CN114014313A - Graphene-based gas-sensitive material and preparation method thereof - Google Patents
Graphene-based gas-sensitive material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000012360 testing method Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000013329 compounding Methods 0.000 claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 10
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 10
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 5
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 claims abstract description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011787 zinc oxide Substances 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims description 22
- 238000005096 rolling process Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000009830 intercalation Methods 0.000 claims description 4
- 230000002687 intercalation Effects 0.000 claims description 4
- 239000007789 gas Substances 0.000 description 35
- 239000000047 product Substances 0.000 description 10
- 230000004044 response Effects 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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Abstract
The invention belongs to the technical field of gas sensor materials, and particularly relates to a graphene-based gas sensitive material and a preparation method thereof. The product developed by the invention comprises compound graphene oxide and metal oxide particles; the compound graphene oxide is prepared by compounding 1# graphene oxide with D50 of 10-50nm, 2# graphene oxide with D50 of 100-200nm and 3# graphene oxide with D50 of 500-1200 nm; the metal oxide is selected from: any one of cobalt oxide, cobaltous oxide, tin oxide, cuprous oxide, zinc oxide, ferroferric oxide, ferric oxide, tungsten oxide and manganese dioxide; the OI value of the graphene-based gas-sensitive material is 10-25; the graphene-based gas-sensitive material has an OI value of: and (3) testing the ratio of the peak area of the 004 characteristic peak to the peak area of the 110 characteristic peak by using an XRD diffractometer.
Description
Technical Field
The invention belongs to the technical field of gas sensor materials. More particularly, relates to a graphene-based gas-sensitive material and a preparation method thereof.
Background
Metal oxide semiconductors have long been important gas sensitive materials, and there have been a large number of reports on metal oxides as gas sensitive materials. With the discovery of graphene materials, researchers have tried to use graphene derivatives rGO for gas sensors, and particularly, have reported that rGO is obtained by low-temperature step annealing under an atmosphere of argon at normal pressure, so that gas sensors are prepared and tested for their response to nitrogen dioxide and ammonia gas at room temperature. The response of the sensor to nitrogen dioxide can be completely recovered within 10-30min, and the response to ammonia gas is unstable. Meanwhile, researchers begin to add graphene into metal oxides for compounding, particularly rGO, and study the gas-sensitive characteristics of the metal oxides, and hopefully, the mechanical, chemical and electrical characteristics of the metal oxides are improved through the compounding among the metal oxides. The addition of graphene may bring problems in the gas sensitive material, such as response non-restorability when certain gases are encountered, but the conductivity of the original metal oxide is improved, and the advantages of the compounded material in gas response, working temperature, selectivity or working under an oxygen-free environment are not ignored.
In the last decade of discovery, graphene is a promising approach to develop its application field by combining with other materials. The application of metal oxides to gas sensitive materials is relatively mature, but has many problems that have not been solved, such as selectivity, operating temperature, stability, and operation under anaerobic conditions. Therefore, the combination of graphene and metal oxide has attracted the attention of researchers, and some problems need to be solved, such as response recovery time at room temperature, and a gas-sensitive response mechanism of a composite material remains to be clarified.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the problems of general gas-sensitive performance, especially gas-sensitive performance under room temperature condition, such as longer recovery response and recovery time under room temperature condition in the existing gas-sensitive material, and provides a graphene-based gas-sensitive material and a preparation method thereof.
The invention aims to provide a graphene-based gas-sensitive material.
The invention also aims to provide a preparation method of the graphene-based gas-sensitive material.
The above purpose of the invention is realized by the following technical scheme:
a graphene-based gas-sensitive material comprises compound graphene oxide and metal oxide particles;
the compound graphene oxide is prepared by compounding 1# graphene oxide with D50 of 10-50nm, 2# graphene oxide with D50 of 100-200nm and 3# graphene oxide with D50 of 500-1200 nm;
the metal oxide is selected from: any one of cobalt oxide, cobaltous oxide, tin oxide, cuprous oxide, zinc oxide, ferroferric oxide, ferric oxide, tungsten oxide and manganese dioxide;
the OI value of the graphene-based gas-sensitive material is 10-25;
the graphene-based gas-sensitive material has an OI value of: and (3) testing the ratio of the peak area of the 004 characteristic peak to the peak area of the 110 characteristic peak by using an XRD diffractometer.
According to the technical scheme, different D50 graphene oxide materials are compounded, and the OI value of the gas sensitive material is regulated, so that for graphene oxide with a layered structure, two crystal planes 004 and 110 which are perpendicular to each other are arranged in the crystal structure, the larger the OI value is, the more the 004 planes are parallel to the surface of the base material, and the smaller the OI value is, the more the 004 planes tend to be perpendicular to the surface of the base material, and at the moment, the 'openings' of the layered structure of the graphene oxide are exposed, so that when the graphene oxide is used as the gas sensitive material, gas can more easily enter and exit the layered structure; however, as the gas sensitive material, in order to enable gas to smoothly enter and exit between graphene oxide layers, the interlayer spacing is generally widened through a related treatment process, so that the structural stability of the widened graphene oxide is remarkably reduced, and therefore, a part of crystal faces in a crystal structure of the graphene oxide can be randomly oriented by reasonably adjusting the OI value of the graphene oxide, so that the crystal faces of the crystal can be supported with each other, and the stability and reliability of the properties are ensured; when the OI value is within the above numerical range, the above properties can be taken into consideration.
Further, at least partial intercalation of the No. 1 graphene oxide and the No. 2 graphene oxide is distributed between the No. 3 graphene oxide layers; and at least partial intercalation of the No. 1 graphene oxide is distributed among the No. 2 graphene oxide layers.
According to the technical scheme, the graphene oxide gas-sensitive materials with more stable structures are obtained under the condition of the OI value by utilizing the mutual intercalation of the graphene oxide with different sizes, so that mutual support can be realized through crystal faces with different sizes and preferential orientation is carried out inside the graphene oxide gas-sensitive materials.
Further, the compound graphene oxide is prepared by compounding the following graphene oxide in parts by weight: 20-30 parts of No. 1 graphene oxide, 15-20 parts of No. 2 graphene oxide and 10-15 parts of No. 3 graphene oxide.
Further, the particle size distribution range of the metal oxide particles is 5-30 nm.
A preparation method of a graphene-based gas-sensitive material comprises the following specific preparation steps:
compounding the following graphene oxide in parts by weight: 20-30 parts of 1# graphene oxide with D50 of 10-50nm, 15-20 parts of 2# graphene oxide with D50 of 100-200nm, and 10-15 parts of 3# graphene oxide with D50 of 500-1200 nm;
dispersing the compounded graphene oxide in water, carrying out ultrasonic stripping, adding metal oxide particles, continuing ultrasonic dispersion, carrying out suction filtration, and drying to obtain a dry filter cake;
rolling the obtained dry filter cake to adjust the OI value to 10-25;
the metal oxide is selected from: any one of cobalt oxide, cobaltous oxide, tin oxide, cuprous oxide, zinc oxide, ferroferric oxide, ferric oxide, tungsten oxide and manganese dioxide;
the OI value is: and (3) testing the ratio of the peak area of the 004 characteristic peak to the peak area of the 110 characteristic peak by using an XRD diffractometer.
According to the technical scheme, the graphene oxide laminated structures with different sizes are peeled off to form the single-layer structure by utilizing the cavitation action of ultrasonic waves, so that the crystal single-layer structures with different sizes can be assembled and supported mutually in the subsequent suction filtration process, the interlayer spacing is widened, the graphene laminated structures can be supported mutually, the OI value of a product is regulated and controlled by matching with the rolling process, gas can enter and exit the laminated structures quickly, and the propagation path of the gas is reduced.
Further, the particle size distribution range of the metal oxide particles is 5-30 nm.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
Sequentially taking the following components in parts by weight: introducing 30 parts of 1# graphene oxide with the D50 of 50nm, 20 parts of 2# graphene oxide with the D50 of 200nm and 15 parts of 3# graphene oxide with the D50 of 1200nm into a mixer, stirring and mixing for 60min at the rotating speed of 1200r/min, and discharging to obtain compound graphene oxide;
and then compounding the compounded graphene oxide with water according to a mass ratio of 1: 10, after mixing, carrying out ultrasonic stripping for 80min under the ultrasonic frequency of 180kHz, adding metal oxide particles with the mass of 15% of the compound graphene oxide, wherein the particle size distribution range of the metal oxide is 5-30nm, continuously carrying out ultrasonic dispersion for 40min under the ultrasonic frequency of 70kHz, carrying out suction filtration to obtain a filter cake, washing the filter cake for 5 times by using deionized water, transferring the washed filter cake into an oven, and drying to constant weight under the temperature of 120 ℃ to obtain a dried filter cake;
laying the obtained dry filter cake on an objective table, controlling the thickness of the filter cake to be 3mm, adjusting the rolling pressure and the rolling time, and performing rolling treatment to adjust the OI value to be 25; specifically, the testing process of the OI value is as follows: transferring the rolled material into an XRD diffractometer, performing data processing by using JADE software after testing to obtain peak areas of 004 and 110 diffraction peaks of the rolled material, and dividing the 004 diffraction peak area by the 110 diffraction peak area to obtain an OI value of the product;
the metal oxide is selected from: tungsten oxide.
Example 2
Sequentially taking the following components in parts by weight: introducing 25 parts of 1# graphene oxide with D50 of 30nm, 18 parts of 2# graphene oxide with D50 of 180nm and 12 parts of 3# graphene oxide with D50 of 800nm into a mixer, stirring and mixing for 50min at the rotating speed of 1000r/min, and discharging to obtain compound graphene oxide;
and then compounding the compounded graphene oxide with water according to a mass ratio of 1: 8, after mixing, carrying out ultrasonic stripping for 70min under the ultrasonic frequency of 160kHz, adding metal oxide particles with the mass of 12% of the compound graphene oxide, wherein the particle size distribution range of the metal oxide particles is 10-30nm, continuing carrying out ultrasonic dispersion for 30min under the ultrasonic frequency of 65kHz, carrying out suction filtration to obtain a filter cake, washing the filter cake for 4 times by using deionized water, transferring the washed filter cake into an oven, and drying to constant weight under the temperature of 110 ℃ to obtain a dried filter cake;
laying the obtained dry filter cake on an objective table, controlling the thickness of the filter cake to be 2mm, adjusting the rolling pressure and the rolling time, and performing rolling treatment to adjust the OI value to be 20; specifically, the testing process of the OI value is as follows: transferring the rolled material into an XRD diffractometer, performing data processing by using JADE software after testing to obtain peak areas of 004 and 110 diffraction peaks of the rolled material, and dividing the 004 diffraction peak area by the 110 diffraction peak area to obtain an OI value of the product;
the metal oxide is selected from: tin oxide.
Example 3
Sequentially taking the following components in parts by weight: introducing 20 parts of 1# graphene oxide with the D50 of 10nm, 15 parts of 2# graphene oxide with the D50 of 100nm and 10 parts of 3# graphene oxide with the D50 of 500nm into a mixer, stirring and mixing for 40min at the rotating speed of 800r/min, and discharging to obtain compound graphene oxide;
and then compounding the compounded graphene oxide with water according to a mass ratio of 1: 5, after mixing, carrying out ultrasonic stripping for 60min under the condition that the ultrasonic frequency is 100kHz, then adding metal oxide particles with the mass of 10% of the compound graphene oxide, wherein the particle size distribution range of the metal oxide particles is 5-10nm, continuing carrying out ultrasonic dispersion for 20min under the condition that the ultrasonic frequency is 60kHz, carrying out suction filtration to obtain a filter cake, washing the filter cake for 3 times by using deionized water, then transferring the washed filter cake into an oven, and drying to constant weight under the condition that the temperature is 100 ℃ to obtain a dried filter cake;
laying the obtained dry filter cake on an objective table, controlling the thickness of the filter cake to be 1mm, adjusting the rolling pressure and the rolling time, and performing rolling treatment to adjust the OI value to be 10; specifically, the testing process of the OI value is as follows: transferring the rolled material into an XRD diffractometer, performing data processing by using JADE software after testing to obtain peak areas of 004 and 110 diffraction peaks of the rolled material, and dividing the 004 diffraction peak area by the 110 diffraction peak area to obtain an OI value of the product;
the metal oxide is selected from: and (3) oxidizing the cobalt.
Example 4
This example is compared with example 1, with the difference that the OI value of the product is adjusted to 5, and the remaining conditions are kept unchanged.
Example 5
This example is different from example 1 in that the OI value of the control product was 35, and the remaining conditions were kept constant.
Comparative example 1
The difference between this example and example 1 is that no 1# graphene oxide and no 2# graphene oxide are used, and equal mass of 3# graphene oxide is used to replace the two specifications of graphene oxide, and the rest conditions are kept unchanged.
The products obtained in the above examples and comparative examples were subjected to performance tests, and the specific test methods and test results are as follows:
testing the gas-sensitive performance of the product at room temperature by adopting a Henan Hanwei electronic HW-30A gas-sensitive testing system;
the ammonia concentration was measured at 30ppm and the ammonia concentration at 20ppm, respectively, and the response time and recovery time were measured, and the specific test results are shown in table 1.
Table 1: product performance test results
The test results in table 1 show that the product obtained by the invention has good gas-sensitive performance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. A graphene-based gas-sensitive material is characterized by comprising compound graphene oxide and metal oxide particles;
the compound graphene oxide is prepared by compounding 1# graphene oxide with D50 of 10-50nm, 2# graphene oxide with D50 of 100-200nm and 3# graphene oxide with D50 of 500-1200 nm;
the metal oxide is selected from: any one of cobalt oxide, cobaltous oxide, tin oxide, cuprous oxide, zinc oxide, ferroferric oxide, ferric oxide, tungsten oxide and manganese dioxide;
the OI value of the graphene-based gas-sensitive material is 10-25;
the graphene-based gas-sensitive material has an OI value of: and (3) testing the ratio of the peak area of the 004 characteristic peak to the peak area of the 110 characteristic peak by using an XRD diffractometer.
2. The graphene-based gas-sensitive material according to claim 1, wherein the 1# graphene oxide and the 2# graphene oxide are at least partially intercalated and distributed between the 3# graphene oxide layers; and at least partial intercalation of the No. 1 graphene oxide is distributed among the No. 2 graphene oxide layers.
3. The graphene-based gas-sensitive material according to claim 2, wherein the compound graphene oxide is prepared by compounding the following graphene oxide in parts by weight: 20-30 parts of No. 1 graphene oxide, 15-20 parts of No. 2 graphene oxide and 10-15 parts of No. 3 graphene oxide.
4. The graphene-based gas-sensitive material according to claim 1, wherein the metal oxide particles have a particle size distribution in the range of 5-30 nm.
5. A preparation method of a graphene-based gas-sensitive material is characterized by comprising the following specific preparation steps:
compounding the following graphene oxide in parts by weight: 20-30 parts of 1# graphene oxide with D50 of 10-50nm, 15-20 parts of 2# graphene oxide with D50 of 100-200nm, and 10-15 parts of 3# graphene oxide with D50 of 500-1200 nm;
dispersing the compounded graphene oxide in water, carrying out ultrasonic stripping, adding metal oxide particles, continuing ultrasonic dispersion, carrying out suction filtration, and drying to obtain a dry filter cake;
rolling the obtained dry filter cake to adjust the OI value to 10-25;
the metal oxide is selected from: any one of cobalt oxide, cobaltous oxide, tin oxide, cuprous oxide, zinc oxide, ferroferric oxide, ferric oxide, tungsten oxide and manganese dioxide;
the OI value is: and (3) testing the ratio of the peak area of the 004 characteristic peak to the peak area of the 110 characteristic peak by using an XRD diffractometer.
6. The method for preparing the graphene-based gas-sensitive material according to claim 5, wherein the metal oxide particles have a particle size distribution range of 5-30 nm.
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