CN103182293A - Method for preparing manganese oxide nanowire by deposition on surface of natural porous diatomite - Google Patents
Method for preparing manganese oxide nanowire by deposition on surface of natural porous diatomite Download PDFInfo
- Publication number
- CN103182293A CN103182293A CN2013101104338A CN201310110433A CN103182293A CN 103182293 A CN103182293 A CN 103182293A CN 2013101104338 A CN2013101104338 A CN 2013101104338A CN 201310110433 A CN201310110433 A CN 201310110433A CN 103182293 A CN103182293 A CN 103182293A
- Authority
- CN
- China
- Prior art keywords
- diatomite
- water
- weighing
- room temperature
- ammonium persulfate
- 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
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a method for preparing a manganese oxide nanowire by deposition on the surface of natural porous diatomite. The method is characterized by comprising the following steps: 1, weighing a diatomite powder body, placing the diatomite powder body into a beaker filled with water, placing the beaker into a water bath pond, and stirring to prepare a diatomite suspension solution; 2, weighing ammonium persulfate (NH4)2S2O8, placing ammonium persulfate (NH4)2S2O8 into the diatomite suspension solution, magnetically stirring for more than 30 min, fully impregnating into the diatomite, weighing KMnO4, placing KMnO4 into a mortar, fully grinding, dissolving in water, dripping into the diatomite suspension solution, continuing to stir for more than 30 min, and cooling to the room temperature; and 3, transferring the solution into a reaction kettle for water bath/hydrothermal reaction at the temperature of 50-160 DEG C, ageing, cooling to the room temperature, washing by de-ionized water and absolute ethanol for multiple times, and drying to obtain a final sample. According to the method, the adsorption efficiency of a composite material on heavy metal ions is improved; and the method is low in production cost, simple in operation process and easy for industrial production.
Description
Technical field
The present invention relates to the material field, is a kind of method for preparing the manganese oxide nano wire at the diatom original soil surface deposition with natural loose structure.
Background technology
Heavy metal ion and compound thereof can cause crops, water body severe contamination, and enter human body by biological chain, and human health is caused very big injury, and its pollutant control is enjoyed domestic and international concern always.At present, heavy metal polluted waste water improvement method has tens kinds, but really can scale use have only medical method, electric flocculence, secondary embrane method and absorption method.Comparatively speaking, absorption method is easy, practical, use at most, but absorption method mainly is subject to the absorption usefulness of material (adsorbent) in application.Having porous, Large ratio surface and enrich surface functional group, is excellent heavy metal ion adsorbing material, and wherein the orderly pore passage structure of material and reasonable pore-size distribution are particularly important.The porous material that is fit to Adsorption of Heavy Metal Ions at present mainly is activated carbon, molecular sieve, porous fibre etc.Because molecular sieve, porous fibre cost are very high, limit its commercial Application; Have only activated carbon to use in commerce, and the activated carbon pore passage structure is irregular, and is perforate shape structure, desorb easily can't reach the requirement of advanced treatment for heavy metal ion.Therefore efficient, low-cost preparation of adsorbent becomes the key problem in technology that the restriction absorption method is handled heavy metal ion with application.
Diatomite is a kind of inorganic mineral material with natural long-range order microcellular structure, and small aperture is that 20～50nm, macropore diameter are 100～300nm, and main chemical is amorphous state SiO
2, by the network structure that the mutual bridging of silicon-oxy tetrahedron forms, the uncertainty owing to the silicon atom number causes existing in the network coordination defective and oxo bridge defective etc.Therefore on surperficial Si-O-" dangling bonds ", form Si-OH, i.e. surface silanol group easily in conjunction with H.Surface silanol group easily is dissociated into Si-O in water
-And H
+, make the diatomite surface present elecrtonegativity.Therefore, diatomite absorption heavy metal cation has natural structural advantage, and in commercial Application.Because the natural sex of diatomite microcellular structure, the feasible processing of reduction significantly heavy metal ion adsorbing material prepares expense becomes possibility.But there are two problems in diatomite when the adsorption treatment heavy metal ion, the one, and specific area is lower, and adsorption capacity is influenced; The 2nd, to heavy metal acid radical anion (H in the water body
2AsO
3 -, HasO
3 2-, AsO
3 3-H
2AsO
4 -, HAsO
4 2-, AsO
4 3-CrO
4 2-, Cr
2O
7 2-) clearance low (listed in the lead, zinc, mercury, cadmium, chromium, arsenic six heavy metal species ions of improvement by country, both having the metal ion lead, zinc, mercury, cadmium of positive valence state etc., also have the negative valency attitude acid radical anion chromium,
Arsenic; Comparatively speaking, negative valency attitude arsenic, chromium ion are more difficult).How effectively to address the above problem, be the preparation of diatom great soil group adsorbent and the key problem in technology that is applied to the effluent containing heavy metal ions processing.Therefore, surface treatment or modification infusorial earth are used for heavy metal ion adsorbed processing research, become the research focus, and with the diatomite after molysite or the modification of manganese salt, treatment effect is best, and its Adsorption of Heavy Metal Ions (also comprising acid radical anion) ability improves significantly.Up to the present diatomite modification is handled, all show as modifier (molysite, manganese salt, aluminium salt, organic matter etc.) and mix (unordered compound) with diatomaceous mechanicalness, and most is cost to destroy diatomite natural micropore structure, and heavy metal ion adsorbed removal usefulness is subjected to very big the influence.
Nano structural material is the abundantest material, especially ordered nano-structure material of surface-active functional group, can significantly improve the specific area of material.Therefore, on diatomaceous algae dish, prepare nano-structural ordered iron or Mn oxide, both increased it to heavy metal ion adsorbed universal (the positive and negative valence state heavy metal ion of simultaneous adaptation), can increase the material surface active function groups simultaneously again, significantly improve the specific area of composite, and then significantly improve this composite Adsorption of Heavy Metal Ions usefulness, be of practical significance very much.
Summary of the invention
The objective of the invention is to all heavy metal be had at diatomite and Mn oxide the characteristics of good adsorption, provide a kind of preparation to have the diatomaceous method of nanometer line feature manganese-oxide deposition, thereby, further improved the absorption usefulness of this composite (adsorbent) to heavy metal ion.This method production cost is low, and operating procedure is simple, is easy to suitability for industrialized production.
Manganese oxide nanowire deposition diatomite provided by the present invention is synthesized by diatomite, potassium permanganate, ammonium persulfate, water, employing coprecipitation.The material proportion of building-up process is: water: diatomite (weight part ratio): potassium permanganate: ammonium persulfate=120:10:(4.56～10.635): (3.828～8.894)
The nanowire supported diatomaceous preparation method of a kind of manganese oxide provided by the present invention is characterized in that, may further comprise the steps:
The first step takes by weighing a certain amount of diatomite powder and puts into the beaker that fills water, and places sea water bath to stir in beaker, makes the diatomite suspension.
In second step, accurately take by weighing a certain amount of (NH again
4)
2S
2O
8Go in the diatomaceous suspension, fully be impregnated into diatomite more than the magnetic agitation 30min after, take by weighing certain mass KMnO
4Earlier soluble in water (mol ratio of ammonium persulfate and potassium permanganate is 1:1～1:1.5), splash into diatomite suspension, continues to stir 30min and is cooled to room temperature after above as for fully grinding the back in the mortar.
The 3rd step changed solution over to that 50-160 ℃ of water-bath 3-24h carries out ageing in the reactor, was cooled to room temperature, then with deionized water and absolute ethanol washing for several times afterwards drying obtain the nanowire supported diatomite microporous adsorbent material of manganese oxide final sample.
The present invention adopts chemical precipitation method to pass through depositing nano line style manganese oxide on diatom soil matrix nuclear, prepare the composite microporous adsorbent with good adsorption heavy metal acid radical anion performance, by adopting the composite microporous adsorbent of this process gained support type, adsorb at the low concentrations of chromium acid solution.
Description of drawings:
The X-ray diffraction curve of Fig. 1 embodiment 1 product and diatom original soil, wherein, a is the X-ray diffraction curve of diatom original soil, b is the X-ray diffraction curve of embodiment 1 product.
The corresponding part scanning electron microscope image of Fig. 2 embodiment 2 products and diatom original soil, wherein, a is the scanning electron microscope image of diatom original soil, and b is the scanning electron microscope image of diatom original soil plate edge, c is the SEM of embodiment 2 products, and d is the scanning electron microscope image at embodiment 2 product edges.
The TEM of Fig. 3 embodiment 3 products and diatom original soil and HRTEM picture, wherein, a is the images of transmissive electron microscope of diatom original soil, and b is the TEM of embodiment 3 products, and c is the partial enlarged drawing projection sem image of embodiment 3 product plate edges, and d is the HRTEM of embodiment 3.
Fig. 4 embodiment 4,5 products and diatom original soil N
2The adsorption desorption curve, wherein, a is the N2 adsorption desorption curve of diatom original soil, b, c are respectively the N of embodiment 4,5 products
2The adsorption desorption curve.
Fig. 5 embodiment 4,5 products and diatom original soil pore structure adsorption curve and pore size distribution curve, wherein, a is diatom original soil, b, c are respectively embodiment 4,5 product pore size distribution curves
With diatomite original soil Fourier infrared spectrum, wherein, a is diatom original soil behind Fig. 6 embodiment 1 product and the absorption heavy metal chromium, and b is the manganese-oxide deposition diatom original soil, and c is the manganese oxide load diatom original soil behind the absorption heavy metal anion chromium
The specific embodiment
This experiment preparation 5mg/L low concentrations of chromium acid solution, the chromium ion clearance can reach 96%.
Embodiment 1
1. take by weighing 4.2g diatomite and be suspended in the 50mL water, and place the thermostatted water bathing pool to stir into uniform suspension.
2. take by weighing ammonium persulfate 3.7g and add in the diatomite suspension, after the constant temperature magnetic agitation makes it fully be impregnated into diatomite, after adding the abundant reaction of potassium permanganate 4.424g continuation stirring, be cooled to room temperature.
3. solution is changed over to 90 ℃ of water-bath 12h carry out ageing in the reactor, be cooled to room temperature, the back is dry for several times to use deionized water and absolute ethanol washing then.
Embodiment 2
1. take by weighing 4.2g diatomite and be suspended in the 50mL water, and place the thermostatted water bathing pool to stir into uniform suspension.
2. take by weighing ammonium persulfate 4.146g and add in the diatomite suspension, after the constant temperature magnetic agitation makes it fully be impregnated into diatomite, after adding a potassium permanganate 4.957g continuation constant temperature stirring abundant reaction in hour, be cooled to room temperature.
3. solution is changed over to 50 ℃ of water-bath 24h carry out ageing in the reactor, be cooled to room temperature, the back is dry for several times to use deionized water and absolute ethanol washing then.
Embodiment 3
1. take by weighing 4.2g diatomite and be suspended in the 50mL water, and place the thermostatted water bathing pool to stir into uniform suspension.
2. take by weighing ammonium persulfate 3.06g and add in the diatomite suspension, after the constant temperature magnetic agitation makes it fully be impregnated into diatomite, after adding potassium permanganate 3.66g continuation constant temperature stirring abundant reaction in an and a half hours, be cooled to room temperature.
3. solution is changed over to 120 ℃ of water-bath 16h carry out ageing in the reactor, be cooled to room temperature, the back is dry for several times to use deionized water and absolute ethanol washing then.
Embodiment 4
1. take by weighing 4.2g diatomite and be suspended in the 50mL water, and place the thermostatted water bathing pool to stir into uniform suspension.
2. take by weighing ammonium persulfate 2.422g and add in the diatomite suspension, after the constant temperature magnetic agitation makes it fully be impregnated into diatomite, continue constant temperature and stir half an hour and be cooled to room temperature after fully reacting adding potassium permanganate 2.898g.
3. solution is changed over to 160 ℃ of water-bath 8h carry out ageing in the reactor, be cooled to room temperature, the back is dry for several times to use deionized water and absolute ethanol washing then.
Embodiment 5
1. take by weighing 4.2g diatomite and be suspended in the 50mL water, and place the thermostatted water bathing pool to stir into uniform suspension.
2. take by weighing ammonium persulfate 1.595g and add in the diatomite suspension, after the constant temperature magnetic agitation makes it fully be impregnated into diatomite, continue constant temperature and stir half an hour and be cooled to room temperature after fully reacting adding potassium permanganate 1.9g.
3. solution is changed over to 90 ℃ of water-bath 3h carry out ageing in the reactor, be cooled to room temperature, the back is dry for several times to use deionized water and absolute ethanol washing then.
Table 1
| Sample number into spectrum | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Clearance % | 96% | 84% | 83% | 86% | 80% |
Claims (1)
1. the preparation method of a natural porous diatom soil matrix deposition manganese oxide nanowire is characterized in that, may further comprise the steps:
The weight of material proportioning of preparation process is: water: diatomite: potassium permanganate: ammonium persulfate=120:10:(4.56～10.635): (3.828～8.894);
The first step takes by weighing the diatomite powder and puts into the beaker that fills water, and places sea water bath to stir in beaker, makes the diatomite suspension;
In second step, take by weighing ammonium persulfate (NH again
4)
2S
2O
8Go in the diatomaceous suspension, fully be impregnated into diatomite more than the magnetic agitation 30min after, take by weighing KMnO
4Splash into diatomite suspension earlier after soluble in water after abundant grinding the in the mortar, continuation is cooled to room temperature after stirring more than the 30min;
The 3rd step changed solution over to that 50-160 ℃ of water-bath 3-24h carries out ageing in the reactor, was cooled to room temperature, afterwards obtained final sample after the drying for several times with deionized water and absolute ethanol washing then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101104338A CN103182293A (en) | 2013-04-01 | 2013-04-01 | Method for preparing manganese oxide nanowire by deposition on surface of natural porous diatomite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013101104338A CN103182293A (en) | 2013-04-01 | 2013-04-01 | Method for preparing manganese oxide nanowire by deposition on surface of natural porous diatomite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103182293A true CN103182293A (en) | 2013-07-03 |
Family
ID=48673888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013101104338A Pending CN103182293A (en) | 2013-04-01 | 2013-04-01 | Method for preparing manganese oxide nanowire by deposition on surface of natural porous diatomite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103182293A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105236480A (en) * | 2014-07-03 | 2016-01-13 | 南京理工大学 | HCOOBiO nanocrystalline with unique morphology and preparation method therefor |
| JP2018530102A (en) * | 2015-06-22 | 2018-10-11 | プリンテッド・エネルギー・ピーティーワイ・リミテッド | Diatom energy storage device |
| CN109499523A (en) * | 2018-11-28 | 2019-03-22 | 北京工业大学 | A kind of FeOOH/MnO2The preparation method of@diatomite composite material |
| CN109499524A (en) * | 2018-11-28 | 2019-03-22 | 北京工业大学 | A kind of AlOOH/MnO2The preparation method of@diatomite composite material |
| US11063265B2 (en) | 2012-07-18 | 2021-07-13 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
| US11066306B2 (en) | 2012-07-18 | 2021-07-20 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
| US11502311B2 (en) | 2012-10-10 | 2022-11-15 | Printed Energy Pty Ltd | Printed energy storage device |
-
2013
- 2013-04-01 CN CN2013101104338A patent/CN103182293A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| TONG ZHANG, ETC.: "Removal of bisphenol a via a hybrid process combining oxidation on β-MnO<sub>2</sub> nanowires with microfiltration", 《COLOIDS AND SURFACES A: PHYSICOCHEMICAL AND ENGINEERING ASPECTS》 * |
| 詹树林等: "氧化锰改性硅藻土吸附剂的制备及其染料吸附性能", 《稀有金属材料与工程 增刊2》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11063265B2 (en) | 2012-07-18 | 2021-07-13 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
| US11066306B2 (en) | 2012-07-18 | 2021-07-20 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
| US11637292B2 (en) | 2012-07-18 | 2023-04-25 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
| US11673811B2 (en) | 2012-07-18 | 2023-06-13 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
| US11962017B2 (en) | 2012-07-18 | 2024-04-16 | Printed Energy Pty Ltd | Diatomaceous energy storage devices |
| US11502311B2 (en) | 2012-10-10 | 2022-11-15 | Printed Energy Pty Ltd | Printed energy storage device |
| CN105236480A (en) * | 2014-07-03 | 2016-01-13 | 南京理工大学 | HCOOBiO nanocrystalline with unique morphology and preparation method therefor |
| JP2018530102A (en) * | 2015-06-22 | 2018-10-11 | プリンテッド・エネルギー・ピーティーワイ・リミテッド | Diatom energy storage device |
| CN109499523A (en) * | 2018-11-28 | 2019-03-22 | 北京工业大学 | A kind of FeOOH/MnO2The preparation method of@diatomite composite material |
| CN109499524A (en) * | 2018-11-28 | 2019-03-22 | 北京工业大学 | A kind of AlOOH/MnO2The preparation method of@diatomite composite material |
| CN109499523B (en) * | 2018-11-28 | 2021-11-05 | 北京工业大学 | FeOOH/MnO2Preparation method of @ diatomite composite material |
| CN109499524B (en) * | 2018-11-28 | 2021-11-05 | 北京工业大学 | AlOOH/MnO2Preparation method of @ diatomite composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103182293A (en) | Method for preparing manganese oxide nanowire by deposition on surface of natural porous diatomite | |
| Cui et al. | Phosphorus recovery by core-shell γ-Al2O3/Fe3O4 biochar composite from aqueous phosphate solutions | |
| Xu et al. | Enhanced phosphorus locking by novel lanthanum/aluminum–hydroxide composite: implications for eutrophication control | |
| Asfaram et al. | Experimental design and modeling of ultrasound assisted simultaneous adsorption of cationic dyes onto ZnS: Mn-NPs-AC from binary mixture | |
| Yuan et al. | Facile preparation of MoS2@ Kaolin composite by one-step hydrothermal method for efficient removal of Pb (II) | |
| Purwajanti et al. | Mesoporous magnesium oxide hollow spheres as superior arsenite adsorbent: synthesis and adsorption behavior | |
| Pan et al. | Development of polymer-based nanosized hydrated ferric oxides (HFOs) for enhanced phosphate removal from waste effluents | |
| Liu et al. | Insight into simultaneous selective removal of nitrogen and phosphorus species by lanthanum-modified porous polymer: Performance, mechanism and application | |
| Du et al. | Adsorption and photoreduction of Cr (VI) via diatomite modified by Nb2O5 nanorods | |
| Feng et al. | Synchronous removal of ammonium and phosphate from swine wastewater by two agricultural waste based adsorbents: Performance and mechanisms | |
| Wang et al. | Strong adsorption of tetracycline on octahedral Cu2O nanocrystals exposed with {111} facets: Adsorption behavior and mechanism insight | |
| Ko et al. | CeO2-covered nanofiber for highly efficient removal of phosphorus from aqueous solution | |
| Li et al. | Uniform surface modification of diatomaceous earth with amorphous manganese oxide and its adsorption characteristics for lead ions | |
| CN103962094B (en) | A kind of ordered structure nanometer γ-Al 2o 3the preparation method of chemical modification diatomite adsorbant | |
| CN108031433A (en) | A kind of preparation method of mesoporous calcium silicates load nano zero-valence iron composite material | |
| Zheng et al. | Fabrication of free-standing bio-template mesoporous hybrid film for high and selective phosphate removal | |
| Chen et al. | One-pot synthesis of porous TiO2/BiOI adsorbent with high removal efficiency and excellent recyclability towards tetracyclines | |
| Kang et al. | Morphology controlled synthesis of hierarchical structured Fe2O3 from natural ilmenite and its high performance for dyes adsorption | |
| Song et al. | Efficient and sustainable phosphate removal from water by small-sized Al (OH) 3 nanocrystals confined in discarded Artemia Cyst-shell: Ultrahigh sorption capacity and rapid sequestration | |
| CN107469765B (en) | Preparation method of diatomite/magnesium ferrite composite material | |
| Yan et al. | Effective removal of ruthenium (III) ions from wastewater by amidoxime modified zeolite X | |
| CN104001471B (en) | Preparation method of silicon dioxide immobilized hydroxyapatite material | |
| Prabhu et al. | Synthesis of sucrose-derived porous carbon-doped ZrxLa1-xOOH materials and their superior performance for the simultaneous immobilization of arsenite and fluoride from binary systems | |
| Song et al. | A novel MIL-125 (Ti)-based nanocomposite for enhanced adsorption and catalytic degradation of tetracycline hydrochloride: Synergetic mechanism of calcination and the nitrogen-containing reticulated surface layer | |
| CN111036175B (en) | Active carbon-Ag2O-CuO-Bi2O3Adsorbing material and preparation method and application thereof |
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: 20130703 |