CN114275810B - Preparation method of gas-sensitive material for acetone gas sensor - Google Patents
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 26
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 12
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 16
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- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
A preparation method of a gas-sensitive material for an acetone gas sensor comprises the following steps: (a) ti is prepared by adopting one-step titanium steam auxiliary annealing process 3+ Self-doping TiO 2 Nanoparticles of TiO 2 @B‑TiO 2 A nanoparticle; (b) preparation of TiO by chemical solution method 2 @B‑TiO 2 @ ZnO core-shell nanoparticle material; (c) adding TiO into the mixture 2 @B‑TiO 2 The @ ZnO core-shell nanoparticle material is ground to be pasty and is coated on an interdigital electrode, aging treatment is carried out, and an air-sensitive test system is adopted to evaluate the air-sensitive performance of acetone. The invention provides a method for preparing TiO 2 @B‑TiO 2 The method for preparing the @ ZnO core-shell nanoparticle material is high in safety, does not introduce impurities, does not need expensive equipment, reduces the production cost, is suitable for large-scale production, and prepares TiO 2 @B‑TiO 2 The @ ZnO sensor can be used for detecting acetone gas with low concentration and high speed.
Description
Technical Field
The invention belongs to the technical field of gas sensing materials, and relates to TiO for an acetone gas sensor 2 @B-TiO 2 A preparation method of @ ZnO core-shell nano-particle material.
Background
Gas sensors have grown enormously over the last decade, with the potential to improve industrial productivity and quality of life. Among these, acetone gas sensors are of significant interest, especially in assessing health levels. According to the international union for diabetes report, there are 4.25 million diabetics in total in 2017 globally, and this value is expected to increase to 6.29 million by 2045. In conventional blood glucose testing, the sampling of a patient is often accompanied by pain. It was found that the exhaled acetone gas from the human body is highly correlated to blood glucose concentration, with the concentration of acetone in the exhaled breath of diabetic patients being 1.8 ppm higher than that of healthy people (0.3-0.9 ppm). The acetone gas sensor prepared based on the phenomenon provides a noninvasive blood sugar detection method for diabetics, and can greatly improve the life quality of the diabetics.
TiO 2 Is a common electrochemical gas sensor material based on TiO 2 The prototype acetone sensor of (1) was operated at 300 ℃. TiO for acetone sensing 2 Practical applications of materials are limited by their high operating temperatures. To reduce TiO 2 The operating temperature of a gas sensor generally adopts two methods: doping and modifying. Improvement of TiO by Nb doping 2 The performance of the sensor is such that the sensor shows good response to 25-400ppm acetone at the working temperature of 300-400 ℃. In TiO 2 The preparation of the single-selective acetone sensor is realized by doping 2% of ZnO, and the response time and the recovery time of the single-selective acetone sensor are as short as 2 seconds. Ti 3+ Self-doping TiO 2 （B-TiO 2 ) Is a novel doping method, provides impurity-free adjusted TiO 2 A bandgap method. First synthesized B-TiO 2 An optical band gap of 1.54 eV, and intrinsic anatase TiO 2 Compared with 1.66 eV. Due to efficient absorption of visible light, B-TiO 2 The photogenerated carrier concentration of (2) is also improved. B-TiO 2 The excellent photoelectric property and the photocatalytic potential of the material are proved, and the material also has potential application prospect in the field of gas sensors. So far, based on TiO 2 Acetone gas sensors of materials have been intensively and systematically studied. However, there are few reports on the study of TiO 2 Acetone gasNon-invasive blood glucose detection performance of the sensitive sensor. Thus to TiO 2 The acetone gas-sensitive performance of the material is optimized, so that the acetone gas-sensitive material has important significance in the actual working capacity in the aspect of noninvasive blood glucose detection. Thus, a method based on B-TiO is proposed 2 The acetone gas sensing material of (1).
At present, B-TiO 2 A common preparation method is H 2 Reduction, metallothermic reduction, chemical reduction, and the like. Wherein H 2 The reduction method is dangerous at high temperature, and impurities are easily introduced into the metallothermic reduction method and the chemical reduction method to influence the material performance.
Disclosure of Invention
The invention aims to provide TiO for an acetone gas sensor 2 @B-TiO 2 A preparation method of @ ZnO core-shell nano-particle material. The method has high safety, does not introduce impurities, does not need expensive equipment, reduces the production cost, is suitable for large-scale production, and the prepared gas sensing material has quick response to low-concentration acetone gas, can be used for detecting the blood sugar of a human body, and has good application prospect.
The invention is realized by the following technical scheme.
The preparation method of the gas-sensitive material for the acetone gas sensor specifically comprises the following steps.
(1) Ultrasonically cleaning a corundum boat and a glass beaker by adopting soapy water, deionized water, ethanol and deionized water in sequence, and airing for use.
(2) Synthesis of TiO 2 @B-TiO 2 Nanoparticles and dispersing them in deionized water.
(3) According to TiO aspect 2 @B-TiO 2 And the mass ratio of the nanoparticles to Cetyl Trimethyl Ammonium Bromide (CTAB) is 1: 1-2, and the cetyl trimethyl ammonium bromide is added into the suspension and stirred until the nanoparticles are completely dissolved.
(4) According to TiO aspect 2 @B-TiO 2 Adding zinc nitrate (Zn (NO) into the suspension respectively, wherein the mass ratio of the zinc nitrate to the hexamethylenetetramine in the nanoparticles is 100: 14-167 3 ) 2 ) And Hexamethylenetetramine (HMTA), Zn: (NO 3 ) 2 The mass ratio of the HMTA to the HMTA is 1.5-2.5: 1.
Preferably, Zn (NO) 3 ) 2 And HMTA in a mass ratio of 2: 1.
(5) And heating the suspension to 80-90 ℃ through a water bath, and stirring for 6 hours.
(6) The suspension was washed with deionized water, centrifuged, repeated three times, and dried.
Wherein the synthetic TiO described in the step (2) 2 @B-TiO 2 Nanoparticles comprising the following steps.
1) Ti powder and TiO 2 Placing the nanoparticles: mixing Ti powder and TiO according to a mass ratio of 4.5-5.5: 2 2 The nano particles are respectively placed at the middle part and the outlet of the tubular furnace, and the Ti powder and the TiO powder are 2 The distance between the nano particles is 10-15 cm to form stable titanium vapor.
Preferably, Ti powder and TiO 2 The mass ratio of the nano particles to the Ti powder to the TiO powder is 5:2 2 The distance between the nanoparticles was 13 cm.
2) And (3) heat treatment: at 10 ℃ min -1 Heating the quartz tube to 600-650 ℃ at the heating rate, preserving the heat for 4-5 hours, and then naturally cooling in a tube furnace to obtain TiO 2 @B-TiO 2 A nanoparticle; preferably, the mixture is heated to 650 ℃ and kept for 5 hours. H is introduced in the heat treatment process 2 An atmosphere of mixed gas of/Ar in a ratio of H 2 :Ar=30:10 sccm。
The principle of the invention is as follows: according to the depletion layer theory in the field of gas sensors, the electron concentration near the surface can improve the sensitivity of the sensing reaction. And with intrinsic TiO 2 B-TiO compared with ZnO 2 Has a lower bandgap and can therefore be used as an electron collecting layer. Inspired by the above theory, B-TiO 2 Is designed to be placed in the core TiO 2 And decorative ZnO layers. Due to B-TiO 2 Electron trapping effect of, core intrinsic TiO 2 Increased electrons generated in (2), which means that more electrons are concentrated in TiO 2 @B-TiO 2 @ ZnO nanoparticle surface vicinity. Thus, in TiO 2 @B-TiO 2 O formation on @ ZnO nanoparticles in combination with oxygen 2- /O - The number of ions increases, resulting in a depletion layer of greater thickness, with a corresponding increase in resistance. After the acetone gas is injected, the adsorbed oxygen reacts with acetone, resulting in electron release and a decrease in the thickness of the depletion layer, and therefore, the resistance of the material in the acetone atmosphere decreases. Insertion of B-TiO 2 TiO of electron-capturing layer 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material releases more electrons into a conduction band during sensing, so that the resistance difference is larger, and the more excellent acetone sensing performance is obtained by virtue of a thick initial depletion layer.
The invention provides a one-step titanium steam auxiliary annealing process for preparing B-TiO 2 And wet chemical processes are used on TiO 2 @B-TiO 2 Depositing ZnO on the surface to prepare TiO 2 @B-TiO 2 The method for preparing the @ ZnO core-shell nanoparticle material is high in safety, does not introduce impurities, does not need expensive equipment, reduces production cost, and is suitable for large-scale production. The invention adopts a one-step titanium steam auxiliary annealing process and a wet chemical method to prepare TiO in combination 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material has the advantages that a sensor made of interdigital electrodes can quickly respond to low-concentration acetone gas, and can be applied to human blood sugar detection.
The invention has the beneficial technical effects that: (1) the raw materials adopted by the invention are all environmentally compatible, so that the environment is not damaged, and chemical drugs or reagents which are difficult to degrade or pollute the environment are avoided; (2) TiO prepared by the invention 2 @B-TiO 2 The @ ZnO nano-particle material has a core-shell structure, forms a larger oxygen depletion layer and has excellent acetone gas sensing performance; (3) the one-step titanium steam auxiliary annealing process adopted by the invention avoids H at high temperature 2 The use of the method is high in safety and does not introduce impurities; (4) the wet chemical method adopted by the invention does not need expensive equipment, reduces the production cost, is suitable for large-scale production and has wide application prospect.
Drawings
FIG. 1 is a view of TiO prepared in comparative example 2 2 @B-TiO 2 Transmission electron micrograph (a) and high-magnification transmission electron microscopyMirror image (b).
FIG. 2 is the TiO prepared in example 2 2 @B-TiO 2 The transmission electron microscope (a) and high-magnification transmission electron microscope (b-c) of @ ZnO and the element distribution chart (d).
FIG. 3 is TiO prepared in comparative example 1 2 B-TiO prepared in comparative example 2 2 And TiO prepared in examples 1, 3, 6, and 7 2 @B-TiO 2 X-ray diffraction pattern of @ ZnO.
FIG. 4 shows TiO prepared in example 3 2 @B-TiO 2 The Ti 2p X ray photoelectron spectrum high resolution graph of @ ZnO.
FIG. 5 is the TiO prepared in example 3 2 @B-TiO 2 The Zn 2p X ray photoelectron spectrum high resolution of @ ZnO.
FIG. 6 shows TiO prepared in examples 1, 3, 6, and 7 2 @B-TiO 2 Response plot of @ ZnO to 50ppm acetone.
FIG. 7 shows TiO prepared in examples 1, 3, 6, and 7 2 @B-TiO 2 Graph of response versus recovery time for @ ZnO at 50ppm acetone.
FIG. 8 shows TiO prepared in example 3 2 @B-TiO 2 Graph of response of @ ZnO to different concentrations of acetone.
FIG. 9 is TiO prepared in comparative example 1 2 B-TiO prepared in comparative example 2 2 And TiO prepared in example 3 2 @B-TiO 2 The responsivity-concentration of @ ZnO is fitted to a straight line graph.
FIG. 10 is the TiO prepared in example 3 2 @B-TiO 2 @ ZnO responsivity graph for 50ppm acetone at different temperatures.
FIG. 11 is the TiO prepared in example 3 2 @B-TiO 2 Graph of responsivity of @ ZnO to 50ppm of different gases.
Detailed Description
The present invention is further described with reference to the following examples, which should not be construed as limiting the scope of the invention.
Comparative example 1.
Commercially available analytical pure drug P25 powder, intrinsic TiO 2 . Will be provided withTiO 2 Grinding the nano-particle material to be pasty, coating the nano-particle material on an interdigital electrode, carrying out aging treatment, and evaluating the air-sensitive performance of acetone by using an air-sensitive test system.
Comparative example 2. TiO 2 2 @B-TiO 2 And (4) preparing nanoparticles.
The specific process parameters are as follows: 0.5g of Ti powder and 0.2g of TiO were weighed 2 The nanoparticles were placed in the middle and at the outlet of the tube furnace, respectively, with a distance of 13cm between the two reagents to form a stable titanium vapor. At 10 ℃ min -1 Heating the quartz tube to 650 ℃, keeping the temperature at 650 ℃ for 5 hours, and cooling the quartz tube by a smelting furnace to obtain TiO 2 @B-TiO 2 And (3) nanoparticles. Using H in the annealing process 2 An atmosphere of mixed gas of/Ar in a ratio of H 2 :Ar=30:10 sccm。
Mixing TiO with 2 @B-TiO 2 Grinding the nano-particle material to be pasty, coating the nano-particle material on an interdigital electrode, carrying out aging treatment, and evaluating the air-sensitive performance of acetone by using an air-sensitive test system.
Example 1.
This example prepares TiO 2 @B-TiO 2 @ ZnO core-Shell nanoparticle Material Using TiO prepared in comparative example 2 2 @B-TiO 2 A nanoparticle material.
The specific process parameters of this example are as follows: ultrasonically cleaning a glass beaker by adopting soapy water, deionized water, ethanol and deionized water in sequence, and airing. 0.1g of the TiO prepared in comparative example 2 was weighed 2 @B-TiO 2 The nanoparticles are dispersed in deionized water. 0.15g of cetyltrimethylammonium bromide was added to the suspension and stirred until all dissolved. To the suspension was then added 0.01g of zinc nitrate and 0.005g of hexamethylenetetramine, and the suspension was heated to 85 ℃ by means of a water bath and stirred for 6 hours. Centrifuging and washing the suspension with deionized water for three times, and drying to obtain TiO 2 @B-TiO 2 @ ZnO core-shell nanoparticle material, named BTZ 1.
Adding TiO into the mixture 2 @B-TiO 2 Grinding the @ ZnO core-shell nano-particle material to be pasty, coating the pasty material on an interdigital electrode, carrying out aging treatment, and adopting gasThe sensitivity test system evaluates the air-sensitive performance of acetone.
Example 2.
This example prepares TiO 2 @B-TiO 2 @ ZnO core-Shell nanoparticle Material Using TiO prepared in comparative example 2 2 @B-TiO 2 A nanoparticle material.
The specific process parameters of this example are as follows: ultrasonically cleaning a glass beaker by adopting soapy water, deionized water, ethanol and deionized water in sequence, and airing. 0.1g of the TiO prepared in comparative example 2 was weighed 2 @B-TiO 2 The nanoparticles are dispersed in deionized water. 0.1g of cetyltrimethylammonium bromide was added to the suspension and stirred until all dissolved. To the suspension was then added 0.02g of zinc nitrate and 0.08g of hexamethylenetetramine, and the suspension was heated to 85 ℃ by means of a water bath and stirred for 6 hours. Centrifuging and washing the suspension with deionized water for three times, and drying to obtain TiO 2 @B-TiO 2 @ ZnO core-shell nanoparticle material.
Adding TiO into the mixture 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material is ground to be pasty and is coated on an interdigital electrode, aging treatment is carried out, and an air-sensitive test system is adopted to evaluate the air-sensitive performance of acetone.
Example 3.
This example prepares TiO 2 @B-TiO 2 @ ZnO core-Shell nanoparticle Material Using TiO prepared in comparative example 2 2 @B-TiO 2 A nanoparticle material.
The specific process parameters of this example are as follows: ultrasonically cleaning a glass beaker by adopting soapy water, deionized water, ethanol and deionized water in sequence, and airing. 0.1g of the TiO prepared in comparative example 2 was weighed 2 @B-TiO 2 The nanoparticles are dispersed in deionized water. 0.15g of cetyltrimethylammonium bromide was added to the suspension and stirred until all dissolved. To the suspension was then added 0.02g of zinc nitrate and 0.01g of hexamethylenetetramine, and the suspension was heated to 85 ℃ by means of a water bath and stirred for 6 hours. Centrifuging and washing the suspension with deionized water for three times, and drying to obtain TiO 2 @B-TiO 2 @ ZnO core-shell nanoparticle material namedBTZ2。
Adding TiO into the mixture 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material is ground to be pasty and is coated on an interdigital electrode, aging treatment is carried out, and an air-sensitive test system is adopted to evaluate the air-sensitive performance of acetone.
Example 4.
This example prepares TiO 2 @B-TiO 2 @ ZnO core-Shell nanoparticle Material Using TiO prepared in comparative example 2 2 @B-TiO 2 A nanoparticle material.
The specific process parameters of this example are as follows: ultrasonically cleaning a glass beaker by adopting soapy water, deionized water, ethanol and deionized water in sequence, and airing. 0.1g of the TiO prepared in comparative example 2 was weighed 2 @B-TiO 2 The nanoparticles are dispersed in deionized water. 0.2g of cetyltrimethylammonium bromide was added to the suspension and stirred for 30 min. To the suspension was then added 0.02g of zinc nitrate and 0.0134g of hexamethylenetetramine, and the suspension was heated to 85 ℃ by means of a water bath and stirred for 6 hours. Centrifuging and washing the suspension with deionized water for three times, and drying to obtain TiO 2 @B-TiO 2 @ ZnO core-shell nanoparticle material.
Adding TiO into the mixture 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material is ground to be pasty and is coated on an interdigital electrode, aging treatment is carried out, and an air-sensitive test system is adopted to evaluate the air-sensitive performance of acetone.
Example 5.
This example prepares TiO 2 @B-TiO 2 @ ZnO core-Shell nanoparticle Material Using TiO prepared in comparative example 2 2 @B-TiO 2 A nanoparticle material.
The specific process parameters of this example are as follows: ultrasonically cleaning a glass beaker by adopting soapy water, deionized water, ethanol and deionized water in sequence, and airing. 0.1g of the TiO prepared in comparative example 2 was weighed 2 @B-TiO 2 The nanoparticles are dispersed in deionized water. 0.15g of cetyltrimethylammonium bromide was added to the suspension and stirred until all dissolved. 0.02g of zinc nitrate and 0.01g of hexamethylenetetramine are then added to the suspension byThe suspension was heated to 90 ℃ in a water bath and stirred for 6 hours. Centrifuging and washing the suspension with deionized water for three times, and drying to obtain TiO 2 @B-TiO 2 @ ZnO core-shell nanoparticle material.
Adding TiO into the mixture 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material is ground to be pasty and is coated on an interdigital electrode, aging treatment is carried out, and an air-sensitive test system is adopted to evaluate the air-sensitive performance of acetone.
Example 6.
This example prepares TiO 2 @B-TiO 2 @ ZnO core-Shell nanoparticle Material, Using TiO prepared in comparative example 2 2 @B-TiO 2 A nanoparticle material.
The specific process parameters of the embodiment are as follows: ultrasonically cleaning a glass beaker by adopting soapy water, deionized water, ethanol and deionized water in sequence, and airing. 0.1g of the TiO prepared in comparative example 2 was weighed 2 @B-TiO 2 The nanoparticles are dispersed in deionized water. 0.15g of cetyltrimethylammonium bromide was added to the suspension and stirred until all dissolved. To the suspension was then added 0.05g of zinc nitrate and 0.025g of hexamethylenetetramine, and the suspension was heated to 85 ℃ by means of a water bath and stirred for 6 hours. Centrifuging and washing the suspension with deionized water for three times, and drying to obtain TiO 2 @B-TiO 2 @ ZnO core-shell nanoparticle material, named BTZ 5.
Adding TiO into the mixture 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material is ground to be pasty and is coated on an interdigital electrode, aging treatment is carried out, and an air-sensitive test system is adopted to evaluate the air-sensitive performance of acetone.
Example 7.
This example prepares TiO 2 @B-TiO 2 @ ZnO core-Shell nanoparticle Material Using TiO prepared in comparative example 2 2 @B-TiO 2 A nanoparticle material.
The specific process parameters of this example are as follows: ultrasonically cleaning a glass beaker by adopting soapy water, deionized water, ethanol and deionized water in sequence, and airing. 0.1g of the TiO prepared in comparative example 2 was weighed 2 @B-TiO 2 The nano particles are dispersed inIonized water. 0.15g of cetyltrimethylammonium bromide was added to the suspension and stirred until all dissolved. To the suspension were then added 0.1g of zinc nitrate and 0.05g of hexamethylenetetramine, and the suspension was heated to 85 ℃ by means of a water bath and stirred for 6 hours. Centrifuging and washing the suspension with deionized water for three times, and drying to obtain TiO 2 @B-TiO 2 @ ZnO core-shell nanoparticle material, named BTZ 10.
Adding TiO into the mixture 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material is ground to be pasty and is coated on an interdigital electrode, aging treatment is carried out, and an air-sensitive test system is adopted to evaluate the air-sensitive performance of acetone.
The technical scheme of the invention is further described by combining the drawings in the specification.
FIG. 1 shows TiO prepared in comparative example 2 2 @B-TiO 2 (a) and (B) high-magnification transmission electron micrographs, it can be seen that B-TiO prepared in comparative example 2 was prepared 2 The nanoparticles have an average particle size of 25nm and a lattice-disordered layer is present on the surface.
FIG. 2 shows TiO prepared in example 3 2 @B-TiO 2 In the transmission electron microscope image (a) and the high-magnification transmission electron microscope image (b-c) of @ ZnO, the boundaries and the internal gray scale of the nanoparticles are clearly changed, indicating that the internal and external element compositions are different. FIG. 2 (d) is the TiO prepared in example 3 2 @B-TiO 2 The elemental distribution picture of @ ZnO illustrates that the deposited ZnO has a high degree of uniformity.
FIG. 3 is TiO prepared in comparative example 1 2 B-TiO prepared in comparative example 2 2 And TiO prepared in examples 1, 3, 6, and 7 2 @B-TiO 2 X-ray diffraction pattern of @ ZnO. TiO prepared from comparative example 1 2 And B-TiO prepared in comparative example 2 2 Can conclude that TiO has been heat treated 2 Still maintaining the anatase phase structure. TiO prepared in example 1 2 @B-TiO 2 No significant ZnO signal was observed in @ ZnO core-shell nanoparticle materials, which was mainly due to the lower concentration of ZnO in this sample. However, in examples 3, 6 and 7TiO prepared in (1) 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material can observe obvious characteristic signal peaks belonging to ZnO, and the signal intensity is gradually increased. This is because the number of starting points of ZnO nucleation increases as the concentration of the Zn source increases, resulting in a corresponding increase in the relative ZnO content in the finally prepared sample.
FIG. 4 shows TiO prepared in example 3 2 @B-TiO 2 The Ti 2p X ray photoelectron spectrum of @ ZnO is high resolution, and it can be seen that the two peaks of Ti 2p3/2 and Ti 2p1/2 are centered at 458.20 eV and 464.01 eV, respectively. Compared with pure TiO 2 In other words, the positions of these characteristic peaks are slightly shifted to a low energy direction, which indicates the presence of Ti in the test sample 3+ 。
FIG. 5 shows TiO prepared in example 3 2 @B-TiO 2 The Zn 2p X ray photoelectron spectrum high resolution of @ ZnO. The binding energy interval corresponding to the two peaks Zn 2p1/2 and Zn 2p3/2 is 23 eV, which proves that the TiO prepared in example 3 2 @B-TiO 2 The Zn element in the @ ZnO core-shell nano-particle material exists in a ZnO form.
FIG. 6 shows TiO prepared in examples 1, 3, 6, and 7 2 @B-TiO 2 Response plot of @ ZnO to 50ppm acetone. As shown, Zn (NO) is added during ZnO deposition 3 ) 2 The acetone sensing sensitivity of the corresponding sample is also greatly changed due to the increase of the concentration. For both TiO prepared in examples 1, 3 2 @B-TiO 2 @ ZnO core-shell nanoparticle material, a strong response was observed when 50ppm acetone was injected into the chamber. Wherein the TiO prepared in example 3 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material has the highest responsivity. When Zn (NO) 3 ) 2 In a concentration of more than 2.10mmol L -1 The sensitivity of the corresponding sample rapidly decreased. For TiO prepared in examples 6, 7 2 @B-TiO 2 For the @ ZnO core-shell nanoparticle material, the relative response to 50ppm acetone was only 2.54 and 6.65, respectively.
FIG. 7 shows TiO prepared in examples 1, 3, 6, and 7 2 @B-TiO 2 Graph of response versus recovery time for @ ZnO at 50ppm acetone. And phaseThe trends in response are similar for the TiO prepared in examples 6 and 7 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material has slow response to acetone in the environment. For recovery time, the TiO prepared in example 3 2 @B-TiO 2 The longest recovery time of the @ ZnO core-shell nanoparticle material is 26 s. This is probably due to the fact that it consumes a large amount of surface adsorbed oxygen during the acetone gas-sensitive reaction, and therefore, it takes longer time to adsorb the depleted oxygen during the subsequent resistance recovery process.
FIG. 8 shows TiO prepared in example 3 2 @B-TiO 2 Graph of response of @ ZnO to different concentrations of acetone. TiO prepared in example 2 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material shows strong response to acetone with the concentration range of 10-300ppm at the working temperature of 275 ℃. Their relative responses to 10, 30, 50, 80, 100, 200 and 300ppm acetone were 22.36, 33.53, 49.25, 58.82, 80.45, 131.36 and 203.25, respectively.
FIG. 9 is TiO prepared in comparative example 1 2 B-TiO prepared in comparative example 2 2 And TiO prepared in example 3 2 @B-TiO 2 The responsivity-concentration of @ ZnO is fitted to a straight line graph. Pure TiO at 275 deg.C 2 There was little reaction with acetone at concentrations of 10-300 ppm. After the ZnO film is deposited on the surface of the sample, the acetone gas-sensitive performance is obviously improved. By linear fitting, the TiO prepared in example 3 can be found 2 @B-TiO 2 A strict linear relation exists between the responsivity of the @ ZnO core-shell nanoparticle material and the concentration of acetone: r = 0.613C +15.23 [ C.gtoreq.10 ppm]Where C is the acetone concentration injected during the test.
FIG. 10 is the TiO prepared in example 3 2 @B-TiO 2 @ ZnO responsivity graph for 50ppm acetone at different temperatures. The TiO prepared in example 3 varied with operating temperature 2 @B-TiO 2 The acetone relative responsiveness of the @ ZnO core-shell nanoparticle material is also changed. The TiO prepared in example 3 can be determined by comparison 2 @B-TiO 2 The optimal working temperature of the @ ZnO core-shell nanoparticle material is 275 ℃.
FIG. 11 is the TiO prepared in example 3 2 @B-TiO 2 Graph of responsivity of @ ZnO to 50ppm of different gases. As shown in FIG. 11, TiO prepared in example 3 2 @B-TiO 2 The @ ZnO core-shell nanoparticle material shows ideal selectivity for acetone. It is considered that various other organic gases included in exhaled breath of the human body are hardly added to the TiO prepared in example 3 2 @B-TiO 2 The acetone detection performance of the @ ZnO core-shell nanoparticle material causes interference.
Claims (3)
1. A preparation method of a gas-sensitive material for an acetone gas sensor is characterized by comprising the following steps:
(1) ultrasonically cleaning a corundum boat and a glass beaker by adopting soapy water, deionized water, ethanol and deionized water in sequence, and airing for use;
(2) synthesis of TiO 2 @B-TiO 2 Nanoparticles, and dispersing them in deionized water;
(3) according to TiO aspect 2 @B-TiO 2 The mass ratio of the nano particles to the cetyl trimethyl ammonium bromide is 1: 1-2, the cetyl trimethyl ammonium bromide is added into the suspension, and the suspension is stirred until the nano particles are completely dissolved;
(4) according to TiO aspect 2 @B-TiO 2 The mass ratio of zinc nitrate to hexamethylenetetramine is 100: 14-167, and the zinc nitrate and the hexamethylenetetramine are respectively added into the suspension, wherein the mass ratio of the zinc nitrate to the hexamethylenetetramine is 1.5-2.5: 1;
(5) heating the suspension to 80-90 ℃ through a water bath, and stirring for 6 hours;
(6) washing the suspension with deionized water, centrifuging, repeating for three times, and drying;
wherein, the synthetic TiO in the step (2) 2 @B-TiO 2 Nanoparticles comprising the steps of:
1) ti powder and TiO 2 Placing the nanoparticles: mixing Ti powder and TiO according to the mass ratio of 4.5-5.5: 2 2 The nano particles are respectively placed at the middle part and the outlet of the tubular furnace, and Ti powder and TiO are respectively placed at the outlet 2 The distance between the nano particles is 10-15cm to form a stable titanium vapor;
2) and (3) heat treatment: at 10 ℃ min -1 Heating the quartz tube to 600-650 ℃ at the heating rate, preserving the heat for 4-5 hours, and then naturally cooling in a tube furnace to obtain TiO 2 @B-TiO 2 A nanoparticle; h is introduced in the heat treatment process 2 An atmosphere of mixed gas of/Ar in a ratio of H 2 :Ar=30:10 sccm。
2. The method for preparing a gas-sensitive material for an acetone gas sensor according to claim 1, wherein in the step (2), Ti powder and TiO are added 2 The mass ratio of the nano particles to the Ti powder to the TiO powder is 5:2 2 The distance between the nanoparticles was 13 cm.
3. The method for preparing the gas-sensitive material for the acetone gas sensor according to claim 1, wherein the mass ratio of the zinc nitrate to the hexamethylenetetramine in the step (4) is 2: 1.
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