CN103359726B - Preparation method of rare earth and its oxide improved graphite oxide - Google Patents
Preparation method of rare earth and its oxide improved graphite oxide Download PDFInfo
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- CN103359726B CN103359726B CN201310308501.1A CN201310308501A CN103359726B CN 103359726 B CN103359726 B CN 103359726B CN 201310308501 A CN201310308501 A CN 201310308501A CN 103359726 B CN103359726 B CN 103359726B
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Abstract
A preparation method of rare earth and its oxide improved graphite oxide relates to a preparation method of graphite oxide. The invention aims to solve technical problems of incomplete intercalation and non-ideal oxidation effect existing in graphite oxide prepared by a present method. The preparation method provided by the invention comprises the following steps: 1, uniformly mixing concentrated sulfuric acid, graphite, rare earth and its oxide, potassium permanganate and sodium nitrate, adding the mixture into a reaction pot, reacting at three stages of low temperature, intermediate temperature and high temperature, adding hydrogen peroxide and deionized water to obtain acidic graphite oxide; and 2, washing the acidic graphite oxide obtained from the step 1 by the use of hydrochloric acid, and carrying out vacuum drying to obtain graphite oxide. After the addition of rare earth and its oxide, distance between lamellas of the prepared graphite oxide is larger. Thus, the intercalation effect is better, and it is more beneficial to oxidation of graphite. Under the same conditions, graphite lamellas will suspend more groups and oxidation is fully carried out. The preparation method provided by the invention is applied in the preparation field of graphite oxide.
Description
Technical field:
The present invention relates to the preparation method of graphite oxide.
Background technology:
Graphene is the two-dimensional sheet structure of a kind of carbon atom composition, there is the performance of unique various excellence such as electricity, optics, calorifics, mechanics, be the research active material of current every subjects, and the intermediate that graphite oxide prepares Graphene as chemical method is also extremely important.Because graphite oxide hangs very abundant polar group in its main body graphite linings, and lamella area is large, with features such as negative charges, so graphite oxide can be assembled into various mould material or intercalation composite material etc. as presoma, thus have the performances such as a series of magnetic, electrical, optical, catalysis and molecular recognition, apply very extensive.
Preparation method's majority of graphite oxide adopts Brodie method, sandermaier method and hummers method, this three large chemical oxidization method are all with strong protonic acid process original graphite, form single order type compound between graphite layers, then add strong oxidizer potassium permanganate etc., through low temperature, middle temperature, high temperature three step of reaction are oxidized, and add deionized water and hydrogen peroxide subsequently, through overpickling, dialysis, obtains graphite oxide after oven dry.There is again electrochemical oxidation process afterwards, and the improvement to three kinds of chemical oxidization methods, thus shorten reaction time, improve preparation efficiency, but still there is intercalation not exclusively in the graphite oxide of preparation, the shortcomings such as oxidation effectiveness is undesirable.
The laudatory title that rare earth has " industrial VITAMIN ".Rare earth itself has the physical propertys such as excellent photoelectromagnetism, when joining in other materials, the quality and performance of integral material can be increased substantially, such as, adding steel, aluminium alloy, magnesium alloy etc., can improve its mechanical property, and join in magneticsubstance, high remanent magnetism can be prepared, the permanent magnet material of high-coercive force and high energy product, and in the preparation process of steel, add rare earth metal, refining can be played, desulfurization, in and the effect of low melting point detrimental impurity, and firm processing characteristics can be improved.Based on this feature, in the present invention, prepare in the process of graphite oxide and add rare earth, the preparation process for graphite oxide creates excellent impact.
Summary of the invention
The present invention is that will to solve the intercalation that graphite oxide prepared by existing method exists incomplete, the technical problem that oxidation effectiveness is undesirable, thus provides the preparation method that a kind of rare earth and oxide compound thereof improve graphite oxide.
The preparation method that a kind of rare earth of the present invention and oxide compound thereof improve graphite oxide carries out according to the following steps:
One, by the vitriol oil, graphite, rare earth and oxide compound thereof, potassium permanganate and SODIUMNITRATE mix, and join in retort, react 0.5 ~ 6h successively at low temperature is 0 ~ 20 DEG C, middle temperature is react 4 ~ 12h at 25 ~ 45 DEG C, high temperature is react 1 ~ 10h at 80 ~ 100 DEG C, then adds hydrogen peroxide and deionized water, obtains containing acid graphite oxide; Wherein, the vitriol oil, graphite, rare earth and oxide compound thereof, the weight ratio of potassium permanganate and SODIUMNITRATE is 1 ~ 50: 1: 0.01 ~ 10: 1 ~ 10: 0.5 ~ 20; The mass volume ratio of graphite and hydrogen peroxide is 1g: 5 ~ 20mL; The mass volume ratio of graphite and deionized water is 1g: 70 ~ 300mL;
What two, step one obtained is washed 3 ~ 5 times by hydrochloric acid mixed solution containing acid graphite oxide, and then vacuum drying at temperature is 30 ~ 80 DEG C, namely obtains graphite oxide; Wherein, hydrochloric acid mixed solution is the concentrated hydrochloric acid of 36% ~ 38% by mass concentration, alcohol and deionized water be by volume 0.5 ~ 1.5: 0.5 ~ 1.5: 0.5 ~ 1.5 ratio obtain.
The present invention includes following beneficial effect:
1, the present invention prepares in the process of graphite oxide and adds rare earth and oxide compound thereof, have impact on oxidation and the intercalation process of graphite oxide, after rare earth and oxide compound thereof add, contribute to accelerating potassium permanganate at low temperatures to the oxidising process at graphite edge, be conducive to the oxy radicals such as sulfate radical and enter into carbon-coating, today in pyrohydrolysis process, be conducive to oxy radical and be connected with carbon atom on graphite synusia, be conducive to preparing high quality, the single order intercalation thing that synusia is controlled;
2, the present invention prepares in the process of graphite oxide and adds rare earth and oxide compound thereof, is more conducive to the oxidation of graphite, makes under equal conditions graphite flake layer to hang more groups, is oxidized more abundant.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the graphite oxide adding rare earth and oxide compound thereof and do not add rare earth and Preparation thereof; Wherein, 1 is the XRD figure of the graphite oxide not adding rare earth and Preparation thereof, and 2 for adding the XRD figure of the graphite oxide of rare earth and Preparation thereof;
Fig. 2 is the infrared absorption curve of the graphite oxide adding rare earth and oxide compound thereof and do not add rare earth and Preparation thereof; Wherein, 1 is the infrared absorption curve of the graphite oxide not adding rare earth and Preparation thereof, and 2 for adding the infrared absorption curve of the graphite oxide of rare earth and Preparation thereof.
Embodiment
Embodiment one: the preparation method that a kind of rare earth of present embodiment and oxide compound thereof improve graphite oxide carries out according to the following steps:
One, by the vitriol oil, graphite, rare earth and oxide compound thereof and oxide compound thereof, potassium permanganate and SODIUMNITRATE mix, and join in retort, react 0.5 ~ 6h successively at low temperature is 0 ~ 20 DEG C, middle temperature is react 4 ~ 12h at 25 ~ 45 DEG C, high temperature is react 1 ~ 10h at 80 ~ 100 DEG C, then adds hydrogen peroxide and deionized water, obtains containing acid graphite oxide; Wherein, the vitriol oil, graphite, rare earth and oxide compound thereof, the weight ratio of potassium permanganate and SODIUMNITRATE is 1 ~ 50: 1: 0.01 ~ 10: 1 ~ 10: 0.5 ~ 20; The mass volume ratio of graphite and hydrogen peroxide is 1g: 5 ~ 20mL; The mass volume ratio of graphite and deionized water is 1g: 70 ~ 300mL;
What two, step one obtained is washed 3 ~ 5 times by hydrochloric acid mixed solution containing acid graphite oxide, and then vacuum drying at temperature is 30 ~ 80 DEG C, namely obtains graphite oxide; Wherein, hydrochloric acid mixed solution is the concentrated hydrochloric acid of 36% ~ 38% by mass concentration, alcohol and deionized water be by volume 0.5 ~ 1.5: 0.5 ~ 1.5: 0.5 ~ 1.5 ratio obtain.
Present embodiment comprises following beneficial effect:
1, present embodiment is prepared in the process of graphite oxide and is added rare earth and oxide compound thereof, have impact on oxidation and the intercalation process of graphite oxide, after rare earth and oxide compound thereof add, contribute to accelerating potassium permanganate at low temperatures to the oxidising process at graphite edge, be conducive to the oxy radicals such as sulfate radical and enter into carbon-coating, today in pyrohydrolysis process, be conducive to oxy radical and be connected with carbon atom on graphite synusia, be conducive to preparing high quality, the single order intercalation thing that synusia is controlled;
2, present embodiment is prepared in the process of graphite oxide and is added rare earth and oxide compound thereof, is more conducive to the oxidation of graphite, makes under equal conditions graphite flake layer to hang more groups, is oxidized more abundant.
Embodiment two: present embodiment is identical with embodiment one: react 3h in step one at low temperature is 10 DEG C.Other is identical with embodiment one.
Embodiment three: present embodiment is identical with embodiment one or two: react 8h in step one at middle temperature is 35 DEG C.Other is identical with embodiment one or two.
Embodiment four: present embodiment is identical with one of embodiment one to three: react 5h in step one at high temperature is 90 DEG C.Other is identical with one of embodiment one to three.
Embodiment five: present embodiment is identical with one of embodiment one to four: the vitriol oil in step one, graphite, rare earth and oxide compound thereof, the weight ratio of potassium permanganate and SODIUMNITRATE is 25: 1: 3: 5: 10.Other is identical with one of embodiment one to four.
Embodiment six: present embodiment is identical with one of embodiment one to five: in step one, the mass volume ratio of graphite and hydrogen peroxide is 1g: 15mL.Other is identical with one of embodiment one to five.
Embodiment seven: present embodiment is identical with one of embodiment one to six: in step one, the mass volume ratio of graphite and deionized water is 1g: 100mL.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment is identical with one of embodiment one to seven: dry at temperature is 60 DEG C in step 2.Other is identical with one of embodiment one to seven.
Embodiment nine: present embodiment is identical with one of embodiment one to eight: in step 2, hydrochloric acid mixed solution is the concentrated hydrochloric acid of 36.5% by mass concentration, alcohol and deionized water be by volume 1: 1: 1 ratio obtain.Other is identical with one of embodiment one to eight.
By following verification experimental verification beneficial effect of the present invention:
Test one: the preparation method that a kind of rare earth of this test and oxide compound thereof improve graphite oxide realizes according to the following steps:
One, by the vitriol oil, graphite, rare earth and oxide compound thereof, potassium permanganate and SODIUMNITRATE mix, and join in retort, react 3h successively at low temperature is 10 DEG C, middle temperature is react 8h at 35 DEG C, high temperature is react 5h at 90 DEG C, then adds hydrogen peroxide and deionized water, obtains containing acid graphite oxide; Wherein, the vitriol oil, graphite, rare earth and oxide compound thereof, the weight ratio of potassium permanganate and SODIUMNITRATE is 25: 1: 3: 5: 10; The mass volume ratio of graphite and hydrogen peroxide is 1g: 10mL; The mass volume ratio of graphite and deionized water is 1g: 100mL;
What two, step one obtained washs 3 times containing acid graphite oxide by hydrochloric acid mixed solution, and then vacuum drying at temperature is 60 DEG C, namely obtains graphite oxide; Wherein, hydrochloric acid mixed solution is the concentrated hydrochloric acid of 36.5% by mass concentration, alcohol and deionized water be by volume 1: 1: 1 ratio obtain.
Add rare earth and oxide compound thereof and do not add rare earth and Preparation thereof graphite oxide XRD figure as shown in Figure 1, wherein, 1 is the XRD figure of the graphite oxide not adding rare earth and Preparation thereof, and 2 for adding the XRD figure of the graphite oxide of rare earth and Preparation thereof, as can be seen from the figure, graphite oxide prepared by two kinds of modes has and the graphite peaks of about 23 degree can be removed, the peak position of graphite oxide is produced at about 11 degree, but can obviously find out from figure, the peak position adding the graphite oxide after rare earth and oxide compound thereof is lower, it is 11.5 degree, and the peak position not adding the graphite oxide of rare earth and oxide compound thereof is about 12.2 degree, there is bragg's formula: 2dsin θ=n λ, when θ angle is less, interlamellar spacing d is larger, illustrate that the distance between the graphite oxide synusia after adding rare earth and oxide compound thereof is larger, intercalation effect is better.Also demonstrate after adding rare earth and oxide compound thereof, contribute to potassium permanganate and insert, graphite flake is opened, is beneficial to connect various oxy radical on graphite synusia.
Add rare earth and oxide compound thereof and do not add rare earth and Preparation thereof graphite oxide infrared absorption curve as shown in Figure 2, wherein, 1 is the infrared absorption curve of the graphite oxide not adding rare earth and Preparation thereof, and 2 for adding the infrared absorption curve of the graphite oxide of rare earth and Preparation thereof, as can be seen from the figure, after adding rare earth and oxide compound thereof, the absorption peak showed increased on curve, and also absorption intensity also strengthens, the absorption peak of C-OH key has all been there is at 1048 ° of two curves, but the absorption peak strength adding the graphite oxide of rare earth and oxide compound thereof is larger, explanation creates more oh group, also carboxyl absorption peak has all been there is at 1730 °, equally also be that peak after adding rare earth and oxide compound thereof is more obvious, intensity is larger, the O-H key at 3435 ° of places also illustrates this problem, in addition, add in the graphite oxide of rare earth and Preparation thereof, also occurred that the C-O of carboxyl stretches at 1375 °, above phenomenon all absolutely proves, after adding rare earth and oxide compound thereof, more be conducive to the oxidation of graphite, make graphite flake layer to have hung more group, be oxidized more abundant.
Claims (9)
1. rare earth and oxide compound thereof improve a preparation method for graphite oxide, it is characterized in that the preparation method of rare earth and oxide compound improvement graphite oxide thereof carries out according to the following steps:
One, by the vitriol oil, graphite, rare earth and oxide compound thereof, potassium permanganate and SODIUMNITRATE mix, and join in retort, react 0.5 ~ 6h successively at low temperature is 0 ~ 20 DEG C, middle temperature is react 4 ~ 12h at 25 ~ 45 DEG C, high temperature is react 1 ~ 10h at 80 ~ 100 DEG C, then adds hydrogen peroxide and deionized water, obtains containing acid graphite oxide; Wherein, the vitriol oil, graphite, rare earth and oxide compound thereof, the weight ratio of potassium permanganate and SODIUMNITRATE is 1 ~ 50: 1: 0.01 ~ 10: 1 ~ 10: 0.5 ~ 20; The mass volume ratio of graphite and hydrogen peroxide is 1g: 5 ~ 20mL; The mass volume ratio of graphite and deionized water is 1g: 70 ~ 300mL;
What two, step one obtained is washed 3 ~ 5 times by hydrochloric acid mixed solution containing acid graphite oxide, and then vacuum drying at temperature is 30 ~ 80 DEG C, namely obtains graphite oxide; Wherein, hydrochloric acid mixed solution is the concentrated hydrochloric acid of 36% ~ 38% by mass concentration, alcohol and deionized water be by volume 0.5 ~ 1.5: 0.5 ~ 1.5: 0.5 ~ 1.5 ratio obtain.
2. a kind of rare earth according to claim 1 and oxide compound thereof improve the preparation method of graphite oxide, it is characterized in that at low temperature is 10 DEG C, reacting 3h in step one.
3. a kind of rare earth according to claim 1 and oxide compound thereof improve the preparation method of graphite oxide, it is characterized in that at middle temperature is 35 DEG C, reacting 8h in step one.
4. a kind of rare earth according to claim 1 and oxide compound thereof improve the preparation method of graphite oxide, it is characterized in that at high temperature is 90 DEG C, reacting 5h in step one.
5. a kind of rare earth according to claim 1 and oxide compound thereof improve the preparation method of graphite oxide, and it is characterized in that the vitriol oil in step one, graphite, rare earth and oxide compound thereof, the weight ratio of potassium permanganate and SODIUMNITRATE is 25: 1: 3: 5: 10.
6. a kind of rare earth according to claim 1 and oxide compound thereof improve the preparation method of graphite oxide, it is characterized in that the mass volume ratio of graphite and hydrogen peroxide in step one is 1g: 15mL.
7. a kind of rare earth according to claim 1 and oxide compound thereof improve the preparation method of graphite oxide, it is characterized in that the mass volume ratio of graphite and deionized water in step one is 1g: 100mL.
8. a kind of rare earth according to claim 1 and oxide compound thereof improve the preparation method of graphite oxide, it is characterized in that drying at temperature is 60 DEG C in step 2.
9. a kind of rare earth according to claim 1 and oxide compound thereof improve the preparation method of graphite oxide, it is characterized in that in step 2 that hydrochloric acid mixed solution is is the concentrated hydrochloric acid of 36.5% by mass concentration, alcohol and deionized water be by volume 1: 1: 1 ratio obtain.
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