CN102284706A - Nanoscale zero-valent iron stable in air and preparation method for the same - Google Patents
Nanoscale zero-valent iron stable in air and preparation method for the same Download PDFInfo
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Abstract
The invention discloses nanoscale zero-valent iron stable in air, wherein nanoscale zero-valent iron is taken as a core, and silicon dioxide is covered on the surface thereof. The preparation method comprises the following steps of: (1) adding isopropanol aqueous solution in ferrous sulphate, charging nitrogen, mechanically stirring for 15 to 30 minutes, dropping sodium borohydride solution containing sodium hydroxide while stirring, after that, adding polyethylene glycol, and continuing to react for 0.5 to 1 hours while stirring; (2) adding tetraethoxysilane in the solution, controlling the molar ratio of the sodium hydroxide to the sodium borohydride in the solution to be in a certain range, continuously stirring, and continuously charging nitrogen, after the reaction is finished, staying, vacuum-filtrating, then washing by absolute ethyl alcohol and deionized water respectively; and (3) vacuum-drying the obtained nano-iron to obtain the stable nanoscale zero-valent iron. The nanoscale zero-valent iron has a good inoxidizability in air; and the whole reaction process has the advantages of low material price, simple device, convenient operation, and easily-controlled and safe process condition.
Description
Technical field
The present invention relates to a kind of nano zero valence iron and preparation method thereof, belong to field of nanometer technology.Be specifically related to a kind of nano zero valence iron stable in the air and preparation method thereof.
Background technology
In recent years; nano zero valence iron is applied to environment remediation and the environmental contaminants Study on degradation has become a new focus; compare with common iron powder; nano zero valence iron has the advantages that particle diameter is little, specific area big, the surface can be big; when reacting, has higher activity with other materials; treatment effect is far superior to common iron powder; add its good reduction; make nano zero valence iron have a wide range of applications, have crucial meaning for the reparation of ecological environment and the protection of water environment at field of environment protection.
The preparation method of nano zero valence iron has much at present, but requires not only have reactivity efficiently for the nano zero valence iron in the practical application, should possess certain stability simultaneously.But the high chemical reactivity of nano zero valence iron makes its air stability relatively poor, be exposed to the oxidized even generation spontaneous combustion of meeting in the air, generate the iron oxide film and lose its surface-active on its surface, this makes nano zero valence iron be subjected to very big restriction in actual applications.Therefore the synthetic method of nanometer iron of studying a kind of efficient, cheap, stable performance is very necessary.
The preparation method of nano zero valence iron comprises liquid phase production method, its gas-phase preparation method and solid phase preparation method etc. at present.Wherein the liquid phase reduction method for preparing nano zero valence iron is to use very widely, mainly is that the solution metal molysite is generated nano zero valence iron under the effect of strong reductant.The modification of nano material and finishing are soon at the early-stage at home and abroad, are the research contents that belongs to the comparison forward position.For improve nano zero valence iron in the stability of air to reach the antioxygenic property that improves nanometer iron powder, the main at present anti-oxidant method of modifying that adopts has: (1) surperficial low-level oxidation method, nano zero valence iron is exposed to the method that makes its surperficial eremacausis in little oxygen environment, and this method can make the service efficiency of nanometer iron reduce; (2) organic matter coats method, generally adopt macromolecule organic decorated nanometer iron, but macromolecule organic can bring secondary pollution to environment usually, and operation is complicated; (3) polymer overmold method generally adopt polymer-modified nanometer iron, but this method step is complicated, complicated operation, and can cause certain pollution to environment; (4) alloying is about to noble metal and is coated on the nano zero-valence iron surface and improves its non-oxidizability, but the precious metal material costliness is not suitable for producing in enormous quantities.Shortcomings such as said method all exists apparatus expensive, operating procedure complexity to some extent, step is complicated, product purity is low, productive rate is low.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide under a kind of situation that does not reduce its reducing power and in air, have nano zero valence iron of better non-oxidizability and reactivity and preparation method thereof.
The present invention is achieved through the following technical solutions:
With ethyl orthosilicate as clad material, utilize and synthesize earlier the preparation method who afterwards modifies, liquid phase reduction is combined with finishing, in the synthetic process of nano zero valence iron, modify synchronously, make the skin of the coated with silica of teos hydrolysis generation at nano zero valence iron, reach the purpose of stabilized nanoscale Zero-valent Iron, can improve simultaneously the hydrophobic properties of the surface of nano zero valence iron, it is easilier degraded it with the concurrent former effect of surviving of ester dissolubility difficult degradation pollutant contact.The oxidation resistance of nano zero valence iron is relevant with the thickness of coated with silica layer with reducing power.Concrete steps are as follows:
A kind of nano zero valence iron stable in the air is to be core with the nano zero valence iron, is coated with silicon oxide on its surface.
A kind of preparation method of nano zero valence iron stable in the air may further comprise the steps:
(1) in ferrous sulfate, adds isopropanol water solution, feed nitrogen, behind mechanical agitation 15～30min, drip the sodium borohydride solution that contains NaOH while stirring, dropwise the back and add polyethylene glycol, continue stirring reaction 0.5～1h; The mol ratio of described copperas solution and sodium borohydride solution is 1: 1～1: 2;
(2) in above-mentioned gained solution, add ethyl orthosilicate (TEOS), the mol ratio of NaOH and sodium borohydride is 1: 10～4: 10 in the control solution, continuous stirring 1～7 hour, continue logical nitrogen in the entire reaction course, after reaction finishes, leave standstill, vacuum filtration, wash respectively with absolute ethyl alcohol and deionized water then;
(3) the nanometer iron that obtains is carried out vacuum drying, promptly obtain the stabilized nano Zero-valent Iron.
Preferably, the addition of the described isopropanol water solution of step (1) is 50～100mL, in every adding 1g ferrous sulfate; Wherein the volume ratio of isopropyl alcohol and water is 2: 1～1: 3.
Preferably, the mol ratio of sodium borohydride and NaOH is 10: 1 in the described sodium borohydride solution of step (1).
Preferably, in the step (1), the addition of described polyethylene glycol is 1/3～4/3mL, in every adding 1g ferrous sulfate.
Preferably, in the step (2), the addition of described ethyl orthosilicate is 1/3～4/3mL, in every adding 1g ferrous sulfate.
Preferably, the described vacuum drying temperature of step (3) is 80 ℃, and the time is 12h.
Advantage of the present invention and useful result are:
(1) the present invention adopts ethyl orthosilicate as clad material, utilize and synthesize earlier the preparation method who afterwards modifies, liquid phase reduction is combined with finishing, in the synthetic process of nano zero valence iron, modify synchronously, the nano zero valence iron skin that the coated with silica that teos hydrolysis is produced is generating, reach the purpose of stabilized nanoscale Zero-valent Iron, can improve simultaneously the hydrophobic properties of the surface of nano zero valence iron, it is easilier degraded it with the concurrent former effect of surviving of ester dissolubility difficult degradation pollutant contact.The entire reaction course cost of material is low, equipment is simple, easy to operate, process conditions are easy to control and safety.
(2) nano zero valence iron of the present invention's preparation has good non-oxidizability in air, and ethyl orthosilicate can not bring secondary pollution to environment.
(3) this nano zero valence iron has been because of having improved the oxidation resistance of itself, and is therefore easy to use, can be widely used in environmental improvement and environment remediation field, has market prospects preferably.
Description of drawings
Fig. 1 is the transmission electron microscope photo of nano zero valence iron of the present invention;
Fig. 2 is the XRD figure spectrum of nano zero valence iron of the present invention;
Fig. 3 is nano zero valence iron Pyrogentisinic Acid's of the present invention degradation effect figure.
The specific embodiment
The present invention is described in further detail in conjunction with the accompanying drawings by following examples.
The preparation of sodium borohydride solution: equal working concentration is the 0.5mol/L sodium borohydride solution among the embodiment, and its compound method is to take by weighing the 0.95g sodium borohydride to be dissolved in the sodium hydroxide solution of 5mL, 0.5mol/L, moves into constant volume in the 50mL volumetric flask.Dispose promptly that the mol ratio of sodium borohydride and NaOH is 10: 1 in the sodium borohydride solution.
Embodiment 1
Taking by weighing the 3.0g ferrous sulfate heptahydrate adds in the there-necked flask, and after adding isopropanol water solution 180mL (volume ratio of isopropyl alcohol and water is 2: 1), feed nitrogen, behind the mechanical agitation 15min, dripping concentration while stirring is the sodium borohydride solution 40mL of 0.5mol/L, dropwise the back and add 1mL polyethylene glycol (PEG-400), continue stirring reaction 30min, in reacted solution, add 1mL ethyl orthosilicate (TEOS), continuous stirring 1 hour, continue logical nitrogen in the entire reaction course, after reaction finishes, leave standstill 5 minutes final vacuum suction filtrations, wash respectively 3 times with absolute ethyl alcohol and deionized water then, the nanometer iron that obtains is transferred to 80 ℃ of dry 12h in the vacuum drying chamber, promptly makes the stabilized nano Zero-valent Iron.
Embodiment 2
Taking by weighing the 3.0g ferrous sulfate heptahydrate adds in the there-necked flask, and after adding isopropanol water solution 180mL (volume ratio of isopropyl alcohol and water is 1: 2), feed nitrogen, behind the mechanical agitation 15min, dripping concentration while stirring is the sodium borohydride solution 40mL of 0.5mol/L, dropwise the back and add 3mL polyethylene glycol (PEG-400), continue stirring reaction 30min, the sodium hydroxide solution 8mL that in reacted solution, adds 3mL ethyl orthosilicate (TEOS) and 0.5mol/L, continuous stirring 1 hour, continue logical nitrogen in the entire reaction course, after reaction finishes, leave standstill 5 minutes final vacuum suction filtrations, wash respectively 3 times with absolute ethyl alcohol and deionized water then, the nanometer iron that obtains is transferred to 80 ℃ of dry 12h in the vacuum drying chamber, promptly makes the stabilized nano Zero-valent Iron.
Embodiment 3
Taking by weighing the 3.0g ferrous sulfate heptahydrate adds in the there-necked flask, and after adding isopropanol water solution 180mL (volume ratio of isopropyl alcohol and water is 1: 2), feed nitrogen, behind the mechanical agitation 15min, dripping concentration while stirring is the sodium borohydride solution 40mL of 0.5mol/L, dropwise the back and add 4mL polyethylene glycol (PEG-400), continue stirring reaction 30min, the sodium hydroxide solution 4mL that in reacted solution, adds 3mL ethyl orthosilicate (TEOS) and 0.5mol/L, continuous stirring 3 hours, continue logical nitrogen in the entire reaction course, after reaction finishes, leave standstill 5 minutes final vacuum suction filtrations, wash respectively 3 times with absolute ethyl alcohol and deionized water then, the nanometer iron that obtains is transferred to 80 ℃ of dry 12h in the vacuum drying chamber, promptly makes the stabilized nano Zero-valent Iron.
Embodiment 4
Taking by weighing the 3.0g ferrous sulfate heptahydrate adds in the there-necked flask, and after adding isopropanol water solution 180mL (volume ratio of isopropyl alcohol and water is 1: 2), feed nitrogen, behind the mechanical agitation 15min, dripping concentration while stirring is the sodium borohydride solution 40mL of 0.5mol/L, dropwise the back and add 2mL polyethylene glycol (PEG-400), continue stirring reaction 30min, the sodium hydroxide solution 12mL that in reacted solution, adds 1mL ethyl orthosilicate (TEOS) and 0.5mol/L, continuous stirring 3 hours, continue logical nitrogen in the entire reaction course, after reaction finishes, leave standstill 5 minutes final vacuum suction filtrations, wash respectively 3 times with absolute ethyl alcohol and deionized water then, the nanometer iron that obtains is transferred to 80 ℃ of dry 12h in the vacuum drying chamber, promptly makes the stabilized nano Zero-valent Iron.
Embodiment 5
Taking by weighing the 3.0g ferrous sulfate heptahydrate adds in the there-necked flask, and after adding isopropanol water solution 180mL (volume ratio of isopropyl alcohol and water is 2: 1), feed nitrogen, behind the mechanical agitation 15min, dripping concentration while stirring is the sodium borohydride solution 40mL of 0.5mol/L, dropwise the back and add 2mL polyethylene glycol (PEG-400), continue stirring reaction 30min, the sodium hydroxide solution 8mL that in reacted solution, adds 4mL ethyl orthosilicate (TEOS) and 0.5mol/L, continuous stirring 5 hours, continue logical nitrogen in the entire reaction course, after reaction finishes, leave standstill 5 minutes final vacuum suction filtrations, wash respectively 3 times with absolute ethyl alcohol and deionized water then, the nanometer iron that obtains is transferred to 80 ℃ of dry 12h in the vacuum drying chamber, promptly makes the stabilized nano Zero-valent Iron.
Embodiment 6
Taking by weighing the 3.0g ferrous sulfate heptahydrate adds in the there-necked flask, and after adding isopropanol water solution 180mL (volume ratio of isopropyl alcohol and water is 1: 2), feed nitrogen, behind the mechanical agitation 15min, dripping concentration while stirring is the sodium borohydride solution 40mL of 0.5mol/L, dropwise the back and add 4mL polyethylene glycol (PEG-400), continue stirring reaction 30min, in reacted solution, add 2mL ethyl orthosilicate (TEOS), continuous stirring 5 hours, continue logical nitrogen in the entire reaction course, after reaction finishes, leave standstill 5 minutes final vacuum suction filtrations, wash respectively 3 times with absolute ethyl alcohol and deionized water then, the nanometer iron that obtains is transferred to 80 ℃ of dry 12h in the vacuum drying chamber, promptly makes the stabilized nano Zero-valent Iron.
Embodiment 7
Taking by weighing the 3.0g ferrous sulfate heptahydrate adds in the there-necked flask, and after adding isopropanol water solution 180mL (volume ratio of isopropyl alcohol and water is 2: 1), feed nitrogen, behind the mechanical agitation 15min, dripping concentration while stirring is the sodium borohydride solution 40mL of 0.5mol/L, dropwise the back and add 3mL polyethylene glycol (PEG-400), continue stirring reaction 30min, the sodium hydroxide solution 12mL that in reacted solution, adds 2mL ethyl orthosilicate (TEOS) and 0.5mol/L, continuous stirring 7 hours, continue logical nitrogen in the entire reaction course, after reaction finishes, leave standstill 5 minutes final vacuum suction filtrations, wash respectively 3 times with absolute ethyl alcohol and deionized water then, the nanometer iron that obtains is transferred to 80 ℃ of dry 12h in the vacuum drying chamber, promptly makes the stabilized nano Zero-valent Iron.
Embodiment 8
Taking by weighing the 3.0g ferrous sulfate heptahydrate adds in the there-necked flask, and after adding isopropanol water solution 180mL (volume ratio of isopropyl alcohol and water is 1: 3), feed nitrogen, behind the mechanical agitation 15min, dripping concentration while stirring is the sodium borohydride solution 40mL of 0.5mol/L, dropwise the back and add 1mL polyethylene glycol (PEG-400), continue stirring reaction 30min, the sodium hydroxide solution 4mL that in reacted solution, adds 4mL ethyl orthosilicate (TEOS) and 0.5mol/L, continuous stirring 7 hours, continue logical nitrogen in the entire reaction course, after reaction finishes, leave standstill 5 minutes final vacuum suction filtrations, wash respectively 3 times with absolute ethyl alcohol and deionized water then, the nanometer iron that obtains is transferred to 80 ℃ of dry 12h in the vacuum drying chamber, promptly makes the stabilized nano Zero-valent Iron.
The experiment test explanation:
The interpretation of result of stabilized nano Zero-valent Iron is as follows in the air that the present invention of use TEM (transmission electron microscope), XRD (X-ray diffraction) mensuration obtains:
(1) test result of TEM
TEM result shows about the particle diameter 50nm of nano zero valence iron of acquisition and the coated with uniform layer of silicon dioxide, about coating thickness 10nm.Referring to Fig. 1.
(2) method of testing of XRD
Adopt XRD that product is carried out material phase analysis, exposes nano zero valence iron XRD figure spectrum after ten days when 2 θ are respectively 44.706 ° and 26.729 °, appear as the characteristic peak of Zero-valent Iron and silica respectively, and the oxidation iron peak does not appear in the while.Referring to Fig. 2.
(3) stabilized nano Zero-valent Iron contrast test is as follows in the air of the present invention's preparation:
The degradation effect that utilizes the nano zero valence iron Pyrogentisinic Acid after nano zero valence iron and the coated with silica as shown in Figure 3, the simulated water sample that adds certain phenol concentration in the 50mL reaction bulb, phenol concentration is 155.85mg/L, nano zero valence iron after the coated with silica is 0.6g/L, adds the phenol simulated water sample and add nano zero valence iron simultaneously as parallel laboratory test in an other reaction bulb.Behind the 96h in two reaction bulbs phenol concentration similar, illustrate that the reducing power of the nano zero valence iron after the coated with silica is not affected.Referring to Fig. 3.
Claims (7)
1. a nano zero valence iron stable in the air is characterized in that, is to be core with the nano zero valence iron, is coated with silicon oxide on its surface.
2. the preparation method of a nano zero valence iron stable in the air may further comprise the steps:
(1) in ferrous sulfate, adds isopropanol water solution, feed nitrogen, behind mechanical agitation 15～30min, drip the sodium borohydride solution that contains NaOH while stirring, dropwise the back and add polyethylene glycol, continue stirring reaction 0.5～1h; The mol ratio of described copperas solution and sodium borohydride solution is 1: 1～1: 2;
(2) in above-mentioned gained solution, add ethyl orthosilicate, the mol ratio of NaOH and sodium borohydride is 1: 10～4: 10 in the control solution, continuous stirring 1～7 hour, continue logical nitrogen in the entire reaction course, after reaction finishes, leave standstill, vacuum filtration, wash respectively with absolute ethyl alcohol and deionized water then;
(3) the nanometer iron that obtains is carried out vacuum drying, promptly obtain the stabilized nano Zero-valent Iron.
3. preparation method according to claim 2 is characterized in that: the addition of the described isopropanol water solution of step (1) is 50～100mL, in every adding 1g ferrous sulfate; Wherein the volume ratio of isopropyl alcohol and water is 2: 1～1: 3.
4. preparation method according to claim 3 is characterized in that: the mol ratio of sodium borohydride and NaOH is 10: 1 in the described sodium borohydride solution of step (1).
5. preparation method according to claim 4 is characterized in that: in the step (1), the addition of described polyethylene glycol is 1/3～4/3mL, in every adding 1g ferrous sulfate.
6. according to claim 2 or 3 or 4 or 5 described preparation methods, it is characterized in that: in the step (2), the addition of described ethyl orthosilicate is 1/3～4/3mL, in every adding 1g ferrous sulfate.
7. preparation method according to claim 6 is characterized in that: the described vacuum drying temperature of step (3) is 80 ℃, and the time is 12h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472024A (en) * | 2003-06-27 | 2004-02-04 | 南京大学 | High magnetization intensity and stability iron nanometer particle with SiO coated on surface and preparing method thereof |
| CN1594450A (en) * | 2004-06-30 | 2005-03-16 | 南京大学 | Core/shell structure containing Fe/SiO2 composite nano particles with high stability and method for making same |
| CN1817786A (en) * | 2006-01-18 | 2006-08-16 | 南京大学 | Two-dimensional fractional standing point array with ordered Fe/SiO2 composite nanometer particle and production thereof |
-
2011
- 2011-08-15 CN CN 201110233166 patent/CN102284706B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1472024A (en) * | 2003-06-27 | 2004-02-04 | 南京大学 | High magnetization intensity and stability iron nanometer particle with SiO coated on surface and preparing method thereof |
| CN1594450A (en) * | 2004-06-30 | 2005-03-16 | 南京大学 | Core/shell structure containing Fe/SiO2 composite nano particles with high stability and method for making same |
| CN1817786A (en) * | 2006-01-18 | 2006-08-16 | 南京大学 | Two-dimensional fractional standing point array with ordered Fe/SiO2 composite nanometer particle and production thereof |
Non-Patent Citations (2)
| Title |
|---|
| > 20081215 汪艳梅 核壳型磁性纳米金属铁的制备及表征 第40-42页 1-7 , * |
| 汪艳梅: "核壳型磁性纳米金属铁的制备及表征", <<中南大学硕士学位论文>>, 15 December 2008 (2008-12-15), pages 40 - 42 * |
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| CN112875773B (en) * | 2021-01-06 | 2022-09-23 | 湖南工业大学 | Surface-modified magnetic nano zero-valent iron composite material and preparation method thereof |
| CN113198416A (en) * | 2021-03-26 | 2021-08-03 | 同济大学 | Preparation method and application of zero-valent iron/mesoporous silica composite material |
| CN114192080A (en) * | 2021-12-09 | 2022-03-18 | 安徽工业大学 | Nano iron-based particles and preparation method and application thereof |
| CN114192080B (en) * | 2021-12-09 | 2024-03-26 | 安徽工业大学 | Nanometer iron-based particle and preparation method and application thereof |
| CN115106519A (en) * | 2022-06-09 | 2022-09-27 | 南开大学 | Superparamagnetic nano-iron material, composite material thereof, preparation method and application |
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