Technical Field
Graphene as a novel carbon material has the characteristics of light transmission, electric conduction, heat conduction, high strength, high toughness, high specific surface area and the like, and has wide application prospects in the fields of catalysis, electronic devices, energy conversion and storage, biological medicines and the like. Graphene oxide is an important graphene derivative, and has a two-dimensional lamellar structure similar to graphene. Except that a large number of oxygen-containing groups are introduced, the surface of a sheet layer is distributed with hydroxyl and epoxy groups, and the edge of the sheet layer contains carboxyl and carbonyl. After the oxygen-containing group is introduced, large pi bonds in graphene molecules are damaged, mechanical properties and electrical properties are reduced, and even conductivity is lost. Oxygen-containing functional groups in graphene oxide molecules are removed by means of chemical reduction, hydrothermal reduction, thermal reduction, catalytic reduction and the like to generate reduced graphene oxide, and the performance of graphene can be recovered. Graphene oxide is originally used as a precursor for preparing graphene in a large amount, and is different from the unique physicochemical properties of graphene, so that a great deal of basic and application researches are carried out as a graphene derivative.
The preparation method of the graphene oxide mainly comprises a chemical oxidation method and an electrochemical oxidation method, and the chemical oxidation method has an industrial development prospect. The chemical oxidation method is to treat graphite with inorganic strong acid, insert strong acid micromolecules between graphite layers, and oxidize the graphite layers with strong oxidizing agents to obtain graphene oxide. US patent US9428394B2(2016-08-30) discloses that the inorganic acids prepared by oxidizing graphene are sulfuric acid, chlorosulfonic acid, fluorosulfonic acid and trifluoromethanesulfonic acid and combinations thereof, and the oxidizing agent is selected from the group consisting of permanganates, ferrates, chlorates, chlorites, nitrates, ruthenates and lead dioxide and combinations thereof. US patent US2018/0230014a1(2018-08-16) discloses a low-cost production method of graphene oxide and graphene, using potassium permanganate, sulfuric acid and hydrogen peroxide as oxidants, and hydroiodic acid to reduce graphene oxide. In the graphene oxide and graphene preparation method disclosed in chinese patent CN105293476A (2016-02-03), persulfate, potassium dichromate, potassium permanganate, potassium ferrate, nitrate or concentrated nitric acid is used as an oxidizing agent to prepare graphene oxide, and hydrazine hydrate, hydroiodic acid, lithium aluminum hydride, sodium borohydride, sodium hydroxide, sodium citrate or ascorbic acid is used as a reducing agent to prepare graphene. In the graphene preparation method disclosed in chinese patent CN102718209A (2012-10-10), potassium permanganate, potassium chlorate or potassium dichromate is used as an oxidizing agent, and a divalent iron salt is used as a reducing agent. In the preparation method of the large-batch graphene disclosed in chinese patent CN102583343A (2012-07-18), potassium permanganate, potassium chlorate or potassium dichromate is used as an oxidant, and acetone, ethanol or methanol is used as a reducing agent. The graphene oxide and graphene synthesized by the conventional method have low specific surface area and poor adsorption performance, the application range of the graphene oxide and graphene is limited to a certain extent, and particularly the application in the fields of energy conversion and storage is limited. Chinese patent CN108046242A (2018-05-18) discloses a method for preparing porous graphene, which comprises subjecting graphene oxide to ultrasonic treatment in a strong alkali solution, and then performing chemical reduction to obtain porous graphene. Chinese patent CN103395779A (2013-11-20) discloses a porous graphene and a preparation method thereof, wherein under the action of an oxidant, a graphite substance and sulfur are heated in a solvent to react, so as to obtain the porous graphene. Chinese patent CN104916446A (2015-09-16) discloses that an activating agent and graphene oxide are mixed to be reduced and activated within a certain temperature range, so as to obtain active graphene for a supercapacitor. The disadvantages of these methods are that graphene oxide must be prepared first, the cost of obtaining active graphene is extremely high, and it is difficult to expand the production application. Although many patents exist for preparing graphene and active graphene by chemical methods at home and abroad, the problems of low preparation yield, high production cost and difficult waste disposal are not solved, and the industrial application is not achieved so far. The main problem in the field of graphene is to research and develop a safe and environment-friendly preparation method and produce a graphene product with high yield, low cost and good controllability.
Disclosure of Invention
The invention aims to provide a clean production method of active graphene, which is characterized in that HNO is used3The preparation method comprises the steps of preparing active graphene oxide by oxidizing active graphite with HCl aqueous solution, reducing the active graphene oxide with glyoxal, and producing two products of the active graphene and glyoxylic acid simultaneously, so that the problem that a large amount of waste sulfuric acid is difficult to treat when graphene products are prepared by the conventional chemical method is fundamentally solved.
The intercalation etching activation of the graphite powder is to mix the graphite powder and a potassium compound according to the mass ratio of 1:0.1-1.0, heat to 760-plus-one 850 ℃ under the protection of nitrogen, preserve heat for 0.5-1h, enable potassium atom gas generated by thermal reduction decomposition of potassium salt to be inserted between molecular layers of graphite, enlarge gaps of graphite molecular layers, etch and open pores on crystal faces of the graphite layers for activation, increase the specific surface area of the graphite layers to obtain activated graphite powder, then introduce air for cooling to room temperature, pre-oxidize the surface of the graphite layers into graphite acid, increase the wettability of the surface and facilitate the permeation of subsequent oxidant solution, wherein the potassium compound is K2O、KOH、K2CO3、KNO3Or one of the organic acid potassium salts.
The preparation of the active graphene oxide in the invention is to dip the active graphite powder obtained by intercalation etching activation into 10-25% of HCl and HNO3HNO with the mass percentage concentration of 10-50 percent3Carrying out oxidation reaction in HCl aqueous solution at 40-70 ℃ for 4-6h, and continuously supplementing HNO with the mass percentage concentration of 50% in the reaction process3Solution, control of HNO3The molar charge ratio of the active graphite powder to the active graphite is 0.6-1.2, the active graphite powder is oxidized by nitroxyl chloride to generate active graphene oxide, the molar ratio of C/O in the molecules of the active graphene oxide is 1.6-3, the nitroxyl chloride is reduced to nitrosyl chloride, the nitrosyl chloride is further hydrolyzed to generate nitrogen oxide gas, and the nitrogen oxide tail gas generated in the reaction is recycled after being absorbed by water.
The reduction of the active graphene oxide is to add the oxidation reaction solution into aqueous solution with the mass percent concentration of glyoxal of 15-25% and the mass percent concentration of HCl of 3-5% at 40-60 ℃ in batches, and to control the adding of HNO3The ratio of the mole number of the glyoxal to the mole number of the glyoxal is 0.3-0.6, the oxidation reaction solution is added within 2-4h, then the heat preservation reaction is continued for 0.5-2h, the glyoxal is oxidized into glyoxylic acid, and HNO in the oxidation reaction solution is oxidized3Reducing the active graphene oxide in the oxidation reaction solution into nitrogen oxide gas by glyoxal, discharging the nitrogen oxide gas, reducing the active graphene oxide in the oxidation reaction solution into graphene by glyoxal, precipitating and separating out the graphene oxide so that the C/O molar ratio in the active graphene molecule is 6-9, centrifugally separating the active graphene, cleaning by deionized water, and drying in vacuum to obtain an active graphene product, wherein the specific surface area of the active graphene product is 500-1500m2/g。
The glyoxylic acid is prepared by heating the mother liquor of the reduction reaction to 40-60 ℃, and continuously adding HNO with the mass percentage concentration of 50 percent3Oxidizing agent to ensure that the mass percentage concentration of residual glyoxal in the mother liquor is less than 0.5 percent, then vacuum evaporating and concentrating the glyoxylic acid reaction solution until the mass percentage concentration of glyoxylic acid is more than 40 percent, cooling the glyoxylic acid concentrated solution to 0-5 ℃, crystallizing and separating out oxalic acid, adjusting with deionized water to obtain a glyoxylic acid solution with the mass percentage concentration of 40 percent, wherein the mass content of glyoxal impurities is less than 1.0 percent, the mass content of oxalic acid impurities is less than 1.0 percent, the mass concentration of HCl in the distillate recovered by evaporation is 10-15 percent, and HNO3High qualityThe degree is 0.3-1.0%, and the product can be recycled for HNO3-preparation of aqueous HCl solution.
One of the important reasons that graphite powder is not easily oxidized into graphene is that an oxidant is difficult to permeate into gaps of graphite layers, and concentrated sulfuric acid is usually added for impregnation and intercalation, so that the graphite layers expand and enlarge the gaps, and a large amount of waste sulfuric acid is generated.
Different from the existing active graphene preparation method, the active graphene is prepared by preparing active graphite powder, directly oxidizing the active graphite powder into the active graphene oxide and reducing the active graphene oxide instead of preparing the active graphene oxide firstly and then activating the active graphene oxide. The principle of activated carbon preparation is applied in the preparation of activated graphite powder, potassium salt is thermally reduced at high temperature to generate potassium atom gas, a potassium atom with larger atomic volume is intercalated to etch an activated graphite layer, gaps of the graphite layer are enlarged, the specific surface area of the graphite powder is increased, and a mass transfer channel of a graphite crystal face is increased; the active graphite layer is pre-oxidized by hot air, so that HNO is generated in the subsequent oxidation process3The HCl oxidizing agent readily wets and penetrates into the interstices of the graphite layers for the oxidation reaction.
In the invention, HNO is adopted3Preparation of activated graphene oxide (HNO) from activated graphite powder activated by HCl aqueous solution oxidation intercalation etching3The aqueous solution of-HCl is characterized by a dilute aqua regia, HNO3Nitroxyl chloride (NO) formed by reaction with HCl2Cl) molecules have much higher oxidizing power than the same concentration of HNO3Moderate concentration of NO2The Cl aqueous solution has a strong oxidizing power, and when heated, part of carbon atoms in the active graphite molecular layer can be oxidized into carbonyl and carboxyl. The introduction of the oxygen-containing functional group weakens the acting force between graphite layers and is easy to strip to generate the active graphene oxide. The volume expansion of the nitrogen oxide generated on the reactive sites can promote the exfoliation of the generated active graphene oxide. Glyoxylic acid and oxalic acid generated by the oxidation reaction have intercalation and adsorption effects on the active graphene, and promote the stripping of the active graphene oxide and retard the reaggregation of the active graphene oxide. The increase of the oxidation reaction temperature can accelerate the permeation of the oxidant, the oxidation of the active graphite and the stripping of the active graphene oxide.
Glyoxal is a chemical raw material and an intermediate, and can perform intercalation and adsorption on active graphene oxide molecules, promote interlayer stripping of the active graphene oxide and retard reagglomeration of the active graphene oxide. The glyoxal has strong reducibility, and can reduce, remove and recover oxygen-containing functional groups in the active graphene oxide molecules into an active graphene structure. Glyoxal can also react with nitroxyl chloride (NO) in the reaction solution2Cl) to nitrosyl chloride (NOCl), further hydrolyzed to nitric oxide and HCl removal, itself oxidized to glyoxylic acid, the reaction process is represented as follows:
HNO3+HCl→NO2Cl+H2O (1)
GP+ NO2Cl→GO+NOCl(2)
GO+CHOCHO→G+ CHOCOOH (3)
CHOCHO + NO2Cl→CHOCOOH+ NOCl (4)
CHOCOOH+ NO2Cl →COOHCOOH+ NOCl (5)
2NOCl+H2O→ NO2 + NO+2HCl (6)
GP in the reaction formula represents active graphite; GO represents active graphene oxide; g represents active graphene.
Glyoxylic acid is a widely used fine chemical, is usually sold as a 40% or 50% aqueous solution of glyoxylic acid, and is mainly used for the production of pharmaceutical and chemical products such as p-hydroxyphenylhydantoin, vanillin, hydroxyphosphinic acid and the like. The industrial production method of glyoxylic acid mainly comprises a glyoxal oxidation method, an oxalic acid reduction method, a cis-anhydride ozonization method and the like. The glyoxal oxidation method can use various oxidants to oxidize glyoxal water solution under acidic condition to prepare glyoxylic acid, and the commonly used oxidants mainly include nitric acid, nitrogen oxides, chlorine, air and combination thereof. The method combines the preparation of the active graphene and the production of the glyoxylic acid, solves the problem of treating a large amount of waste acid in the production of graphene products, and simultaneously reduces the production cost of the glyoxylic acid.
The experimental raw materials used in the invention, such as potassium hydroxide, potassium carbonate, potassium nitrate, nitric acid, hydrochloric acid, glyoxal and the like, are commercially available chemical pure reagents. The graphite powder is 5000-mesh flaky graphite powder provided by Guangdong Dongguan synergetic graphite company, and the carbon content is 99%.
The invention has the beneficial effects that:
(1) meanwhile, two products with high added values, namely active graphene and glyoxylic acid, are obtained, so that the production cost is reduced;
(2) the problem that a large amount of waste acid is difficult to treat in the production of graphene products is solved, and the clean production of active graphene is realized;
(3) the intercalation etching activation pretreatment of the graphite enables the aqueous solution of the oxidant to easily permeate into the gaps of the graphite layers, so that the aqueous solution oxidation process of the active graphite can be carried out.