CN109289838B - Titanium dioxide loaded monatomic platinum catalyst prepared by topology conversion method and method - Google Patents
Titanium dioxide loaded monatomic platinum catalyst prepared by topology conversion method and method Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 31
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 27
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 19
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004327 boric acid Substances 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000007547 defect Effects 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 230000009466 transformation Effects 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010335 hydrothermal treatment Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 4
- 229910021650 platinized titanium dioxide Inorganic materials 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- BJAHYFBKECKXCD-UHFFFAOYSA-N O(F)F.N Chemical compound O(F)F.N BJAHYFBKECKXCD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000011426 transformation method Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- -1 salt ions Chemical class 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000004075 alteration Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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Abstract
The invention discloses a titanium dioxide negative prepared by a topology conversion methodA monatomic platinum-supported catalyst and a method for preparing a monatomic platinum-supported titanium dioxide catalyst with a large specific surface area by using a topological transformation method, wherein the catalyst has a specific surface area of 130-132 m2The catalyst has a pore diameter of 14-16 nm, a plurality of burrs are arranged on the hollow surface inside the catalyst, and the catalyst has high catalytic stability and catalytic activity. The preparation method comprises the steps of firstly, respectively taking tetrabutyl titanate and ammonium fluoride as a titanium source and a fluorine source, and synthesizing an intermediate NH by a hydrothermal method4TiOF3Further treatment of the sample obtained with boric acid, NH4TiOF3Pt is loaded in the process of converting into titanium dioxide through topological transformation, and oxygen defects and large specific surface area generated in the conversion process enable Pt to be stably anchored on the surface of the titanium dioxide. And calcining the platinum in the nitrogen atmosphere to further stably load the platinum on the titanium dioxide, thereby reducing the loss of the platinum in the catalytic process. The obtained titanium dioxide supported monatomic platinum catalyst has higher conversion rate for carbon monoxide oxidation at low temperature.
Description
Technical Field
The invention belongs to the field of materials science, and relates to a noble metal monatomic catalyst, in particular to a titanium dioxide loaded monatomic platinum catalyst with a large specific surface area, which is prepared by a brand-new topology conversion method and can be applied to the oxidation of carbon monoxide at low temperature.
Background
Supported metal catalysts are widely used in industrial processes due to their high activity and high stability in many important chemical reactions. The traditional supported metal catalyst is that metal nano particles are dispersed on a carrier, and the catalyst cannot meet the requirements of people due to the high cost of noble metals. In order to optimize the activity and the atom utilization rate of each metal active component, researchers put forward the concept of a single-atom catalyst, and the single-atom catalyst is prepared by the composition work of the billow topic in 2011. Monatomic catalysts have some advantageous properties different from other catalysts, such as quantum size effects, unsaturated coordination environments, dramatically increased surface free energy, and metal-support interactions. Meanwhile, the monatomic catalyst has the defect that when the metal particles are as small as the atomic level, agglomeration is easily caused during preparation and reaction due to the sharp increase of the surface energy of the metal, so that the catalyst is deactivated.
At present, the preparation method of the monatomic catalyst mainly comprises an impregnation method, a coprecipitation method, a photochemical method, an atomic layer deposition method, a mass separation soft landing method and the like. The catalyst system extends from Rh to noble metals such as Au, Pt, Pd and Ir, and the substrate mainly comprises metal, metal oxide, two-dimensional material graphene, hexagonal boron nitride and the like. However, the reported content of metals in the monatomic catalyst is low due to the high surface energy of the metal surface, thereby limiting the wide application of the monatomic catalyst. Theoretically, avoiding agglomeration and increasing metal loading can be started from the following aspects: one is to enhance the interaction between the metal and the support, and the other is to increase the surface area of the support.
To avoid agglomeration and to increase the metal loading, a great deal of research has been conducted on the preparation of monatomic catalysts. The single-atom catalyst Pt1/FeO is prepared by the billow team of the large connected objects of the Chinese academy of sciences for the first time by adopting a coprecipitation methodxAnd Ir1/FeOx(ii) a Pt/theta-Al is obtained by Narula group in national laboratory of Oak Ridge in America by sol-gel method2O3A monatomic catalyst; the Ag-HMO monatomic catalyst prepared by the reverse Ostwald curing method in Lijunhua university and Thankifu university of Compound Dan and the like uses monatomic Ag as a catalytic active center, realizes high-efficiency catalytic formaldehyde oxidation, and achieves the purpose of eliminating harmful gas formaldehyde.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a titanium dioxide catalyst which is loaded with monatomic platinum and has a large specific surface area and is prepared by using a topology conversion method and a preparation method thereof. The method has the advantages of simple preparation process, low price of reactants and no pollution, and can increase the surface area of the carrier and the interaction between the metal and the carrier. The obtained titanium dioxide supported monatomic platinum catalyst has higher conversion rate for carbon monoxide oxidation at low temperature.
The technical purpose of the invention is realized by the following technical scheme:
dioxide prepared by topology conversionTitanium supported monatomic platinum catalyst, which is a monatomic Pt supported catalyst through TiO2Defects generated during the topological transformation of the support are trapped in the TiO2Forming a high-dispersity monatomic catalyst on a carrier, wherein the specific surface area of the catalyst is 130-132 m2The pore diameter is 14-16 nm, and the inner hollow surface of the nano block has a plurality of burrs and oxygen defects.
The preparation method of the titanium dioxide supported monatomic platinum catalyst comprises the following steps:
(1) weighing ammonium fluoride according to the molar ratio of fluorine to titanium of 1: 1-4, adding tetrabutyl titanate (TOBT) into glacial acetic acid according to the volume ratio of 1: 50-53, changing the solution from colorless to milky white, adding the weighed ammonium fluoride solid, and gradually adding isopropanol to completely dissolve the ammonium fluoride;
(2) uniformly stirring the solution obtained in the step (1), pouring the solution into a reaction kettle, sealing, screwing and pressing the reaction kettle, putting the reaction kettle into a constant-temperature heating box, and carrying out hydrothermal treatment at the temperature of 150-180 ℃ for 12-15 hours; cooling to room temperature, centrifuging, washing, drying at 60-80 ℃ in vacuum, and grinding to obtain white mesoscopic crystal ammonium oxyfluoride titanate powder;
(3) adding boric acid solid into deionized water to prepare 0.45-0.65 mol/L H3BO3Solution, denoted as solution a; weighing ammonium fluorooxytitanate powder, adding a chloroplatinic acid solution which is marked as a solution B and stands for 2-3 hours under the condition of keeping out of the sun according to the mass ratio of platinum to titanium dioxide in the product of 0.5-3%; the purpose is to make metal salt ions fully adsorbed on the surface and in the internal pores of the ammonium fluorooxytitanate crystal;
(4) mixing the solution A and the solution B, stirring in a water bath at 50-80 ℃ for 3-4 h, cooling to room temperature, centrifuging, washing, drying in vacuum at 60-80 ℃, and grinding to obtain offwhite platinum-loaded titanium dioxide, which is recorded as Pt/TiO2；
(5) Roasting the product obtained in the step (4) in a tubular furnace under the nitrogen atmosphere at the temperature of 450-500 ℃ for 4-6 hours, and recording the obtained product as Pt/TiO2-C。
Further, in the step (3), the boric acid is excessive, so that the ammonium fluorooxytitanate can be completely converted into titanium dioxide; when the amount of boric acid is relatively small, the composite material of ammonium fluorooxytitanate and titanium dioxide is obtained, and the catalytic effect of the obtained catalyst is poor because the ammonium fluorooxytitanate is unstable and has a smaller specific surface area compared with the titanium dioxide.
The invention has the beneficial effects that: the invention provides a technology for preparing the monatomic catalyst, which has the advantages of very mild conditions, simple and convenient operation, environmental protection and easily controlled reaction process, and can load platinum on titanium dioxide in the process of converting ammonium fluoroxytitanate into the titanium dioxide.
Drawings
FIG. 1 is an X-ray diffraction pattern of a product prepared in the present invention;
FIG. 2 is a scanning electron microscope image of the product prepared in the present invention, (a) is the obtained massive precursor ammonium fluorooxytitanate, and (b) is the catalyst of titanium dioxide supported with monoatomic platinum;
FIG. 3 is a transmission electron micrograph and a high power spherical aberration transmission electron micrograph of the product prepared in the present invention, (a) is a transmission electron micrograph of a catalyst in which monoatomic platinum is supported on titanium dioxide, and the insets are a lattice spacing micrograph of the catalyst, and (b) is a high power spherical aberration transmission electron micrograph of a catalyst in which monoatomic platinum is supported on titanium dioxide;
FIG. 4 is an X-ray photoelectron spectrum of a product prepared in the present invention, (a) is Ti 2p, (b) is O1s, and (c) is Pt 4 f;
FIG. 5 is a graph illustrating the use of the products produced in the present invention in the oxidation of carbon monoxide;
Detailed Description
The present invention is further illustrated by the following specific examples and figures, it should be noted that the following description is intended to illustrate the invention and not to limit the content thereof.
Example 1
0.33g of ammonium fluoride was weighed into a beakerAdding glacial acetic acid 40m L, adding tetrabutyl titanate (TOBT) 770 mu L while stirring, pouring ammonium fluoride solid weighed in advance after the solution is turbid, adding isopropanol 5m L, stirring for 15min, pouring into a reaction kettle, sealing, screwing and compacting the reaction kettle, putting into a constant-temperature heating box, carrying out hydrothermal treatment at 150 ℃ for 12h, cooling to room temperature, carrying out centrifugal washing, and carrying out vacuum drying at 60 ℃ for 6h to obtain NH4TiOF31.266g of boric acid solid was added to 40m L of deionized water to make 0.5 mol/L of H3BO3Solution, weigh 0.3g of NH4TiOF3Placing the powder in a beaker, adding 181 mu L of chloroplatinic acid solution by using a pipette gun, and placing the solution for 2 hours in a dark condition so as to ensure that metal salt ions are fully adsorbed on the surface and the internal pores of the ammonium fluorooxytitanate crystal, adding the impregnated sample into 0.5 mol/L of H prepared in advance3BO3In the solution, water bath is carried out for 3h at the temperature of 60 ℃. Centrifugally washing, and drying for 6h under vacuum at 60 ℃ to obtain Pt/TiO with the Pt mass fraction of 0.1%2A catalyst. The dried catalyst is put into a tubular furnace to be roasted under the roasting condition of nitrogen atmosphere at 450 ℃ for 4 hours, and the obtained product is recorded as 0.1 percent Pt/TiO2-C。
Example 2
Weighing 0.33g of ammonium fluoride, adding 40m L m glacial acetic acid into a beaker, adding 770 mu L of tetrabutyl titanate (TOBT) while stirring, pouring ammonium fluoride solid weighed in advance after the solution is turbid, then adding 5m L of isopropanol, stirring for 15min, pouring into a reaction kettle, sealing, screwing and compacting the reaction kettle, putting into a constant-temperature heating box, carrying out hydrothermal treatment at 150 ℃ for 12h, cooling to room temperature after the hydrothermal treatment, carrying out centrifugal washing, and carrying out vacuum drying at 60 ℃ for 6h to obtain NH4TiOF31.266g of boric acid solid was added to 40m L of deionized water to make 0.5 mol/L of H3BO3Solution, weigh 0.3g of NH4TiOF3Placing the powder in a beaker, adding 906 mu L chloroplatinic acid solution by using a pipette gun, and placing the beaker under a dark condition for 2 hours to ensure that metal salt ions are fully adsorbed on the surface and the internal pores of the ammonium fluorooxytitanate crystal, adding the soaked sample into 0.5 mol/L H prepared in advance3BO3In the solution, water bath is carried out for 3h at the temperature of 60 ℃. Centrifugal washing at 60 deg.CVacuum drying for 6h to obtain Pt/TiO with the Pt mass fraction of 0.5%2A catalyst. The dried catalyst is put into a tubular furnace to be roasted under the roasting condition of nitrogen atmosphere at 450 ℃ for 4 hours, and the obtained product is recorded as 0.5 percent Pt/TiO2-C。
Example 3
Weighing 0.33g of ammonium fluoride, adding 40m L m glacial acetic acid into a beaker, adding 770 mu L of tetrabutyl titanate (TOBT) while stirring, pouring ammonium fluoride solid weighed in advance after the solution is turbid, then adding 5m L of isopropanol, stirring for 15min, pouring into a reaction kettle, sealing, screwing and compacting the reaction kettle, putting into a constant-temperature heating box, carrying out hydrothermal treatment at 150 ℃ for 12h, cooling to room temperature after the hydrothermal treatment, carrying out centrifugal washing, and carrying out vacuum drying at 60 ℃ for 6h to obtain NH4TiOF31.266g of boric acid solid was added to 40m L of deionized water to make 0.5 mol/L of H3BO3Solution, weigh 0.3g of NH4TiOF3Placing the powder in a beaker, adding 181 mu L of chloroplatinic acid solution by using a pipette gun, and placing the solution for 2 hours in a dark condition so as to ensure that metal salt ions are fully adsorbed on the surface and the internal pores of the ammonium fluorooxytitanate crystal, adding the impregnated sample into 0.5 mol/L of H prepared in advance3BO3In the solution, water bath is carried out for 3h at the temperature of 60 ℃. Centrifugally washing, and drying for 6h under vacuum at 60 ℃ to obtain Pt/TiO with the Pt mass fraction of 1%2A catalyst. The dried catalyst is put into a tubular furnace to be roasted under the roasting condition of nitrogen atmosphere at 450 ℃ for 4 hours, and the obtained product is recorded as 1 percent Pt/TiO2-C。
Example 4
Weighing 0.33g of ammonium fluoride, adding 40m L m glacial acetic acid into a beaker, adding 770 mu L of tetrabutyl titanate (TOBT) while stirring, pouring ammonium fluoride solid weighed in advance after the solution is turbid, then adding 5m L of isopropanol, stirring for 15min, pouring into a reaction kettle, sealing, screwing and compacting the reaction kettle, putting into a constant-temperature heating box, carrying out hydrothermal treatment at 150 ℃ for 12h, cooling to room temperature after the hydrothermal treatment, carrying out centrifugal washing, and carrying out vacuum drying at 60 ℃ for 6h to obtain NH4TiOF31.266g of boric acid solid was added to 40m L of deionized water to make 0.5 mol/L of H3BO3Solution, weigh 0.3g of NH4TiOF3Placing the powder in a beaker, adding 5.43m L m chloroplatinic acid solution by using a pipette, and placing the beaker under a dark condition for 2H to ensure that metal salt ions are fully adsorbed on the surface and the inner pores of the ammonium fluorooxytitanate crystal, adding the impregnated sample into 0.5 mol/L H prepared in advance3BO3In the solution, water bath is carried out for 3h at the temperature of 60 ℃. Centrifugally washing, and drying for 6h under vacuum at 60 ℃ to obtain Pt/TiO with the Pt mass fraction of 3%2A catalyst. The dried catalyst is put into a tubular furnace to be roasted under the roasting condition of nitrogen atmosphere at 450 ℃ for 4 hours, and the obtained product is recorded as 3 percent Pt/TiO2-C。
Example 5
Weighing 0.33g of ammonium fluoride, adding 40m L m glacial acetic acid into a beaker, adding 770 mu L of tetrabutyl titanate (TOBT) while stirring, pouring ammonium fluoride solid weighed in advance after the solution is turbid, then adding 5m L of isopropanol, stirring for 15min, pouring into a reaction kettle, sealing, screwing and compacting the reaction kettle, putting into a constant-temperature heating box, carrying out hydrothermal treatment at 150 ℃ for 12h, cooling to room temperature after the hydrothermal treatment, carrying out centrifugal washing, and carrying out vacuum drying at 60 ℃ for 6h to obtain NH4TiOF31.266g of boric acid solid was added to 40m L of deionized water to make 0.5 mol/L of H3BO3Solution, weigh 0.3g of NH4TiOF3Placing the powder in a beaker, adding 181 mu L of chloroplatinic acid solution by using a pipette gun, and placing the solution for 2 hours in a dark condition so as to ensure that metal salt ions are fully adsorbed on the surface and the internal pores of the ammonium fluorooxytitanate crystal, adding the impregnated sample into 0.5 mol/L of H prepared in advance3BO3In the solution, the mixture is bathed for 3 hours at 80 ℃. Centrifugally washing, and drying for 6h under vacuum at 60 ℃ to obtain Pt/TiO with the Pt mass fraction of 3%2A catalyst. The dried catalyst is put into a tubular furnace to be roasted under the roasting condition of nitrogen atmosphere at 450 ℃ for 4 hours, and the obtained product is recorded as 1 percent Pt/TiO2-C。
Example 6
0.33g of ammonium fluoride is weighed, 40m L m glacial acetic acid is added into a beaker, 770 μ L of tetrabutyl titanate (TOBT) is added with stirring, ammonium fluoride solid weighed in advance is poured after the solution is turbid, then 5m L of isopropanol is added, stirring is carried out for 15min, and the mixture is stirredPouring the mixture into a reaction kettle, sealing, screwing and pressing the reaction kettle, putting the reaction kettle into a constant-temperature heating box, and carrying out hydrothermal treatment for 12 hours at the temperature of 150 ℃. Cooling to room temperature after hydrothermal treatment, centrifugally washing, and vacuum drying at 60 ℃ for 6h to obtain NH4TiOF31.266g of boric acid solid was added to 40m L of deionized water to make 0.5 mol/L of H3BO3Solution, weigh 0.3g of NH4TiOF3Placing the powder in a beaker, adding 181 mu L of chloroplatinic acid solution by using a pipette gun, and placing the solution for 2 hours in a dark condition so as to ensure that metal salt ions are fully adsorbed on the surface and the internal pores of the ammonium fluorooxytitanate crystal, adding the impregnated sample into 0.55 mol/L of H prepared in advance3BO3In the solution, the mixture is bathed for 3 hours at 80 ℃. Centrifugally washing, and drying for 6h under vacuum at 60 ℃ to obtain Pt/TiO with the Pt mass fraction of 3%2A catalyst. The dried catalyst is put into a tubular furnace to be roasted under the roasting condition of nitrogen atmosphere at 450 ℃ for 4 hours, and the obtained product is recorded as 1 percent Pt/TiO2-C。
Claims (2)
1. The preparation method of the titanium dioxide loaded monatomic platinum catalyst prepared by the topology conversion method is characterized by comprising the following steps:
(1) weighing ammonium fluoride according to the molar ratio of fluorine to titanium of 1: 1-4, adding tetrabutyl titanate (TOBT) into glacial acetic acid according to the volume ratio of 1: 50-53, changing the solution from colorless to milky white, adding the weighed ammonium fluoride solid, and gradually adding isopropanol to completely dissolve the ammonium fluoride;
(2) uniformly stirring the solution obtained in the step (1), pouring the solution into a reaction kettle, sealing, screwing and pressing the reaction kettle, putting the reaction kettle into a constant-temperature heating box, and carrying out hydrothermal treatment at the temperature of 150-180 ℃ for 12-15 hours; cooling to room temperature, centrifuging, washing, drying at 60-80 ℃ in vacuum, and grinding to obtain white mesoscopic crystal ammonium oxyfluoride titanate powder;
(3) adding boric acid solid into deionized water to prepare 0.45-0.65 mol/L H3BO3Solution, denoted as solution a; weighing ammonium fluorooxytitanate powder, adding a chloroplatinic acid solution which is marked as a solution B and stands for 2-3 hours under the condition of keeping out of the sun according to the mass ratio of platinum to titanium dioxide in the product of 0.5-3%;
(4) mixing the solution A and the solution B, stirring in a water bath at 50-80 ℃ for 3-4 h, cooling to room temperature, centrifuging, washing, drying in vacuum at 60-80 ℃, and grinding to obtain offwhite platinum-loaded titanium dioxide, which is recorded as Pt/TiO2；
(5) Roasting the product obtained in the step (4) in a tubular furnace under the nitrogen atmosphere at the temperature of 450-500 ℃ for 4-6 hours, and recording the obtained product as Pt/TiO2C the catalyst is a monoatomic Pt by TiO2Defects generated during the topological transformation of the support are trapped in the TiO2Forming a high-dispersity monatomic catalyst on a carrier, wherein the specific surface area of the catalyst is 130-132 m2The pore diameter is 14-16 nm, and the inner hollow surface of the nano block is provided with burrs and has oxygen defects.
2. The method for preparing a titanium dioxide supported monatomic platinum catalyst as set forth in claim 1, wherein the boric acid is in excess in the step (3) to ensure that the ammonium fluorooxytitanate can be completely converted into titanium dioxide.
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| CN107552030A (en) * | 2017-09-30 | 2018-01-09 | 大连理工大学 | One kind has the hollow burr cube structure titania nanoparticles of more defect Fluorin dopeds and preparation method |
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| CN107552030A (en) * | 2017-09-30 | 2018-01-09 | 大连理工大学 | One kind has the hollow burr cube structure titania nanoparticles of more defect Fluorin dopeds and preparation method |
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| A Facile Synthesis of Uniform NH4TiOF3 Mesocrystals and Their Conversion to TiO2 Mesocrystals;Lei Zhou等;《J. AM. CHEM. SOC.》;20080109;第130卷;第1309-1320页 * |
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