CN103101885B - Tellurium nanotubes and preparation method and applications thereof - Google Patents
Tellurium nanotubes and preparation method and applications thereof Download PDFInfo
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Abstract
The invention discloses tellurium nanotubes, a preparation method thereof, and the application of the tellurium nanotubes in preparing a tellurium nanotube based ammonia sensor. The tellurium nanotubes are manufactured by using the following method implemented through uniformly mixing tellurium salts with polyalcohol and pure water; reacting for 1-10 minutes under the condition that the microwave power is 200-200W, and reacting for 30-120 seconds under the condition that the microwave power is 400-600 W; after the reaction is completed, carrying out centrifugation on reaction liquid, sequentially washing precipitate a by using pure water and anhydrous ethanol, and carrying out centrifugal separation on the precipitate a; and taking a precipitate b and carrying out vacuum drying on the precipitate b so as to obtain the tellurium nanotubes. The tellurium nanotubes prepared by using the method disclosed by the invention have excellent controllable performances and good stability; the prepared ammonia sensor has good detection sensitivity at room temperature; and the preparation method is simple in operation, short in reaction time, low in reaction temperature, small in energy consumption, and easy for industrial production.
Description
(1) technical field
The present invention relates to inorganic nano material synthetic method and apply in ammonia gas sensor, being specifically related to a kind of tellurium nanotube and preparation method thereof and the application in preparing the nano tube based ammonia gas sensor of tellurium.
(2) background technology
Ammonia is a kind of important basic chemical industry raw material and product, is widely used in the Industrial processes such as chemical fertilizer, pharmacy, medical treatment, finishing.Due to the use of burning, Chemical Manufacture and automobile, in environment, produce a large amount of ammonias simultaneously.Yet ammonia is a kind of colourless poisonous, easily right gas with intense stimulus stink.Ammonia has strong corrosion and hormesis to the skin histology of humans and animals, upper respiratory tract tissue etc., can destroy membrane structure, weakens the resistivity of human body to disease, can cause asystole, breath stopped even dead when serious.
Along with the raising of people's quality of life, more and more higher to the requirement of industrial production and living condition, people are also increasing to the demand of ammonia gas sensor.The gas sensor that detects at present ammonia has been widely used in industries such as municipal administration, fire-fighting, combustion gas, telecommunications, oil, chemical industry, coal, electric power, pharmacy, metallurgy, coking, accumulatings.Yet existing ammonia gas sensor ubiquity working temperature made from gas sensitive is high, sensitivity is not high, the reaction times and time of recovery long problem.In the last few years, nano-sensor was because the advantages such as low, the easy realization of high, the unique chemical property of its specific surface area, energy consumption is microminiaturized and intelligent were by people's extensive concern.
Tellurium is a kind of important low-gap semiconductor (direct band gap 0.35eV), not only has the physical propertiess such as good electric conductivity, pyroelectricity, piezoelectricity, polarizability and nonlinear optics but also aspect gas sensing, has good application.Due to the high anisotropy of its crystalline structure itself, can be without template, crystal seed, tensio-active agent auxiliary, just can form one dimension tubular structure, this has excited the research interest of numerous chemosynthesis man.In in recent years, about the one dimension tubular structure synthetic method of tellurium, there are reports, as physical evaporation method 560 ℃ of evaporation telloys 2 hours under argon shield for: Li Yadong seminar, prepare the tellurium micron tube [J.Mater.Chem. of hexagonal cross-section, 2004,14,244 – 247]; Qian Yitai seminar puts into reactor by hydrothermal method by sodium tellurite and ammoniacal liquor and keeps 180 ℃, 36 hours, prepares the cylindricality tellurium nanotube [Adv.Mater., 2002,14,1658-1662] of both ends open; Xia Younan seminar by orthotelluric acid and the ethylene glycol 2h that refluxes at 197 ℃, prepares the solid tellurium nanotube [Adv.Mater., 2002,14,279-282] with hexagonal cross-section in the middle of both ends open by the method for backflow polyvalent alcohol.But these methods mostly, because complicated operation or reaction times are long or temperature of reaction is higher, cause preparation cost high-leveled and difficult with industrialization promotion.Based on this, develop a kind of method and simply, effectively prepare the novel method of tellurium nanotube and have great importance.
(3) summary of the invention
The object of the invention is to provide a kind of tellurium nanotube and preparation method and the application in preparing the nano tube based ammonia gas sensor of tellurium; Solve that current method is prepared tellurium nanotube complicated operation, long reaction time, temperature of reaction is high, energy expenditure is large, be not easy to the problem of suitability for industrialized production, and solve that existing ammonia gas sensor ubiquity working temperature made from gas sensitive is high, sensitivity is not high, the reaction times and time of recovery long problem.
The technical solution used in the present invention is:
The invention provides a kind of tellurium nanotube, described tellurium nanotube makes as follows: tellurium salt is mixed with polyvalent alcohol and pure water a, at microwave power, be under 200 ~ 600W condition, to react after 1 ~ 10 minute, at microwave power, be to react 30 ~ 120s under 400 ~ 600W condition again, after reaction finishes, reaction solution is centrifugal, get precipitation a and use successively centrifugation again after pure water b, absolute ethanol washing, must precipitate b vacuum-drying, obtain described tellurium nanotube; Described tellurium salt is one or more the mixing in tellurium diethyl dithiocarbamate, biphenyl two telluriums, bromination benzyl dibutyl tellurid or p-methoxyphenyl tellurium oxide; Described polyvalent alcohol is one or more the mixing in ethylene glycol, glycerol or 1,3 butylene glycol; The cumulative volume consumption of described polyvalent alcohol is counted 100 ~ 1000mL/mol with the amount of substance of tellurium salt; The volumetric usage of described pure water a is counted 1 ~ 90mL/mol with the amount of substance of tellurium salt.
Further, described tellurium salt is preferably tellurium diethyl dithiocarbamate.
Further, described polyvalent alcohol is preferably ethylene glycol.
Further, the cumulative volume consumption of preferred described polyvalent alcohol is counted 300 ~ 400mL/mol with the amount of substance of tellurium salt; The volumetric usage of described pure water a is counted 3 ~ 35mL/mol with the amount of substance of tellurium salt.
Further, described tellurium nanotube makes as follows: tellurium salt is mixed with polyvalent alcohol and pure water a, at microwave power, be under 300 ~ 500W condition, to react after 1 ~ 10 minute, at microwave power, be to react 30 ~ 120s under 400 ~ 600W condition again, after reaction finishes, reaction solution is centrifugal, get precipitation a and use successively pure water b, absolute ethanol washing 1 ~ 3 time, remove by filter centrifugation again after washing lotion, must precipitate b vacuum-drying 10 hours at 50 ℃, obtain described tellurium nanotube; Described tellurium salt is a kind of in tellurium diethyl dithiocarbamate, biphenyl two telluriums, bromination benzyl dibutyl tellurid or p-methoxyphenyl tellurium oxide; Described polyvalent alcohol is a kind of in ethylene glycol, glycerol or 1,3 butylene glycol; The cumulative volume consumption of described polyvalent alcohol is counted 300 ~ 400mL/mol with the amount of substance of tellurium salt; The volumetric usage of described pure water b is counted 3 ~ 35mL/mol with the amount of substance of tellurium salt.
The present invention also provides the application of a kind of described tellurium nanotube in preparing the nano tube based ammonia gas sensor of tellurium.
Further, described tellurium nanotube being applied as in preparing the nano tube based ammonia gas sensor of tellurium: described tellurium nanotube is placed in to dehydrated alcohol, and ultrasonic dispersion is 10 ~ 30 minutes under 10 ~ 100KHz condition, obtains dispersion liquid; Dispersion liquid is coated on gas sensor, makes dispersion liquid connect gas sensor electrode two ends, then at room temperature place ethanol is volatilized naturally, obtain the nano tube based ammonia gas sensor of tellurium; Described gas sensor is the dielectric that vitrified pipe, ceramic plate or other two ends that two ends are coated with electrode film are coated with electrode film.
Further, described tellurium nanotube quality consumption is counted 1 ~ 50mg/ml with dehydrated alcohol cumulative volume.
Precipitation a of the present invention and precipitation b are precipitation, for ease of distinguishing the precipitation difference of different step acquisition, name, and described pure water a, pure water b are pure water, for ease of differentiation different step pure water amount used is different, name, and letter itself does not have implication.
Pure water of the present invention refers to that resistance is the deionized water of 18M Ω.
Compared with prior art, beneficial effect of the present invention is mainly reflected in:
(1) the tellurium nanotube that prepared by the present invention has good Modulatory character energy: by changing concentration and the reaction times of tellurium salt, can regulate and control size and the size of tellurium nanotube.
(2) the present invention adopts the tellurium nanotube that microwave process for synthesizing makes, and its good stability makes its good stability that is applied to ammonia gas sensor, can life-time service.
(3) ammonia gas sensor that prepared by the present invention, at room temperature, has good detection sensitivity, can detect the ammonia of 0.5ppm, and response recovery characteristics is fast, time of response 35s left and right, 45s time of recovery left and right.
(4) preparation method of the present invention is simple to operate, the reaction times is short, temperature of reaction is low, energy expenditure is little, is easy to suitability for industrialized production.
(4) accompanying drawing explanation
Fig. 1 is the atlas analysis of the tellurium nanotube of embodiment 1 preparation, and a is X-ray diffraction (XRD) collection of illustrative plates, and b is energy spectrum analysis (EDS) collection of illustrative plates.
Fig. 2 is the scanning electron microscope (SEM) photograph of the tellurium nanotube of embodiment 1 preparation, and a is the tellurium nanotube scanning electron microscope (SEM) photograph under low magnification (10,000 times), and b is the tellurium nanotube scanning electron microscope (SEM) photograph under high-amplification-factor (40,000 times).
Fig. 3 is the transmission electron microscope picture of the tellurium nanotube of embodiment 1 preparation, a is transmission electron microscope (TEM) figure of the tellurium nanotube of embodiment 1 preparation, b is transmission electron microscope picture (TEM) figure in tellurium nanotube under high-amplification-factor (40,000 times), c is high resolving power transmission electron microscope (HRTEM) figure of tellurium nanotube, and d is selected area electron diffraction (SAED) figure of tellurium nanotube.
Fig. 4 is the response diagram of the nano tube based ammonia gas sensor of tellurium that makes of embodiment 5 to different concns ammonia.
(5) embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1 tellurium nanotube
Taking 0.1g(0.14mmol) tellurium diethyl dithiocarbamate puts into Kjeldahl flask, measure 48ml ethylene glycol and 2ml pure water is poured into respectively in Kjeldahl flask, above-mentioned Kjeldahl flask is put into the auxiliary synthesize/extractive reaction instrument of MAS-I type normal pressure microwave that Xinyi Microwave Chemistry Tech Co., Ltd. produces, under 400W power condition, react after five minutes, under 500W power condition, react 60s again, after reaction finishes, reaction solution is centrifugal, get precipitation and use successively pure water, centrifugation after absolute ethanol washing 3 times, get and be deposited at 50 ℃ vacuum-drying 10 hours, obtain Bamboo-shaped single crystal tellurium nanotube 0.13mmol(in tellurium amount of substance, as follows).The structure collection of illustrative plates of tellurium nanotube is shown in shown in Fig. 1, Fig. 2 and Fig. 3, X-ray diffraction (XRD) collection of illustrative plates (in Fig. 1 shown in a), energy spectrum analysis (EDS) collection of illustrative plates (as shown in b in Fig. 1), scanning electron microscope (SEM) figure (as shown in Figure 2), transmission electron microscope TEM schemes (as shown in a in Fig. 3 and b), high resolving power transmission electron microscope (HRTEM) figure (as shown in c in Fig. 3), selected area electron diffraction (SAED) figure (as shown in d in Fig. 3).
Embodiment 2 tellurium nanotubes
Taking 0.1g(0.14mmol) tellurium diethyl dithiocarbamate puts into Kjeldahl flask, measure 48ml ethylene glycol and 6ml pure water is poured into respectively in Kjeldahl flask, above-mentioned Kjeldahl flask is put into microwave reaction instrument, under 500W power, react after five minutes, under 600W power, react 100s again, after reaction finishes, reaction solution is centrifugal, get precipitation and use successively centrifugation after pure water, absolute ethanol washing 3 times, get and be deposited at 50 ℃ vacuum-drying 10 hours, obtain Bamboo-shaped single crystal tellurium nanotube 0.11mmol.
Embodiment 3 tellurium nanotubes
Taking 0.082g(0.2mmol) biphenyl two telluriums put into Kjeldahl flask, measure 48ml ethylene glycol and 2ml pure water and pour into respectively in Kjeldahl flask, above-mentioned Kjeldahl flask is put into microwave reaction instrument, under 400W power, react after 5 minutes, under 500W power, reaction 60s, after reaction finishes afterwards, reaction solution is centrifugal, get precipitation and use successively centrifugation after pure water, absolute ethanol washing 3 times, get and be deposited at 50 ℃ vacuum-drying 10 hours, obtain Bamboo-shaped single crystal tellurium nanotube 0.35mmol.
Embodiment 4 tellurium nanotubes
Taking 0.082g(0.2mmol) biphenyl two telluriums put into Kjeldahl flask, measure 48ml ethylene glycol and 2ml pure water is poured into respectively in Kjeldahl flask, above-mentioned Kjeldahl flask is put into microwave reaction instrument, under 300W power, react after 6 minutes, then react 120s under 500W power, after reaction finishes, reaction solution is centrifugal, get precipitation and use successively centrifugation after pure water, absolute ethanol washing 3 times, get and be deposited at 50 ℃ vacuum-drying 10 hours, obtain Bamboo-shaped single crystal tellurium nanotube 0.31mmol.
The preparation of the nano tube based ammonia gas sensor of embodiment 5 tellurium
The tellurium nanotube powder 30mg that gets embodiment 1 preparation is scattered in 1ml dehydrated alcohol, and under 30KHz condition, ultrasonic dispersion, after 30 minutes, obtains uniform dispersion.Dispersion liquid is coated on the vitrified pipe that is coated with gold electrode film, standing after ethanol volatilizees naturally under room temperature, both obtained the nano tube based ammonia gas sensor of tellurium.
The nano tube based ammonia gas sensor of tellurium that aforesaid method is made is at Testing system of gas-sensor built (WS-30A, Zhengzhou Wei Sheng Electronic Technology Co., Ltd) upper test, first in air, test 5 minutes, then cover lid adds certain density ammonia test 5 minutes, again lid is opened to test 5 minutes, by that analogy, the ammonia that is 0.5ppm, 10ppm, 100ppm, 200ppm, 500ppm to concentration is respectively tested in test, test voltage is 3V, and pull-up resistor is 47K Ω.Test result as shown in Figure 4, the nano tube based ammonia gas sensor of tellurium that the present invention makes can detect the ammonia of 0.5 ~ 500ppm in room temperature, and has good detection sensitivity, and response recovery characteristics is fast, the ammonia time of response of detecting 0.5ppm in room temperature is 35s left and right, and be 45s left and right time of recovery.
Claims (1)
1. the preparation method of a tellurium nanotube, it is characterized in that described tellurium nanotube makes as follows: tellurium salt is mixed with polyvalent alcohol and pure water a, at microwave power, be under 300～500W condition, to react after 1～10 minute, at microwave power, be to react 30～120s under 400～600W condition again, after reaction finishes, reaction solution is centrifugal, get precipitation a and use successively pure water b, absolute ethanol washing 1～3 time, remove by filter centrifugation again after washing lotion, must precipitate b vacuum-drying 10 hours at 50 ℃, obtain described tellurium nanotube; Described tellurium salt is a kind of in tellurium diethyl dithiocarbamate, biphenyl two telluriums; Described polyvalent alcohol is ethylene glycol; The cumulative volume consumption of described polyvalent alcohol is counted 300～400mL/mol with the amount of substance of tellurium salt; The volumetric usage of described pure water a is counted 3～35mL/mol with the amount of substance of tellurium salt; Described pure water refers to that resistance is the deionized water of 18M Ω.
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| CN101759160A (en) * | 2010-01-14 | 2010-06-30 | 南京大学 | Preparation method for spindle-shaped Te nano tube |
| CN102530890A (en) * | 2011-12-15 | 2012-07-04 | 温州大学 | Tellurium semiconductor micro-nanometer crystal and preparation method |
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| CN101759160A (en) * | 2010-01-14 | 2010-06-30 | 南京大学 | Preparation method for spindle-shaped Te nano tube |
| CN102530890A (en) * | 2011-12-15 | 2012-07-04 | 温州大学 | Tellurium semiconductor micro-nanometer crystal and preparation method |
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| DESIGN》.2008,第8卷(第6期),第1902-1908页. * |
| Formation of single-crystal tellurium nanowires and nanotubes via hydrothermal recrystallization and their gas sensing properties at room temperature;Zhenghua Wang,et al.;《Journal of Materials Chemistry》;20100208;第20卷;2457-2463 * |
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