CN103616415B - Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements and preparation method thereof - Google Patents
Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements and preparation method thereof Download PDFInfo
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Abstract
Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements and preparation method thereof, it relates to a kind of ammonia photosensitive elements and preparation method thereof.The present invention is the technical matters that the gas sensor resistance value of ammonia-sensitive material is higher to solve graphene oxide ammonia photosensitive elements reversibility and the poor and metal phthalocyanine of selectivity.This method is as follows: one, prepare graphene oxide/phthalocyanine compound ammonia-sensitive material; Two, graphene oxide/phthalocyanine composite material gas sensor is prepared.Oxidation at room temperature Graphene prepared by the present invention/phthalocyanine composite material ammonia photosensitive elements, under room temperature, at 12.5ppm-3200ppmNH
3there is in concentration range good response, and at low concentration NH
3nH in scope
3between concentration and response, there is good linear relationship, in variable concentrations ammonia, all there is good sensitivity, reversibility, stability.The invention belongs to the preparation field of gas sensor.
Description
Technical field
The present invention relates to a kind of ammonia photosensitive elements and preparation method thereof.
Background technology
Compared 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 domain in recent years and fall over each other one of focus studied both at home and abroad.Stable Graphene (Graphene) is successfully isolated first from A.Geim and K.Novoselov in 2004, 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 countries in the world in Synthesis and applications, expects the commanding elevation capturing this technical field.The research of Graphene gas sensor shows, sensors with auxiliary electrode increases the adsorption area to gas, is exposed in gas and can reaches higher sensitivity fast, can meet and detect fast the harmful gas of actual demand, but adsorbed NH
3be difficult to afterwards return to original state, there is the problem that recovery capability is poor.Although Graphene obtains swift and violent development as the research of gas sensitive material in recent years, and achieve a lot of result highly significant, but its release time shown is slow, selectivity is poor, dissolubility and dispersiveness is undesirable and film forming means are limited etc. that problems demand solves.Take phthalocyanine as the gas sensor of organic semiconducting materials for ammonia-sensitive material of representative, due to phthalocyanine gas sensitive there is good selectivity, the advantage such as higher sensitivity, faster response recovery time, molecular structure can design, occupy an important position in gas sensor domain.But this type of gas sensor resistance value higher (>10G Ω), limits its practical application to a great extent.Utilize the large π bond structure of phthalocyanine plane polyelectron conjugation, and large ring periphery and the substituted radical of multiple given activity that is axially connected, carrying out functional modification to Graphene is one of effective way of its air-sensitive performance of raising.
Summary of the invention
The object of the invention is to solve graphene oxide ammonia photosensitive elements reversibility and the poor and metal phthalocyanine of selectivity is the technical matters that the gas sensor resistance value of ammonia-sensitive material is higher, 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 is made up 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, graphene oxide/phthalocyanine compound ammonia-sensitive material is prepared:
Graphene oxide is scattered in dimethyl formamide, obtain the solution that graphene oxide concentration is 10-50mg/ml, then being 1mg:(1-2 according to graphene oxide quality and thionyl chloride volume ratio) ratio of ml adds thionyl chloride, agitating heating back flow reaction 24-36 hour under the condition of 70-80 DEG C, distillation removing thionyl chloride, be (0.5-5) according to the mass ratio of phthalocyanine and graphene oxide: 1, phthalocyanine quality and triethylamine volume ratio are that the ratio of (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 DEG C, then reactant liquor is poured in distilled water, filter, obtain graphene oxide/thick product of phthalocyanine compound, use tetrahydrofuran centrifuge washing graphene oxide/thick product of phthalocyanine compound colourless to supernatant liquor again, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, by graphene oxide/phthalocyanine compound drying 24 hours in 50 DEG C of vacuum drying chambers, obtain graphene oxide/phthalocyanine compound ammonia-sensitive material,
Two, graphene oxide/phthalocyanine composite material gas sensor is prepared:
The graphene oxide that step 2 is obtained/phthalocyanine compound ammonia-sensitive material in frequency be under the condition of 40kHz ultrasonic disperse in dimethyl formamide, obtain graphene oxide/phthalocyanine composite material DMF suspending liquid that concentration is 0.05mg/mL-1.0mg/mL, by graphene oxide/phthalocyanine composite material DMF uniform suspension is coated in interdigital electrode, after solution evaporation, dry 12-48 hour in the vacuum drying chamber of 80 DEG C, 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, both are formed compound substance by the cyclical variation of component and structure, what realize inorganic/organic material has complementary functions, optimizes and works in coordination with enhancing, thus improve the air-sensitive performance of single gas sensitive, to obtain the more excellent gas sensor of combination property;
Two, Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements of preparing of the present invention, under room temperature, at 12.5ppm-3200ppmNH
3there is in concentration range 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
3be provided with good selectivity;
Four, Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements that prepared by the present invention substantially increases the air-sensitive performance of graphene oxide, can 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 prepared by experiment one;
Fig. 2 is the Oxidation at room temperature Graphene/response recovery curve of phthalocyanine composite material ammonia photosensitive elements in variable concentrations ammonia prepared by experiment one;
Fig. 3 is response and the ammonia concentration relation curve of Oxidation at room temperature Graphene/temple construction compound substance ammonia photosensitive elements prepared by experiment two;
Fig. 4 is the Oxidation at room temperature Graphene/response recovery curve of temple construction compound substance ammonia photosensitive elements in variable concentrations ammonia prepared by experiment two;
Fig. 5 is response and the ammonia concentration relation curve of Oxidation at room temperature Graphene/tetramino FePC compound substance ammonia photosensitive elements prepared by experiment three;
Fig. 6 is the Oxidation at room temperature Graphene/response recovery curve of tetramino FePC compound substance ammonia photosensitive elements in variable concentrations ammonia prepared by experiment three.
Fig. 7 is response and the ammonia concentration relation curve of Oxidation at room temperature Graphene/cobalt tetraaminophthlocyanine compound substance ammonia photosensitive elements prepared by experiment four;
Fig. 8 is the Oxidation at room temperature Graphene/response recovery curve of cobalt tetraaminophthlocyanine compound substance ammonia photosensitive elements in variable concentrations ammonia prepared by experiment four;
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 is made up of interdigital electrode and graphene oxide/phthalocyanine composite material; Phthalocyanine in wherein said graphene oxide/phthalocyanine composite material is ammonobase phthalocyanine.
Under graphene oxide described in present embodiment/phthalocyanine composite material ammonia photosensitive elements room temperature, at 12.5ppm-3200ppmNH
3there is in concentration range good response, and at low concentration NH
3nH in scope
3between concentration and response, there is good linear relationship.
Oxidation at room temperature Graphene described in present embodiment/phthalocyanine composite material ammonia photosensitive elements 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
3be provided with good selectivity.
Embodiment two: present embodiment and embodiment one are MPcR unlike described ammonobase phthalocyanine general formula
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, graphene oxide/phthalocyanine compound ammonia-sensitive material is prepared:
Graphene oxide is scattered in N, in dinethylformamide, obtain the solution that graphene oxide concentration is 10-50mg/ml, then being 1mg:(1-2 according to graphene oxide quality and thionyl chloride volume ratio) ratio of ml adds thionyl chloride, agitating heating back flow reaction 24-36 hour under the condition of 70-80 DEG C, distillation removing thionyl chloride, be (0.5-5) according to the mass ratio of phthalocyanine and graphene oxide: 1, phthalocyanine quality and triethylamine volume ratio are that the ratio of (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 DEG C, then reactant liquor is poured in distilled water, filter, obtain graphene oxide/thick product of phthalocyanine compound, use tetrahydrofuran centrifuge washing graphene oxide/thick product of phthalocyanine compound colourless to supernatant liquor again, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, by graphene oxide/phthalocyanine compound drying 24 hours in 50 DEG C of vacuum drying chambers, obtain graphene oxide/phthalocyanine compound ammonia-sensitive material,
Two, graphene oxide/phthalocyanine composite material gas sensor is prepared:
The graphene oxide that step 2 is obtained/phthalocyanine compound ammonia-sensitive material in frequency be under the condition of 40kHz ultrasonic disperse in N, in dinethylformamide, obtain graphene oxide/phthalocyanine composite material DMF suspending liquid that concentration is 0.05mg/mL-1.0mg/mL, by graphene oxide/phthalocyanine composite material N, dinethylformamide uniform suspension is coated in interdigital electrode, after solution evaporation, dry 12-48 hour in the vacuum drying chamber of 80 DEG C, obtains Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements.
Present embodiment 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, both are formed compound substance by the cyclical variation of component and structure, what realize inorganic/organic material has complementary functions, optimizes and works in coordination with enhancing, thus improve the air-sensitive performance of single gas sensitive, to obtain the more excellent gas sensor of combination property.
Under graphene oxide described in present embodiment/phthalocyanine composite material ammonia photosensitive elements room temperature, at 12.5ppm-3200ppmNH
3there is in concentration range 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, CCH
4and H
2do not respond Deng gas, to NH
3be provided with good selectivity.
The air-sensitive performance substantially increasing graphene oxide with graphene oxide/phthalocyanine composite material gas sensor that is ammonia-sensitive material prepared by present embodiment, can to NH
3detect.
Embodiment four: graphene oxide is scattered in DMF unlike in step one by present embodiment and embodiment three, obtains the solution that graphene oxide concentration is 10mg/ml.Other is identical with embodiment three.
Embodiment five: present embodiment and embodiment three or four add thionyl chloride unlike the ratio being 1mg:1ml according to graphene oxide quality and thionyl chloride volume ratio in step one.Other is identical with embodiment three or four.
Embodiment six: one of present embodiment and embodiment three to five are 5:1 unlike the mass ratio of phthalocyanine in step one and graphene oxide.Other is identical with one of embodiment three to five.
Embodiment seven: one of present embodiment and embodiment three to six are 25mg:1mL unlike phthalocyanine quality in step one and triethylamine volume ratio.Other is identical with one of embodiment three to six.
Embodiment eight: one of present embodiment and embodiment three to seven unlike in step one under nitrogen protection, the condition of 80 DEG C stirring reaction 80 hours.Other is identical with one of embodiment three to seven.
Embodiment nine: one of present embodiment and embodiment three to eight are 0.1mg/mL-0.9mg/mL unlike the concentration of graphene oxide in step 2/phthalocyanine composite material DMF suspending liquid.Other is identical with one of embodiment three to eight.
Embodiment ten: one of present embodiment and embodiment three to nine are 0.5mg/mL unlike the concentration of graphene oxide in step 2/phthalocyanine composite material DMF suspending liquid.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 graphene oxide/phthalocyanine compound ammonia-sensitive material: 10mg graphene oxide is scattered in 1mlN, in dinethylformamide solvent, then 10ml thionyl chloride is added, 70 DEG C of agitating heating back flow reaction are after 24 hours, distillation removing thionyl chloride, add rapidly copper tetraaminophthalocyanine DMF solution and 2ml triethylamine that 10ml concentration is 5.0mg/mL, under nitrogen protection, stirring reaction 80 hours under 80 DEG C of heating conditions, reactant liquor is poured in distilled water, filter, obtain graphene oxide/thick product of copper tetraaminophthalocyanine compound, use tetrahydrofuran centrifuge washing graphene oxide/thick product of copper tetraaminophthalocyanine compound colourless to supernatant liquor again, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, drying 24 hours in 50 DEG C of vacuum drying chambers, namely graphene oxide/phthalocyanine compound ammonia-sensitive material is obtained.
Two, prepare graphene oxide/phthalocyanine composite material gas sensor: the graphene oxide that step 2 is obtained/phthalocyanine compound ammonia-sensitive material in frequency be under the condition of 40kHz ultrasonic disperse in N, in dinethylformamide, obtaining concentration is 0.5mg/mL graphene oxide/copper tetraaminophthalocyanine compound substance N, dinethylformamide suspending liquid, be evenly coated in interdigital electrode, after solution evaporation, in vacuum drying chamber under the condition of 80 DEG C dry 12 hours, namely 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 atmosphere, response time and release time for gas sensor reach change in resistance maximal value 90% needed for time.
Fig. 1 is response and the ammonia concentration relation curve of the Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements of this experiment preparation, and the Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements of this experiment preparation is as can be seen from Figure 1 at 12.5ppm ~ 3200ppmNH
3there is in concentration range good response, and at low concentration 12.5ppm ~ 200ppmNH
3scope NH
3between concentration and response, there is good linear relationship.
Fig. 2 is the graphene oxide/response recovery curve of copper tetraaminophthalocyanine ammonia photosensitive elements in variable concentrations ammonia of this experiment preparation, graphene oxide/copper tetraaminophthalocyanine ammonia the photosensitive elements of this experiment preparation substantially increases the recovery characteristics of Graphene as can be seen from Figure 2, in variable concentrations ammonia, all there is good restorability under room temperature, to 50ppmNH
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 graphene oxide/phthalocyanine compound ammonia-sensitive material: 10mg graphene oxide is scattered in 1mlN, in dinethylformamide solvent, then 10ml thionyl chloride is added, 70 DEG C of agitating heating back flow reaction are after 24 hours, distillation removing thionyl chloride, add rapidly the temple construction N of 10ml5.0mg/mL, dinethylformamide solution and 2ml triethylamine, under nitrogen protection, stirring reaction 80 hours under 80 DEG C of heating conditions, reactant liquor is poured in distilled water, filter, obtain graphene oxide/thick product of temple construction compound, use tetrahydrofuran centrifuge washing colourless to supernatant liquor again, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, drying 24 hours in 50 DEG C of vacuum drying chambers, namely graphene oxide/phthalocyanine compound ammonia-sensitive material is obtained.
Two, prepare graphene oxide/phthalocyanine composite material gas sensor: the graphene oxide that step 2 is obtained/phthalocyanine compound ammonia-sensitive material in frequency be under the condition of 40kHz ultrasonic disperse in N, in dinethylformamide, obtaining concentration is 0.5mg/mL graphene oxide/temple construction compound substance N, dinethylformamide suspending liquid, be evenly coated in interdigital electrode, after solution evaporation, in vacuum drying chamber under the condition of 80 DEG C dry 12 hours, namely obtain Oxidation at room temperature Graphene/temple construction 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 atmosphere, response time and release time for gas sensor reach change in resistance maximal value 90% needed for time.
Fig. 3 is response and the ammonia concentration relation curve of the Oxidation at room temperature Graphene/temple construction compound substance ammonia photosensitive elements of this experiment preparation, and gas sensor is at 12.5ppm ~ 3200ppmNH as can be seen from Figure 3
3there is in concentration range good response, and at low concentration 25ppm ~ 200ppmNH
3scope NH
3between concentration and response, there is good linear relationship.
Fig. 4 is the Oxidation at room temperature Graphene/response recovery curve of temple construction compound substance ammonia photosensitive elements in variable concentrations ammonia of this experiment preparation, compound substance gas sensor substantially increases the recovery characteristics of Graphene as can be seen from Figure 4, in variable concentrations ammonia, all there is good restorability under room temperature, to 50ppmNH
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 graphene oxide/phthalocyanine compound ammonia-sensitive material: 10mg graphene oxide is scattered in 1mlN, in dinethylformamide solvent, then 10ml thionyl chloride is added, 70 DEG C of agitating heating back flow reaction are after 24 hours, distillation removing thionyl chloride, add rapidly the tetramino FePC N that 10ml concentration is 5.0mg/mL, dinethylformamide solution and 2ml triethylamine, under nitrogen protection, stirring reaction 80 hours under 80 DEG C of heating conditions, reactant liquor is poured in a large amount of distilled water, filter, obtain graphene oxide/thick product of tetramino FePC compound, use tetrahydrofuran centrifuge washing graphene oxide/thick product of tetramino FePC compound colourless to supernatant liquor again, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, drying 24 hours in 50 DEG C of vacuum drying chambers, obtain graphene oxide/phthalocyanine compound ammonia-sensitive material.
Two, prepare graphene oxide/phthalocyanine composite material gas sensor: the graphene oxide that step 2 is obtained/phthalocyanine compound ammonia-sensitive material in frequency be under the condition of 40kHz ultrasonic disperse in N, 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 DEG C dry 12 hours, namely 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 atmosphere, response time and release time for gas sensor reach change in resistance maximal value 90% needed for time.
Fig. 5 is response and the ammonia concentration relation curve of the 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
3there is in concentration range good response, and at low concentration 50ppm ~ 400ppmNH
3scope NH
3between concentration and response, there is good linear relationship.
Fig. 6 is the Oxidation at room temperature Graphene/response recovery curve of tetramino FePC compound substance ammonia photosensitive elements in variable concentrations ammonia of this experiment preparation, compound substance gas sensor substantially increases the recovery characteristics of Graphene as can be seen from Figure 6, in variable concentrations ammonia, all there is good restorability under room temperature, to 50ppmNH
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 graphene oxide/phthalocyanine compound ammonia-sensitive material: 10mg graphene oxide is scattered in 1mlN, in dinethylformamide solvent, then 10ml thionyl chloride is added, 70 DEG C of agitating heating back flow reaction are after 24 hours, distillation removing thionyl chloride, add rapidly the cobalt tetraaminophthlocyanine N that 10ml concentration is 5.0mg/mL, dinethylformamide solution and 2ml triethylamine, under nitrogen protection, stirring reaction 80 hours under 80 DEG C of heating conditions, reactant liquor is poured in a large amount of distilled water, filter, obtain graphene oxide/thick product of cobalt tetraaminophthlocyanine compound, use tetrahydrofuran centrifuge washing graphene oxide/thick product of cobalt tetraaminophthlocyanine compound colourless to supernatant liquor again, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, drying 24 hours in 50 DEG C of vacuum drying chambers, obtain graphene oxide/phthalocyanine compound ammonia-sensitive material.
Two, prepare graphene oxide/phthalocyanine composite material gas sensor: the graphene oxide that step 2 is obtained/phthalocyanine compound ammonia-sensitive material in frequency be under the condition of 40kHz ultrasonic disperse in N, in dinethylformamide, obtaining concentration is 0.5mg/mL graphene oxide/cobalt tetraaminophthlocyanine compound substance N, dinethylformamide suspending liquid, be evenly coated in interdigital electrode, after solution evaporation, in vacuum drying chamber under the condition of 80 DEG C dry 12 hours, namely obtain Oxidation at room temperature Graphene/cobalt tetraaminophthlocyanine 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 atmosphere, response time and release time for gas sensor reach change in resistance maximal value 90% needed for time.
Fig. 7 is response and the ammonia concentration relation curve of the Oxidation at room temperature Graphene/cobalt tetraaminophthlocyanine compound substance ammonia photosensitive elements of this experiment preparation, and the graphene oxide/cobalt tetraaminophthlocyanine compound substance ammonia photosensitive elements of this experiment preparation is as can be seen from Figure 7 at 12.5ppm ~ 3200ppmNH
3there is in concentration range good response, and at low concentration 12.5ppm ~ 100ppmNH
3scope NH
3between concentration and response, there is good linear relationship.
Fig. 8 is the Oxidation at room temperature Graphene/response recovery curve of cobalt tetraaminophthlocyanine compound substance ammonia photosensitive elements in variable concentrations ammonia of this experiment preparation, graphene oxide/cobalt tetraaminophthlocyanine compound substance ammonia the photosensitive elements of this experiment preparation substantially increases the recovery characteristics of Graphene as can be seen from Figure 8, in variable concentrations ammonia, all there is good restorability under room temperature, to 50ppmNH
3release time be 108s.
From upper, under room temperature, this experiment preparation with graphene oxide/phthalocyanine composite material gas sensor that is ammonia-sensitive material to NH
3be provided with good selectivity, sensitivity, reversibility and stability, by the compound of Graphene and phthalocyanine material, achieve both have complementary functions, cooperate optimization; Oxidation at room temperature Graphene/phthalocyanine composite material ammonia the photosensitive elements of this experiment preparation can detect 12.5ppm ~ 400ppm concentration range NH
3, be suitable as ammonia photosensitive elements, be with a wide range of applications in actual production, life.
Claims (7)
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 is made up 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.
2. 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, graphene oxide/phthalocyanine compound ammonia-sensitive material is prepared:
Graphene oxide is scattered in N, in dinethylformamide, obtain the solution that graphene oxide concentration is 10-50mg/ml, then being 1mg:(1-2 according to graphene oxide quality and thionyl chloride volume ratio) ratio of ml adds thionyl chloride, agitating heating back flow reaction 24-36 hour under the condition of 70-80 DEG C, distillation removing thionyl chloride, be 5:1 according to the mass ratio of phthalocyanine and graphene oxide, phthalocyanine quality and triethylamine volume ratio are that the ratio of 25mg:1mL adds phthalocyanine N, dinethylformamide solution and triethylamine, in nitrogen protection, stirring reaction 72-96 hour under the condition of 60-100 DEG C, then reactant liquor is poured in distilled water, filter, obtain graphene oxide/thick product of phthalocyanine compound, use tetrahydrofuran centrifuge washing graphene oxide/thick product of phthalocyanine compound colourless to supernatant liquor again, finally adopt ethanol centrifuge washing 5 times, obtain graphene oxide/phthalocyanine compound, by graphene oxide/phthalocyanine compound drying 24 hours in 50 DEG C of vacuum drying chambers, obtain graphene oxide/phthalocyanine compound ammonia-sensitive material,
Two, graphene oxide/phthalocyanine composite material gas sensor is prepared:
The graphene oxide that step one is obtained/phthalocyanine compound ammonia-sensitive material in frequency be under the condition of 40kHz ultrasonic disperse in N, in dinethylformamide, obtain graphene oxide/phthalocyanine composite material DMF suspending liquid that concentration is 0.05mg/mL-1.0mg/mL, by graphene oxide/phthalocyanine composite material N, dinethylformamide uniform suspension is coated in interdigital electrode, after solution evaporation, dry 12-48 hour in the vacuum drying chamber of 80 DEG C, obtains Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements.
3. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 2, is characterized in that being scattered in DMF by graphene oxide in step one, obtains the solution that graphene oxide concentration is 10mg/ml.
4. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 2, is characterized in that the ratio being 1mg:1ml according to graphene oxide quality and thionyl chloride volume ratio in step one adds thionyl chloride.
5. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 2, to is characterized in that in step one under nitrogen protection, the condition of 80 DEG C stirring reaction 80 hours.
6. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 2, is characterized in that the concentration of graphene oxide in step 2/phthalocyanine composite material DMF suspending liquid is 0.1mg/mL-0.9mg/mL.
7. the preparation method of Oxidation at room temperature Graphene/phthalocyanine composite material ammonia photosensitive elements according to claim 2, is characterized in that the concentration of graphene oxide in step 2/phthalocyanine composite material DMF suspending liquid 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 |
| 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 |
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