CN115353101A - Modified graphene oxide film with high sensitivity and high thermal stability - Google Patents
Modified graphene oxide film with high sensitivity and high thermal stability Download PDFInfo
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
Abstract
The invention discloses a modified graphene oxide film with high sensitivity and strong thermal stability. The modified graphene oxide film is prepared by introducing organic molecules between graphene oxide lamella by adopting an evaporation-induced self-assembly method, and has high sensitivity and strong thermal stability. The fire alarm assembled by the modified graphene oxide film is high in sensitivity and has a quick fire response effect, the sensitivity is 1.5 +/-0.5 s when a fire disaster happens and reaches 150 ℃, the fire alarm has good thermal stability, the alarm can be continuously given out after the fire disaster happens, the continuous alarm time is at least 100 min, and the longest alarm time reported at home and abroad at present is about 7 min. The modified graphene oxide film is simple in manufacturing process, low in cost, high in efficiency, easy to popularize and suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of graphene films, and particularly relates to a modified graphene oxide film with high sensitivity and high thermal stability.
Background
In order to avoid fire accidents, two aspects can be mainly dealt with, namely: enhancing the flame retardance of the building material and optimizing the performance of the alarm system; the two factors are respectively the key factors influencing the spread of fire and the early escape of resident. In terms of alarm systems, fire alarms have become a popular research in recent years, wherein the preparation of modified graphene oxide-based materials has made some progress. Researchers report that graphene oxide is modified by different modifiers (phytic acid, boric acid, cellulose, polydopamine and the like), and modified graphene films are prepared by respectively adopting an evaporation-induced self-assembly method or a dipping method and the like; the prepared film is connected with a battery and an alarm lamp through a lead to assemble a fire alarm for fire alarm testing. The result shows that the sensitivity of the fire alarm assembled based on the modified graphene film is gradually improved, but the thermal stability of the fire alarm is still obviously insufficient (the longest alarm time is about 7 min). Therefore, on the premise of ensuring the sensitivity of the graphene oxide-based fire alarm, the improvement of the thermal stability becomes an urgent problem to be solved.
The prior patents (CN 109920600A) and (CN 112457824B) which use graphene as a fire alarm material are obtained through patent search. The prior patent (CN 109920600A) is a nonmetal heat-sensitive probe alarm precursor consisting of an upper graphene conductive film layer, a lower graphene conductive film layer and a nonmetal optical fiber heat-sensitive sensor, and is characterized in that an alarm is given in time when the temperature is higher than 70 ℃, but the heat stability is not researched. The prior patent (CN 112457824B) is to react aminated phosphorus with graphene oxide to obtain an aminated phosphorus/graphene oxide flexible film as an alarm material, and only the thermal conductivity in the plane direction of the flexible film (i.e. the response sensitivity after fire) is studied, but the thermal stability is not studied. In summary, the above two patents do not study the thermal stability of the alarm material, and cannot obtain the characteristics of whether the alarm material can continuously alarm at high temperature and the time of continuous alarm.
Disclosure of Invention
In order to overcome the defect of poor thermal stability of the existing modified graphene oxide film, the invention aims to provide the modified graphene oxide film with high sensitivity and strong thermal stability.
The technical scheme of the invention is as follows:
the modified graphene oxide film is prepared by introducing organic molecules between graphene oxide sheets by adopting an evaporation-induced self-assembly method.
The preparation method of the modified graphene oxide film with high sensitivity and strong thermal stability comprises the following steps:
(1) Synthesizing pure solid graphite oxide GO by adopting an improved Hummers method for later use;
(2) Physically crushing to obtain an organic molecular solution with floccules for later use;
(3) Adding solid graphite oxide GO into water, and obtaining GO dispersion liquid through cell crushing instrument ultrasound for later use;
(4) Mixing the GO dispersion liquid with the organic molecule solution, and continuously stirring under ultrasonic treatment to obtain a mixed dispersion liquid for later use;
(5) And pouring the mixed dispersion liquid after ultrasonic treatment into a polytetrafluoroethylene culture dish, and drying in a drying oven to obtain the modified graphene oxide film.
Specifically, in the step (2), the organic molecule solution is fruit juice.
More specifically, in the step (2), the fruit juice is one of apple juice, lemon juice, pear juice, watermelon juice and pineapple juice.
Specifically, in the step (3), the concentration of the GO dispersion liquid is 2-10 mg mL -1 。
Specifically, in the step (4), the volume ratio of the GO dispersion liquid to the organic molecule solution is 1-10.
Specifically, in the step (4), the continuous stirring time is 30-120 min.
Specifically, in the step (5), the drying temperature in the drying oven is 40-80 ℃.
Specifically, in the step (5), the drying time in the drying oven is 48-120 h.
The application of the modified graphene oxide film is high in sensitivity and high in thermal stability, and the modified graphene oxide film is applied to the field of fire alarms.
Effects of the invention
The invention provides a modified graphene oxide film with high sensitivity and strong thermal stability. The modified graphene oxide film is obtained by introducing organic molecules (such as organic substance solutions of apple juice, lemon juice, pear juice, watermelon juice or pineapple juice and the like) between graphene oxide sheets by an evaporation-induced self-assembly method, and has high sensitivity and high thermal stability.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, organic molecules are introduced between graphene oxide lamella layers by an evaporation-induced self-assembly method to form a modified graphene oxide film, and compared with the traditional alarm material, the modified graphene oxide film has more excellent sensitivity and thermal stability. Although graphene is also used as an alarm material in the traditional alarm material, no organic molecular solution is introduced, the thermal stability is poor, and the longest alarm time is about 7 min after a fire alarm occurs. The fire alarm assembled by the modified graphene oxide film can continuously alarm after a fire disaster occurs, the continuous alarm time is at least 100 min, and the fire alarm has excellent thermal stability.
2. The fire alarm assembled by the modified graphene oxide film is high in sensitivity and has a quick fire response effect, and when a fire disaster happens and reaches 150 ℃, the sensitivity of the fire alarm is 1.5 +/-0.5 s. The modified graphene oxide film is simple in manufacturing process, low in cost, high in efficiency, easy to popularize and suitable for large-scale production. The novel process route for preparing the modified graphene oxide in China is realized while a novel idea of comprehensive utilization of organic matters is provided, and the innovation is strong. By adopting a simple and easy-to-operate evaporation-induced self-assembly method, organic molecules are successfully introduced between graphene oxide lamella layers, and the modified graphene oxide film with high sensitivity and strong thermal stability is prepared and shows good flexibility. The film is connected with the battery and the alarm lamp through the conducting wire to form the fire alarm. When the insulating modified graphene oxide film encounters flame, the insulating modified graphene oxide film is quickly reduced (the sensitivity =1.5 +/-0.5 s and high sensitivity is shown) to be a conductive graphene film, so that a closed loop is formed to light the alarm lamp; due to the modification of organic molecules, the thermal stability of the film is improved, and an overlong and continuous alarm signal is shown (the alarm time is more than or equal to 100 min).
Drawings
FIG. 1a is an XPS test chart of an apple juice modified graphene oxide film GO-AJ prepared in example 1 of the present invention;
FIG. 1b is a FRIT test chart of the apple juice modified graphene oxide thin film GO-AJ prepared in the embodiment 1 of the present invention;
FIG. 2a TEM image of GO surface;
FIG. 2b SEM image of GO-AJ surface;
FIG. 2c is a partially magnified SEM image of the GO-AJ surface;
FIG. 2d cross-sectional SEM image of GO;
FIG. 2e is a cross-sectional SEM image of GO-AJ;
FIG. 2f EDS diagrams of GO-AJ;
FIG. 2g element C analytical test chart;
FIG. 2h elemental O analysis test chart;
FIG. 2i elemental Fe analysis test chart;
FIG. 2j element K analysis test chart;
FIG. 2k elemental Ca assay test chart;
fig. 3 is a flexibility test chart of the apple juice modified graphene oxide thin film GO-AJ prepared in the embodiment of the invention (fig. 3a-b are multi-fold, and fig. 3c is a folded airplane).
Detailed Description
Example 1:
the preparation method of the modified graphene oxide film comprises the following steps:
(1) Synthesizing pure solid Graphite Oxide (GO) by adopting an improved Hummers method for later use;
(2) Physically crushing to obtain Apple Juice (AJ) with floccule for later use;
(3) Adding the prepared GO into water, and obtaining 4 mg mL by using a cell crushing instrument to perform ultrasonic treatment -1 GO dispersion of (2) for later use;
(4) Mixing the GO dispersion liquid with the AJ, wherein the volume ratio of the GO dispersion liquid to the AJ is 6;
(5) And pouring the mixed dispersion liquid after ultrasonic treatment into a polytetrafluoroethylene culture dish, and drying in a drying oven at 70 ℃ for 120 hours to obtain the GO-AJ film.
Example 2:
the preparation method of the modified graphene oxide film comprises the following steps:
(1) Synthesizing pure solid Graphite Oxide (GO) by adopting an improved Hummers method for later use;
(2) Physically crushing to obtain Apple Juice (AJ) with floccule for later use;
(3) Adding the prepared GO into water, and obtaining 2 mg mL by using a cell crushing instrument to perform ultrasonic treatment -1 GO dispersion for use;
(4) GO dispersion was mixed with AJ, the volume ratio of GO dispersion to AJ was 3. Continuously stirring for 30 min under ultrasonic treatment;
(5) And pouring the mixed dispersion liquid after ultrasonic treatment into a polytetrafluoroethylene culture dish, and drying in a drying oven at 50 ℃ for 72 hours to obtain the GO-AJ film.
Example 3:
the preparation method of the modified graphene oxide film comprises the following steps:
(1) Synthesizing pure solid Graphite Oxide (GO) by adopting an improved Hummers method for later use;
(2) Physically crushing to obtain Apple Juice (AJ) with floccules for later use;
(3) Adding the prepared GO into water, and obtaining 3 mg mL by using a cell crushing instrument to perform ultrasonic treatment -1 GO dispersion for use;
(4) The GO dispersion was mixed with AJ in a volume ratio of GO dispersion to AJ of 2. Continuously stirring for 120 min under ultrasonic treatment;
(5) And pouring the mixed dispersion liquid after ultrasonic treatment into a polytetrafluoroethylene culture dish, and drying in a drying oven at 40 ℃ for 48 hours to obtain the GO-AJ film.
Example 4:
the preparation method of the modified graphene oxide film comprises the following steps:
(1) Synthesizing pure solid Graphite Oxide (GO) by adopting an improved Hummers method for later use;
(2) Physically crushing to obtain Lemon Juice (LJ) with floccules for later use;
(3) Adding the prepared GO into water, and obtaining 2 mg mL by using a cell crushing instrument to perform ultrasonic treatment -1 GO dispersion for use;
(4) The GO dispersion is mixed with the LJ, and the volume ratio of the GO dispersion to the LJ is 3. Continuously stirring for 30 min under ultrasonic treatment;
(5) And pouring the mixed dispersion liquid after ultrasonic treatment into a polytetrafluoroethylene culture dish, and drying in a drying oven at 50 ℃ for 72 hours to obtain the GO-LJ film.
Example 5:
the preparation method of the modified graphene oxide film comprises the following steps:
(1) Synthesizing pure solid Graphite Oxide (GO) by adopting an improved Hummers method for later use;
(2) Physically crushing to obtain Pear Juice (PJ) with floccules for later use;
(3) Adding the prepared GO into water, and obtaining 2 mg mL by using a cell crushing instrument to perform ultrasonic treatment -1 GO dispersion for use;
(4) GO dispersion was mixed with PJ, the volume ratio of GO dispersion to PJ was 3. Stirring was continued for 30 min under sonication.
And pouring the mixed dispersion liquid after ultrasonic treatment into a polytetrafluoroethylene culture dish, and drying in a drying oven at 80 ℃ for 72 hours to obtain the GO-PJ film.
Example 6:
the preparation method of the modified graphene oxide film comprises the following steps:
(1) Synthesizing pure solid Graphite Oxide (GO) by adopting an improved Hummers method for later use;
(2) Physically crushing to obtain Pear Juice (PJ) with floccules for later use;
(3) Adding the prepared GO into water, and obtaining 10 mg mL by using a cell disruptor to perform ultrasonic treatment -1 GO dispersion for use;
(4) The GO dispersion was mixed with the PJ, the volume ratio of GO dispersion to PJ was 10. Stirring was continued for 90 min under sonication.
And pouring the mixed dispersion liquid after ultrasonic treatment into a polytetrafluoroethylene culture dish, and drying in a drying oven at 50 ℃ for 96 h to obtain the GO-PJ film.
Example 7:
the preparation method of the modified graphene oxide film comprises the following steps:
(1) Synthesizing pure solid Graphite Oxide (GO) by adopting an improved Hummers method for later use;
(2) Physically crushing to obtain Pear Juice (PJ) with floccules for later use;
(3) Adding the prepared GO into water, and obtaining 1mg mL by using a cell crushing instrument to perform ultrasonic treatment -1 GO dispersion for use;
(4) The GO dispersion was mixed with the PJ, the volume ratio of GO dispersion to PJ was 1. Stirring was continued for 60 min under sonication.
And pouring the mixed dispersion liquid after ultrasonic treatment into a polytetrafluoroethylene culture dish, and drying in a drying oven at 40 ℃ for 48 hours to obtain the GO-PJ film.
Example 8:
the preparation method of the modified graphene oxide film comprises the following steps:
(1) Synthesizing pure solid Graphite Oxide (GO) by adopting an improved Hummers method for later use;
(2) Physically crushing to obtain Watermelon Juice (WJ) with floccules for later use;
(3) Adding the prepared GO into water, and obtaining 1mg mL by using a cell crushing instrument to perform ultrasonic treatment -1 GO dispersion of (2) for later use;
(4) GO dispersion was mixed with WJ, the volume ratio of GO dispersion to WJ was 3. Stirring was continued for 60 min under sonication.
And pouring the mixed dispersion liquid after ultrasonic treatment into a polytetrafluoroethylene culture dish, and drying in a drying oven at 60 ℃ for 72 hours to obtain the GO-WJ film.
Example 9:
the preparation method of the modified graphene oxide film comprises the following steps:
(1) Synthesizing pure solid Graphite Oxide (GO) by adopting an improved Hummers method for later use;
(2) Physically crushing to obtain pineapple juice (PIJ) with floccules for later use;
(3) Adding the prepared GO into water, and obtaining 1mg mL by using a cell crushing instrument to perform ultrasonic treatment -1 GO dispersion for use;
(4) The GO dispersion is mixed with PIJ, and the volume ratio of the GO dispersion to the PIJ is 3. Stirring was continued for 60 min under sonication.
And pouring the mixed dispersion liquid after ultrasonic treatment into a polytetrafluoroethylene culture dish, and drying in a drying oven at 60 ℃ for 72 hours to obtain the GO-PIJ film.
The inventors carried out the following experiments to verify the effects of the present invention:
experimental example:
1. control extract preparation method
1.1 test materials and reagent instrumentation
1.1.1 test materials and reagents
Graphite powder (particle size 30 μm, 99.9%) was purchased from Shanghai Allantin Biotechnology Ltd. The organic materials used in the works are purchased from a John fruit shop in the Huaxi district. Potassium persulfate (K) 2 S 2 O 8 ) Phosphorus pentoxide (P) 2 O 5 ) And potassium permanganate (KMnO) 4 ) Purchased from sigma aldrich trade ltd. Sulfuric acid (H) produced by chemical Limited of Zhuhaihuachengda in China 2 SO 4 98 wt%) and hydrochloric acid (HCl, 37 wt%). Hydrogen peroxide (H) 2 O 2 30 wt%) was purchased from pharmaceutical chemicals, ltd, china. All reagents were used directly without further purification.
Testing instrument
Cell disruptor (KQ-5200) Ningbo Xinzhi Biotech Co., ltd.; electrothermal blowing dry box (101-3 AB) Tianjin Tiantai instruments ltd; electronic analytical balance (AL 204) mettler-toledo instruments (shanghai) ltd; a desk vacuum freeze dryer (FD-1A-80) Jiangsu feather instruments ltd; scanning electron microscope (SEM, S4800) hitachi corporation; infrared Spectroscopy (FTIR, avatar 360) Thermo Nicolet, USA; x-ray photoelectron spectroscopy (XPS, PHI-1600) Perkin-Elmer, USA.
Test method
1.2.1 XPS and FTIR spectroscopic testing
XPS and FTIR spectra are effective means for analyzing the chemical composition of the sample, and the apple juice modified graphene oxide thin film (GO-AJ) prepared by using pure graphene oxide film (GO) and Apple Juice (AJ) as modifiers is used as a characterization sample, and the preparation method is performed according to example 1.
(1) FIG. 1a is an XPS plot of samples with GO having major peaks at C1 s, O1 s; the GO-AJ has main peaks of C1 s, O1 s, P2 s and P2P, which indicates that the GO-AJ consists of C, O and P elements, and confirms that AJ molecules are successfully inserted into GO sheet layers in the water evaporation induced self-assembly process. FIG. 1b is an FTIR spectrum of the sample at 3420, 1738 and 1624 cm -1 The characteristic peaks are shown, respectively, O-H, C = O and the stretching vibration of water molecule adsorption, the stretching vibration peak of C-OH is located at 1053 cm -1 To (3). The FTIR spectrum of GO-AJ retains the characteristic signal of oxygen-containing function of GO, but in 1155 and 956 cm -1 Two new peaks appear, respectively the tensile vibration peaks of P = O and P-OH. O-H from 3420 cm -1 Migration to 3410 cm -1 As a result of hydrogen bonding interactions between GO and AJ. This confirms that AJ molecules have successfully inserted into the GO lamellae during water evaporation induced self-assembly, corresponding to XPS results.
(2) The microscopic morphology of the film was observed by SEM images. It can be seen that the appearance of GO shows a flat surface without significant wrinkles (fig. 2 a). SEM images of the GO-AJ surface showed that the surface was wrinkled (fig. 2 b). Fig. 2c is a partial magnified view of the GO-AJ surface, and from the SEM cross-sectional view of the GO membrane in fig. 2d, a typical graphene layered structure can be observed. As shown in fig. 2e, the SEM cross-sectional layer layered structure of GO-AJ is denser, and it can be seen that AJ molecules have successfully inserted into the GO lamellae during the water evaporation induced self-assembly process. Furthermore, the elemental distribution also confirms that AJ molecules have successfully inserted into the GO lamellae during the water evaporation induced self-assembly process; where C, O, fe and K are distributed mainly around (FIG. 2 g-j), while Ca is distributed in the middle (FIG. 2K).
(3) An evaporation-induced self-assembly method is adopted, organic molecules are introduced between graphene oxide lamella layers, a modified graphene oxide film with high sensitivity and strong thermal stability is prepared, flexibility test is carried out, and the test result is shown in figure 3. As can be seen in FIG. 3, the GO-AJ can be folded several times (as in FIGS. 3 a-b) and also folded into the desired shape (as in FIG. 3c: into an airplane). The film has better flexibility than similar products.
1.2.2 sensitivity and thermal stability test
The apple juice modified graphene oxide thin film prepared in example 1 and having high sensitivity and strong thermal stability was subjected to sensitivity and thermal stability (i.e. response time) tests, and graphene-based materials disclosed in the prior art (controls 1 to 11) were used as a control, wherein the graphene-based materials disclosed in the prior art and the preparation method thereof are specifically shown in the preparation methods provided in reference documents in table 1.
It can be seen from table 2 that the thermal stability of the modified graphene oxide thin film with high sensitivity and strong thermal stability prepared by the present invention is significantly higher than that of the currently reported graphene-based material on the premise of not affecting the high sensitivity.
TABLE 1 control and corresponding references
TABLE 2 comparison of sensitivity and thermal stability
Summary of the invention
The modified graphene oxide film with high sensitivity and strong thermal stability is prepared; taking apple juice modified graphene oxide film as an example, a fire alarm assembled based on the modified graphene oxide film has fast fire response (sensitivity =1.5 ± 0.5 s) and good thermal stability (alarm time is at least 100 min), and the alarm time is significantly higher than the longest alarm time reported at home and abroad at present by about 7 min (the longest duration of the control 8 in the control group is 433.0 s).
Claims (10)
1. A modified graphene oxide film with high sensitivity and strong thermal stability is characterized in that: the modified graphene oxide film is prepared by introducing organic molecules between graphene oxide lamella layers by adopting an evaporation-induced self-assembly method.
2. The preparation method of the modified graphene oxide film with high sensitivity and strong thermal stability according to claim 1, is characterized in that: the preparation method of the modified graphene oxide film comprises the following steps:
(1) Synthesizing pure solid graphite oxide GO by adopting an improved Hummers method for later use;
(2) Physically crushing to obtain an organic molecular solution with floccules for later use;
(3) Adding solid graphite oxide GO into water, and obtaining GO dispersion liquid through cell crushing instrument ultrasound for later use;
(4) Mixing the GO dispersion liquid with the organic molecule solution, and continuously stirring under ultrasonic treatment to obtain a mixed dispersion liquid for later use;
(5) And pouring the mixed dispersion liquid after ultrasonic treatment into a polytetrafluoroethylene culture dish, and drying in a drying oven to obtain the modified graphene oxide film.
3. The preparation method of the modified graphene oxide film with high sensitivity and strong thermal stability according to claim 2, is characterized in that: in the step (2), the organic molecule solution is fruit juice.
4. The method for preparing the modified graphene oxide film with high sensitivity and strong thermal stability according to claim 2 or 3, is characterized in that: in the step (2), the fruit juice is one of apple juice, lemon juice, pear juice, watermelon juice or pineapple juice.
5. The method for preparing the modified graphene oxide film with high sensitivity and thermal stability according to claim 2, is characterized in that: in the step (3), the concentration of the GO dispersion liquid is 2-10 mg mL -1 。
6. The preparation method of the modified graphene oxide film with high sensitivity and strong thermal stability according to claim 2, is characterized in that: in the step (4), the volume ratio of the GO dispersion liquid to the organic molecule solution is 1-10.
7. The preparation method of the modified graphene oxide film with high sensitivity and strong thermal stability according to claim 2, is characterized in that: in the step (4), the continuous stirring time is 30-120 min.
8. The preparation method of the modified graphene oxide film with high sensitivity and strong thermal stability according to claim 2, is characterized in that: in the step (5), the drying temperature in the drying oven is 40-80 ℃.
9. The preparation method of the modified graphene oxide film with high sensitivity and strong thermal stability according to claim 2, is characterized in that: in the step (5), the drying time in the drying box is 48-120 h.
10. The application of the modified graphene oxide film with high sensitivity and strong thermal stability is characterized in that: the modified graphene oxide film is applied to the field of fire alarms.
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