CN115837274A - Pt-doped composite inorganic metal oxide nanoparticles, and preparation method and application thereof - Google Patents
Pt-doped composite inorganic metal oxide nanoparticles, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a Pt-doped composite inorganic metal oxide nanoparticle, and a preparation method and application thereof. The preparation method comprises the following steps: step S1, dissolving a soluble metal source and chloroplatinic acid in a first polar solvent to form a solution A; wherein the soluble metal source is selected from at least two of soluble ferric salt, soluble zinc salt, soluble lanthanum salt and titanate; s2, dissolving urea in a second polar solvent to form a solution B; s3, heating the solution A, and adding the solution B into the solution A under a stirring state to form a solution C; s4, cooling and aging the solution C, and then carrying out centrifugal separation to obtain a precursor material; and S5, drying and calcining the precursor material in sequence to obtain the Pt-doped composite inorganic metal oxide nano-particles. The invention solves the problem of insufficient gas sensitivity or photocatalytic performance of inorganic metal nanoparticles.
Description
Technical Field
The invention relates to the technical field of metal oxide nano materials, in particular to Pt-doped composite inorganic metal oxide nano particles, and a preparation method and application thereof.
Background
Inorganic metal nano materials have important application in many fields, such as the field of gas sensitive materials, the field of photocatalysis and the like.
Hydrogen sulfide (H) 2 S) is a hazardous, toxic and malodorous gas originating from bacterial decomposition of organic matter and waste produced by humans and animals, industrial activities such as food processing, industrial paper mills, tanneries and refineries. At the same time, H 2 S gas is also a flammable acid gas and, if too high a concentration is mixed with air, may cause an explosion. Furthermore, H 2 S gas has an effect on both the human eye and central nervous system. Therefore, in some specific occasions, such as the operations of overhauling in equipment, entering a sewer, cleaning an oil pool, checking production, stopping leakage and the like and other production processes, H is often required to be treated 2 And detecting the concentration of the S gas.
Sensor detection method is currently H 2 The important method for detecting S gas has the core component of a gas sensor, and the important factor for determining the sensitivity of the gas sensor is the gas sensitivity of the gas sensitive material used by the gas sensor. Commonly used gas-sensitive materials are ZnO nanoparticles and ZnFe 2 O 4 Nanoparticles, tiO 2 For improving the gas sensitivity, there are also ways of doping Pt and rare earth oxide to inorganic metal oxide nanoparticles, such as:
in the literature, "microwave synthesis of ZnO nanorods and improvement of gas-sensitive property by Pt doping", sodium nitrate hexahydrate, sodium hydroxide, absolute ethyl alcohol and CTAB are used as raw materials, and are dissolved in deionized water, stirred for 30min and kept stand for 1h. And (3) putting the solution into a microwave oven, heating for 30min at the temperature of 90 ℃, naturally cooling to room temperature, and aging for 12h. Then centrifugally washing, drying at 80 ℃ for 10h, and calcining the dried material at 600 ℃ for 1h to obtain a calcined product. A defined amount of the calcined product was weighed and 0.5wt% of H was added 2 PtCl 6 Wet grinding the solution, drying, and calcining at 600 ℃ for 1h to obtain the Pt-doped ZnO material. The material has a working temperature of 273 ℃ and a concentration of 50ppm H 2 The sensitivity of S is 480.44. However, in this method, two times of calcination are required, and the nanoparticles may grow during the two times of calcination. Meanwhile, the wet milling method is adopted for Pt doping, so that the doping uniformity is insufficient. These factors all contribute to the situation where the gas-sensitive properties of the material are insufficient.
In the literature, preparation and gas-sensitive property of rare earth oxide-doped ZnO materials, 10g of zinc acetate dihydrate and 2.5mL of ethylene glycol are refluxed at 150 ℃ for 15 minutes and slowly cooled to room temperature to obtain a white solid. The white solid was dissolved in 20ml of propanol solution, a small amount of water was added to form a clear sol, which was dried at 80 ℃ for a period of time to give a gel powder. Calcining the gel powder at 700 ℃ for 4h, naturally cooling, and submerging in an agate lapping body to obtain the nano ZnO. Finally, Y with different mass fractions 2 O 3 、La 2 O 3 And CeO 2 Adding into ZnO powder and grindingUniformly grinding, and calcining again at 700 ℃ for 4h to obtain doped ZnO powder. The study showed that about 305 ℃ of working temperature was doped with 8% CeO 2 ZnO to H of 2 S has good sensitivity, selectivity and response-recovery characteristics. However, this method also has two calcinations and the physical grinding method has uneven doping, so the gas-sensitive performance of the material is also affected.
According to the literature, "ZnS/ZnO nanomaterial preparation and gas sensitivity research" 0.38g of thiourea is placed in a beaker, 35mL of hydrazine hydrate solution is poured into the beaker and stirred until the solution is clear, then 3.2g of zinc powder is weighed, the solution and the zinc powder are placed in the beaker and stirred for 30min, and then the beaker is placed in a high-pressure reaction kettle and reacted for 6 hours in a constant-temperature oven at 140 ℃. And after the temperature is reduced to room temperature, washing to obtain the Zn/ZnS material. And putting the powder into a porcelain boat, then putting the porcelain boat into a muffle furnace for high-temperature annealing, raising the temperature from room temperature to 500 ℃, keeping the temperature for 3 hours, and naturally cooling to obtain the Zn/ZnS/ZnO composite material. The diluted hydrochloric acid solution is used for corroding the Zn/ZnS/ZnO composite material, so that the gas-sensitive performance of the Zn/ZnS/ZnO composite material can be improved. However, when the Zn/ZnS material is put into a muffle furnace for high-temperature annealing, znO is obtained by oxidizing Zn or ZnS, the respective content ratios of Zn, znS and ZnO in the Zn/ZnS/ZnO composite material cannot be ensured, the repeatability is not provided, and the gas sensitivity of the material cannot be stably ensured.
Literature Synthesis of TiO 2 /LaFeO 3 Mixing substances for the photochemical hydrogen evolution, solid particles of lanthanum nitrate (La (NO) 3 ) 3 ·6H 2 O) and iron nitrate (Fe (NO) 3 ) 3 ·9H 2 O) is put into a mortar to be uniformly mixed, the mixed material is kept warm at 900 ℃ for 12h,0.1mol/LHCl solution is used for washing the calcined material, and the cleaned material is dried at 70 ℃ for standby use, namely LaFeO 3 And (3) particles. LaFeO is added 3 Uniformly mixing the particles and titanium dioxide (anatase type) particles in a mortar, and keeping the temperature of the mixed material at 500 ℃ for 12h to finally obtain TiO 2 /LaFeO 3 Composite particles. However, theIn the method, the mixing of materials is only wet mixing in a solid state, the phenomenon of uneven material distribution is very easy to occur in the mixed materials, and TiO 2 /LaFeO 3 The size of the composite particles is limited by the size of the raw material particles, and thus the gas sensitivity of the material is also insufficient.
In the field of photocatalysis, inorganic metal oxide nanoparticles are also used in many applications. Such as:
in the literature, preparation of ZnO/ZnFe2O4 composite nanoparticles and characteristic research thereof, 0.1M Zn (NO) is added 3 ) 2 ·6H 2 O、0.2M Fe(NO 3 ) 3 ·4H 2 Fully dissolving the O medicine in absolute ethyl alcohol, then adding 10% ammonia water, and fully stirring by using a magnetic stirrer to promote metal ions to fully precipitate; secondly, the precursor solution is transferred into the inner container of a polytetrafluoroethylene reaction kettle and kept at the constant temperature of 80 ℃ for 12 hours. And taking out the reaction kettle after the reaction is finished, and naturally cooling in the air. Centrifuging the solution to obtain a precipitate, and drying at the constant temperature of 60 ℃ for 12 hours; annealing the dried powder in a tubular annealing furnace at 800 ℃ for 2h to finally obtain Zn/ZnFe 2 O 4 Composite nanoparticles. For ZnO/ZnFe after annealing treatment 2 O 4 The composite nano particles are subjected to a photocatalysis test, and the degradation rate of methyl orange can reach 50.48% after being illuminated for 3 hours. However, the ZnO/ZnFe prepared by this method 2 O 4 The photocatalytic performance of the composite nanoparticles still needs to be improved.
Chinese patent CN109082140A discloses a preparation method of a composite high infrared reflection nano pigment, which comprises the following steps: 1) Dispersing P123 and deionized water in a proper amount of absolute ethyl alcohol for magnetic stirring; 2) Adding LaFeO after P123 is fully dissolved 3 Setting the stirring temperature, adding butyl titanate after the temperature of the stirrer is stable, and dropwise adding ammonia water to adjust the pH value; 3) After the reaction is finished, washing for several times by using water and ethanol respectively until impurities are completely removed, clarifying the upper-layer solution, and centrifuging to obtain a precipitate; 4) Drying the precipitate obtained in the step 3), calcining the dried precipitate in a furnace, and grinding the calcined precipitate to obtain the composite high infrared reflection nano pigment. However, the nano material prepared by the method has uneven component distribution, and the photocatalytic performance of the nano material is stillTo be improved.
In a word, the inorganic metal nanoparticles in the prior art have the problems of uneven doping, poor particle morphology and the like in the preparation process, so that the gas sensitivity or the photocatalytic performance of the material is insufficient.
Disclosure of Invention
The invention mainly aims to provide a Pt-doped composite inorganic metal oxide nanoparticle, a preparation method and application thereof, and aims to solve the problem that the gas sensitivity or the photocatalytic performance of a material is insufficient due to the defects of uneven doping, poor particle morphology and the like existing in the preparation process of the inorganic metal nanoparticle in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing Pt-doped composite inorganic metal oxide nanoparticles, comprising the steps of: step S1, dissolving a soluble metal source and chloroplatinic acid in a first polar solvent to form a solution A; wherein the soluble metal source is selected from at least two of soluble trivalent ferric salt, soluble zinc salt, soluble lanthanum salt and titanate; s2, dissolving urea in a second polar solvent to form a solution B; s3, heating the solution A, and adding the solution B into the solution A under a stirring state to form a solution C; s4, cooling and aging the solution C, and then carrying out centrifugal separation to obtain a precursor material; and S5, drying and calcining the precursor material in sequence to obtain the Pt-doped composite inorganic metal oxide nano-particles.
Further, the soluble ferric salt is ferric nitrate; and/or, the soluble zinc salt is zinc nitrate; and/or the soluble lanthanum salt is lanthanum nitrate; and/or the titanate is tetrabutyl titanate.
Further, the soluble metal source is selected from soluble ferric salts and soluble zinc salts; alternatively, the soluble metal source is selected from soluble zinc salts and titanates; alternatively, the soluble metal source is selected from the group consisting of soluble lanthanum salts, soluble ferric salts, and titanates; preferably, when the soluble metal source is selected from soluble ferric salts and soluble zinc salts, the molar ratio of soluble zinc salts to soluble ferric salts is 1.05 to 1.2; preferably, the molar ratio of urea to soluble zinc salt in solution B is 7; when the soluble metal source is selected from soluble zinc salt and titanate, the mol ratio of the soluble zinc salt to the titanate is 0.5-1.5; preferably, the molar ratio of urea to soluble zinc salt in solution B is 1.8 to 2.2; when the soluble metal source is selected from soluble lanthanum salt, soluble ferric salt and titanate, the molar ratio of the soluble lanthanum salt to the soluble ferric salt to the titanate is 0.5-1.5; preferably, the molar ratio of urea to soluble lanthanum salt in solution B is 2.7 to 3.3.
Further, the soluble metal source is selected from the group consisting of iron nitrate and zinc nitrate; preferably, the doping amount of Pt in the composite inorganic metal oxide nano-particles is 0.3-3 wt%; alternatively, the soluble metal source is selected from zinc nitrate and tetrabutyl titanate; preferably, the Pt doping amount in the composite inorganic metal oxide nano-particles is 3-8 wt%; alternatively, the soluble metal source is selected from lanthanum nitrate, ferric nitrate and tetrabutyl titanate; preferably, the doping amount of Pt in the composite inorganic metal oxide nano-particles is 1-10 wt%.
Further, the mass concentration of the solution A is 40-60 wt%, and the mass concentration of the solution B is 30-50 wt%; preferably, the first polar solvent is ethanol and the second polar solvent is water; preferably, in step S3, after heating the solution a to 70 to 90 ℃, the solution B is added dropwise to the solution a while stirring, more preferably at a rate of 30 to 90 drops/minute during the dropwise addition.
Further, in the step S4, the time of the aging process is 10-14 h; preferably, after the centrifugal separation is finished, the step S4 further includes: washing solid products obtained by centrifugal separation in sequence to obtain a precursor material; preferably, in step S5, the drying conditions are as follows: drying for 1-3 h in a drying oven at 100-110 ℃.
Further, in step S5, the conditions of calcination are as follows: calcining for 1-3 h at 400-700 ℃ in an inert atmosphere; preferably, when the soluble metal source is selected from soluble ferric salt and soluble zinc salt, the calcining temperature is 500-700 ℃; when the soluble metal source is selected from soluble zinc salt and titanate, or from soluble lanthanum salt, soluble ferric salt and titanate, the calcining temperature is 400-600 ℃.
According to another aspect of the present invention, there is also provided a Pt-doped composite inorganic metal oxide nanoparticle, which is prepared using the above-described preparation method.
Further, the Pt-doped composite inorganic metal oxide nanoparticles are Pt-doped ZnO/ZnFe 2 O 4 Composite nanoparticles, pt-doped ZnO/TiO 2 Composite nanoparticles or Pt-doped LaFeO 3 /TiO 2 Composite nanoparticles; preferably, the particle size of the Pt-doped composite inorganic metal oxide nanoparticles is 10 to 50nm.
According to another aspect of the present invention, there is also provided an application of the above Pt-doped composite inorganic metal oxide nanoparticles as a gas sensitive material or a photocatalytic material.
The invention provides a preparation method of Pt-doped composite inorganic metal oxide nanoparticles, which comprises the following steps: step S1, dissolving a soluble metal source and chloroplatinic acid in a first polar solvent to form a solution A; wherein the soluble metal source is selected from at least two of soluble ferric salt, soluble zinc salt, soluble lanthanum salt and titanate; s2, dissolving urea in a second polar solvent to form a solution B; s3, heating the solution A, and adding the solution B into the solution A under a stirring state to form a solution C; s4, cooling and aging the solution C, and then carrying out centrifugal separation to obtain a precursor material; and S5, drying and calcining the precursor material in sequence to obtain the Pt-doped composite inorganic metal oxide nano-particles.
In the method provided by the invention, at least two of soluble ferric salt, soluble zinc salt, soluble lanthanum salt and titanate are selected as soluble metal sources, and are prepared into solution with chloroplatinic acid, then urea solution is added into the solution to generate precursor material in situ by a sol-gel method, and then the precursor material is dried and calcined to form the Pt-doped composite inorganic metal oxide nano-particles. On one hand, the doping of Pt can be effectively improved by adopting a sol-gel methodThe impurity uniformity is high, and the nano particles formed after calcination have good appearance and uniform size, so that the gas-sensitive performance or the photocatalytic performance of the material can be improved; on the other hand, the at least two soluble metal sources are selected to form Pt-doped composite inorganic metal oxide nanoparticles by a sol-gel method, and the main composite component of the Pt-doped composite inorganic metal oxide nanoparticles can be ZnO or ZnFe 2 O 4 、TiO 2 、LaFeO 3 The composition of at least two of the components is more stable and uniform, and the Pt-doped composite material has better gas-sensitive performance or photocatalytic performance.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the gas sensitive material in the prior art has the problems of uneven doping, poor particle morphology and the like during the preparation process, resulting in insufficient gas sensitivity of the material.
In order to solve the above problems, the present invention provides a method for preparing Pt-doped composite inorganic metal oxide nanoparticles, which comprises the steps of: step S1, dissolving a soluble metal source and chloroplatinic acid in a first polar solvent to form a solution A; wherein the soluble metal source is selected from at least two of soluble trivalent ferric salt, soluble zinc salt, soluble lanthanum salt and titanate; s2, dissolving urea in a second polar solvent to form a solution B; s3, heating the solution A, and adding the solution B into the solution A under a stirring state to form a solution C; s4, cooling and aging the solution C, and then carrying out centrifugal separation to obtain a precursor material; and S5, drying and calcining the precursor material in sequence to obtain the Pt-doped composite inorganic metal oxide nano-particles.
In the method provided by the invention, at least two of soluble trivalent ferric salt, soluble zinc salt, soluble lanthanum salt and titanate are selected as soluble metal sources, and are prepared into solution with chloroplatinic acid, and then urea solution is added into the solution to generate precursor material in situ by a sol-gel methodAnd then drying and calcining to form the Pt-doped composite inorganic metal oxide nano-particles. On one hand, the doping uniformity of Pt can be effectively improved by adopting a sol-gel method, and the nano particles formed after calcination have good appearance and uniform size, so that the gas-sensitive performance or photocatalytic performance of the material can be improved; on the other hand, the at least two soluble metal sources are selected to form Pt-doped composite inorganic metal oxide nanoparticles by a sol-gel method, and the main composite component of the Pt-doped composite inorganic metal oxide nanoparticles can be ZnO or ZnFe 2 O 4 、TiO 2 、LaFeO 3 The composition of at least two of the components is more stable and uniform, and the Pt-doped composite material has better gas-sensitive performance or photocatalytic performance.
Under the heating condition, the urea in the solution B can generate hydrolysis reaction. Carbon dioxide and ammonia water formed by decomposing urea further undergo hydrolysis reaction with metal ions and chloroplatinic acid in the solution A to form a colloidal precursor material with uniformly distributed components. To further improve stability during the hydrolysis reaction, in a preferred embodiment, the soluble ferric salt is ferric nitrate; and/or, the soluble zinc salt is zinc nitrate; and/or the soluble lanthanum salt is lanthanum nitrate; and/or the titanate ester is tetrabutyl titanate.
The type of the soluble metal salt can be further optimized, and the purpose of improving the gas sensitivity of the material is further achieved through the synergistic interaction between the composite materials. In a preferred embodiment, the soluble metal source is selected from the group consisting of soluble ferric salts and soluble zinc salts; alternatively, the soluble metal source is selected from soluble zinc salts and titanates; alternatively, the soluble metal source is selected from the group consisting of soluble lanthanum salts, soluble ferric salts, and titanate esters.
When the soluble metal source is selected from soluble ferric salt and soluble zinc salt, the carbon dioxide and ammonia water formed by the decomposition of urea further react with Zn in the solution A 2+ 、Fe 3+ And H 2 PtCl 6 Hydrolysis reaction occurs to gradually form basic zinc carbonate, feOOH and platinum hydroxide.
CO(NH 2 ) 2 +3H 2 O→CO 2 +2NH 3 ·H 2 O
3Zn 2+ +CO 3 -2 +4OH - +H 2 O→ZnCO 3 ·2Zn(OH) 2 ·H 2 O
Fe 3+ +3OH - →FeOOH+H 2 O
Pt 4+ +4OH - →Pt(OH) 4
By the process of gelation, znCO 3 、Zn(OH) 2 、FeOOH、Pt(OH) 4 A uniformly distributed colloid can be formed. The colloid can form Pt-doped ZnO/ZnFe after being calcined at a certain temperature 2 O 4 Composite nanoparticles.
When the soluble metal source is selected from soluble zinc salt and titanate, the carbon dioxide and ammonia water formed by the decomposition of urea further neutralize Zn in the solution A 2+ Hydrolysis reaction occurs to gradually form basic zinc carbonate.
CO(NH 2 ) 2 +3H 2 O→CO 2 +2NH 3 ·H 2 O
3Zn 2+ +CO 3 -2 +4OH - +H 2 O→ZnCO 3 ·2Zn(OH) 2 ·H 2 O
Pt 4+ +4OH - →Pt(OH) 4
By the process of gelation, znCO 3 、Zn(OH) 2 Titanate, pt (OH) 4 A homogeneously distributed colloid can be formed. The colloid can form Pt-doped ZnO/TiO after being calcined at a certain temperature 2 Composite nanoparticles.
When the soluble metal source is selected from the group consisting of soluble lanthanum salts, soluble ferric salts and titanates, the carbon dioxide and ammonia formed by the decomposition of urea further neutralize the La in solution A 3+ 、Fe 3+ 、Pt 4+ A hydrolysis reaction takes place.
CO(NH 2 ) 2 +3H 2 O→CO 2 +2NH 3 ·H 2 O
La 3+ +3OH - →La(OH) 3
Fe 3+ +3OH - →FeOOH+H 2 O
Pt 4+ +4OH - →Pt(OH) 4
By gel process, la (OH) 3 、FeOOH、Pt(OH) 4 Titanate can form uniformly distributed colloid. The colloid can form Pt doped LaFeO after being calcined at a certain temperature 3 /TiO 2 Composite nanoparticles.
Compared with the composition among other inorganic metal oxides, the Pt-doped ZnO/ZnFe formed by compounding the soluble metal sources of the types 2 O 4 Composite nano-particle and Pt doped ZnO/TiO 2 Composite nanoparticles and Pt-doped LaFeO 3 /TiO 2 The composite nano-particles have better gas sensitivity or photocatalysis performance.
The ratio between the different soluble metal sources can be adjusted, but in order to make the ratio in the composite inorganic metal oxide more suitable in order to further improve the gas sensitivity or catalytic performance of the material, in a preferred embodiment, when the soluble metal source is selected from soluble ferric salt and soluble zinc salt, the molar ratio of the soluble zinc salt to the soluble ferric salt is 1.05-1.2; preferably, the molar ratio of urea to soluble zinc salt in solution B is 7; when the soluble metal source is selected from soluble zinc salt and titanate, the molar ratio of the soluble zinc salt to the titanate is 0.5-1.5; preferably, the molar ratio of urea to soluble zinc salt in solution B is 1.8 to 2.2; when the soluble metal source is selected from soluble lanthanum salt, soluble ferric salt and titanate, the molar ratio of the soluble lanthanum salt to the soluble ferric salt to the titanate is 0.5-1.5; preferably, the molar ratio of urea to soluble lanthanum salt in solution B is 2.7 to 3.3.
As described above, the present invention can make Pt doping more uniform by using the sol-gel method. The specific doping level of Pt can be adjusted during actual production, and in a preferred embodiment, the soluble metal source is selected from the group consisting of ferric nitrate and zinc nitrate; preferably, the doping amount of Pt in the composite inorganic metal oxide nano-particles is 0.3-3 wt%; alternatively, the soluble metal source is selected from zinc nitrate and tetrabutyl titanate; preferably, the Pt doping amount in the composite inorganic metal oxide nano-particles is 3-8 wt%; alternatively, the soluble metal source is selected from lanthanum nitrate, ferric nitrate and tetrabutyl titanate; preferably, the doping amount of Pt in the composite inorganic metal oxide nano-particles is 1-10 wt%. The Pt doping amount is controlled within the range, so that the material performance is improved. The dosage of the chloroplatinic acid can be adjusted according to the doping amount of Pt in the actual preparation process.
In order to stabilize the sol-gel reaction process and further improve the dispersion uniformity of the components, in a preferred embodiment, the mass concentration of solution a is 40 to 60wt% and the mass concentration of solution B is 30 to 50wt%.
Preferably, the first polar solvent is ethanol and the second polar solvent is water. The reaction in the solvent has better improvement effect on the morphology of final material particles, and the particles have more uniform size, better morphology and smaller size.
Preferably, in step S3, after heating the solution a to 70 to 90 ℃, the solution B is added dropwise to the solution a while stirring, more preferably at a rate of 30 to 90 drops/minute during the dropwise addition. Under the process conditions, after the solution B is dripped into the solution A, the urea can be more stably decomposed and has hydrolysis reaction with ions in a system, the reaction is more sufficient and stable, the components are better and uniform in dispersion, and the morphology of final material particles is further improved. The above factors are all beneficial to further improving the gas sensitivity or photocatalytic performance of the material. More preferably, in step S4, the aging process is carried out for 10 to 14 hours.
Preferably, after the centrifugal separation is finished, the step S4 further includes: and washing solid products obtained by centrifugal separation in sequence to obtain a precursor material. By washing, impurities remaining in the precursor material can be removed. The detergent used in the washing process can be ethanol, deionized water and the like. Preferably, in step S5, the drying conditions are as follows: drying for 1-3 h in a drying oven at 100-110 ℃.
In order to make the calcination process more sufficient, in a preferred embodiment, in step S5, the calcination conditions are as follows: calcining for 1-3 h at 400-700 ℃ in an inert atmosphere; preferably, when the soluble metal source is selected from soluble ferric salt and soluble zinc salt, the calcining temperature is 500-700 ℃; when the soluble metal source is selected from soluble zinc salt and titanate, or from soluble lanthanum salt, soluble ferric salt and titanate, the calcining temperature is 400-600 ℃.
According to another aspect of the present invention, there is also provided a Pt-doped composite inorganic metal oxide nanoparticle, which is prepared using the above-described preparation method. In the method provided by the invention, at least two of soluble ferric salt, soluble zinc salt, soluble lanthanum salt and titanate are selected as soluble metal sources, and are prepared into solution with chloroplatinic acid, urea solution is added into the solution to generate a precursor material in situ by a sol-gel method, and then the precursor material is dried and calcined to form the Pt-doped composite inorganic metal oxide nano-particles. On one hand, the doping uniformity of Pt can be effectively improved by adopting a sol-gel method, and the nano particles formed after calcination have good appearance and uniform size, so that the gas-sensitive performance or photocatalytic performance of the material can be improved; on the other hand, the at least two soluble metal sources are selected to form Pt-doped composite inorganic metal oxide nanoparticles by a sol-gel method, and the main composite component of the Pt-doped composite inorganic metal oxide nanoparticles can be ZnO or ZnFe 2 O 4 、TiO 2 、LaFeO 3 The composition of at least two of the components is more stable and uniform, and the Pt-doped composite material has better gas-sensitive performance or photocatalytic performance.
In a preferred embodiment, the Pt-doped composite inorganic metal oxide nanoparticles are Pt-doped ZnO/ZnFe 2 O 4 Composite nanoparticles, pt-doped ZnO/TiO 2 Composite nanoparticles or Pt-doped LaFeO 3 /TiO 2 Composite nanoparticles; preferably, the particle size of the Pt-doped composite inorganic metal oxide nanoparticles is 10 to 50nm.
According to another aspect of the present invention, there is also provided a use of the Pt-doped composite inorganic metal oxide nanoparticles as a gas-sensitive material or a photocatalytic material.
More preferably, the Pt is doped with ZnO/ZnFe 2 O 4 Composite nanoparticles as H 2 S gas sensitive material prepared by doping the Pt with ZnO/TiO 2 Composite nanoparticles and Pt-doped LaFeO 3 /TiO 2 The composite nano-particles are used as a photocatalytic material.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
To H 2 The sensitivity test method of S gas is as follows: the method is completed on a WS-30A type gas sensor testing system, a static gas distribution method is adopted, and the working temperature is set to be 40-400 ℃.
The method for testing the photocatalytic degradation rate of methylene blue comprises the following steps: and carrying out ultraviolet and visible light absorption spectrum test on the methylene blue solution of 20mg/L under the condition of the wavelength of 664nm, and calculating the photocatalytic degradation effect according to the absorbance.
The method for testing the photocatalytic degradation rate of methyl orange comprises the following steps: and carrying out ultraviolet visible light absorption spectrum test on the 20mg/L methyl orange solution under the condition of the wavelength of 664nm, and calculating the photocatalytic degradation effect according to the absorbance.
Pt doped ZnO/ZnFe 2 O 4 Preparation example of composite nanoparticles
Example 1
1.05mol of zinc nitrate, 2mol of ferric nitrate and 0.0018 mol of chloroplatinic acid are dissolved in a proper amount of absolute ethyl alcohol to obtain a solution A, and 7mol of urea is dissolved in a proper amount of deionized water to obtain a solution B. Solution A was heated to 90 ℃ and solution B was added to solution A at a rate of 90 drops/min while stirring to give solution C. And naturally cooling the solution C to room temperature, aging for 12h, and centrifuging and washing to obtain a precursor. The precursor is put into a drying oven to be dried for 2 hours at the temperature of 100-110 ℃, and finally the precursor is calcined for 1 hour at the temperature of 500 ℃, and the precursor is naturally cooled to the room temperature to obtain the Pt0.3wt% doped ZnO/ZnFe 2 O 4 The composite nano-particles have a particle size of 20-50 nm. The composite nanomaterial pair was measured at 175 ℃ to 100ppmH 2 The sensitivity of S gas was 166.1.
Example 2
1.2mol of zinc nitrate, 2mol of ferric nitrate and 0.033 mol of chloroplatinic acid are dissolved in a proper amount of absolute ethyl alcohol to obtain a solution A, and 7mol of urea is dissolved in a proper amount of deionized water to obtain a solution B. Solution A was heated to 90 ℃ and solution B was added to solution A at a rate of 30 drops/min while stirring to give solution C. And naturally cooling the solution C to room temperature, aging for 12h, and centrifuging and washing to obtain a precursor. The precursor is put into a drying oven to be dried for 2 hours at the temperature of 100-110 ℃, and finally the precursor is calcined for 1 hour at the temperature of 700 ℃, and the precursor is naturally cooled to the room temperature to obtain ZnO/ZnFe doped with 5wt% of Pt 2 O 4 The composite nano-particles have a particle size of 40-70 nm. The composite nano material pair is measured at the optimum working temperature of 225 ℃ and has the concentration of 100ppmH 2 The sensitivity of S gas was 217.4.
Example 3
1.1mol of zinc nitrate, 2mol of ferric nitrate and 0.019 mol of chloroplatinic acid are dissolved in a proper amount of absolute ethyl alcohol to obtain a solution A, and 7mol of urea is dissolved in a proper amount of deionized water to obtain a solution B. Solution A was heated to 90 ℃ and solution B was added to solution A at a rate of 30 drops/min while stirring to give solution C. And naturally cooling the solution C to room temperature, aging for 12h, and centrifuging and washing to obtain a precursor. The precursor is put into a drying oven to be dried for 2 hours at the temperature of 100-110 ℃, and finally the precursor is calcined for 1 hour at the temperature of 600 ℃, and the precursor is naturally cooled to the room temperature, thus obtaining ZnO/ZnFe doped with 3wt% of Pt 2 O 4 The composite nano-particles have a particle size of 30-60 nm. The composite nano material pair is measured at 195 ℃ for 100ppmH 2 The sensitivity of S gas was 230.9.
Comparative example 1
Dissolving 1mol of zinc nitrate and 2mol of ferric nitrate in a proper amount of absolute ethyl alcohol to obtain a solution A, and dissolving 7mol of urea in a proper amount of deionized water to obtain a solution B. Solution A was heated to 90 ℃ and solution B was added to solution A at a rate of 30 drops/min while stirring to give solution C. And naturally cooling the solution C to room temperature, aging for 12h, and centrifuging and washing to obtain a precursor. The precursor is put into a drying oven to be dried for 2 hours at the temperature of 100-110 ℃, and finally the precursor is calcined for 1 hour at the temperature of 600 ℃, and the precursor is naturally cooled to room temperature to obtain ZnO/ZnFe 2 O 4 The composite nano-particles have a particle size of 30 to 60nm. The composite nano material pair is measured at 150 ℃ for 100ppmH 2 The sensitivity of S gas was 145.
2 Preparation example of Pt-doped ZnO/TiO composite nanoparticles
Example 1
0.5mol of zinc nitrate, 1mol of tetrabutyl titanate and 0.011mol of chloroplatinic acid are dissolved in a proper amount of absolute ethyl alcohol to obtain a solution A, and 1mol of urea is dissolved in a proper amount of deionized water to obtain a solution B. Solution A was heated to 90 ℃ and solution B was added to solution A at a rate of 90 drops/min while stirring to give solution C. And naturally cooling the solution C to room temperature, aging for 12h, and centrifuging and washing to obtain a precursor. Drying the precursor in a drying oven at 100-110 deg.C for 2h, calcining the precursor at 600 deg.C for 1h, and naturally cooling to room temperature to obtain 3wt% Pt-doped ZnO/TiO 2 The composite nano-particles have a particle size of 30-60 nm. 3wt% of Pt doped with ZnO/TiO 2 The photocatalytic degradation effect of the composite nano-particles on methylene blue is 85.4%.
Example 2
1.5mol of zinc nitrate, 1mol of tetrabutyl titanate and 0.025mol of chloroplatinic acid are dissolved in a proper amount of absolute ethyl alcohol to obtain a solution A, and 3mol of urea is dissolved in a proper amount of deionized water to obtain a solution B. Solution A was heated to 90 ℃ and solution B was added to solution A at a rate of 90 drops/min while stirring to give solution C. And naturally cooling the solution C to room temperature, aging for 12h, and centrifuging and washing to obtain a precursor. Drying the precursor in a drying oven at 100-110 deg.C for 2h, calcining the precursor at 500 deg.C for 2h, and naturally cooling to room temperature to obtain 5wt% Pt-doped ZnO/TiO 2 The composite nano-particles have a particle size of 20-50 nm. 5wt% of Pt doped with ZnO/TiO 2 The photocatalytic degradation effect of the composite nano-particles on methylene blue is 94.1%.
Example 3
Dissolving 1mol of zinc nitrate, 1mol of tetrabutyl titanate and 0.05mol of chloroplatinic acid in a proper amount of absolute ethyl alcohol to obtain a solution A, and dissolving 2mol of urea in a proper amount of deionized water to obtain a solution B. Heating the solution A toSolution B was added to solution A at 90 drops/min with stirring to give solution C. And naturally cooling the solution C to room temperature, aging for 12h, and centrifuging and washing to obtain a precursor. Drying the precursor in a drying oven at 100-110 deg.C for 2h, calcining the precursor at 400 deg.C for 3h, and naturally cooling to room temperature to obtain the final product with the Pt doped ZnO/TiO in the 8wt% 2 The composite nano-particles have a particle size of 20-50 nm. 8% by weight of Pt doped with ZnO/TiO 2 The photocatalytic degradation effect of the composite nano-particles on methylene blue is 90.1%.
Comparative example 1
Dissolving 1mol of tetrabutyl titanate iron in a proper amount of absolute ethyl alcohol to obtain a solution A, heating the solution A to 90 ℃, naturally cooling to room temperature, aging for 24h, and obtaining a precursor through centrifugation and washing operations. Drying the precursor in a drying oven at 100-110 deg.C for 2h, calcining the precursor at 500 deg.C for 1h, and naturally cooling to room temperature to obtain TiO 2 Nanoparticles having a particle size of 20 to 50nm. The TiO being 2 The photocatalytic degradation effect of the nanoparticles on methylene blue is 77.4%.
3 2 Preparation example of Pt-doped LaFeO/TiO composite nanoparticles
Example 1
Dissolving 0.5mol of lanthanum nitrate, 0.5mol of ferric nitrate, 0.031mol of chloroplatinic acid and 1mol of tetrabutyl titanate in a proper amount of absolute ethyl alcohol to obtain a solution A, and dissolving 1.5mol of urea in a proper amount of deionized water to obtain a solution B. Solution A was heated to 90 ℃ and solution B was added to solution A at a rate of 30 drops/min while stirring to give solution C. And naturally cooling the solution C to room temperature, aging for 12h, and centrifuging and washing to obtain a precursor. Drying the precursor in a drying oven at 100-110 deg.C for 2h, calcining the precursor at 500 deg.C for 1h, and naturally cooling to room temperature to obtain 5wt% Pt-doped LaFeO 3 /TiO 2 The composite nano-particles have a particle size of 20-50 nm. 5wt% of Pt doped LaFeO 3 /TiO 2 The photocatalytic degradation effect of the composite nano-particles on methyl orange is 94.4%.
Example 2
Dissolving 1.5mol of lanthanum nitrate, 1.5mol of ferric nitrate, 0.146mol of chloroplatinic acid and 1mol of tetrabutyl titanate in a proper amount of absolute ethyl alcohol to obtain a solution A, and dissolving 2.25mol of urea in a proper amount of deionized water to obtain a solution B. Solution A was heated to 90 ℃ and solution B was added to solution A at a rate of 60 drops/min while stirring to give solution C. And naturally cooling the solution C to room temperature, aging for 12h, and centrifuging and washing to obtain a precursor. Drying the precursor in a drying oven at 100-110 deg.C for 2h, calcining the precursor at 600 deg.C for 2h, and naturally cooling to room temperature to obtain 10wt% Pt-doped LaFeO 3 /TiO 2 The composite nano-particles have a particle size of 30-60 nm. 10wt% of Pt doped LaFeO 3 /TiO 2 The photocatalytic degradation effect of the composite nano-particles on methyl orange is 85.8%.
Example 3
Dissolving 1mol of lanthanum nitrate, 1mol of ferric nitrate, 0.010mol of chloroplatinic acid and 1mol of tetrabutyl titanate in a proper amount of absolute ethyl alcohol to obtain a solution A, and dissolving 1.5mol of urea in a proper amount of deionized water to obtain a solution B. Solution A was heated to 90 ℃ and solution B was added to solution A at a rate of 90 drops/min while stirring to give solution C. And naturally cooling the solution C to room temperature, aging for 12h, and centrifuging and washing to obtain a precursor. Drying the precursor in a drying oven at 100-110 deg.C for 2h, calcining the precursor at 400 deg.C for 3h, and naturally cooling to room temperature to obtain 1wt% Pt-doped LaFeO 3 /TiO 2 The composite nano-particles have a particle size of 20-50 nm. The 1wt% Pt-doped LaFeO 3 /TiO 2 The photocatalytic degradation effect of the composite nano-particles on methyl orange is 88.1%.
Comparative example 1
Dissolving 1mol of tetrabutyl titanate in a proper amount of absolute ethyl alcohol to obtain a solution A, heating the solution A to 90 ℃, naturally cooling to room temperature, aging for 24h, and obtaining a precursor through centrifugation and washing operations. Drying the precursor in a drying oven at 100-110 deg.C for 2h, calcining the precursor at 500 deg.C for 1h, and naturally cooling to room temperature to obtain TiO 2 And (3) nanoparticles. The TiO compound is 2 The nano-particles have the photocatalytic degradation effect on methyl orange82.5％。
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of Pt-doped composite inorganic metal oxide nanoparticles is characterized by comprising the following steps:
step S1, dissolving a soluble metal source and chloroplatinic acid in a first polar solvent to form a solution A; wherein the soluble metal source is selected from at least two of soluble ferric salt, soluble zinc salt, soluble lanthanum salt and titanate;
s2, dissolving urea in a second polar solvent to form a solution B;
s3, heating the solution A, and adding the solution B into the solution A under a stirring state to form a solution C;
s4, cooling and aging the solution C, and then carrying out centrifugal separation to obtain a precursor material;
and S5, drying and calcining the precursor material in sequence to obtain the Pt-doped composite inorganic metal oxide nano-particles.
2. The method of claim 1, wherein the soluble ferric salt is ferric nitrate; and/or the soluble zinc salt is zinc nitrate; and/or the soluble lanthanum salt is lanthanum nitrate; and/or the titanate is tetrabutyl titanate.
3. The method of claim 2, wherein the soluble metal source is selected from the group consisting of the soluble ferric salt and the soluble zinc salt; alternatively, the soluble metal source is selected from the soluble zinc salt and the titanate; or, the soluble metal source is selected from the group consisting of the soluble lanthanum salt, the soluble ferric salt, and the titanate; preferably, the first and second electrodes are formed of a metal,
when the soluble metal source is selected from the group consisting of the soluble ferric salt and the soluble zinc salt, the molar ratio of the soluble zinc salt to the soluble ferric salt is 1.05-1.2; preferably, the molar ratio of urea to the soluble zinc salt in the solution B is 7;
when the soluble metal source is selected from the soluble zinc salt and the titanate, the molar ratio of the soluble zinc salt to the titanate is 0.5-1.5; preferably, the molar ratio of urea to the soluble zinc salt in the solution B is 1.8 to 2.2;
when the soluble metal source is selected from the group consisting of the soluble lanthanum salt, the soluble ferric salt, and the titanate, the molar ratio of the soluble lanthanum salt, the soluble ferric salt, and the titanate is from 0.5 to 1.5; preferably, the molar ratio of urea to the soluble lanthanum salt in the solution B is 2.7 to 3.3.
4. The production method according to claim 3,
the soluble metal source is selected from the group consisting of ferric nitrate and zinc nitrate; preferably, the doping amount of Pt in the composite inorganic metal oxide nano-particles is 0.3-3 wt%; alternatively, the first and second electrodes may be,
the soluble metal source is selected from zinc nitrate and tetrabutyl titanate; preferably, the doping amount of Pt in the composite inorganic metal oxide nano-particles is 3-8 wt%; alternatively, the first and second liquid crystal display panels may be,
the soluble metal source is selected from lanthanum nitrate, ferric nitrate and tetrabutyl titanate; preferably, the doping amount of Pt in the composite inorganic metal oxide nano-particles is 1-10 wt%.
5. The production method according to any one of claims 1 to 4, wherein the mass concentration of the solution A is 40 to 60wt%, and the mass concentration of the solution B is 30 to 50wt%;
preferably, the first polar solvent is ethanol and the second polar solvent is water;
preferably, in the step S3, after the solution a is heated to 70 to 90 ℃, the solution B is added dropwise to the solution a while stirring, and more preferably, the speed during the dropwise addition is 30 to 90 drops/minute.
6. The preparation method according to claim 5, wherein in the step S4, the aging process is carried out for 10 to 14 hours;
preferably, after the centrifugal separation is finished, the step S4 further includes: washing the solid products obtained by centrifugal separation in sequence to obtain the precursor material;
preferably, in step S5, the drying conditions are as follows: drying for 1-3 h in a drying oven at 100-110 ℃.
7. The method according to claim 3 or 4, wherein in the step S5, the calcination conditions are as follows: calcining for 1-3 h at 400-700 ℃ in an inert atmosphere; preferably, the first and second electrodes are formed of a metal,
when the soluble metal source is selected from the soluble ferric salt and the soluble zinc salt, the calcining temperature is 500-700 ℃;
when the soluble metal source is selected from the soluble zinc salt and the titanate, or from the soluble lanthanum salt, the soluble ferric salt and the titanate, the calcining temperature is 400-600 ℃.
8. A Pt-doped composite inorganic metal oxide nanoparticle, characterized by being produced by the production method according to any one of claims 1 to 7.
9. The Pt-doped composite inorganic metal oxide nanoparticle of claim 8, wherein the Pt-doped composite inorganic metal oxide nanoparticle is Pt-doped ZnO/ZnFe 2 O 4 Composite nanoparticles, pt dopingHetero ZnO/TiO 2 Composite nanoparticles or Pt-doped LaFeO 3 /TiO 2 Composite nanoparticles; preferably, the particle size of the Pt-doped composite inorganic metal oxide nanoparticle is 10 to 50nm.
10. Use of the Pt-doped composite inorganic metal oxide nanoparticle of claim 8 or 9 as a gas-sensitive or photocatalytic material.
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