CN103616415A - Room-temperature oxidized graphene/phthalocyanin composite ammonia sensitive element and preparation method thereof - Google Patents
Room-temperature oxidized graphene/phthalocyanin composite ammonia sensitive element and preparation method thereof Download PDFInfo
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- CN103616415A CN103616415A CN201310703538.4A CN201310703538A CN103616415A CN 103616415 A CN103616415 A CN 103616415A CN 201310703538 A CN201310703538 A CN 201310703538A CN 103616415 A CN103616415 A CN 103616415A
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Abstract
The invention discloses a room-temperature oxidized graphene/phthalocyanin composite ammonia sensitive element and a preparation method thereof, relating to an ammonia sensitive element and a preparation method thereof. The invention aims to solve the technical problems that the reversibility and selectivity of an oxidized graphene ammonia sensitive element are poor and a gas sensitive element with metal phthalocyanin as an ammonia sensitive material has a relatively high resistance value. The method comprises the steps of firstly, preparing an oxidized graphene/phthalocyanin composite ammonia sensitive material; secondly, preparing an oxidized graphene/phthalocyanin composite gas sensitive element. The room-temperature oxidized graphene/phthalocyanin composite ammonia sensitive element has better response at room temperature within the NH3 concentration range of 12.5-3200ppm, has a good linear relation between NH3 concentration and the response within a relatively low NH3 concentration range, and has favorable sensitivity, reversibility and stability in different-concentration ammonia gases. The room-temperature oxidized graphene/phthalocyanin composite ammonia sensitive element and the preparation method thereof belong to the preparation field of gas sensitive elements.
Description
Technical field
The present invention relates to a kind of ammonia photosensitive elements and preparation method thereof.
Background technology
Compare with traditional gas sensitive, Graphene has unique two-dimensional nanostructure, huge specific surface area, quite high conductivity, carrier mobility and stable physicochemical property, be the class gas sensitization nano material that Recent study is maximum, with fastest developing speed, have research and practical value most, become gas sensor field in recent years and fall over each other one of focus of research both at home and abroad.From A.Geim in 2004 and K.Novoselov, successfully isolate first stable Graphene (Graphene), since in succession within 2010, obtaining the Nobel Prize, Graphene is with its outstanding attribute, be subject to the very big attention of physics, chemistry and material supply section educational circles and new high-tech industry department, a large amount of research and development strengths is all dropped in preparation and application aspect in countries in the world, and expectation can be captured the commanding elevation of this technical field.Graphene gas sensor research shows, sensors with auxiliary electrode were has increased the adsorption area to gas, is exposed in gas and can reaches fast higher sensitivity, can meet the harmful gas of actual demand is carried out to fast detecting, but adsorb NH
3be difficult to afterwards return to original state, have the poor problem of recovery capability.Although Graphene has obtained swift and violent development as the research of gas sensitive material in recent years, and obtained a lot of results highly significant, but its release time showing is slow, selectivity is poor, dissolubility and dispersed undesirable and film forming means are limited etc. that problem is urgently to be resolved hurrily.The gas sensor that the organic semiconducting materials that the phthalocyanine of take is representative is ammonia-sensitive material, because phthalocyanine gas sensitive has good selectivity, higher sensitivity, response recovery time, molecular structure such as can design at the advantage faster, in gas sensor field, occupy an important position.Yet this type of gas sensor resistance value higher (>10G Ω), has limited its practical application to a great extent.Utilize the large π bond structure of phthalocyanine plane polyelectron conjugation, and the substituted radical that encircles greatly periphery and the multiple given activity being axially connected, it is one of effective way improving its air-sensitive performance that Graphene is carried out to functional modification.
Summary of the invention
The object of the invention is, in order to solve the higher technical matters of gas sensor resistance value that graphene oxide ammonia photosensitive elements reversibility and selectivity are poor and metal phthalocyanine is ammonia-sensitive material, provides a kind of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements and preparation method thereof.
Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements consists of interdigital electrode and graphene oxide/phthalocyanine composite material; Phthalocyanine in wherein said graphene oxide/phthalocyanine composite material is ammonobase phthalocyanine.
Described ammonobase phthalocyanine general formula is MPcR
x(NH
2)
y, x be wherein 0 or 3, y be 1 or 4, R be alkyl or alkoxy, M is wherein Cu, Ni, Fe, Co, Pb or Zn.
The preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements carries out according to following steps:
One, prepare the compound ammonia-sensitive material of graphene oxide/phthalocyanine:
Graphene oxide is scattered in dimethyl formamide, obtain the solution that graphene oxide concentration is 10-50mg/ml, then according to graphene oxide quality and thionyl chloride volume ratio, being 1mg:(1-2) ratio of ml adds thionyl chloride, agitating heating back flow reaction 24-36 hour under the condition of 70-80 ℃, thionyl chloride is removed in distillation, according to the mass ratio of phthalocyanine and graphene oxide, be (0.5-5): 1, the ratio that phthalocyanine quality and triethylamine volume ratio are (10-30) mg:1mL adds phthalocyanine dimethyl formamide solution and triethylamine, in nitrogen protection, stirring reaction 72-96 hour under the condition of 60-100 ℃, then reactant liquor is poured in distilled water, filter, obtain the thick product of graphene oxide/phthalocyanine compound, use again the thick product of tetrahydrofuran centrifuge washing graphene oxide/phthalocyanine compound colourless to supernatant liquor, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, in 50 ℃ of vacuum drying chambers, graphene oxide/phthalocyanine compound is dried to 24 hours, obtain the compound ammonia-sensitive material of graphene oxide/phthalocyanine,
Two, prepare graphene oxide/phthalocyanine composite material gas sensor:
Ultrasonic being scattered in dimethyl formamide under the condition that the compound ammonia-sensitive material of graphene oxide/phthalocyanine that step 2 is obtained is 40kHz in frequency, obtaining concentration is graphene oxide/phthalocyanine composite material DMF suspending liquid of 0.05mg/mL-1.0mg/mL, graphene oxide/phthalocyanine composite material DMF suspending liquid is evenly coated in interdigital electrode, after solution evaporation, in the vacuum drying chamber of 80 ℃, dry 12-48 hour, obtains Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements.
The present invention has the following advantages:
One, the present invention utilizes electric conductivity and heat, light and the chemical stability of inorganic material excellence, the features such as organic material molecule Scalability, fast, the easy processing of response, cyclical variation by both by component and structure forms compound substance, that realizes inorganic/organic material has complementary functions, optimizes and work in coordination with enhancing, thereby improve the air-sensitive performance of single gas sensitive, to obtain the gas sensor that combination property is more excellent;
Two, Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements that prepared by the present invention, under room temperature, at 12.5ppm-3200ppmNH
3in concentration range, there is good response, and at low concentration NH
3nH in scope
3between concentration and response, there is good linear relationship;
Three, Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements that prepared by the present invention all has good sensitivity, reversibility, stability in variable concentrations ammonia, and the CO to same concentration
2, CO, CH
4and H
2not response, to NH
3there is good selectivity;
Four, Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements that prepared by the present invention has improved the air-sensitive performance of graphene oxide greatly, can be to NH
3detect.
Accompanying drawing explanation
Fig. 1 is response and the ammonia concentration relation curve of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements of experiment one preparation;
The response recovery curve of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements that Fig. 2 is experiment one preparation in variable concentrations ammonia;
Fig. 3 is response and the ammonia concentration relation curve of Oxidation at room temperature Graphene/tetramino Nickel Phthalocyanine compound substance ammonia photosensitive elements of experiment two preparations;
The response recovery curve of Oxidation at room temperature Graphene/tetramino Nickel Phthalocyanine compound substance ammonia photosensitive elements that Fig. 4 is experiment two preparations in variable concentrations ammonia;
Fig. 5 is response and the ammonia concentration relation curve of Oxidation at room temperature Graphene/tetramino FePC compound substance ammonia photosensitive elements of experiment three preparations;
The response recovery curve of Oxidation at room temperature Graphene/tetramino FePC compound substance ammonia photosensitive elements that Fig. 6 is experiment three preparations in variable concentrations ammonia.
Fig. 7 is response and the ammonia concentration relation curve of Oxidation at room temperature Graphene/tetramino Cobalt Phthalocyanine compound substance ammonia photosensitive elements of experiment four preparations;
The response recovery curve of Oxidation at room temperature Graphene/tetramino Cobalt Phthalocyanine compound substance ammonia photosensitive elements that Fig. 8 is experiment four preparations in variable concentrations ammonia;
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: present embodiment Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements consists of interdigital electrode and graphene oxide/phthalocyanine composite material; Phthalocyanine in wherein said graphene oxide/phthalocyanine composite material is ammonobase phthalocyanine.
Under graphene oxide/phthalocyanine composite material ammonia photosensitive elements room temperature described in present embodiment, at 12.5ppm-3200ppmNH
3in concentration range, there is good response, and at low concentration NH
3nH in scope
3between concentration and response, there is good linear relationship.
Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements described in present embodiment all has good sensitivity, reversibility, stability in variable concentrations ammonia, and the CO to same concentration
2, CO, CH
4and H
2not response, to NH
3there is good selectivity.
Embodiment two: what present embodiment was different from embodiment one is that described ammonobase phthalocyanine general formula is MPcR
x(NH
2)
y, x be wherein 0 or 3, y be 1 or 4, R be alkyl or alkoxy, M is wherein Cu, Ni, Fe, Co, Pb or Zn.。Other is identical with embodiment one.
Embodiment three: the preparation method of present embodiment Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements carries out according to following steps:
One, prepare the compound ammonia-sensitive material of graphene oxide/phthalocyanine:
Graphene oxide is scattered in to N, in dinethylformamide, obtain the solution that graphene oxide concentration is 10-50mg/ml, then according to graphene oxide quality and thionyl chloride volume ratio, being 1mg:(1-2) ratio of ml adds thionyl chloride, agitating heating back flow reaction 24-36 hour under the condition of 70-80 ℃, thionyl chloride is removed in distillation, according to the mass ratio of phthalocyanine and graphene oxide, be (0.5-5): 1, the ratio that phthalocyanine quality and triethylamine volume ratio are (10-30) mg:1mL adds phthalocyanine N, dinethylformamide solution and triethylamine, in nitrogen protection, stirring reaction 72-96 hour under the condition of 60-100 ℃, then reactant liquor is poured in distilled water, filter, obtain the thick product of graphene oxide/phthalocyanine compound, use again the thick product of tetrahydrofuran centrifuge washing graphene oxide/phthalocyanine compound colourless to supernatant liquor, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, in 50 ℃ of vacuum drying chambers, graphene oxide/phthalocyanine compound is dried to 24 hours, obtain the compound ammonia-sensitive material of graphene oxide/phthalocyanine,
Two, prepare graphene oxide/phthalocyanine composite material gas sensor:
The ultrasonic N of being scattered under the condition that the compound ammonia-sensitive material of graphene oxide/phthalocyanine that step 2 is obtained is 40kHz in frequency, in dinethylformamide, obtaining concentration is graphene oxide/phthalocyanine composite material DMF suspending liquid of 0.05mg/mL-1.0mg/mL, by graphene oxide/phthalocyanine composite material N, dinethylformamide suspending liquid is evenly coated in interdigital electrode, after solution evaporation, in the vacuum drying chamber of 80 ℃, dry 12-48 hour, obtains Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements.
Present embodiment is utilized electric conductivity and heat, light and the chemical stability of inorganic material excellence, the features such as organic material molecule Scalability, fast, the easy processing of response, cyclical variation by both by component and structure forms compound substance, that realizes inorganic/organic material has complementary functions, optimizes and work in coordination with enhancing, thereby improve the air-sensitive performance of single gas sensitive, to obtain the gas sensor that combination property is more excellent.
Under graphene oxide/phthalocyanine composite material ammonia photosensitive elements room temperature described in present embodiment, at 12.5ppm-3200ppmNH
3in concentration range, there is good response, and at low concentration NH
3nH in scope
3between concentration and response, there is good linear relationship.
Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements prepared by present embodiment all has good sensitivity, reversibility, stability in variable concentrations ammonia, and the CO to same concentration
2, CO, C CH
4and H
2deng not response of gas, to NH
3there is good selectivity.
Prepared by present embodiment take gas sensor that graphene oxide/phthalocyanine composite material is ammonia-sensitive material and has greatly improved the air-sensitive performance of graphene oxide, can be to NH
3detect.
Embodiment four: what present embodiment was different from embodiment three is in step 1, graphene oxide to be scattered in DMF, obtains the solution that graphene oxide concentration is 10mg/ml.Other is identical with embodiment three.
Embodiment five: present embodiment is different from embodiment three or four is to be 1mg:1ml according to graphene oxide quality and thionyl chloride volume ratio in step 1 ratio adds thionyl chloride.Other is identical with embodiment three or four.
Embodiment six: present embodiment is different from one of embodiment three to five is that in step 1, the mass ratio of phthalocyanine and graphene oxide is 5:1.Other is identical with one of embodiment three to five.
Embodiment seven: present embodiment is different from one of embodiment three to six is that in step 1, phthalocyanine quality and triethylamine volume ratio are 25mg:1mL.Other is identical with one of embodiment three to six.
Embodiment eight: present embodiment is different from one of embodiment three to seven be in step 1 under nitrogen protection, the condition of 80 ℃ stirring reaction 80 hours.Other is identical with one of embodiment three to seven.
Embodiment nine: present embodiment is different from one of embodiment three to eight is that the concentration of graphene oxide/phthalocyanine composite material DMF suspending liquid in step 2 is 0.1mg/mL-0.9mg/mL.Other is identical with one of embodiment three to eight.
Embodiment ten: present embodiment is different from one of embodiment three to nine is that the concentration of graphene oxide/phthalocyanine composite material DMF suspending liquid in step 2 is 0.5mg/mL.Other is identical with one of embodiment three to nine.
Adopt following experimental verification effect of the present invention:
Experiment 1:
The preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements carries out according to the following steps:
One, prepare the compound ammonia-sensitive material of graphene oxide/phthalocyanine: 10mg graphene oxide is scattered in to 1mlN, in dinethylformamide solvent, then add 10ml thionyl chloride, 70 ℃ of agitating heating back flow reaction are after 24 hours, thionyl chloride is removed in distillation, adding rapidly 10ml concentration is tetramino CuPc DMF solution and the 2ml triethylamine of 5.0mg/mL, under nitrogen protection, under 80 ℃ of heating conditions, stirring reaction is 80 hours, reactant liquor is poured in distilled water, filter, obtain the thick product of graphene oxide/tetramino CuPc compound, use again the thick product of tetrahydrofuran centrifuge washing graphene oxide/tetramino CuPc compound colourless to supernatant liquor, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, in 50 ℃ of vacuum drying chambers, be dried 24 hours, obtain the compound ammonia-sensitive material of graphene oxide/phthalocyanine.
Two, prepare graphene oxide/phthalocyanine composite material gas sensor: the ultrasonic N of being scattered under the condition that the compound ammonia-sensitive material of graphene oxide/phthalocyanine that step 2 is obtained is 40kHz in frequency, in dinethylformamide, obtaining concentration is 0.5mg/mL graphene oxide/tetramino CuPc compound substance N, dinethylformamide suspending liquid, be evenly coated in interdigital electrode, after solution evaporation, in vacuum drying chamber, under the condition of 80 ℃, be dried 12 hours, obtain Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements.
The response of gas sensor is the changing value of resistance value in ammonia and 100 times of the ratio of resistance value in air, and response time and release time are that gas sensor reaches peaked 90% required time of change in resistance.
Fig. 1 is response and the ammonia concentration relation curve of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements of this experiment preparation, and Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements of this experiment preparation is at 12.5ppm～3200ppmNH as can be seen from Figure 1
3in concentration range, there is good response, and at low concentration 12.5ppm～200ppmNH
3scope NH
3between concentration and response, there is good linear relationship.
The response recovery curve of graphene oxide/tetramino phthalocyanine cuprammonium photosensitive elements that Fig. 2 is this experiment preparation in variable concentrations ammonia, graphene oxide/tetramino phthalocyanine cuprammonium photosensitive elements of this experiment preparation has improved the recovery characteristics of Graphene greatly as can be seen from Figure 2, under room temperature, in variable concentrations ammonia, all there is good restorability, to 50ppm NH
3release time be 55s.
Experiment 2:
The preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements carries out according to the following steps:
One, prepare the compound ammonia-sensitive material of graphene oxide/phthalocyanine: 10mg graphene oxide is scattered in to 1mlN, in dinethylformamide solvent, then add 10ml thionyl chloride, 70 ℃ of agitating heating back flow reaction are after 24 hours, thionyl chloride is removed in distillation, the tetramino Nickel Phthalocyanine N that adds rapidly 10ml5.0mg/mL, dinethylformamide solution and 2ml triethylamine, under nitrogen protection, under 80 ℃ of heating conditions, stirring reaction is 80 hours, reactant liquor is poured in distilled water, filter, obtain the thick product of graphene oxide/tetramino Nickel Phthalocyanine compound, use again tetrahydrofuran centrifuge washing colourless to supernatant liquor, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, in 50 ℃ of vacuum drying chambers, be dried 24 hours, obtain the compound ammonia-sensitive material of graphene oxide/phthalocyanine.
Two, prepare graphene oxide/phthalocyanine composite material gas sensor: the ultrasonic N of being scattered under the condition that the compound ammonia-sensitive material of graphene oxide/phthalocyanine that step 2 is obtained is 40kHz in frequency, in dinethylformamide, obtaining concentration is 0.5mg/mL graphene oxide/tetramino Nickel Phthalocyanine compound substance N, dinethylformamide suspending liquid, be evenly coated in interdigital electrode, after solution evaporation, in vacuum drying chamber, under the condition of 80 ℃, be dried 12 hours, obtain Oxidation at room temperature Graphene/tetramino Nickel Phthalocyanine compound substance ammonia photosensitive elements.
The response of gas sensor is the changing value of resistance value in ammonia and 100 times of the ratio of resistance value in air, and response time and release time are that gas sensor reaches peaked 90% required time of change in resistance.
Fig. 3 is response and the ammonia concentration relation curve of Oxidation at room temperature Graphene/tetramino Nickel Phthalocyanine compound substance ammonia photosensitive elements of this experiment preparation, and gas sensor is at 12.5ppm～3200ppmNH as can be seen from Figure 3
3in concentration range, there is good response, and at low concentration 25ppm～200ppmNH
3scope NH
3between concentration and response, there is good linear relationship.
The response recovery curve of Oxidation at room temperature Graphene/tetramino Nickel Phthalocyanine compound substance ammonia photosensitive elements that Fig. 4 is this experiment preparation in variable concentrations ammonia, compound substance gas sensor has improved the recovery characteristics of Graphene greatly as can be seen from Figure 4, under room temperature, in variable concentrations ammonia, all there is good restorability, to 50ppm NH
3release time be 600s.
Experiment 3:
The preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements carries out according to the following steps:
One, prepare the compound ammonia-sensitive material of graphene oxide/phthalocyanine: 10mg graphene oxide is scattered in to 1mlN, in dinethylformamide solvent, then add 10ml thionyl chloride, 70 ℃ of agitating heating back flow reaction are after 24 hours, thionyl chloride is removed in distillation, adding rapidly 10ml concentration is the tetramino FePC N of 5.0mg/mL, dinethylformamide solution and 2ml triethylamine, under nitrogen protection, under 80 ℃ of heating conditions, stirring reaction is 80 hours, reactant liquor is poured in a large amount of distilled water, filter, obtain the thick product of graphene oxide/tetramino FePC compound, use again the thick product of tetrahydrofuran centrifuge washing graphene oxide/tetramino FePC compound colourless to supernatant liquor, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, in 50 ℃ of vacuum drying chambers, be dried 24 hours, obtain the compound ammonia-sensitive material of graphene oxide/phthalocyanine.
Two, prepare graphene oxide/phthalocyanine composite material gas sensor: the ultrasonic N of being scattered under the condition that the compound ammonia-sensitive material of graphene oxide/phthalocyanine that step 2 is obtained is 40kHz in frequency, in dinethylformamide, obtaining concentration is 0.5mg/mL graphene oxide/tetramino FePC compound substance N, dinethylformamide suspending liquid, be evenly coated in interdigital electrode, after solution evaporation, in vacuum drying chamber, under the condition of 80 ℃, be dried 12 hours, obtain Oxidation at room temperature Graphene/tetramino FePC compound substance ammonia photosensitive elements.
The response of gas sensor is the changing value of resistance value in ammonia and 100 times of the ratio of resistance value in air, and response time and release time are that gas sensor reaches peaked 90% required time of change in resistance.
Fig. 5 is response and the ammonia concentration relation curve of Oxidation at room temperature Graphene/tetramino FePC compound substance ammonia photosensitive elements of this experiment preparation, and gas sensor is at 50ppm～3200ppmNH as can be seen from Figure 5
3in concentration range, there is good response, and at low concentration 50ppm～400ppmNH
3scope NH
3between concentration and response, there is good linear relationship.
The response recovery curve of Oxidation at room temperature Graphene/tetramino FePC compound substance ammonia photosensitive elements that Fig. 6 is this experiment preparation in variable concentrations ammonia, compound substance gas sensor has improved the recovery characteristics of Graphene greatly as can be seen from Figure 6, under room temperature, in variable concentrations ammonia, all there is good restorability, to 50ppm NH
3release time be 45s.
Experiment 4:
The preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements carries out according to the following steps:
One, prepare the compound ammonia-sensitive material of graphene oxide/phthalocyanine: 10mg graphene oxide is scattered in to 1mlN, in dinethylformamide solvent, then add 10ml thionyl chloride, 70 ℃ of agitating heating back flow reaction are after 24 hours, thionyl chloride is removed in distillation, adding rapidly 10ml concentration is the tetramino Cobalt Phthalocyanine N of 5.0mg/mL, dinethylformamide solution and 2ml triethylamine, under nitrogen protection, under 80 ℃ of heating conditions, stirring reaction is 80 hours, reactant liquor is poured in a large amount of distilled water, filter, obtain the thick product of graphene oxide/tetramino Cobalt Phthalocyanine compound, use again the thick product of tetrahydrofuran centrifuge washing graphene oxide/tetramino Cobalt Phthalocyanine compound colourless to supernatant liquor, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, in 50 ℃ of vacuum drying chambers, be dried 24 hours, obtain the compound ammonia-sensitive material of graphene oxide/phthalocyanine.
Two, prepare graphene oxide/phthalocyanine composite material gas sensor: the ultrasonic N of being scattered under the condition that the compound ammonia-sensitive material of graphene oxide/phthalocyanine that step 2 is obtained is 40kHz in frequency, in dinethylformamide, obtaining concentration is 0.5mg/mL graphene oxide/tetramino Cobalt Phthalocyanine compound substance N, dinethylformamide suspending liquid, be evenly coated in interdigital electrode, after solution evaporation, in vacuum drying chamber, under the condition of 80 ℃, be dried 12 hours, obtain Oxidation at room temperature Graphene/tetramino Cobalt Phthalocyanine compound substance ammonia photosensitive elements.
The response of gas sensor is the changing value of resistance value in ammonia and 100 times of the ratio of resistance value in air, and response time and release time are that gas sensor reaches peaked 90% required time of change in resistance.
Fig. 7 is response and the ammonia concentration relation curve of Oxidation at room temperature Graphene/tetramino Cobalt Phthalocyanine compound substance ammonia photosensitive elements of this experiment preparation, and graphene oxide/tetramino Cobalt Phthalocyanine compound substance ammonia photosensitive elements of this experiment preparation is at 12.5ppm～3200ppmNH as can be seen from Figure 7
3in concentration range, there is good response, and at low concentration 12.5ppm～100ppmNH
3scope NH
3between concentration and response, there is good linear relationship.
The response recovery curve of Oxidation at room temperature Graphene/tetramino Cobalt Phthalocyanine compound substance ammonia photosensitive elements that Fig. 8 is this experiment preparation in variable concentrations ammonia, graphene oxide/tetramino Cobalt Phthalocyanine compound substance ammonia photosensitive elements of this experiment preparation has improved the recovery characteristics of Graphene greatly as can be seen from Figure 8, under room temperature, in variable concentrations ammonia, all there is good restorability, to 50ppm NH
3release time be 108s.
From upper, under room temperature, this experiment preparation take gas sensor that graphene oxide/phthalocyanine composite material is ammonia-sensitive material to NH
3had good selectivity, sensitivity, reversibility and stability, compound by Graphene and phthalocyanine material, has realized both have complementary functions, cooperate optimization; Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements of this experiment preparation can detect 12.5ppm～400ppm concentration range NH
3, be suitable as ammonia photosensitive elements, in actual production, life, be with a wide range of applications.
Claims (10)
1. Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements, is characterized in that Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements consists of interdigital electrode and graphene oxide/phthalocyanine composite material; Phthalocyanine in wherein said graphene oxide/phthalocyanine composite material is ammonobase phthalocyanine.
2. Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 1, is characterized in that described ammonobase phthalocyanine general formula is MPcR
x(NH
2)
y, x be wherein 0 or 3, y be 1 or 4, R be alkyl or alkoxy, M is wherein Cu, Ni, Fe, Co, Pb or Zn.
3. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 1, is characterized in that the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements carries out according to following steps:
One, prepare the compound ammonia-sensitive material of graphene oxide/phthalocyanine:
Graphene oxide is scattered in to N, in dinethylformamide, obtain the solution that graphene oxide concentration is 10-50mg/ml, then according to graphene oxide quality and thionyl chloride volume ratio, being 1mg:(1-2) ratio of ml adds thionyl chloride, agitating heating back flow reaction 24-36 hour under the condition of 70-80 ℃, thionyl chloride is removed in distillation, according to the mass ratio of phthalocyanine and graphene oxide, be (0.5-5): 1, the ratio that phthalocyanine quality and triethylamine volume ratio are (10-30) mg:1mL adds phthalocyanine N, dinethylformamide solution and triethylamine, in nitrogen protection, stirring reaction 72-96 hour under the condition of 60-100 ℃, then reactant liquor is poured in distilled water, filter, obtain the thick product of graphene oxide/phthalocyanine compound, use again the thick product of tetrahydrofuran centrifuge washing graphene oxide/phthalocyanine compound colourless to supernatant liquor, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, in 50 ℃ of vacuum drying chambers, graphene oxide/phthalocyanine compound is dried to 24 hours, obtain the compound ammonia-sensitive material of graphene oxide/phthalocyanine,
Two, prepare graphene oxide/phthalocyanine composite material gas sensor:
The ultrasonic N of being scattered under the condition that the compound ammonia-sensitive material of graphene oxide/phthalocyanine that step 2 is obtained is 40kHz in frequency, in dinethylformamide, obtaining concentration is graphene oxide/phthalocyanine composite material DMF suspending liquid of 0.05mg/mL-1.0mg/mL, by graphene oxide/phthalocyanine composite material N, dinethylformamide suspending liquid is evenly coated in interdigital electrode, after solution evaporation, in the vacuum drying chamber of 80 ℃, dry 12-48 hour, obtains Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements.
4. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 3, is characterized in that in step 1, graphene oxide being scattered in DMF, obtains the solution that graphene oxide concentration is 10mg/ml.
5. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 3, is characterized in that the ratio that is 1mg:1ml according to graphene oxide quality and thionyl chloride volume ratio in step 1 adds thionyl chloride.
6. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 3, is characterized in that in step 1, the mass ratio of phthalocyanine and graphene oxide is 5:1.
7. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 3, is characterized in that in step 1 that phthalocyanine quality and triethylamine volume ratio are 25mg:1mL.
8. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 3, is characterized in that in step 1 under nitrogen protection, the condition of 80 ℃ stirring reaction 80 hours.
9. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 3, is characterized in that the concentration of graphene oxide/phthalocyanine composite material DMF suspending liquid in step 2 is 0.1mg/mL-0.9mg/mL.
10. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 3, is characterized in that the concentration of graphene oxide/phthalocyanine composite material DMF suspending liquid in step 2 is 0.5mg/mL.
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| CN105797779A (en) * | 2016-04-11 | 2016-07-27 | 常州大学 | Preparation method of amino zinc phthalocyanine/few-Iayered GO (graphene oxide) composite catalytic material |
| CN109030589A (en) * | 2018-07-11 | 2018-12-18 | 黑龙江工程学院 | Four-β-carboxyphenoxy metal phthalocyanine/graphene composite material and method |
| CN109283770A (en) * | 2018-09-30 | 2019-01-29 | 黑龙江大学 | Naphthalene phthalocyanine-graphene oxide composite non-linear optical material and preparation method thereof |
| CN110186966A (en) * | 2019-05-05 | 2019-08-30 | 浙江大学 | A kind of preparation method and application for the composite material modified electrode detecting lactic acid concn |
| CN110208323A (en) * | 2019-05-30 | 2019-09-06 | 济南大学 | For detecting the organic/inorganic composite material and gas sensor of nitrogen dioxide |
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| CN104003378A (en) * | 2014-05-29 | 2014-08-27 | 黑龙江科技大学 | Preparation method of reduction-oxidation oxidized graphene vinyl photoelectric active composite material |
| CN104003378B (en) * | 2014-05-29 | 2016-08-24 | 黑龙江科技大学 | A kind of preparation method of redox graphene base photoelectric activity composite |
| CN105797779A (en) * | 2016-04-11 | 2016-07-27 | 常州大学 | Preparation method of amino zinc phthalocyanine/few-Iayered GO (graphene oxide) composite catalytic material |
| CN109030589A (en) * | 2018-07-11 | 2018-12-18 | 黑龙江工程学院 | Four-β-carboxyphenoxy metal phthalocyanine/graphene composite material and method |
| CN109030589B (en) * | 2018-07-11 | 2020-10-02 | 黑龙江工程学院 | Tetra-beta-carboxyphenoxy metal phthalocyanine/graphene composite material and method |
| CN109283770A (en) * | 2018-09-30 | 2019-01-29 | 黑龙江大学 | Naphthalene phthalocyanine-graphene oxide composite non-linear optical material and preparation method thereof |
| CN110186966A (en) * | 2019-05-05 | 2019-08-30 | 浙江大学 | A kind of preparation method and application for the composite material modified electrode detecting lactic acid concn |
| CN110208323A (en) * | 2019-05-30 | 2019-09-06 | 济南大学 | For detecting the organic/inorganic composite material and gas sensor of nitrogen dioxide |
| CN113029239A (en) * | 2021-03-11 | 2021-06-25 | 昆山联鲸仪智能科技有限公司 | Multifunctional sensor and preparation method thereof |
| CN113311036A (en) * | 2021-05-23 | 2021-08-27 | 山东化工职业学院 | MOFs/GO composite gas sensitive material and preparation method and application thereof |
| CN113311036B (en) * | 2021-05-23 | 2024-01-12 | 山东化工职业学院 | MOFs/GO composite gas-sensitive material and preparation method and application thereof |
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