TW201226315A - Chelating agent modified graphene oxides, methods of preparation and use - Google Patents

Abstract

The invention is directed to chelating agent modified graphene oxides having the following formula G(AB)x; wherein G is graphene oxide, A is selected from the group consisting of -(CH2)m-, -NH-, -S-, -O-Si(-OR1)2(-CH2)m-, -C(=O)-, -C(=O)-O-, -C(=O)-O(CH2)m-, -C(=O)-NH-, -C(=O)-NH-(CH2)m-, -P(=O)2-O-, wherein m is 1-12 and R1 is H, or C1-C12 alkyl; and B is a chelating moiety; wherein the ratio of basic graphene oxide units: x is from about 1: 0.00001 to about 1: 0.5. Such chelating modified graphene oxides have broad applications in diverse technical fields.

Description

201226315 VI. Description of the invention: [Rhyme ^ Ming Hu Jin Ge_Control ^ Xuan Mubei] This patent application is based on the US Provisional Patent Application (Application No. 61/282,191) filed on December 29, 2009. FIELD OF THE INVENTION The present invention relates to the use of an integrator to modify the oxidation of graphene oxide by a chemical modification method, as well as the chelation of the (four) graphite oxide (four) material in drinking water purification, waste nuclear, electrical materials, battery, solar power, polymerization Applications in composites, catalyst loading materials, etc., as well as materials for the preparation of catalysts and water treatment equipment. L Prior Art J Background of the Invention Graphite is a carbon element which is formed by arranging atoms in a hexagonal lattice neatly arranged, and the junction is often stable. This stable lattice structure gives the stone (4) excellent electrical conductivity. For example, graphite thinning has proven to be the thinnest and strongest material found in the world. Due to the unique mechanical and electrical properties of graphene, it has been shown to have unique applications in many respects. In general, since there are many hydrophilic groups such as a hydroxyl group, a carboxyl group, and an epoxy group, the vaporized graphite has good water solubility, but the graphite oxide is thin and thus loses large B conductivity. Correspondingly, after the graphene oxide is reduced to reduced graphene oxide, the hydrophilic groups on the surface, such as hydroxyl groups, epoxy groups, etc., are removed, and the surface π·π conjugated structure is restored. When the conductivity is restored (4), the graphite oxide is lost _ water-soluble. From another aspect, the reduction of the compatibility of graphite oxide with most polymers limits this.

S 3 201226315 Its further use. A number of chemical methods have mainly included chemical modification techniques to modify the reduced graphene oxide in order to change the surface of the graphite crucible, the compatibility with other substances, and to expand its water solubility and oil solubility. These methods include (1) physical adsorption to adsorb a covalent group to the graphene surface. (2) Covalent bonds and methods for attaching functional groups to the surface of graphene ^ These techniques have made initial progress. Graphene adsorbing a polymer such as a surface can increase its solubility. However, this method of physical adsorption limits its further use. The dispersion of single-layer graphene in water and organic solvents is very difficult due to the τι-π interaction between the individual molecular layers. Thus, the behavior of reduced graphene oxide in aqueous solution has not been further studied. Scientists try various methods (park Sungjin; Ruoff R〇dney s.

Nature Nanotechnology, (2009), 4(4), 217-24), mainly including chemical modification techniques to modify reduced graphene oxides in order to change the properties of graphene oxide surfaces, each with its own advantages and disadvantages, but also Develop new graphene derivatives with good water solubility while expanding their industrial applications. SUMMARY OF THE INVENTION The present invention relates to molecular design and artificial formation of novel graphite rare derivatives, and a series of organic synthesis methods for chemically modifying graphene by using a decylating agent, a carboxyl group and an amide, and the like. Related applications of such derivatives. The materials and molecules used include a base material, graphite, including yttrium oxide graphite, graphite oxide (G〇), and reduced graphite oxide (rg〇). Inorganic graphite refers to a single or multi-layered graphite thin material obtained from graphite. The thick product 201226315 is from 0.1 nm to 0.1 mm. The chelating agent includes ethylenediaminetetrazide and other possible chelating agents ranging in size from 10 nm to 1 mil. In the present invention, acetophenone and ethylenediamine triacetate (both known as EDTA) 蚤 蚤 蚤 include the following molecular structure: G(AB)x, wherein G generation is annihilated and emulsified graphene, and A represents a connection. The group, A has the following possible structures: _(CH2)m_, _NH_, each, -〇-Si(_CH2)m(_〇Rl)2·, <(Which, _c(〇〇_, -C( =0)-0(CH2)m- ^ -C(=〇)_NH_ . .C(,0).NH.(CH2)m„ . -Ρ(=0)2·0., where m^12, Rl is or a CL group. B represents an integrator group. The basic ratio of oxidized stone (iv) to a chelating agent group (4) c graphene oxide units: x) 4 丨: 〇〇〇〇1 to 丨: 〇 5. The present invention includes chelating Mixing process to modify graphite thinning (4): Firstly, it is equipped with Shi Xixuan's solution of decyl alcohol, ethanol, water or Fuxiangu organic> Gu Zhongyu. (b): The graphene oxide is recorded and mixed with Wei materials. The Weihua process is carried out, and then Weihua's gasified graphene is obtained. (4): After the reduction of the stone oxide of graphene, the weiwei stone material is obtained. - A specific matter: the integrator is ethylenediaminetriacetic acid and Its sodium salt. Another specific case of octanane II has the following structure: B-(CH2)m-Si-X3 B-(CH2)m-Ning)-x2 or B_(CH2)msi ((DRim + is C Bu B_, Ri is H, Ch3... or ch3ch2. ', ' = Surface Example) - is a mixture of the silk The graphite oxide is dilute. The synthesis process includes: reacting with graphene oxide and S〇Cl2 and chamber 2, reducing, (), ΐ#ϋ groups, and then reacting the above groups with the corresponding complex reagents to form a chelate-transfer graphite oxide. Alkene

-B in S 201226315 is a chelating agent group, and A- represents the following groups: HO-(CH2)m-, H-NH-, HS-, Rl-0-Si(-CH2)m(-ORi)2 -, HO-C(=0)-, H0-C(=0)-0-, H0-C(=0)-N-, and H0-P(=0)2-0-; where m is 1 -12, R1 is Η, C丨-C12 alkyl. One of the application examples of the present invention is the use of a chelating agent to bond (anchor) a metal ion and then synthesize a nano or micro metal particle catalyst using in situ synthesis techniques. The specific process includes (1) dispersing the chelating agent-modified graphene oxide in an organic or aqueous solution; (ii) adding a metal salt to the solution of (i), the salt of which is a salt compound of the following metals: Ni, Co, Fe, Pt , Ru, Au, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U, V, or Zr; (iii) Reduction of the metal compound in (ii) to obtain nano or micro metal particles, As a catalyst. One of the application examples of the present invention is the use of a chelating agent modified graphene oxide to remove metal ions in water. The specific process includes (i) loading a chelating agent-modified oxy graphene into a filter; (ii) passing a metal ion-containing water sample through the filter prepared in (1) to remove metal ions. At the same time, the chelating agent-modified oxidized graphene can be directly placed in a metal ion-containing water sample to directly remove the metal ions. The following metal ions may be removed, but are not limited to the following metal ions: Ni, Co, Fe, Pt, Ru, Au, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, U. , V, or Zr. This metal ion removal property and material can be used in drinking water preparation, wastewater treatment or as metal ion extraction. One of the application examples of the present invention is that a chelating agent-modified graphene oxide adsorbs cerium, lanthanum and any other quinone derivative, and a chelating agent-modified oxy graphene can be used as a catalyst for oxygen reduction after adsorbing hydrazine. 201226315 Example - is a chelating agent modified graphite oxide graphite oxide 埽 material: the specific process includes materials modified with f mixture. & preparation of raw materials_sub-anode and cathode batteries

The application example of the present invention is to modify the graphene-amine diethyl alcohol by using a chelating agent (ethylidene and its sodium salt) decane, and to include (a): preparing a solution of water, or an organic solvent of Shixiyuan. .卬): In the solvent of the machine, mix with the solution of Shi Xiyuan, the actual amount of Μ 到 到 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 魏 魏 魏 魏 魏 魏 魏 魏 魏(4): After reduction, reduced graphene oxide is obtained.埽 ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ ΪΓ One of the application examples of the present invention is the use of chelation. One of the application examples of the present invention is the use of chelation as a drug delivery body for medical device preparation. The emulsified graphite of the present invention is an application example of the present invention - a oxidized dilute preparation solar cell material modified with a chelating agent. An application example of the ink-based invention is an alkylene oxide using a meal mixture as a base material for use as a field emission display, an ink i- _ °, and a capacitor, an electrode, a lithium ion battery material, and a conventional lead battery improvement. .应用 An application example of the present invention is to use an alkylene oxide and a Naficm® film material composed of an integrator to form a composite as an electrode modification material ink. 201226315 An application example of the present invention is to use graphite to form a graphite thinning agent. In the process of modification, this financial correction stone 'turns (four) material and Wei mixed, and then returns after refining, one of the structures as shown in Figure 3. The contents of the patents and articles cited herein, as well as the contents of the documents cited in these patents and articles, are incorporated herein by reference. Brief Description of the Drawings Figure 1 shows the gentleman structure of rare graphite oxide and reduced graphite oxide. Figure 2 is a structure of a common Wei, which contains a coordination (the phono group decane. 1 Figure 3 is a blue (10) burn: called trimethoxy propyl propyl) ethylenediamine triacetate and its sodium The structure of the salt. Both of these compounds have been reduced to EDTA-silane in this case. Figure 4 is the four most common functional or chelating agent groups that can be attached to the graphene oxide surface. Figure 5 is a basic chelating agent attached to the surface of the graphene oxide after the gentleman structure. Figure 6 is a basic EDTA modified graphene oxide surface structure. Figure 7 is a modification of the basic f mixture on the surface of graphene oxide. Figure 8 is an infrared spectrum of the basic reduced graphene oxide, graphene oxide, modified reduced graphene oxide, and EDta modified graphene oxide. Figure 9 is a photograph of basic graphene oxide (&), EDTA-modified graphene oxide (b), reduced graphene oxide (C), and EDTA-modified reduced graphene oxide (phantom aqueous solution. Fig. 10 is Photographs of EDTA-RGO(a) and EDTA-GO(b) solutions at different concentrations of water 201226315. Figures 10 (C) and (d) are EDTA-RGO(c) and EDTA-GO(d) UV spectra. EDTA -RGO and EDTA-GO concentration: 1: 〇.〇19 mg/ml, 2: 0.038 mg/ml ' 3 : 〇.〇75 mg/m b 4 : 0.15 mg/m b 5 : 0.30 mg/ml. It is an electron micrograph of basic EDTA modified graphene oxide. Fig. 12 is a cyclic voltammogram of basic EDTA modified graphene oxide electrode catalyzed sterol oxidation. C real mode; J preferred embodiment as a detailed description , graphite oxide 埽, English "Ph or abbreviation "G〇" specifically refers to graphene oxide 'reduced graphene oxide, English, "reduced gl * aPhene (10) coffee, abbreviated "RG 〇" specifically refers to reduced graphene oxide, its structure As described in I and II:

S

Molecular formula I 9 201226315

Each of the basic graphene oxide units of the formula II includes a single carbon atom and any functional groups associated therewith. Graphene oxide includes a single layer of graphite, a multilayer graphene, a graphite oxide layer, a graphene oxide sheet, and also includes graphene oxide oxidized by a strong oxidizing agent such as h2S〇4, HNO3, KMn〇4, KCIO3, chemical vapor deposition. Graphene prepared by a method (CVD). The emulsified graphene further includes a graphite oxide layer, a graphene oxide sheet, and a single layer graphene having a width of between 1 nm and 1 mm and a thickness of between 0.1 nm and 0.1 mm. The single layer graphene has a width and thickness between 0.385 nm and 5 nm and a size between 10 nm and 1 mm. The thickness of the multilayer graphene ranges from 〇1 nm to 100 μm. Graphene sheets have a variety of electronic, mechanical and chemical properties. The reduced state can be obtained by reduction of NHyNH2' LiAlRt, NaBH4 or other reducing agents, or by thermal expansion techniques. Wherein, the chelating agent refers to any organic compound having a coordination function, and we can form a complex by a coordinate bond through two or more atoms (mainly 〇, N, p and S) and a metal ion contained therein. . 10 201226315 containing two coordinating atoms is called a bidentate complex, and a tridentate ligand containing three coordinating atoms is called a tridentate compound, and so on. EDTA is a hexadentate complex whose chemical name is ethylenediaminetetraacetic acid. Wherein 'A' or 'linking group,' represents any atom or group that can attach a chelating agent and graphene oxide. Common structures include ·(CH2)m-, -NH-, -S-, -〇 _Si(_OR丨)2(CH2)m_, _c(=〇) 〇(CH2)m, -C(=0)-NH-^-C(=〇)-NH-(CH2)m- . .〇 (=〇). , -〇(=〇).〇- ' -C(=0)-N-, -P(=〇)2_〇_ ; where the claw is ", Rl means ^ or heart 5 alkyl. Wherein, "A" represents HO-(CH2)m-, H-NH-, HS-, H-0-Si(-0R')2(CH2)m- > -C(=0)-〇(CH2 )m- > -C(=〇)_nH- ' C(=0)-NH_(CH2)m-, h〇-C(=〇)_, h〇-C(=〇)-〇-, H0 -C(=0)-N-, HO-P(=〇)2-〇_; mgM2, R>H, alkyl, aryl, alkene, alkyne, amine or hydroxyl. Among them, the amine group and the carboxy group may be a substituent of an alkyl group and an aryl group. The optimized ruler 1 is 11, or the Ci_c port ’ base is more optimized R1 is Η, or CrC4 alkyl. Wherein 'integrator group or "B" means that any hydrazine having a coordination function is bonded to the surface of the graphene oxide (4) via a linker IS "A", which may first form a covalent bond compound with A and then As a starting material, it is connected to the thin surface of the graphite oxide by a synthesis reaction. Wherein "Shi Xixuan," refers to a Shi Xiyuan compound containing the structure of Y_(CH2)m_Si_X3, n=1~2; x is a hydrolyzable group; Y is an organic functional group, such as a chelating agent group X is usually a chloro group, an oxy group, an ethoxy group, a methoxyethoxy group, an acetoxy group, etc. 'These groups are hydrolyzed to form a linalool (10) (4) 3), and combined with the oxidized stone money Oxygen-burning. γ is an ethylene group, an amino group, a ring 11 201226315 oxy group, a decyl acryloyloxy group, a fluorenyl group or a ureido group. These reactive groups can be reacted with an organic substance to bind. Therefore, 'by coupling with Shi Xiyuan The agent can bridge the "molecular bridge" between the interface of the inorganic substance and the organic substance, and connect two materials with different properties to improve the performance of the composite material and increase the bonding strength. The optimization scheme of the invention, oxidation Graphene contains _COOH, -OH and -〇-groups are mainly _C00H, or _〇H groups. The optimal ratio of a basic graphene unit to a work flb group is 1: 0.00001 to 1: 0.5 The more optimized ratio is 1: 0.0001 to 1: 0.35, the more optimized ratio is 1: o.ooo^H : 0.32 The ratio of 'optimized is 1: 〇〇〇1 to 1: 〇3, the ratio of optimization is 1. 0.0005 to 1: 〇·25, the ratio of optimization is 1: 0 01 to 1: 〇2, more optimized The ratio is 1: 〇.〇2 to 1: 0.15. The improved linking group in the optimization scheme of the present invention is -O-SK-OR1)2·, where 'r1 is fluorene, alkyl, aryl, alkene An alkyne group, an amine group, a hydroxyl group, which allows the amine group or hydroxyl group to be optimized as an aryl group or an alkyl group. The alkyl group in the optimization scheme of the present invention comprises a linear or branched alkane having a length of CVC! a linear alkyl group of 8, or a cycloalkyl group of (c4-c8). The aryl group in the optimization scheme of the present invention includes a phenyl group, a tolyl group, a naphthyl group, a phenanthrenyl group or a pyridyl group. Substituted groups include straight-chain or branched (Ci_c6)-alkyl compound '(CVC7)-cycloalkyl compounds, straight or branched (Ci_c6)-alkoxy, hydroxy, amine, and CrC6) alkylamine, nitroalkane, or cyanoquinone to the rare sulfonic acid group, available ethylene or propyl group. For the alkynyl group, acetylene group can be used. The optimized group is R1 'where r is a burning group Better group R is 11 or (: 1-(: 4 leucoyl), and chelating agent may be replaced by _〇r. 12 201226315 The chelating agent in the optimization scheme of the present invention is a compound including the following groups or their salts, "mm" is 1-12, and more optimized mm is 1-4. Another optimized product is CrC12 alkyl-linked ethylenediaminetriacetic acid, diethyltriaminetetraacetic acid and their salts.

Ethylenediaminetriacetic acid diethylenetriaminetetraacetic acid nitrodiacetic acid

Diethylenetriamine Ethylene glycol triacetic acid The following examples are specific to the invention, and it should be noted that the invention is not limited to the specific description in the examples. Portions and percentages in the specific examples of the invention are by weight unless otherwise indicated. The scope of the data recited in the present specification and the following paragraphs, when used to describe the scope of the various claims of the present invention, such as to represent a particular set of properties, units of measure, conditions, physical state or percentage, the inventor intends Includes any number within this data range and any subset or subset number range within this data range. The term "about" is used to modify a variable or when used with this variable, it means that the value and data range of this variable is variable within a certain range, and that the skilled person can at temperature, rich 13 201226315 degrees, The intended effects of the present invention can also be achieved by using the present invention in addition to the data ranges of quantity, content, carbon number and physical properties, such as good solubility, higher metal ion adsorption capacity and the like. In order to more fully describe the state of the art in the field to which this invention pertains, this patent application references various references and publications. The contents described in these references and publications are also incorporated herein by reference. The transitions in the present invention are included as synonyms for "including", "including" or "characterizing". This term is inclusive and open, allowing for the addition of additional undeclared conditions and method steps. Example 1 Preparation of Pretreated Graphite Graphene oxide was produced from graphite using a modified Hummer method. The graphite powder is first oxidized by sulfuric acid, and the graphite powders of O.lg, 〇.5g, lg, 5g and l〇g are first dispersed into 1,5, 1 〇, 5 〇 and 1 〇〇mi concentrated sulfuric acid, and then 0.1 respectively. , 0.5, 1, 5 and 20 g of potassium persulfate (k2S208) and 2, 5, 10, 15 and 20 g of phosphorus pentoxide (P2〇5" mixture are maintained at 2 〇 to 90 ° C for 1 to 24 hours, then 'mixture After descending to room temperature, it was diluted with deionized water with l〇〇m b 250m b 500m b 1.0 and 2.0 liters, and left overnight. The mixture was filtered, washed with distilled water, and dried to obtain pre-oxidized graphite. The graphene powder was prepared by taking O.lg, 0_5g, lg, 5g and 50g of the sample of pre-oxidized graphite in Example 1 and placing them in 1ml, 5ml, 10ml, 20ml and 50ml of cold concentrated sulfuric acid (0. Lg.lg, 〇.5g, lg, 5g and 50gKMnO4, note that the solution reaction temperature is controlled below 20 ° C. The mixture is heated to 25 ° C ~ 95 ° C under stirring, and the reaction is stirred at this temperature for 4 hours, 10, 50, 100, 200, and 14 201226315 5〇〇ml steaming water diluted. Dilutate in ~ catch overnight. Then add an excess of crane water. Then add 5G, 25G, 5GG' 100G and 2500ml steamed crane water. After h, add i, 5, 1〇, 2〇 and 5_ 3〇〇 /. H2〇2. The color of the mixture is redundant. After the reaction is filtered, After washing with 0.1 M hydrochloric acid, washing with distilled water and drying to obtain graphene oxide powder. Example 3 Preparation of EDTA-graphene oxide 1, 2, 5, 10 and 100 mg of graphene oxide were added to a three-necked flask, and then 10, 20, 50, 1 〇〇 and 5 〇〇 ml of sterol or ethanol, sonicated for 1 to 60 minutes. Then add 1 to 50 ml of 0.1 to 15 hexane, acetonitrile, or ethanol N-(trimethoxy)矽 propyl) ethylenediamine triacetic acid and its sodium salt solution, 30~85t stirring for 1~48 hours to complete the decaneization process. After the reaction is completed, add 100 ml of water, ethanol and methanol to neutralize unreacted decane. (Trimethoxydecyl propyl) ethylenediamine triacetic acid modified graphene oxide can be obtained by a series of steps such as filtration, decyl alcohol, water and hydrochloric acid to obtain EDTA modified graphene oxide (EDTA-GO). Example 4 EDTA - Reduction of reduced graphite oxide to reduce EDTA modified graphene oxide to reduced EDTA modified oxygen Graphene, 100 mg EDTA modified graphene oxide was vacuum dried for 1 to 36 hours, then dissolved in 10-500 ml of water, and then added to hydrazine, and EDTA modified graphene oxide was reduced to EDTA modified reduced graphene oxide (EDTA-RGO). After the reduction, the color of the solution changed from brown to black. EDTA modified reduced graphite oxide was diluted by filtration, methanol, water and hydrochloric acid to obtain EDTA modified reduced graphene oxide (EDTA-RGO).

S 15 201226315 Example 5 Infrared spectra of graphene materials taken from graphene oxide (GO), reduced graphene oxide (RGO), EDTA-graphene oxide (EDTA-GO) and EDTA modified graphene oxide (EDTA-RGO) powders, respectively The mixture was compressed with KBr, and analyzed by infrared analysis using a Fourier transform infrared spectrometer in the range of 500 to OOcnT1, and the infrared spectrum was as shown in Fig. 8. Example 6 Electron micrographs of graphene oxide (GO), reduced graphene oxide (RGO), EDTA-graphene oxide (EDTA-GO) and EDTA modified graphene oxide (EDTA-RGO) materials by JEOL 2010 F microscope (JEOL Ltd. , Japan) Get. Figure 10 is a photograph of a single layer of EDTA-GO on an ultra-flat gold film surface. The sample was prepared by dropping a drop of diluted EDTA-GO and EDTA-RGO onto the surface of the substrate (1 hour sonication). EDTA-RG sizes range from tens of nanometers to hundreds of microns. EDTA-RGO exhibits light transmission and folds at the corners. Some small fragments can be found on the surface. It shows that the soluble EDTA-RG◦ has the same structure as its surface peeling off from the graphene. Transmission electron microscopy was used to characterize the structural changes and surface morphology of each step. Example 7 EDTA-RGO and EDTA-GO can be characterized by infrared spectroscopy, and the red radiance spectra of EDTA-RGO, EDTA-GO 'GO and RGO are as shown in Fig. 8. By comparing the spectra of EDTA-GO and EDTA-RGO with the spectra of GO and RGO, several new infrared absorption peaks can be demonstrated by the presence of graphene surface decane 16 201226315. Among them, in the ugly 0 D8-00 and £0 D8-^^0 spectra, the two new absorption peaks at 2917 and 2800 CHT1 are attributed to the shock absorption of the methylene group, which is derived from EDTA-silane decane. In addition, the absorption peaks at 1401〇111-1 (have 0 D8-00) and 1409〇111-1 (£0丁八-1^}〇) are attributed to the r CH2 group which is ugly. After decaneization, the ionizing buffer on the EDTA chain can be determined by the new peak at 1628〇111-1· of the EDTA-GO infrared spectrum. This characteristic peak can be obtained in EDTA-GO and EDTA-RGO samples. At the same time, the absorption peak of the EDTA-GO infrared spectrum at 694 cm·1 is attributed to the stretching vibration of Si-O-C. When EDTA_G0 is reduced by hydrazine, the absorption peak at the nanometer moves to 712 (^-1 (EDTA-RGO). In addition, the infrared spectrum of EDTA-GO is 923 cm·1 and 856 cm in EDTA-RG◦ infrared spectrum. The absorption peak of 1 corresponds to KSi_〇H vibration absorption. In addition, the absorption peak at 1066 cm·1 in the EDTA-RGO spectrum is attributed to Si_〇_c. Among all four substances, the presence of carboxyl group is confirmed by the absorption peak simultaneously. The absorption peak at '1732 cm·1 is a slow or a few (c=〇) stretching peak. This peak is present in four compounds. (3〇 In the infrared spectrum, the absorption peak and the coffee in the 咖--丨The absorption peak measured by (6) is attributed to the reduced symmetrical vibration absorption. This stable absorption peak indicates that the graphite-rich filament and the county cannot be reduced to C-OH. The absorption peak at i(3) in the infrared spectrum of EDTA.GQ (10) Infrared light strikes 7Gem.% of the read peak table • The bad oxy group on the surface of the secret. When reduced by hydrazine, U2 in the infrared spectrum of EDTa_g〇 (the absorption peak at W and the infrared spectrum in G〇 infrared spectrum ^ The absorption at the point is Xiao, indicating that the reduction process converts the epoxy group on the surface of the graphite crucible into a η total light bond. This conclusion is also X_ray. Proof. We will discuss it later.

S 17 201226315 Example 8 A graphene suspension of 1 mg/ml of GO, RGO, EDTA-GO and EDTA-RGO was obtained by a conventional method. Figures 9a and b are suspensions of 1.0 mg/ml GO and RGO after ultrasonic preparation in water for 1.5 hours. GO suspensions are very stable, as reported in other literature. The stability of RGO in water is very poor and it sinks to the bottom after 12 hours. This precipitation is due to the mutual aggregation of RGO and the disappearance of hydrophilic groups. Figures 9c and d are suspensions of 1.0 mg/ml EDTA-GO and EDTA-RGO after ultrasonic preparation for 1.5 hours in water. EDTA-GO and EDTA-RGO are very stable in water. In particular, the EDTA-RGO solution had no phase separation for 1.5 hours, and the EDTA-RGO solution was stored for 3 months without precipitation. Example 9 Figures 10a and b are photographs of different concentrations of EDTA-RGO and EDTA-GO suspensions, which are photographs after three weeks of preparation. The solution concentration was from 0.019 to 3.3 mg/ml. The color of the solution gradually deepens as the concentration increases. The EDTA-GO solution was light brown, while the brown EDTA-RGO solution demonstrated that the reduction process restored the conjugated structure of graphene. The presence of EDTA increases the stability of graphene in water, allowing us to analyze the UV adsorption characteristics of EDTA-RGO solutions using UV spectroscopy. The UV spectrum was measured from different concentrations of EDTA-RGO and EDTA-GO solutions (from 〇, 〇i9 mg/ml to 0.30 mg/ml), and the light wave was 200 to 600 nm. The EDTA-RGO solution has a clear absorption curve with a peak at 280 nm' and is always tailed to 800 nrn. Compared with EDTA-RGO, the peak absorption of the EDTA-GO solution was at 23 〇 nm, and the peak value of EDTA-RGO was red shifted by 280 nm. The peak absorption intensity is proportional to the concentration. As the absorption curve of the 18 201226315 photo EDTA-GO solution is asymmetrical, and the jump increases with the increase of the wave length, the peak value is 230 nm, and the tailing is 800 nm. The peak absorption intensity is proportional to the EDTA-G◦ concentration. Example 10 One use of EDTA-GO is for the removal of heavy metal ions in environmental protection, and the adsorption capacity for heavy metal ions is determined by mixing EDTA-GO with a metal ion solution. Since the ship is the most common environmental pollutant, its adsorption capacity for lead ions is determined by mixing EDTA-GO with a lead ion solution. The experiment found that EDTA-GO has a large adsorption capacity for the right and wrong. In a typical experiment, EDTA-GO is mixed with a different lead mixture. The adsorption test in the optimization scheme of the present invention was carried out by mixing 1 to 2 mg of EDTA-GO with 100 mL of a solution containing different metal ions. The initial concentration of metal ions is from 0.01 to 111 卩卩 111, and the value of 卩1 is 2.5 to 10.5 (adjusted with NH4C1-NH3 'NaAc-HAc, and the buffer solution). The mixed solution was kept for 1 to 64 hours and then filtered through a membrane having a pore size of 0.2 μm. The filtered GO was detected by SEM EDAX. The filtered solution can be used to detect particle concentrations using ultraviolet (ICP) and aaS. The adsorption capacity qe (mg/g EDTA-GO) was obtained by the following method qe = [(Ci-cf) v / w]; where 'q and cf are the starting and final concentrations (mg/ml) of the metal ion, V (ml) is the solution volume w (g) is the EDTA-GO weight. The effect of pH on adsorption is the same, but the pH values are 3.〇, 4.5, 5.5, 7.2 and 8.2. All experiments were filtered using a μ2μιη membrane. The adsorption capacities of the materials of the present invention and other materials used as commercial products are listed in Table 1. In addition, Table 1 lists some of the EDTA-GO and other heavy metals such as copper (II) 'zinc (II), mercury (II) and the like. These tests were obtained by mixing 3^19 201226315 EDTA-GQ with different heavy metal solutions and the test results are listed in Table 1 below. σ Table 1 Adsorption capacity of EDTA-modified graphene oxide for different heavy metals compared with resin

Example 11 Another use of EDTA-GO is fuel cells. Because of its high chemical stability and large specific surface area, graphene oxide and its derivatives can be used as surface synthesis catalytic materials and carriers. Many scientists have Graphene was found to be useful as a catalyst carrier for fuel cells. The pt, Ru, Pt and Ru alloys, which are supported by graphite oxide, exhibit extremely high catalytic properties for methanol oxidation. The synthesis method in the optimization scheme of the present invention comprises: dispersing Q1 mg to gram EDTA-GO powder in 1~1 〇〇mi ethylene glycol for 5~3 〇 minutes, adding 7.4 mg of H2PtCl6, and then stirring for 2 hours, The pH of the solution was adjusted to 13 ' with K〇H and then at 13 〇. (: reflux for 3 hours, transition solid, rinsed with water and dried at 80 ° C for 12 hours. 20 201226315 Synthesis of chelating agent-modified graphene-supported Pt_Ru nanoparticles as above. Just add a mixture of 7.4 mg of H2PtCl6 and 7-4 mg of RuCl3. EDTA-GO/Pt Catalysts for Electrochemical Catalytic Oxidation of Furfuryl Alcohols' Cyclic Voltammetry for Studying the Catalytic Process of EDTA-GO/Pt Catalyst Modified Electrode for Oxidation of Sterols. Experiment with Sulfuric Acid Containing 0.5 M of Sterol The solution is carried out in solution. Figure 12 is a catalytic cyclic voltammogram of EDTA-GO/Pt catalyst for sterol oxidation. Typical sterol catalytic oxidation peaks can be observed in cyclic voltammograms: two at 0.67V and 0.42V The oxidation peaks correspond to the sterol oxidation peak and the intermediate oxidation peak, respectively. The peak current ratio of the pre-oxidation peak (If) and the oxidization peak (lb) in the cyclic voltammogram 疋 evaluate the key constant of the catalytic effect. The If/Ib value of 咼 indicates that methanol oxidation is more complete, that is, methanol can be completely converted to carbon dioxide' and the low value of ^/^ indicates that methanol oxidation is incomplete, that is, methanol is turned into an intermediate. On the other hand, this ratio is To evaluate the resistance of the catalyst to the toxicity of the oxidizing intermediate. As can be seen from the cyclic voltammogram, the If/Ib value of the EDTA-GO/Pt catalyst is 2.45 (20 scans), this value and the conventional GO/Pt catalyst. The (If/Ib value: 0.73 to 1.26) and the CNTs/Pt catalyst (If/Ib value: 0.5 to 1.2) are much higher than this. The high value indicates that the sterol can be completely oxidized to one step on the catalyst surface. Carbon dioxide indicates that the EDTA-GO/Pt catalyst has high catalytic activity for the oxidation of methanol. This result indicates that the EDTA group on the graphite thin surface can significantly increase the catalytic activity and stability of the platinum catalyst, EDTA-GO/ The surface structure of Pt can significantly reduce the poisoning of the CO-side catalyst. In the present invention, the If/Ib of EDTA-GO/Pt is 2 to 2.5, which is better than the If/Ib of GO/Pt and CNT/Pt (〇.73~1). · 3) High value 21 201226315 Many, indicating better catalytic properties. Example 12 The formula R-(CH2)m-Si-X3-decane compound can be used as a modified graphene oxide, wherein X and R are the above-mentioned a base, a gas sulfhydryl group, a benzyl group, a vinyl group, and an amine group, wherein X is a group to be reacted with graphene oxide During the reaction, the bond between the X and the ruthenium atom is replaced by a bond between the graphene oxide and the ruthenium atom. In general, X is an easily hydrolyzable hydrazine such as an alkoxy group, an acyloxy group, an amine group, or a gas. Common are methoxy and ethoxy groups which release sterols and ethanol during the bonding process.

Preparation of EDTA-graphene by oximation

Preparation of EDTA-graphene by decaneization 2012 201215 The properties of EDTA-modified graphene, as a water-soluble group, can increase the solubility of graphene in water. This result is advantageous in the preparation of graphene derivatives and graphene-based compositions. Example 13 The decylating agent of Example 10 was substituted with ethylenediaminetriacetic acid, nitrodiacetic acid, diethylenetriaminetetraacetic acid, and ethylene glycol triacetic acid to produce a corresponding chelating agent-modified graphene oxide. Example 14 Graphene oxide can be activated by the following reaction.

EDTA-Silane Example 15

j ] J

〇> T S %

OH

The chelating agent-modified graphene can be synthesized by the following reaction, wherein G is graphene oxide, B is a chelating agent, wherein X is -OR1; R1 is hydrazine or CrC12 alkyl; m is 1-12. 23 201226315 h2n,

IB + 〇 One q II step ij G—C—OH = q—0 u I : H in

m HO

+ q Two II steps G—C—OH = q

i·; H? ; "i >C fGHi r-B 〇<i; H3CO H3C〇—Si h3go/

G-OH

Two steps

A Example 16 The present invention develops a technique and method for functionalizing graphene oxide using a chemical modification process, characterized by N-(trimethoxymethoxymercaptopropyl)ethylenediaminetriacetic acid and its sodium salt (EDTA) EDTA is attached to graphene by a covalent bond, and the modified compound can be dissolved in water, tetrahydrofuran, ethylene glycol to form a single layer graphene solution. And this substance has many uses. Example 17 The present invention developed a process for preparing a graphene oxide derivative which can be carried out by a decylating agent and an amide group, and the corresponding applications thereof are also developed at the same time. The starting materials are graphene, graphene oxide, and reduced graphene oxide. The layers are one to many layers, the thickness is 0.1 nm to 0.1 mm, the size is 10 nm to 1 cm, and the functional groups are EDTA and other chelate. mixture. Functionalized groups, EDTA or chelating agents, typically organic compounds, may also be referred to as ligands, which form a water-soluble complex with metal ions. These complexes can form more than two coordinate bonds with a single metal ion through a multidentate chelating agent. 24 201226315 Chemical techniques for the attachment of EDTA groups to the surface of graphene oxide by decaneization are described in Figures 1, 2 and 7. The novel materials or molecular compounds of the present invention depend on the structure and properties of the starting graphene, graphene oxide and reductive oxidized graphene, such as electrical conductivity, and the chemical and physical properties of EDTA. The novel materials or molecular compounds of the present invention can be used as novel nanomaterials for the preparation, extraction and separation of electrode materials, supercapacitor materials, fuel cell materials, solar cell materials, catalyst materials, and series of chemical materials. Used for battery and membrane filtration. In addition, the high dispersibility of this material allows it to be polymerized to form polymer composites for use in other Maochen materials. The foregoing has described the principles of the invention as a preferred embodiment and mode of operation but the invention is not limited to the specific forms disclosed. Modifications may be made by those skilled in the art based on the principles of the invention. The basic concepts, best practices and modes of the present invention have been previously described.

C is simple: 3⁄43⁄4 明; J Figure 1 is the structure of graphene oxide and reduced graphene oxide. Figure 2 is a common Shi Xilang structure, one of which is a coordination (complexation) group. Figure 3 is a structure of EDTA-decane: team (trimethoxydecylpropyl) ethylenediamine triacetic acid and its sodium salt. Both of these compounds are abbreviated as EDTA-silane in the present invention. Figure 4 is the four most common functional or chelating agent groups that can be attached to the graphene oxide surface. Figure 5 is the structure after the basic chelating agent is attached to the surface of the graphene oxide.

S 25 201226315 Figure 6 is a basic EDTA modified graphene oxide surface structure. Figure 7 is a modification of the basic chelating agent on the surface of graphene oxide. Figure 8 is the basic reduction of graphene oxide, oxidation; ^

^ Porous graphene, EDTA modified reduced graphene oxide and EDTA modified graphite oxide rare infrared spectrum. Fig. 9 is a photograph of an aqueous solution of basic graphene oxide (a), EDTA-modified graphene oxide (b), reduced graphene oxide (c), and EDTA-modified reduced graphene oxide (d). Figure 10 is a photograph of EDTA-RGO(a) and EDTA-GO(b) at different concentrations of water/valley. Figures 10(c) and (4) are EDTA-RGO(c) and EDTA-GO(d) UV spectra. EDTA-RGO and EDTA-GO concentrations: 1: 0.0i9 mg/ml, 2: 〇-〇38 mg/mi, 3: 〇.〇75 mg/ml > 4 : 0.15 mg/ml * 5 : 0.30 mg/ml ° U-graph is an electron micrograph of basic EDTA modified graphene oxide. Figure 12 is a cyclic voltammogram of the oxidative oxidation of sterol by a basic EDTA modified graphene oxide electrode. [Main component symbol description] (none) 26

Claims (1)

201226315 VII. Patent application scope: 1. A chelating agent modified graphene oxide having the following structure: its molecular formula is G(AB)X; wherein G is graphene oxide; A is selected from a linking group having the following structure: -(CH2)m-, -NH-, -S-, -O-SK-CHJJ-ORi-, -C(=0)-, -C(=0)-0-, -C(=0)- 0(CH2)m-, -C(=0)-NH-, -C(=0)-NH-(CH2)m-, -P(=0)2-0-; wherein m is 1-12 R1 is H or a CrC12 alkyl group; B is a chelating agent having a coordination function in which the ratio of basic graphene oxide units to X is 1: 0.00001 to 1:0.5. 2. The chelating agent modified graphene oxide of claim 1, wherein the graphene oxide comprises the following groups: -COOH, -OH and -0-. 3. The chelating agent modified graphene oxide of claim 1, wherein the graphene oxide comprises the group: -COOH, or -OH. 4. The chelating agent modified graphene oxide of claim 1, wherein the ratio of the basic graphene oxide unit to the chelating agent is: 1: 0.00001 to 1: 0.04. 5. The chelating agent modified graphene oxide of claim 1 of the patent application. The linking group is: -O-SiC-OR^M-CH^-; wherein R1 is Η or C1 - C12 alkyl ' Hi = 1 -12. 6. A chelating agent modified graphene oxide according to claim 5, wherein R1 is an HSCrCt alkyl group. 7. The chelating agent modified graphene oxide according to claim 1, wherein the chelating agent is selected from the group consisting of the following groups or a salt thereof: S 27 201226315 — instrument nitro diacetic acid ethylenediamine triacetic acid Diethylene triamine tetraacetic acid ethylene glycol triacetic acid. 8. The chelating agent modified graphene oxide of claim 7, wherein m is 1-4. 9. The chelating agent-modified graphene oxide according to claim 7, wherein the chelating agent is ethylenediaminetriacetic acid or a salt thereof. 10. A process for synthesizing a chelating agent modified graphene oxide, the process comprising the step of reacting graphene oxide with a decane reagent, wherein the decane reagent is selected from the group consisting of: 28 201226315 Ethylenediaminetriacetic acid-decane (EDTA-Silane) Ethylenediaminetriacetic acid trisodium-decane (EDTA-Silane) The reaction is carried out as follows: Correction. )m1 八r,r" },J rJ Ί巧—T,?T0, COOH axil Na* OCX; FactoryΝ'*t, \xx» ^OOONa* 11. A synthetic chelating agent modified graphene oxide The reaction process, wherein the process comprises the following steps: (1) selecting to treat the graphene oxide with S0C12 or SOBr2, converting the carboxyl group into an acid or acid bromide, and (2) reacting the graphene oxide compound in the process (1) with AB, Producing a chelating agent modified graphene oxide; wherein B is a chelating agent, and A is selected from the group consisting of: HO-(CH2)m- 'H-NH- ' HS- ' R1-0-Si(-0R1) 2 ( -CH2)m- ' H0-C(=0)-, H0-C(=0)-0-, H0-C(=0)-0(CH2)m-, 29 201226315 H0-C(=0) -NH-, H0-C(=0)-NH-(CH2)m- and H0-P(=0)2-0-; wherein m is 1-12 and R1 is H, and (:丨-0: 12. Alkyl group 12. The reaction process of claim 11, wherein -(CH2)_-B is selected from the following complexes or their salt compounds, mm is 1-12: Ethylenediaminetriacetic acid diethylenetriaminetetraacetic acid nitrodiacetic acid Ethylene glycol triacetate Diethylenetriamine. 13. The process of claim 12, wherein mm is 1-4. 14. The process of claim 11, wherein A-B refers to N-(trimethoxysilylpropyl)ethylenediamine triacetic acid. 15. A method for preparing a metal catalyst by using a chelating agent modified graphene oxide according to claim 1 of the patent application, the method comprising the steps of: (1) dissolving the chelating agent-modified graphene oxide in an aqueous solution or an organic solvent; 2) adding a metal salt to the solution or suspension of step (1), wherein the metal 30 201226315 salt is selected from the group consisting of the following metal salts Cu, Mg, Μη, Mo, Rh, Si, Ta, Ti, w, υ, ν ' 2 or Li; (3) The metal complex of the cerium fossil modified by the step (2) (4) mixture is precipitated into fine particles or nanoparticles to be used as a catalyst. 16. If the method of applying the full-time @ item 15, the towel particles or nanoparticles can be used as a catalyst for a fuel cell. Hey, please ask for the scope of the patent! A method for removing metal ions from water by a chelating agent-modified graphite oxide, the method comprising the steps of: (1) placing a chelating agent-modified graphene oxide in a filtering device; (7) passing the metal ion-containing solution through the transition device, the metal ion. • Method as in item 17 of the material range] wherein the metal ion is selected from the group consisting of scratch, Hg, Cd, C°, Fe, Pt, RU, Au, Cr, Cu, Mg, Mn, M°, Rh, Si, Ta 'Ti, w, u, v, Zr, As, c" 〇 Li. 19. The method of item (4), wherein the purpose of removing metal ions is to prepare drinking water. II: = The method of the 17th item, in which the gold is removed and the metal is taken. Q 21. As for the method of applying for patent scope 17, the environmental governance. The removal of metal ions in the target 22·2 is oxidized by the chelating agent-modified graphite oxide chelating agent modified in the first application of the patent scope; the use of the above (iv) emulsified stone (four) to replace all of its carbon materials in the rotor battery 31 201226315 a step; thereby producing the above-described high-performance lithium ion battery.