CN104858425A - Method for weakening oxidization of metal nanoparticles - Google Patents
Method for weakening oxidization of metal nanoparticles Download PDFInfo
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- CN104858425A CN104858425A CN201510240140.0A CN201510240140A CN104858425A CN 104858425 A CN104858425 A CN 104858425A CN 201510240140 A CN201510240140 A CN 201510240140A CN 104858425 A CN104858425 A CN 104858425A
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- macromolecule organic
- metal nanoparticle
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Abstract
The invention relates to a simple method for weakening oxidization of metal nanoparticles. Macromolecule organic electrolyte (polyacrylamide, polyacrylic acid and polyethylene glycol) is added into metal nanoparticle suspension liquid or added in the preparation process of the metal nanoparticles, and the macromolecule organic electrolyte wraps the surfaces of the metal nanoparticles to play a protection role; reaction of high-activity sites on the surfaces of the metal nanoparticles and surrounding media is prevented, and therefore the oxidization prevention effect is achieved. The method is easy to operate, low in cost and suitable for weakening oxidization in the storage and application processes of the metal nanoparticles, so that the application efficiency of the metal nanoparticles is increased, for example, the metal nanoparticles are adopted for the water pollution control process.
Description
Technical field
The invention provides a kind of method weakening metal nanoparticle oxidation, belong to technical field of waste water processing, be specially and add the oxidation that macromolecule organic bath weakens metal nanoparticle, improve the service efficiency of particle and the ability of process pollutant.
Background technology
In recent years, metal nanoparticle is used for the improvement of environmental contaminants and to repair be the hot subject of home and abroad environment research field always, is subject to extensive concern.Metal nanoparticle size is little, specific area is large, surface energy is high, surface atom coordination is incomplete, and have superior catalytic selectivity and high reaction activity, widely applied in environmental pollution field, the removal for many environmental contaminants is very effective.But due to the strong reactivity of high-ratio surface sum of metal nanoparticle, when nanoparticle be exposed to outer (as with air or other oxide interface) time, surface atom very easily and oxygen (refer to the oxygen in all possible oxidant, i.e. active oxygen [O]) combine and oxidized, spontaneous combustion even in atmosphere.As catalyst in use, can not namely make i.e. use, and under being placed on atmospheric environment for a long time, surface is very easily oxidized and loss of activity, now the character of particle changes metal nanoparticle.In aqueous easily and the dissolved oxygen, oxide and the water that exist in water body react, or metal nanoparticle surface is very easily oxidized loss of activity and produces surface passivation phenomenon in atmosphere, passivation layer is coated on nano particle skin and hinders internal layer outwards to transmit electronics, not only reduce its reducing property, and the further reaction of obstruction and pollutant, thus reducing the ability of process pollutant, simultaneous oxidation also causes the life cycle of metal nanoparticle to change.Such as, when nano zero valence iron is placed in the aqueous solution, reacts and generate divalence (Fe
2+) and ferric ion (Fe
3+), and be precipitated out with the form such as FeOOH and (or) tri-iron tetroxide.Oxide layer (FeOOH) in its nucleocapsid structure can react with water and be gathered into new mixed valence (Fe
2+-Fe
3+) oxide layer, cause Fe0 content to reduce, reduce the ability of going back parent pollutant.Nano aluminum particle is oxidized in atmosphere, first forms the θ-Al containing nano microcrystalline structure
2o
3with γ-Al
2o
3the microcrystalline coating of 6-10 nm, oxygen occurs to the diffusion of metal inner core (or metal exterior surface) and oxidation reaction simultaneously then, and oxide is transformed into α-Al
2o
3.The process that oxidation reaction occurs nano copper particle is in an oxygen-containing environment Cu-Cu
2o-CuO, nano nickle granules metal ion and free electron under internal electric field effect control the growth of metal oxide film surface by the Nonlinear Diffusion of nano particle oxide layer, affect the oxidation rate of nano particle.And lack a kind of effective method at present and weaken metal nanoparticle oxidation in aqueous.For weaken particle oxidation, improve pollutant treatment effect, increase the operation efficiency of particle, be necessary to seek a kind of not only economy but also can realize weakening the method for metal nanoparticle oxidation fast.
Summary of the invention
The present invention mainly weakens metal nanoparticle oxidative phenomena problem in water treatment procedure to solve, and provides a kind of method weakening metal nanoparticle oxidation.By adding macromolecule organic bath (flocculant PAM in metal nanoparticle suspension; dispersant PAA and PEG) or add macromolecule organic bath preparing in metal nanoparticle process; in macromolecule organic bath, organo-functional group carries out chemisorbed or chemical reaction to nano grain surface; thus the surface making macromolecule organic be covered in metal nanoparticle shields; prevent the medium of particle surface high activity site and surrounding (dissolved oxygen and water) to react, thus play and prevent oxidation effectiveness.
The method weakening metal nanoparticle oxidation of the present invention's proposition, concrete steps are as follows:
Utilize measuring pump to add in metal nanoparticle suspension macromolecule organic electrolyte solution that mass concentration is 0.1-3 ‰ or add the macromolecule organic bath that mass concentration is 0.1-3% in preparation process, macromolecule organic bath dosage is 0.1-3 % of metal nanoparticle quality in mixed liquor; After mixing, macromolecule organic bath is coated on nano grain surface, stops the reaction of particle surface high activity site and surrounding medium, weakens itself and water and oxygen in water and react and produce oxidative phenomena.
In the present invention, described metal nanoparticle is any one in Nanoscale Iron, nano aluminum, Nano Silver or nanogold particle etc.
In the present invention, the preparation of macromolecule organic electrolyte solution adopts mechanical agitation, and G value controls at 600 s
-1-1000 s
-1, water temperature controls at 2 DEG C-55 DEG C.
In the present invention, described macromolecule organic bath is flocculant or dispersant, described flocculant is any one in PAMA (APAM), PAMC (CPAM) or non-ionic polyacrylamide (NPAM), described dispersant is any one in polyacrylic acid (PAA) or polyethylene glycol (PEG), and molecular weight is more than 4,000,000.
In the present invention, macromolecule organic electrolyte solution adopts peristaltic pump to be added in metal nanoparticle suspension or adds preparing in metal nanoparticle process.
Beneficial effect of the present invention is:
(1) the present invention only needs to use a certain amount of macromolecule organic electrolyte solution, by hybrid reaction be coated on surface weaken metal nanoparticle oxidation, simple to operate, be easy to realize.
(2) soluble in water, the non-corrosiveness of PAM, PAA and PEG and cheap, is the conventional flocculant of water treatment field and dispersant, is suitable as water treatment and commonly uses Water purification medicament;
(3) the present invention can weaken the oxidation of metal nanoparticle effectively, does not produce any impact to the effect of metal nanoparticle, and situation of can dividing is accelerated or stoped the reunion of nano particle.
Accompanying drawing explanation
The concentration map of supernatant iron ion in nano zero valence iron and macromolecule organic bath mixed liquor in Fig. 1 embodiment 1 and example 2.
The X-ray diffractometer figure of residual solids in nano zero valence iron and macromolecule organic bath mixed liquor in Fig. 2 embodiment 1.
The X-ray diffractometer figure of residual solids in nano zero valence iron and macromolecule organic bath mixed liquor in Fig. 3 embodiment 2.
Detailed description of the invention
The present invention is further illustrated below by embodiment.
In the present invention, the macromolecule organic bath adopted in specific embodiment 1,2 is flocculating agent A PAM, CPAM and NPAM; Dispersant PAA and PEG.
Embodiment 1:
In five beakers, add APAM, CPAM, NPAM, PAA, PEG and 200 mL deionized waters that mass fraction is 1% respectively, be 800 s with G value
-1stir, add the nano zero valence iron of 5 mg/L subsequently, continue stirring reaction 2 h, after having reacted, centrifugation solids in suspension material, supernatant measures the concentration (Fig. 1) of iron ion in supernatant after 0.45 um membrane filtration by Inductively coupled plasma optical emission spectrometer (ICP-Agilent720ES), and bottom solid matter gives over to mensuration XRD sign (Fig. 2).As can be seen from Table 1 in dissimilar polyacrylamide, in APAM mixed liquor, the concentration of supernatant iron ion is minimum, show that the extent of corrosion of nano zero valence iron is lower, and maximum without the extent of corrosion of nano zero valence iron in polyacrylamide solution, and in supernatant, the concentration of iron ion is the highest.As can be seen from Figure 2 without under polyacrylamide existence condition; after nano zero valence iron and reactant aqueous solution 2 h; the peak value of oxide and the peak value ratio of Zero-valent Iron of the iron formed obviously increase; and under having polyacrylamide to exist; intensity rate is less, therefore show that the protective effect of dissimilar polyacrylamide to nano zero valence iron is followed successively by NPAM, APAM, CPAM.And for dispersant; without under dispersant existence condition; after nano zero valence iron and reactant aqueous solution 2 h; the peak value of ferriferous oxide formed and the peak value ratio of Zero-valent Iron obviously increase; and under having dispersant to exist; intensity rate is less, and the protective effect of PAA and PEG to nano zero valence iron is followed successively by PEG, PAA.It can thus be appreciated that under having polyelectrolyte existent condition, the degree of oxidation of nano zero valence iron is lower, and namely macromolecule organic bath can slow down the oxidation of nano zero valence iron.
Embodiment 2:
APAM, CPAM, NPAM, PAA and PEG that mass fraction is 1% is added respectively in five beakers containing sodium borohydride solution, being added drop-wise to gradually in liquor ferri trichloridi by sodium borohydride solution containing macromolecule electricity organic bath with peristaltic pump, is 800 s with G value
-1stirring, dropwise rear continuation stirring reaction 30 min, leave standstill centrifugation solids in suspension material, solid matter is made into the suspension of 5 g/L, is 800 s with G value at ambient temperature
-1stirring reaction 10 min, centrifugation solid matter measures XRD and characterizes (Fig. 3).As can be seen from Figure 3 without under polyelectrolyte existence condition, after nano zero valence iron and reactant aqueous solution 10 min, the peak value of ferriferous oxide formed and the peak value ratio of Zero-valent Iron obviously increase, and under having polyelectrolyte existence condition, intensity rate is less, and nano zero valence iron degree of oxidation is lower.
Claims (5)
1. weaken a method for metal nanoparticle oxidation, it is characterized in that concrete steps are as follows:
Utilize measuring pump to add in metal nanoparticle suspension macromolecule organic electrolyte solution that mass concentration is 0.1-3 ‰ or add the macromolecule organic bath that mass concentration is 0.1-3% in preparation process, macromolecule organic bath dosage is 0.1-3 % of metal nanoparticle quality in mixed liquor; After mixing, macromolecule organic bath is coated on nano grain surface, stops the reaction of particle surface high activity site and surrounding medium, weakens itself and water or oxygen in water and oxide and reacts and produce oxidative phenomena.
2. method according to claim 1, is characterized in that any one in described metal nanoparticle Nanoscale Iron, nano aluminum, Nano Silver or nanogold particle.
3. method according to claim 1, it is characterized in that the preparation of macromolecule organic electrolyte solution adopts mechanical agitation, G value controls at 600 s
-1-1000 s
-1, water temperature controls at 2 DEG C-55 DEG C.
4. method according to claim 1, it is characterized in that described macromolecule organic bath is flocculant or dispersant, described flocculant is any one in PAMA, PAMC or non-ionic polyacrylamide, described dispersant is any one in polyacrylic acid or polyethylene glycol, and molecular weight is more than 4,000,000.
5. method according to claim 1, is characterized in that, when adding macromolecule organic bath, does not stop stirred suspension and makes it mix completely.
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| CN105344377A (en) * | 2015-11-26 | 2016-02-24 | 河北麦森钛白粉有限公司 | Preparation method of nanometer titania modified photocatalyst for sewage treatment |
| CN111515383A (en) * | 2020-04-03 | 2020-08-11 | 江苏师范大学 | Silver nano triangular protection method based on ferrous ions |
| WO2021018038A1 (en) * | 2019-07-26 | 2021-02-04 | 昆山卡德姆新材料科技有限公司 | Polymer material-coated metal powder, preparation method therefor and use thereof |
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| CN105344377A (en) * | 2015-11-26 | 2016-02-24 | 河北麦森钛白粉有限公司 | Preparation method of nanometer titania modified photocatalyst for sewage treatment |
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| CN111515383A (en) * | 2020-04-03 | 2020-08-11 | 江苏师范大学 | Silver nano triangular protection method based on ferrous ions |
| CN111515383B (en) * | 2020-04-03 | 2022-05-27 | 江苏师范大学 | Silver nano triangular protection method based on ferrous ions |
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