CN114751445A - Noble metal sensitized nano porous SnO2Preparation method of base gas sensitive material - Google Patents

Noble metal sensitized nano porous SnO2Preparation method of base gas sensitive material Download PDF

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CN114751445A
CN114751445A CN202210365991.8A CN202210365991A CN114751445A CN 114751445 A CN114751445 A CN 114751445A CN 202210365991 A CN202210365991 A CN 202210365991A CN 114751445 A CN114751445 A CN 114751445A
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万辉明
姜新亮
严辉
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Shanghai Fugan Technology Co ltd
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Abstract

The invention provides noble metal sensitized nano porous SnO2A preparation method of a gas-sensitive material belongs to the field of advanced porous nano materials. The preparation method adopts dihydric alcohol as a solvent and a metal precursor modifier, and an amphiphilic block copolymer as a structure inducer; structure inducer pair SnO2Precursor and nobleWhen the metal precursor is assembled together, the dihydric alcohol is firstly mixed with SnO2Chelating the precursor to form a metal chelate, and then forming an inverse composite micelle with the amphiphilic block copolymer; when the solvent is volatilized after the assembly is finished, the reversed-phase composite micelle is further accumulated to form a super-macromolecular assembly body, a framework is provided for calcination, and a mesoporous pore passage with large pore diameter is formed after the structure-decomposing inducer is calcined, so that the nano-porous SnO sensitized by the noble metal is obtained2A gas sensitive material. The synthesis method has low requirements on synthesis conditions, high reaction yield and easy industrial production, and can be applied to development and application of various high-performance gas sensors.

Description

Noble metal sensitized nano porous SnO2Preparation method of base gas sensitive material
Technical Field
The invention belongs to the field of advanced porous nano materials, and particularly relates to nano porous SnO sensitized by noble metals2A preparation method of a base gas-sensitive material.
Background
Tin oxide is a typical n-type semiconductor, is a commonly used metal oxide semiconductor gas-sensitive material, and has the properties of high electron mobility, wide bandgap, non-stoichiometry, good thermal stability and the like. However, single component SnO2When the semiconductor gas sensitive material is used for gas sensing, the problems of slow response, long recovery time, poor stability and the like exist.
In the prior art, SnO is improved2The gas sensitive performance strategy of semiconductor materials includes three directions: firstly, the composite material is subjected to component modification, such as precious metal modification, and for example, Chinese patent with the publication number of CN112225255A discloses a precious metal-loaded ordered double-mesoporous metal oxide composite material and a preparation method thereof; secondly, SnO is added2The heterojunction is compounded with one or more metal oxides to construct a heterojunction, the heterojunction can effectively accelerate the transmission of electrons, can enhance oxygen adsorption at the same time, form rich oxygen vacancies and provide new active sites for reaction, thereby obviously improving the gas-sensitive performance; thirdly, in bulk SnO2A porous structure is constructed on the gas-sensitive material.
Although nanoporous SnO has been reported2But due to the common SnO2Precursors such as SnCl4、SnCl2The hydrolytic polymerization rate is high, a large amount of organic solvent and acid-base catalyst are generally needed to regulate the hydrolytic polymerization process of the metal oxide precursor, and the synthesis conditions such as environment humidity, reaction temperature, hydrolysis time and the like are strictly controlled, so that the mesoporous SnO is caused2The synthesis cost is high and the yield is low, so that the industrial application of the synthesis is greatly limited; in addition, traditional nanoporous SnO2During the synthesis process, when the template agent is removed by high-temperature calcination, the material framework is easy to shrink and recombine, so that the whole mesoporous framework is collapsed, and the large aperture is formedThe synthesis of nanoporous tin oxide still faces significant challenges.
Disclosure of Invention
In view of the above problems, the embodiment of the invention provides a preparation method of a noble metal sensitized nano-porous SnO 2-based gas sensitive material, which is simple, controllable, strong in universality and easy to realize industrial production, and reaction parameters and processes are better controlled by modifying a solvent and a metal precursor; meanwhile, the volume of inorganic tin salt micromolecules is increased, so that a huge reverse phase composite micelle is formed when the chelate and the amphiphilic block copolymer are assembled, the hydrolysis of a tin oxide precursor can be obviously inhibited, the aperture is increased on the premise of ensuring the integrity of a framework, and the sensitization performance of the material is improved.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
noble metal sensitized nano porous SnO2A method of preparing a gas-sensitive material, comprising:
dihydric alcohol is used as a solvent and a metal precursor modifier, an amphiphilic block copolymer is used as a structure inducer, wherein a hydrophilic block can react with SnO2Polymers in which the precursors interact through electrostatic interaction, coordination and/or hydrogen bonding;
structure inducer pair SnO2When the precursor and the noble metal precursor are assembled together, the dihydric alcohol is firstly mixed with SnO2The precursor and the noble metal precursor are chelated to form a metal chelate, and then the metal chelate and the amphiphilic block copolymer form an inverse composite micelle;
when the solvent is volatilized after the assembly is finished, the reversed-phase composite micelle is further accumulated to form a super-macromolecule assembly to provide a framework for the calcination, and the nano-porous with large pore diameter is obtained after the structure inducer is removed by the calcination to obtain the nano-porous SnO sensitized by the noble metal2A gas sensitive material.
The nano-porous SnO2The gas-sensitive material comprises nano-porous SnO2Gas sensitive material and nano-porous SnO2The gas sensitive material is based on composite other metal oxides.
Wherein the dihydric alcohol is SnO2Precursor chelation Formation of metal chelate not only capable of being inhibited as SnO2Hydrolyzing inorganic tin salt of a precursor, promoting the full self-assembly of the inorganic tin salt and the amphiphilic block copolymer, simultaneously increasing the volume of inorganic tin salt micromolecules, forming an inverse composite micelle by the microphase separation of the amphiphilic block copolymer when the chelate is assembled with the amphiphilic block copolymer, further stacking the inverse composite micelle in the solvent volatilization process to form a supermolecule assembly, and obtaining the noble metal sensitized nano porous SnO after calcining and removing the block copolymer2The obtained nano-porous is large aperture based on gas sensitive material. When the metal oxide precursor contains only SnO2Precursor to obtain single-component ordered large-aperture mesoporous SnO2A gas sensitive material; when the metal oxide precursor comprises SnO2When the precursor also comprises other metal oxide precursors, such as one or more metal oxide precursors of nickel oxide, zinc oxide, tungsten oxide, niobium oxide, zirconium oxide, titanium oxide, etc., SnO is obtained2The ordered large-aperture mesoporous gas-sensitive material compounded with other metal oxides has a plurality of intermetallic heterojunction structures.
The reversed-phase composite micelle and the super-large molecule assembly can finally obtain mesopores with large pore diameters, and the order of the mesopores ensures that the mesopores have uniform and open nanopores, thereby being beneficial to the directional transmission of electrons in the reaction process; the large aperture can obtain high specific surface area, large pore volume, adjustable chemical composition and surface property, can provide more active sites, and is beneficial to the gas-sensitive catalysis of a gas-solid interface; the highly interconnected large-aperture pore channels are beneficial to the diffusion and mass transfer of gas in the sensitive material, increase the interface reaction probability of the gas and the sensitive material, and are beneficial to the adsorption of gas molecules and the catalytic reaction, thereby obviously improving the gas sensing sensitivity and reducing the detection limit; the sensitized noble metal loaded by the nano-porous with large aperture can increase the chemical sensitization, the electronic sensitization and the construction of heterojunction, thereby obviously reducing the working temperature, improving the sensitivity and the response/recovery time, and improving the gas-sensitive performance and the selectivity.
In a preferred embodiment of the present invention, the noble metal comprises one or two or more alloys of platinum, palladium, gold, silver, rhodium, ruthenium, osmium and iridium.
In a preferred embodiment of the invention, the noble metal-sensitized nanoporous SnO is 2The preparation method of the gas-sensitive material comprises the following specific steps:
step S1, adding inorganic tin salt and a precious metal precursor into a glycol solvent, and stirring for 5-20 min to form a uniform first mixed solution; wherein the mass ratio of the inorganic tin salt to the glycol solvent is 1: 5-1: 20, and the added noble metal precursor accounts for 0.5 wt% -2 wt% of the inorganic tin salt.
Step S2, adding the amphiphilic block copolymer and a concentrated acid solution into the first mixed solution, and stirring for 1-2 hours to obtain a second mixed solution; wherein the mass ratio of the amphiphilic block copolymer to the inorganic tin salt is 1: 5-1: 1, and the mass ratio of the concentrated acid solution to the inorganic tin salt is 1: 1-1: 5;
step S3, transferring the second mixed solution into a culture dish, placing the culture dish at 25-70 ℃ to volatilize the solvent, transferring the second mixed solution into a drying oven at 100-150 ℃ after 10-24 hours, curing the second mixed solution for 10-24 hours to obtain a uniform transparent film, scraping the transparent film from the culture dish, and grinding the transparent film to obtain first powder;
step S4, transferring the first powder to a tube furnace in N2Heating to 300-400 ℃ at a heating rate of 1-5 ℃/min in the atmosphere, and calcining for 1-3 h to obtain second powder;
step S5, transferring the second powder into a muffle furnace, heating to 350-500 ℃ in air at a heating rate of 5-10 ℃/min, and calcining for 1-3 h to obtain the nano-porous SnO sensitized by the noble metal 2A gas sensitive material.
In a preferred embodiment of the invention, the noble metal-sensitized nanoporous SnO is2The preparation method of the gas-sensitive material includes the above steps S1 to S5, except that, in step S1, the inorganic tin salt, the inorganic zinc salt, and the noble metal precursor are simultaneously added to the glycol solvent; in step S5, precious metal sensitized nanoporous SnO is obtained2Based ZnO composite gasA sensitive material.
In a preferred embodiment of the present invention, the ZnO in the steps S1 and S5 may be replaced by one or two of nickel oxide, tungsten oxide, niobium oxide, zirconium oxide, and titanium oxide.
Preferably, the glycol solvent used in the above embodiment may be a glycol having 2 to 12 carbon atoms, specifically selected from one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, 1, 5-pentylene glycol, 1, 6-hexylene glycol, 1, 7-heptylene glycol, 1, 8-octylene glycol, 1, 10-decylene glycol, and 1, 12-dodecylene glycol; the inorganic tin salt may be one of tin tetrachloride, stannous chloride, stannous sulfate, sodium stannate, etc.
Preferably, the concentrated acid solution used in the above embodiment may be one or more of concentrated hydrochloric acid, concentrated nitric acid, concentrated sulfuric acid, and the like; the amphiphilic block copolymer used can be a diblock, triblock or multiblock copolymer, and has a number average molecular weight of 5000-60000. The hydrophilic block is a polymer which can interact with inorganic tin salt through electrostatic interaction, coordination, hydrogen bond interaction or other acting forces, the number average molecular weight is 1000-10000, and the hydrophilic block can be specifically selected from one or more of polyethylene oxide (PEO), poly (N-isopropylacrylamide) (PNIPAM), Polyacrylamide (PAM), poly- (2-vinylpyridine) (P2VP) and poly- (4-vinylpyridine) (P4 VP); the hydrophobic block is a polymer with hydrophobic property, the number average molecular weight is 4000-50000, and the hydrophobic block can be selected from one or more of Polystyrene (PS), polypropylene oxide (PPO), Polybutadiene (PB) and polymethyl methacrylate (PMMA).
The noble metal sensitized nano porous SnO prepared by the preparation method2Based gas sensitive material with specific surface area of 80m2·g-1～200m2·g-1The pore size is 15 nm-50 nm, and the pore volume is 0.1cm3·g-1～1.5cm3·g-1The size of the noble metal nano particles is 1-5 nm, and the noble metal nano particles are uniform in size and highly dispersed.
The noble metal sensitized nano porous SnO prepared by the preparation method2Based on gas-sensitive materials having ordered mediaThe pore canal structure is one of vertically divergent tubular pore canal, spherical pore canal and worm-shaped pore canal, and has pore canal structure in the space group of P6mm,
Figure BDA0003585853400000051
Figure BDA0003585853400000052
P63/mmc、
Figure BDA0003585853400000053
One or more of.
The noble metal sensitized nano porous SnO prepared by the preparation method2Gas-sensitive material for toxic and harmful gas (CO, H)2S, etc.), volatile organic compounds VOCs (benzene, formaldehyde, etc.), exhaled breath of the human body (acetone, NH3Etc.) and flammable and explosive gases (CH)4、H2) The gas sensor has excellent gas-sensitive performance.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the noble metal sensitized nanoporous SnO2The preparation method of the gas-sensitive material increases chelation by adding the modifier so as to adjust the co-assembly rate of the precursor under the structure inducer, forms large micelles, has low requirement on synthesis conditions, has relatively thorough reaction and high yield, and is easy to realize industrial production;
(2) The noble metal sensitized nanoporous SnO2According to the preparation method of the gas-sensitive material, the size of the micelle is increased by chelation, a solid and stable framework is provided for the calcining process, the framework structure of the material is maintained when the template agent is removed, and meanwhile, the large-size micelle obtains the nano-porous with large pore diameter, so that the improvement of the sensitization performance is ensured;
(3) the noble metal sensitized nanoporous SnO2The preparation method of the gas-sensitive material can realize flexible regulation and control of the aperture by regulating and controlling the type, the molecular weight and the hydrophilic-hydrophobic segment ratio of the amphiphilic block copolymer, and can also change SnO2Precursor and amphiphilic blockThe proportion of the segmented copolymer realizes the adjustment of the pore wall thickness, so that the segmented copolymer is widely applicable to the detection of various toxic, harmful, flammable and explosive gases;
(4) the noble metal sensitized nanoporous SnO2The preparation method of the gas-sensitive material has strong universality, and the method can be applied to the synthesis of any large nano porous metal oxide taking inorganic metal salt which is easy to hydrolyze as a precursor; and the supported noble metal is uniform in size and highly dispersed.
Of course, it is not necessary for any method of practicing the invention to achieve all of the above-described advantages at the same time.
Detailed Description
The technical problems, aspects and advantages of the present invention will be explained in detail below with reference to exemplary embodiments. The following exemplary embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
This example provides a Pt sensitized nanoporous SnO2The preparation method of the gas sensitive material comprises the following steps:
step S1, adding 200mg SnCl4And 0.5ml of 2 mg. multidot.L-1Adding a chloroplatinic acid solution into 1g of glycol solvent, and stirring for 5min to form a uniform first mixed solution;
step S2, adding 40mg of amphiphilic block copolymer polyethylene oxide-b-polystyrene (PEO-b-PS, Mn is approximately equal to 25000) and 40mg of concentrated hydrochloric acid solution into the first mixed solution, and stirring for 1h to obtain a second mixed solution;
Step S3, transferring the second mixed solution to a culture dish, placing the culture dish at 25 ℃ to volatilize the solvent, transferring the culture dish to an oven at 100 ℃ after 10 hours, curing the culture dish for 10 hours to obtain a uniform and transparent film, scraping the transparent film from the culture dish, and grinding the transparent film to obtain first powder;
step S4, transferring the first powder into a tube furnace, and introducing N2Forming an inert atmosphere, raising the temperature to 300 ℃ at a heating rate of 1 ℃/min, and calcining for 3h to obtain second powder;
step S5, transferring the second powder into a muffle furnace, heating to 350 ℃ in air at a heating rate of 5 ℃/min, and calcining for 3h to obtain Pt-sensitized nano-porous SnO2A gas sensitive material.
The obtained Pt-sensitized nanoporous SnO2Gas sensitive material with specific surface area of 84m2·g-1Pore size of 23nm and pore volume of 0.3cm3·g-1The size of the noble metal nano-particles is 3.8nm, and CO and H can be effectively detected2S、VOCs、NH3And the like.
Example 2
This example provides a Pd-sensitized nanoporous SnO2The preparation method of the/NiO gas-sensitive material comprises the following steps:
step S1, adding 200mg SnCl2、200mg NiCl2And 1ml of 2 mg. L-1Adding the potassium hexachloropalladate solution into 2g of 1, 3-propanediol solvent, and stirring for 15min to form a uniform first mixed solution;
Step S2, adding 100mg of amphiphilic triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO, Mn is approximately equal to 15000) and 100mg of concentrated nitric acid solution into the first mixed solution in the step S1, and stirring for 1.5h to obtain a second mixed solution.
Step S3, transferring the second mixed solution to a culture dish, placing the culture dish at 35 ℃ to volatilize the solvent, transferring the second mixed solution to a 120 ℃ oven after 15h, curing the second mixed solution for 12h to obtain a uniform transparent film, scraping the transparent film from the culture dish and grinding the transparent film to obtain first powder;
step S4, transferring the first powder into a tube furnace, and introducing N2Form inertiaRaising the temperature to 350 ℃ at the heating rate of 2 ℃/min in the atmosphere, and calcining for 2h to obtain second powder;
step S5, transferring the second powder into a muffle furnace, heating to 400 ℃ at a heating rate of 8 ℃/min in air, and calcining for 2h to obtain Pd-sensitized nano-porous SnO2the/NiO gas sensitive material.
The obtained Pd-sensitized nanoporous SnO2The specific surface area of the/NiO gas-sensitive material is 1108m2·g-1Pore size of 15nm and pore volume of 0.22cm3·g-1The size of the noble metal nano-particles is 3.2nm, and CO and H can be effectively detected2S、VOCs、NH3And the like.
Example 3
This example provides an Au sensitized nanoporous SnO2The preparation method of the/ZnO gas-sensitive material comprises the following steps:
step S1, adding 200mg SnCl4、200mg ZnCl2And 2ml of 2 mg. L-1Adding chloroauric acid solution into 4g of 1, 4-butanediol solvent, and stirring for 20min to form uniform first mixed solution;
step S2, adding 200mg of amphiphilic block copolymer polyethylene oxide-b-polymethyl methacrylate (PEO-b-PMMA, Mn is approximately equal to 30000) and 200mg of concentrated nitric acid solution into the first mixed solution in the step S1, and stirring for 2 hours to obtain a second mixed solution.
Step S3, transferring the second mixed solution obtained in the step S2 to a culture dish, placing the culture dish at 70 ℃ to volatilize the solvent, transferring the culture dish to an oven at 150 ℃ after 24 hours, curing the culture dish for 24 hours to obtain a uniform and transparent film, scraping the transparent film from the culture dish, and grinding the transparent film to obtain first powder;
step S4, transferring the first powder obtained in step S3 to a tube furnace, and introducing N2Forming an inert atmosphere, raising the temperature to 400 ℃ at the heating rate of 2 ℃/min, and calcining for 1h to obtain second powder;
step S5, transferring the second powder obtained in the step S4 to a muffle furnace, raising the temperature to 500 ℃ at a heating rate of 10 ℃/min in the air, and calcining for 1h to obtain Au-sensitized nano-porous Sn O2/ZnO gas-sensitive material.
The obtained Au-sensitized nano-porous SnO2/ZnO gas-sensitive material with a specific surface area of 77m2·g-1Pore size of 31nm and pore volume of 0.52cm3·g-1The size of the noble metal nano particles is 3.8nm, and CO and H can be effectively detected2S、VOCs、NH3And the like.
Example 4
This example provides an Ag sensitized nanoporous SnO2/WO3The preparation method of the gas sensitive material comprises the following steps:
step S1, adding 200mg of SnCl4, 200mg of WCl6 and 1.5ml of 2 mg of L-1 silver nitrate solution into 3g of 1, 5-pentanediol solvent, and stirring for 10min to form a uniform first mixed solution;
step S2, 70mg of amphiphilic block copolymer poly- (4-vinylpyridine) -b-polystyrene (P4VP-b-PS, Mn ≈ 33000) and 100mg of concentrated nitric acid solution are added into the first mixed solution in the step S1, and stirring is carried out for 1.5h, so as to obtain a second mixed solution.
Step S3, transferring the second mixed solution obtained in the step S2 to a culture dish, placing the culture dish at 50 ℃ to volatilize the solvent, transferring the culture dish to an oven at 130 ℃ after 18 hours, curing the culture dish for 18 hours to obtain a uniform and transparent film, scraping the transparent film from the culture dish, and grinding the transparent film to obtain first powder;
step S4, transferring the first powder obtained in step S3 to a tube furnace, and introducing N 2Forming an inert atmosphere, raising the temperature to 350 ℃ at the heating rate of 2 ℃/min, and calcining for 2h to obtain second powder;
step S5, transferring the second powder obtained in the step S4 into a muffle furnace, heating to 450 ℃ in air at a heating rate of 5 ℃/min, and calcining for 2h to obtain Ag sensitized ordered macroporous and mesoporous SnO2/WO3A gas sensitive material.
The obtained Ag sensitized nano porous SnO2/WO3Gas sensitive material with specific surface area of 128m2·g-1Pore size of 27nm and pore volume of 0.46cm3·g-1The noble metal nanoparticles have a size of4.0nm, can effectively detect CO and H2S、VOCs、NH3And the like.
Example 5
This example provides an Rh sensitized nanoporous SnO2/ZrO2The preparation method of the gas sensitive material comprises the following steps:
step S1, adding 200mg SnCl4、200mg ZrCl4And 1ml of 2 mg. L-1Adding the potassium hexachlororhodate solution into 2g of glycol solvent, and stirring for 20min to form a uniform first mixed solution;
step S2, adding 50mg of amphiphilic block copolymer poly- (2-vinylpyridine) -b-polystyrene (P2VP-b-PS, Mn is approximately equal to 50000) and 50mg of concentrated sulfuric acid solution into the first mixed solution in the step S1, and stirring for 2h to obtain a second mixed solution.
Step S3, transferring the second mixed solution obtained in the step S2 to a culture dish, placing the culture dish at 60 ℃ to volatilize the solvent, transferring the culture dish to an oven at 120 ℃ after 12 hours, curing the culture dish for 12 hours to obtain a uniform and transparent film, scraping the transparent film from the culture dish, and grinding the transparent film to obtain first powder;
Step S4, transferring the first powder of step S3 to a tube furnace, and introducing N2Forming an inert atmosphere, raising the temperature to 400 ℃ at a heating rate of 5 ℃/min, and calcining for 2h to obtain second powder;
step S5, transferring the second powder obtained in the step S4 to a muffle furnace, heating to 500 ℃ at a heating rate of 8 ℃/min in air, and calcining for 2h to obtain Rh-sensitized ordered macroporous and mesoporous SnO2/ZrO2A gas sensitive material.
The obtained Rh-sensitized nanoporous SnO2/ZrO2Gas-sensitive material with a specific surface area of 72m2·g-1Pore size of 37nm and pore volume of 0.63cm3·g-1The size of the noble metal nano-particles is 4.6nm, and CO and H can be effectively detected2S、VOCs、NH3And the like.
Example 6
This example provides an Ir sensitized nanoporous SnO2/Nb2O5The preparation method of the gas sensitive material comprises the following steps:
step S1, adding 200mg SnCl4、200mg NbCl5And 0.5ml of 2 mg. multidot.L-1Adding the chloroiridic acid solution into 3g of 1, 6-hexanedioic alcohol solvent, and stirring for 10min to form a uniform first mixed solution;
step S2, adding 80mg of amphiphilic block copolymer polyethylene oxide-b-polystyrene (PEO-b-PS, Mn ≈ 33000) and 60mg of concentrated hydrochloric acid solution into the first mixed solution in the step S1, and stirring for 1h to obtain a second mixed solution.
Step S3, transferring the second mixed solution obtained in the step S2 to a culture dish, placing the culture dish at 55 ℃ to volatilize the solvent, transferring the culture dish to a 110 ℃ oven after 20 hours, curing the culture dish for 12 hours to obtain a uniform and transparent film, scraping the transparent film from the culture dish and grinding the transparent film to obtain first powder;
Step S4, transferring the first powder obtained in step S3 to a tube furnace, and introducing N2Forming an inert atmosphere, raising the temperature to 300 ℃ at the heating rate of 1 ℃/min, and calcining for 2.5h to obtain second powder;
step S5, transferring the second powder obtained in the step S4 to a muffle furnace, raising the temperature to 450 ℃ in air at a heating rate of 5 ℃/min, and calcining for 2h to obtain Ir-sensitized ordered macroporous mesoporous SnO2/Nb2O5A gas sensitive material.
The obtained Ir sensitized nano-porous SnO2/Nb2O5Gas-sensitive material with specific surface area of 90m2·g-1Pore size of 30nm and pore volume of 0.8cm3·g-1The size of the noble metal nano-particles is 3nm, and CO and H can be effectively detected2S、VOCs、NH3And the like.
Example 7
This example provides a Pt sensitized nanoporous SnO2/WO3The preparation method of the/NiO gas-sensitive material comprises the following steps:
step S1, adding 200mg SnCl4、200mg WCl6、200mg NiCl2And 1ml of 2 mg. L-1Chloroplatinic acid solution is addedAdding into 2g of glycol solvent, and stirring for 20min to form a uniform first mixed solution;
step S2, adding 50mg of amphiphilic block copolymer polyethylene oxide-b-polystyrene (PEO-b-PS, Mn is approximately equal to 35000) and 50mg of concentrated hydrochloric acid solution into the first mixed solution in the step S1, and stirring for 2h to obtain a second mixed solution.
Step S3, transferring the second mixed solution obtained in the step S2 to a culture dish, placing the culture dish at 40 ℃ to volatilize the solvent, transferring the culture dish to an oven at 100 ℃ after 24 hours, curing the culture dish for 12 hours to obtain a uniform and transparent film, scraping the transparent film from the culture dish, and grinding the transparent film to obtain first powder;
Step S4, transferring the first powder of step S3 to a tube furnace, and introducing N2Forming an inert atmosphere, raising the temperature to 350 ℃ at the heating rate of 2 ℃/min, and calcining for 2h to obtain second powder;
step S5, transferring the second powder obtained in the step S4 to a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min in air, and calcining for 1h to obtain the Pt-sensitized ordered macroporous and mesoporous SnO2/WO3the/NiO gas sensitive material.
The resulting Pt-sensitized nanoporous SnO2/WO3NiO gas sensitive material with specific surface area of 76m2·g-1Pore size of 28nm and pore volume of 0.3cm3·g-1The size of the noble metal nano-particles is 2.0nm, and CO and H can be effectively detected2S、VOCs、NH3And the like.
Example 8
This example provides a Pd-sensitized nanoporous SnO2/ZnO/Nb2O5The preparation method of the gas sensitive material comprises the following steps:
step S1, adding 200mg SnCl4、200mg ZnCl2、200mg NbCl5And 2ml of 2 mg. L-1Adding the potassium hexachloropalladate solution into 1.5g of 1, 3-propanediol solvent, and stirring for 15min to form a uniform first mixed solution;
step S2, adding 100mg of amphiphilic block copolymer polyethylene oxide-b-polystyrene (PEO-b-PS, Mn is approximately equal to 40000) and 100mg of concentrated hydrochloric acid solution into the first mixed solution in the step S1, and stirring for 1h to obtain a second mixed solution.
Step S3, transferring the second mixed solution obtained in the step S2 into a culture dish, placing the culture dish at 45 ℃ to volatilize the solvent, transferring the culture dish into an oven at 120 ℃ after 12 hours, curing the culture dish for 12 hours to obtain a uniform and transparent film, scraping the transparent film from the culture dish, and grinding the transparent film to obtain first powder;
step S4, transferring the first powder of step S3 to a tube furnace, and introducing N2Forming an inert atmosphere, raising the temperature to 400 ℃ at a heating rate of 1 ℃/min, and calcining for 1h to obtain second powder;
step S5, transferring the second powder obtained in the step S4 to a muffle furnace, heating to 400 ℃ at a heating rate of 10 ℃/min in air, and calcining for 3h to obtain Pd-sensitized ordered macroporous and mesoporous SnO2/ZnO/Nb2O5A gas sensitive material.
The resulting Pd-sensitized nanoporous SnO2/ZnO/Nb2O5Gas sensitive material with a specific surface area of 46m2·g-1Pore size of 34nm and pore volume of 0.57cm3·g-1The size of the noble metal nano-particles is 5nm, and CO and H can be effectively detected2S、VOCs、NH3And the like.
While the foregoing is directed to the preferred embodiment of the present invention, it is understood that the invention is not limited to the exemplary embodiments disclosed, but is made merely for the purpose of providing those skilled in the relevant art with a comprehensive understanding of the specific details of the invention. It will be apparent to those skilled in the art that various modifications and adaptations of the present invention can be made without departing from the principles of the invention and the scope of the invention is to be determined by the claims.

Claims (10)

1. Noble metal sensitized nano porous SnO2The preparation method of the gas-sensitive material is characterized by comprising the following steps:
adopting dihydric alcohol as solvent and metal precursorModifier, amphiphilic block copolymer as structure inducing agent, and hydrophilic block capable of reacting with SnO2Polymers of which the precursors interact through electrostatic interaction, coordination and/or hydrogen bonding;
structure inducer pair SnO2When the precursor and the noble metal precursor are assembled together, the dihydric alcohol is firstly mixed with SnO2The precursor and the noble metal precursor are chelated to form a metal chelate, and then the metal chelate and the amphiphilic block copolymer form an inverse composite micelle;
when the solvent is volatilized after the assembly is finished, the reversed-phase composite micelle is further accumulated to form a super-macromolecule assembly to provide a framework for the calcination, and the nano-porous with large pore diameter is obtained after the structure inducer is removed by the calcination to obtain the nano-porous SnO sensitized by the noble metal2A gas sensitive material.
2. Noble metal sensitized nanoporous SnO according to claim 12The preparation method of the gas-sensitive material is characterized in that the nano-porous SnO2The gas-sensitive material comprises nano-porous SnO2Gas sensitive material and nano-porous SnO2The gas sensitive material is based on composite other metal oxides.
3. Noble metal sensitized nanoporous SnO according to claim 22The preparation method of the base gas-sensitive material is characterized in that the other metal oxide comprises one or more of nickel oxide, zinc oxide, tungsten oxide, niobium oxide, zirconium oxide and titanium oxide.
4. Noble metal sensitized nanoporous SnO according to any of claim 12The preparation method of the gas-sensitive material is characterized in that the noble metal comprises one or two or more alloys of platinum, palladium, gold, silver, rhodium, ruthenium, osmium and iridium.
5. Noble metal sensitized nanoporous SnO according to any of claims 1-42A method for preparing a gas-sensitive material, characterized in that the method comprisesThe method comprises the following steps:
step S1, adding inorganic tin salt and a precious metal precursor into a glycol solvent, and stirring for 5-20 min to form a uniform first mixed solution; wherein the mass ratio of the inorganic tin salt to the glycol solvent is 1: 5-1: 20, and the added noble metal precursor accounts for 0.5-2 wt% of the inorganic tin salt;
step S2, adding the amphiphilic block copolymer and the concentrated acid solution into the first mixed solution, and stirring for 1-2 hours to obtain a second mixed solution; wherein the mass ratio of the amphiphilic block copolymer to the inorganic tin salt is 1: 5-1: 1, and the mass ratio of the concentrated acid solution to the inorganic tin salt is 1: 1-1: 5;
Step S3, transferring the second mixed solution into a culture dish, placing the culture dish at 25-70 ℃ to volatilize the solvent, transferring the culture dish into a drying oven at 100-150 ℃ after 10-24 hours, curing the culture dish for 10-24 hours to obtain a uniform transparent film, scraping the transparent film from the culture dish, and grinding the transparent film to obtain first powder;
step S4, transferring the first powder to a tube furnace in N2Heating to 300-400 ℃ at a heating rate of 1-5 ℃/min in the atmosphere, and calcining for 1-3 h to obtain second powder;
step S5, transferring the second powder into a muffle furnace, heating to 350-500 ℃ in air at a heating rate of 5-10 ℃/min, and calcining for 1-3 h to obtain the nano-porous SnO sensitized by the noble metal2A gas sensitive material.
6. Noble metal sensitized nanoporous SnO according to claim 52A preparation method of a base gas sensitive material is characterized in that,
step S1, adding at least one oxide precursor of nickel oxide, zinc oxide, tungsten oxide, niobium oxide, zirconium oxide, and titanium oxide into a glycol solvent;
in step S5, obtaining the noble metal sensitized nano porous SnO2A composite metal oxide-based gas-sensitive material.
7. Noble metal sensitized nanoporous SnO according to claim 5 2The preparation method of the gas sensitive material is characterized in that the dihydric alcohol is a dihydric alcohol with the carbon number of 2-12, and comprises one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, 1, 5-pentylene glycol, 1, 6-hexylene glycol, 1, 7-heptylene glycol, 1, 8-octylene glycol, 1, 10-decylene glycol and 1, 12-dodecylene glycol.
8. Noble metal sensitized nanoporous SnO according to claim 52The preparation method of the gas sensitive material is characterized in that the inorganic tin salt is selected from one of stannic chloride, stannous sulfate and sodium stannate.
9. Noble metal sensitized nanoporous SnO according to claim 52The preparation method of the gas-sensitive material is characterized in that the concentrated acid solution can be one or more of concentrated hydrochloric acid, concentrated nitric acid, concentrated sulfuric acid and the like; the amphiphilic block copolymer is a diblock copolymer, a triblock copolymer or a multiblock copolymer, and the number average molecular weight is 5000-60000.
10. Noble metal sensitized nanoporous SnO according to claim 52The preparation method of the gas-sensitive material is characterized in that the obtained noble metal sensitized nano-porous SnO2Based gas sensitive material with specific surface area of 80m 2·g-1～200m2·g-1The pore size is 15 nm-50 nm, and the pore volume is 0.1cm3·g-1～1.5cm3·g-1The size of the noble metal nano particles is 1-5 nm, and the noble metal nano particles are uniform in size and highly dispersed.
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