CN115155546B - Graphene oxide and preparation method thereof, and method and application for adsorbing unsymmetrical dimethylhydrazine in aqueous solution by using graphene oxide - Google Patents
Graphene oxide and preparation method thereof, and method and application for adsorbing unsymmetrical dimethylhydrazine in aqueous solution by using graphene oxide Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 312
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 278
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 title claims abstract description 27
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 152
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000011282 treatment Methods 0.000 claims abstract description 25
- 239000003112 inhibitor Substances 0.000 claims abstract description 10
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- 125000000524 functional group Chemical group 0.000 claims description 27
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
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- 230000006872 improvement Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- 239000011572 manganese Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
- B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/08—Nanoparticles or nanotubes
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Abstract
The invention discloses graphene oxide, a preparation method thereof, a method for adsorbing unsymmetrical dimethylhydrazine in an aqueous solution by using the graphene oxide and application of the graphene oxide, and belongs to the technical field of safety treatment of aerospace fuel. The invention provides a graphene oxide exogenous additive structure based on a first principle, and adopts an improved Hummers method to synthesize a carboxyl-rich graphene oxide material; the method for inhibiting the escape of the unsymmetrical dimethylhydrazine in the aqueous solution based on the carboxyl-rich graphene oxide material is provided, and the unsymmetrical dimethylhydrazine leakage accident is treated by using the method, so that the maximum escape amount of unsymmetrical dimethylhydrazine gas is reduced, and more precious time is also striven for subsequent emergency rescue work; aiming at the subsequent requirements of emergency treatment, on the basis of excessively damaging the escape inhibition capability of the carboxyl-rich graphene oxide, the environment-friendly recyclable performance of the exogenously added escape inhibitor is improved by loading the ferroferric oxide magnetic material.
Description
Technical Field
The invention relates to the technical field of safety treatment of aerospace fuel, in particular to carboxyl-rich graphene oxide, a preparation method thereof, a method for adsorbing unsymmetrical dimethylhydrazine in an aqueous solution by using the carboxyl-rich graphene oxide and application of the carboxyl-rich graphene oxide.
Background
As the world-wide space launching activities become more frequent, the demands and the frequency of use of various hydrazine fuels also increase. As a hydrazine fuel widely used, unsymmetrical dimethylhydrazine (UDMH, unsymmetrical Dimethylhydrazine) has the outstanding characteristics of flammability, explosiveness, extremely toxicity, strong corrosiveness and the like, and the safety problem in a transmitting field or a storage warehouse is always highly concerned by related personnel. Among many safety accidents, leakage accidents are most interesting due to the fact that prevention difficulty is high, accident reasons are many, occurrence frequency is high and hazard is caused. Accidents show that leakage accidents of UDMH have strong randomness, burst, diversity, serious harmfulness and intractability. The existing dangerous chemical safety management theory and method cannot comprehensively estimate the reasons, types, time and places of leakage accidents, and the situation that the leakage accidents occur is not practical is completely eradicated. Therefore, when a leakage accident happens suddenly, how to adopt an effective emergency treatment mode quickly prevents or slows down the spread of toxic substances, lightens the harm caused by the accident, and strives for precious time for subsequent emergency rescue activities becomes a key point.
The existing UDMH storage places mostly select water spraying devices to deal with the leakage risk of propellants, and the device utilizes the characteristic that the UDMH is easy to dissolve in water, slows down the diffusion speed of the unsymmetrical dimethylhydrazine poison gas by a water curtain absorption method, and reduces the harm caused by leakage accidents. However, the treatment mode can lead a large amount of unsymmetrical dimethylhydrazine aqueous solution with a large volatilization area to be formed in the whole storage place, and experimental researches show that toxic substances in the aqueous solution can continuously escape into the air, pollute the surrounding environment and threaten the life health and safety of rescue workers. Therefore, the construction of a material and a method for treating the leakage accident of the unsymmetrical dimethylhydrazine and reducing the escape amount of the unsymmetrical dimethylhydrazine gas are important.
Disclosure of Invention
The invention provides graphene oxide, a preparation method thereof, a method for adsorbing the unsymmetrical dimethylhydrazine in an aqueous solution and application thereof, and aims to solve the technical problems that in the process of treating the unsymmetrical dimethylhydrazine aqueous solution in the prior art, the unsymmetrical dimethylhydrazine volatilizes to enable toxic substances to escape into the air, pollute the surrounding environment and threaten the life health safety of rescue workers; meanwhile, aiming at the realistic problem of leakage of the unsymmetrical dimethylhydrazine in water spray treatment, the escape phenomenon of the unsymmetrical dimethylhydrazine in emergency treatment is inhibited by introducing an exogenous additive.
The invention aims at providing a preparation method of graphene oxide.
The main technical scheme comprises the following steps: structural design and preparation of graphene oxide; the structural design of the graphene oxide is based on a Density Functional Theory (DFT) method; the preparation of the graphene oxide is the preparation of carboxyl-rich graphene oxide; the preparation method of the carboxyl-rich graphene oxide mainly comprises the steps of mixing natural graphite powder and concentrated sulfuric acid, adding potassium permanganate into an ice-water bath, stirring with polytetrafluoroethylene, carrying out high-temperature reaction on the graphene oxide after water treatment, adding hydrogen peroxide, carrying out suction filtration to obtain a filter cake, and stirring and dispersing to obtain a graphite oxide ink system dispersion liquid.
Further, the graphene oxide structural design based on the Density Functional Theory (DFT) method comprises performing calculation by using simulation software based on Ab-initio Simulation Package software (VASP5.4.4), wherein the Vienna Ab-initio Simulation Package software (VASP5.4.4) is existing commercially available software; and (3) calculating potential energy related to electronic exchange by adopting Generalized Gradient Approximation (GGA), and performing pseudo potential analysis by selecting Perdew-Burke-Ernzerhof (PBE).
Further, the preparation method of the carboxyl-rich graphene oxide comprises the following steps:
S101, slowly mixing 0.5 g-1.5 g of natural graphite powder and 40 mL-50 mL of concentrated sulfuric acid in a three-neck flask, and uniformly stirring;
s102, slowly adding 2.0 g-4.0 g of potassium permanganate into a three-neck flask by a spoon in a divided manner, cooling in an ice water bath, and vigorously stirring at 100-300 rpm by using a polytetrafluoroethylene stirring paddle;
s103, adding 1-3 mL of deionized water, and stirring until the graphite flakes are uniformly dispersed in the system;
s104, after the system is cooled, placing the reaction system into a constant temperature water bath device at 30-50 ℃, and stirring for 60-120 minutes at 200-400 rpm;
s105, after the medium-temperature oxidation process is finished at 30-50 ℃, slowly adding 50-150 mL deionized water into the reaction system, heating to 80-98 ℃ and continuing to react for 10-20 minutes;
s106, after the oxidation process is finished, slowly splashing the reaction liquid into a beaker containing 0.1-0.3L of deionized water, and then dropwise adding hydrogen peroxide (3-8 mL, 30%) until the suspension turns from brown to yellow;
s107, carrying out suction filtration on the suspension, and washing away residual manganese ions and potassium ions by using aqueous solution (25 mL-75 mL,1 time-3 times) diluted by hydrochloric acid in a ratio of 1:5-1:20;
s108, after the filter cake is dried, tearing off and tearing up, and stirring overnight with 0.25L-0.75L of deionized water for dispersion to obtain the oxidized stone ink system dispersion liquid.
Further, the preparation of the carboxyl-rich graphene oxide is that of the carboxyl-rich graphene oxide loaded with ferroferric oxide; the preparation method comprises the following steps:
s201, slowly mixing 0.5 g-1.5 g of natural graphite powder and 40 mL-50 mL of concentrated sulfuric acid in a three-neck flask, and uniformly stirring;
s202, slowly adding 2.0 g-4.0 g of potassium permanganate into a three-neck flask by a spoon in a divided manner, cooling in an ice water bath, and vigorously stirring at 100-300 rpm by using a polytetrafluoroethylene stirring paddle;
s203, adding 1-3 mL of deionized water, and stirring until the graphite flakes are uniformly dispersed in the system;
s204, after the system is cooled, placing the reaction system into a constant temperature water bath device at 30-50 ℃, and stirring for 60-120 minutes at 200-400 rpm;
s205, slowly adding 50-150 mL deionized water into the reaction system after the medium-temperature oxidation process at 30-50 ℃ is finished, and heating to 80-98 ℃ for continuous reaction for 10-20 minutes;
s206, after the oxidation process is finished, slowly splashing the reaction liquid into a beaker containing 0.1-0.3L of deionized water, and then dropwise adding hydrogen peroxide (3-8 mL, 30%) until the suspension turns from brown to yellow;
s207, carrying out suction filtration on the suspension, and washing out residual manganese ions and potassium ions by using aqueous solution (25 mL-75 mL,1 time-3 times) diluted by hydrochloric acid in a ratio of 1:5-1:20;
S208, after the filter cake is dried, tearing off and shredding, and stirring overnight with 0.25L-0.75L of deionized water for dispersion to obtain an oxidized stone ink system dispersion liquid;
s209, obtaining carboxyl-rich graphene oxide solid powder by adopting a freeze-drying treatment mode;
s210, a proper amount of carboxyl-rich graphene oxide is taken and mixed with 25-75 mL of ethylene glycol in advance for standby;
s211, feCl 3 ·6H 2 Adding O into the pre-prepared carboxyl-rich graphene oxide and glycol solution, and carrying out ultrasonic treatment for 2-4 hours;
s212, adding sodium acetate after ultrasonic treatment, wherein the ratio of the sodium acetate to ferric ions is 5:1-12:1;
s213, stirring by using a polytetrafluoroethylene stirring paddle at 100-300 rpm, and heating and refluxing for 8-12 h after uniform stirring;
s214, centrifuging, and then washing with pure water and ethylene glycol for 1 to 3 times;
s215, vacuum drying for 6-10 h to obtain the carboxyl-enriched graphene oxide powdery solid loaded with the ferroferric oxide.
Another object of the present invention is to provide graphene oxide.
The graphene oxide is prepared by the preparation method of the graphene oxide; the graphene oxide is carboxyl-rich graphene oxide; preferably, the carboxyl-rich graphene oxide edges are carboxyl functional groups.
Further, the STM image of the carboxyl-rich graphene oxide has obvious folds; preferably, the carboxyl-rich graphene oxide has a size distribution of 0-25 μm.
Further, the carboxyl-rich graphene oxide is ferroferric oxide-loaded carboxyl-rich graphene oxide; preferably, the ferroferric oxide loaded carboxyl group-rich graphene oxide SEM image covers spherical particles in the folds.
The invention provides a method for adsorbing the unsymmetrical dimethylhydrazine in the aqueous solution by utilizing the graphene oxide.
The graphene oxide is prepared by the preparation method of the graphene oxide; the method for adsorbing the unsymmetrical dimethylhydrazine in the aqueous solution by using the graphene oxide comprises the steps of treating the graphene oxide suspension rich in carboxyl groups to form a graphene oxide suspension rich in carboxyl groups-unsymmetrical dimethylhydrazine solution; preferably, the method of adsorbing the unsymmetrical dimethylhydrazine in the aqueous solution using graphene oxide comprises treating with a ferric oxide loaded carboxyl group rich graphene oxide suspension to form a ferric oxide loaded carboxyl group rich graphene oxide suspension-unsymmetrical dimethylhydrazine solution.
Further, the carboxyl-rich graphene oxide suspension can form a barrier film on a gas-liquid interface so as to reduce the liquid surface area of the unsymmetrical dimethylhydrazine, which can generate escape phenomenon; preferably, the ferroferric oxide loaded carboxyl-rich graphene oxide has magnetic properties, so that the magnetic recoverability can be improved.
The invention aims at providing an application of adsorbing the unsymmetrical dimethylhydrazine in the aqueous solution by utilizing graphene oxide.
Further, the application of the unsymmetrical dimethylhydrazine in the graphene oxide adsorption aqueous solution as an exogenously added escape inhibitor to leakage accident treatment; preferably, the graphene oxide is ferroferric oxide loaded carboxyl-rich graphene oxide, and the graphene oxide is used as an exogenously added escape inhibitor to increase the green recyclable performance.
Compared with the prior art, the invention provides graphene oxide, and the preparation method and application thereof, as well as a method and application for adsorbing the unsymmetrical dimethylhydrazine in the aqueous solution, which have the following beneficial effects:
1. the invention provides a graphene oxide exogenous additive structure based on a first sexual principle, which is synthesized into a carboxyl-rich graphene oxide material by adopting an improved Hummers method, so that the structural characteristics required by the exogenous additive are met, and the environmental pollution in the material synthesis process is reduced;
2. the invention provides a method for inhibiting the escape of unsymmetrical dimethylhydrazine in an aqueous solution based on a carboxyl-rich graphene oxide material, which adopts graphene oxide with a carboxyl-rich structure to treat unsymmetrical dimethylhydrazine leakage accidents, so that the maximum escape amount of unsymmetrical dimethylhydrazine gas is reduced, and more precious time is also striven for subsequent emergency rescue work;
3. According to the invention, aiming at the emergency treatment requirement, on the basis of excessively damaging the escape inhibition capability of the carboxyl-rich graphene oxide, the environment-friendly recyclable performance of the exogenously added escape inhibitor is improved by loading the ferroferric oxide magnetic material.
Drawings
Fig. 1 shows a specific model structure diagram of graphene according to an embodiment of the present invention; wherein the labeling sites in the labeling range are oxygen-containing groups of graphene;
FIG. 2 shows a unsymmetrical dimethylhydrazine slave-CH of an embodiment of the present invention 3 The direction is close to the edge of graphene oxide and-NH 2 A schematic diagram with the direction close to the edge of the graphene oxide; wherein a is a schematic diagram of adsorption of unsymmetrical dimethylhydrazine by graphene oxide containing epoxy groups; b is a schematic diagram of adsorption of the unsymmetrical dimethylhydrazine by the graphene oxide containing carbonyl; c is a schematic diagram of adsorption of the unsymmetrical dimethylhydrazine by the graphene oxide containing hydroxyl; d is a schematic diagram of adsorption of the unsymmetrical dimethylhydrazine by the graphene oxide containing carboxyl;
FIG. 3 shows a charge differential graph of adsorption of a unsymmetrical dimethylhydrazine molecule by graphene oxide containing hydroxyl and carboxyl groups according to an embodiment of the present invention; wherein a is a charge differential diagram of adsorption of a unsymmetrical dimethylhydrazine molecule by graphene oxide containing hydroxyl; b is a charge differential diagram of carboxyl-containing graphene oxide adsorbed unsymmetrical dimethylhydrazine molecules;
FIG. 4 shows a microscopic view of a carboxyl-rich graphene oxide according to an embodiment of the present invention; wherein, the graph (a) is a 40 μm Scanning Tunneling Microscope (STM) graph of the carboxyl-rich graphene oxide; (b) A 500nm Scanning Tunneling Microscope (STM) diagram of the carboxyl-rich graphene oxide; (c) Is a 200nm transmission microscope (STM) diagram of the carboxyl-rich graphene oxide; (d) Is a 100nm transmission microscope (STM) diagram of the carboxyl-rich graphene oxide;
FIG. 5 shows an XRD and Raman characterization diagram of a carboxyl-rich graphene oxide in accordance with an embodiment of the invention; wherein, (a) is XRD patterns of carboxyl-rich graphene oxide; (b) is a Raman spectra of carboxyl-rich graphene oxide map;
FIG. 6 is a graph showing the analysis results of oxygen-containing functional groups of carboxyl-rich graphene oxide according to an embodiment of the present invention; wherein, (a) is FT-IR patterns of carboxyl-rich graphene oxide; (b) Scanning a fine structure of the carboxyl-rich graphene oxide XPS C1 s with high resolution; (c) is a full spectrum scan of carboxyl-rich graphene oxide XPS;
FIG. 7 shows a schematic diagram of a suppression effect verification test apparatus in accordance with an embodiment of the present invention; 1, a first measuring port; 2. a second measurement port; 3. a third measurement port; 4. the entrance and the exit can be opened and closed;
FIG. 8 shows a graph of UDMH escape over time in three different modes of an embodiment of the present invention; wherein the concentration of UDMH is 0.2g/L, 0.5g/L and 1g/L respectively;
FIG. 9 shows a microscopic view of a carboxyl-rich graphene oxide-supported ferroferric oxide in accordance with an embodiment of the present invention; wherein, the graph (a) is a 2 mu m Scanning Tunneling Microscope (STM) graph of carboxyl-rich graphene oxide loaded ferroferric oxide; (b) 300nm Scanning Tunneling Microscope (STM) images of carboxyl-rich graphene oxide loaded ferroferric oxide; (c) A 200nm transmission microscope (STM) image of carboxyl-rich graphene oxide loaded ferroferric oxide; (d) A 100nm transmission microscope (STM) image of carboxyl-rich graphene oxide loaded ferroferric oxide;
FIG. 10 shows a graph of UDMH escape volume over time for two different treatments according to an embodiment of the present invention; wherein the UDMH concentration is 0.2g/L, 0.5g/L and 1g/L respectively.
Detailed Description
For a better understanding of the present invention, specific examples will be given to further illustrate the invention, however, it should be understood that the illustrated examples are exemplary embodiments and that the invention may be embodied in various forms and should not be limited to the examples set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
In the examples which follow, the technical means employed are conventional means well known to those skilled in the art, and the reagents and materials of the invention are commercially available or otherwise publicly available, unless otherwise indicated.
The invention is more practical than the improvement mode of enhancing the water adsorption capacity by the exogenous additive in a short time in the storage place of the large-storage-capacity unsymmetrical dimethylhydrazine, which is proved by experimental results.
The invention relies on a Lerf-Klinowski model, and utilizes a first principle to systematically study the adsorption effect of UDMH on graphene and graphene oxides with different configurations. The calculation result shows that among four oxygen-containing functional groups which may exist at the edge of the graphene oxide, the epoxy and carbonyl structures are unfavorable for the graphene oxide to adsorb the unsymmetrical dimethylhydrazine molecules, and the hydroxyl and carboxyl structures are favorable for the graphene oxide to adsorb the unsymmetrical dimethylhydrazine molecules, wherein the adsorption energy of the carboxyl is 0.532eV at most, and the charge transfer of 0.517eV occurs. And by combining the first sexual principle calculation result, the carboxyl-rich graphene oxide is prepared by adopting a green Hummers method, so that the emission of nitrogen oxides in the preparation process is reduced, and the pollution of the preparation process to the environment is reduced. The carboxyl functional groups at the edge of the graphene oxide are controllably prepared by adding a high-temperature reaction stage in the preparation process of the graphene oxide. The effectiveness of the carboxyl-rich graphene oxide in the emergency treatment of the unsymmetrical dimethylhydrazine is examined through experiments. Experimental results show that with the increase of the leakage amount of the unsymmetrical dimethylhydrazine, the effect of the carboxyl-enriched graphene oxide suspension in emergency treatment is far superior to that of pure water treatment, for example, when the solution concentration is 0.5g/L after the unsymmetrical dimethylhydrazine leakage is treated by adopting the carboxyl-enriched graphene oxide suspension, the maximum unsymmetrical dimethylhydrazine content in gas is reduced by 75%, and the early-stage remediation time is increased by 2 minutes, so that convenience is brought to follow-up leakage stopping and rescue activities.
Meanwhile, graphene oxide is a precursor of reduced graphene oxide, the quality of the reduced graphene oxide determines the quality of the reduced graphene oxide obtained later, and macro and controllable preparation of the reduced graphene oxide is an important basis and a precondition for large-scale preparation and application of the subsequent graphene material, so that preparation and structure control of the graphene oxide are always important research directions in the field of a chemical oxidation-reduction method and even the graphene material, and the graphene oxide with a carboxyl-rich structure prepared by the method further realizes the structure control of the graphene oxide.
In addition, the escape inhibitor with green recoverable performance is prepared by loading the ferroferric oxide based on a calculation result, so that the damage of the unsymmetrical dimethylhydrazine emergency treatment to ecology and environment is effectively reduced, and the economic performance of the unsymmetrical dimethylhydrazine escape inhibitor is further improved.
Example 1
In some embodiments of the present invention, a graphene oxide structural design based on a density functional theory (Density functional theory, DFT) method is provided.
Graphene Oxide (GO) is one of important graphene derivatives, and due to the coexistence of oxygen-containing functional groups and graphene structures on graphene oxide sheets, the structural characteristics can be used as an efficient adsorption material and used for detecting low-concentration gas. The electronic exchange correlation potential was calculated using generalized gradient approximation (generalized gradient approximation, GGA) with the option of performing the correlation calculation using Vienna ab-initio Simulation Package (VASP5.4.4) software. In terms of pseudopotential, perdew-Burke-Ernzerhof (PBE) with higher precision is selected. Carbon involved in modeling (2 s 2 2p 2 ) Oxygen (2 s) 2 2p 4 ) Nitrogen (2 s) 2 2p 3 ) And hydrogen (1 s) 1 ) The four elements consider 4, 6, 5 and 1 outermost valence electrons, respectively. In the charge analysis, a Mulliken analysis method is adopted to calculate the charge transfer between UDMH and different graphene oxides, and a related charge differential graph is manufactured by VESTA software. Graphene composed of 54 carbon atoms was selected as a basic structure for simulation calculation, and a specific model structure (see fig. 1). Meanwhile, as the key point of the invention is concentrated at the edge part of the graphene oxide, various oxygen-containing functional groups only exist at the edge of the model, and the oxygen-containing functional groups mainly comprise: epoxy, hydroxy, carboxyl and carbonyl.
In the process of model design, all the related structures are geometrically optimized without any symmetry limitation, the structure optimization calculation adopts plane wave cutoff energy of 500eV, atomic force convergence criterion of 1×10) -4 The energy convergence criterion for eV to ensure that the total energy of all structures is within 0.5 meV/atom. In the subsequent treatment, a Mulliken analysis method is adopted to calculate the charge transfer condition between different molecular structures. Graphene oxide models with different oxygen-containing functional groups and a unsymmetrical dimethylhydrazine molecule are firstly placed at the side length of +. >And then structural optimization is performed. The magnitude of the interaction between graphene oxide having different oxygen-containing functional groups and unsymmetrical dimethylhydrazine is calculated from the following formula:
E a ＝(E UDMH +E GO )-(E UDMH+GO )
wherein E is GO And E is UDMH For the total energy of isolated graphene oxide and unsymmetrical dimethylhydrazine, E UDNH+GO Is the total energy after adsorption of the unsymmetrical dimethylhydrazine by graphene oxide. Differential energy E a Represents adsorption energy, i.e. the energy absorbed or released by the absorption of the unsymmetrical dimethylhydrazine molecule by graphene oxide, E a The size of (2) can be used for measuring the difficulty of adsorption.
Example 2
In some embodiments of the invention, an analysis of the effect of graphene oxide adsorption to different structural donors or acceptors is provided.
The invention is carried out by E a Different precise adsorption structures are distinguished and the charge transfer is further analyzed to determine the donor or acceptor behavior of the molecules and the type of interaction force (seeTable 1).
Table 1: summary table of structural optimization results of various graphene oxides
Note that: C-C bond means bond length of carbon connecting oxygen-containing group to adjacent carbon
from-CH by means of unsym-dimethylhydrazine 3 Direction and-NH 2 Analysis of the orientation close to graphene oxide (see FIG. 2), when the graphene oxide edge is augmented with epoxy and carbonyl groups, the sp of the adjacent carbocyclic ring 2 The carbon network is destroyed and a certain local relaxation phenomenon occurs, and the C-C bond adjacent to the carbocycle is removed fromRespectively change to->And->The carbocyclic bond angles also changed to 119 ° and 117 °. But no matter whether UDMH is from-CH 3 Direction is also-NH 2 When the direction is close to the edge of the graphene oxide, the adsorption capacity of the graphene oxide with the epoxy group (shown in figure 2 a) and carbonyl group (shown in figure 2 b) on the unsymmetrical dimethylhydrazine molecules is very weak, and even a certain repulsive interaction exists, so that the two structures are not beneficial to adsorbing the unsymmetrical dimethylhydrazine molecules.
When the graphene oxide edge is added with hydroxyl functional groups (see fig. 2 c), the relaxation phenomenon of adjacent carbocycles is not obvious. The bond length of C-C isReduced to->The carbon ring bond angle was varied to 122 °. When UDMH is from-NH 2 When the direction is close to the edge of the graphene oxide with a hydroxyl structure, the graphene oxide is producedA strong adsorption effect is generated, the hydroxyl charge quantity is increased by 0.596eV, and the mutual adsorption energy reaches 0.307eV. But if when UDMH is from-CH 3 When the direction approaches, weak repulsive force is generated. This suggests that the hydroxyl functionality may enhance adsorption of the unsymmetrical dimethylhydrazine molecule but may be severely affected by the orientation of the unsymmetrical dimethylhydrazine molecule.
Example 3
In some embodiments of the invention, there is provided an adsorption effect on unsymmetrical dimethylhydrazine after adding carboxyl functional groups to the graphene oxide edge.
After adding carboxyl functional groups at the graphene oxide edge (see FIG. 2 d), the C-C bond length of the adjacent carbocycle is increased fromReduced to->The increase of the carbocyclic bond angle to 122 °, the local relaxation phenomenon is not obvious, and the sp of the graphene surface 2 The carbon network is not destroyed. At this time, 0.383eV charge is transferred from the carbon surface to the carboxyl group, and an electron-rich region is formed near the oxygen atom, which contributes to stronger interaction force with the adsorbate. Based on the barder charge calculation, whether or not the unsymmetrical dimethylhydrazine is derived from-CH 3 Direction is also-NH 2 The direction is close to the edge of the graphene oxide, the charge transfer amount between the graphene oxide with the carboxyl oxygen-containing functional group and the unsymmetrical dimethylhydrazine molecule is larger than that of the other graphene oxide structures with oxygen-containing functional groups, and the charge transfer amount reaches 0.517eV, which further indicates that the carboxyl structure is favorable for adsorbing the unsymmetrical dimethylhydrazine molecule, and the related charge difference diagrams are shown in fig. 3 (a) and fig. 3 (b).
As can be seen from the calculation results (see Table 2), no matter whether UDMH is from-CH 3 Direction is also-NH 2 When the direction is close to the edge of the graphene oxide, the adsorption effect of the graphene oxide structure with carboxyl is optimal. By combining the calculation results, when the graphene edge has more carboxyl groups, the adsorption capacity to UDMH molecules can be enhanced. If through chemistry The preparation of the carboxyl-rich graphene oxide is realized by means of the method, so that the interaction between the graphene oxide and UDMH can be greatly enhanced. Meanwhile, the research result on the oxygen-containing functional groups on the surface of the graphene shows that the epoxy structure on the surface can be converted into a hydroxyl structure along with the deepening of the oxidation degree of the graphene, and the adsorption of the unsymmetrical dimethylhydrazine molecules by the graphene oxide is facilitated.
Table 2: calculation result summary table of UDMH adsorbed by various graphene oxides
Example 4
In some embodiments of the present invention, a preparation and property evaluation of carboxyl-rich graphene oxide is provided.
The test materials used include, but are not limited to (see table 3):
table 3 pharmaceutical and instrument information
The preparation method mainly comprises the following steps: (1) Slowly mixing 1g of natural graphite powder with the fineness of 1200 meshes with 46mL of concentrated sulfuric acid in a three-neck flask and uniformly stirring; the 1200-mesh graphite powder is selected as a precursor of the material, so that more space is provided for the generation of carboxyl; (2) Slowly adding 3g of potassium permanganate into a three-neck flask by a medicine spoon in portions, cooling in an ice water bath, and vigorously stirring at 200rpm by a polytetrafluoroethylene stirring paddle; (3) Adding 2mL of deionized water, and stirring until the graphite flakes are uniformly dispersed in the system; (4) After the system is cooled, the reaction system is put into a 40 ℃ constant temperature water bath device and stirred for 90 minutes at 300 rpm; (5) After the medium-temperature oxidation process at 40 ℃ is finished, slowly adding 100mL deionized water into the reaction system, and heating to 95 ℃ for continuous reaction for 15 minutes; before graphene oxide is subjected to high-temperature reaction, adding a certain amount of water, and introducing an additional oxygen source for the reaction, so that conditions are provided for generating more carboxyl groups; (6) After the oxidation process is finished, the reaction solution is slowly reacted Pouring into a beaker with 0.5L volume and containing 0.2L deionized water, and then dropwise adding hydrogen peroxide (5 mL, 30%), wherein the color of the suspension is changed from tan to yellow; (7) Suction filtration of the suspension and washing out residual manganese and potassium ions with aqueous 1:10 diluted hydrochloric acid (50 ml,3 times); (8) After the filter cake was air dried, it was torn off and dispersed overnight with 0.5L deionized water to give a dispersion of the oxidized stone ink system. The use of sodium nitrate is removed in the preparation process, and the generation of NO due to the use of sodium nitrate in the traditional mode is further avoided 2 /N 2 O 4 The preparation method disclosed by the invention increases the environmental friendliness of material preparation, and the oxidation degree of graphene oxide can still reach relevant requirements.
Microscopic analysis of the prepared carboxyl-rich graphene oxide shows that (see fig. 4), as shown in fig. 4 (a) and fig. 4 (b), the STM image of the carboxyl-rich graphene oxide has obvious fold shape, and obvious stacking marks are generated between material sheets due to pi-pi bond effect, which is typical of the morphology structure of the graphene oxide. Statistical analysis of the carboxyl-rich graphene oxide sizes in TEM measurements, as shown in fig. 4 (c) and 4 (d), found that the carboxyl-rich graphene oxide size was mostly distributed in the range of 0-25 microns with an average size of 11.8 microns, whereas the graphene oxide size prepared by the conventional Hummers method was mostly distributed in the range of 5-90 microns. The surface structure of the carboxyl-rich graphene oxide is seriously damaged by high-temperature reaction, and the graphene oxide undergoes the oxidative cleavage or self-decomposition process of residual heptavalent manganese compound, so that the size of the carboxyl-rich graphene oxide is smaller than that of the graphene oxide prepared by a general method.
Analysis of the oxidation degree of the prepared carboxyl-rich graphene oxide shows (see fig. 5), an XRD ray diffraction pattern diagram 5 (a) of the carboxyl-rich graphene oxide shows a characteristic (001) diffraction peak of graphene oxide, namely a diffraction peak with a diffraction angle 2θ=10.9°, which corresponds to an interlayer spacing of 0.81nm, and the larger interlayer spacing is due to the fact that oxygen-containing functional groups introduced by a strong oxidation reaction prop open the interlayer spacing of original graphite. On the other hand, as is known from the Debye-Scherrer formula, the half-height width of the XRD diffraction peak is generally inversely proportional to the crystallinity of the test material. Therefore, the carboxyl-rich graphene oxide has higher oxidation degree and more oxygen-containing functional groups, so that the corresponding region with complete structure is smaller, the XRD half-peak width (0.54 DEG) is larger than that of the graphene oxide prepared by the traditional Hummers method, and the material is fully oxidized from the other side surface.
The raman spectrum of the carboxyl-rich graphene oxide is shown in fig. 5 (b). The raman spectrum of a typical graphene material has characteristic D and G peaks, wherein the G peak is a characteristic peak of graphitized carbon in the material, corresponding to the first order scattering of graphite E2G. Whereas the D peak corresponds to a structurally defective or partially irregular graphite region, caused by K phonons of A1g, and affected by the typical sp3 vibration of carbon atoms in disordered graphite. The raman spectrum of the carboxyl-rich graphene oxide shows a wide and combined D peak and G peak with the characteristics of the graphene oxide to a certain extent, wherein the D peak is strong and the G peak is wide, which indicates that the original graphite structure is quite damaged due to functionalization. Meanwhile, the D/G intensity ratio of the D peak and the G peak is also interesting for researchers because the disordered structure of the material can be effectively reflected. According to the characterization result, the D/G intensity ratio of the carboxyl-rich graphene oxide is 0.886, and the D/G intensity ratio of the graphene oxide prepared by the traditional Hummers method is generally more than 0.9, which indicates that the carboxyl-rich graphene oxide has more oxygen-containing functional groups.
In addition, the result of the C1s fine structure spectrum 6 (b) of XPS of the carboxyl-rich graphene oxide also confirms the structure, the ratio (I) of the oxidized carbon (C-O-C/C-OH, C=O and O-C=O) and the intact carbon (C-C/C=C) in the carboxyl-rich graphene oxide OC /I CC ) 2.11, which is 1.2-1.5 higher than that of graphene oxide prepared by the traditional Hummers method. Furthermore, the suspension of carboxyl-rich graphene oxide in the previous experiments was clear yellow, which also indicates that the material has been fully oxidized.
Analysis of oxygen-containing functional groups of the carboxyl-rich graphene oxide shows (see fig. 6), the type and the number of the oxygen-containing functional groups of the carboxyl-rich graphene oxide are researched through FT-IR Fourier infrared spectroscopy, and the characterization result proves that a plurality of oxygen-containing functional groups exist in the carboxyl-rich graphene oxideAnd (3) graphene oxide. For example C-O-C (. About.1000 cm) -1 )，C-O(～1230cm -1 ) O-H bending vibration (1620 cm) combined with water -1 )，C＝O(～1740-1720cm -1 ) And O-H stretching vibration (3600-3300 cm) -1 ) The specific distribution is shown in fig. 6 (a). Compared with graphene oxide prepared by the traditional Hummers method, the carboxyl-rich graphene oxide is 3600-3300cm -1 The vibration intensity in frequency is stronger, and the preparation method provided by the invention proves that the carboxyl at the edge of the graphene oxide is effectively increased. The increase in carboxyl groups also resulted in an increase in the interlayer spacing of graphene oxide, which is consistent with XRD characterization results. On the other hand, the result of full spectrum scanning by XPS 6 (C) shows that the C/O of the carboxyl group-rich graphene oxide is 2.03, which is lower than that of the C/O (2.2-2.9) prepared by the general method. At the same time, the fine structure spectrum of XPS C1s is peaked and identifies four carbon atoms, namely C-C/C=C (284.8 eV), C-O-C/C-OH (286.8 eV), C=O (287.8 eV), and the content of O-C=O (289.0 eV) also reflects the kind of functional group on the carboxyl-rich graphene oxide. The hydrophilic oxygen-containing functional groups also ensure good dispersibility of the carboxyl-rich graphene oxide in water, compared with graphene oxide prepared by the traditional Hummers method, which shows that the number of oxygen-containing functional groups on the carboxyl-rich graphene oxide is more.
The above related characteristic analysis data show that the carboxyl-rich graphene oxide prepared by the method has a typical graphene oxide morphology structure, has high-content carboxyl oxygen-containing functional groups, and accords with the structural characteristics of the graphene oxide high-efficiency adsorption unsymmetrical dimethylhydrazine molecule designed by theoretical calculation.
Example 5
In some embodiments of the invention, there is provided an inhibition and escape inhibition effect of carboxyl-rich graphene oxide on unsymmetrical dimethylhydrazine.
The inhibition test of carboxyl-rich graphene oxide on the unsymmetrical dimethylhydrazine is developed in a transparent epoxy resin experiment box with the size of 20cm multiplied by 20cm, the experiment temperature is 25 ℃, the experiment device is a closed experiment box (see figure 7), when in measurement, a first measurement port 1, a second measurement port 2 or a third measurement port 3 are opened according to measurement sites in a distinguishing way, and any one or the 3 measurement ports can be opened simultaneously; the rest of the time is closed. The openable and closable inlet and outlet 4 is opened when the unsymmetrical dimethylhydrazine and the emergency treatment liquid are placed, and is closed in the rest time. The first measuring port 1, the second measuring port 2, the third measuring port 3 and the openable and closable inlet and outlet 4 are all provided with cover bodies, and the cover bodies are in openable and closable airtight connection with the experimental device main body through pivots. In order to prevent UDMH gas from adhering to the wall surface of the experiment box and affecting the detection of the concentration of toxic gas, the wall surface of the experiment box is coated by using tinfoil. The specific experimental method comprises the following steps: for the leakage condition of the UDMH with different dosages, the same volume of pure water and carboxyl-rich graphene oxide suspension are respectively used for treatment, so that corresponding UDMH solution is formed. After the same interval time, the effectiveness of the inhibition material is verified by comparing the UDMH concentration in the air by using a handheld unsymmetrical dimethylhydrazine detector UPWS-1-10T of Hangzhou Yongjie technology Co.
The UDMH solution in the experiment was placed in a glass beaker and placed in the center of the bottom surface of an epoxy resin experiment box, the total volume of the solution was 100mL, and the surface area of the solution was 19.625cm 2 . The gas sampling is carried out by a medical 50mL syringe, and a large amount of pure water is used for flushing after each sampling, so that no UDMH gas adhesion residue exists in the syringe. Three sampling points are distributed at the left upper part, the right lower part and the top of the experimental device, so that experimental errors caused by uneven gas diffusion can be avoided. The hand-held UDMH gas detector is used for detecting the concentration of the unsymmetrical dimethylhydrazine gas, the measuring range of the instrument is 0-1000ppm, the precision is 0.1ppm, and the requirements of experimental measurement can be met. In the aspect of waste gas recovery, 10g/L oxalic acid solution is used for absorbing waste gas generated in the experimental process, so that pollution to experimental environment is avoided.
The secondary escape amount of UDMH is C UDMH,t ，mg/m 3 UDMH, which represents cumulative escape over a period of time (t), is shown. The value x is measured directly by a gas detector. To facilitate comparison of the results of subsequent experiments, the unit of measurement needs to be converted from ppm to mg/m 3 The specific conversion formula is as follows:
v in UDMH The volume of UDMH that escapes; v (V) Z The total volume of the experimental instrument; n is the amount of material escaping from the UDMH; m is M UDMH Molar mass of UDMH for escape; since the experimental temperature was 25 ℃, the gas molar volume was 24.5mol/L.
The three leakage doses of UDMH were selected to be 0.1g, 0.05g, 0.02g, limited by the experimental space and the range of the gas detection instrument. Equal volumes of pure water and carboxyl-rich graphene oxide dispersion were then added to form 100mL solutions with concentrations of 1g/L, 0.5g/L, 0.2g/L (see FIG. 8). After the equal time interval, gas samples were taken from three different detection points, respectively, and the concentration of unsymmetrical dimethylhydrazine therein was detected. After the detection experimental data results are arranged, a trend chart of the UDMH escape amount along with the time change under two different processing modes can be drawn.
As can be seen from fig. 8, there are differences in key data such as initial escape time and equilibration time of the unsymmetrical dimethylhydrazine in both treatment modes. Considering that the gas-liquid interface plays an important role in the escape process, according to the conclusion of related experimental study, the volatilization speed of the unsymmetrical dimethylhydrazine is positively related to the surface area of the liquid, and each 20cm is increased 2 The surface area and the volatilization speed of the unsymmetrical dimethylhydrazine are doubled. And the carboxyl-rich graphene oxide exists in a suspension form, and a barrier film is formed on a gas-liquid interface, so that the liquid surface area capable of generating escape phenomenon is effectively reduced. Experimental data show that the escape rate of UDMH in the carboxyl-rich graphene oxide suspension is far lower than that in pure water Degree. By comparing the initial escape time, the initial escape time of the unsymmetrical dimethylhydrazine can be delayed by using the carboxyl-rich graphene oxide dispersion liquid to treat the unsymmetrical dimethylhydrazine leakage accident. When pure water is used for treating the unsymmetrical dimethylhydrazine leakage accident, the unsymmetrical dimethylhydrazine toxic gas starts to obviously escape within one minute, and when carboxyl-rich graphene oxide dispersion liquid is used for treating the unsymmetrical dimethylhydrazine leakage accident, the escape phenomenon can be delayed to be behind 2 minutes, and the rule is not easily influenced by the unsymmetrical dimethylhydrazine leakage amount; in the aspect of balance time, because the carboxyl-rich graphene oxide can inhibit the escape of the unsymmetrical dimethylhydrazine toxic gas from the liquid, the balance time can be influenced by the inhibition effect and the unsymmetrical dimethylhydrazine leakage amount at the same time, and when the inhibition effect is obvious, the balanced state can be reached more quickly by using the carboxyl-rich graphene oxide dispersion liquid to treat the unsymmetrical dimethylhydrazine leakage accident.
The reason for the test results is that in pure water solution, the fluid element rises from the inside of the solution to the surface of the liquid at a high speed, and the residence time at the interface is long, so that the mass transfer interface can reach the saturated concentration quickly, and the initial escape time is short. In contrast, the carboxyl-rich graphene oxide is used for treating the leakage accident of the unsymmetrical dimethylhydrazine, the unsymmetrical dimethylhydrazine in the fluid microelements is continuously captured by the inhibitor in the process of rising to the surface of the liquid, so that the time for reaching the saturation concentration of the mass transfer interface is late, and the initial escape time is delayed. In terms of maximum escape, whether the accident of unsymmetrical dimethylhydrazine leakage is treated by pure water or a carboxyl-rich graphene oxide suspension, the number of free unsymmetrical dimethylhydrazine molecules in the fluid infinitesimal is directly related to the maximum escape. When free unsymmetrical dimethylhydrazine molecules are adsorbed and captured by a large amount of carboxyl-rich graphene oxide, unsymmetrical dimethylhydrazine molecules which can escape from a liquid phase are greatly reduced. Compared with graphene oxide prepared by a traditional Hummer method, the reasons for better capture effect of carboxyl-rich graphene oxide are mainly two: firstly, carboxyl groups tend to be distributed on the edges of graphene, and graphene oxide in the dispersion liquid tends to aggregate, so that the aggregation can influence the surface area between layers, but the influence on the edge area is small, and the position distribution characteristic is beneficial to capturing free UDMH molecules; secondly, due to acid-base neutralization reaction, the synergistic effect of physical acting force and chemical acting force exists between the carboxyl-rich graphene oxide and the UDMH molecules, so that the captured UDMH molecules are firmer and are not easy to escape again.
Example 6
In some embodiments of the present invention, an escape inhibitor having green recoverable properties is provided.
The preparation method mainly comprises the following steps: (1) 1g of natural graphite powder (1200 mesh) and 46mL of concentrated sulfuric acid were slowly mixed and stirred well in a three-necked flask. (2) Slowly adding 3g of potassium permanganate into a three-neck flask by a medicine spoon in portions, cooling in an ice water bath, and vigorously stirring at 200rpm by a polytetrafluoroethylene stirring paddle; (3) Adding 2mL of deionized water, and stirring until the graphite flakes are uniformly dispersed in the system; (4) After the system is cooled, the reaction system is put into a 40 ℃ constant temperature water bath device and stirred for 90 minutes at 300 rpm; (5) Slowly adding 100mL deionized water into the reaction system after the medium-temperature oxidation process at 40 ℃ is finished, and continuing to react for 15 minutes at a high temperature of 95 ℃; (6) After the oxidation process is finished, slowly pouring the reaction liquid into a beaker with 0.5L volume which is filled with 0.2L of deionized water, and then dropwise adding hydrogen peroxide (5 mL, 30%), wherein the color of the suspension is changed from tan to yellow; (7) Suction filtration of the suspension and washing out residual manganese and potassium ions with aqueous 1:10 diluted hydrochloric acid (50 ml,3 times); (8) After the filter cake is dried in the air, tearing off and shredding, and stirring overnight with 0.5L of deionized water for dispersion to obtain graphene oxide water system dispersion liquid; (9) Finally, obtaining carboxyl-rich graphene oxide solid powder by adopting a freeze-drying treatment mode; (10) Taking a proper amount of carboxyl-rich graphene oxide and 50mL of ethylene glycol, and pre-mixing for later use; (11) A certain dosage of FeCl3.6H 2 Adding O into the pre-prepared carboxyl-rich graphene oxide and glycol solution, and carrying out ultrasonic treatment for 3 hours; (12) After the ultrasonic treatment is finished, adding sodium acetate, wherein the ratio of the sodium acetate to ferric ions is 8:1; (13) Stirring by using a polytetrafluoroethylene stirring paddle at 200rpm, and heating and refluxing for 10 hours after uniform stirring; (14) Centrifuging, and then washing with pure water and ethylene glycol for multiple times; (15) Vacuum drying for 8h to obtain the load tetraoxideThe carboxyl-rich graphene oxide powder solid of the ferroferric.
Analysis of morphology and size of the carboxyl-rich graphene oxide-loaded ferroferric oxide shows (see fig. 9), and analysis of fig. 9 (a) and 9 (b) shows that when the ferroferric oxide is loaded, the carboxyl-rich graphene oxide has characteristic fold structures, which is very beneficial to covering the surface of the ferroferric oxide particles, so that a plurality of spherical particles, namely Fe, can be observed through SEM images 3 O 4 Magnetic particles. Meanwhile, since a large amount of oxygen-containing functional groups are well retained on the carbon surface during the loading of the ferroferric oxide, the composite material can still be peeled off in water and form a stable dispersion composed of a single layer sheet, and the effect is also verified in TEM fig. 9 (c) and fig. 9 (d). It can also be observed in TEM images that the carboxyl-rich graphene oxide loaded ferroferric oxide still presents a thin two-dimensional sheet microstructure with a large number of wrinkles, further indicating that the original carboxyl-rich graphene oxide microstructure is not greatly affected after the ferroferric oxide is loaded.
In order to compare and analyze the escape inhibition effect before and after loading, the experimental environment and equipment are consistent with the selection of the carboxyl-rich graphene oxide. In the measurement mode, after the equal time interval, gas sampling is carried out from three different detection points respectively, the concentration of the unsymmetrical dimethylhydrazine in the gas is detected, and finally, a trend chart of the UDMH escape amount with time is drawn (see figure 10). The escape inhibition effect of the carboxyl-rich graphene oxide loaded ferroferric oxide and the carboxyl-rich graphene oxide exogenous additives is compared, so that the key data of the unsymmetrical dimethylhydrazine such as the balance time and the like are different in the two treatment modes. In the aspect of initial escape time, the characteristic of escape phenomenon delay does not change greatly, and the carboxyl-rich graphene oxide loaded with ferroferric oxide or the carboxyl-rich graphene oxide before doping modification can delay the escape phenomenon, and the rule is not easily influenced by the leakage amount of the unsymmetrical dimethylhydrazine; in the aspect of balance, due to the double influences of the inhibition effect and the leakage amount of the unsymmetrical dimethylhydrazine, under the condition of the same leakage dosage, the carboxyl-rich graphene oxide loaded with the ferroferric oxide is similar to the carboxyl-rich graphene oxide in balance time, but the magnetic recoverability is improved on the basis of the original material.
The foregoing is merely exemplary of the present application and is not intended to limit the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the application are to be included in the scope of the claims of the present application.
Claims (9)
1. The preparation method of the graphene oxide is characterized by comprising the following steps of: structural design and preparation of graphene oxide;
the structural design of the graphene oxide is based on a density functional theory method;
the preparation of the graphene oxide is that of carboxyl-rich graphene oxide;
the graphene oxide structure design based on the density functional theory method comprises the steps of calculating by using simulation software, adopting generalized gradient approximation to calculate electronic exchange related potential energy, and selecting Perdew-Burke-Ernzenzerhof for pseudo potential analysis;
the magnitude of the interaction between graphene oxide having different oxygen-containing functional groups and unsymmetrical dimethylhydrazine is calculated from the following formula:
E a ＝(E UDMH +E GO )-(E UDMH+GO )
wherein E is GO And E is UDMH For the total energy of isolated graphene oxide and unsymmetrical dimethylhydrazine, E UDNH+GO Is the total energy after the graphene oxide adsorbs the unsymmetrical dimethylhydrazine; differential energy E a Represents adsorption energy, i.e. the energy absorbed or released by the absorption of the unsymmetrical dimethylhydrazine molecule by graphene oxide, E a The size of the adsorption layer can be used for measuring the difficulty of adsorption;
the preparation method of the carboxyl-rich graphene oxide mainly comprises the steps of mixing natural graphite powder and concentrated sulfuric acid, adding potassium permanganate into an ice-water bath, stirring with polytetrafluoroethylene, carrying out high-temperature reaction on the graphene oxide after water treatment, adding hydrogen peroxide, carrying out suction filtration to obtain a filter cake, and stirring and dispersing to obtain a graphite oxide ink system dispersion liquid.
2. The method for preparing graphene oxide according to claim 1, wherein the preparing step of the carboxyl-rich graphene oxide comprises:
s101, slowly mixing 0.5 g-1.5 g of natural graphite powder and 40 mL-50 mL of concentrated sulfuric acid in a three-neck flask, and uniformly stirring;
s102, slowly adding 2.0 g-4.0 g of potassium permanganate into a three-neck flask by a spoon in a divided manner, cooling in an ice water bath, and vigorously stirring at 100-300 rpm by using a polytetrafluoroethylene stirring paddle;
s103, adding 1-3 mL of deionized water, and stirring until the graphite flakes are uniformly dispersed in the system;
s104, after the system is cooled, placing the reaction system into a constant temperature water bath device at 30-50 ℃, and stirring for 60-120 minutes at 200-400 rpm;
S105, after the medium-temperature oxidation process is finished at 30-50 ℃, slowly adding 50-150 mL deionized water into the reaction system, heating to 80-98 ℃ and continuing to react for 10-20 minutes;
s106, after the oxidation process is finished, slowly splashing the reaction liquid into a beaker containing 0.1-0.3L of deionized water, and then dropwise adding 3-8 mL of 30% hydrogen peroxide until the suspension turns from brown to yellow;
s107, carrying out suction filtration on the suspension, and washing for 1 to 3 times by using 25 to 75mL of aqueous solution diluted by hydrochloric acid in a ratio of 1:5 to 1:20 to wash residual manganese ions and potassium ions;
s108, after the filter cake is dried, tearing off and tearing up, and stirring overnight with 0.25L-0.75L of deionized water for dispersion to obtain the oxidized stone ink system dispersion liquid.
3. The method for preparing graphene oxide according to claim 2, wherein the preparation of the carboxyl-rich graphene oxide is the preparation of the ferroferric oxide-loaded carboxyl-rich graphene oxide; the preparation method comprises the following steps:
s201, slowly mixing 0.5 g-1.5 g of natural graphite powder and 40 mL-50 mL of concentrated sulfuric acid in a three-neck flask, and uniformly stirring;
s202, slowly adding 2.0 g-4.0 g of potassium permanganate into a three-neck flask by a spoon in a divided manner, cooling in an ice water bath, and vigorously stirring at 100-300 rpm by using a polytetrafluoroethylene stirring paddle;
S203, adding 1-3 mL of deionized water, and stirring until the graphite flakes are uniformly dispersed in the system;
s204, after the system is cooled, placing the reaction system into a constant temperature water bath device at 30-50 ℃, and stirring for 60-120 minutes at 200-400 rpm;
s205, slowly adding 50-150 mL deionized water into the reaction system after the medium-temperature oxidation process at 30-50 ℃ is finished, and heating to 80-98 ℃ for continuous reaction for 10-20 minutes;
s206, after the oxidation process is finished, slowly splashing the reaction liquid into a beaker containing 0.1-0.3L of deionized water, and then dropwise adding 3-8 mL of 30% hydrogen peroxide until the suspension turns from brown to yellow;
s207, carrying out suction filtration on the suspension, and washing for 1 to 3 times by using 25 to 75mL of aqueous solution diluted by hydrochloric acid in a ratio of 1:5 to 1:20 to wash residual manganese ions and potassium ions;
s208, after the filter cake is dried, tearing off and shredding, and stirring overnight with 0.25L-0.75L of deionized water for dispersion to obtain an oxidized stone ink system dispersion liquid;
s209, obtaining carboxyl-rich graphene oxide solid powder by adopting a freeze-drying treatment mode;
s210, a proper amount of carboxyl-rich graphene oxide is taken and mixed with 25-75 mL of ethylene glycol in advance for standby;
S211, feCl 3 ·6H 2 Adding O into the pre-prepared carboxyl-rich graphene oxide and glycol solution, and carrying out ultrasonic treatment for 2-4 hours;
s212, adding sodium acetate after ultrasonic treatment, wherein the ratio of the sodium acetate to ferric ions is 5:1-12:1;
s213, stirring by using a polytetrafluoroethylene stirring paddle at 100-300 rpm, and heating and refluxing for 8-12 h after uniform stirring;
s214, centrifuging, and then washing with pure water and ethylene glycol for 1 to 3 times;
s215, vacuum drying for 6-10 h to obtain the carboxyl-enriched graphene oxide powdery solid loaded with the ferroferric oxide.
4. Graphene oxide, characterized in that the graphene oxide is prepared according to the preparation method of the graphene oxide according to any one of claims 1 to 3; the graphene oxide is carboxyl-rich graphene oxide; and the edge of the carboxyl-rich graphene oxide is a carboxyl functional group.
5. The graphene oxide of claim 4, wherein the carboxyl-rich graphene oxide has a significant pucker shape in the STM image; the size distribution of the carboxyl-rich graphene oxide is 0-25 mu m.
6. The graphene oxide of claim 5, wherein the carboxyl-rich graphene oxide is a ferroferric oxide-loaded carboxyl-rich graphene oxide; the ferroferric oxide loaded carboxyl-rich graphene oxide SEM image covers spherical particles in the folds.
7. A method for adsorbing unsymmetrical dimethylhydrazine in an aqueous solution by using graphene oxide, which is characterized in that the graphene oxide is prepared by the preparation method of the graphene oxide according to any one of claims 1 to 3; the method for adsorbing the unsymmetrical dimethylhydrazine in the aqueous solution by using the graphene oxide comprises the steps of treating the aqueous solution by using a carboxyl-rich graphene oxide suspension to form a carboxyl-rich graphene oxide suspension-unsymmetrical dimethylhydrazine solution; the method for adsorbing the unsymmetrical dimethylhydrazine in the aqueous solution by using the graphene oxide comprises the step of treating by using a loaded ferroferric oxide carboxyl-rich graphene oxide suspension to form a loaded ferroferric oxide carboxyl-rich graphene oxide suspension-unsymmetrical dimethylhydrazine solution.
8. The method of adsorbing unsymmetrical dimethylhydrazine in an aqueous solution of graphene oxide according to claim 7, wherein the carboxyl group-rich graphene oxide suspension can form a barrier film on a gas-liquid interface to reduce the liquid surface area of unsymmetrical dimethylhydrazine that can generate escape phenomenon; the loaded ferroferric oxide carboxyl-rich graphene oxide has magnetic performance, and can increase magnetic recoverability.
9. An application of utilizing graphene oxide to adsorb unsymmetrical dimethylhydrazine in an aqueous solution is characterized in that the graphene oxide is prepared by the preparation method of the graphene oxide according to any one of claims 1 to 3; the application of the unsymmetrical dimethylhydrazine in the graphene oxide adsorption aqueous solution as an exogenously added escape inhibitor in leakage accident treatment; the graphene oxide is carboxyl-rich graphene oxide loaded with ferroferric oxide, and the carboxyl-rich graphene oxide is taken as an exogenously added escape inhibitor to increase the green recyclable performance.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709057A (en) * | 2012-05-23 | 2012-10-03 | 天津大学 | Method for preparing composite of grapheme with different oxidation degrees and manganese dioxide |
| CN106084232A (en) * | 2016-07-27 | 2016-11-09 | 齐齐哈尔大学 | The preparation of fluorescence magnetic graphite oxide thiazolinyl 4 chlorophenol molecularly imprinted polymer and application |
| CN106563477A (en) * | 2016-10-25 | 2017-04-19 | 湖南大学 | Ternary composite visible light photocatalyst, preparation method and application thereof |
| CN114307980A (en) * | 2021-12-27 | 2022-04-12 | 中国人民解放军火箭军工程大学 | Composite material and composition for treating unsymmetrical dimethylhydrazine pollutants, and treatment method and experimental method thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709057A (en) * | 2012-05-23 | 2012-10-03 | 天津大学 | Method for preparing composite of grapheme with different oxidation degrees and manganese dioxide |
| CN106084232A (en) * | 2016-07-27 | 2016-11-09 | 齐齐哈尔大学 | The preparation of fluorescence magnetic graphite oxide thiazolinyl 4 chlorophenol molecularly imprinted polymer and application |
| CN106563477A (en) * | 2016-10-25 | 2017-04-19 | 湖南大学 | Ternary composite visible light photocatalyst, preparation method and application thereof |
| CN114307980A (en) * | 2021-12-27 | 2022-04-12 | 中国人民解放军火箭军工程大学 | Composite material and composition for treating unsymmetrical dimethylhydrazine pollutants, and treatment method and experimental method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Selectivity Tuning of Graphene Oxide Based Reliable Gas Sensor Devices by Tailoring the Oxygen Functional Groups: A DFT Study Based Approach;I. Maity等;《IEEE TRANSACTIONS ON DEVICE AND MATERIALS RELIABILITY》;第17卷(第4期);第738-745页 * |
| 赵艳红 著.《石墨烯与过渡金属氧化物复合材料制备》.哈尔滨工业大学出版社,2021,第56-61页. * |
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