CN102650077A - Chitosan-finishing iron nanowire, method for producing same and application thereof - Google Patents
Chitosan-finishing iron nanowire, method for producing same and application thereof Download PDFInfo
- Publication number
- CN102650077A CN102650077A CN201110046910XA CN201110046910A CN102650077A CN 102650077 A CN102650077 A CN 102650077A CN 201110046910X A CN201110046910X A CN 201110046910XA CN 201110046910 A CN201110046910 A CN 201110046910A CN 102650077 A CN102650077 A CN 102650077A
- Authority
- CN
- China
- Prior art keywords
- nanowire
- chitosan
- porous alumina
- modified
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Cosmetics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a chitosan-finishing iron nanowire, a method for producing the same and an application thereof. The iron nanowire is externally finished with chitosan, is positioned in a pore of a porous alumina mouldboard, keeps a clearance of 1-5nm with a pore wall, grows along the (110) direction, and has the wire diameter of 50-55nm and the length of 380-420nm, and the porous alumina mouldboard has the pore diameter of 55-60nm, the pore length of 380-420nm and the pore density of 3.5 multiplied by 1014/m<2>. The method comprises the steps that an anodic oxidation method is firstly used to obtain the porous alumina mouldboard; an electrolytic deposition method is used to treat the porous alumina mouldboard to obtain the porous alumina mouldboard with a pore in which an iron nanowire is arranged; then, the porous alumina mouldboard is firstly put into strong alkali solution to be etched for 2-5 minutes, so the porous alumina mouldboard in the state that the iron nanowire in the pore keeps the clearance with the pore wall is obtained; and the porous alumina mouldboard is then put in chitosan solution with the concentration of 0.05-0.15wt% to be soaked for 10-20 seconds, and then taken out and dried, so the chitosan-finishing iron nanowire is produced. The chitosan-finishing iron nanowire can be used as adsorbent, and is used in the solution which is polluted by hexavalent chromium for adsorption treatment.
Description
Technical field
The present invention relates to a kind of nano wire and preparation method and purposes, especially a kind of Fe nanowire that is modified with chitosan.
Background technology
As everyone knows, iron nano-particle has good reduction and absorption property, can also exist the defective that the surface is prone to be prone between oxidation, the particle reunion, thereby has reduced the ability of its reductive activity and absorption widely.For addressing this problem; Have among the people it is carried out the change of pattern and in the finishing chitosan, as just it having been done introduction in " analytical chemistry research notes " the 37th the 2nd phase of volume the 275th～278 page " preparation of Fe nanowire/chitosan/antibody bioprobe and chromatography detection " of publishing in February, 2009.It is earlier with aluminium foil through electrochemical etching, clean after, use anonizing to obtain alumina formwork, re-use electrodip process and in the hole of alumina formwork, deposit Fe nanowire; Then; Use earlier saturated tin chloride solution to remove the template aluminum substrate, again template be dissolved in the sodium hydroxide solution, with deionized water clean repeatedly, magnetic support is settled down to pH value of solution=7.0; Obtain homodisperse Fe nano wire solution after ultrasonic; Afterwards, earlier Fe nano wire, whiteruss and span-80 are added back ultra-sonic dispersion in the chitosan acetic acid soln, again after wherein adding glutaraldehyde solution; With sherwood oil, acetone, deionized water repetitive scrubbing, magnetic support sedimentation, at last the final product that obtains is dispersed in 4 ℃ of preservations in the phosphate buffer soln (pH=7.0).But, no matter be Fe nanowire/chitosan/antibody bioprobe, or its preparation method, all exist weak point, at first, the Fe nanowire in the final product is wrapped in the chitosan, and this will restrict giving full play to of Fe nanowire performance widely; Secondly, alleviate to some extent, so still fail fundamentally to solve though reunite; Once more, the condition of harsh preservation final product has improved the cost of its application; At last, the raw material that the preparation method need use is many, and technology is too numerous and diverse.
Summary of the invention
The technical problem that the present invention will solve provides a kind of rational in infrastructure for overcoming weak point of the prior art, the Fe nanowire that is modified with chitosan easy to use.
Another technical problem that the present invention will solve is that a kind of above-mentioned preparation method who is modified with the Fe nanowire of chitosan is provided.
Technical problem in addition that the present invention will solve is that a kind of above-mentioned purposes that is modified with the Fe nanowire of chitosan is provided.
For solving technical problem of the present invention, the technical scheme that is adopted is: the Fe nanowire that is modified with chitosan comprises the outer chitosan of modifying of Fe nanowire and its, particularly,
Said its outer Fe nanowire that is modified with chitosan is arranged in the hole of porous alumina formwork, and between itself and the hole wall space of 1～5nm is arranged;
Said Fe nanowire is along the growth of (110) direction, and its linear diameter is that 50～55nm, line length are 380～420nm;
The bore dia of said porous alumina formwork is that 55～60nm, Kong Changwei 380～420nm, hole density are 3.5 * 10
14/ m
2
For solving another technical problem of the present invention, another technical scheme that is adopted is: the above-mentioned preparation method who is modified with the Fe nanowire of chitosan comprises anonizing, and particularly completing steps is following:
Step 1; Earlier aluminium flake being placed concentration is the oxalic acid solution of 0.2～0.4M; Anodic oxidation 25～35min under volts DS 35～45V is placed on temperature again and is 35～45 ℃, concentration and be in the phosphoric acid solution of 4～6wt% and soaks 20min at least, obtains porous alumina formwork;
Step 3, earlier the porous alumina formwork that the space is arranged between Fe nanowire in the hole and the hole wall being placed concentration is that the chitosan solution of 0.05～0.15wt% soaks 10～20s, it is taken out dryly again, makes the Fe nanowire that is modified with chitosan.
As the preparing method's of the Fe nanowire that is modified with chitosan further improvement, the purity of described aluminium flake is>=99.9%; Described electrolytic iron liquid is the ferric sulfate (FeSO of 80g/L by concentration
4), the boric acid (H of 30g/L
3BO
3) and the xitix of 15g/L mix; Described strong base solution is a sodium hydroxide solution, or potassium hydroxide solution, or lithium hydroxide solution; The concentration of described sodium hydroxide solution is that 5wt%, temperature are 35 ℃; Described chitosan solution is by being that 1: 5: 1000 ratio is formulated in mass ratio between chitosan, acetate and the water.
For solving the technical problem that also has of the present invention, the technical scheme that also has that is adopted is: the above-mentioned purposes that is modified with the Fe nanowire of chitosan does,
The Fe nanowire that is modified with chitosan as sorbent material, is placed to receive hexavalent chromium polluted solution to carry out adsorption treatment.
Beneficial effect with respect to prior art is; One of which; Use ESEM and X-ray diffractometer to characterize respectively to the title product that makes, can be known by its result, title product is that on end it is modified with thread of chitosan outward in the orderly hole of the arrangement of template.The spacing that 1～5nm wherein, is arranged between thread and the template hole wall; Thread is that its linear diameter is that 50～55nm, line length are 380～420nm along the Fe nanowire of (110) direction growth; Template is a porous alumina formwork, and its bore dia is that 55～60nm, Kong Changwei 380～420nm, hole density are 3.5 * 10
14/ m
2Title product with above-mentioned pattern and size had both been guaranteed that Fe nanowire wherein can be not oxidized, thereby had been influenced effective performance of its original performance, had stopped the generation of reuniting again, also because of the cost of using that reduced widely easy to use.They are two years old; With repeatedly many placing the hexavalent chromium polluted water that receive different amounts to adsorb respectively and reduces the test of processing in batches of title product; Its result shows; Title product also can become nontoxic trivalent chromium with deleterious hexavalent chrome reduction except that concentration being low to moderate sexavalent chrome solution more than the 0.5mg/L all can adsorb effectively.Its three, preparing method's science, effectively, not only materials are few and environmental protection; Also there is technology convenient; Be beneficial to the characteristics of suitability for industrialized production,, thereby do not have influence on the performance of Fe nanowire especially because the chitosan of outside Fe nanowire, modifying is merely the thickness of molecular layer; Make Fe nanowire at the normal lotus of chitosan band, other alumina formwork itself also positively charged, sexavalent chrome group (Cr
2O
7 2-) electronegative, there is stronger electrostatic interaction between the positive electricity of chitosan and oxidation aluminium strip and the sexavalent chrome group and when adsorbing each other, is able to sexavalent chrome is carried out reduction reaction, it is reduced into trivalent chromium.
As the further embodiment of beneficial effect, the one, the purity of aluminium flake is preferably >=and 99.9%, be beneficial to the template that obtains better quality; The 2nd, electrolytic iron liquid is that the ferric sulfate of 80g/L, the boric acid of 30g/L and the xitix of 15g/L mix by concentration preferably, is beneficial to and obtains Fe nanowire; The 3rd, strong base solution is preferably sodium hydroxide solution, or potassium hydroxide solution, or lithium hydroxide solution, except that making the source of raw material than the horn of plenty, also makes preparation technology more be prone to implement and flexibly; The 4th, the concentration of sodium hydroxide solution is preferably 5wt%, temperature is 35 ℃, is easy to control the corrosive degree, obtains the title product of appropriate clearance; The 5th, preferably by being that 1: 5: 1000 ratio is formulated in mass ratio between chitosan, acetate and the water, the chitosan solution of this kind concentration is easy to infiltrate between Fe nanowire and the template hole wall chitosan solution, and on Fe nanowire beautify chitosan.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 uses one of result that ESEM (SEM) and X-ray diffraction (XRD) appearance characterize respectively to the porous alumina formwork that obtains and the title product that makes.Wherein, Fig. 1 a is the SEM photo of porous alumina formwork; Fig. 1 b is the SEM photo of title product; The SEM photo that Fig. 1 c has amplified for the part of title product shown in Fig. 1 b; Section and Fig. 1 c by title product shown in Fig. 1 b can find out; The linear diameter of title product is about 50～55nm, and length is about 400nm, between the nano wire in the title product and the hole wall of template tangible space is arranged; Fig. 1 d is the XRD spectra of title product, and it has shown the Fe nanowire in the title product along (110) direction growth, and does not have oxidation by air, has proved that porous alumina formwork protected the iron in the hole not oxidized.
Fig. 2 uses the ultraviolet-visible sub-ray spectrometer to adsorb one of result of test to the title product that makes.The condition of test does, respectively title product 2.4mg placed the 10mL sexavalent chrome solution of different concns, and absorption is tested behind the 400min.Wherein, Fig. 2 a is that concentration is the absorption curve figure of 59mg/L, and Fig. 2 b is that concentration is the absorption curve figure of 10mg/L, can find out that by Fig. 2 a and Fig. 2 b the adsorption effect of title product is fine.
To be title product that use is made carry out solution after the adsorption treatment to sexavalent chrome solution to Fig. 3 uses one of result that x-ray photoelectron power spectrum (XPS) appearance characterizes.Can be found out that by XPS spectrum figure the sexavalent chrome after the absorption has been transformed into trivalent chromium, its toxicity has been reduced widely.
Embodiment
At first buy or make with ordinary method from market:
The aluminium flake of purity >=99.9%; Oxalic acid solution; Phosphoric acid solution; By concentration the electrolytic iron liquid that the xitix of boric acid and 15g/L of ferric sulfate, the 30g/L of 80g/L mixes; Sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution as strong base solution; By the formulated chitosan solution of ratio that between chitosan, acetate and the water is 1: 5: 1000 in mass ratio.Then,
Embodiment 1
The concrete steps of preparation are:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.2M, anodic oxidation 35min under volts DS 35V; Be placed on temperature again and be 35 ℃, concentration and be in the phosphoric acid solution of 4wt% and soak 24min, obtain being similar to the porous alumina formwork shown in Fig. 1 a.
Step 3, earlier the porous alumina formwork that the space is arranged between Fe nanowire in the hole and the hole wall being placed concentration is that the chitosan solution of 0.05wt% soaks 20s.Again it is taken out dryly, make and be similar to shown in Fig. 1 b and Fig. 1 c, and the Fe nanowire that is modified with chitosan shown in the curve among Fig. 1 d.
The concrete steps of preparation are:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.25M, anodic oxidation 33min under volts DS 38V; Be placed on temperature again and be 38 ℃, concentration and be in the phosphoric acid solution of 4.5wt% and soak 23min, obtain being similar to the porous alumina formwork shown in Fig. 1 a.
Step 3, earlier the porous alumina formwork that the space is arranged between Fe nanowire in the hole and the hole wall being placed concentration is that the chitosan solution of 0.08wt% soaks 18s.Again it is taken out dryly, make and be similar to shown in Fig. 1 b and Fig. 1 c, and the Fe nanowire that is modified with chitosan shown in the curve among Fig. 1 d.
Embodiment 3
The concrete steps of preparation are:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.3M, anodic oxidation 30min under volts DS 40V; Be placed on temperature again and be 40 ℃, concentration and be in the phosphoric acid solution of 5wt% and soak 22min, obtain the porous alumina formwork shown in Fig. 1 a.
Step 3, earlier the porous alumina formwork that the space is arranged between Fe nanowire in the hole and the hole wall being placed concentration is that the chitosan solution of 0.1wt% soaks 15s.Again it is taken out drying, make shown in Fig. 1 b and Fig. 1 c, and the Fe nanowire that is modified with chitosan shown in the curve among Fig. 1 d.
Embodiment 4
The concrete steps of preparation are:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.35M, anodic oxidation 28min under volts DS 43V; Be placed on temperature again and be 43 ℃, concentration and be in the phosphoric acid solution of 5.5wt% and soak 21min, obtain being similar to the porous alumina formwork shown in Fig. 1 a.
Step 3, earlier the porous alumina formwork that the space is arranged between Fe nanowire in the hole and the hole wall being placed concentration is that the chitosan solution of 0.13wt% soaks 13s.Again it is taken out dryly, make and be similar to shown in Fig. 1 b and Fig. 1 c, and the Fe nanowire that is modified with chitosan shown in the curve among Fig. 1 d.
Embodiment 5
The concrete steps of preparation are:
Step 1, earlier aluminium flake being placed concentration is the oxalic acid solution of 0.4M, anodic oxidation 25min under volts DS 45V; Be placed on temperature again and be 45 ℃, concentration and be in the phosphoric acid solution of 6wt% and soak 20min, obtain being similar to the porous alumina formwork shown in Fig. 1 a.
Step 3, earlier the porous alumina formwork that the space is arranged between Fe nanowire in the hole and the hole wall being placed concentration is that the chitosan solution of 0.15wt% soaks 10s.Again it is taken out dryly, make and be similar to shown in Fig. 1 b and Fig. 1 c, and the Fe nanowire that is modified with chitosan shown in the curve among Fig. 1 d.
Select potassium hydroxide solution or lithium hydroxide solution more respectively for use, repeat the foregoing description 1～5 as strong base solution, made equally as or be similar to shown in Fig. 1 b and Fig. 1 c and the Fe nanowire that is modified with chitosan shown in the curve among Fig. 1 d.
The purposes that is modified with the Fe nanowire of chitosan does, the Fe nanowire that is modified with chitosan as sorbent material, is placed to receive hexavalent chromium polluted solution to carry out adsorption treatment, obtain as or be similar to absorption shown in the curve among Fig. 2 and Fig. 3 and reduction result.
Obviously, those skilled in the art can to the Fe nanowire that is modified with chitosan of the present invention and its production and use carry out various changes and modification and do not break away from the spirit and scope of the present invention.Like this, belong within the scope of claim of the present invention and equivalent technologies thereof if of the present invention these are revised with modification, then the present invention also is intended to comprise these changes and modification interior.
Claims (8)
1. a Fe nanowire that is modified with chitosan comprises the outer chitosan of modifying of Fe nanowire and its, it is characterized in that:
Said its outer Fe nanowire that is modified with chitosan is arranged in the hole of porous alumina formwork, and between itself and the hole wall space of 1～5nm is arranged;
Said Fe nanowire is along the growth of (110) direction, and its linear diameter is that 50～55nm, line length are 380～420nm;
The bore dia of said porous alumina formwork is that 55～60nm, Kong Changwei 380～420nm, hole density are 3.5 * 10
14/ m
2
2. the said preparation method who is modified with the Fe nanowire of chitosan of claim 1 comprises anonizing, it is characterized in that completing steps is following:
Step 1; Earlier aluminium flake being placed concentration is the oxalic acid solution of 0.2～0.4M; Anodic oxidation 25～35min under volts DS 35～45V is placed on temperature again and is 35～45 ℃, concentration and be in the phosphoric acid solution of 4～6wt% and soaks 20min at least, obtains porous alumina formwork;
Step 2; Earlier porous alumina formwork is placed electrolytic iron liquid; Galvanic deposit 1～5min under the voltage of alternating current of 7～9V; Obtain being equipped with in the hole porous alumina formwork of Fe nanowire, place strong base solution to corrode 2～5min the porous alumina formwork that is equipped with Fe nanowire in the hole again, obtain having between Fe nanowire and the hole wall in the hole porous alumina formwork in space;
Step 3, earlier the porous alumina formwork that the space is arranged between Fe nanowire in the hole and the hole wall being placed concentration is that the chitosan solution of 0.05～0.15wt% soaks 10～20s, it is taken out dryly again, makes the Fe nanowire that is modified with chitosan.
3. the preparation method who is modified with the Fe nanowire of chitosan according to claim 2, the purity that it is characterized in that aluminium flake is >=99.9%.
4. the preparation method who is modified with the Fe nanowire of chitosan according to claim 2 is characterized in that electrolytic iron liquid is that the ferric sulfate of 80g/L, the boric acid of 30g/L and the xitix of 15g/L mix by concentration.
5. the preparation method who is modified with the Fe nanowire of chitosan according to claim 2 is characterized in that strong base solution is a sodium hydroxide solution, or potassium hydroxide solution, or lithium hydroxide solution.
6. the preparation method who is modified with the Fe nanowire of chitosan according to claim 5, the concentration that it is characterized in that sodium hydroxide solution are that 5wt%, temperature are 35 ℃.
7. the preparation method who is modified with the Fe nanowire of chitosan according to claim 2 is characterized in that chitosan solution is by being that 1: 5: 1000 ratio is formulated in mass ratio between chitosan, acetate and the water.
8. said purposes that is modified with the Fe nanowire of chitosan of claim 1 is characterized in that:
The Fe nanowire that is modified with chitosan as sorbent material, is placed to receive hexavalent chromium polluted solution to carry out adsorption treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110046910XA CN102650077A (en) | 2011-02-24 | 2011-02-24 | Chitosan-finishing iron nanowire, method for producing same and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110046910XA CN102650077A (en) | 2011-02-24 | 2011-02-24 | Chitosan-finishing iron nanowire, method for producing same and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102650077A true CN102650077A (en) | 2012-08-29 |
Family
ID=46692199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110046910XA Pending CN102650077A (en) | 2011-02-24 | 2011-02-24 | Chitosan-finishing iron nanowire, method for producing same and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102650077A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300713A (en) * | 1999-12-22 | 2001-06-27 | 南京大学 | Process for synthesizing nm carbon tubes containing nm metal wires |
| CN1715458A (en) * | 2004-06-30 | 2006-01-04 | 中南大学 | Aliminium base wave absorbing material and preparing method |
| WO2007103135A2 (en) * | 2006-03-02 | 2007-09-13 | The Trustees Of Columbia University In The City Of New York | Active cell growth substrates and uses thereof |
-
2011
- 2011-02-24 CN CN201110046910XA patent/CN102650077A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300713A (en) * | 1999-12-22 | 2001-06-27 | 南京大学 | Process for synthesizing nm carbon tubes containing nm metal wires |
| CN1715458A (en) * | 2004-06-30 | 2006-01-04 | 中南大学 | Aliminium base wave absorbing material and preparing method |
| WO2007103135A2 (en) * | 2006-03-02 | 2007-09-13 | The Trustees Of Columbia University In The City Of New York | Active cell growth substrates and uses thereof |
Non-Patent Citations (3)
| Title |
|---|
| 姜海波，等: "多孔氧化铝模板电化学沉积铁纳米线结构及磁性能", 《过程工程学报》, vol. 8, no. 2, 30 April 2008 (2008-04-30) * |
| 孔祥存: "氧化铝模板电沉积制备磁性纳米线阵列及其性能研究", 《合肥工业大学硕士学位论文》, 31 March 2009 (2009-03-31) * |
| 杨昊，等: "铁纳米线/壳聚糖/抗体生物探针的制备和层析检测", 《分析化学》, vol. 37, no. 2, 28 February 2009 (2009-02-28) * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Guo et al. | Synthesis and characterization of ZnNiCr-layered double hydroxides with high adsorption activities for Cr (VI) | |
| Huang et al. | Efficient removal of methylene blue from aqueous solutions using magnetic graphene oxide modified zeolite | |
| Ou et al. | Efficient removal of Cr (VI) by magnetic and recyclable calcined CoFe-LDH/g-C3N4 via the synergy of adsorption and photocatalysis under visible light | |
| Hao et al. | Rapid, efficient and economic removal of organic dyes and heavy metals from wastewater by zinc-induced in-situ reduction and precipitation of graphene oxide | |
| Li et al. | Polydopamine coating assisted synthesis of MnO2 loaded inorganic/organic composite electrospun fiber adsorbent for efficient removal of Pb2+ from water | |
| Wang et al. | Removal and recovery of heavy metal ions by two-dimensional MoS2 nanosheets: performance and mechanisms | |
| Hu et al. | Ternary assembly of g-C3N4/graphene oxide sheets/BiFeO3 heterojunction with enhanced photoreduction of Cr (VI) under visible-light irradiation | |
| Hao et al. | Facile additive-free synthesis of iron oxide nanoparticles for efficient adsorptive removal of Congo red and Cr (VI) | |
| Yang et al. | Flocculation performance and mechanism of graphene oxide for removal of various contaminants from water | |
| Du et al. | Adsorption and photoreduction of Cr (VI) via diatomite modified by Nb2O5 nanorods | |
| CN102258978B (en) | Method for preparing nano Fe3O4 coated attapulgite magnetic composite adsorbent | |
| Ahmed et al. | Hydrothermal preparation of nanostructured manganese oxides (MnOx) and their electrochemical and photocatalytic properties | |
| Zhang et al. | Metal oxide nanoparticles deposited onto carbon-coated halloysite nanotubes | |
| Zhao et al. | Elevated removal of di-n-butyl phthalate by catalytic ozonation over magnetic Mn-doped ferrospinel ZnFe2O4 materials: Efficiency and mechanism | |
| CN107051377B (en) | A kind of nanocomposite and preparation method thereof for synchronous removal carbon nitrogen phosphorus | |
| CN111111612B (en) | Preparation and use method of magnetic porous biochar for removing chromium in water | |
| Chen et al. | Highly efficient As (III) removal in water using millimeter-sized porous granular MgO-biochar with high adsorption capacity | |
| Gao et al. | Magnetic composite Fe3O4/CeO2 for adsorption of azo dye | |
| Li et al. | Efficient removal of cadmium ions from water by adsorption on a magnetic carbon aerogel | |
| CN102464357B (en) | Ferriferous oxide nano-grade fiber, preparation method thereof, and purpose thereof | |
| Yuan et al. | Preparation and application of Mg–Al composite oxide/coconut shell carbon fiber for effective removal of phosphorus from domestic sewage | |
| Huang et al. | Polyethylenimine modified potassium tungsten oxide adsorbent for highly efficient Ag+ removal and valuable Ag0 recovery | |
| CN103172123B (en) | Nano ferric hydroxide and preparation method thereof | |
| Wu et al. | Synthesis of acidified magnetic sludge-biochar and its role in ammonium nitrogen removal: perception on effect and mechanism | |
| Nezhad et al. | One-step Preparation of graphene oxide/polypyrrole magnetic nanocomposite and its application in the removal of methylene blue dye from aqueous solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120829 |