CN107285304A - A kind of method for removing sulfate radical foreign matter in graphene oxide synthetic system - Google Patents
A kind of method for removing sulfate radical foreign matter in graphene oxide synthetic system Download PDFInfo
- Publication number
- CN107285304A CN107285304A CN201710457827.9A CN201710457827A CN107285304A CN 107285304 A CN107285304 A CN 107285304A CN 201710457827 A CN201710457827 A CN 201710457827A CN 107285304 A CN107285304 A CN 107285304A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- metal cation
- synthetic system
- sulfate radical
- organic solvent
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The embodiments of the invention provide a kind of method for removing sulfate radical foreign matter in graphene oxide synthetic system, comprise the following steps:(1) using Hummers methods or improved Hummers methods synthesis graphene oxide, after end of synthesis, graphene oxide synthetic system is obtained;(2) graphene oxide synthetic system is mixed with the aqueous solution containing metal cation, adds density and be more than water, and water-immiscible organic solvent, stirring obtains mixed system, stratification;Wherein described metal cation can be precipitated with sulfate radical formation.The method of the present invention can also remove the manganese ion in graphene oxide synthetic system while sulfate radical is removed.Moreover, compared with the mode of centrifuge washing, the method for removing sulfate radical foreign matter in graphene oxide synthetic system that the present invention is provided more succinctly, is more suitable for industrial production.
Description
Technical field
It is more particularly to a kind of to remove graphene oxide synthetic system the present invention relates to graphene oxide synthesis technical field
The method of middle sulfate radical foreign matter.
Background technology
Graphene is single layer of carbon atom structure, by sp2The stable two-dimensional structure of hydridization formation, the net of Hexagonal close arrangement
Shape crystal, unique structure imparts the unique physicochemical properties of graphene.At present, the research on graphene composite material
The numerous areas such as catalysis, luminous, energy storage and biological medicine are had been directed to, and present huge application prospect.Oxidation
Graphene (GO) is one kind in the numerous derivatives of graphene, the characteristic with polymer, colloid, film and amphiphatic molecule.
Graphene oxide is mainly made up of carbon atom and some polarity oxygen-containing functional groups (such as-OH ,-COOH, C=O ,-O-), is retained
Delocalization pi-conjugated system in graphene.Graphene oxide has good hydrophily, and high-specific surface area is acted on pi-pi accumulation, this
A little advantages provide great advantage for the application of graphene oxide, one of research emphasis as graphene composite material.
Because the production cost of improved Hummers methods synthesis graphene oxide is relatively low, general in current industrial production
Graphene oxide is synthesized all over using improved Hummers methods;But it is whole after improved Hummers methods synthesis graphene oxide
In individual synthetic system removal is needed containing substantial amounts of impurity sulfate ion and micro manganese ion.It is industrial at present to remove sulfuric acid
The method of radical ion, is all the mode of centrifuge washing.But centrifuge washing inefficiency and to the rotation speed requirements pole of centrifuge
Height, these are all highly detrimental to industrial production, therefore need a kind of easier sulfate ion minimizing technology of exploitation badly.
The content of the invention
A kind of easier method for removing sulfate radical foreign matter in graphene oxide synthetic system of this offer.Particular technique side
Case is as follows:
1st, a kind of method for removing sulfate radical foreign matter in graphene oxide synthetic system, comprises the following steps:
(1) using Hummers methods or improved Hummers methods synthesis graphene oxide, after end of synthesis, obtain aoxidizing stone
Black alkene synthetic system;
(2) graphene oxide synthetic system is mixed with the aqueous solution containing metal cation, adds density and be more than water, and
Water-immiscible organic solvent, stirring, obtains mixed system, stratification;Wherein described metal cation can be with sulfuric acid
Root formation precipitation.
Alternatively, also include after step (2):The graphene oxide for removing sulfate radical is separated.
Alternatively, the metal cation is in calcium ion, barium ions, lead ion, mercury ion, strontium ion or silver ion
One or more, preferably barium ions.
Alternatively, the aqueous solution containing metal cation is baryta water.
Alternatively, the metal cation is relative to using Hummers methods or improved Hummers methods synthesis graphite oxide
The stoichiometric excess of the sulfate radical added during alkene.
Alternatively, the organic solvent is more than 1.3 with the density ratio of water at the same temperature.
Alternatively, the organic solvent is selected from least one of chloroform, carbon tetrachloride, dichloromethane, dichloroethanes.
Alternatively, the volume ratio of the aqueous solution containing metal cation and organic solvent is (1-5):1.
Alternatively, the volume ratio of the aqueous solution containing metal cation and graphene oxide synthetic system is (5-
15):1.
The present invention uses water-organic solvent two-phase system, and can be sunk using the precipitation of metal cation and sulfate radical formation
Enter in organic solvent phase, and graphene oxide is present in aqueous phase due to hydrophily.2 points based on more than, we can utilize
This method removes the sulfate ion in graphene oxide synthetic system.Moreover, method of the invention is removing sulfate radical
While, the manganese ion in graphene oxide synthetic system can also be removed.Moreover, compared with the mode of centrifuge washing, this hair
The method for removing sulfate radical foreign matter in graphene oxide synthetic system of bright offer, more succinctly, is more suitable for industrial production.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the accompanying drawing used required in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is XRD (the X-Ray Diffraction, X-ray for the white powder that embodiment 2 is obtained from carbon tetrachloride layer
Diffraction) figure.
Fig. 2 is the XRD for the black powder that embodiment 2 is obtained from middle aqueous layer.
The XRD for the white crystal that Fig. 3 is dried to obtain for the colourless transparent solution in the upper aqueous layer of embodiment 2.
The XRD for the atrament that Fig. 4 is dried to obtain for the colourless transparent solution in the upper aqueous layer of embodiment 2.
Embodiment
The invention provides a kind of method for removing sulfate radical foreign matter in graphene oxide synthetic system, including following step
Suddenly:
(1) using Hummers methods or improved Hummers methods synthesis graphene oxide, after end of synthesis, obtain aoxidizing stone
Black alkene synthetic system;
(2) graphene oxide synthetic system is mixed with the aqueous solution containing metal cation, adds density and be more than water, and
Water-immiscible organic solvent, stirring, obtains mixed system, stratification;Wherein described metal cation can be with sulfuric acid
Root formation precipitation.
Firstly the need of explanation, " Hummers methods " mentioned herein is the classical way for synthesizing graphene oxide (GO),
It passes through proton acid system and strong oxidizer comprising the concentrated sulfuric acid, such as potassium permanganate oxidation graphite, so as to obtain graphite oxide
Alkene.For Hummers methods, the present invention is herein without be repeated, and those skilled in the art, can be with according to the record of existing literature
Know its embodiment.
" improved Hummers methods " mentioned herein is also referred to as the Hummers methods or modified Hummers of amendment
method.It is technical staff on the basis of Hummers methods, by it for example, proton acid system, strong oxidizer, reaction
Method formed by the adjustment of condition (such as temperature);The work such as Zhu Hongwei, Xu Zhiping, Xie Dan《Graphene --- structure,
Preparation method and performance characterization》The 2nd section of page 32 of (publishing house of Tsing-Hua University, the 1st printing November in 2011) is just described
With including NaNO3, dense H2SO4Proton acid system, with KMnO4For the improved Hummers methods of strong oxidizer;Document
(MARCANO D C,KOSYNKIN D V,BERLIN J M,et al.Improved synthesis of graphene
oxide.ACS Nano 4:4806-4814[J].Acs Nano,2010,4(8):4806-14.)) also describe with including dense
H2SO4And H3PO4Proton acid system, with KMnO4For the improved Hummers methods of strong oxidizer.
It should be noted that the proton acid system in improved Hummers methods, still mainly includes the concentrated sulfuric acid.For changing
The Hummers methods entered, have been reported that, the present invention is herein without limiting prior art more;As long as the proton of improved Hummers methods
Acid system still includes the concentrated sulfuric acid, and its graphene oxide synthetic system for synthesizing after graphene oxide can just be carried using the present invention
The method of sulfate radical foreign matter is handled in the removing graphene oxide synthetic system of confession.
Described graphene oxide synthetic system refers to closing by Hummers methods or improved Hummers methods in step (1)
Into graphene oxide process terminate after, the summation of each material of resulting whole reaction;It is without any post processing, for example
Washing, filtering, dry etc..
In the step (2) of the present invention, a period of time, such as after 1-10 days, mixed system are stood adding organic solvent
Layering, it can be divided into three layers of two-phase;Specifically, two-phase is respectively aqueous phase and following organic solvent phase above;Three layers points
Not Wei upper strata water white transparency water layer, lower floor is the organic solvent layer of white emulsion, and centre is the water layer containing yellow substance.
In specific implementation process, in step (2), add after organic solvent, be sufficiently stirred for, for example, can stir 6-40 hours.Example
Such as, can be 6-40 hours with mechanical agitation.And mixed by graphene oxide synthetic system with the aqueous solution containing metal cation
When, preferably stir while mixing.
The present invention is reacted by the sulfate radical in the metal cation in the aqueous solution and graphene oxide synthetic system, raw
Into sulfate precipitation, so that the sulfate radical in graphene oxide synthetic system be removed;In order to realize generated precipitation and oxygen
Graphite alkene is separated, and the present inventor's design makes generated precipitation sink in organic solvent phase;And make hydrophilic oxidation stone
Black alkene is stayed in aqueous phase, so as to realize the removal of sulfate radical.Inventor has found, after step (2) adds organic solvent, by filling
Point stirring, then after standing, it is possible to so that the precipitation generated is sunk in organic solvent phase.In a kind of specific reality of the present invention
Apply in mode, the one kind of the metal cation in calcium ion, barium ions, lead ion, mercury ion, strontium ion or silver ion
Or a variety of, preferably barium ions.More specifically, the anion corresponding to the metal cation can be hydroxyl, or it is other
The metal cation can be made at least partly to be dissolved in the anion of water, such as nitrate anion, chlorion is (cloudy during using silver ion
Ion can not be chlorion) etc..Preferably, the anion selection hydroxyl corresponding to metal cation, because hydroxyl may be used also
To play the hydrionic effect neutralized in graphene oxide synthetic system, and other impurity will not be introduced.Therefore, in the present invention
A kind of embodiment in, the aqueous solution containing metal cation can be baryta water.
Sulfate radical during this is is synthesized in order to fully remove graphene oxide, in a kind of specific implementation of the present invention
In mode, the amount of the material of the metal cation in the aqueous solution is closed relative to using Hummers methods or improved Hummers methods
The amount of the material of the sulfate radical added during into graphene oxide, stoichiometric excess.For example, metal cation is Ba2+When, such as
During fruit is using Hummers methods or improved Hummers methods synthesis graphene oxide, 1mol sulfuric acid is added, then metal
Cation is Ba2+Amount be preferably greater than 1mol.
In a kind of embodiment of the present invention, in order to the separation of good guarantee aqueous phase and organic solvent phase,
The organic solvent is more than 1.3 with the density ratio of water at the same temperature.It is highly preferred that the organic solvent is selected from chloroform, four
At least one of chlorination carbon, dichloromethane, dichloroethanes.
For the volume of the aqueous solution containing metal cation and organic solvent, it can be synthesized according to graphene oxide
The concrete condition of the cumulative volume of sulfuric acid dosage and synthetic system in system is determined, in a kind of specific embodiment party of the present invention
In formula, the volume ratio of the aqueous solution containing metal cation and organic solvent is (1-5):1.
, equally can basis for the aqueous solution containing metal cation and the volume of graphene oxide synthetic system
The concrete condition of the cumulative volume of sulfuric acid dosage and Yu architectonicals in graphene oxide synthetic system is determined, the present invention's
In a kind of embodiment, the aqueous solution containing metal cation and the volume ratio of graphene oxide synthetic system are
(5-15):1.
In a kind of embodiment of the present invention, also include after step (2):The oxidation stone of sulfate radical will be removed
Black alkene separation, and according to the follow-up processing of the actual conditions of graphene oxide progress;Including but not limited to according to effect after drying
Decide whether wash.If conventional drying processing can dry product, it was demonstrated that sulfate ion remove more then without
Washing is needed, if product can not be dried, it was demonstrated that there is a small amount of sulfate ion to retain and then use distillation water washing 1-2 times, re-dry
.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
The improved Hummers methods synthesis graphene oxide of embodiment 1
3g crystalline flake graphites are weighed in 2L large beaker on pan paper with assay balance, and 360ml is weighed respectively with graduated cylinder
It is added to together in graphite with the 40ml concentrated sulfuric acids and phosphoric acid.Weigh 18g potassium permanganate with small beaker to be smashed with mortar, 0 DEG C
Under the conditions of stir while being slowly added into mixture.Relief mixture stirred 12 hours under conditions of 50 DEG C.Take
Addition 400ml mixture of ice and water after room temperature is cooled to after going out, 3ml 30% hydrogen peroxide is quickly stirred and be gradually added into.Stand
3 days, obtain graphene oxide synthetic system.
Embodiment 2 removes sulfate ion using the sulfate radical cleaning solution of barium hydroxide solution-carbon tetrachloride two-phase system
The graphene oxide synthetic system 30mL that embodiment 1 is obtained, is fitted into 500ml beaker.Add while stirring
0.84mol/L barium hydroxide solution 300ml, adds and terminates to continue to stir 24 hours, 100ml carbon tetrachloride is added afterwards molten
Liquid, is stirred 12 hours, static three days, mixed system was divided into three layers of two-phase;Specifically, two-phase is respectively aqueous phase above and following
Organic solvent phase;Three layers be respectively upper strata water white transparency water layer, lower floor is the carbon tetrachloride layer of white emulsion, and centre is
Water layer containing yellow substance.
The XRD of embodiment 3 is detected
White emulsion in carbon tetrachloride layer in Example 2 is dried, and obtains white powder;Take middle aqueous layer
Yellow gum, dry after black powder;Take the colourless transparent solution in upper aqueous layer to dry, obtain atrament and white
Crystal.Dried each material is subjected to XRD tests.As a result respectively as Figure 1-Figure 4.
Fig. 1 is the XRD of the white powder obtained from carbon tetrachloride layer;As can be seen from Figure 1 white precipitate is sulphur
Sour barium, it was demonstrated that the method provided using the present invention can remove sulfate radical foreign matter in graphene oxide synthetic system.
Fig. 2 is the XRD of the black powder obtained from middle aqueous layer;It is observed that graphene oxide exists from Fig. 2
There is one very strong diffraction maximum at 2 θ=12.839, and interlamellar spacing isIt can be seen that the graphite layers after being oxidized
It is due to that there is substantial amounts of hydrone and hydroxyl, carboxyl, epoxy between layers after graphite is oxidized away from obvious increase
The oxygen-containing functional groups such as base.There is a diffraction maximum in 2 θ=43.198, it is graphene planes diffraction maximum, it is possible to find out Huang
Color substance is exactly graphene oxide.
The XRD for the white crystal that Fig. 3 is dried to obtain for the colourless transparent solution in upper aqueous layer;Can from Fig. 3
It is manganese sulfate to go out white crystal;This explanation, the method provided using the present invention can not only remove sulfate ion, moreover it is possible to go
Except the manganese ion in graphene oxide synthetic system.
The XRD for the atrament that Fig. 4 is dried to obtain for the colourless transparent solution in upper aqueous layer;It is provable from figure to be somebody's turn to do
Material is GO and contains a small amount of graphene.
Experiment is absolutely proved more than, and the method that the present invention is provided can remove sulfuric acid in graphene oxide synthetic system
Root impurity;Moreover, additionally it is possible to remove the manganese ion in graphene oxide synthetic system.And this method is easy, fit very much
Close industrial production.
A kind of method for removing sulfate radical foreign matter in graphene oxide synthetic system provided by the present invention is carried out above
It is discussed in detail.Specific embodiment used herein is set forth to the principle and embodiment of the present invention, and the above is implemented
The explanation of example is only intended to the method and its central idea for helping to understand the present invention.It should be pointed out that for the common skill of this area
For art personnel, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, these change
Enter and modify the protection for also falling into the claims in the present invention.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all
Any modification, equivalent substitution and improvements made within the spirit and principles in the present invention etc., are all contained in protection scope of the present invention
It is interior.
Claims (9)
1. a kind of method for removing sulfate radical foreign matter in graphene oxide synthetic system, it is characterised in that comprise the following steps:
(1) using Hummers methods or improved Hummers methods synthesis graphene oxide, after end of synthesis, graphene oxide is obtained
Synthetic system;
(2) graphene oxide synthetic system is mixed with the aqueous solution containing metal cation, add density be more than water, and not with
The miscible organic solvent of water, stirring, obtains mixed system, stratification;Wherein described metal cation can be with sulfate radical shape
Into precipitation.
2. the method as described in claim 1, it is characterised in that also include after step (2):The oxidation of sulfate radical will be gone
Graphene is separated.
3. the method as described in claim 1, it is characterised in that the metal cation be selected from calcium ion, barium ions, lead from
One or more in son, mercury ion, strontium ion or silver ion, preferably barium ions.
4. method as claimed in claim 3, it is characterised in that the aqueous solution containing metal cation is that barium hydroxide is water-soluble
Liquid.
5. the method as described in claim 1, it is characterised in that the metal cation is relative to use Hummers methods or changes
The stoichiometric excess of the sulfate radical added during the Hummers methods synthesis graphene oxide entered.
6. the method as described in claim 1, it is characterised in that density ratio of the organic solvent with water at the same temperature is big
In 1.3.
7. method as claimed in claim 6, it is characterised in that the organic solvent is selected from chloroform, carbon tetrachloride, dichloromethane
At least one of alkane, dichloroethanes.
8. the method as described in claim 1, it is characterised in that the aqueous solution containing metal cation and organic solvent
Volume ratio is (1-5):1.
9. the method as described in claim 1, it is characterised in that the aqueous solution and graphene oxide containing metal cation
The volume ratio of synthetic system is (5-15):1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710457827.9A CN107285304B (en) | 2017-06-16 | 2017-06-16 | A method of removing sulfate radical foreign matter in graphene oxide synthetic system |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710457827.9A CN107285304B (en) | 2017-06-16 | 2017-06-16 | A method of removing sulfate radical foreign matter in graphene oxide synthetic system |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107285304A true CN107285304A (en) | 2017-10-24 |
CN107285304B CN107285304B (en) | 2019-03-29 |
Family
ID=60097248
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710457827.9A Expired - Fee Related CN107285304B (en) | 2017-06-16 | 2017-06-16 | A method of removing sulfate radical foreign matter in graphene oxide synthetic system |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107285304B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114316655A (en) * | 2022-01-17 | 2022-04-12 | 山东金利特新材料有限责任公司 | Preparation process and application of graphene oxide/nano barium sulfate composite material |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
CN104609399A (en) * | 2014-12-29 | 2015-05-13 | 南京大学 | Graphene oxide, preparation method and application thereof |
-
2017
- 2017-06-16 CN CN201710457827.9A patent/CN107285304B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
CN104609399A (en) * | 2014-12-29 | 2015-05-13 | 南京大学 | Graphene oxide, preparation method and application thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114316655A (en) * | 2022-01-17 | 2022-04-12 | 山东金利特新材料有限责任公司 | Preparation process and application of graphene oxide/nano barium sulfate composite material |
Also Published As
Publication number | Publication date |
---|---|
CN107285304B (en) | 2019-03-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Calandra et al. | How self-assembly of amphiphilic molecules can generate complexity in the nanoscale | |
CN106633051B (en) | A kind of titanium carbide/polyaniline composite material and preparation method thereof | |
Li et al. | Controllable synthesis of CuS nanostructures from self-assembled precursors with biomolecule assistance | |
CN101372363B (en) | Synthetic alpha-MnO 2 Method for micron hollow sphere and nanocluster | |
CN104760968B (en) | A kind of nanoscale method for preparing organobentonite | |
CN106076244A (en) | A kind of preparation method of the long-life lithium ion sieve adsorbant of nano-oxide cladding | |
Chen et al. | α-calcium sulfate hemihydrate nanorods synthesis: A method for nanoparticle preparation by mesocrystallization | |
CN102086025A (en) | Preparation method of one-dimensional (1D) flexible nano-material assembly body | |
CN104817106B (en) | TiO2The solvent process for thermosynthesizing of hollow-core construction sub-micron ball | |
CN108525679A (en) | A method of preparing ZnS quantum dots and redox graphene compound by presoma of metal organic frame | |
Huang et al. | Photoluminescence of graphene quantum dots enhanced by microwave post-treatment | |
Li et al. | Construction of Z-scheme BiOCl/Bi24O31Br10 hierarchical heterostructures with enhanced photocatalytic activity | |
CN107416882A (en) | A kind of method that metastable state vaterite calcium carbonate is prepared based on ethylene glycol calcium method | |
Zhao et al. | One-and two-photon luminescence in graphene oxide quantum dots | |
CN107285304B (en) | A method of removing sulfate radical foreign matter in graphene oxide synthetic system | |
Liu et al. | Gelatin-assisted sol–gel derived TiO2 microspheres for hydrogen storage | |
CN109796974B (en) | Preparation method of graphene quantum dots with adjustable fluorescence properties | |
CN107486160A (en) | A kind of nano-cellulose/composite diatomite sorbing material and preparation method thereof | |
Gorai et al. | Shape selective solvothermal synthesis of copper sulphides: role of ethylenediamine–water solvent system | |
CN105776253A (en) | Method for preparing potassium nitrate and nanometer kaolinite with kaliophilite powder bodies | |
CN107673384A (en) | A kind of method that metastable state vaterite calcium carbonate is prepared based on glycerine calcium method | |
CN107364856B (en) | A method of removing sulfate radical foreign matter in graphene oxide synthetic system | |
CN101497020A (en) | Method for preparing mesoporous silicon adsorption material with high specific surface area | |
CN106670499A (en) | Environment-friendly preparing method of nanometer copper with ascorbic acid and Arabic gum serving as reducing agent and protective agent | |
Yu et al. | Hierarchically nanostructured shuttle-like aragonite mesocrystals: Preparation, characterization, growth mechanism, and removal ability to La (III) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190329 Termination date: 20200616 |