CN106290489A - A kind of porous graphene gas sensor and preparation method thereof - Google Patents
A kind of porous graphene gas sensor and preparation method thereof Download PDFInfo
- Publication number
- CN106290489A CN106290489A CN201610959550.5A CN201610959550A CN106290489A CN 106290489 A CN106290489 A CN 106290489A CN 201610959550 A CN201610959550 A CN 201610959550A CN 106290489 A CN106290489 A CN 106290489A
- Authority
- CN
- China
- Prior art keywords
- graphene
- porous
- gas sensor
- preparation
- graphene oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
Abstract
The invention discloses a kind of porous graphene gas sensor and preparation method thereof, by using high power ultraviolet irradiation one step to reduce and etching oxidation graphite, and obtained porous redox graphene dispersion liquid is spun to electrode surface, thus obtain porous graphene gas sensor.Porous graphene gas sensor obtained by the present invention has high sensitivity to ammonia molecule；Its preparation method technique is simple, is suitable for a large amount of preparations of sensor.
Description
Technical field
The present invention relates to sensor technical field, be specifically related to a kind of nano-sensor and preparation method thereof, particularly relate to
A kind of porous graphene gas sensor and preparation method thereof.
Background technology
Gas sensor plays the most important effect in fields such as environmental monitoring, food safety, health cares.With
The development of nanotechnology, use metal-oxide semiconductor (MOS) nano-particle, carbon nanomaterial and two-dimensional nano-film etc. the most
Constitute gas sensor through being used as sensitive material, there is compared with traditional sensors more excellent detection performance.Wherein,
Graphene, since 2004 are found, have caused and has paid close attention to widely.Due to the bi-dimensional cellular structure of its uniqueness, Graphene has
Have many irreplaceable advantages of conventional sensors material, therefore, its as sensing material biology, chemistry, machinery, aviation,
The aspects such as military affairs have development prospect widely.
Various methods (such as stripping method, chemical vapor infiltration, epitaxial growth method, chemistry or thermal reduction graphite oxide method
Deng) Graphene prepared all shows good response performance to gas molecule.Wherein, solwution method is a kind of extensive system
The method of standby Graphene is it is considered to be the most potential technology realizing Graphene industrialization.The oxygen reduction fossil that solwution method obtains
Ink alkene shows good gas sensing performance, owing to its surface modificability is strong, it is simple to realize sensor to gas molecule
High selectivity responds, and therefore, redox graphene gas sensor application potential is huge.
In view of easily the piling up property of Graphene, the compact texture of formation is unfavorable for the abundant work of sensing material and gas molecule
With and response, it is therefore necessary to improve the specific surface area of Graphene network, give full play to graphene film unit and gas molecule
Contact area.So, research and develop new method to utilize solwution method to prepare the Graphene network of porous, for realizing highly sensitive stone
Preparing on a large scale of ink alkene sensor is significant.
Summary of the invention
The present invention is directed to deficiencies of the prior art, it is provided that a kind of porous graphene gas sensor and preparation thereof
Method, uses high power ultraviolet one step etching redox graphene, while realizing graphene oxide etching, it is achieved oxidation
The partial reduction of Graphene, ammonia is shown the sensitiveest by the gas sensor using this porous redox graphene to make
Response performance.
The present invention is achieved by the following technical solutions, the preparation method of a kind of porous graphene gas sensor, bag
Include following steps:
(1) liquid oxidizer and sulfate are added in graphene oxide water solution, be 1～4 with acid for adjusting pH；The most ultrasonic
Process forms graphene oxide dispersion；
(2) carry out dialysis treatment after graphene oxide dispersion ultraviolet being processed, obtain porous redox graphene dispersion liquid；
The power that described ultraviolet processes is 1500 W～3000 W, and the time is 30 s～30 min；
(3) porous redox graphene dispersion liquid is spun to electrode surface, dried, obtains porous graphene air-sensitive and pass
Sensor.
In technique scheme, step (1) is the preparation of graphene oxide dispersion；Described graphene oxide can pass through
Hummers method, Brodie method or Staudenmaier method are prepared from；Preferably before adding liquid oxidizer and sulfate
First graphene oxide water solution dispersion being processed 1～5 hour, beneficially graphene oxide dispersion is avoided gathering, and and liquid oxidation
Agent and the good reaction interface of sulfate formation.
In technique scheme, in step (1), liquid oxidizer adds graphene oxide water with aqueous oxidizing agent solution form
In solution, sulfate adds in graphene oxide water solution with sulfate solution form；Described graphene oxide water solution
Concentration is 0.2～5 mg/mL, preferably 0.5～3 mg/mL；The concentration of sulfate solution is 0.2mM～5mM, is preferably
0.5mM～2mM；The concentration of aqueous oxidizing agent solution is 1wt%～4wt%, preferably 1.5wt%～3wt%；Graphene oxide is water-soluble
Liquid, aqueous oxidizing agent solution, the volume ratio of sulfate solution are (150～250): (80～120): 1, are preferably (190～210)
: (90～105): 1.The parameter area that the present invention limits, can realize nano-pore being uniformly distributed at graphene film, crosses vast scale and carves
Erosion will obtain the broken little nano-graphene sheet of atresia, and what too small concentration obtained is the graphene film with oxy radical.
In technique scheme, in step (1), liquid oxidizer is hydrogen peroxide；Sulfate is ferrous sulfate；Acid is salt
Acid.Mixed solution realizes etching and the reduction offer media environment of graphene oxide sheet for a step.
In technique scheme, in step (1), the power of supersound process is 50～100 kHz, and the time is 10 min～1
h.Graphite oxide is placed in mixed solution, can attract each other between particle, causes dispersion stability poor, and ultrasonic disperse can drop
Low interparticle concentration effect, provides good basis for forming uniform Graphene.
In technique scheme, step (2) is the preparation of porous redox graphene dispersion liquid, is porous stone of the present invention
The key of ink alkene gas sensor；The preparation of porous redox graphene dispersion liquid refers to be placed in graphene oxide dispersion
Next step reduction etching reaction of high power ultraviolet lamp, reaction end is placed in bag filter, dialyses in deionized water and obtains
Porous redox graphene dispersion liquid；Limit the power of uviol lamp as 1500 W～3000 W, preferably 1500 W～2000 W,
It is 30 s～30 min that ultraviolet processes the time, preferably 30 s～60s, can not only redox graphene, and etched
Graphene, the just creative place of the present invention.The present invention uses ultraviolet to process graphene oxide dispersion, high-power purple first
Outer process not only obtains porous graphene, and is simultaneously achieved the reduction of graphene oxide, and the color of graphene solution is by shallow
Ash is transparent becomes atrous, and nanometer sheet is become conduction by insulation, and along with the intensification of reducing degree, resistance is gradually lowered, it is to avoid
Existing reduction treatment must utilize the defect of chemical reagent, provides new approach for green chemistry；Particularly, obtain
Porous graphene has nanoscale hole, and the specific surface area of Graphene network can be greatly improved, and solves existing graphene mesh
The defect of the compact structure that network causes due to Graphene easily piling up property, and it is simple to etch pore process, can large-scale production, it is to avoid
Existing porous graphene needs high temperature (temperature of carbon thermal reduction), productivity is low, porosity is low and uncontrollable, pore size distribution uniformity
The problem of difference；Especially present invention achieves the graphene oxide reduction under the conditions of oxidant, prior art thinks oxidant
Existence cannot redox graphene, but the present invention strengthen UV power, limit ultraviolet process the time, simultaneously compatibility close
The oxidant of suitable ratio and sulfate, and limit dispersion liquid acid number, it is achieved that the reduction of graphene oxide, not only obtain comparing table
The Graphene that area is excellent, and obtained the redox graphene of excellent electrical property, it is used for for bigger serface Graphene
Gas sensor plays a crucial role, and achieves beyond thought technique effect.
The present invention uses high power ultraviolet means, energy one step to realize etching and the reduction of graphene oxide sheet, and this is existing
Technology institute under oxidant hydrogen peroxide environment is inaccessiable.Under prior art, due to double containing oxidant in graphene solution
Oxygen water, only there is the etching of graphene oxide in solution, it is impossible to the drastic reduction of graphene oxide sheet, the porous oxidation obtained occur
Graphene film is insulation, it is impossible to realize its electric conductivity.Therefore, high power ultraviolet irradiation of the present invention processes and significantly simplifies porous
The preparation process of graphene film, and speed is fast, prepared by the beneficially low-coat scale of senser element.
In technique scheme, in step (2), the described dialysis treatment time is 3 days～15 days, and molecular cut off is generally
About 10000, dialysis act as removing in solution the impurity such as metal ion, hydrion and the hydrogen peroxide of residual.
In technique scheme, in step (3), by porous redox graphene dispersion liquid rotation steam, formed concentration be 1～
The porous redox graphene dispersion liquid of 5 mg/mL；It is spun to electrode surface again, vacuum drying, thus obtain porous graphite
Alkene gas sensor；The present invention uses spin-coating method to coordinate vacuum drying technique, it is to avoid Graphene transfer easily causes damaged and is stained with
Dirty thus the problem that affects information conversion；Concentrated by rotary evaporation graphene oxide solution, conveniently obtains higher concentration and homodisperse
Porous redox graphene solution, it is to avoid graphene film reunion during dry redispersion and ultrasonic lamella fragmentation are existing
As occurring；Porous graphene sheet forms, at electrode surface, the necessary bar that uniform and stable continuous film is Graphene gas sensor
Part, electrode is positive and negative electrode, uses the photoetching in micro-processing technology and lift-off technology to prepare, controls the spacing of positive and negative electrode
Being 100～800 μm, the spacing of adjacent electrode is 5～50 μm；The present invention is by porous reduction-oxidation that concentration is 1～5 mg/mL
Graphene dispersing solution 0.1～1 mL is spun on electrode surface, 75～85 DEG C of vacuum drying, forms graphene film at electrode surface
Layer, is evenly distributed, and overlap joint electrode forms galvanic circle, has effectively played the excellent electrical of porous redox graphene sheet,
Avoid breakage, stain, gather, fragmentation problem, the gas sensor obtained goes out the sensitiveest response to ammonia molecule displays
Energy
The invention also discloses the porous graphene gas sensor prepared according to above-mentioned preparation method, the wherein conduction of Graphene
Property, excellent in stability, especially good with semi-conducting material Ohmic contact, ammonia molecule is had the sensing capabilities of excellence.
The invention also discloses the preparation method of a kind of porous redox graphene, comprise the following steps:
(1) liquid oxidizer and sulfate are added in graphene oxide water solution, be 1～4 with acid for adjusting pH；The most ultrasonic
Process forms graphene oxide dispersion；
(2) carry out dialysis treatment after graphene oxide dispersion ultraviolet being processed, obtain porous redox graphene dispersion liquid,
Remove solvent and be porous redox graphene；The power that described ultraviolet processes is 1500 W～3000 W, and the time is 30 s
～30 min；The described dialysis treatment time is 3 days～15 days.
Porous redox graphene even pore distribution prepared by the present invention, has good reducing property, especially
Utilize and process outside high-power purple, a step etching reduction, simple to operate, it is not necessary to other reagent, can large-scale production；The porous of preparation is also
Former graphene oxide has the signal conversion performance of excellence after being prepared as gas sensor, have the sensing of excellence to gas molecule
Performance；Therefore the present invention further discloses the application in preparing gas sensor of the above-mentioned porous redox graphene.
Due to the utilization of technique scheme, the present invention compared with prior art, has the advantage that
Outside first passage high-power purple the most of the present invention process graphene oxide and one-step method obtains porous redox graphene,
Not only surface of graphene oxide oxy radical is reduced, and in graphene film, prepare equally distributed hole, collection etching
Reduction one, especially solves the problem that graphene oxide in the presence of oxidant cannot reduce, and is a kind of simple and quick, green
The industrial method of environmental protection.
2. the method comprises the steps of firstly, preparing the graphene oxide dispersion of stably dispersing, then outside high-power purple at process, dialysis
Reason obtains porous redox graphene, is finally spun on electrode surface and obtains gas sensor, the electric conductivity of Graphene, stable
Property excellent, especially good with semi-conducting material Ohmic contact, thus ammonia molecule is had the sensing capabilities of excellence.
High power ultraviolet irradiation the most disclosed by the invention processes the preparation process significantly simplifying porous graphene sheet, has
Prepared by the low-coat scale being beneficial to realize high performance device；The Graphene of preparation also has except having huge specific surface area
Excellent electric conductivity, such that it is able to prepare gas sensor of good performance.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of the porous graphene gas sensor of embodiment one preparation；
Fig. 2 is the porous graphene gas sensor of the embodiment one preparation electrical response curve chart to 50 ppm ammonia molecules；
Fig. 3 is the porous graphene gas sensor of the embodiment three preparation electrical response curve chart to 50 ppm ammonia molecules；
Fig. 4 is the porous graphene gas sensor of the embodiment five preparation electrical response curve chart to 50 ppm ammonia molecules.
Detailed description of the invention
Embodiment one
The preparation method of a kind of porous graphene gas sensor, comprises the following steps:
(1) the 1 mg/mL graphene oxide water solution ultrasonic disperse obtained in 20 mL Hummers methods adds after processing 3 hours
Hydrochloric acid, makes the pH value of graphene oxide water solution reach 4；Being subsequently adding concentration is 3 wt% hydrogen peroxide solution 10 mL, adds
Concentration is ultrasonic 10 min of copperas solution 0.1 mL, 80 Hz of 1 mM, forms graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 1500 W uviol lamps after reactive ion etching 30 s, is placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid obtained；
(3) using the photoetching in micro-processing technology and lift-off technology to prepare gold electrode, the spacing controlling positive and negative electrode is 500 μm,
The spacing of adjacent electrode is 8 μm；Take 0.2 mL porous graphene dispersion liquid (2 mg/L) and be spun to electrode surface, 80 DEG C of vacuum
Being dried 1h, thus obtain porous graphene gas sensor, electrical response value is 1.2 M Ω.
Fig. 1 is the scanning electron microscope diagram of above-mentioned porous graphene sensor, it can be seen that electrode surface covers one layer
Uniform Graphene, overlap joint electrode forms galvanic circle.
Fig. 2 is the sensor electrical response curve chart to 50 ppm ammonia molecules, and sensor is to ammonia molecule displays
Go out the sensitiveest response performance.
Embodiment two
The preparation method of a kind of porous graphene gas sensor, comprises the following steps:
(1) the 0.5 mg/mL graphene oxide water solution ultrasonic disperse obtained in 20 mL Hummers methods adds after processing 3 hours
Enter hydrochloric acid, make the pH value of graphene oxide water solution reach 4；Being subsequently adding concentration is 3 wt% hydrogen peroxide solution 10 mL, then adds
Enter copperas solution 0.1 ultrasonic 10 min of mL, 80 Hz that concentration is 1 mM, form graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 1500 W uviol lamps after reactive ion etching 30 s, is placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid obtained；
(3) using the photoetching in micro-processing technology and lift-off technology to prepare gold electrode, the spacing controlling positive and negative electrode is 500 μm,
The spacing of adjacent electrode is 8 μm；Take 0.2 mL porous graphene dispersion liquid (2 mg/L) and be spun to electrode surface, 80 DEG C of vacuum
Being dried 1h, thus obtain porous graphene gas sensor, resistance value is 3.1 M Ω.
Embodiment three
The preparation method of a kind of porous graphene gas sensor, comprises the following steps:
(1) the 1mg/mL graphene oxide water solution dispersion obtained in 20 mL Hummers methods adds hydrochloric acid after processing 3 hours,
The pH value making graphene oxide water solution reaches 4；Being subsequently adding concentration is 1.5 wt% hydrogen peroxide solution 10 mL, adds concentration
It is ultrasonic 10 min of copperas solution 0.1 mL, 80 Hz of 1 mM, forms graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 1500 W uviol lamps after reactive ion etching 30 s, is placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid obtained；
(3) using the photoetching in micro-processing technology and lift-off technology to prepare gold electrode, the spacing controlling positive and negative electrode is 500 μm,
The spacing of adjacent electrode is 8 μm；Take 0.2 mL porous graphene dispersion liquid (2 mg/L) and be spun to electrode surface, 80 DEG C of vacuum
Being dried 1h, thus obtain porous graphene gas sensor, resistance value is 1.0 M Ω.
Fig. 3 is the sensor electrical response curve chart to 50 ppm ammonia molecules, and sensor is to ammonia molecule displays
Go out the sensitiveest response performance.
Embodiment four
The preparation method of a kind of porous graphene gas sensor, comprises the following steps:
(1) the 1 mg/mL graphene oxide water solution dispersion obtained in 20 mL Hummers methods adds hydrochloric acid after processing 3 hours,
The pH value making graphene oxide water solution reaches 4；Being subsequently adding concentration is 3 wt% hydrogen peroxide solution 10 mL, and adding concentration is
Ultrasonic 10 min of copperas solution 0.1 mL, 80 Hz of 1 mM, form graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 1500 W uviol lamps after reactive ion etching 1 min, is placed in bag filter
After deionized water is dialysed 7 days, the porous graphene dispersion liquid obtained；
(3) using the photoetching in micro-processing technology and lift-off technology to prepare gold electrode, the spacing controlling positive and negative electrode is 500 μm,
The spacing of adjacent electrode is 8 μm；Take 0.2 mL porous graphene dispersion liquid (2 mg/L) and be spun to electrode surface, 80 DEG C of vacuum
Being dried 1h, thus obtain porous graphene gas sensor, resistance value is 2.1 M Ω.
Embodiment five
The preparation method of a kind of porous graphene gas sensor, comprises the following steps:
(1) the 1 mg/mL graphene oxide water solution dispersion obtained in 20 mL Hummers methods adds hydrochloric acid after processing 1 hour,
The pH value making graphene oxide water solution reaches 4；Being subsequently adding concentration is 3 wt% hydrogen peroxide solution 10 mL, and adding concentration is
Ultrasonic 10 min of copperas solution 0.1 mL, 80Hz of 1 mM, form graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 2000 W uviol lamps after reactive ion etching 30 s, is placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid obtained；
(3) using the photoetching in micro-processing technology and lift-off technology to prepare gold electrode, the spacing controlling positive and negative electrode is 500 μm,
The spacing of adjacent electrode is 8 μm；Take 0.2 mL porous graphene dispersion liquid (2 mg/L) and be spun to electrode surface, 80 DEG C of vacuum
Being dried 1h, thus obtain porous graphene gas sensor, resistance value is 1.5 M Ω.
Fig. 4 is the sensor electrical response curve chart to 50 ppm ammonia molecules, and sensor is to ammonia molecule displays
Go out the sensitiveest response performance.
Embodiment six
The preparation method of a kind of porous graphene gas sensor, comprises the following steps:
(1) the 1 mg/mL graphene oxide water solution dispersion obtained in 20 mL Hummers methods adds hydrochloric acid after processing 3 hours,
The pH value making graphene oxide water solution reaches 4；Being subsequently adding concentration is 3 wt% hydrogen peroxide solution 10 mL, and adding concentration is
Ultrasonic 10 min of copperas solution 0.1 mL, 80Hz of 1 mM, form graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 1500 W uviol lamps after reactive ion etching 30 s, is placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid obtained；
(3) using the photoetching in micro-processing technology and lift-off technology to prepare gold electrode, the spacing controlling positive and negative electrode is 500 μm,
The spacing of adjacent electrode is 8 μm；Take 0.2 mL porous graphene dispersion liquid (5 mg/L) and be spun to electrode surface, 80 DEG C of vacuum
Being dried 1h, thus obtain porous graphene gas sensor, resistance value is 0.6 M Ω.
Embodiment seven
The preparation method of a kind of porous graphene gas sensor, comprises the following steps:
(1) the 1 mg/mL graphene oxide water solution dispersion obtained in 20 mL Hummers methods adds hydrochloric acid after processing 5 hours,
The pH value making graphene oxide water solution reaches 4；Being subsequently adding concentration is 3 wt% hydrogen peroxide solution 10 mL, and adding concentration is
Ultrasonic 10 min of copperas solution 0.1 mL, 100Hz of 1 mM, form graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 1500 W uviol lamps after reactive ion etching 30 s, is placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid obtained；
(3) using the photoetching in micro-processing technology and lift-off technology to prepare gold electrode, the spacing controlling positive and negative electrode is 500 μm,
The spacing of adjacent electrode is 8 μm；Take 0.5 mL porous graphene dispersion liquid (2 mg/L) and be spun to electrode surface, 80 DEG C of vacuum
Being dried 1h, thus obtain porous graphene gas sensor, resistance value is 0.8 M Ω.
Embodiment eight
The preparation method of a kind of porous graphene gas sensor, comprises the following steps:
(1) the 1 mg/mL graphene oxide water solution dispersion obtained in 20 mL Hummers methods adds hydrochloric acid after processing 3 hours,
The pH value making graphene oxide water solution reaches 4；Being subsequently adding concentration is 2 wt% hydrogen peroxide solution 10 mL, and adding concentration is
Ultrasonic 10 min of copperas solution 0.1 mL, 100Hz of 1 mM, form graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 1500 W uviol lamps after reactive ion etching 30s, be placed in bag filter go from
After sub-water is dialysed 7 days, the porous graphene dispersion liquid obtained；
(3) using the photoetching in micro-processing technology and lift-off technology to prepare gold electrode, the spacing controlling positive and negative electrode is 500 μm,
The spacing of adjacent electrode is 8 μm；Take 0.5 mL porous graphene dispersion liquid (3 mg/L) and be spun to electrode surface, 80 DEG C of vacuum
Being dried 1h, thus obtain porous graphene gas sensor, resistance value is 1.7 M Ω.
Embodiment nine
The preparation method of a kind of porous graphene gas sensor, comprises the following steps:
(1) the 1 mg/mL graphene oxide water solution dispersion obtained in 25 mL Hummers methods adds hydrochloric acid after processing 2 hours,
The pH value making graphene oxide water solution reaches 4；Being subsequently adding concentration is 3 wt% hydrogen peroxide solution 10 mL, and adding concentration is
Ultrasonic 10 min of copperas solution 0.1 mL, 100Hz of 1 mM, form graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 2000 W uviol lamps after reactive ion etching 30 s, is placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid obtained；
(3) using the photoetching in micro-processing technology and lift-off technology to prepare gold electrode, the spacing controlling positive and negative electrode is 400 μm,
The spacing of adjacent electrode is 15 μm；Take 0.8 mL porous graphene dispersion liquid (2 mg/L) and be spun to electrode surface, 80 DEG C of vacuum
Being dried 1h, thus obtain porous graphene gas sensor, resistance value is 0.6 M Ω.
Embodiment ten
The preparation method of a kind of porous graphene gas sensor, comprises the following steps:
(1) the 1 mg/mL graphene oxide water solution dispersion obtained in 20 mL Hummers methods adds hydrochloric acid after processing 3 hours,
The pH value making graphene oxide water solution reaches 3；Being subsequently adding concentration is 3 wt% hydrogen peroxide solution 9 mL, and adding concentration is 2
Ultrasonic 10 min of copperas solution 0.1 mL, 80Hz of mM, form graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 1500 W uviol lamps after reactive ion etching 70 s, is placed in bag filter
After ionized water is dialysed 15 days, the porous graphene dispersion liquid obtained；
(3) using the photoetching in micro-processing technology and lift-off technology to prepare gold electrode, the spacing controlling positive and negative electrode is 500 μm,
The spacing of adjacent electrode is 8 μm；Take 0.5 mL porous graphene dispersion liquid (2 mg/L) and be spun to electrode surface, 80 DEG C of vacuum
Being dried 1h, thus obtain porous graphene gas sensor, resistance value is 1.6 M Ω.
Comparative example one
The preparation method of a kind of porous graphene gas sensor, comprises the following steps:
(1) the 1 mg/mL graphene oxide water solution dispersion obtained in 20 mL Hummers methods adds hydrochloric acid after processing 3 hours,
The pH value making graphene oxide water solution reaches 4；Being subsequently adding concentration is 3 wt% hydrogen peroxide solution 10 mL, and adding concentration is
Ultrasonic 10 min of copperas solution 0.1 mL, 80 Hz of 1 mM, form graphene oxide dispersion；
(2) above-mentioned graphene oxide dispersion is placed under 500 W uviol lamps after reactive ion etching 400 s, is placed in bag filter
After ionized water is dialysed 7 days, the porous graphene dispersion liquid obtained；
(3) using the photoetching in micro-processing technology and lift-off technology to prepare gold electrode, the spacing controlling positive and negative electrode is 500 μm,
The spacing of adjacent electrode is 8 μm；Take 0.2 mL porous graphene dispersion liquid (2 mg/L) and be spun to electrode surface, 80 DEG C of vacuum
Being dried 1h, thus obtain porous graphene gas sensor, resistance is without response.
It can be seen that porous redox graphene even pore distribution prepared by the present invention, there is good reproducibility
Can, process especially with outside high-power purple, a step etching reduction, there is while there is loose structure good electric conductivity,
Electrode surface covers one layer of uniform Graphene, and overlap joint electrode forms galvanic circle；Simple to operate, it is not necessary to other reagent, can advise
Mould produces；The porous redox graphene of preparation has the signal conversion performance of excellence after being prepared as gas sensor, to gas
Body molecule has the sensing capabilities of excellence；Achieve beyond thought technique effect.
Claims (10)
1. the preparation method of a porous graphene gas sensor, it is characterised in that comprise the following steps:
(1) liquid oxidizer and sulfate are added in graphene oxide water solution, be 1～4 with acid for adjusting pH；The most ultrasonic
Process forms graphene oxide dispersion；
(2) carry out dialysis treatment after graphene oxide dispersion ultraviolet being processed, obtain porous redox graphene dispersion liquid；
The power that described ultraviolet processes is 1500 W～3000 W, and the time is 30 s～30 min；
(3) porous redox graphene dispersion liquid is spun to electrode surface, dried, obtains porous graphene air-sensitive and pass
Sensor.
The preparation method of porous graphene gas sensor the most according to claim 1, it is characterised in that: in step (1),
Liquid oxidizer adds in graphene oxide water solution with aqueous oxidizing agent solution form, and sulfate adds with sulfate solution form
Enter in graphene oxide water solution；The concentration of described graphene oxide water solution is 0.2～5 mg/mL, sulfate solution
Concentration is 0.2 mM～5 mM, and the concentration of aqueous oxidizing agent solution is 1 wt%～4 wt%；Graphene oxide water solution, oxidant water
Solution, the volume ratio of sulfate solution are (150～250): (80～120): 1；The power of described supersound process is 50～100
KHz, the time is 10 min～1 h.
The preparation method of porous graphene gas sensor the most according to claim 2, it is characterised in that: in step (1), use
Salt acid for adjusting pH；Liquid oxidizer is hydrogen peroxide；Sulfate is ferrous sulfate；Regulation pH is 4；Graphene oxide water solution, oxygen
Agent aqueous solution, the volume ratio of sulfate solution are (190～210): (90～105): 1.
The preparation method of porous graphene gas sensor the most according to claim 1, it is characterised in that: in step (2),
The power that described ultraviolet processes is 1500 W～2000 W, and the time is 30 s～60s.
The preparation method of porous graphene gas sensor the most according to claim 1, it is characterised in that: in step (2), institute
Stating the dialysis treatment time is 3 days～15 days；Dialysis is carried out in deionized water.
The preparation method of porous graphene gas sensor the most according to claim 1, it is characterised in that: in step (3),
The rotation of porous redox graphene dispersion liquid being steamed, forming concentration is 1～5 mg/mL porous redox graphene dispersion liquids,
Take this dispersion liquid 0.1～1 mL and be spun to electrode surface；Described dried is 75～85 DEG C of vacuum drying treatment；Described electrode
In, the spacing of positive and negative electrode is 100～800 μm, and the spacing of adjacent electrode is 5～50 μm.
Porous stone prepared by the preparation method of any one porous graphene gas sensor the most according to claims 1 to 6
Ink alkene gas sensor.
8. the preparation method of a porous redox graphene, it is characterised in that comprise the following steps:
(1) liquid oxidizer and sulfate are added in graphene oxide water solution, be 1～4 with acid for adjusting pH；The most ultrasonic
Process forms graphene oxide dispersion；
(2) carry out dialysis treatment after graphene oxide dispersion ultraviolet being processed, obtain porous redox graphene dispersion liquid,
Remove solvent and be porous redox graphene；The power that described ultraviolet processes is 1500 W～3000 W, and the time is 30 s
～30 min；The described dialysis treatment time is 3 days～15 days.
The porous redox graphene that the most according to claim 8, prepared by the preparation method of porous redox graphene.
10. porous redox graphene application in preparing porous graphene gas sensor described in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610959550.5A CN106290489A (en) | 2016-10-27 | 2016-10-27 | A kind of porous graphene gas sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610959550.5A CN106290489A (en) | 2016-10-27 | 2016-10-27 | A kind of porous graphene gas sensor and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106290489A true CN106290489A (en) | 2017-01-04 |
Family
ID=57719219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610959550.5A Pending CN106290489A (en) | 2016-10-27 | 2016-10-27 | A kind of porous graphene gas sensor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106290489A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109142466A (en) * | 2018-07-20 | 2019-01-04 | 西安交通大学 | The pollution-free shifting process of CVD graphene obtains the air-sensitive film sensor and method of graphene oxide and graphene composite structure |
| CN110609067A (en) * | 2018-06-16 | 2019-12-24 | 浙江晨阳新材料有限公司 | Alcohol sensor and preparation method thereof |
| CN112226104A (en) * | 2020-09-22 | 2021-01-15 | 广东极客亮技术有限公司 | Ultraviolet-proof graphene coating with hierarchical pore structure, ultraviolet-proof material and preparation method of ultraviolet-proof graphene coating |
| CN112758918A (en) * | 2021-02-22 | 2021-05-07 | 陕西科技大学 | Preparation method and application of purple phosphorus/graphene composite material |
| CN117030802A (en) * | 2023-08-08 | 2023-11-10 | 天津大学 | Ammonia gas sensor based on thermal reduction graphene oxide and preparation method thereof |
| WO2023231191A1 (en) * | 2022-05-30 | 2023-12-07 | 苏州大学 | Sno2/nio/graphene ternary composite material, and preparation method therefor and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103196962A (en) * | 2013-04-18 | 2013-07-10 | 苏州大学 | Oxidized graphene film vertical type micro-nano structured gas sensor and preparation method thereof |
| CN103257156A (en) * | 2013-05-15 | 2013-08-21 | 苏州大学 | Gas sensor based on reduction-oxidation graphene and preparation method of gas sensor |
| CN103616413A (en) * | 2013-12-12 | 2014-03-05 | 苏州大学 | Gas sensor based on reduction-oxidation graphene and preparation method of gas sensor |
| KR20140093930A (en) * | 2011-09-19 | 2014-07-29 | 유니버시티 오브 울롱공 | Reduced graphene oxide and method of producing same |
-
2016
- 2016-10-27 CN CN201610959550.5A patent/CN106290489A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140093930A (en) * | 2011-09-19 | 2014-07-29 | 유니버시티 오브 울롱공 | Reduced graphene oxide and method of producing same |
| CN103196962A (en) * | 2013-04-18 | 2013-07-10 | 苏州大学 | Oxidized graphene film vertical type micro-nano structured gas sensor and preparation method thereof |
| CN103257156A (en) * | 2013-05-15 | 2013-08-21 | 苏州大学 | Gas sensor based on reduction-oxidation graphene and preparation method of gas sensor |
| CN103616413A (en) * | 2013-12-12 | 2014-03-05 | 苏州大学 | Gas sensor based on reduction-oxidation graphene and preparation method of gas sensor |
Non-Patent Citations (3)
| Title |
|---|
| D. H. WANG: ""Holey reduced graphene oxide nanosheets for high performance room temperature gas sensing"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| L. GUARDIA 等: ""UV light exposure of aqueous graphene oxide suspensions to promote their direct reduction, formation of graphene–metal nanoparticle hybrids and dye degradation"", 《CARBON》 * |
| XUEJIAO ZHOU 等: ""Photo-Fenton Reaction of Graphene Oxide: A New Strategy to Prepare Graphene Quantum Dots for DNA Cleavage"", 《ACS NANO》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110609067A (en) * | 2018-06-16 | 2019-12-24 | 浙江晨阳新材料有限公司 | Alcohol sensor and preparation method thereof |
| CN110609067B (en) * | 2018-06-16 | 2022-08-23 | 浙江晨阳新材料有限公司 | Alcohol sensor and preparation method thereof |
| CN109142466A (en) * | 2018-07-20 | 2019-01-04 | 西安交通大学 | The pollution-free shifting process of CVD graphene obtains the air-sensitive film sensor and method of graphene oxide and graphene composite structure |
| CN109142466B (en) * | 2018-07-20 | 2022-05-20 | 西安交通大学 | Gas-sensitive thin film sensor and method for obtaining graphene oxide and graphene composite structure by CVD graphene pollution-free transfer process |
| CN112226104A (en) * | 2020-09-22 | 2021-01-15 | 广东极客亮技术有限公司 | Ultraviolet-proof graphene coating with hierarchical pore structure, ultraviolet-proof material and preparation method of ultraviolet-proof graphene coating |
| CN112226104B (en) * | 2020-09-22 | 2021-08-31 | 广东极客亮技术有限公司 | Ultraviolet-proof graphene coating with hierarchical pore structure, ultraviolet-proof material and preparation method of ultraviolet-proof graphene coating |
| CN112758918A (en) * | 2021-02-22 | 2021-05-07 | 陕西科技大学 | Preparation method and application of purple phosphorus/graphene composite material |
| WO2023231191A1 (en) * | 2022-05-30 | 2023-12-07 | 苏州大学 | Sno2/nio/graphene ternary composite material, and preparation method therefor and application thereof |
| CN117030802A (en) * | 2023-08-08 | 2023-11-10 | 天津大学 | Ammonia gas sensor based on thermal reduction graphene oxide and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106290489A (en) | A kind of porous graphene gas sensor and preparation method thereof | |
| Li et al. | Graphene oxide-enzyme hybrid nanoflowers for efficient water soluble dye removal | |
| CN106556677B (en) | A kind of three-dimensional porous graphene extra-thin film gas sensor and preparation method thereof | |
| CN105883781B (en) | A kind of preparation method of large area redox graphene film | |
| Chu et al. | Phosphorus doped and defects engineered graphene for improved electrochemical sensing: synergistic effect of dopants and defects | |
| CN109706507A (en) | A kind of two-dimentional MXene film and preparation method thereof with vertical channel structure | |
| CN107235486B (en) | The preparation method of water-soluble graphene | |
| CN107954420B (en) | A kind of method that Anodic removing graphite prepares three-dimensional grapheme | |
| CN105319242A (en) | Application of tungsten oxide-vanadium oxide heterojunction nanowire array as gas sensitive material | |
| CN107703195A (en) | A kind of preparation method of graphene metal organic frame composite modified electrode | |
| Zarei et al. | Zirconia nanoparticle-modified graphitic carbon nitride nanosheets for effective photocatalytic degradation of 4-nitrophenol in water | |
| Kaniyoor et al. | Enhanced efficiency in dye sensitized solar cells with nanostructured Pt decorated multiwalled carbon nanotube based counter electrode | |
| CN109745865A (en) | It is a kind of based on graphite/composite titania material Kynoar electro-catalysis ultrafiltration membrane | |
| CN101764007B (en) | Method for producing nano graphite field emission vacuum electronic cathode | |
| CN110272100A (en) | Ti4O7Preparation method of ceramic microfiltration membrane electrode of coating | |
| CN107983161A (en) | A kind of application of two dimension MXene films in water and separation of ethanol | |
| CN106596654B (en) | Vertical response type gas sensor based on three-dimensional porous graphene extra-thin film and preparation method thereof | |
| CN106587277A (en) | Carbon black-nanometer iron oxide/polytetrafluoroethylene heterogeneous tubular membrane electrode | |
| CN109694056A (en) | A kind of method that liquid phase removing graphite oxide prepares graphene | |
| CN106770493B (en) | A kind of acetone gas sensor and preparation method thereof based on CNTs@α-Fe2O3 heterojunction composite | |
| CN108615617A (en) | A kind of graphene/PEDOT：Preparation method of PSS composite Nano self-supporting films and products thereof and application | |
| CN102698741A (en) | Method for preparing grapheme platinum nanocomposite material by using argon plasma | |
| CN106277059A (en) | A kind of method preparing tungsten disulfide/Graphene heterojunction structure | |
| CN105869892B (en) | A kind of High-performance graphene membrane electrode and preparation method thereof | |
| CN111545437B (en) | Metal and carbon-based material electrode surface carbon nano tube coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170104 |