, in the ferrous solution prepared to step 2, NaBH is added dropwise4Solution, wherein n (Fe2+) and n (BH4 —) molar ratio Example 1：2, the NaBH4Solution is by NaBH4Powder is dissolved in absolute ethyl alcohol and the mixed solution of deionized water, wherein described anhydrous Ethanol and deionized water and volume ratio are 2：3；Complete in 15-20min to be added dropwise, after completion of dropwise addition rotating speed for 1500- 20-30min is stirred under the mechanical agitation of 2000r/min；Step 4, the zeroth order Fe nano particles obtained after the completion of step 3 washing is placed in absolute ethyl alcohol, and be added dropwise thereto NiCl2·6H2O ethanol solutions, described be added dropwise is completed in 15-25min, in the mechanical agitation of 1000-1500r/min Under the conditions of be sufficiently mixed, after titration, mix 20-40min, the dosage of the nickel is 2%-the 5% of divalence weight of iron；Step 5, after above-mentioned preparation process is completed, washed after being collected with magnetic method, obtain Ni/Fe bimetallic face-centered cubics Crystalline nanoparticles.
- 2. Ni/Fe bimetallics face-centered cubic crystal nano particle according to claim 1 answering in Polychlorinated biphenyls is removed With, it is characterised in that in the step 2, the volume ratio of the PVP solution, deionized water and absolute ethyl alcohol is 3：9：8.
- 3. Ni/Fe bimetallics face-centered cubic crystal nano particle according to claim 1 answering in Polychlorinated biphenyls is removed With, it is characterised in that in the step 2, the inert gas is nitrogen either argon gas or helium.
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| CN201510435864.0A CN105170990B (en) | 2014-01-02 | 2014-01-02 | Application of the Ni/Fe bimetallic face-centered cubic crystal nano particles in Polychlorinated biphenyls is removed |
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| CN201410008400.7A CN103894619B (en) | 2014-01-02 | 2014-01-02 | Ni/Fe bimetallic face-centered cubic crystal nano particle and its preparation method and application |
| CN201510435864.0A CN105170990B (en) | 2014-01-02 | 2014-01-02 | Application of the Ni/Fe bimetallic face-centered cubic crystal nano particles in Polychlorinated biphenyls is removed |
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| CN107032299B (en) * | 2016-02-03 | 2019-03-08 | 天津大学 | Carry platinum wolframic acid zinc nano material and its application in air-sensitive field |
| CN107008919A (en) * | 2017-03-07 | 2017-08-04 | 沈阳化工大学 | A kind of manganese dioxide load nano nickel iron double metal functional material preparation method |
| CN109705636A (en) * | 2019-01-24 | 2019-05-03 | 天津城建大学 | The modified Nano Fe/Cu bimetallic filler and preparation method of CMC cladding |
| CN111804930B (en) * | 2020-07-22 | 2022-10-14 | 成都理工大学 | Nano zero-valent ferro-manganese bimetal and preparation method and application thereof |
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| WO2007136757A2 (en) * | 2006-05-19 | 2007-11-29 | Usa As Represented By The Administrator Of The National Aeronautics And Space Administration | Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds |
| CN101406962A (en) * | 2008-11-12 | 2009-04-15 | 中国地质大学（北京） | Nano Ni/Fe bimetallic material for degrading halogenated hydrocarbons in water |
| CN103157810A (en) * | 2013-03-11 | 2013-06-19 | 华南师范大学 | Manufacturing method and application of poly brominated diphenyl ethers polluted soil in-situ remediation material |
| CN103317144A (en) * | 2013-06-26 | 2013-09-25 | 昆明理工大学 | Production method for iron-based nanometer thermometal particles modified by surface modifiers |
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| JPS60234904A (en) * | 1984-05-04 | 1985-11-21 | Ube Ind Ltd | Production of magnetic metallic powder |
| TWI243725B (en) * | 2003-05-27 | 2005-11-21 | Samsung Electronics Co Ltd | Method for preparing non-magnetic nickel powders |
| CN100563878C (en) * | 2003-12-01 | 2009-12-02 | 小岛化学药品株式会社 | Manufacture method with metal fine powder of uniform grading |
| TWI307297B (en) * | 2006-12-14 | 2009-03-11 | Ind Tech Res Inst | Method for manufacturing metal nano particles having hollow structure |
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2014
- 2014-01-02 CN CN201510435865.5A patent/CN104985192A/en active Pending
- 2014-01-02 CN CN201510435864.0A patent/CN105170990B/en not_active Expired - Fee Related
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| WO2007136757A2 (en) * | 2006-05-19 | 2007-11-29 | Usa As Represented By The Administrator Of The National Aeronautics And Space Administration | Mechanical alloying of a hydrogenation catalyst used for the remediation of contaminated compounds |
| CN101406962A (en) * | 2008-11-12 | 2009-04-15 | 中国地质大学（北京） | Nano Ni/Fe bimetallic material for degrading halogenated hydrocarbons in water |
| CN103157810A (en) * | 2013-03-11 | 2013-06-19 | 华南师范大学 | Manufacturing method and application of poly brominated diphenyl ethers polluted soil in-situ remediation material |
| CN103317144A (en) * | 2013-06-26 | 2013-09-25 | 昆明理工大学 | Production method for iron-based nanometer thermometal particles modified by surface modifiers |
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| CN103894619B (en) | 2016-03-30 |
| CN105170990A (en) | 2015-12-23 |
| CN103894619A (en) | 2014-07-02 |
| CN104985192A (en) | 2015-10-21 |
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