CN106241781A - The removing method of metal ion in graphite oxide - Google Patents
The removing method of metal ion in graphite oxide Download PDFInfo
- Publication number
- CN106241781A CN106241781A CN201610580659.8A CN201610580659A CN106241781A CN 106241781 A CN106241781 A CN 106241781A CN 201610580659 A CN201610580659 A CN 201610580659A CN 106241781 A CN106241781 A CN 106241781A
- Authority
- CN
- China
- Prior art keywords
- metal ion
- aqueous solution
- acidic aqueous
- graphite oxide
- complexing
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses metal ion in a kind of graphite oxide and remove method, the method is the acidic aqueous solution that first preparation contains complexing of metal ion agent, then washs to wherein concentration of metal ions graphite oxide less than 10ppm with it；The preparation of the acidic aqueous solution containing complexing of metal ion agent is under stirring, complexing of metal ion agent is stirred by adding in acidic aqueous solution than for 1:800～1:80 with deionized water quality in acidic aqueous solution.In graphite oxide disclosed by the invention, metal ion removes method, acidic aqueous solution offer sour environment, thus the ionization of effective inhibited oxidation graphite edge carboxylic acid ion；There is the complexing of metal ion agent of strong complexing simultaneously, capture the metal ion that carboxylate radical discharges, reach to rapidly remove the effect of wherein metal ion.
Description
Technical field
The invention belongs to graphite material impurity removing technology field, be specifically related to the removing side of metal ion in a kind of graphite oxide
Method.
Background technology
2004, the two of University of Manchester scientist An Delie Jim and Ke Siteyanuowoxiao love send out
Now use and tear the method for adhesive tape and can prepare single-layer graphene, and since obtaining Nobel Prize in physics in 2010, due to stone
The ink excellent mechanical property of alkene and good heat conductivity (5300W/m K), electric conductivity (15000cm2/ V s) and light transmission
(absorbing the light of 2.3%), is considered to be expected to be widely applied to such as new forms of energy battery, sensor, computer, quasiconductor etc. multiple
Field.
At present, the method preparing Graphene has mechanical stripping method, oxidation-reduction method, SiC epitaxial growth method and chemical gaseous phase
Sedimentation (CVD), but only oxidation-reduction method is capable of large-scale production.And oxide-reduction method is commonly used permanganic acid
Potassium, potassium ferrate, potassium hyperchlorate etc. first aoxidize prepared graphite oxide as oxidant to graphite, then by ultrasonic or
The methods such as mechanical shock carry out stripping to graphite oxide and obtain graphene oxide, re-use hydrazine hydrate etc. and have the change of reduction
Graphene oxide is reduced and i.e. can get Graphene by material.Wherein, conventional method for oxidation is by improving
Hummer ' s method prepares graphite oxide, and hummer ' the s method improved be tradition hummer ' s method (Hummers,
W.S.&Offeman,R.E.Preparation of graphitic oxide.J.Am.Chem.Soc.80,1339–1339
(1958), on the basis of), the proportioning of oxidizing temperature, oxidization time and graphite Yu potassium permanganate is improved and obtains oxidation stone
Ink.Due to metal ion (the such as Mn introduced because of use oxidant during graphite oxidation2+、Fe2+), can be by graphite oxide
The complexing that alkene edge carboxylic acid ion is strong, causes being difficult in water-washing process later be washed away.And metal ion
There is the problem easily producing following several respects: (1) is due to the complexing of metal ion so that graphene oxide electrostatic interaction
Power weakens, and then affects the stripping of graphite oxide；(2) easy at graphene edge product owing to metal-oxide itself is non-conductive
Raw defect, thus affect the mechanical property during Graphene uses and electric property；(3) it is expected to be used for wearing due to Graphene
The manufacture (such as Flexible graphene mobile phone) of wearing electronic product, meeting and direct physical contact, serious threat biology is healthy, and works as
When electronic product containing Graphene abandons as electronic waste, there is also the potential hazard polluting environment.
Owing to metal ion can produce the problems referred to above present in graphite oxide, the application of Graphene is caused greatly to be limited
System.The most quickly remove a small amount of metal ion present in graphite oxide and become a technical barrier in the urgent need to address.
Summary of the invention
The purpose of the present invention aims to above-mentioned problems of the prior art, it is provided that in a kind of graphite oxide metal from
The removing method of son, can remove metal ion present in graphite oxide fast and effectively, the stripping making graphite oxide is suitable
Profit is carried out, and improves mechanical property and the electric property of Graphene further.
To achieve these goals, the present invention takes techniques below scheme to realize.
The invention provides the removing method of metal ion in a kind of graphite oxide, the method be first preparation containing metal from
The acidic aqueous solution of sub-chelating agent, then washs to wherein concentration of metal ions less than 10ppm graphite oxide with it, then
With deionized water carry out washing to solution be neutrality.
The preparation of the acidic aqueous solution containing complexing of metal ion agent in the removing method of above-mentioned metal ion is in stirring
Under state, add complexing of metal ion agent to acidity by with deionized water quality in acidic aqueous solution than for 1:800～1:80
Aqueous solution stirs.Here, the complexing of the complexing of metal ion agent of selection must be better than carboxylic acid ion,
Thus just can capture the metal ion that carboxylate radical discharges, reach to rapidly remove the effect of wherein metal ion.Therefore, do not drawing
On the premise of entering other foreign ion, complexing of metal ion agent still has the widest selectable range, and it can be alcamines
At least one in compound, aminocarboxylate, organic phosphate, phosphate and polyacrylic compounds.Wherein, alcamines
Compound can be monoethanolamine, diethanolamine, triethanolamine etc.；Aminocarboxylate can be sodium ammonium triacetate (NTA), ethylenediamine
Tetraacetate (EDETATE SODIUM or four sodium), diethylenetriamine pentacarboxylic acid salt (DTPA) etc.；Organic phosphate can be phytic acid, second two
Amine four methene sodium phosphate (EDTMPS), diethylene triamine pentamethylene phosphonic salt (DETPMPS), amine three methene phosphate etc.；Phosphoric acid
Salt can be sodium phosphate, potassium phosphate etc.；Polyacrylic compounds can be hydrolytic polymaleic anhydride (HPMA), polyacrylic acid
(PAA), poly-hydroxy acrylic acid, maleic acrylic copolymer and polyacrylamide etc..Due to metal in graphite oxide itself
Ion concentration is the highest, and when complexing of metal ion agent concentration is too high in acidic aqueous solution, can increase production cost undoubtedly, warp
Cross research to find, when in complexing of metal ion agent with acidic aqueous solution, deionized water quality is more permissible than for 1:800～1:80
Meet the present invention and remove require that of metal ion in graphite oxide；When deionization in complexing of metal ion agent with acidic aqueous solution
Water quality ratio is during more than 1:200, although can be by increasing cleaning mixture consumption mode, and in raising graphite oxide, metal ion goes
Except rate, but so still can cause the waste of cleaning mixture to a certain extent, when metal ion chelating agent and acidic aqueous solution
Middle deionized water quality ratio, during for 1:200～1:80, both can meet the present invention and remove the requirement of metal ion in graphite oxide,
The consumption of cleaning mixture can also be reduced simultaneously further, reduce the wasting of resources, reduce cost.
The pH value of the acidic aqueous solution prepared in the removing method of above-mentioned metal ion is 1～6.Acidic aqueous solution is permissible
Deionized water is directly used to be diluted obtaining to acid.The acid of above-mentioned preparation acidic aqueous solution is in hydrochloric acid, sulphuric acid and nitric acid
At least one.Here, owing to the effect of acidic aqueous solution is to provide sour environment, with effective inhibited oxidation graphite edge carboxylic acid
The ionization of radical ion, therefore in addition to the selection of above-mentioned conventional acid, on the premise of not introducing other foreign ion, it is also possible to adopt
It is provided that the aqueous solution of sour environment with other.
The method using the present invention to provide can not only make concentration of metal ions in graphite oxide be reduced to below 8.33ppm,
And if if the preferred edetate of complexing of metal ion agent (EDETATE SODIUM or four sodium), also can under these conditions,
Make the concentration of metal ions in washing rear oxidation graphite less than 1ppm, reach below 0.85ppm.At this moment it is believed that graphite oxide
In metal ion the most substantially remove totally.
Additionally, if graphite oxide is to use hummer ' the s method improved to obtain, employ a large amount of during due to preparation
Concentrated sulphuric acid, acidity in graphite oxide also can be made too high, if now by need preparation containing complexing of metal ion agent
If acidic aqueous solution pH sets the most higher (limit as on the upper side in pH value), such as preferably 3～6, the use of acid so on the one hand can be reduced
Amount, reduces cost, the most also graphite oxide can be carried out pickling with killing two birds with one stone while removing metal ion, save
Remove the pickling process of routine or reduce the difficulty of pickling process.
The removing method of above-mentioned metal ion is to use the acidic aqueous solution containing complexing of metal ion agent by conventional
Graphite oxide is washed by centrifugal or natural sedimentation, and washing times is generally 1-5 time, from removing metal ion effect
Consider that washing times is preferably 3-5 time.
In the graphite oxide that the present invention provides, the removing method of metal ion, has the advantages that
1, the remove impurity aqueous solution used due to the inventive method can not only provide sour environment, possibly together with strong complexing
Complexing of metal ion agent, thus can the ionization of effective inhibited oxidation graphite edge carboxylic acid ion, carboxylate radical can be captured again
The metal ion discharged, reaches to rapidly remove the purpose of wherein metal ion.
2, the metal ion in graphite oxide can be removed due to the inventive method, thus the carboxylic acid in graphite oxide can be made
Root is in complete ionized state, adds electrostatic interaction between lamella so that graphite oxide is easier to be stripped in the later stage and obtains
Graphene oxide.
3, can carry out processing by centrifugation due to the inventive method, it is thus possible to accelerate graphite oxide in solution
The rate of settling, improve metal ion in graphite oxide and remove efficiency.
4, due to the inventive method be containing complexing of metal ion agent acid water washing graphite oxide, be possible not only to remove
Metal ion in graphite oxide, the most also has a preferable pickling effect, and relatively conventional graphene oxide preparation process
For middle water carries out pickling amount (every g graphite oxide washs every time to be needed to use water 1000mL), when being applied to industrialized production,
Water consumption can greatly reduce, and while saving water resource, decreases the pollution to water resource, reduces sewage load.
5, there is not interaction between complexing of metal ion agent and the graphite oxide chosen due to the present invention, because of without
Introduce new impurity.
6, after the metal ion in graphite oxide can being removed due to the inventive method, thus reduction can be improved further
The Graphene purity obtained, reduces the bio-toxicity that metal ion brings and the pollution producing environment.
Accompanying drawing explanation
In order to be illustrated more clearly that the difference of the embodiment of the present invention and technical scheme of the prior art, below to embodiment
Or the required accompanying drawing used is briefly described in description of the prior art, it should be apparent that, the accompanying drawing in below describing is only
It is some embodiments of the present invention, for those of ordinary skills, on the premise of not paying creative work, also
Other embodiment and accompanying drawing thereof can be obtained according to these accompanying drawing illustrated embodiments, but protection scope of the present invention should be included in
In.
Fig. 1 shows that the embodiment of the present invention 1 (a), embodiment 2 (b), comparative example 1 (e) use different washing with comparative example 2 (d)
Liquid is to Mn in graphite oxide washing process2+The amount of washing out uses containing metal with change block diagram, the comparative example 3 (c) of wash number
The acidic aqueous solution of ionic complexing agent is to Mn in the graphene oxide washing process after graphite oxide stripping2+The amount of washing out is secondary with cleaning
Mn in the change block diagram of number and respective end product2+Content block diagram.
Fig. 2 shows the embodiment of the present invention 1 (a), embodiment 2 (b), comparative example 1 (e), comparative example 2 (d) and comparative example 3
C block diagram that in the end product of (), S content changes with washing liquid kind.
Fig. 3 shows the end product of the embodiment of the present invention 1 (a), embodiment 2 (b), embodiment 3 (f) and embodiment 4 (g)
Middle Mn2+The block diagram that content changes with complexing of metal ion agent kind.
Fig. 4 shows the embodiment of the present invention 6 (h), embodiment 7 (i) and Mn in the end product of embodiment 8 (j)2+Content with
The block diagram that in washing liquid, complexing of metal ion agent changes with deionized water proportioning.
Fig. 5 shows graphite oxide in the embodiment of the present invention 6 (h), embodiment 7 (i), embodiment 8 (j) and embodiment 9 (k)
The block diagram that after washing, washing liquid pH value changes with washing times.
Detailed description of the invention
Below with reference to accompanying drawing, the technical scheme of various embodiments of the present invention is carried out clear, complete description, it is clear that retouched
State a part of embodiment rather than whole embodiments that embodiment is only the present invention.Based on the embodiment in the present invention, this
All other embodiments that field those of ordinary skill is obtained on the premise of not making creative work, broadly fall into this
Bright protected scope.
In oxidation graphite solid given by following example and comparative example, the content of manganese ion is to use ICP
(Inductively coupled plasma, inductively coupled plasma) is tested.
Embodiment 1
The graphite oxide that the present embodiment uses is obtained by following preparation method: in 0 DEG C～15 DEG C of ice-water baths, by 1g stone
Ink adds that to fill 100mL mass concentration be 95～98% in concentrated sulphuric acid, under stirring, point adds 3g altogether 6 times high in 1h
Potassium manganate, continues to stir 1h in ice-water bath, then temperature rises to 35 DEG C, keep 2h, add 215mL deionization after adding
Water, then temperature is risen to 98 DEG C, it is sequentially added into 200mL deionized water after maintaining 1h and the hydrogen peroxide that mass concentration is 30% is the most molten
Liquid bubble-free produces, and sucking filtration completes i.e. to obtain graphite oxide.
Be first the acidic aqueous solution of 3 with hydrochloric acid and deionized water secure ph, then by EDETATE SODIUM by and deionized water
Mass ratio is that 1:200 adds in acidic aqueous solution and stirs；Take obtained graphite oxide, prepared by taking every time
800mL acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally three
Secondary；Using 800mL deionized water again, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant, by gained
Graphite oxide joins in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
Testing through ICP, in this oxidation graphite solid, the content of manganese ion is 0.74889ppm.
Embodiment 2
The graphite oxide preparation method that the present embodiment uses is same as in Example 1, slightly.
First preparing pH for 1:500 with phytic acid in mass ratio with deionized water is the acidic aqueous solution of 1.6；Take obtained oxygen
Graphite, by taking prepared 800mL acidic aqueous solution every time, under the conditions of rotating speed is 3000r/min in centrifugal 10min removal
Clear liquid, repeated washing totally three times；Using 800mL deionized water again, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min, goes
After supernatant, gained graphite oxide is joined dispersion the freeze-dried graphite oxide that obtains in 800ml deionized water and consolidates
Body.
Testing through ICP, in this oxidation graphite solid, the content of manganese ion is 4.7449ppm.
Embodiment 3
The graphite oxide preparation method that the present embodiment uses is same as in Example 1, slightly.
Be first the acidic aqueous solution of 3 with nitric acid and deionized water secure ph, then by sodium phosphate by and deionized water
Measure and stir than adding in acid washing water solution for 1:500；Take obtained graphite oxide, prepared by taking every time
800mL acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally three
Secondary, then use 800mL deionized water, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant, by gained
Graphite oxide joins in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
Testing through ICP, in this oxidation graphite solid, the content of manganese ion is 8.326ppm.
Embodiment 4
The graphite oxide preparation method that the present embodiment uses is same as in Example 1, slightly.
Be first the acidic aqueous solution of 3 with hydrochloric acid and deionized water secure ph, then by diethanolamine by and deionized water
Mass ratio is that 1:500 adds in acidic aqueous solution and stirs；Take obtained graphite oxide, prepared by taking every time
800mL acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally three
Secondary；Using 800mL deionized water again, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant, by gained
Graphite oxide joins in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
Testing through ICP, in this oxidation graphite solid, the content of manganese ion is 6.269ppm.
Embodiment 5
The graphite oxide preparation method that the present embodiment uses is same as in Example 1, slightly.
Be first the acidic aqueous solution of 3 with nitric acid and deionized water secure ph, then by polyacrylic acid by and deionized water
Mass ratio is that 1:800 adds in acid washing water solution and stirs；Take obtained graphite oxide, prepared by taking every time
800mL acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally three
Secondary；Using 800mL deionized water again, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant, by gained
Graphite oxide joins in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
Testing through ICP, in this graphite oxide, the content of manganese ion is 8.234ppm.
Embodiment 6
The graphite oxide preparation method that the present embodiment uses is same as in Example 1, slightly.
Be first the acidic aqueous solution of 6 with hydrochloric acid and deionized water secure ph, then by EDETATE SODIUM by and deionized water
Mass ratio is that 1:80 adds in acidic aqueous solution and stirs；Take obtained graphite oxide, prepared by taking every time
800mL acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally three
Secondary；Using 800mL deionized water again, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant, by gained
Graphite oxide joins in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
Testing through ICP, in this oxidation graphite solid, the content of manganese ion is 0.6549ppm.
Embodiment 7
The graphite oxide preparation method that the present embodiment uses is same as in Example 1, slightly.
Be first the acidic aqueous solution of 6 with sulphuric acid and deionized water secure ph, then by EDETATE SODIUM by and deionized water
Mass ratio is that 1:200 adds in acidic aqueous solution and stirs；Take obtained graphite oxide, prepared by taking every time
100mL acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally three
Secondary；Using 800mL deionized water again, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant, by gained
Graphite oxide joins in 100ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
Testing through ICP, in this oxidation graphite solid, the content of manganese ion is 0.7267ppm.
Embodiment 8
The graphite oxide preparation method that the present embodiment uses is same as in Example 1, slightly.
Be first the acidic aqueous solution of 6 with sulphuric acid and deionized water secure ph, then by EDETATE SODIUM by and deionized water
Mass ratio is that 1:800 adds in acidic aqueous solution and stirs；Take obtained graphite oxide, prepared by taking every time
3200mL acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally three
Secondary；Use 3200mL deionized water wash again, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant,
Gained graphite oxide is joined in 3200ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
Testing through ICP, in this oxidation graphite solid, the content of manganese ion is 53.289ppm.
Embodiment 9
The graphite oxide preparation method that the present embodiment uses is same as in Example 1, slightly.
Be first the acidic aqueous solution of 6 with sulphuric acid and deionized water secure ph, then by EDETATE SODIUM by and deionized water
Mass ratio 1:800 adds in acidic aqueous solution and stirs；Take obtained graphite oxide, prepared by taking every time
5000mL acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally three
Secondary；Use 3200mL deionized water again, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant, will
To graphite oxide join in 5000ml deionized water dispersion and freeze-dried obtain oxidation graphite solid.
Testing through ICP, in this graphite oxide, the content of manganese ion is 0.8453ppm.
Embodiment 10
The graphite oxide preparation method that the present embodiment uses is same as in Example 1, slightly.
Be first the acidic aqueous solution of 3 with hydrochloric acid and deionized water secure ph, then by EDTA tetra-sodium by and deionized water
Mass ratio 1:200 adds in acidic aqueous solution and stirs；Take obtained graphite oxide, prepared by taking every time
800mL acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally five
Secondary；Use 800mL deionized water again, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant, will obtain
Graphite oxide join in 800ml deionized water dispersion and freeze-dried obtain oxidation graphite solid.
Testing through ICP, in this graphite oxide, the content of manganese ion is 0.6534ppm.
Embodiment 11
The graphite oxide preparation method that the present embodiment uses is same as in Example 1, slightly.
Be first the acidic aqueous solution of 4 with hydrochloric acid and deionized water secure ph, then by EDTA tetra-sodium by and deionized water
Mass ratio 1:200 adds in acidic aqueous solution and stirs；Take obtained graphite oxide, prepared by taking every time
800mL acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally three
Secondary；Use 800mL deionized water again, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant, will obtain
Graphite oxide join in 800ml deionized water dispersion and freeze-dried obtain oxidation graphite solid.
Testing through ICP, in this graphite oxide, the content of manganese ion is 0.7543ppm.
Embodiment 12
The graphite oxide preparation method that the present embodiment uses is same as in Example 1, slightly.
Be first the acidic aqueous solution of 3 with hydrochloric acid and deionized water secure ph, then by EDETATE SODIUM by and deionized water
Mass ratio 1:150 adds in acidic aqueous solution and stirs；Take obtained graphite oxide, prepared by taking every time
800mL acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally three
Secondary；Use 800mL deionized water again, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant, will obtain
Graphite oxide join in 800ml deionized water dispersion and freeze-dried obtain oxidation graphite solid.
Testing through ICP, in this graphite oxide, the content of manganese ion is 0.7943ppm.
Comparative example 1
The graphite oxide preparation method that this comparative example uses is same as in Example 1, slightly.
With deionized water as washing liquid, take obtained graphite oxide, by taking 800mL deionized water every time, at rotating speed be
Under the conditions of 3000r/min, centrifuge washing 10min abandons supernatant, repeated washing totally four times；Gained graphite oxide is joined 800ml
Dispersion freeze-dried obtain oxidation graphite solid in deionized water.
Testing through ICP, in this oxidation graphite solid, the content of manganese ion is 567.34ppm.
Comparative example 2
The graphite oxide preparation method that this comparative example uses is same as in Example 1, slightly.
It is first the acidic aqueous solution of 3 with hydrochloric acid and deionized water secure ph；Take obtained graphite oxide, by taking every time
The 800mL acidic aqueous solution prepared, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeats to wash
Wash totally three times；Use 800mL deionized water again, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant,
Gained graphite oxide is joined in 800ml deionized water dispersion and freeze-dried obtains oxidation graphite solid.
Testing through ICP, in this oxidation graphite solid, the content of manganese ion is 612.85ppm.
Comparative example 3
The graphite oxide preparation method that this comparative example uses is same as in Example 1, slightly.
Be first the acidic aqueous solution of 3 with hydrochloric acid and deionized water secure ph, then by EDETATE SODIUM by and deionized water
Mass ratio 1:200 adds in acidic aqueous solution and stirs；Take obtained graphite oxide to use under the conditions of power is 300W
The ultrasonic 10min of ultrasonic machine peels off and obtains graphene oxide；Again to the graphene oxide obtained, by taking prepared 800mL every time
Acidic aqueous solution, under the conditions of rotating speed is 3000r/min, centrifuge washing 10min removes supernatant, repeated washing totally three times；Use again
800mL deionized water, centrifuge washing 10min under the conditions of rotating speed is 3000r/min, after removing supernatant, gained is aoxidized stone
Ink alkene joins in 800ml deionized water dispersion and freeze-dried obtains graphene oxide solid.
Testing through ICP, in this graphene oxide, the content of manganese ion is 7.41848ppm.
There is provided the feasibility of the metal ion method of going out in graphite oxide to probe into the present invention, the present invention to embodiment 1,
In embodiment 2 and comparative example 1 to 3 cleaning process, Mn in solid product2+The amount of washing out is with the situation of change of wash number and final
Mn in product2+Content and S content are analyzed, and analysis result is as shown in Figures 1 and 2.It will be seen from figure 1 that use EDTA bis-
The acidic aqueous solution of sodium or the solution washing graphite oxide of phytic acid, along with wash number, the Mn washed out every time2+Amount is gradually
Reduce, Mn in end product2+Content is respectively less than 10ppm；And use acidic aqueous solution or deionized water wash graphite oxide,
The Mn every time washed out2+Amount is substantially similar, Mn in end product2+Content is still above 500ppm, and the Mn washed out is described2+Seldom.
As can be seen here, the acidic aqueous solution containing complexing of metal ion agent is used can effectively to remove the metal ion in graphite oxide.
Meanwhile, the acidic aqueous solution washing graphite oxide containing complexing of metal ion agent is used as can be seen from Figure 2, equally to washing oxygen
Sulfate ion in graphite also has very good effect.
Although it is additionally, graphite oxide is being carried out after stripping obtains graphene oxide, more water-soluble by the acidity containing EDTA
Liquid washing graphene oxide, removes Mn2+Effect also it is also possible that Mn in end product2+Content reaches 7.41848ppm；But knot
Close Fig. 2 and can be seen that the graphene oxide after using stripping can adsorb more sulphuric acid due to huge specific surface area, cause
The residual volume of element sulphur is significantly larger than other and uses graphite oxide, so using the acidic aqueous solution of metal ion chelating agent
Washing graphene oxide is unreasonable.
In order to probe into the action effect of various complexing of metal ion agent, the present invention is to embodiment 1-embodiment 4 end product
Middle Mn2+Content is analyzed, and result is as shown in Figure 3；It can be seen that in various complexing of metal ion agent, containing EDTA
The acidic aqueous solution of disodium is to Mn2+Wash out efficiency the highest.Owing to aminocarboxylate structure being all amino and carboxyl, rely on this two
Plant group and play complexing, so the acidic aqueous solution that all aminocarboxylates are prepared as complexing of metal ion agent is removing oxygen
Metal ion aspect in graphite, has the effect similar to EDETATE SODIUM.
Remove the shadow of a good appetite suddenly appearing in a serious disease than metal ion in graphite oxide in order to probe into complexing of metal ion agent and deionized water quality
Ringing, the present invention is to Mn in embodiment 6-embodiment 8 end product2+Content is analyzed, and result is as shown in Figure 4；From figure permissible
Find out, when complexing of metal ion agent EDETATE SODIUM and deionized water quality ratio are during for 1:80 and 1:200, in graphite oxide metal from
Son to wash out efficiency the most fairly obvious；And when EDETATE SODIUM and deionized water quality ratio are during less than 1:800, owing to acidity is water-soluble
In liquid, EDETATE SODIUM concentration is too small, and this kind of its removing metal ion effect of acidic aqueous solution is unsatisfactory.
In order to probe into the Acidity of Aikalinity after graphite oxide washs, the pH of the washing liquid after embodiment 6-embodiment 9 is washed every time
Value carries out detection and analyzes, and testing result is as shown in Figure 5.From fig. 5, it can be seen that along with the increase of washing times, graphite oxide is washed
The pH value washing rear washing liquid is gradually increased, when after three acid solution washings and a deionized water wash, and the pH of washing liquid
Value is close to neutral.For embodiment 6, each washing liquid consumption is 800mL, and after four times are washed, in graphite oxide, pickling goes out effect
Rate is the highest, even if being further added by each washing liquid consumption (see embodiment 8,9), washed out efficiency change is the most fairly obvious.Right
In embodiment 7, each washing liquid consumption is 100mL, after three acid solution washings and a deionized water wash, although
Metal ion is effectively removed, but the pH value of the washing liquid after four washings is the most relatively low, in order to meet the application of graphite oxide
Demand, it is still necessary to continue to be washed with deionized to neutrality.It can thus be seen that when processing graphite oxide prepared by 1g graphite
Time, each washing liquid consumption should control 100～800mL.
Those of ordinary skill in the art is it will be appreciated that embodiment here is to aid in the reader understanding present invention's
Principle, it should be understood that protection scope of the present invention is not limited to such special statement and embodiment.This area common
Technical staff can make various other various tools without departing from essence of the present invention according to these technology disclosed by the invention enlightenment
Body deformability and combination, these deformation and combination are the most within the scope of the present invention.
Claims (10)
1. the removing method of metal ion in a graphite oxide, it is characterised in that the method is that first preparation is containing metal ion network
The acidic aqueous solution of mixture, then washs to wherein concentration of metal ions less than 10ppm graphite oxide with it.
The removing method of metal ion in graphite oxide the most according to claim 1, it is characterised in that the method preparating acid
Property aqueous solution be under stirring, by complexing of metal ion agent by with the ratio of deionized water quality in acidic aqueous solution for 1:800
～1:80 adds in acidic aqueous solution and stirs.
In graphite oxide the most according to claim 1 and 2, metal ion removes method, it is characterised in that the method preparation
In acidic aqueous solution containing complexing of metal ion agent, complexing of metal ion agent is pressed and deionized water quality ratio in acidic aqueous solution
For 1:200～1:80.
The removing method of metal ion in graphite oxide the most according to claim 1 and 2, it is characterised in that the method is prepared
Complexing of metal ion agent used by acidic aqueous solution containing complexing of metal ion agent be alcamine compound, aminocarboxylate,
At least one in organic phosphate, phosphate and polyacrylic compounds.
The removing method of metal ion in graphite oxide the most according to claim 3, it is characterised in that the method preparation contains
The complexing of metal ion agent used by the acidic aqueous solution of complexing of metal ion agent is had to be alcamine compound, aminocarboxylate, have
At least one in machine phosphate, phosphate and polyacrylic compounds.
The removing method of metal ion in graphite oxide the most according to claim 1 and 2, it is characterised in that the method is joined
The pH value of the acidic aqueous solution of system is 1～6；The acid of preparation acidic aqueous solution is at least one in hydrochloric acid, sulphuric acid and nitric acid.
The removing method of metal ion in graphite oxide the most according to claim 3, it is characterised in that the method is prepared
The pH value of acidic aqueous solution be 1～6；The acid of preparation acidic aqueous solution is at least one in hydrochloric acid, sulphuric acid and nitric acid.
The removing method of metal ion in graphite oxide the most according to claim 5, it is characterised in that the method is prepared
The pH value of acidic aqueous solution be 1～6；The acid of preparation acidic aqueous solution is at least one in hydrochloric acid, sulphuric acid and nitric acid.
The removing method of metal ion in graphite oxide the most according to claim 1 and 2, it is characterised in that the method is with containing
The acidic aqueous solution having complexing of metal ion agent is 1～5 time to graphene oxide washing times.
The removing method of metal ion in graphite oxide the most according to claim 8, it is characterised in that the method is with containing
The acidic aqueous solution of complexing of metal ion agent is 1～5 time to graphene oxide washing times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610580659.8A CN106241781B (en) | 2016-07-22 | 2016-07-22 | The removing method of metal ion in graphite oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610580659.8A CN106241781B (en) | 2016-07-22 | 2016-07-22 | The removing method of metal ion in graphite oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106241781A true CN106241781A (en) | 2016-12-21 |
| CN106241781B CN106241781B (en) | 2019-10-01 |
Family
ID=57603271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610580659.8A Active CN106241781B (en) | 2016-07-22 | 2016-07-22 | The removing method of metal ion in graphite oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106241781B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793134A (en) * | 2018-08-07 | 2018-11-13 | 高维佳 | A kind of preparation method of graphene |
| CN109292767A (en) * | 2018-12-07 | 2019-02-01 | 四川聚创石墨烯科技有限公司 | A kind of purification process of graphene oxide |
| CN109319773A (en) * | 2018-12-07 | 2019-02-12 | 四川聚创石墨烯科技有限公司 | A kind of integrated conduct method of graphene oxide slurry |
| CN109502580A (en) * | 2018-12-07 | 2019-03-22 | 四川聚创石墨烯科技有限公司 | A kind of purification devices of graphene oxide |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111249765B (en) * | 2020-02-25 | 2021-04-06 | 中国科学院化学研究所 | Pressurized fluid extraction system and method for removing metal ions from carbon material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103395780A (en) * | 2013-08-19 | 2013-11-20 | 济宁利特纳米技术有限责任公司 | Method for reducing manganese content in graphene oxide |
| JP2014144892A (en) * | 2013-01-29 | 2014-08-14 | Okayama Univ | Flaky graphite oxide carrying metal and manufacturing method thereof |
| US20140323596A1 (en) * | 2011-11-30 | 2014-10-30 | Korea Electrotechnology Research Institute | Graphene oxide reduced material dispersed at high concentration by cation-ii interaction and method for manufacturing same |
| CN104787759A (en) * | 2015-04-20 | 2015-07-22 | 德阳烯碳科技有限公司 | Impurity removal method in preparation process of graphene |
-
2016
- 2016-07-22 CN CN201610580659.8A patent/CN106241781B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140323596A1 (en) * | 2011-11-30 | 2014-10-30 | Korea Electrotechnology Research Institute | Graphene oxide reduced material dispersed at high concentration by cation-ii interaction and method for manufacturing same |
| JP2014144892A (en) * | 2013-01-29 | 2014-08-14 | Okayama Univ | Flaky graphite oxide carrying metal and manufacturing method thereof |
| CN103395780A (en) * | 2013-08-19 | 2013-11-20 | 济宁利特纳米技术有限责任公司 | Method for reducing manganese content in graphene oxide |
| CN104787759A (en) * | 2015-04-20 | 2015-07-22 | 德阳烯碳科技有限公司 | Impurity removal method in preparation process of graphene |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108793134A (en) * | 2018-08-07 | 2018-11-13 | 高维佳 | A kind of preparation method of graphene |
| CN108793134B (en) * | 2018-08-07 | 2022-02-22 | 中山市悦泰汽车零部件有限公司 | Preparation method of graphene |
| CN109292767A (en) * | 2018-12-07 | 2019-02-01 | 四川聚创石墨烯科技有限公司 | A kind of purification process of graphene oxide |
| CN109319773A (en) * | 2018-12-07 | 2019-02-12 | 四川聚创石墨烯科技有限公司 | A kind of integrated conduct method of graphene oxide slurry |
| CN109502580A (en) * | 2018-12-07 | 2019-03-22 | 四川聚创石墨烯科技有限公司 | A kind of purification devices of graphene oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106241781B (en) | 2019-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106241781B (en) | The removing method of metal ion in graphite oxide | |
| CN105810761B (en) | Texturing method for diamond wire cutting polycrystalline silicon wafer | |
| Kanoh et al. | Electrochemical recovery of lithium ions in the aqueous phase | |
| JP4916546B2 (en) | Acid corrosion solution for forming textured surface of polycrystalline silicon and method of using the same | |
| CN111508824B (en) | Wool making cleaning method and heterojunction battery | |
| CN103318953B (en) | Bleaching method of titanium dioxide | |
| CN105870263B (en) | A kind of preparation method of crystal silicon solar energy battery suede structure | |
| CN102616824B (en) | Method for preparing ultrafine high-whiteness active barite powder | |
| CN104860311B (en) | Preparation method of graphene | |
| CN102709401B (en) | Manufacturing method of N-type solar battery | |
| CN103484673A (en) | Method for vadaium precipitation from balck acid leaching vanadium liquid | |
| CN104475390A (en) | Diode chip pickling technique and equipment | |
| CN108360058A (en) | A kind of electrolyte and stainless steel engraving method for etching stainless steel | |
| CN108950570A (en) | A kind of preparation method of negative electrode of lithium ion battery collector porous copper foil | |
| CN106633047A (en) | Method for preparing polyaniline | |
| CN102020280A (en) | Method for inhibiting yellow smog during pickling of silicon materials | |
| US8383523B2 (en) | Method for texturing silicon wafers, treatment liquid therefor, and use | |
| CN106449808A (en) | Preparation method of suede structure of crystalline silicon solar cell | |
| CN114180545B (en) | Copper removal method and method for preparing iron phosphate from waste lithium iron phosphate battery cell powder | |
| CN104018340A (en) | Continuous carbon fiber surface modification method | |
| CN104532241A (en) | Chemical sanding agent for aluminum material and sanding process thereof | |
| CN108793510A (en) | A kind of processing method of oilfield sulfur-containing sewage | |
| CN107601486A (en) | A kind of graphene production method | |
| CN103871865A (en) | Method for cleaning side wall of plasma reaction cavity | |
| CN102230228B (en) | Wool making agent used for surface treatment on single crystalline silicon solar cell and application method 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |