CN114889175A - Preparation and application of modified graphene oxide/hydroxyapatite nanowire composite paper - Google Patents
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Abstract
The invention discloses preparation of modified graphene oxide/hydroxyapatite nanowire composite paper and application of the modified graphene oxide/hydroxyapatite nanowire composite paper in fire early warning. The modified graphene oxide/hydroxyapatite nanowire composite paper prepared by the invention has quick fire response performance and good structural stability, so that the modified graphene oxide/hydroxyapatite nanowire composite paper can be connected with devices such as a low-voltage direct-current power supply and an early warning lamp in series to form a set of fire early warning device, the defects of the traditional smoke alarm sensor and the traditional infrared alarm sensor in use are overcome, the fire risk is effectively prevented, and the generation of fire and the loss caused by the fire are reduced or even avoided.
Description
Technical Field
The invention belongs to the field of functional materials, and particularly relates to preparation of modified graphene oxide/hydroxyapatite nanowire composite paper and application of the modified graphene oxide/hydroxyapatite nanowire composite paper in fire early warning.
Background
In recent years, fire accidents occur frequently, and the frequent fire accidents cause huge economic loss and casualties to the society. Therefore, how to prevent and reduce fire accidents has gradually attracted a great deal of attention. The fire early warning sensors commonly used in the market at present mainly comprise smoke sensors, infrared sensors and the like. The smoke sensor can work only when smoke reaches a certain concentration after a fire disaster occurs, which causes serious early warning delay; the infrared sensor is easily affected by other heat sources, distances, dust, same frequency interference, installation positions, angles and the like, the anti-interference capability is poor, and the false alarm ratio of the early infrared sensor is as high as 7.5. Therefore, the development of a rapid and reliable fire early warning system is urgently needed.
Graphene oxide is a novel fire early warning sensor, and the working mechanism thereof is as follows: the oxygen-containing groups (carboxyl, hydroxyl, epoxy and the like) on the surface of the graphene oxide destroy the conjugated structure of the graphene, so that the graphene oxide is electrically insulating at normal temperature, the oxygen-containing groups on the surface of the graphene oxide can be eliminated in the high-temperature environment of a fire, the conductivity is obviously improved, and the conversion speed from the insulating property to the conductivity is very high (the response time is less than 5 seconds). However, the graphene oxide-based fire alarm device has two disadvantages: (1) the thermal stability and fire resistance of the graphene oxide are poor, so that the fire early warning time is short; (2) the graphene oxide has poor structural stability after combustion and poor reliability of fire early warning. In order to solve the problems, the invention develops the modified graphene oxide/hydroxyapatite nanowire composite paper, which can solve the difficulties of practical application of the existing graphene oxide fire hazard early warning device and has important scientific significance and application value.
Disclosure of Invention
The invention aims to provide a preparation method of modified graphene oxide/hydroxyapatite nanowire composite paper and application of the modified graphene oxide/hydroxyapatite nanowire composite paper in a fire early warning system, aiming at the existing defects.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of modified graphene oxide/hydroxyapatite nanowire composite paper comprises the following steps:
(1) placing graphene oxide in water, and ultrasonically stripping for 20-60 min to obtain graphene oxide dispersion liquid with the concentration of 1 mg/mL;
(2) adding 1-2mg/mL of organic molecule solution and 1-2.5 mg/mL of hydroxyapatite nanowire solution into the prepared graphene oxide dispersion liquid, heating in an oil bath at 50-100 ℃, and stirring for 1-6 h until the solutions are fully mixed;
(3) and standing and cooling the mixed solution to room temperature, and drying after vacuum-assisted suction filtration to obtain the independent self-supporting modified graphene oxide/hydroxyapatite nanowire composite paper.
The raw materials comprise the following components in parts by weight: 0.5-2 parts of organic molecules, 1 part of graphene oxide and 2-8 parts of hydroxyapatite nanowires. The graphene oxide is single-layer graphene oxide. The organic molecule is branched polyethyleneimine or deoxyribonucleic acid.
The drying temperature in the step (3) is 30-100 ℃, and the drying time is 0.5-12 h.
The modified graphene oxide/hydroxyapatite nanowire composite paper prepared by the method can be used for preparing a fire early warning system, and specifically, the modified graphene oxide/hydroxyapatite nanowire composite paper is used as an inductor and is connected with devices such as a low-voltage direct-current power supply (4V) and an early warning lamp in series through a copper wire to form a set of fire early warning device.
The invention has the advantages of
(1) In the invention, amino on a molecular chain of modified organic molecule branched polyethyleneimine and carboxyl, epoxy and the like on the surface of graphene oxide are subjected to nucleophilic substitution reaction; the sodium phosphate group in the structure of the modified organic molecule deoxyribonucleic acid can be used as a nucleophilic intermediate in organic reaction, and the disentangled single-chain deoxyribonucleic acid can be assembled on the graphene oxide nanosheet layer through hydrogen bonds and pi-pi interaction, so that the thermal stability and the flame retardance of the modified graphene oxide are obviously improved, and the built fire early warning device can exert an early warning effect for a long time.
(2) The hydroxyapatite nanowire is intrinsically non-combustible and can be used as a stable framework; and the hydroxyapatite nanowire surface is negatively charged, and can be well combined with the modified graphene oxide with the positively charged surface through electrostatic interaction. In the flame combustion process, due to the excellent thermal stability of the hydroxyapatite nanowires, the structure of the modified graphene oxide/hydroxyapatite nanowire composite paper can be kept stable, and the mechanical property is not remarkably reduced, so that the stable operation of the fire early warning device is ensured.
(3) On one hand, the graphene oxide is modified by using organic molecules, so that the thermal stability of the graphene oxide is improved, and the fire early warning duration of the prepared fire early warning device is prolonged; on the other hand, hydroxyapatite nanowires are used as a stable framework to ensure the structural stability and the mechanical strength of the prepared fire early warning device in flame, so that the difficulty in practical application of the existing graphene oxide fire early warning device is solved.
Drawings
Fig. 1 is an SEM comparison of hydroxyapatite nanowires, graphene oxide, and graphene oxide/hydroxyapatite nanowire composite paper prepared in examples 2 and 3 and comparative example 1;
FIG. 2 is a FTIR comparison graph of branched polyethyleneimine modified graphene oxide composite paper prepared in comparative example 2 and deoxyribonucleic acid modified graphene oxide composite paper prepared in comparative example 3;
fig. 3 is a graph showing a comparison of vertical combustion experiments between the modified graphene oxide/hydroxyapatite nanowire composite paper prepared in example 4 and the unmodified graphene oxide/hydroxyapatite nanowire composite paper prepared in comparative example 1;
fig. 4 is a comparison graph of mechanical properties and flexibility of the modified graphene oxide/hydroxyapatite nanowire composite paper prepared in example 4 before and after combustion;
fig. 5 is a schematic connection diagram of a fire early warning device constructed by using modified graphene oxide/hydroxyapatite nanowire composite paper;
fig. 6 is a comparison graph of the fire early warning duration of the modified graphene oxide/hydroxyapatite nanowire composite paper prepared in examples 2, 3 and 5 and the unmodified graphene oxide/hydroxyapatite nanowire composite paper prepared in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
Preparing hydroxyapatite nano-wires:
1) stirring and mixing 64 g of oleic acid and 84 g of ethanol uniformly;
2) adding 120 mL of aqueous solution containing 1.764 g of calcium chloride dihydrate, stirring for 20 min, adding 120 mL of aqueous solution containing 6.000 g of sodium hydroxide, stirring for 20 min, adding 60 mL of aqueous solution containing 1.685 g of sodium dihydrogen phosphate dihydrate, and stirring for 20 min;
3) transferring the mixed solution into a reaction kettle, sealing, heating to 180 ℃, and preserving heat for 24 hours;
4) and cooling the obtained product to room temperature, respectively washing the product for multiple times by using deionized water and hot ethanol, and storing the obtained hydroxyapatite nanowire in the deionized water.
Example 2
Preparing branched polyethyleneimine modified graphene oxide/hydroxyapatite nanowire composite paper:
1) measuring 5 mg of graphene oxide, placing the graphene oxide in water, and ultrasonically stripping for 20 min to obtain a graphene oxide dispersion liquid with the concentration of 1 mg/mL;
2) dispersing 10 mg of branched polyethyleneimine in water to prepare a branched polyethyleneimine solution of 2mg/mL, then adding the branched polyethyleneimine solution into the prepared graphene oxide dispersion solution, heating by using an oil bath at 70 ℃, and stirring for 2 hours by magnetic force to fully mix the branched polyethyleneimine solution and the graphene oxide dispersion solution uniformly;
3) dispersing 30 mg of hydroxyapatite nano-wire in water to prepare 2mg/mL hydroxyapatite nano-wire solution, then adding the hydroxyapatite nano-wire solution into the mixed solution, continuing to heat the mixed solution in an oil bath at 70 ℃ and stirring the mixed solution by magnetic force for 2 hours to fully mix the mixed solution to be uniform;
3) and standing and cooling the mixed solution to room temperature, performing vacuum-assisted suction filtration, and drying in an oven at 60 ℃ for 0.5 h to obtain the independent self-supporting branched polyethyleneimine modified graphene oxide/hydroxyapatite nanowire composite paper.
Example 3
Preparing deoxyribonucleic acid modified graphene oxide/hydroxyapatite nanowire composite paper:
1) measuring 10 mg of graphene oxide, placing the graphene oxide in water, and ultrasonically stripping for 20 min to obtain a graphene oxide dispersion liquid with the concentration of 1 mg/mL;
2) dispersing 10 mg of deoxyribonucleic acid into a tris buffer solution to prepare a 1 mg/mL deoxyribonucleic acid solution, heating the solution in an oil bath at the temperature of 98 ℃ and magnetically stirring the solution for 1 hour to obtain a single-stranded deoxyribonucleic acid solution, adding the prepared graphene oxide dispersion solution, continuing heating the solution in the oil bath at the temperature of 98 ℃ and magnetically stirring the solution for 1 hour to fully mix the solution to be uniform;
2) dispersing 40 mg of hydroxyapatite nanowire in water to prepare 2mg/mL hydroxyapatite nanowire solution, adding the hydroxyapatite nanowire solution into the mixed solution, continuously heating the mixed solution in an oil bath at 98 ℃ and stirring the mixed solution by magnetic force for 1 hour to fully mix the mixed solution to be uniform;
3) and standing and cooling the mixed solution to room temperature, performing vacuum-assisted suction filtration, and drying in an oven at 60 ℃ for 0.5 h to obtain the independent self-supporting deoxyribonucleic acid modified graphene oxide/hydroxyapatite nanowire composite paper.
Example 4
Preparing branched polyethyleneimine modified graphene oxide/hydroxyapatite nanowire composite paper:
1) measuring 5 mg of graphene oxide, placing the graphene oxide in water, and ultrasonically stripping for 20 min to obtain a graphene oxide dispersion liquid with the concentration of 1 mg/mL;
2) dispersing 20 mg of branched polyethyleneimine into water to prepare a branched polyethyleneimine solution of 2mg/mL, then adding the branched polyethyleneimine solution into the prepared graphene oxide dispersion solution, heating by using an oil bath at 70 ℃, and stirring for 2 hours by magnetic force to fully mix the branched polyethyleneimine solution and the graphene oxide dispersion solution uniformly;
2) dispersing 30 mg of hydroxyapatite nano-wire in water to prepare 2mg/mL hydroxyapatite nano-wire solution, then adding the hydroxyapatite nano-wire solution into the mixed solution, continuing to heat the mixed solution in an oil bath at 70 ℃ and stirring the mixed solution by magnetic force for 2 hours to fully mix the mixed solution to be uniform;
3) and standing and cooling the mixed solution to room temperature, performing vacuum-assisted suction filtration, and drying in an oven at 60 ℃ for 0.5 h to obtain the independent self-supporting branched polyethyleneimine modified graphene oxide/hydroxyapatite nanowire composite paper.
Example 5
Preparing deoxyribonucleic acid modified graphene oxide/hydroxyapatite nanowire composite paper:
1) measuring 10 mg of graphene oxide, placing the graphene oxide in water, and ultrasonically stripping for 20 min to obtain a graphene oxide dispersion liquid with the concentration of 1 mg/mL;
2) dispersing 20 mg of deoxyribonucleic acid into a tris buffer solution to prepare a 1 mg/mL deoxyribonucleic acid solution, heating the solution in an oil bath at the temperature of 98 ℃ and magnetically stirring the solution for 1 hour to obtain a single-stranded deoxyribonucleic acid solution, adding the prepared graphene oxide dispersion solution, continuing heating the solution in the oil bath at the temperature of 98 ℃ and magnetically stirring the solution for 1 hour to fully mix the solution to be uniform;
2) dispersing 40 mg of hydroxyapatite nano-wire in water to prepare 2mg/mL hydroxyapatite nano-wire solution, then adding the hydroxyapatite nano-wire solution into the mixed solution, continuing to heat in oil bath at 98 ℃ and stirring by magnetic force for 1 h to fully mix the hydroxyapatite nano-wire solution to be uniform.
3) And standing and cooling the mixed solution to room temperature, performing vacuum-assisted suction filtration, and drying in an oven at 60 ℃ for 0.5 h to obtain the independent self-supporting deoxyribonucleic acid modified graphene oxide/hydroxyapatite nanowire composite paper.
Comparative example 1
Preparing unmodified graphene oxide/hydroxyapatite nanowire composite paper:
1) measuring 5 mg of graphene oxide, placing the graphene oxide in water, and ultrasonically stripping for 20 min to obtain a graphene oxide dispersion liquid with the concentration of 1 mg/mL;
2) dispersing 30 mg of hydroxyapatite nanowire in water to prepare 2mg/mL hydroxyapatite nanowire solution, then adding the hydroxyapatite nanowire solution into the graphene oxide dispersion liquid, heating the solution in an oil bath at 70 ℃, and stirring the solution by magnetic force for 2 hours to fully mix the solution to be uniform;
2) and standing and cooling the mixed solution to room temperature, carrying out vacuum-assisted suction filtration, and drying in a 60-DEG C oven for 0.5 h to obtain the unmodified graphene oxide/hydroxyapatite nanowire composite paper.
Comparative example 2
Preparing branched polyethyleneimine modified graphene oxide composite paper:
1) measuring 5 mg of graphene oxide, placing the graphene oxide in water, and ultrasonically stripping for 20 min to obtain a graphene oxide dispersion liquid with the concentration of 1 mg/mL;
2) dispersing 10 mg of branched polyethyleneimine into water to prepare a 2mg/mL branched polyethyleneimine aqueous solution, then adding the branched polyethyleneimine aqueous solution into the prepared graphene oxide dispersion liquid, heating the solution in an oil bath at 70 ℃ and stirring the solution for 2 hours by magnetic force to fully mix the solution uniformly;
2) and standing and cooling the mixed solution to room temperature, performing vacuum-assisted suction filtration, and drying in a 60-DEG C oven for 0.5 h to obtain the branched polyethyleneimine-modified graphene oxide composite paper.
Comparative example 3
Preparing deoxyribonucleic acid modified graphene oxide composite paper:
1) measuring 10 mg of graphene oxide, placing the graphene oxide in water, and ultrasonically stripping for 20 min to obtain a graphene oxide dispersion liquid with the concentration of 1 mg/mL;
2) dispersing 10 mg of deoxyribonucleic acid into a tris buffer solution to prepare a 1 mg/mL deoxyribonucleic acid solution, heating the solution in an oil bath at the temperature of 98 ℃ and magnetically stirring the solution for 1 hour to obtain a single-stranded deoxyribonucleic acid solution, adding the prepared graphene oxide dispersion solution, continuing heating the solution in the oil bath at the temperature of 98 ℃ and magnetically stirring the solution for 1 hour to fully mix the solution to be uniform;
2) and standing and cooling the mixed solution to room temperature, performing vacuum-assisted suction filtration, and drying in a 60 ℃ oven for 0.5 h to obtain the deoxyribonucleic acid modified graphene oxide composite paper.
Application test example
1) The samples prepared in examples 1 to 3 and comparative example 1 were subjected to SEM test to observe the microstructures thereof, and the results are shown in fig. 1.
2) FTIR tests were performed on the branched polyethyleneimine-modified graphene oxide composite paper prepared in comparative example 2 and the deoxyribonucleic acid-modified graphene oxide composite paper prepared in comparative example 3, and the results are shown in FIG. 2.
3) The branched polyethyleneimine-modified graphene oxide/hydroxyapatite nanowire composite paper prepared in example 4 and comparative example 1 were subjected to a vertical combustion experiment test, and the result is shown in fig. 3.
4) The branched polyethyleneimine-modified graphene oxide/hydroxyapatite nanowire composite paper prepared in example 4 was subjected to mechanical property test and flexibility test before and after combustion, and the results are shown in fig. 4.
5) The fire early warning device is constructed by using the modified graphene oxide/hydroxyapatite nanowire composite paper, and the connection schematic diagram is shown in fig. 5.
6) The branched polyethyleneimine modified graphene oxide/hydroxyapatite nanowire composite paper prepared in examples 2, 3 and 5 and comparative example 1 were subjected to a fire early warning work test, and the results are shown in fig. 6.
Analysis of results
As is evident from fig. 1, Hydroxyapatite (HAP) nanowires self-assemble into bundles and intertwine with each other in a nearly parallel manner (a); graphene Oxide (GO) is an ultra-thin wrinkled film with warping (b) at the edges; gaps among the hydroxyapatite nanowires in the modified graphene oxide/hydroxyapatite nanowire composite paper are covered or filled by the folded graphene oxide nanosheets to form a multilayer three-dimensional structure (c, d) similar to 'steel bar-concrete', and the closely-contacted network is helpful for forming a continuous conductive path and improving the structural stability, so that fire early warning is quickly and continuously sent out. The unmodified graphene oxide/hydroxyapatite nanowire composite paper prepared in comparative example 1 can obviously observe that a large gap exists between the hydroxyapatite nanowires and the graphene oxide thin films which are arranged in parallel, and a part of the nanowires are short and broken (e).
Fig. 2 shows the FTIR spectrum change before and after modification of graphene oxide with branched polyethyleneimine and deoxyribonucleic acid molecules. As can be seen from the figure, the FTIR spectrum of the graphene oxide is 1736 cm −1 Has a C = O expansion vibration peak and is 1252 cm −1 And 1052 cm −1 Respectively is a stretching vibration peak of C-O in epoxy resin and alkoxy; furthermore, 1621 cm −1 The band at (a) is due to vibration of C = C in adsorbed water molecules or aromatics. And branched polyethyleneimine modified graphene oxide (PEI/GO) is at 2927 and 2852 cm −1 The absorption band of (b) corresponds to-CH 2 Symmetric and asymmetric stretching vibration of-1582 cm −1 Bands of (a) are attributed to N-H in-plane bending vibration of secondary amine groups, indicating that some primary amine groups are converted to secondary amine groups; 1638 cm −1 And 1380 cm −1 The new bands at (A) correspond to amide (O = C-NH) and C-N bond, respectively, while the absorption band intensity of C = O and C-O in epoxy resin is significantly reduced. These changes indicate that amine groups in PEI molecules are successfully grafted on the surface of GO through a ring-opening reaction with epoxy groups of GO and a covalent bond between amine groups of PEI and carboxyl groups of GO. Deoxyribonucleic acid modified graphene oxide (DNA/GO) is 3187 cm −1 Peaks at 2982 cm associated with DNA functionalized hydroxyl and amine groups −1 The absorption band of (b) corresponds to-CH 2 Symmetric stretching vibration peak of-1629 cm −1 And 1552 cm −1 Bands of (a) are a stretching vibration peak assigned to P = O and a vibration peak assigned to C = N in the DNA molecule, respectively, which preliminarily indicate that a characteristic peak of DNA exists in the DNA/GO structure; at the same time, 1296 cm −1 The band at (B) corresponds to stretching vibration of P-O bond, and shifts to lower wave number (from 1052 cm) relative to the stretching vibration peak of C-O bond in GO −1 Moved to 1040 cm −1 ) The fact that most of characteristic peaks of oxygen groups of the GO modified by DNA are reserved proves that the GO modified by DNA is successfully prepared, and the improvement of fire early warning performance is explained from the level of molecular structureFor the reason.
From fig. 3, it can be found that when the unmodified graphene oxide/hydroxyapatite nanowire composite paper is exposed to flame, it rapidly changes from black to white, which is due to the decomposition of GO nanosheets in the flame, and the remaining white substrate is HAP framework (a), indicating that the HAP nanowire has higher thermal stability. And the branched polyethyleneimine modified graphene oxide/hydroxyapatite nanowire composite paper can keep the original shape in the combustion process without ignition (b). Even after 28 seconds, only a very small amount of the branched polyethyleneimine-modified graphene oxide structure was destroyed. The result shows that the composite paper prepared by modifying the graphene oxide with the branched polyethyleneimine molecules can play a good flame retardant role, and the defect of poor fire resistance of the graphene oxide is greatly overcome, so that the service life of the graphene oxide in a fire early warning system is further prolonged.
As shown in FIG. 4, the average tensile strength and Young's modulus of the composite paper before burning were 3.23. + -. 0.31 MPa and 226.56. + -. 10.53 MPa (a), respectively, and the tensile strength and Young's modulus of the composite paper after flame treatment were 2.5. + -. 0.44 MPa and 165.08. + -. 19.05 MPa, respectively, and the tensile strength and Young's modulus were only decreased by 22.6% and 27.1% (b), respectively. The composite paper before burning has good flexibility, can bear the physical deformation of folding (c), and the composite paper after burning still has higher flexibility, and keeps the structural integrity without being damaged (d), which proves that the composite paper prepared by the invention has better structural stability in a fire early warning device.
As can be seen from fig. 6, the prepared composite paper is connected in series with devices such as a low-voltage direct-current power supply (4V) and an early warning lamp through copper wires to form a set of fire early warning device, and tests show that the unmodified graphene oxide/hydroxyapatite nanowire composite paper of the comparative example 1 can only emit weak light within 8 s and stop working within about 30 s (a); meanwhile, the GO nano-sheets can be clearly observed to be heated and decomposed in flame, and the rest white substrate is a flame-retardant HAP nano-wire framework, so that a conductive path is easily cut off, and discontinuous fire early warning is caused. In the embodiment 2, when the branched polyethyleneimine modified graphene oxide/hydroxyapatite nanowire composite paper is attacked by flame, the warning lamp can immediately give out early warning. Its rapid response to a flame can be attributed to the more compact and smoother surface forming a continuous conductive path; on the other hand, the thermal stability of the branched polyethyleneimine modified graphene oxide/hydroxyapatite nanowire composite paper is improved, so that a warning signal can be exposed in flame for 30 s; in addition, as the HAP nanowire has extremely high thermal stability, the branched polyethyleneimine modified graphene oxide/hydroxyapatite nanowire composite paper keeps good structural integrity in flame, ensures continuity of a conductive path, and still keeps continuous fire early warning after the flame is removed (b). The difficulty of the graphene oxide fire early warning device in practical application is greatly solved, and the graphene oxide fire early warning device has important scientific significance and application value. In example 3, the deoxyribonucleic acid modified graphene oxide/hydroxyapatite nanowire composite paper can rapidly give out an early warning within 1 s, shows extremely rapid and sensitive response time, can work for 82 s under continuous attack of external flame, and can still work for 2 s (c) under the condition that an external fire source is further removed. While the deoxyribonucleic acid modified graphene oxide/hydroxyapatite nanowire composite paper works within 2 s in the embodiment 5, the brightness of the early warning lamp after the continuous working for 82 s is obviously brighter than that of the embodiment 3, and the damaged area of the composite paper in flame is only at the fire source attack position, so that the flame spreading condition cannot be presented. When the external fire source is further removed, the composite paper in the connecting circuit can continuously send out obvious early warning for 2 min, and the development of the fire early warning sensor is greatly promoted. Therefore, compared with the branched polyethyleneimine modified graphene oxide/hydroxyapatite nanowire composite paper, the graphene oxide/hydroxyapatite nanowire composite paper has greater advantages and application space in fire early warning sensors.
It will be understood by those skilled in the art that the foregoing is merely a preferred embodiment of the invention, and is not intended to limit the invention, and that any modification, equivalent replacement or improvement made within the spirit and principle of the invention should be included within the scope of protection of the invention.
Claims (7)
1. A preparation method of modified graphene oxide/hydroxyapatite nanowire composite paper is characterized by comprising the following steps: the method comprises the following steps:
(1) placing graphene oxide in water, and carrying out ultrasonic stripping to obtain a graphene oxide dispersion liquid with the concentration of 1 mg/mL;
(2) adding 1-2mg/mL of organic molecular solution and 1-2.5 mg/mL of hydroxyapatite nanowire solution into the prepared graphene oxide dispersion liquid, and heating and stirring the solution by using an oil bath until the solution is fully mixed;
(3) and standing and cooling the mixed solution to room temperature, and drying after vacuum-assisted suction filtration to obtain the modified graphene oxide/hydroxyapatite nanowire composite paper.
2. The preparation method of the modified graphene oxide/hydroxyapatite nanowire composite paper according to claim 1, characterized in that: the raw materials comprise the following components in parts by weight: 0.5-2 parts of organic molecules, 1 part of graphene oxide and 2-8 parts of hydroxyapatite nanowires.
3. The preparation method of the modified graphene oxide/hydroxyapatite nanowire composite paper according to claim 1 or 2, characterized in that: the organic molecule is branched polyethyleneimine or deoxyribonucleic acid.
4. The preparation method of the modified graphene oxide/hydroxyapatite nanowire composite paper according to claim 1, characterized in that: the ultrasonic stripping time in the step (1) is 20-60 min.
5. The preparation method of the modified graphene oxide/hydroxyapatite nanowire composite paper according to claim 1, characterized in that: the heating temperature of the oil bath in the step (2) is 50-100 ℃; the stirring time is 1-6 h.
6. The preparation method of the modified graphene oxide/hydroxyapatite nanowire composite paper according to claim 1, characterized in that: the drying temperature in the step (3) is 30-100 ℃, and the drying time is 0.5-12 h.
7. Use of the modified graphene oxide/hydroxyapatite nanowire composite paper prepared according to any one of claims 1 to 6 in preparation of a fire early warning system.
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