A kind of preparation of nanomaterials of magnetic and application thereof
Technical field
The present invention relates to preparation of nanomaterials and application thereof, particularly the preparation method of carbon-cladded magnetic metal nanometer material and application thereof.
Background technology
Traditional preparation carbon-cladded magnetic metal nanometer material is to utilize physical means as vapour deposition process, arc-discharge technique, pyrolysismethod, ion beam sputtering, electron beam irradiation method, metallic charcoal gel explosion method, laser evaporation method, plasma evaporation method etc., the equipment complexity that these methods are used, complex operation, cost height, preparation temperature height, energy consumption are greatly, reaction is violent and accessory substance is many, thereby are difficult to realize large-scale production.Chinese patent CN1951608A has introduced a kind of preparation method of carbon-cladded magnetic metal nanometer material, and this method is the reduction route under inert gas shielding and highly basic condition, therefore, and severe reaction conditions; Simultaneously, this method is not used the auxiliary of any surfactant, and the nano material of gained magnetic does not have the surface topography of rule.
Summary of the invention
The 1st technical problem to be solved by this invention provide a kind of simple magnetic Nano material the preparation method.
The 2nd technical problem to be solved by this invention is the application of above-mentioned magnetic Nano material.
The technical scheme of the technical problem that the present invention solves is: a kind of preparation of nanomaterials of magnetic, comprise that nano metallic nickel granular material preparation process, carbon coat process,
Described nano metallic nickel granular material preparation process is:
With anionic surfactant, soluble nickel salt and strong reductant are dissolved in the distilled water, successively with N, dinethylformamide (DMF) and highly basic slowly add in the above-mentioned solution, after mixing under the situation of magnetic agitation, heat up 140~180 ℃, reacted 10-12 hour, and be cooled to room temperature, spend deionised water for several times, 50-60 ℃ is dried to constant weight in vacuum drying chamber, and products therefrom is a magnetic nano-balls.
The mol ratio 1 of soluble nickel salt and anion surfactant: 0.15-0.3.
Described anion surfactant is neopelex (SDBS), lauryl sodium sulfate (SDS).
Described soluble nickel salt is a nickel chloride, nickelous sulfate, and nickel acetate, its chemical formula is respectively NiCl
2, NiSO
4, Ni (CH
3COO)
2
Described strong reductant is hydrazine hydrate, sodium hypophosphite, sodium borohydride.
Described carbon coating process is:
With the ultrasonic weight concentration that is scattered in of made magnetic nano-particle is in the 10-15% glucose solution, and reaction was cooled to room temperature after 3-4 hour under 160-170 ℃, spent deionised water, was dried to constant weight in vacuum drying chamber under 50-60 ℃, got final product.
The application of the nano material of the magnetic that the present invention is made heavy metal ions in the absorption industrial wastewater.
Can selective absorption contain Pb especially
2+, Cu
2+, Cd
2+The heavy metal solution of ion.
The present invention controls the magnetic nanoparticle pattern by anion surfactant, obtains the nanosphere of size homogeneous; Anion surfactant attaches to the surface of nanosphere, makes the webbed structure of glucose carbonization in the solution; Because adsorbent is the magnetic nano-balls nucleocapsid structure that reticulated carbon coats, and has very big specific area; In use, owing to contain nickel in the nano material, therefore after having adsorbed heavy metal,, nano material is separated with waste water by externally-applied magnetic field.
The present invention compared with prior art, the reaction condition gentleness, the magnetic adsorbent that made reticulated carbon coats has the selective absorption heavy metal ion, specific area is bigger, high adsorption capacity; The characteristics that are easy to from adsorbed solution, separate.
Description of drawings
Fig. 1 is the X-ray powder diffraction pattern of embodiment 1 gained nano material.
Fig. 2 is the energy spectrogram (EDS) of embodiment 1 gained nano material
Fig. 3 is SEM (SEM) photo of embodiment 1 gained magnetic metal nanosphere
Fig. 4 is SEM (SEM) photo of embodiment 1 gained nano material
Fig. 5 is transmission electron microscope (TEM) photo of embodiment 1 gained nano material.
Fig. 6 is the room temperature hysteresis curve of embodiment 1, and 51 is room temperature hysteresis curve, the 52 room temperature hysteresis curves for the nano material of embodiment 1 gained of embodiment 1 gained magnetic metal Nano microsphere.
Fig. 7 is the Raman spectrogram of embodiment 1 gained nano material.
Fig. 8 is the Pb that contains of embodiment 1 gained nano material
2+The adsorption curve of solution:
Fig. 9 is the Cu that contains of embodiment 1 gained nano material
2+The adsorption curve of solution:
Figure 10 is the Cd that contains of embodiment 1 gained nano material
2+The adsorption curve of solution:
The specific embodiment
Embodiment 1:
1, nano metallic nickel granular material preparation process:
Lauryl sodium sulfate (SDS) with 0.3mmol, the sodium hypophosphite of 2mmol nickel chloride and 8mmol, be dissolved in the 15mL distilled water, under the situation of magnetic agitation successively with 5mL N, dinethylformamide (DMF) and 25mmol KOH slowly add in the above-mentioned solution, the gained mixed solution is poured in the stainless steel autoclave of polytetrafluoroethylene (PTFE) as liner, be heated to 160 ℃ of reactions 10 hours.Reaction is cooled to room temperature with autoclave after finishing, and spends deionised water gained black product for several times, 50 ℃ of dryings in vacuum drying chamber, and products therefrom is the metal magnetic nanosphere.
2, carbon coats process:
2g glucose is dissolved in the 20mL water, adds the above-mentioned product of 20mg in this glucose solution ultrasonic 20 minutes, it is changed in the stainless steel autoclave, be heated to 160 ℃ of reactions 4 hours.Reaction is cooled to room temperature with autoclave after finishing, and spends deionised water gained black product for several times, and 50 ℃ of dryings get final product in vacuum drying chamber.
With day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument to the product of implementing experiment 1 (Cu K alpha ray, λ=0.154060nm, 0.02 ° of sweep speed/s) carry out the thing identification of phases, as shown in fig. 1.Contrast JCPDS standard card (04-0850), all diffraction maximums fit like a glove with face-centered cubic magnetic nano-particle Ni mutually.Because diffraction maximum is very strong, illustrates that product has degree of crystallinity preferably.In addition, angle is the carbon that 20 °-30 ° baseline projection results from the crystallinity difference among Fig. 1.Fig. 2 elementary analysis shows that make and contain C, Ni, Cu and O element in the product, wherein element Cu comes from the copper sheet that supports sample.Fig. 3 and Fig. 4 show that respectively products therefrom has the nucleocapsid structure of reticulated carbon coated magnetic nano particle.Fig. 5 confirms that this product has magnetic, and saturation magnetization changes before and after the bag carbon.Fig. 6 shows, at 1387cm
-1(D band) and 1587cm
-1(G band) locates two big peaks, corresponding carbon atom sp
2The characteristic peak of hydridization has further proved the existence of carbon in the product.
Embodiment 2:
1, nano metallic nickel granular material preparation process:
Neopelex (SDBS) with 0.3mmol, the sodium hypophosphite of 2mmol nickel acetate and 8mmol, be dissolved in the 15mL distilled water, under the situation of magnetic agitation successively with 5mLN, dinethylformamide (DMF) and 25mmol KOH slowly add in the above-mentioned solution, the gained mixed solution is poured in the stainless steel autoclave of polytetrafluoroethylene (PTFE) as liner, be heated to 160 ℃ of reactions 10 hours.Reaction is cooled to room temperature with autoclave after finishing, and spends deionised water gained black product for several times, 50 ℃ of dryings in vacuum drying chamber, and products therefrom is the metal magnetic nanosphere.
2, carbon coats process:
2g glucose is dissolved in the 20mL water, adds the above-mentioned product of 20mg in this glucose solution ultrasonic 20 minutes, it is changed in the stainless steel autoclave, be heated to 160 ℃ of reactions 4 hours.Reaction is cooled to room temperature with autoclave after finishing, and spends deionised water gained black product for several times, and 50 ℃ of dryings get final product in vacuum drying chamber.
Embodiment 3:
The Pb that 20mg embodiment 1 products therefrom is added 50 milliliters of 10mg/L
2+In the solion, ultrasonic absorption 30 minutes, the atom absorptiometry shows Pb
2+The absorbance of solion 0.039 drops to 0.005 before adsorb, i.e. Pb
2+Ion concentration drops to 1.42mg/L (shown in Figure 8) by the preceding 10mg/L of absorption.As calculated, adsorbent is at the Pb of 10mg/L
2+Absorption Pb in the solion
2+Ability be 21.38mg/g.
Embodiment 4:
The Cd that 20mg embodiment 1 products therefrom is added 50 milliliters of 10mg/L
2+In the solion, ultrasonic absorption 30 minutes, the atom absorptiometry shows Cd
2+The absorbance of solion 0.413 drops to 0.195 before adsorb, i.e. Cd
2+Ion concentration drops to 2.43mg/L (as shown in Figure 9) by the preceding 5mg/L of absorption, and as calculated, adsorbent is at the Cd of 5mg/L
2+Adsorb Cd in the solion
2+Ability be 6.425mg/g;
Embodiment 5:
The Cu that 20mg embodiment 2 products therefroms is added 50 milliliters of 10mg/L
2In the solion, ultrasonic absorption 30 minutes, Cu
2+The absorbance of solion 0.330 drops to 0.139 before adsorb, i.e. Cu
2+Ion concentration drops to 4.28mg/L (as shown in figure 10) by the preceding 10mg/L of absorption, and as calculated, adsorbent is at the Cu of 10mg/L
2+Adsorption of Cu in the solion
2+Ability be 14.3mg/g.
Embodiment 6:
20mg embodiment 2 products therefroms are added in As (V) solion of 50 milliliters of 10mg/L, ultrasonic absorption 30 minutes adopts the ICP Atomic Emission Spectrometer AES to test, and the result shows that As (V) ion concentration is constant.
Embodiment 7:
20mg embodiment 2 products therefroms are added in Cr (VI) solion of 50 milliliters of 10mg/L, ultrasonic absorption 30 minutes adopts the ICP Atomic Emission Spectrometer AES to measure, and the result shows that Cr (VI) ion concentration is constant.
Above presentation of results, Ci Xingnamilizi @C core-shell nano structure adsorbent for heavy metal has the selection absorption property, to Pb
2+, Cu
2+, Cd
2+Can effectively adsorb, and to the absorption of heavy metal ion As (V) and Cr (VI) to no effect.