CN103894619B - Ni/Fe bimetallic face-centered cubic crystal nano particle and its preparation method and application - Google Patents
Ni/Fe bimetallic face-centered cubic crystal nano particle and its preparation method and application Download PDFInfo
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- CN103894619B CN103894619B CN201410008400.7A CN201410008400A CN103894619B CN 103894619 B CN103894619 B CN 103894619B CN 201410008400 A CN201410008400 A CN 201410008400A CN 103894619 B CN103894619 B CN 103894619B
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- deionized water
- ethyl alcohol
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Abstract
The invention discloses Ni/Fe bimetallic face-centered cubic crystal nano particle and its preparation method and application, adopt liquid phase reduction, using PVP as stabilizing agent, with NaBH
4as reducing agent, substep adds ferrous ion and nickel ion reduces, and the Ni/Fe duplex metal nano granule prepared is the face-centerd cubic structure of rule, even particle size distribution, and specific area is large, and stability is good, not easily polymerism occurs.The nano particle utilizing technical solution of the present invention to prepare can catalytic degradation Polychlorinated biphenyls effectively.Consersion unit required for the present invention is simple, equipment cost is also lower.Preparation technology's controllability is comparatively strong, easy and simple to handle, and reaction condition is gentle, for further suitability for industrialized production provides possibility.
Description
Technical field
The invention belongs to technical field of nano material, more particularly, relate to a kind of preparation method and application of face-centered cube nano crystal particles, be specifically related to a kind of using PVP as macromolecular template, utilize liquid phase reduction to prepare the methods and applications of Ni/Fe double-metal-face body-centred cube nano crystal particles.
Background technology
Polychlorinated biphenyls (PolychlorinatedBiphenyls is called for short PCBs) is a kind of typical persistence organic pollutant in environment.Because it has higher chemical inertness, heat endurance, anti-flammability, thermal conductivity and insulating properties, be once widely used in the fields such as power industry, Plastics Processing Industry, chemical industry and printing.According to the World Health Organization's statistics, since eighties of last century to start production the twenties, to the end of the eighties, the whole world produces about 2 × 10 altogether
7t Industrial PC Bs, wherein about 31% is discharged in environment.Because PCBs has biological accumulation and " three cause " effect, can long-distance migration in the world, and in its migration, conversion process, amplification can be bioaccumulation, its concentration level may improve decades of times even hundreds of times, produces threaten greatly ecological environment and health.United Nations Environment Programme is classified as one of 12 kinds of persistence toxic organic pollutants of Global Priority control, and most industryization country is after 20 century 70s, stop producing Polychlorinated biphenyls, but due to its stable in properties, not easily degrade in the environment, Polychlorinated biphenyls also will continue a very long time to the pollution of environment.
In view of the generality that PCBs exists in water body, Chinese scholars has carried out a series of research for the degraded of PCBs in recent ten years, research shows, the committed step of PCBs degraded is dechlorination reaction, and the method for employing mainly contains hydrogenization method, chlorinolysis method, reversion method and metal deoxidization etc.Wherein, utilize metal deoxidization process Polychlorinated biphenyls to be a most active investigative technique at present, there is very large potential, be even considered to one of method having application prospect most abroad.Zero-valent metal is owing to having very strong reproducibility, and cheap and easy to get, therefore can be used as reducing agent, makes Polychlorinated biphenyls slough chlorine atom, thus reduces the toxicity of Polychlorinated biphenyls.Conventional zero-valent metal has iron, aluminium, magnesium, zinc and tin etc., in numerous zero-valent metal, utilize Zero-valent Iron and compound reduction thereof to remove the most study of halogenated organic and Polychlorinated biphenyls, and iron is safe from harm for environment, so become relatively more conventional Polychlorinated biphenyls catalysis dechlorination method.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of the Ni/Fe bimetallic face-centered cubic crystal nano particle for degradation of polychlorinated biphenyl is provided, this preparation method is easy and simple to handle, reaction condition is gentle, course of reaction is easily controlled, environmentally friendly, and obtained reactor product is stablized, and not easily polymerism occurs.
Ni/Fe bimetallic face-centered cubic crystal nano particle and preparation method thereof, is prepared according to following step:
Step 1, is dissolved in deionized water by the PVP of 4-5 mass parts, is fully mixed by magnetic agitation, obtains the PVP solution that mass body volume concentrations is 8-10%;
Step 2, by FeSO
47H
2o dissolves in a solvent, to obtain ferrous solution, described solvent is made up of PVP solution, deionized water and absolute ethyl alcohol, and the volume ratio of described PVP solution, deionized water and absolute ethyl alcohol is 3:(9-10): (8-10), preferred volume ratio is 3:9:8; Select inert gas to pass into remove oxygen in solvent, wherein said inert gas is nitrogen or argon gas or helium, and the deoxygenation time is 20-30min;
Step 3, in ferrous solution prepared by step 2, drips NaBH
4solution, wherein n (Fe
2+) and n (BH
4-) molar ratio 1:2, for making reduction reaction fully carry out, preferably excessive NaBH
4solution, described NaBH
4solution is by NaBH
4powder is dissolved in the mixed solution of absolute ethyl alcohol and deionized water, and wherein said absolute ethyl alcohol and deionized water and volume ratio are 2:3; In 15-20min, complete dropping, drip after terminating and stir 20-30min under rotating speed is the mechanical agitation of 1500-2000r/min;
Step 4, the zeroth order Fe nano particle obtained after step 3 being completed washing is placed in absolute ethyl alcohol, and drips NiCl wherein
26H
2o ethanol solution, described dropping completes in 15-25min, fully mixes under the mechanical agitation of 1000-1500r/min, and after titration terminates, mixing 20-40min, the consumption of described nickel is 2%-5% of ferrous iron (i.e. ferro element) quality.
Step 5, after after completing above-mentioned preparation process, namely mechanical agitation terminates, collect by magnetic method, the Ni/Fe duplex metal nano granule absolute ethanol washing obtained 3 times, obtains product finally free from foreign meter.
Ni/Fe bimetallic face-centered cubic crystal nano particle according to technique scheme is removing the application in Polychlorinated biphenyls.
Realize following whole course of reaction in the inventive solutions step by step:
Fe(H
2O)
6 2++2BH
4-→Fe↓+2Be(OH)
3+7H
2↑
Ni
2++Fe
0→Fe
2++Ni↓
In this course, first generate iron, then at addition element nickel, to react with iron, owing to fully mixing under the condition that the less and system of the addition of elemental nickel stirs at continued mechanical and reacting, after drop reaction terminates, 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, usually selects Ni/Fe duplex metal nano granule degradation of polychlorinated biphenyl cheap and easy to get.The liquid phase reduction selected has simple to operate, process control is strong, cost is the advantage such as lower also, usually sodium borohydride liquid phase reduction is selected to prepare Ni/Fe duplex metal nano granule, but the nano particle prepared easily is reunited, and affects degradation efficiency, so add stabilizing agent PVP(K30 in liquid phase preparation process), PVP(K30) reunion of nano particle can be prevented, also can not have an impact to the degradation process of bimetallic system.Compared with prior art, advantage of the present invention and beneficial effect are:
(1) consersion unit required for the present invention is simple, equipment cost is also lower.
(2) bimetallic preparation technology controllability of the present invention is comparatively strong, easy and simple to handle, and reaction condition is gentle, for further suitability for industrialized production provides possibility, and PVP(K30) cheap and easy to get, be widely used in medicine and accurate chemical industry.
(3) the Ni/Fe bimetal nano face-centered cubic crystal specific grain surface obtained by the present invention is long-pending large, dispersed and be not easily polymerized, product structure is stablized, observed by sweep electron microscope, the Ni/Fe duplex metal nano granule generated is the face-centered cube of rule, even particle size distribution concentrates between 50-150nm, and specific area is 30-35m
2/ g, to the removal ability of Polychlorinated biphenyls far away higher than nano iron particles.
Accompanying drawing explanation
Fig. 1 is SEM (SEM) picture of Ni/Fe bimetallic face-centered cubic crystal nano particle prepared by the present invention.
Fig. 2 is the Ni/Fe bimetallic face-centered cubic crystal nano particle prepared of the present invention in degradation water during PCB77, measures concentration C and initial concentration C
0the change curve of ratio (h) in time.
Detailed description of the invention
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
(1) by 4gPVP(K30) be dissolved in deionized water, fully mixed by magnetic agitation, be settled to 50ml, obtain the PVP solution that mass body volume concentrations is 8%.
(2) get as described in (1) 7.5mlPVP solution be dissolved in the mixed solution of deionized water and absolute ethyl alcohol, proceed in there-necked flask, letting nitrogen in and deoxidizing 30min.This overall solution volume is 50ml, PVP solution 7.5ml, deionized water 22.5ml, ethanol 20ml, and volume ratio is 3:9:8.
(3) 0.417gFeSO is taken
47H
2o powder adds in above-mentioned solution, is to mix 20min under the mechanical agitation of 2000r/min at rotating speed, makes FeSO
47H
2o powder fully dissolves, now FeSO
47H
2the molar concentration of O is 0.03mol/L.
(4) slowly in there-necked flask, NaBH is dripped
4solution, according to n (Fe
2+) and n (BH
4-) ratio 1:2, NaBH
4for 0.003mol, for making reduction reaction fully carry out, configuration NaBH
4the NaBH little over amount is claimed during solution
4powder, weighs the NaBH of 0.125g
4powder is dissolved in the mixed solution of 4ml absolute ethyl alcohol and 6ml deionized water, obtains NaBH after stirring
4solution, completes dropping at 20min, drips after terminating and stir 30min under rotating speed is the mechanical agitation of 2000r/min.
(5), after stirring terminates, collect by magnetic method, the nano zero-valence Fe nano particle deoxidation distilled water obtained washs 4 times, to remove ion residual in solution and compound, for making washing thorough, when washing for the last time, and the ultrasonic disperse several seconds.After washing terminates, in there-necked flask, add 24ml absolute ethyl alcohol.
(6) by NiCl
26H
2o powder is placed in absolute ethyl alcohol, and wherein the quality of elemental nickel is 5% of elemental iron quality, by 36mlNiCl
26H
2o ethanol solution slowly instills in above-mentioned solution, drips and completes in 25min.Fully mix under the mechanical agitation of 1500r/min, after titration terminates, mixing 20min, this process is Fe and Ni
2+metal reduction reaction.
(7) after mechanical agitation terminates, collect by magnetic method, the Ni/Fe duplex metal nano granule absolute ethanol washing obtained 3 times, obtains product finally free from foreign meter, vacuum drying, weighs, is about about 0.1g.
Embodiment 2
(1) by 5gPVP(K30) be dissolved in deionized water, fully mixed by magnetic agitation, be settled to 50ml, obtain the PVP solution that mass body volume concentrations is 10%.
(2) get as described in (1) 7.5mlPVP solution be dissolved in the mixed solution of deionized water and absolute ethyl alcohol, proceed in there-necked flask, letting nitrogen in and deoxidizing 30min.This overall solution volume is 50ml, PVP solution 7.5ml, deionized water 22.5ml, ethanol 20ml, and volume ratio is 3:10:10.
(3) 0.417gFeSO is taken
47H
2o powder adds in above-mentioned solution, is to mix 15min under the mechanical agitation of 2000r/min at rotating speed, makes FeSO
47H
2o powder fully dissolves, now FeSO
47H
2the molar concentration of O is 0.03mol/L.
(4) slowly in there-necked flask, NaBH is dripped
4solution, according to n (Fe
2+) and n (BH
4-) ratio 1:2, NaBH
4for 0.003mol, for making reduction reaction fully carry out, configuration NaBH
4the NaBH little over amount is claimed during solution
4powder, weighs the NaBH of 0.120g
4powder is dissolved in the mixed solution of 4ml absolute ethyl alcohol and 6ml deionized water, obtains NaBH after stirring
4solution, completes dropping in 20min, drips after terminating and stir 30min under rotating speed is the mechanical agitation of 2000r/min.
(5), after stirring terminates, collect by magnetic method, the nano zero-valence Fe nano particle deoxidation distilled water obtained washs 4 times, to remove ion residual in solution and compound, for making washing thorough, when washing for the last time, and the ultrasonic disperse several seconds.After washing terminates, in there-necked flask, add 24ml absolute ethyl alcohol.
(6) by NiCl
26H
2o powder is placed in absolute ethyl alcohol, and wherein the quality of elemental nickel is 2% of elemental iron quality, by 36mlNiCl
26H
2o ethanol solution slowly instills in above-mentioned solution, drips and completes in 20min.Fully mix under the mechanical agitation of 1200r/min, after titration terminates, mixing 30min, this process is Fe and Ni
2+metal reduction reaction.
(7) after mechanical agitation terminates, collect by magnetic method, the Ni/Fe duplex metal nano granule absolute ethanol washing obtained 3 times, obtains product finally free from foreign meter, vacuum drying, weighs, is about about 0.1g.
Embodiment 3
(1) by 5gPVP(K30) be dissolved in deionized water, fully mixed by magnetic agitation, be settled to 50ml, obtain the PVP solution that mass body volume concentrations is 10%.
(2) get as described in (1) 7.5mlPVP solution be dissolved in the mixed solution of deionized water and absolute ethyl alcohol, proceed in there-necked flask, letting nitrogen in and deoxidizing 30min.This overall solution volume is 50ml, PVP solution 7.5ml, deionized water 22.5ml, ethanol 20ml, and volume ratio is 3:9:9.
(3) 0.417gFeSO is taken
47H
2o powder adds in above-mentioned solution, is to mix 20min under the mechanical agitation of 2000r/min at rotating speed, makes FeSO
47H
2o powder fully dissolves, now FeSO
47H
2the molar concentration of O is 0.03mol/L.
(4) slowly in there-necked flask, NaBH is dripped
4solution, according to n (Fe
2+) and n (BH
4-) ratio 1:2, NaBH
4for 0.003mol, for making reduction reaction fully carry out, configuration NaBH
4the NaBH little over amount is claimed during solution
4powder, weighs the NaBH of 0.125g
4powder is dissolved in the mixed solution of 4ml absolute ethyl alcohol and 6ml deionized water, obtains NaBH after stirring
4solution, completes dropping at about 20min, drips after terminating and stir 30min under rotating speed is the mechanical agitation of 2000r/min.
(5), after stirring terminates, collect by magnetic method, the nano zero-valence Fe nano particle deoxidation distilled water obtained washs 4 times, to remove ion residual in solution and compound, for making washing thorough, when washing for the last time, and the ultrasonic disperse several seconds.After washing terminates, in there-necked flask, add 24ml absolute ethyl alcohol.
(6) by NiCl
26H
2o powder is placed in absolute ethyl alcohol, and wherein the quality of elemental nickel is 3% of elemental iron quality, by 36mlNiCl
26H
2o ethanol solution slowly instills in above-mentioned solution, drips and completes in 25min.Fully mix under the mechanical agitation of 1500r/min, after titration terminates, mixing 40min, this process is Fe and Ni
2+metal reduction reaction.
(7) after mechanical agitation terminates, collect by magnetic method, the Ni/Fe duplex metal nano granule absolute ethanol washing obtained 3 times, obtains product finally free from foreign meter, vacuum drying, weighs, is about about 0.1g.
The static experiment of PCB77 of degrading is carried out: be that the PCB77 solution of 5mg/L is placed in conical flask by 40ml concentration with the nano particle of above-mentioned preparation, logical nitrogen 20-30min, remove the oxygen in PCB77 solution, add the Ni/Fe duplex metal nano granule of about about 0.3g again, sealing, degradation reaction is under anaerobic carried out.Conical flask is placed in constant temperature oscillation case, carries out under remaining on 30 DEG C of constant temperatures.Reacting the 0h carried out respectively, 1h, 2h, 4h, 8h, 12h, 24h, 36h, 48h sample, and are obtained the concentration of the PCB77 of each sample point by GC-ECD Instrument measuring.The concentration of 0h is designated as initial concentration C
0, the concentration recorded is designated as measurement concentration C, and degradation rate is obtained by following formulae discovery, degraded figure as shown in Figure 2, and degradation rate can realize more than 82% substantially, preferably can realize the degradation rate of 89%.
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.
Claims (3)
1.Ni/Fe bimetallic face-centered cubic crystal nano particle, it is characterized in that, even particle size distribution concentrates between 50-150nm, and specific area is 30-35m
2/ g, is prepared according to following step:
Step 1, is dissolved in deionized water by the PVP of 4-5 mass parts, is fully mixed by magnetic agitation, obtains the PVP solution that mass body volume concentrations is 8-10%;
Step 2, by FeSO
47H
2o dissolves in a solvent, and to obtain ferrous solution, described solvent is made up of PVP solution, deionized water and absolute ethyl alcohol, and the volume ratio of described PVP solution, deionized water and absolute ethyl alcohol is 3:(9-10): (8-10); Select inert gas to pass into remove oxygen in solvent, the deoxygenation time is 20-30min;
Step 3, in ferrous solution prepared by step 2, drips NaBH
4solution, wherein n (Fe
2+) and n (BH
4 -) molar ratio 1:2, described NaBH
4solution is by NaBH
4powder is dissolved in the mixed solution of absolute ethyl alcohol and deionized water, and the volume ratio of wherein said absolute ethyl alcohol and deionized water is 2:3; In 15-20min, complete dropping, drip after terminating and stir 20-30min under rotating speed is the mechanical agitation of 1500-2000r/min;
Step 4, the zeroth order Fe nano particle obtained after step 3 being completed washing is placed in absolute ethyl alcohol, and drips NiCl wherein
26H
2o ethanol solution, described dropping completes in 15-25min, fully mixes under the mechanical agitation of 1000-1500r/min, after titration terminates, mixing 20-40min, the consumption of described nickel is 2%-5% of ferrous iron quality;
Step 5, after completing above-mentioned preparation process, washs after collecting, obtain Ni/Fe bimetallic face-centered cubic crystal nano particle by magnetic method.
2. Ni/Fe bimetallic face-centered cubic crystal nano particle according to claim 1, is characterized in that, in described step 2, the volume ratio of described PVP solution, deionized water and absolute ethyl alcohol is 3:9:8.
3. Ni/Fe bimetallic face-centered cubic crystal nano particle according to claim 1, is characterized in that, in described step 2, described inert gas is nitrogen or argon gas or helium.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510435865.5A CN104985192A (en) | 2014-01-02 | 2014-01-02 | Method for preparing Ni/Fe bi-metal face-centered cubic crystal nano particles |
| 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 |
| 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 |
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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 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510435865.5A Division CN104985192A (en) | 2014-01-02 | 2014-01-02 | Method for preparing Ni/Fe bi-metal face-centered cubic crystal nano particles |
| CN201510435864.0A Division 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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| CN103894619A CN103894619A (en) | 2014-07-02 |
| CN103894619B true CN103894619B (en) | 2016-03-30 |
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| CN201510435865.5A Pending CN104985192A (en) | 2014-01-02 | 2014-01-02 | Method for preparing Ni/Fe bi-metal face-centered cubic crystal nano particles |
| CN201510435864.0A Expired - Fee Related 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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| CN201510435864.0A Expired - Fee Related 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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|---|---|---|---|---|
| JPS60234904A (en) * | 1984-05-04 | 1985-11-21 | Ube Ind Ltd | Production of magnetic metallic powder |
| JP2004353089A (en) * | 2003-05-27 | 2004-12-16 | Samsung Electronics Co Ltd | Method for producing non-magnetic nickel powder |
| CN1913995A (en) * | 2003-12-01 | 2007-02-14 | 小岛化学药品株式会社 | Process for producing metal micropowder having particle diameter uniformalized |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7842639B2 (en) * | 2006-05-19 | 2010-11-30 | The United States Of America 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 |
| TWI307297B (en) * | 2006-12-14 | 2009-03-11 | Ind Tech Res Inst | Method for manufacturing metal nano particles having hollow structure |
-
2014
- 2014-01-02 CN CN201410008400.7A patent/CN103894619B/en not_active Expired - Fee Related
- 2014-01-02 CN CN201510435865.5A patent/CN104985192A/en active Pending
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60234904A (en) * | 1984-05-04 | 1985-11-21 | Ube Ind Ltd | Production of magnetic metallic powder |
| JP2004353089A (en) * | 2003-05-27 | 2004-12-16 | Samsung Electronics Co Ltd | Method for producing non-magnetic nickel powder |
| CN1913995A (en) * | 2003-12-01 | 2007-02-14 | 小岛化学药品株式会社 | Process for producing metal micropowder having particle diameter uniformalized |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103894619A (en) | 2014-07-02 |
| CN105170990A (en) | 2015-12-23 |
| CN104985192A (en) | 2015-10-21 |
| CN105170990B (en) | 2018-05-08 |
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