CN102814158A - Preparation method and application of porous magnetic superstructure nanocomposite - Google Patents
Preparation method and application of porous magnetic superstructure nanocomposite Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a porous magnetic superstructure nanocomposite. The porous magnetic superstructure nanocomposite is prepared by using a soluble nickel salt as a raw material and a mixed solution of N,N-dimethyl formamide and glycol or glycol containing a dissolved surfactant as a medium, uniformly mixing the raw material and the medium under stirring at room temperature, adding a strong reducing agent, carrying out stirring for 5 min, reacting the obtained mixture in a reaction vessel for 1h to 10h at a temperature of 150 to 170 DEG C, cooling an obtained product to room temperature, rinsing the product with deionized water several times and drying the product under vacuum until the product has a constant weight. Compared with the prior art, the invention has the following advantages: morphology of the magnetic nanocomposite is controlled through the soluble nickel salt and hydroboron so as to obtain porous microspheres with a uniform size; the porous magnetic superstructure nanocomposite has a large specific surface area; during application, since the prepared porous superstructure nanocomposite is magnetic, the nanocomposite can be easily separated from waste water through an applied magnetic field after adsorption of heavy metals; meanwhile, the nanocomposite has good electrochemical performance and can be used for electrochemical detection of small molecules.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of porous magnetic superstructure nano composite material
Background technology
Along with development of science and technology, people's life is maked rapid progress, but also is faced with severe environmental problem.In recent years, the annual industrial wastewater of discharging of China was about 8 * 10
8m
3, and discharge capacity significantly increases progressively year by year, wherein contains plurality of heavy metal ions such as chromium, zinc, copper, mercury.Owing to should pass through strict processing before its advantages of higher stability and the extremely strong toxicity, industrial wastewater discharge.Yet, in practical application, be that regeneration all can not be separated and be difficult to the active carbon or the metal oxide of classification effectively from a large amount of water bodys.Must carry out further post processing like this, thereby increase the cost of using, visible these problems must take in actual applications.The magnetic composite porous material not only have strong adsorptivity but also can outside magnetic field under the characteristics of separating just remedied above-mentioned shortcoming, yet the magnetic composite porous material is at the rare report of the application in heavy metal ion adsorbed field.
Traditional preparation process Ni (OH)
2The method of nano material mainly comprises solid phase precipitation conversion method, liquid-phase precipitation reaction method, high-energy ball milling method etc., and synthetic product pattern has petal-shaped, tubulose, sheet, spherical.Is precipitating reagent like Fu etc. with the concentrated ammonia liquor, in the system of pH 9.0, has successfully obtained the Ni (OH) of different-shape behind the hydro-thermal 48h
2Material.Experiment shows that reaction temperature is to Ni (OH)
2Pattern very large influence is arranged: synthesized petal-shaped β-Ni (OH) under 180 ℃
2Ball; And 240 ℃ next be β-Ni (OH)
2Nanometer sheet (" rare metal and carbide alloy ", 2012,40 (2), 29-32).Li etc. are template with the Woelm Alumina, 0.1 mol/LNiCl
2Solution and 1 mol/L ammoniacal liquor are reactant, adopt chemical deposition to prepare Ni (OH)
2Nanotube (" chemical journal ", 2005,63 (5), 411-415).But the method step is more and need repetitive operation, and is comparatively loaded down with trivial details.Foreign literature has also carried out certain report to this type of material, and Cao etc. adopt reverse micro emulsion-hydro-thermal route, in the mixed system of the n-amyl alcohol that contains surfactant softex kw (CTAB), cyclohexane and water with Ni (NO
3)
22H
2O and urea are reactant, and shaggy α-Ni (OH) was prepared in 140 ℃ of following reactions in 12 hours
2Microballoon, and studied its application on alkaline charging battery electrode (Crystal Growth & Design, 2007,7 (1), 170-174).Simultaneously, Latha etc. goes out the β-Ni (OH) of hollow through no template (template-free) path of preparing
2Microballoon (Physics E, 2009,41 (7), 1289-1292.But the method needs nickel foil as the nickel source, and in the ammoniacal liquor system, 150 ℃ of hydro-thermal reactions are more than 24 hours.Raw material is difficult for obtaining, and the reaction time is longer.In addition, Bala etc. are surfactant with lauryl sodium sulfate (SDS) in the oleic acid system, sodium borohydride (NaBH
4) successfully synthesize Ni/Ni (OH) for reducing agent
2Nucleocapsid structure (Nanotechnology, 2009,20,415603).Godsell etc. have further studied the magnetic property (Journal of Physics D:Applied Physics, 2011,44,325004) of this nucleocapsid structure.But this material is a smooth sphere, does not have the characteristic of porous, aspect adsorption of metal ions, can't use.At present, the Ni (OH) that is synthesized of major part
2Material all is used for nickel positive active material.
As aspect the metal ion adsorbent, Chinese patent CN101658933A has introduced a kind of preparation method of NiC magnetic Nano material at magnetic material, and this magnetic Nano material is twice hydro-thermal synthetic route; The first step is with anionic surfactant, and soluble nickel salt and strong reductant are dissolved in the distilled water, under the situation of magnetic agitation successively with N; Dinethylformamide (DMF) and highly basic slowly add in the above-mentioned solution, after mixing, and intensification 140-180 ℃; Reacted 10-12 hour; Be cooled to room temperature, spend deionised water for several times, 50-60 ℃ is dried to constant weight in vacuum drying chamber.Second step was to be in the 10-15% glucose solution with the ultrasonic weight concentration that is scattered in of made magnetic nano-particle, and 160-170 ℃ down reaction be cooled to room temperature after 3-4 hour, spend deionised water, in vacuum drying chamber, be dried to constant weight under 50-60 ℃.Chinese patent CN102350296A introduces the preparation of the magnetic mesoporous sorbing material of a kind of cationic dyes; This method is to the effect that: certain density oxalic acid (salt) aqueous solution is carried out chemical reaction; Prepare composition metal oxalates presoma; Synthetic composition metal oxalates presoma under the control process conditions, calcining, is obtained magnetic mesoporous oxide; Magnetic mesoporous oxide promptly gets the magnetic mesoporous adsorbent of cationic dyes through the activation of sodium citrate aqueous solution hydro-thermal.But this method relates to the presoma preparation, calcining, and the operation of multisteps such as hydro-thermal activation can't be accomplished in a step, and preparation time is longer.Chinese patent CN101733065A introduces a kind of nuclear shell structure mesoporous heavy metal ion adsorbent capable of magnetic separating.This method was divided into for four steps, and α-Fe is synthesized in (1)
2O
3Particle, (2) coat fine and close silicon oxide intermediate, and (3) coat silicon oxide mesoporous layer, and (4) are reduced into Fe 3 O 4 magnetic nuclear with kernel.This method step is complicated, and is not easy to operate.The present invention relates to the Ni/Ni (OH) of porous magnetic
2One step of composite is synthetic and in heavy metal ion adsorbed and application electrochemical field.Do not find as yet in the relevant at present report document.
Summary of the invention
The 1st technical problem to be solved by this invention provides a kind of simple Ni/Ni (OH)
2Compound porous magnetic superstructure preparation methods.
The 2nd application that technical problem is above-mentioned porous magnetic superstructure material to be solved by this invention.
The technical scheme of the technical problem that the present invention solves: a kind of preparation method of porous magnetic superstructure nano composite material:
With the soluble nickel salt is raw material, is dissolved with the ethylene glycol (EG) or the N of surfactant, and the mixed solution of dinethylformamide (DMF) and ethylene glycol (EG) is a medium; After at room temperature stirring, add strong reductant, stir and be placed in the agitated reactor in 5 minutes; 150-170 ℃ was reacted 1-10 hour down, was cooled to room temperature, spent the deionised water product for several times;, get final product to constant weight in 60 ℃ of following vacuum drying.
Soluble nickel salt and strong reductant molal weight are than being 1:0.33-1;
The amount of substance ratio of the quality of surfactant and soluble nickel salt is 0-0.07 g/mmol;
Ethylene glycol and N, the volume ratio 1:0-2 of dinethylformamide.
Said soluble nickel salt is Nickel dichloride hexahydrate, six hydration nickel sulfate, nickel nitrate, nickel acetate, and its chemical formula is respectively NiCl
26H
2O, NiSO
46H
2O, Ni (NO
3)
2, Ni (CH
3COO)
2
Said strong reductant is alkali-metal boron hydride, like sodium borohydride, potassium borohydride.Its chemical formula is NaBH
4, KBH
4
Described surfactant is: softex kw (CTAB), polyvinylpyrrolidone (PVP).
The made porous magnetic superstructure material of the present invention can urge into some organic molecule electronics to shift and in the absorption industrial wastewater heavy metal ions important use is arranged.Alternative absorption contains Pb
2+, Cu
2+The heavy metal solution of ion.
In the mixed solvent of the ethylene glycol of certain reaction temperature, proper proportion and DMF, the nickel salt of solubility and strong reductant are (like NaBH
4) generation redox generation Ni/Ni (OH)
2Compound porous magnetic Nano superstructure material.Owing to contain water-wet side and hydrophobic side in the DMF molecule, thus DMF in reaction not only as cosolvent but also playing the part of influence of surfactant, simultaneously, N atomic energy in its hydrophilic radical and nickle atom formation coordination.Because the sterically hindered Ni (OH) that forces of DMF molecule
2Examining the surface at Ni can only grow along specific direction, thereby finally obtains the Ni/Ni (OH) of porous magnetic
2Compound superstructure.But too much DMF can make the aperture on surface reduce; In addition, excessive strong reductant is (like NaBH
4) can change the pH value of system significantly, thus be unfavorable for the Ni/Ni (OH) of porous magnetic
2The formation of compound superstructure.
And in containing the glycol system of surfactant the Ni/Ni of above-mentioned porous magnetic (OH)
2Superstructure still can form then should be owing to the surfactant structure directive function.
The pattern that the present invention controls the magnetic micro Nano material through the nickel salt and the boron hydride of solubility obtains the cellular microballoon of size homogeneous; It has very big specific area.In the process of using,, therefore after having adsorbed heavy metal,, this micro Nano material is separated with waste water through externally-applied magnetic field because gained porous superstructure material is magnetic.
The porous Ni/Ni (OH) that the present invention is made
2The magnetic superstructure has excellent electrochemical properties, and this material is evenly distributed on the naphthols film, for induction micro-content organism (glucose, catechol, hydroquinones) provides good activated centre.In different solution environmentals, all show good catalytic oxidation performance, possibility is provided for detecting micro-content organism.
Reaction condition of the present invention is gentle, made Ni/Ni (OH)
2The compound superstructure of porous magnetic has bigger specific area, ability selective absorption heavy metal ion and high adsorption capacity, is easy to from adsorbed solution, separate; Simultaneously, the adsorbent of recovery can easily regenerate and reuse.
The Ni/Ni (OH) that the present invention is made
2The compound superstructure material of porous magnetic has good electro-chemical activity, can promote in alkalescence and neutral solution that the micromolecular electronics of organic matter shifts, thereby can carry out the detection of organic molecule quickly and easily.
Description of drawings
Fig. 1 is the X-ray powder diffraction pattern of the compound superstructure of embodiment 1 gained porous magnetic.
Fig. 2 is the thermogravimetric analysis curve map (TGA) of the compound superstructure of instance 1 gained porous magnetic.
Fig. 3 is SEM (SEM) photo of the compound superstructure of embodiment 1 gained porous magnetic.
Fig. 4 is the room temperature hysteresis curve of the compound superstructure of embodiment 1 porous magnetic.
Fig. 5 is the N of the compound superstructure of embodiment 1 gained porous magnetic
2Adsorption isotherm and graph of pore diameter distribution are conciliate in absorption.
Fig. 6 be the compound superstructure of embodiment 1 gained porous magnetic to Pb in the solution
2+Adsorption curve.
Fig. 7 be the compound superstructure of embodiment 1 gained porous magnetic to Cu in the solution
2+Adsorption curve.
Fig. 8 be the compound superstructure of embodiment 1 gained porous magnetic to Cd in the solution
2+Adsorption curve.
Fig. 9 is that the compound superstructure of embodiment 1 gained porous magnetic is to containing Pb
2+, Cu
2+And Cd
2+The time adsorption curve of solution.
Figure 10 be the compound superstructure of embodiment 1 gained porous magnetic to Pb in the solution
2+Repeat adsorption curve.
Figure 11 is the embodiment compound superstructure Ni/Ni of 6 gained porous magnetics (OH)
2And naphthols (Nf) modified glassy carbon electrode (GCE) is Ni/Ni (OH)
2/ Nf/GCE electrode is surveyed the cyclic voltammetry curve of the glucose solution of variable concentrations in liquid at the bottom of the 0.1M NaOH.Sweeping speed is 0.05v/s.
Figure 12 is the embodiment compound superstructure Ni/Ni of 6 gained porous magnetics (OH)
2And naphthols (Nf) modified glassy carbon electrode (GCE) is Ni/Ni (OH)
2/ Nf/GCE electrode is surveyed the cyclic voltammetry curve of the hydroquinones solution of variable concentrations in liquid at the bottom of the 0.1M NaOH.Sweeping speed is 0.05v/s.
Figure 13 is the embodiment compound superstructure Ni/Ni of 6 gained porous magnetics (OH)
2And naphthols (Nf) modified glassy carbon electrode (GCE) is Ni/Ni (OH)
2/ Nf/GCE electrode is surveyed the cyclic voltammetry curve of the catechol solution of variable concentrations in liquid at the bottom of the 0.1M NaOH.Sweeping speed is 0.05v/s.
Figure 14 is the embodiment compound superstructure Ni/Ni of 6 gained porous magnetics (OH)
2And naphthols (Nf) modified glassy carbon electrode (GCE) is to add in 0.1M PBS (pH=7.0) solution in the hydroquinones solution of 6mM to use Ni/Ni (OH) respectively
2/ Nf/GCE electrode and Nf/GCE electrode test gained cyclic voltammetry curve.
Figure 15 is the embodiment compound superstructure Ni/Ni of 6 gained porous magnetics (OH)
2And naphthols (Nf) modified glassy carbon electrode (GCE) is to add in 0.1M PBS (pH=7.0) solution in the catechol solution of 6mM to use Ni/Ni (OH) respectively
2/ Nf/GCE electrode and Nf/GCE electrode test gained cyclic voltammetry curve.
Figure 16 is the embodiment compound superstructure Ni/Ni of 6 gained porous magnetics (OH)
2And naphthols (Nf) modified glassy carbon electrode (GCE) is Ni/Ni (OH)
2/ Nf/GCE electrode is surveyed the cyclic voltammetry curve of the hydroquinones solution of variable concentrations in 0.1M PBS (pH=7.0) solution.Sweeping speed is 0.05v/s.
Figure 17 is the embodiment compound superstructure Ni/Ni of 6 gained porous magnetics (OH)
2And naphthols (Nf) modified glassy carbon electrode (GCE) is Ni/Ni (OH)
2/ Nf/GCE electrode is surveyed the cyclic voltammetry curve of the catechol solution of variable concentrations in 0.1M PBS (pH=7.0) solution.Sweeping speed is 0.05v/s.
The specific embodiment
Embodiment 1:
Ni/Ni (OH)
2The preparation of the compound superstructure of porous magnetic:
With 0.713g Nickel dichloride hexahydrate (NiCl
26H
2O) be dissolved in 30 mL ethylene glycol (EG) and N, in the mixed system that dinethylformamide (DMF) forms (EG/DMF=18/12), after fully magnetic agitation forms homogeneous solution, add 0.038g sodium borohydride (NaBH
4), magnetic agitation is 10 minutes again; Mixed solution is transferred in the polytetrafluoroethyllining lining of 40 mL autoclaves, sealed tight stainless steel cauldron, be heated to 170 ℃ of reaction 8h down.After reaction finished, question response still temperature was reduced to room temperature, collected the black product with magnet, with deionized water centrifuge washing product for several times.At last 60 ℃ of following vacuum drying 5 hours.
With product (Cu K alpha ray, λ=0.154060 nm, the sweep speed 0.02 of day island proper Tianjin XRD-6000 type x-ray powder diffraction instrument to enforcement experiment 1
o/ s) carrying out the thing identification of phases, Fig. 1 is the XRD diffraction pattern before and after the products therefrom calcining, showing in the product of calcining front and back all has Ni to exist.Simultaneously, the XRD diffraction pattern shows, contains Ni (OH) in the product before the calcining
2It is thus clear that product is Ni and Ni (OH)
2Composite construction.As shown in Figure 2, locate that at 100 ℃ and 300 ℃ obvious weightlessness is all arranged, the former is weightless 15%, should be to have lost the water that adsorbs in the product; Latter's weightlessness 15% should be Ni (OH)
2Decomposition.When product behind 350 ℃ of calcining 3h under the air atmosphere, XRD analysis shows that in the composite construction, the diffraction maximum of Ni strengthens, and Ni (OH)
2Diffraction maximum disappear and some new diffraction maximums occur.Analyze and show that new diffraction maximum is NiO, shows Ni (OH)
2Changed NiO into.So, can conclude that the calcine (see figure 2) of at last last ~ 70% in the thermogravimetric analysis should be Ni and NiO.In addition, the diffraction maximum of calcining back Ni simple substance still exist and the strength ratio calcining before obvious enhancing is arranged, show that former magnetic porous shape superstructure should be that Ni is a nuclear, and Ni (OH)
2Be to be grown in Ni nuclear surface.
Fig. 3 shows that products therefrom has the porous pattern.Fig. 4 confirms that products therefrom has magnetic.Fig. 5 is the N of products therefrom
2Absorption-desorption attaches curve, proves that products therefrom has bigger specific area (114 m2/g).
Embodiment 2:
Ni/Ni (OH) that 20 mg embodiment 1 are made under ultrasonic agitation
2The compound superstructure of porous is scattered in the Pb that 50 ml concns are all 10mg/L
2+, Cu
2+And Cd
2+In the mixed solution of ion, mechanical agitation with the concentration of inductively coupled plasma (ICP) Atomic Emission Spectrometer AES mensuration residual ion, was found: Pb after 30 minutes
2+The concentration of ion drops to 4.84mg/L from adsorbing preceding 10mg/L.At this moment, 51.6% Pb
2+Ion is removed.Adsorbent is to Pb
2+The adsorption capacity of ion is 12.9 mg/g (see figure 6)s.Cu
2+Ion concentration drops to 4.25mg/L, 57.5%Cu by absorption is preceding from adsorbing preceding 10mg/L
2+Ion is removed (see figure 7), Adsorption of Cu
2+The ability of ion is 14.4mg/g.But Cd in same system
2+Ion does not have the significant change (see figure 8) through measuring concentration.
The The above results explanation, porous magnetic Ni/Ni (OH)
2Nano combined superstructure can the selective absorption heavy metal Pb
2+, Cu
2+Ion, and to Cd
2+The absorption of ion does not have positive effect.
Embodiment 3:
The Cd that 10 mg embodiment, 1 products therefrom is added 50 milliliter of 10 mg/L
2+, Pb
2+And Cu
2+In the ion mixed solution, the stirring and adsorbing different time adopts the ICP Atomic Emission Spectrometer AES to measure, the result be presented at absorption after 50 minutes adsorbent to Pb
2+, Cu
2+Absorption reach capacity, its adsorption effect is ~ 65% and ~ 70% (like Fig. 9).
The adsorbent that absorption is reached capacity separates with waste water through externally-applied magnetic field, and the adsorbent after the separation is put into the deionized water of 50ml, and supersound washing is removed the heavy metal ion of surface adsorption for several times.Figure 10 is 3 absorption of adsorbent recycling Pb
2+Absorption figure.The result shows: adsorbent still has adsorption effect preferably after repeating 3 times.
Embodiment 4:
With 0.738g six hydration nickel sulfate (NiSO
46H
2O) be dissolved in 30 mL ethylene glycol (EG) and N, in the mixed system that dinethylformamide (DMF) forms (volume ratio is 2:1, i.e. EG/DMF=20/10), magnetic agitation forms homogeneous solution.Add 0.038g sodium borohydride (NaBH then
4), magnetic agitation was poured into mixed solution in the polytetrafluoroethyllining lining of 40 mL autoclaves after 10 minutes, sealed tight stainless steel cauldron, was heated to 170 ℃ of reaction 8h down.After reaction finished, question response still temperature was reduced to room temperature, collected the black product with magnet, with deionized water centrifuge washing product for several times.At last 60 ℃ of following vacuum drying 5 hours.
Embodiment 5:
With 0.36g Nickelous nitrate hexahydrate (Ni (NO
3)
2) be dissolved in 30 mL ethylene glycol (EG) and N, in the mixed system that dinethylformamide (DMF) forms (volume ratio is 3:2, i.e. EG/DMF=18/12), fully stir the formation homogeneous solution through magnetic stirring apparatus.Add 0.054g potassium borohydride (KBH then
4), magnetic agitation was poured into mixed solution in the polytetrafluoroethyllining lining of 40 mL autoclaves after 10 minutes, sealed tight stainless steel cauldron, was heated to 170 ℃ of reaction 8h down.After reaction finished, question response still temperature was reduced to room temperature, collected the black product with magnet, with deionized water centrifuge washing product for several times.At last 60 ℃ of following vacuum drying 5 hours.
Embodiment 6:
NiCl with 0.713g
26H
2The softex kw of O and 0.2g (CTAB) is dissolved in the ethylene glycol solution of 30mL, with this mixed liquor under the room temperature on magnetic stirring apparatus vigorous stirring 40 minutes, add the NaBH of 0.038g then
4, use to stir after 5 minutes this mixed liquor is poured in the polytetrafluoroethyllining lining that volume is 40 mL stainless steel autoclaves, agitated reactor is put into thermostatic drying chamber, 170 ℃ were reacted 1 hour down.After reaction finished, question response still temperature was reduced to room temperature, opens agitated reactor, and liquid in the still is poured in the clean beaker, can see that black solid generates.Spend the deionised water product for several times,, promptly get black powder shape product 60 ℃ of following vacuum drying 6 hours.
Embodiment 7:
NiCl with 0.713g
26H
2The polyvinylpyrrolidone of O and 0.2g (PVP) is dissolved in the ethylene glycol solution of 30mL, with this mixed liquor under the room temperature on magnetic stirring apparatus vigorous stirring 40 minutes, add the NaBH of 0.038g then
4, use to stir after 5 minutes this mixed liquor is poured in the polytetrafluoroethyllining lining that volume is 40 mL stainless steel autoclaves, agitated reactor is put into thermostatic drying chamber, 170 ℃ were reacted 1 hour down.After reaction finished, question response still temperature was reduced to room temperature, opens agitated reactor, and liquid in the still is poured in the clean beaker, can see that black solid generates.Spend the deionised water product for several times,, promptly get black powder shape product 60 ℃ of following vacuum drying 6 hours.
Embodiment 8:
Electrochemistry experiment partly usefulness be CHI 660 electrochemical workstations of the three-electrode cell used always.What working electrode was used is to have modified Ni/Ni (OH)
2And the glass-carbon electrode (GCE) of naphthols (Nf), Ag/AgCl is as reference electrode, and the platinum electrode conduct is to electrode.Experiment is at room temperature carried out.Before electrode is modified, want to use the chamois leather ground smooth to GCE earlier, use distilled water and ethanol ultrasonic cleaning then.Dried a last Ni/Ni (OH) afterwards at electrode with dissolved in distilled water
2Solution drips the Nf solution of going up 0.5wt% after having done, Ni/Ni (OH) after drying again
2/ Nf/GCE electrode has just made.
Embodiment 9:
To have modified Ni/Ni (OH)
2The glass-carbon electrode of-Nf (GCE) is a working electrode, and Ag/AgCl is as reference electrode, and platinum electrode is for to measure respectively in the 0.1M NaOH solution electrode: the glucose solution of (1) variable concentrations (4Mm, 6mM, 8mM, 10mM) (seeing Figure 11); (2) the hydroquinones solution of variable concentrations (4mM, 6mM, 8mM, 10mM, 12mM) (seeing Figure 12); (3) cyclic voltammetry curve of the catechol solution of variable concentrations (2mM, 4mM, 6mM, 8mM, 10mM) (seeing Figure 13), sweeping speed all is 0.05v/s.It is thus clear that Ni/Ni (OH)
2Material all has electrochemical response to little molecules such as glucose, hydroquinones, catechols in NaOH solution, and reduction peak is apparent in view, and Ni/Ni (OH) is described
2Material can promote the electronics of above-mentioned organic molecule to shift.
Embodiment 10:
With Ag/AgCl is reference electrode, and platinum electrode is to electrode, uses Ni/Ni (OH) respectively
2-Nf/GCE electrode and Nf/GCE are the working electrode test: (1) adds the hydroquinones solution (seeing Figure 14) of 6mM and (2) add the catechol solution (seeing Figure 15) of 6mM in 0.1M PBS (pH 7.0) solution chemical property in 0.1M PBS (pH 7.0) solution.Can clearly find out from two groups of cyclic voltammetry curves and to have added Ni/Ni (OH)
2The electrode of material has redox peak clearly, explains that this composite has good electrochemical properties.
Embodiment 11:
To have modified Ni/Ni (OH)
2The glass-carbon electrode of-Nf (GCE) is a working electrode; Ag/AgCl is a reference electrode, and platinum electrode is for to measure respectively in 0.1M PBS (pH=7.0) solution electrode: the hydroquinones solution of (1) variable concentrations (0mM, 2mM, 4mM, 6mM, 8mM, 10mM, 12mM) (seeing Figure 16); (2) cyclic voltammetry curve of the catechol solution of variable concentrations (0mM, 2mM, 4mM, 6mM, 8mM, 10mM, 12mM) (seeing Figure 17).Sweeping speed all is 0.05v/s.Two width of cloth figure have redox peak clearly, show Ni/Ni (OH)
2Material also can promote the electronics of hydroquinones and catechol to shift in PBS solution.
Claims (8)
1. the preparation method of a porous magnetic superstructure nano composite material is characterized in that:
With the soluble nickel salt is raw material, is dissolved with the ethylene glycol or the N of surfactant, and the mixed solution of dinethylformamide and ethylene glycol is a medium; After at room temperature stirring, add strong reductant, stir and be placed in the agitated reactor in 5 minutes; 150-170 ℃ was reacted 1-10 hour down, was cooled to room temperature, spent the deionised water product for several times;, get final product to constant weight in 60 ℃ of following vacuum drying.
2. according to the preparation method of claim 1 porous magnetic superstructure nano composite material, it is characterized in that:
Described soluble nickel salt and strong reductant molal weight are than being 1:0.33-1.
3. according to the preparation method of claim 1 porous magnetic superstructure nano composite material, it is characterized in that:
The amount of substance ratio of the quality of surfactant and soluble nickel salt is 0-0.07 g/mmol.
4. according to the preparation method of claim 1 porous magnetic superstructure nano composite material, it is characterized in that:
Ethylene glycol and N, the volume ratio 1:0-2 of dinethylformamide.
5. according to the preparation method of claim 1 porous magnetic superstructure nano composite material, it is characterized in that:
Said soluble nickel salt is Nickel dichloride hexahydrate, six hydration nickel sulfate, nickel nitrate, nickel acetate.
6. according to the preparation method of claim 1 porous magnetic superstructure nano composite material, it is characterized in that:
Said strong reductant is alkali-metal boron hydride.
7. according to the preparation method of claim 1 porous magnetic superstructure nano composite material, it is characterized in that:
Described surfactant is: softex kw, polyvinylpyrrolidone.
8. the application of the described a kind of porous magnetic superstructure nano composite material of claim 1 heavy metal ions in the absorption industrial wastewater.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170649A (en) * | 2013-04-15 | 2013-06-26 | 南京理工大学 | Preparation method of magnetic nickel nano material |
| CN104743609A (en) * | 2015-03-25 | 2015-07-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing transition metal oxide microspheres with controllable morphology |
| CN104439278B (en) * | 2014-11-28 | 2017-03-15 | 深圳康特腾科技有限公司 | A kind of preparation method of nanometer spherical nikel powder |
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| CN101417341A (en) * | 2008-11-07 | 2009-04-29 | 江苏科技大学 | Method for preparing metal nickel nano hollow bal |
| CN101658933A (en) * | 2009-09-21 | 2010-03-03 | 安徽师范大学 | Preparation method of magnetic nano-materials and application thereof |
| CN101703917A (en) * | 2009-11-25 | 2010-05-12 | 湖南大学 | Magnetic nano hydroxyapatite adsorbent, preparation and application thereof |
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| CN103170649A (en) * | 2013-04-15 | 2013-06-26 | 南京理工大学 | Preparation method of magnetic nickel nano material |
| CN104439278B (en) * | 2014-11-28 | 2017-03-15 | 深圳康特腾科技有限公司 | A kind of preparation method of nanometer spherical nikel powder |
| CN104743609A (en) * | 2015-03-25 | 2015-07-01 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for preparing transition metal oxide microspheres with controllable morphology |
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