CN103308563A - Gas sensitive element by taking single-walled carbon nanotube/phthalocyanine composite material as ammonia-sensitive material and preparation method thereof - Google Patents
Gas sensitive element by taking single-walled carbon nanotube/phthalocyanine composite material as ammonia-sensitive material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a gas sensitive element by taking a single-walled carbon nanotube/phthalocyanine composite material as an ammonia-sensitive material and a preparation method thereof and relates to a gas sensitive element for measuring ammonia concentration and a preparation method thereof. The invention aims to solve the problems that a gas sensitive element by taking a single single-walled carbon nanotube as an ammonia-sensitive material is poor in reversibility and a gas sensitive element by taking metal phthalocyanine as an ammonia-sensitive material is high in resistance value. The gas sensitive element by taking the single-walled carbon nanotube/phthalocyanine composite material as the ammonia-sensitive material consists of an interdigital electrode and a single-walled carbon nanotube/phthalocyanine composite material. The preparation method comprises the following steps: 1. preparing a carboxylated single-walled carbon nanotube; 2. preparing the single-walled carbon nanotube/phthalocyanine composite material; and 3. dispensing to obtain the gas sensitive element by taking the single-walled carbon nanotube/phthalocyanine composite material as the ammonia-sensitive material. The invention can be used for preparing the gas sensitive element by taking the single-walled carbon nanotube/phthalocyanine composite material as the ammonia-sensitive material.
Description
Technical field
The present invention relates to a kind of gas sensor of measuring ammonia concentration and preparation method thereof.
Background technology
Along with the mankind to the deepening continuously of strategy of sustainable development understanding, environmental pollution and weather variation issue have caused the great attention of countries in the world.Simultaneously people produce and life in institute gaseous species and the quantity using and produce but increase year by year harmful gas wherein, not only contaminated environment and affect weather, and the danger that generation blast, fire is arranged and the people is poisoned.One of effective way that gas sensor detects as harmful gas has been subject to the extensive concern of countries in the world group of enterprises and research institution in recent years.Traditional based semiconductor metal oxide materials (such as ZnO, SnO
2And Fe
2O
3Deng) sensor, take its lower cost for material, make simple, sensitivity is higher, and (sensing range is widely used for detecting nitrogenous harmful gas as advantages such as 1ppm～1000ppm) and life-span are long usually.The weak point of these sensors is that working temperature high (hundreds of even thousands of degrees centigrade), power requirement are high, and the film-forming apparatus cost is high, to the poor selectivity of gas and when detecting some gas (such as sulfide), also easily poisons.Because the quasi-one dimensional nanostructure of carbon nano-tube uniqueness, huge specific surface area, abundant pore texture, special electronic band structure, quite high conductivity and stable physicochemical property, become in recent years the gas sensor field and fall over each other one of focus of studying both at home and abroad.The problems such as but its release time that shows is slow, selectivity is relatively poor, dissolubility and dispersed undesirable and film forming means are limited need to be resolved hurrily at present.Organic semiconducting materials take phthalocyanine as representative, with its distinctive performance, such as high selectivity, high sensitivity, respond resume speed, molecular structure faster and can design, can at normal temperature or near working under the normal temperature and available liquid phase method with low cost (as revolving Tu and czochralski method) film forming etc., in the gas sensor field, occupy an important position.Yet, the measured resistance value that this type of gas sensor shows high (〉 10G Ω) and the problem such as long-time stability are relatively poor, become again its practical and problem that must solve that limits.
Summary of the invention
The present invention is that will to solve single Single Walled Carbon Nanotube be that the relatively poor and metal phthalocyanine of the gas sensor reversibility of ammonia-sensitive material is the higher problem of gas sensor resistance value of ammonia-sensitive material, and a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material and preparation method thereof is provided.
A kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of the present invention is made of interdigital electrode and Single Walled Carbon Nanotube/phthalocyanine composite material; Phthalocyanine in wherein said Single Walled Carbon Nanotube/phthalocyanine composite material is pentane oxygen Base Metal phthalocyanine.
The preparation method of a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of the present invention, carry out according to the following steps:
One, prepare carboxylated Single Walled Carbon Nanotube: it is in 2mol/L～3mol/L aqueous solution of nitric acid that Single Walled Carbon Nanotube is joined concentration, back flow reaction 36h～48h under 80 ℃～90 ℃ temperature, obtain filter cake after the filtration, it is ultrasonic concussion 10min～30min in 0.5mol/L～2mol/L aqueous hydrochloric acid solution that filter cake is scattered in concentration, filter, obtain the purifying Single Walled Carbon Nanotube, then the purifying Single Walled Carbon Nanotube that obtains is placed the nitration mixture heat treated, obtain reacted solution, in reacted solution, add the deionized water dilution, then use 0.20 μ m teflon filtering membrane suction filtration, obtain carboxylated Single Walled Carbon Nanotube crude product, the carboxylated Single Walled Carbon Nanotube crude product that obtains is washed to filtrate is neutral, last is under 80 ℃ the condition dry 1 day in temperature in vacuum drying chamber, obtains carboxylated Single Walled Carbon Nanotube; The quality of wherein said Single Walled Carbon Nanotube and concentration are that the volume ratio of 2mol/L～3mol/L aqueous solution of nitric acid is 1g:(100～200) mL, described nitration mixture is that the aqueous sulfuric acid of 18mol/L and aqueous solution of nitric acid that concentration is 16mol/L mix by concentration, and concentration is that the aqueous sulfuric acid of 18mol/L and the volume ratio of the aqueous solution of nitric acid that concentration is 16mol/L are 3:1, the quality of described purifying Single Walled Carbon Nanotube and the volume ratio of nitration mixture are 1g:(100～200) mL, the volume ratio of described nitration mixture and deionized water is 1:(5～10);
Two, preparation Single Walled Carbon Nanotube/phthalocyanine composite material: the carboxylated Single Walled Carbon Nanotube that step 1 is obtained is under the condition of 40kHz among the ultrasonic DMF of being scattered in frequency, obtaining concentration is the carboxylated Single Walled Carbon Nanotube DMF suspending liquid of 10mg/mL, be that the phthalocyanine DMF solution of 10mg/mL is added drop-wise in the carboxylated Single Walled Carbon Nanotube DMF suspending liquid that concentration is 10mg/mL with concentration, then be the ultrasonic concussion reaction of lucifuge 13h～48h under the 40kHz condition in frequency, obtain reacted solution, with reacted solution with 0.20 μ m teflon filtering membrane suction filtration, obtain Single Walled Carbon Nanotube/phthalocyanine composite material crude product, adopt DMF to obtain Single Walled Carbon Nanotube/phthalocyanine composite material crude product centrifuge washing is colourless to the upper strata clear liquid, then adopt the chloroform centrifuge washing colourless to the upper strata clear liquid, adopt at last the ethanol centrifuge washing 3 times, discard clear liquid, obtain Single Walled Carbon Nanotube/phthalocyanine composite material precipitation, then Single Walled Carbon Nanotube/phthalocyanine composite material precipitation being placed temperature is 60 ℃ the dry 2h of vacuum drying chamber, obtains Single Walled Carbon Nanotube/phthalocyanine composite material; Described concentration is that the carboxylated Single Walled Carbon Nanotube DMF suspending liquid of 10mg/mL and the volume ratio of the phthalocyanine DMF solution that concentration is 10mg/mL are 1:(2～4), the phthalocyanine in the described phthalocyanine DMF solution is pentane oxygen Base Metal phthalocyanine;
Three, drip and to be coated with: Single Walled Carbon Nanotube/phthalocyanine composite material that step 2 is obtained is under the condition of 40kHz among the ultrasonic DMF of being scattered in frequency, ultrasonic 2h, obtain concentration and be the Single Walled Carbon Nanotube of 0.1mg/mL～1.0mg/mL/phthalocyanine composite material DMF suspending liquid, then be that the Single Walled Carbon Nanotube/phthalocyanine composite material DMF suspending liquid 1 μ L～30 μ L of 0.1mg/mL～1.0mg/mL is dripped and is coated on the interdigital electrode with syringe with concentration, after the solution evaporation, put it in the vacuum drying chamber, be dry 12h～48h under 80 ℃ the condition in temperature, namely obtain the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material.
Advantage of the present invention: one, the present invention utilizes electric conductivity and heat, light and the chemical stability of inorganic material excellence, the characteristics such as organic material molecule Scalability, fast, the easy processing of response, with both cyclical variation formation compound substances by component and structure, 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 more excellent gas sensor of combination property; Two, the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of the present invention's preparation is under the room temperature, at 0.6ppm～80ppmNH
3Have preferably response in the concentration range, and at 0.6ppm～40ppm low concentration NH
3NH in the scope
3Have good linear relationship between concentration and response, can detect 600ppb level NH
3Three, the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of the present invention's preparation all has good sensitivity, reversibility, stability in the variable concentrations ammonia, and to the CO with concentration
2, CO, CH
4And H
2Deng not response of gas, to NH
3Had good selectivity; Four, the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of the present invention's preparation has improved the air-sensitive performance of Single Walled Carbon Nanotube greatly, can be to NH
3Detect.
Description of drawings
Fig. 1 is response and the ammonia concentration relation curve take Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance as the gas sensor of ammonia-sensitive material of this test preparation;
Fig. 2 is the response recovery curve of gas sensor in the variable concentrations ammonia take Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance as ammonia-sensitive material of this test preparation;
Fig. 3 is response and the ammonia concentration relation curve take Single Walled Carbon Nanotube/four-4-isoamoxy CuPc compound substance as the gas sensor of ammonia-sensitive material of this test preparation;
Fig. 4 is the response recovery curve of gas sensor in the variable concentrations ammonia take Single Walled Carbon Nanotube/four-4-isoamoxy CuPc compound substance as ammonia-sensitive material of this test preparation;
Fig. 5 for this test preparation with Single Walled Carbon Nanotube/four-3-2,2,4 trimethyls-3-amoxy CuPc compound substance is response and the ammonia concentration relation curve of the gas sensor of ammonia-sensitive material;
Fig. 6 for this test preparation with Single Walled Carbon Nanotube/four-3-2,2,4 trimethyls-3-amoxy CuPc compound substance is the response recovery curve of gas sensor in the variable concentrations ammonia of ammonia-sensitive material.
Embodiment
Embodiment one: a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of present embodiment is made of interdigital electrode and Single Walled Carbon Nanotube/phthalocyanine composite material; Phthalocyanine in wherein said Single Walled Carbon Nanotube/phthalocyanine composite material is pentane oxygen Base Metal phthalocyanine.
Under the described gas sensor room temperature take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of present embodiment, at 0.6ppm～80ppmNH
3Have preferably response in the concentration range, and at 0.6ppm～40ppm low concentration NH
3NH in the scope
3Have good linear relationship between concentration and response, can detect 600ppb level NH
3
The described gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of present embodiment all has good sensitivity, reversibility, stability in the variable concentrations ammonia, and to the CO with concentration
2, CO, CH
4And H
2Deng not response of gas, to NH
3Had good selectivity.
Embodiment two: what present embodiment and embodiment one were different is: described pentane oxygen Base Metal phthalocyanine structure formula is
Or
Wherein
In M be Cu, Pb, Ni, Co or Zn; Wherein
In M be Cu, Pb, Ni, Co or Zn; Wherein
In M be Cu, Ni, Co or Zn.Other is identical with embodiment one.
Embodiment three: the preparation method of a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of present embodiment, carry out according to the following steps:
One, prepare carboxylated Single Walled Carbon Nanotube: it is in 2mol/L～3mol/L aqueous solution of nitric acid that Single Walled Carbon Nanotube is joined concentration, back flow reaction 36h～48h under 80 ℃～90 ℃ temperature, obtain filter cake after the filtration, it is ultrasonic concussion 10min～30min in 0.5mol/L～2mol/L aqueous hydrochloric acid solution that filter cake is scattered in concentration, filter, obtain the purifying Single Walled Carbon Nanotube, then the purifying Single Walled Carbon Nanotube that obtains is placed the nitration mixture heat treated, obtain reacted solution, in reacted solution, add the deionized water dilution, then use 0.20 μ m teflon filtering membrane suction filtration, obtain carboxylated Single Walled Carbon Nanotube crude product, the carboxylated Single Walled Carbon Nanotube crude product that obtains is washed to filtrate is neutral, last is under 80 ℃ the condition dry 1 day in temperature in vacuum drying chamber, obtains carboxylated Single Walled Carbon Nanotube; The quality of wherein said Single Walled Carbon Nanotube and concentration are that the volume ratio of 2mol/L～3mol/L aqueous solution of nitric acid is 1g:(100～200) mL, described nitration mixture is that the aqueous sulfuric acid of 18mol/L and aqueous solution of nitric acid that concentration is 16mol/L mix by concentration, and concentration is that the aqueous sulfuric acid of 18mol/L and the volume ratio of the aqueous solution of nitric acid that concentration is 16mol/L are 3:1, the quality of described purifying Single Walled Carbon Nanotube and the volume ratio of nitration mixture are 1g:(100～200) mL, the volume ratio of described nitration mixture and deionized water is 1:(5～10);
Two, preparation Single Walled Carbon Nanotube/phthalocyanine composite material: the carboxylated Single Walled Carbon Nanotube that step 1 is obtained is under the condition of 40kHz among the ultrasonic DMF of being scattered in frequency, obtaining concentration is the carboxylated Single Walled Carbon Nanotube DMF suspending liquid of 10mg/mL, be that the phthalocyanine DMF solution of 10mg/mL is added drop-wise in the carboxylated Single Walled Carbon Nanotube DMF suspending liquid that concentration is 10mg/mL with concentration, then be the ultrasonic concussion reaction of lucifuge 13h～48h under the 40kHz condition in frequency, obtain reacted solution, with reacted solution with 0.20 μ m teflon filtering membrane suction filtration, obtain Single Walled Carbon Nanotube/phthalocyanine composite material crude product, adopt DMF to obtain Single Walled Carbon Nanotube/phthalocyanine composite material crude product centrifuge washing is colourless to the upper strata clear liquid, then adopt the chloroform centrifuge washing colourless to the upper strata clear liquid, adopt at last the ethanol centrifuge washing 3 times, discard clear liquid, obtain Single Walled Carbon Nanotube/phthalocyanine composite material precipitation, then Single Walled Carbon Nanotube/phthalocyanine composite material precipitation being placed temperature is 60 ℃ the dry 2h of vacuum drying chamber, obtains Single Walled Carbon Nanotube/phthalocyanine composite material; Described concentration is that the carboxylated Single Walled Carbon Nanotube DMF suspending liquid of 10mg/mL and the volume ratio of the phthalocyanine DMF solution that concentration is 10mg/mL are 1:(2～4), the phthalocyanine in the described phthalocyanine DMF solution is pentane oxygen Base Metal phthalocyanine;
Three, drip and to be coated with: Single Walled Carbon Nanotube/phthalocyanine composite material that step 2 is obtained is under the condition of 40kHz among the ultrasonic DMF of being scattered in frequency, ultrasonic 2h, obtain concentration and be the Single Walled Carbon Nanotube of 0.1mg/mL～1.0mg/mL/phthalocyanine composite material DMF suspending liquid, then be that the Single Walled Carbon Nanotube/phthalocyanine composite material DMF suspending liquid 1 μ L～30 μ L of 0.1mg/mL～1.0mg/mL is dripped and is coated on the interdigital electrode with syringe with concentration, after the solution evaporation, put it in the vacuum drying chamber, be dry 12h～48h under 80 ℃ the condition in temperature, namely obtain the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material.
Present embodiment is utilized electric conductivity and heat, light and the chemical stability of inorganic material excellence, the characteristics such as organic material molecule Scalability, fast, the easy processing of response, with both cyclical variation formation compound substances by component and structure, 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 more excellent gas sensor of combination property.
The gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of present embodiment preparation is under the room temperature, at 0.6ppm～80ppmNH
3Have preferably response in the concentration range, and at 0.6ppm～40ppm low concentration NH
3NH in the scope
3Have good linear relationship between concentration and response, can detect 600ppb level NH
3
The gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of present embodiment preparation all has good sensitivity, reversibility, stability in the variable concentrations ammonia, and to the CO with concentration
2, CO, CH
4And H
2Deng not response of gas, to NH
3Had good selectivity.
The gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of present embodiment preparation has improved the air-sensitive performance of Single Walled Carbon Nanotube greatly, can be to NH
3Detect.
Embodiment four: what present embodiment and embodiment three were different is: the specific operation process of heat treated described in the step 1 is as follows: be heat treated 6h～12h under 40 ℃～60 ℃ the condition in temperature.Other is identical with embodiment three.
Embodiment five: what present embodiment and embodiment four were different is: described heat treated specific operation process is as follows: be heat treated 6h under 60 ℃ the condition in temperature.Other is identical with embodiment four.
Embodiment six: what present embodiment was different from one of embodiment three to five is: the quality of the Single Walled Carbon Nanotube described in the step 1 and concentration are that the volume ratio of 2mol/L～3mol/L aqueous solution of nitric acid is 1g:(150～200) mL.Other is identical with one of embodiment three to five.
Embodiment seven: what present embodiment was different from one of embodiment three to six is: the pentane oxygen Base Metal phthalocyanine structure formula described in the step 2 is
Or
Wherein
Embodiment eight: what present embodiment was different from one of embodiment three to seven is: the concentration described in the step 2 is that the carboxylated Single Walled Carbon Nanotube DMF suspending liquid of 10mg/mL and the volume ratio of the phthalocyanine DMF solution that concentration is 10mg/mL are 1:2.Other is identical with one of embodiment three to seven.
Embodiment nine: what present embodiment was different from one of embodiment three to eight is: the phthalocyanine DMF solution that in the step 2 with concentration is 10mg/mL is added drop-wise in the carboxylated Single Walled Carbon Nanotube DMF suspending liquid that concentration is 10mg/mL, is the ultrasonic concussion reaction of lucifuge 24h under the 40kHz condition in frequency then.Other is identical with one of embodiment three to eight.
Embodiment ten: what present embodiment was different from one of embodiment three to nine is: be that Single Walled Carbon Nanotube/phthalocyanine composite material 10 μ LDMF hanging drops of 0.5mg/mL are coated on the interdigital electrode with syringe with concentration in the step 3.Other is identical with one of embodiment three to nine.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of preparation method of the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material, carry out according to the following steps:
One, prepare carboxylated Single Walled Carbon Nanotube: it is in the 2.6mol/L aqueous solution of nitric acid that the 1g Single Walled Carbon Nanotube is joined 100mL concentration, back flow reaction 48h under 90 ℃ of temperature, obtain filter cake after the filtration, it is ultrasonic concussion 10min in the 1mol/L aqueous hydrochloric acid solution that filter cake is scattered in concentration, filter, obtain the purifying Single Walled Carbon Nanotube, then the purifying Single Walled Carbon Nanotube that obtains is placed 100mL nitration mixture heat treated, the heat treated temperature is 60 ℃, the heat treated time is 6h, obtain reacted solution, in reacted solution, add the dilution of 500mL deionized water, then use 0.20 μ m teflon filtering membrane suction filtration, obtain carboxylated Single Walled Carbon Nanotube crude product, with deionized water the carboxylated Single Walled Carbon Nanotube crude product that obtains is washed to filtrate and is neutral, last is under 80 ℃ the condition dry 1 day in temperature in vacuum drying chamber, obtains carboxylated Single Walled Carbon Nanotube; Described nitration mixture is that the aqueous sulfuric acid of 18mol/L and aqueous solution of nitric acid that concentration is 16mol/L mix by concentration, and concentration is that the aqueous sulfuric acid of 18mol/L and the volume ratio of the aqueous solution of nitric acid that concentration is 16mol/L are 3:1;
Two, preparation Single Walled Carbon Nanotube/phthalocyanine composite material: the carboxylated Single Walled Carbon Nanotube that step 1 is obtained is under the condition of 40kHz among the ultrasonic DMF of being scattered in frequency, obtaining concentration is the carboxylated Single Walled Carbon Nanotube DMF suspending liquid of 10mg/mL, be that four-3-isoamoxy CuPc DMF solution of 10mg/mL is added drop-wise in the carboxylated Single Walled Carbon Nanotube DMF suspending liquid that 10mL concentration is 10mg/mL with 20mL concentration, then be the ultrasonic concussion reaction of lucifuge 13h～48h under the 40kHz condition in frequency, obtain reacted solution, with reacted solution with 0.20 μ m teflon filtering membrane suction filtration, obtain Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance crude product, adopt DMF to obtain Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance crude product centrifuge washing is colourless to the upper strata clear liquid, then adopt the chloroform centrifuge washing colourless to the upper strata clear liquid, adopt at last the ethanol centrifuge washing 3 times, discard clear liquid, obtain Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance precipitation, then Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance precipitation being placed temperature is 60 ℃ the dry 2h of vacuum drying chamber, obtains Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance;
Three, drip and to be coated with: the Single Walled Carbon Nanotube that step 2 is obtained/four-3-isoamoxy CuPc compound substance is under the condition of 40kHz among the ultrasonic DMF of being scattered in frequency, ultrasonic 2h, obtain the Single Walled Carbon Nanotube that concentration is 0.5mg/mL/four-3-isoamoxy CuPc compound substance DMF suspending liquid, then be that the Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance DMF suspending liquid, 10 μ L of 0.5mg/mL is dripped and is coated on the interdigital electrode with syringe with concentration, after the solution evaporation, put it in the vacuum drying chamber, be dry 12h under 80 ℃ the condition in temperature, namely obtain the gas sensor take Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance as ammonia-sensitive material.
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 the required time of change in resistance peaked 90%.
Fig. 1 is response and the ammonia concentration relation curve take Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance as the gas sensor of ammonia-sensitive material of this test preparation, and the gas sensor take Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance as ammonia-sensitive material of this test preparation is at 0.6ppm～80ppmNH as can be seen from Figure 1
3Have preferably response in the concentration range, and at low concentration 2.5ppm～20ppmNH
3Scope NH
3Has good linear relationship between concentration and response.
Fig. 2 is the response recovery curve of gas sensor in the variable concentrations ammonia take Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance as ammonia-sensitive material of this test preparation, this test preparation has improved the recovery characteristics of Single Walled Carbon Nanotube greatly take Single Walled Carbon Nanotube/four-3-isoamoxy CuPc compound substance as the gas sensor of ammonia-sensitive material as can be seen from Figure 2, all have good restorability under the room temperature in the variable concentrations ammonia, be 550s release time.
Test two: a kind of preparation method of the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material, carry out according to the following steps:
One, prepare carboxylated Single Walled Carbon Nanotube: it is in the 2.6mol/L aqueous solution of nitric acid that the 1g Single Walled Carbon Nanotube is joined 100mL concentration, back flow reaction 48h under 90 ℃ of temperature, obtain filter cake after the filtration, it is ultrasonic concussion 10min in the 1mol/L aqueous hydrochloric acid solution that filter cake is scattered in concentration, filter, obtain the purifying Single Walled Carbon Nanotube, then the purifying Single Walled Carbon Nanotube that obtains is placed 100mL nitration mixture heat treated, the heat treated temperature is 60 ℃, the heat treated time is 6h, obtain reacted solution, in reacted solution, add the dilution of 500mL deionized water, then use 0.20 μ m teflon filtering membrane suction filtration, obtain carboxylated Single Walled Carbon Nanotube crude product, with deionized water the carboxylated Single Walled Carbon Nanotube crude product that obtains is washed to filtrate and is neutral, last is under 80 ℃ the condition dry 1 day in temperature in vacuum drying chamber, obtains carboxylated Single Walled Carbon Nanotube; Described nitration mixture is that the aqueous sulfuric acid of 18mol/L and aqueous solution of nitric acid that concentration is 16mol/L mix by concentration, and concentration is that the aqueous sulfuric acid of 18mol/L and the volume ratio of the aqueous solution of nitric acid that concentration is 16mol/L are 3:1;
Two, preparation Single Walled Carbon Nanotube/phthalocyanine composite material: the carboxylated Single Walled Carbon Nanotube that step 1 is obtained is under the condition of 40kHz among the ultrasonic DMF of being scattered in frequency, obtaining concentration is the carboxylated Single Walled Carbon Nanotube DMF suspending liquid of 10mg/mL, be that four-4-isoamoxy CuPc DMF solution of 10mg/mL is added drop-wise in the carboxylated Single Walled Carbon Nanotube DMF suspending liquid that 10mL concentration is 10mg/mL with 20mL concentration, then be the ultrasonic concussion reaction of lucifuge 13h～48h under the 40kHz condition in frequency, obtain reacted solution, with reacted solution with 0.20 μ m teflon filtering membrane suction filtration, obtain Single Walled Carbon Nanotube/four-4-isoamoxy CuPc compound substance crude product, adopt DMF to obtain Single Walled Carbon Nanotube/four-4-isoamoxy CuPc compound substance crude product centrifuge washing is colourless to the upper strata clear liquid, then adopt the chloroform centrifuge washing colourless to the upper strata clear liquid, adopt at last the ethanol centrifuge washing 3 times, discard clear liquid, obtain Single Walled Carbon Nanotube/four-4-isoamoxy CuPc compound substance precipitation, then Single Walled Carbon Nanotube/four-4-isoamoxy CuPc compound substance precipitation being placed temperature is 60 ℃ the dry 2h of vacuum drying chamber, obtains Single Walled Carbon Nanotube/four-4-isoamoxy CuPc compound substance;
Three, drip and to be coated with: the Single Walled Carbon Nanotube that step 2 is obtained/four-4-isoamoxy CuPc compound substance is under the condition of 40kHz among the ultrasonic DMF of being scattered in frequency, ultrasonic 2h, obtain the Single Walled Carbon Nanotube that concentration is 0.5mg/mL/four-4-isoamoxy CuPc compound substance DMF suspending liquid, then be that the Single Walled Carbon Nanotube/four-4-isoamoxy CuPc compound substance DMF suspending liquid, 10 μ L of 0.5mg/mL is dripped and is coated on the interdigital electrode with syringe with concentration, after the solution evaporation, put it in the vacuum drying chamber, be dry 12h under 80 ℃ the condition in temperature, namely obtain the gas sensor take Single Walled Carbon Nanotube/four-4-isoamoxy CuPc compound substance as ammonia-sensitive material.
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 the required time of change in resistance peaked 90%.
Fig. 3 is response and the ammonia concentration relation curve take Single Walled Carbon Nanotube/four-4-isoamoxy CuPc compound substance as the gas sensor of ammonia-sensitive material of this test preparation, and gas sensor is at 0.15ppm～80ppmNH as can be seen from Figure 3
3Have preferably response in the concentration range, and at low concentration 0.15ppm～2.5ppmNH
3Scope NH
3Has good linear relationship between concentration and response.
Fig. 4 is the response recovery curve of gas sensor in the variable concentrations ammonia take Single Walled Carbon Nanotube/four-4-isoamoxy CuPc compound substance as ammonia-sensitive material of this test preparation, the compound substance gas sensor has improved the recovery characteristics of Single Walled Carbon Nanotube greatly as can be seen from Figure 4, all have good restorability under the room temperature in the variable concentrations ammonia, be 900s release time.
Test three: a kind of preparation method of the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material, carry out according to the following steps:
One, prepare carboxylated Single Walled Carbon Nanotube: it is in the 2.6mol/L aqueous solution of nitric acid that the 1g Single Walled Carbon Nanotube is joined 100mL concentration, back flow reaction 48h under 90 ℃ of temperature, obtain filter cake after the filtration, it is ultrasonic concussion 10min in the 1mol/L aqueous hydrochloric acid solution that filter cake is scattered in concentration, filter, obtain the purifying Single Walled Carbon Nanotube, then the purifying Single Walled Carbon Nanotube that obtains is placed 100mL nitration mixture heat treated, the heat treated temperature is 60 ℃, the heat treated time is 6h, obtain reacted solution, in reacted solution, add the dilution of 500mL deionized water, then use 0.20 μ m teflon filtering membrane suction filtration, obtain carboxylated Single Walled Carbon Nanotube crude product, with deionized water the carboxylated Single Walled Carbon Nanotube crude product that obtains is washed to filtrate and is neutral, last is under 80 ℃ the condition dry 1 day in temperature in vacuum drying chamber, obtains carboxylated Single Walled Carbon Nanotube; Described nitration mixture is that the aqueous sulfuric acid of 18mol/L and aqueous solution of nitric acid that concentration is 16mol/L mix by concentration, and concentration is that the aqueous sulfuric acid of 18mol/L and the volume ratio of the aqueous solution of nitric acid that concentration is 16mol/L are 3:1;
Two, preparation Single Walled Carbon Nanotube/phthalocyanine composite material: the carboxylated Single Walled Carbon Nanotube that step 1 is obtained is under the condition of 40kHz among the ultrasonic DMF of being scattered in frequency, obtaining concentration is the carboxylated Single Walled Carbon Nanotube DMF suspending liquid of 10mg/mL, be four-3-2 of 10mg/mL with 20mL concentration, 2,4 trimethyls-3-amoxy CuPc DMF solution is added drop-wise in the carboxylated Single Walled Carbon Nanotube DMF suspending liquid that 10mL concentration is 10mg/mL, then be the ultrasonic concussion reaction of lucifuge 13h～48h under the 40kHz condition in frequency, obtain reacted solution, with reacted solution with 0.20 μ m teflon filtering membrane suction filtration, obtain Single Walled Carbon Nanotube/four-3-2,2,4 trimethyls-3-amoxy CuPc compound substance crude product, adopt DMF to the Single Walled Carbon Nanotube that obtains/four-3-2,2,4 trimethyls-3-amoxy CuPc compound substance crude product centrifuge washing is colourless to the upper strata clear liquid, then adopt the chloroform centrifuge washing colourless to the upper strata clear liquid, adopt at last the ethanol centrifuge washing 3 times, discard clear liquid, obtain Single Walled Carbon Nanotube/four-3-2,2,4 trimethyls-3-amoxy CuPc compound substance precipitation, then with Single Walled Carbon Nanotube/four-3-2,2, it is 60 ℃ the dry 2h of vacuum drying chamber that 4 trimethyls-3-amoxy CuPc compound substance precipitation places temperature, obtain Single Walled Carbon Nanotube/four-3-2,2,4 trimethyls-3-amoxy CuPc compound substance;
Three, drip and to be coated with: the Single Walled Carbon Nanotube that step 2 is obtained/four-3-2,2,4 trimethyls-3-amoxy CuPc compound substance is ultrasonic being scattered among the DMF under the condition of 40kHz in frequency, ultrasonic 2h, obtain the Single Walled Carbon Nanotube that concentration is 0.5mg/mL/four-3-2,2,4 trimethyls-3-amoxy CuPc compound substance DMF suspending liquid, then be the Single Walled Carbon Nanotube/four-3-2 of 0.5mg/mL with concentration with syringe, 2,4 trimethyls-3-amoxy CuPc compound substance DMF suspending liquid 10 μ L drip and are coated on the interdigital electrode, after the solution evaporation, put it in the vacuum drying chamber, be dry 12h under 80 ℃ the condition in temperature, namely obtain with Single Walled Carbon Nanotube/four-3-2,2,4 trimethyls-3-amoxy CuPc compound substance is the gas sensor of ammonia-sensitive material.
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 the required time of change in resistance peaked 90%.
Fig. 5 for this test preparation with Single Walled Carbon Nanotube/four-3-2,2,4 trimethyls-3-amoxy CuPc compound substance is response and the ammonia concentration relation curve of the gas sensor of ammonia-sensitive material, gas sensor is at 0.6ppm～80ppmNH as can be seen from Figure 5
3Have preferably response in the concentration range, and at low concentration 2.5ppm～40ppmNH
3Scope NH
3Has good linear relationship between concentration and response.
Fig. 6 for this test preparation with Single Walled Carbon Nanotube/four-3-2,2,4 trimethyls-3-amoxy CuPc compound substance is the response recovery curve of gas sensor in the variable concentrations ammonia of ammonia-sensitive material, the compound substance gas sensor has improved the recovery characteristics of Single Walled Carbon Nanotube greatly as can be seen from Figure 6, all have good restorability under the room temperature in the variable concentrations ammonia, be 200s release time.
In sum, under the room temperature, the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of the present invention's preparation is to NH
3Had good selectivity, sensitivity, reversibility and stability, compound by Single Walled Carbon Nanotube and phthalocyanine material realized both have complementary functions, cooperate optimization; The gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material of the present invention's preparation can detect 0.6ppm～80ppm concentration range NH
3, be suitable as the ammonia photosensitive elements, in actual production, life, be with a wide range of applications.
Claims (10)
1. the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material is characterized in that the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material is made of interdigital electrode and Single Walled Carbon Nanotube/phthalocyanine composite material; Phthalocyanine in wherein said Single Walled Carbon Nanotube/phthalocyanine composite material is pentane oxygen Base Metal phthalocyanine.
2. a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material according to claim 1 is characterized in that described pentane oxygen Base Metal phthalocyanine structure formula is
Or
Wherein
In M be Cu, Pb, Ni, Co or Zn; Wherein
In M be Cu, Pb, Ni, Co or Zn; Wherein
In M be Cu, Ni, Co or Zn.
3. the preparation method of a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material as claimed in claim 1, the preparation method who it is characterized in that the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material carries out according to the following steps:
One, prepare carboxylated Single Walled Carbon Nanotube: it is in 2mol/L～3mol/L aqueous solution of nitric acid that Single Walled Carbon Nanotube is joined concentration, back flow reaction 36h～48h under 80 ℃～90 ℃ temperature, obtain filter cake after the filtration, it is ultrasonic concussion 10min～30min in 0.5mol/L～2mol/L aqueous hydrochloric acid solution that filter cake is scattered in concentration, filter, obtain the purifying Single Walled Carbon Nanotube, then the purifying Single Walled Carbon Nanotube that obtains is placed the nitration mixture heat treated, obtain reacted solution, in reacted solution, add the deionized water dilution, then use 0.20 μ m teflon filtering membrane suction filtration, obtain carboxylated Single Walled Carbon Nanotube crude product, the carboxylated Single Walled Carbon Nanotube crude product that obtains is washed to filtrate is neutral, last is under 80 ℃ the condition dry 1 day in temperature in vacuum drying chamber, obtains carboxylated Single Walled Carbon Nanotube; The quality of wherein said Single Walled Carbon Nanotube and concentration are that the volume ratio of 2mol/L～3mol/L aqueous solution of nitric acid is 1g:(100～200) mL, described nitration mixture is that the aqueous sulfuric acid of 18mol/L and aqueous solution of nitric acid that concentration is 16mol/L mix by concentration, and concentration is that the aqueous sulfuric acid of 18mol/L and the volume ratio of the aqueous solution of nitric acid that concentration is 16mol/L are 3:1, the quality of described purifying Single Walled Carbon Nanotube and the volume ratio of nitration mixture are 1g:(100～200) mL, the volume ratio of described nitration mixture and deionized water is 1:(5～10);
Two, preparation Single Walled Carbon Nanotube/phthalocyanine composite material: the carboxylated Single Walled Carbon Nanotube that step 1 is obtained is under the condition of 40kHz among the ultrasonic DMF of being scattered in frequency, obtaining concentration is the carboxylated Single Walled Carbon Nanotube DMF suspending liquid of 10mg/mL, be that the phthalocyanine DMF solution of 10mg/mL is added drop-wise in the carboxylated Single Walled Carbon Nanotube DMF suspending liquid that concentration is 10mg/mL with concentration, then be the ultrasonic concussion reaction of lucifuge 13h～48h under the 40kHz condition in frequency, obtain reacted solution, with reacted solution with 0.20 μ m teflon filtering membrane suction filtration, obtain Single Walled Carbon Nanotube/phthalocyanine composite material crude product, adopt DMF to obtain Single Walled Carbon Nanotube/phthalocyanine composite material crude product centrifuge washing is colourless to the upper strata clear liquid, then adopt the chloroform centrifuge washing colourless to the upper strata clear liquid, adopt at last the ethanol centrifuge washing 3 times, discard clear liquid, obtain Single Walled Carbon Nanotube/phthalocyanine composite material precipitation, then Single Walled Carbon Nanotube/phthalocyanine composite material precipitation being placed temperature is 60 ℃ the dry 2h of vacuum drying chamber, obtains Single Walled Carbon Nanotube/phthalocyanine composite material; Described concentration is that the carboxylated Single Walled Carbon Nanotube DMF suspending liquid of 10mg/mL and the volume ratio of the phthalocyanine DMF solution that concentration is 10mg/mL are 1:(2～4), the phthalocyanine in the described phthalocyanine DMF solution is pentane oxygen Base Metal phthalocyanine;
Three, drip and to be coated with: Single Walled Carbon Nanotube/phthalocyanine composite material that step 2 is obtained is under the condition of 40kHz among the ultrasonic DMF of being scattered in frequency, ultrasonic 2h, obtain concentration and be the Single Walled Carbon Nanotube of 0.1mg/mL～1.0mg/mL/phthalocyanine composite material DMF suspending liquid, then be that the Single Walled Carbon Nanotube/phthalocyanine composite material DMF suspending liquid 1 μ L～30 μ L of 0.1mg/mL～1.0mg/mL is dripped and is coated on the interdigital electrode with syringe with concentration, after the solution evaporation, put it in the vacuum drying chamber, be dry 12h～48h under 80 ℃ the condition in temperature, namely obtain the gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material.
4. the preparation method of a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material according to claim 3 is characterized in that the specific operation process of heat treated described in the step 1 is as follows: be heat treated 6h～12h under 40 ℃～60 ℃ the condition in temperature.
5. the preparation method of a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material according to claim 4 is characterized in that described heat treated specific operation process is as follows: be heat treated 6h under 60 ℃ the condition in temperature.
6. the preparation method of a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material according to claim 3 is characterized in that the quality of the Single Walled Carbon Nanotube described in the step 1 and the volume ratio that concentration is 2mol/L～3mol/L aqueous solution of nitric acid are 1g:(150～200) mL.
7. the preparation method of a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material according to claim 3 is characterized in that the pentane oxygen Base Metal phthalocyanine structure formula described in the step 2 is
Or
Wherein
In M be Cu, Pb, Ni, Co or Zn; Wherein
In M be Cu, Pb, Ni, Co or Zn; Wherein
In M be Cu, Ni, Co or Zn.
8. the preparation method of a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material according to claim 3 is characterized in that the concentration described in the step 2 is that the carboxylated Single Walled Carbon Nanotube DMF suspending liquid of 10mg/mL and the volume ratio of the phthalocyanine DMF solution that concentration is 10mg/mL are 1:2.
9. the preparation method of a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material according to claim 3, it is characterized in that in the step 2 with concentration being that the phthalocyanine DMF solution of 10mg/mL is added drop-wise in the carboxylated Single Walled Carbon Nanotube DMF suspending liquid that concentration is 10mg/mL, is the ultrasonic concussion reaction of lucifuge 24h under the 40kHz condition in frequency then.
10. the preparation method of a kind of gas sensor take Single Walled Carbon Nanotube/phthalocyanine composite material as ammonia-sensitive material according to claim 3 is characterized in that in the step 3 that be that Single Walled Carbon Nanotube/phthalocyanine composite material 10 μ LDMF hanging drops of 0.5mg/mL are coated on the interdigital electrode with syringe with concentration.
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