CN108802112B - Platinum particle modified tin oxide-iron oxide nano composite particle and preparation method and application thereof - Google Patents
Platinum particle modified tin oxide-iron oxide nano composite particle and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a platinum particle modified tin oxide-iron oxide nano composite particle and a preparation method and application thereof. The tin oxide-iron oxide nano composite particle modified by the platinum particles can be used as a sensing material in a gas sensing device and is used for carrying out high-sensitivity trace detection on styrene gas. The invention has good gas sensitivity, can be used as a gas-sensitive sensing layer to realize the monitoring of styrene gas, has low use cost, does not need expensive detection equipment, and has simple operation, rapidness and high efficiency.
Description
Technical Field
The invention relates to the field of gas-sensitive sensing materials, in particular to a platinum particle modified tin oxide-iron oxide nano composite particle and a preparation method and application thereof.
Background
Styrene is a chronic toxic gas that presents a serious hazard to the human nervous and respiratory systems, and can cause leukemia and cancer in long-term exposure. According to the emission standard of malodorous pollutants (GB14554-93), the minimum critical value of the concentration of the discharged styrene gas into the atmosphere cannot exceed 0.6ppm, so that trace detection of the styrene is required.
At present, the technologies for detecting styrene gas mainly include gas chromatography-mass spectrometry, laser detection methods, surface acoustic wave sensing technologies and piezoelectric optical sensors; however, these detection techniques have the problems of expensive detection equipment and complex operation process, so it is necessary to develop a method for detecting trace amount of styrene with low cost and simple operation. The metal oxide resistance type gas sensor has the advantages of small volume, low cost, high sensitivity, high response and recovery speed, simple operation and the like, so the metal oxide resistance type gas sensor is favored by extensive researchers. However, in the prior art, a metal oxide resistance type gas sensor capable of detecting styrene gas has not been developed.
Disclosure of Invention
In order to solve the technical problems that styrene gas detection equipment is expensive and the operation process is complex in the prior art, and a metal oxide resistance type gas sensor capable of detecting styrene gas is not developed, the invention provides platinum particle modified tin oxide-iron oxide nano composite particles and a preparation method and application thereof; the platinum particle modified tin oxide-iron oxide nano composite particle has good gas sensitivity, can be used as a sensing layer to realize high-sensitivity trace detection on styrene gas, and has the advantages of low use cost, no need of expensive detection equipment, simple operation, rapidness and high efficiency.
The purpose of the invention is realized by the following technical scheme:
a preparation method of platinum particle modified tin oxide-iron oxide nano composite particles comprises the following steps:
step A, dispersing tin oxide-iron oxyhydroxide nano composite particles into an ethanol-acetonitrile mixed solution to enable the concentration of the tin oxide-iron oxyhydroxide nano composite particles in the mixed solution to be 0.1-1.5 mg/mL, stirring for 10-30 min, then sequentially adding ammonia water and 3-aminopropyltriethoxysilane, stirring for 10-48 h at the temperature of 20-100 ℃, and then carrying out solid-liquid separation and washing to obtain amino modified tin oxide-iron oxyhydroxide nano composite particles;
b, dispersing the amino-modified tin oxide-iron oxyhydroxide nano composite particles into deionized water, controlling the concentration of the amino-modified tin oxide-iron oxyhydroxide nano composite particles to be 0.1-2.5 mg/mL, then adding potassium chloroplatinate, stirring for 2-12 h at the temperature of 25-60 ℃, and then performing centrifugal separation to obtain platinum ion-modified tin oxide-iron oxyhydroxide nano composite particles; dispersing the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum ions into deionized water, adding sodium borohydride, reacting at 25-60 ℃ for 2-10 h, and performing solid-liquid separation and washing to obtain tin oxide-iron oxyhydroxide nano composite particles modified by the platinum nanoparticles;
and step C, calcining the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum nano particles under the protection of inert gas, wherein the calcining temperature is 300-600 ℃, the heating rate is 0.5-10 ℃/min, and the calcining time is 0.5-5 h, so that the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum particles are obtained.
Preferably, the method for preparing the tin oxide-iron oxyhydroxide nanocomposite particle includes the steps of:
step A1, adding tin tetrachloride pentahydrate into ethanol according to the weight ratio of 35-40 wt% of hydrochloric acid solution to 0.5-2: 50-150: 1, stirring for 10-30 min, adding 35-40 wt% of hydrochloric acid solution, placing at 150-200 ℃ for closed reaction for 5-24 h, and performing solid-liquid separation and washing to obtain the tin oxide hollow spheres;
step A2, dispersing the tin oxide hollow spheres obtained in the step A1 into deionized water, controlling the concentration of the tin oxide hollow spheres to be 0.1-2.5 mg/mL, and stirring for 5-30 min to obtain a tin oxide dispersion liquid; adding ferric trichloride into the tin oxide dispersion liquid, controlling the concentration of the ferric trichloride to be 0.5-3.5 mg/mL, and stirring for 5-30 min to obtain a mixed dispersion liquid; and transferring the mixed dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out closed reaction at the temperature of 90-150 ℃ for 20-240 min, and carrying out solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particles.
Preferably, in the step A, the volume ratio of ethanol to acetonitrile in the ethanol-acetonitrile mixed solution is 1: 0.5-10; the dosage of the ammonia water is 0.01-0.2 times of the total mass of the tin oxide-iron oxyhydroxide nano composite particles; the dosage of the 3-aminopropyltriethoxysilane is 0.01-0.25 time of the total mass of the tin oxide-iron oxyhydroxide nano composite particles.
Preferably, in the step B, the dosage of the potassium chloroplatinate is 0.001-0.05 times of the total mass of the amino-modified tin oxide-iron oxyhydroxide nano composite particles; the mass of the sodium borohydride is 0.05-0.5 times of the total mass of the amino-modified tin oxide-iron oxyhydroxide nano composite particles.
Preferably, in step C, the inert gas is at least one of nitrogen and argon.
The platinum particle modified tin oxide-iron oxide nano composite particle is prepared by adopting the preparation method of the platinum particle modified tin oxide-iron oxide nano composite particle.
The application of the tin oxide-iron oxide nano composite particles modified by the platinum particles is to use the tin oxide-iron oxide nano composite particles modified by the platinum particles as a sensing material in a gas sensing device.
Preferably, the sensing material in the gas sensing device is used for detecting styrene gas.
According to the technical scheme provided by the invention, the preparation method of the platinum particle modified tin oxide-iron oxide nano composite particle comprises the steps of firstly modifying the surface of the tin oxide-iron oxyhydroxide nano composite particle by using 3-aminopropyltriethoxysilane, then loading platinum particles with ultra-small sizes on the surface of the tin oxide-iron oxyhydroxide composite particle through an in-situ reduction process, and finally carrying out high-temperature calcination in the protection of inert gas. The tin oxide-iron oxide nano composite particle modified by the platinum particles can be used as a sensing material in a gas sensing device and is used for carrying out high-sensitivity trace detection on styrene gas. The invention has good gas sensitivity, can be used as a gas-sensitive sensing layer to realize real-time monitoring on styrene gas, has low use cost, does not need expensive detection equipment, and has simple operation, rapidness and high efficiency.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of tin oxide-iron oxyhydroxide nanocomposite particles obtained in step b1, tin oxide-iron oxyhydroxide nanocomposite particles modified with platinum nanoparticles obtained in step d1, and tin oxide-iron oxide nanocomposite particles modified with platinum particles obtained in step e1 of example 1 according to the present invention.
FIG. 2 shows SEM pictures and TEM pictures of Pt particle-modified tin oxide-iron oxide nanocomposite particles obtained in step e1 of example 1.
Fig. 3 is a schematic diagram of a styrene gas sensitivity performance test result of the platinum particle-modified tin oxide-iron oxide nanocomposite particle prepared in step e1 in example 1 of the present invention.
Fig. 4 is a schematic diagram of a styrene gas-sensitive gradient performance test result of the platinum particle-modified tin oxide-iron oxide nanocomposite particle prepared in step e1 in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The platinum particle-modified tin oxide-iron oxide nanocomposite particles provided by the present invention, and the preparation method and application thereof are described in detail below. Details of the present invention not described in detail are well within the skill of those in the art.
A preparation method of platinum particle modified tin oxide-iron oxide nano composite particles can comprise the following steps:
and A, dispersing the tin oxide-iron oxyhydroxide nano composite particles into an ethanol-acetonitrile mixed solution to enable the concentration of the tin oxide-iron oxyhydroxide nano composite particles in the mixed solution to be 0.1-1.5 mg/mL, carrying out magnetic stirring for 10-30 min, then sequentially adding ammonia water and 3-aminopropyltriethoxysilane, carrying out magnetic stirring for 10-48 h at the temperature of 20-100 ℃, and carrying out solid-liquid separation and washing to obtain the amino modified tin oxide-iron oxyhydroxide nano composite particles. Wherein the volume ratio of ethanol to acetonitrile in the ethanol-acetonitrile mixed solution is 1: 0.5-10; the dosage of the ammonia water is 0.01-0.2 times of the total mass of the tin oxide-iron oxyhydroxide nano composite particles; the dosage of the 3-aminopropyltriethoxysilane is 0.01-0.25 time of the total mass of the tin oxide-iron oxyhydroxide nano composite particles. The main function of the step A is to modify the surface of the tin oxide-iron oxyhydroxide nano composite particles by using 3-aminopropyl triethoxysilane.
And B, dispersing the amino modified tin oxide-iron oxyhydroxide nano composite particles into deionized water, controlling the concentration of the amino modified tin oxide-iron oxyhydroxide nano composite particles to be 0.1-2.5 mg/mL, then adding potassium chloroplatinate, magnetically stirring for 2-12 h at the temperature of 25-60 ℃, and then performing centrifugal separation to obtain the platinum ion modified tin oxide-iron oxyhydroxide nano composite particles. Dispersing the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum ions into deionized water, adding sodium borohydride, reacting at 25-60 ℃ for 2-10 h, and performing solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum nanoparticles. Wherein the dosage of the potassium chloroplatinate is 0.001-0.05 times of the total mass of the amino-modified tin oxide-iron oxyhydroxide nano composite particles; the mass of the sodium borohydride is 0.05-0.5 times of the total mass of the amino-modified tin oxide-iron oxyhydroxide nano composite particles. The main function of the step B is to load platinum particles with ultra-small size on the surface of the tin oxide-iron oxyhydroxide composite particles through an in-situ reduction process.
And step C, calcining the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum nano particles under the protection of inert gas (the inert gas can adopt at least one of nitrogen and argon), wherein the calcining temperature is 300-600 ℃, the heating rate is 0.5-10 ℃/min, and the calcining time is 0.5-5 h, so that the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum particles are obtained.
Specifically, the tin oxide-iron oxyhydroxide nanocomposite particle can be prepared by a hydrothermal method, and the preparation method can comprise the following steps:
and A1, adding the stannic chloride pentahydrate into ethanol according to the weight ratio of 35-40 wt% of hydrochloric acid solution to 0.5-2: 50-150: 1, magnetically stirring for 10-30 min, adding 35-40 wt% of hydrochloric acid solution, placing the mixture at 150-200 ℃ for closed reaction for 5-24 h, and performing solid-liquid separation and washing to obtain the stannic oxide hollow sphere.
Step A2, dispersing the tin oxide hollow spheres obtained in the step A1 into deionized water, controlling the concentration of the tin oxide hollow spheres to be 0.1-2.5 mg/mL, and magnetically stirring for 5-30 min to obtain a tin oxide dispersion liquid; adding ferric trichloride into the tin oxide dispersion liquid, controlling the concentration of the ferric trichloride to be 0.5-3.5 mg/mL, and magnetically stirring for 5-30 min to obtain a mixed dispersion liquid; and transferring the mixed dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out closed reaction at the temperature of 90-150 ℃ for 20-240 min, and carrying out solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particles.
Compared with the styrene gas detection technology in the prior art, the platinum particle modified tin oxide-iron oxide nano composite particle and the preparation method thereof provided by the invention have at least the following beneficial effects:
(1) in the platinum particle modified tin oxide-iron oxide nano composite particles provided by the invention, the tin oxide-iron oxide nano composite particles are hollow structures, the size of the tin oxide-iron oxide nano composite particles is 180-220 nm, and the platinum particles are ultra-small platinum particles with the size of about 1.8 nm. The tin oxide-iron oxide nano composite particle modified by the platinum particles not only has a large number of semiconductor nano heterojunction effects, but also has the catalytic effect and Schottky effect generated by the platinum nanoparticles, and the hollow structure of the tin oxide-iron oxide nano composite particle greatly improves the specific surface area of the tin oxide-iron oxide nano composite particle, so that the gas-sensitive performance of the tin oxide-iron oxide nano composite particle is greatly improved.
(2) The platinum particle modified tin oxide-iron oxide nano composite particle provided by the invention can be used as a sensing material or a gas sensitive element in a gas sensing device, has excellent sensing performance on styrene gas, and can realize high-sensitivity trace detection on the styrene gas. Through tests on styrene gas under different concentrations, when the concentration of the styrene gas to be tested is as low as 50ppb, the tin oxide-iron oxide nano composite particles modified by the platinum particles provided by the invention can still be effectively detected, and the detection consistency and repeatability are very good.
(3) The platinum particle modified tin oxide-iron oxide nano composite particle provided by the invention can be coated on a gas-sensitive test electrode for carrying out high-sensitivity trace detection on styrene gas, so that the platinum particle modified tin oxide-iron oxide nano composite particle for carrying out styrene gas detection has the advantages of low use cost, no need of expensive detection equipment, simplicity in operation, rapidness, high efficiency and the like, and the platinum particle modified tin oxide-iron oxide nano composite particle provided by the invention can be very easily and widely applied to the high-sensitivity trace detection on the styrene gas.
(4) The preparation method of the platinum particle modified tin oxide-iron oxide nano composite particle provided by the invention is simple, convenient, rapid and efficient.
In conclusion, the embodiment of the invention has good gas sensitivity, can be used as a sensing layer to realize high-sensitivity trace detection on styrene gas, and has the advantages of low use cost, no need of expensive detection equipment, simple operation, rapidness and high efficiency.
In order to more clearly show the technical scheme and the technical effects provided by the present invention, the platinum particle modified tin oxide-iron oxide nanocomposite particles provided by the embodiments of the present invention, and the preparation method and the application thereof are described in detail in the following with specific examples.
Example 1
A preparation method of platinum particle modified tin oxide-iron oxide nano composite particles can comprise the following steps:
step a1, adding tin tetrachloride pentahydrate into an ethanol aqueous solution according to the weight ratio of the tin tetrachloride pentahydrate to the ethanol aqueous solution, namely 35-40 wt% hydrochloric acid solution, stirring for 20min, then adding 35-40 wt% hydrochloric acid solution, placing the mixture at 200 ℃ for closed reaction for 12h, and then carrying out solid-liquid separation and washing treatment, thereby obtaining the tin oxide hollow sphere.
B1, dispersing 50mg of the tin oxide hollow spheres into 50mL of deionized water, and magnetically stirring for 10min to obtain a tin oxide dispersion liquid; adding ferric trichloride into the tin oxide dispersion liquid, controlling the concentration of the ferric trichloride to be 0.8mg/mL, and magnetically stirring for 30min to obtain a mixed dispersion liquid; and transferring the mixed dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out closed reaction at 120 ℃ for 60min, and carrying out solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particles.
And c1, dispersing 50mg of the tin oxide-iron oxyhydroxide nano composite particle into 80mL of ethanol-acetonitrile mixed solution (the volume ratio of ethanol to acetonitrile is 1:4), magnetically stirring for 30min, then sequentially adding 3mL of ammonia water and 3mL of 3-aminopropyltriethoxysilane, magnetically stirring for 24h at 80 ℃, and then carrying out solid-liquid separation and washing to obtain the amino-modified tin oxide-iron oxyhydroxide nano composite particle.
And d1, dispersing 50mg of the amino-modified tin oxide-iron oxyhydroxide nano composite particles into 50mL of deionized water, then adding 10mL of potassium chloroplatinate solution with the concentration of 0.1mg/mL, magnetically stirring for 5 hours at 25 ℃, and then performing centrifugal separation to obtain the platinum ion-modified tin oxide-iron oxyhydroxide nano composite particles. Dispersing the tin oxide-iron oxyhydroxide nano composite particle modified by the platinum ions into 30mL of deionized water, adding 4mL of sodium borohydride aqueous solution with the concentration of 0.1mg/mL, reacting for 5h at 25 ℃, and then performing solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particle modified by the platinum nanoparticles.
And e1, calcining the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum nano particles under the protection of nitrogen, wherein the calcining temperature is 500 ℃, the heating rate is 5 ℃/min, and the calcining time is 2h, so that the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum particles are obtained.
Specifically, the following morphology and performance tests were performed on the platinum particle-modified tin oxide-iron oxide nanocomposite particles provided in embodiment 1 of the present invention:
(1) the tin oxide-iron oxyhydroxide nanocomposite particles obtained in step b1, the tin oxide-iron oxyhydroxide nanocomposite particles obtained in step d1, and the tin oxide-iron oxyhydroxide nanocomposite particles obtained in step e1 of example 1 of the present invention were examined with an X-ray diffractometer to obtain an X-ray diffraction pattern shown in fig. 1. In FIG. 1, curve (a) is an X-ray diffraction pattern of tin oxide-iron oxyhydroxide nanocomposite particles obtained in step b1 of example 1 of the present invention, curve (b) is an X-ray diffraction pattern of platinum-nanoparticle-modified tin oxide-iron oxyhydroxide nanocomposite particles obtained in step d1 of example 1 of the present invention, and curve (c) is an X-ray diffraction pattern of platinum-particle-modified tin oxide-iron oxyhydroxide nanocomposite particles obtained in step e1 of example 1 of the present invention. As can be seen from fig. 1: the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum nano particles are successfully prepared in the embodiment 1 of the invention.
(2) The tin oxide-iron oxide nanocomposite particles modified with platinum particles obtained in step e1 of example 1 of the present invention were observed with a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), respectively, to obtain a scanning electron micrograph (i.e., SEM image) and a transmission electron micrograph (i.e., TEM image) as shown in fig. 2. Fig. 2a is a first SEM image of the platinum particle-modified tin oxide-iron oxide nanocomposite particle obtained in step e1 of example 1 of the present invention, fig. 2b is a second SEM image of the platinum particle-modified tin oxide-iron oxide nanocomposite particle obtained in step e1 of example 1 of the present invention, fig. 2c is a low-magnification TEM image of the object shown in fig. 2a, fig. 2d is a local STEM image of the object shown in fig. 2a, fig. 2e is a high-magnification TEM image of the object shown in fig. 2a, and fig. 2f is a local high-resolution TEM image of the object shown in fig. 2 e. As can be seen from fig. 2: the ultra-small platinum nano-particles are well dispersed on the surface of the tin oxide-iron oxide with the hollow structure.
(3) The tin oxide-iron oxide nanocomposite particle modified with platinum particles prepared in step e1 in example 1 of the present invention was subjected to a styrene gas sensitivity performance test using a static gas sensitivity test system, so as to obtain a styrene gas sensitivity performance test result schematic diagram shown in fig. 3. Fig. 3a is a graph showing an optimum operating temperature test of the platinum particle-modified tin oxide-iron oxide nanocomposite particle prepared in step e1 in example 1 of the present invention with respect to styrene gas, fig. 3b is a graph showing a response and recovery time of the platinum particle-modified tin oxide-iron oxide nanocomposite particle prepared in step e1 in example 1 of the present invention with respect to styrene gas, fig. 3c is a graph showing a small concentration sensitivity test of the platinum particle-modified tin oxide-iron oxide nanocomposite particle prepared in step e1 in example 1 of the present invention with respect to styrene gas, and fig. 3d is a graph showing a repeatability test of the platinum particle-modified tin oxide-iron oxide nanocomposite particle prepared in step e1 in example 1 of the present invention with respect to styrene gas. As can be seen from fig. 3: the platinum particle modified tin oxide-iron oxide nano composite particle prepared in the step e1 in the embodiment 1 of the invention has the advantages of optimal operation temperature of 206 ℃, response time of 2 seconds, recovery time of 15 seconds, good sensitivity to styrene gas with small concentration of 250ppb, and excellent repeatability.
(4) A static gas-sensitive test system is adopted to perform a styrene gas-sensitive gradient performance test on the platinum particle modified tin oxide-iron oxide nano-composite particles prepared in step e1 in example 1 of the invention, so as to obtain a styrene gas-sensitive gradient performance test result schematic diagram shown in fig. 4. As can be seen from fig. 4: the tin oxide-iron oxide nanocomposite particles modified by platinum particles prepared in step e1 in example 1 of the present invention have a very low detection lower limit.
Example 2
A preparation method of platinum particle modified tin oxide-iron oxide nano composite particles can comprise the following steps:
step a2, adding tin tetrachloride pentahydrate into an ethanol aqueous solution according to the weight ratio of the tin tetrachloride pentahydrate to the ethanol aqueous solution, namely 35-40 wt% hydrochloric acid solution, stirring for 20min, then adding 35-40 wt% hydrochloric acid solution, placing the mixture at 200 ℃ for closed reaction for 10h, and then carrying out solid-liquid separation and washing treatment, thereby obtaining the tin oxide hollow sphere.
B2, dispersing 50mg of the tin oxide hollow spheres into 50mL of deionized water, and magnetically stirring for 10min to obtain a tin oxide dispersion liquid; adding ferric trichloride into the tin oxide dispersion liquid, controlling the concentration of the ferric trichloride to be 0.8mg/mL, and magnetically stirring for 30min to obtain a mixed dispersion liquid; and transferring the mixed dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out closed reaction at 120 ℃ for 60min, and carrying out solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particles.
And c2, dispersing 50mg of the tin oxide-iron oxyhydroxide nano composite particle into 80mL of ethanol-acetonitrile mixed solution (the volume ratio of ethanol to acetonitrile is 1:3), magnetically stirring for 30min, then sequentially adding 4mL of ammonia water and 3mL of 3-aminopropyltriethoxysilane, magnetically stirring for 24h at 80 ℃, and then carrying out solid-liquid separation and washing to obtain the amino-modified tin oxide-iron oxyhydroxide nano composite particle.
And d2, dispersing 50mg of the amino-modified tin oxide-iron oxyhydroxide nano composite particles into 50mL of deionized water, then adding 10mL of potassium chloroplatinate solution with the concentration of 0.2mg/mL, magnetically stirring for 5 hours at 25 ℃, and then performing centrifugal separation to obtain the platinum ion-modified tin oxide-iron oxyhydroxide nano composite particles. Dispersing the tin oxide-iron oxyhydroxide nano composite particle modified by the platinum ions into 30mL of deionized water, adding 4mL of sodium borohydride aqueous solution with the concentration of 0.1mg/mL, reacting for 5h at 25 ℃, and then performing solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particle modified by the platinum nanoparticles.
And e2, calcining the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum nano particles under the protection of argon, wherein the calcining temperature is 450 ℃, the heating rate is 2 ℃/min, and the calcining time is 2h, so that the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum particles are obtained.
Example 3
A preparation method of platinum particle modified tin oxide-iron oxide nano composite particles can comprise the following steps:
step a3, adding tin tetrachloride pentahydrate into an ethanol aqueous solution according to the weight ratio of the tin tetrachloride pentahydrate to the ethanol aqueous solution, namely 35-40 wt% hydrochloric acid solution, stirring for 20min, then adding 35-40 wt% hydrochloric acid solution, placing the mixture at 200 ℃ for closed reaction for 10h, and then carrying out solid-liquid separation and washing treatment, thereby obtaining the tin oxide hollow sphere.
B3, dispersing 50mg of the tin oxide hollow spheres into 50mL of deionized water, and magnetically stirring for 10min to obtain a tin oxide dispersion liquid; adding ferric trichloride into the tin oxide dispersion liquid, controlling the concentration of the ferric trichloride to be 0.8mg/mL, and magnetically stirring for 30min to obtain a mixed dispersion liquid; and transferring the mixed dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out closed reaction at 120 ℃ for 60min, and carrying out solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particles.
And c3, dispersing 50mg of the tin oxide-iron oxyhydroxide nano composite particle into 80mL of ethanol-acetonitrile mixed solution (the volume ratio of ethanol to acetonitrile is 1:5), magnetically stirring for 30min, then sequentially adding 3mL of ammonia water and 4mL of 3-aminopropyltriethoxysilane, magnetically stirring for 12h at 80 ℃, and then carrying out solid-liquid separation and washing to obtain the amino-modified tin oxide-iron oxyhydroxide nano composite particle.
And d3, dispersing 50mg of the amino-modified tin oxide-iron oxyhydroxide nano composite particles into 40mL of deionized water, then adding 10mL of potassium chloroplatinate solution with the concentration of 0.1mg/mL, magnetically stirring for 6 hours at 25 ℃, and then performing centrifugal separation to obtain the platinum ion-modified tin oxide-iron oxyhydroxide nano composite particles. Dispersing the tin oxide-iron oxyhydroxide nano composite particle modified by the platinum ions into 30mL of deionized water, adding 3mL of sodium borohydride aqueous solution with the concentration of 0.1mg/mL, reacting for 5h at 25 ℃, and then performing solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particle modified by the platinum nanoparticles.
And e3, calcining the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum nano particles under the protection of nitrogen, wherein the calcining temperature is 450 ℃, the heating rate is 5 ℃/min, and the calcining time is 3h, so that the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum particles are obtained.
Example 4
A preparation method of platinum particle modified tin oxide-iron oxide nano composite particles can comprise the following steps:
step a4, adding tin tetrachloride pentahydrate into an ethanol aqueous solution according to the weight ratio of the tin tetrachloride pentahydrate to the ethanol aqueous solution, namely 35-40 wt% hydrochloric acid solution, stirring for 20min, then adding 35-40 wt% hydrochloric acid solution, placing the mixture at 200 ℃ for closed reaction for 8h, and then carrying out solid-liquid separation and washing treatment, thereby obtaining the tin oxide hollow sphere.
B4, dispersing 50mg of the tin oxide hollow spheres into 50mL of deionized water, and magnetically stirring for 10min to obtain a tin oxide dispersion liquid; adding ferric trichloride into the tin oxide dispersion liquid, controlling the concentration of the ferric trichloride to be 0.8mg/mL, and magnetically stirring for 30min to obtain a mixed dispersion liquid; and transferring the mixed dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out closed reaction at 120 ℃ for 60min, and carrying out solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particles.
And c4, dispersing 50mg of the tin oxide-iron oxyhydroxide nano composite particle into 80mL of ethanol-acetonitrile mixed solution (the volume ratio of ethanol to acetonitrile is 1:4), magnetically stirring for 30min, then sequentially adding 3mL of ammonia water and 3mL of 3-aminopropyltriethoxysilane, magnetically stirring for 24h at 80 ℃, and then carrying out solid-liquid separation and washing to obtain the amino-modified tin oxide-iron oxyhydroxide nano composite particle.
And d4, dispersing 50mg of the amino-modified tin oxide-iron oxyhydroxide nano composite particles into 50mL of deionized water, then adding 10mL of potassium chloroplatinate solution with the concentration of 0.1mg/mL, magnetically stirring for 5 hours at 25 ℃, and then performing centrifugal separation to obtain the platinum ion-modified tin oxide-iron oxyhydroxide nano composite particles. Dispersing the tin oxide-iron oxyhydroxide nano composite particle modified by the platinum ions into 30mL of deionized water, adding 4mL of sodium borohydride aqueous solution with the concentration of 0.1mg/mL, reacting for 5h at 25 ℃, and then performing solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particle modified by the platinum nanoparticles.
And e4, calcining the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum nano particles under the protection of nitrogen, wherein the calcining temperature is 500 ℃, the heating rate is 3 ℃/min, and the calcining time is 2h, so that the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum particles are obtained.
In conclusion, the embodiment of the invention has good gas sensitivity, can be used as a sensing layer to realize high-sensitivity trace detection on styrene gas, and has the advantages of low use cost, no need of expensive detection equipment, simple operation, rapidness and high efficiency.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A preparation method of platinum particle modified tin oxide-iron oxide nano composite particles is characterized by comprising the following steps:
step A, dispersing tin oxide-iron oxyhydroxide nano composite particles into an ethanol-acetonitrile mixed solution to enable the concentration of the tin oxide-iron oxyhydroxide nano composite particles in the mixed solution to be 0.1-1.5 mg/mL, stirring for 10-30 min, then sequentially adding ammonia water and 3-aminopropyltriethoxysilane, stirring for 10-48 h at the temperature of 20-100 ℃, and then carrying out solid-liquid separation and washing to obtain amino modified tin oxide-iron oxyhydroxide nano composite particles;
b, dispersing the amino-modified tin oxide-iron oxyhydroxide nano composite particles into deionized water, controlling the concentration of the amino-modified tin oxide-iron oxyhydroxide nano composite particles to be 0.1-2.5 mg/mL, then adding potassium chloroplatinate, stirring for 2-12 h at the temperature of 25-60 ℃, and then performing centrifugal separation to obtain platinum ion-modified tin oxide-iron oxyhydroxide nano composite particles; dispersing the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum ions into deionized water, adding sodium borohydride, reacting at 25-60 ℃ for 2-10 h, and performing solid-liquid separation and washing to obtain tin oxide-iron oxyhydroxide nano composite particles modified by the platinum nanoparticles;
and step C, calcining the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum nano particles under the protection of inert gas, wherein the calcining temperature is 300-600 ℃, the heating rate is 0.5-10 ℃/min, and the calcining time is 0.5-5 h, so that the tin oxide-iron oxyhydroxide nano composite particles modified by the platinum particles are obtained.
2. The method for preparing platinum particle-modified tin oxide-iron oxide nanocomposite particles according to claim 1, wherein the method for preparing tin oxide-iron oxyhydroxide nanocomposite particles comprises the steps of:
step A1, adding tin tetrachloride pentahydrate into ethanol according to the weight ratio of 35-40 wt% of hydrochloric acid solution to 0.5-2: 50-150: 1, stirring for 10-30 min, adding 35-40 wt% of hydrochloric acid solution, placing at 150-200 ℃ for closed reaction for 5-24 h, and performing solid-liquid separation and washing to obtain the tin oxide hollow spheres;
step A2, dispersing the tin oxide hollow spheres obtained in the step A1 into deionized water, controlling the concentration of the tin oxide hollow spheres to be 0.1-2.5 mg/mL, and stirring for 5-30 min to obtain a tin oxide dispersion liquid; adding ferric trichloride into the tin oxide dispersion liquid, controlling the concentration of the ferric trichloride to be 0.5-3.5 mg/mL, and stirring for 5-30 min to obtain a mixed dispersion liquid; and transferring the mixed dispersion liquid into a polytetrafluoroethylene reaction kettle, carrying out closed reaction at the temperature of 90-150 ℃ for 20-240 min, and carrying out solid-liquid separation and washing to obtain the tin oxide-iron oxyhydroxide nano composite particles.
3. The method for preparing platinum-particle-modified tin oxide-iron oxide nanocomposite particles according to claim 1 or 2, wherein in step a, the volume ratio of ethanol to acetonitrile in the ethanol-acetonitrile mixed solution is 1:0.5 to 10; the dosage of the ammonia water is 0.01-0.2 times of the total mass of the tin oxide-iron oxyhydroxide nano composite particles; the dosage of the 3-aminopropyltriethoxysilane is 0.01-0.25 time of the total mass of the tin oxide-iron oxyhydroxide nano composite particles.
4. The method for preparing platinum particle-modified tin oxide-iron oxide nanocomposite particles according to claim 1 or 2, wherein in step B, the amount of potassium chloroplatinate is 0.001 to 0.05 times the total mass of the amino-modified tin oxide-iron oxyhydroxide nanocomposite particles; the mass of the sodium borohydride is 0.05-0.5 times of the total mass of the amino-modified tin oxide-iron oxyhydroxide nano composite particles.
5. The method for preparing platinum particle-modified tin oxide-iron oxide nanocomposite particles according to claim 1 or 2, wherein in step C, at least one of nitrogen and argon is used as the inert gas.
6. A platinum particle-modified tin oxide-iron oxide nanocomposite particle characterized by being produced by the method for producing a platinum particle-modified tin oxide-iron oxide nanocomposite particle according to any one of claims 1 to 5.
7. Use of platinum particle-modified tin oxide-iron oxide nanocomposite particles according to claim 6 as a sensing material in a gas sensing device.
8. The use of platinum particle-modified tin oxide-iron oxide nanocomposite particles according to claim 7, wherein the sensing material in the gas sensing device is used for detecting styrene gas.
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