CN117899916A - Porous heterojunction composite photocatalyst and preparation method and application thereof - Google Patents
Porous heterojunction composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 12
- 229930195729 fatty acid Natural products 0.000 claims abstract description 12
- 239000000194 fatty acid Substances 0.000 claims abstract description 12
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 230000002195 synergetic effect Effects 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 85
- 239000000843 powder Substances 0.000 claims description 59
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 claims description 40
- 239000002105 nanoparticle Substances 0.000 claims description 30
- 229910052697 platinum Inorganic materials 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 24
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 5
- 238000002256 photodeposition Methods 0.000 claims description 5
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- SLIOYUPLNYLSSR-UHFFFAOYSA-J tetrachloroplatinum;hydrate;dihydrochloride Chemical compound O.Cl.Cl.Cl[Pt](Cl)(Cl)Cl SLIOYUPLNYLSSR-UHFFFAOYSA-J 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000010748 Photoabsorption Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000011259 mixed solution Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- 238000005406 washing Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000006555 catalytic reaction Methods 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 235000021355 Stearic acid Nutrition 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- 239000008117 stearic acid Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 238000000151 deposition Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 11
- 238000011049 filling Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000010926 purge Methods 0.000 description 11
- 239000011949 solid catalyst Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- 239000004408 titanium dioxide Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Abstract
The invention discloses a porous heterojunction composite photocatalyst, a preparation method and application thereof. The Pt/TiO 2-C3NX catalyst has excellent photo-thermal catalytic performance, strong photo-absorption capability, wide photo-catalytic response range, more excellent photo-generated electron-hole separation capability under photo-thermal synergistic catalytic condition, and extremely high application value in the field of photo-thermal synergistic catalytic fatty acid hydrogenation.
Description
Technical Field
The invention relates to a heterojunction composite material and a preparation method and application thereof, in particular to a porous heterojunction composite photocatalyst and a preparation method and application thereof.
Background
With the rapid development of socioeconomic performance, environmental problems caused by the shortage of conventional energy and the consumption of primary energy are increasingly prominent, and the consumption of fossil energy is increasing, so that it is urgent to find a green substitute for fossil energy. Although fatty acids widely existing in nature can be efficiently converted into long paraffins to produce high-value chemicals such as aviation kerosene by conventional catalytic means such as thermocatalysis, the application of the catalyst is greatly limited because the temperature required for thermocatalysis is high, the hydrogen pressure is high, and aggregation of active metals easily occurs during the reaction, so that the catalyst activity is reduced. The process of converting the photocatalytic fatty acid into long-chain alkane has the advantages of environment friendliness, low energy consumption, safe process, economic sustainability and the like, however, in the process of hydrogenating the photocatalytic fatty acid, due to serious photo-generated carrier recombination and single band response to light, the single-component photocatalyst such as TiO 2 and the like, the efficiency of hydrogenating the photocatalytic fatty acid is lower. In recent years, although many methods for improving the catalytic activity of the catalyst have been proposed, the catalytic efficiency of the photocatalyst is still low, and thus, there is a need to explore a simple and effective preparation method and use other means such as a thermal field to realize the hydroconversion of catalytic fatty acids.
Disclosure of Invention
The invention aims to: the invention aims to provide a porous heterojunction composite photocatalyst for photo-thermal catalysis of fatty acid hydrogenation reaction; the invention also aims at providing a preparation method of the porous heterojunction photocatalyst; the invention also aims to provide an application of the porous heterojunction photocatalyst in photo-thermal catalytic fatty acid hydrogenation reaction.
The technical scheme is as follows: the preparation method of the porous heterojunction photocatalyst comprises the following steps:
(1) Mixing MIL-125 with a carbon nitride precursor, and then calcining the mixed solid;
(2) Dispersing the powder calcined in the step (1) in a solvent, adding a metal precursor solution, uniformly mixing, and performing photo-deposition treatment to obtain a suspension;
(3) And (3) centrifugally separating and drying the suspension to obtain the Pt/TiO 2-C3Nx heterojunction composite photocatalyst.
Further, in the step (1), the mass ratio of MILs-125 to graphite phase carbon nitride precursor is 10:1-1: within 10; the carbon nitride precursor is one of melamine, urea, dicyandiamide or 3-amino-1, 2, 4-triazole; the temperature rising rate of calcination is between 1 ℃/min and 20 ℃/min; the corresponding temperature is between 300 ℃ and 600 ℃; the calcination time is between 10min and 10 h.
Further, in the step (2), the platinum precursor is at least one of chloroplatinic acid, chloroplatinic acid polymer, potassium chloroplatinate or other soluble salts of chloroplatinic acid, the mass ratio of metal to calcined powder is 0.1-5wt%, and the photo-deposition treatment time is 10-300 min, preferably 30-120 min.
The catalyst prepared by the method is a porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles, and the specific surface area of the catalyst is more than 50m 2/g.
The prepared porous titanium dioxide-carbon nitride heterojunction composite material loaded with the platinum nano particles can be applied to Yu Guangre catalytic fatty acid hydrogenation reaction.
The specific operation of the photo-thermal catalytic fatty acid hydrogenation reaction is as follows: dispersing a certain amount of prepared porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles in n-hexane, then adding a certain amount of reactant stearic acid, and adding the mixed solution into a photo-thermal reaction device. And (3) introducing nitrogen to empty the air in the reaction kettle, and finally, introducing hydrogen to the reaction pressure. And after the photo-thermal reaction kettle is heated to the corresponding temperature, a light source is turned on, and the corresponding reaction time is irradiated. After the reaction, the reaction product was collected and ready for further treatment.
The hydrogen pressure range of the photo-thermal catalytic reaction is between 0.1MPa and 5MPa, the reaction time range is between 0.5h and 10h, the reaction temperature is more than 50 ℃, and the mass ratio of the photo-catalyst to the reaction substance is between 0.1wt% and 50 wt%.
According to the invention, the porous titanium dioxide carbon nitride heterojunction composite material loaded with the platinum nano particles is constructed, and enough energy is provided to cross band gap energy in a photo-thermal combination mode, so that the generation of photo-generated electrons and holes is promoted, the service life of carriers is prolonged, and the photocatalysis efficiency of Pt/TiO 2-g-C3Nx is improved; the light absorption range of the semiconductor catalyst can be widened by loading metal and constructing heterojunction, the response capability of the catalyst under visible light is enhanced, and the separation efficiency of photo-generated electrons and photo-induced holes can be further improved by loading noble metal.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) The Pt/TiO 2-C3NX catalyst has excellent photo-thermal catalysis performance, strong photo-absorption capability and wide photo-catalytic response range, has more excellent photo-generated electron-hole separation capability under the photo-thermal synergistic catalysis condition, and has extremely high application value in the field of photo-thermal synergistic catalysis of fatty acid hydrogenation;
(2) According to the preparation method, the titanium dioxide-carbon nitride heterojunction composite material is prepared through a calcination method, and finally, the platinum metal is loaded through a photo-deposition method, so that the preparation process is simple, raw materials are easy to obtain, and the obtained catalytic material has excellent photo-thermal catalytic performance.
Drawings
FIG. 1 is an SEM image of (a) MIL-125, (b) a Pt nanoparticle-loaded porous titania graphite-phase carbon nitride heterojunction composite material prepared in example 1;
fig. 2 is an XRD pattern of the Pt nanoparticle-loaded porous titania graphite-phase carbon nitride heterojunction composite material prepared in example 1.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
The preparation method of the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles comprises the following steps:
s1, taking 1gMIL-125, mixing MIL-125 with a graphite phase carbon nitride precursor (melamine) according to a mass ratio of 1:3, mixing, then placing the mixed solid in a tube furnace, heating to 550 ℃ at 5 ℃/min, and calcining for 4 hours to obtain light yellow powder.
S2, dispersing 0.2g of the yellow powder obtained in the step S1 in 50mL of deionized water by ultrasonic, adding a certain mass of potassium chloroplatinite into the solution to ensure that the mass ratio of Pt metal to the yellow powder is 0.5wt%, and stirring the solution for 3 hours to uniformly mix the Pt metal and the yellow powder.
S3, then placing the mixed solution under a light source for light deposition for 120min. And then centrifugally separating the obtained suspension, washing the solid with ethanol for 3 times, washing with deionized water for 3 times to obtain a solid catalyst, and drying to obtain powder which is the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles.
The porous titanium dioxide-carbon nitride heterojunction composite material prepared according to the above steps was taken to disperse 0.05g in 25mL of n-hexane, followed by adding 0.119g of stearic acid, and the mixed solution was added into a photo-thermal catalytic reaction kettle. And (3) introducing nitrogen, purging for several times, and then filling hydrogen to 0.5MPa. When the temperature of the reaction kettle is raised to 80 ℃, a light source is turned on, the light source irradiates for two hours, reactants are collected and centrifugally filtered, and the supernatant is taken for further analysis.
Example 2
The preparation method of the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles comprises the following steps:
s1, taking 1.33gMIL-125, and mixing MIL-125 with a graphite phase carbon nitride precursor (melamine) according to a mass ratio of 1:2, then placing the mixed solid in a tube furnace, heating to 550 ℃ at 5 ℃/min, and calcining for 4 hours to obtain light yellow powder.
S2, dispersing 0.2g of the yellow powder obtained in the step S1 in 50mL of deionized water by ultrasonic, adding a certain mass of potassium chloroplatinite into the solution to make the mass ratio of Pt relative to the yellow powder be 0.5wt%, and stirring the solution for 3h to uniformly mix the Pt and the yellow powder.
S3, then placing the mixed solution under a light source for light deposition for 120min. And then centrifugally separating the obtained suspension, washing the solid with ethanol for 3 times, washing with deionized water for 3 times to obtain a solid catalyst, and drying to obtain powder which is the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles.
The porous titanium dioxide-carbon nitride heterojunction composite material prepared according to the above steps was taken to disperse 0.05g in 25mL of n-hexane, followed by adding 0.119g of stearic acid, and the mixed solution was added into a photo-thermal catalytic reaction kettle. And (3) introducing nitrogen, purging for several times, and then filling hydrogen to 0.5MPa. When the temperature of the reaction kettle is raised to 80 ℃, a light source is turned on, the light source irradiates for two hours, reactants are collected and centrifugally filtered, and the supernatant is taken for further analysis.
Example 3
The preparation method of the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles comprises the following steps:
S1, taking 2gMIL-125, and mixing MIL-125 with a graphite phase carbon nitride precursor (melamine) according to a mass ratio of 1:1, and then placing the mixed solid in a tube furnace, heating to 550 ℃ at 5 ℃/min, and calcining for 4 hours to obtain light yellow powder.
S2, dispersing 0.2g of the yellow powder obtained in the step S1 in 50mL of deionized water by ultrasonic, adding a certain mass of potassium chloroplatinite into the solution to make the mass ratio of Pt relative to the yellow powder be 0.5wt%, and stirring the solution for 3h to uniformly mix the Pt and the yellow powder.
S3, then placing the mixed solution under a light source for light deposition for 120min. And then centrifugally separating the obtained suspension, washing the solid with ethanol for 3 times, washing with deionized water for 3 times to obtain a solid catalyst, and drying to obtain powder which is the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles.
The porous titanium dioxide-carbon nitride heterojunction composite material prepared according to the above steps was taken to disperse 0.05g in 25mL of n-hexane, followed by adding 0.119g of stearic acid, and the mixed solution was added into a photo-thermal catalytic reaction kettle. And (3) introducing nitrogen, purging for several times, and then filling hydrogen to 0.5MPa. When the temperature of the reaction kettle is raised to 80 ℃, a light source is turned on, the light source irradiates for two hours, reactants are collected and centrifugally filtered, and the supernatant is taken for further analysis.
Example 4
The preparation method of the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles comprises the following steps:
S1, taking 2.66gMIL-125, and mixing MIL-125 with a graphite phase carbon nitride precursor (melamine) according to a mass ratio of 2:1, and then placing the mixed solid in a tube furnace, heating to 550 ℃ at 5 ℃/min, and calcining for 4 hours to obtain light yellow powder.
S2, dispersing 0.2g of the yellow powder obtained in the step S1 in 50mL of deionized water by ultrasonic, adding a certain mass of potassium chloroplatinite into the solution to make the mass ratio of Pt relative to the yellow powder be 0.5wt%, and stirring the solution for 3h to uniformly mix the Pt and the yellow powder.
S3, then placing the mixed solution under a light source for light deposition for 120min. And then centrifugally separating the obtained suspension, washing the solid with ethanol for 3 times, washing with deionized water for 3 times to obtain a solid catalyst, and drying to obtain powder which is the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles.
The porous titanium dioxide-carbon nitride heterojunction composite material prepared according to the above steps was taken to disperse 0.05g in 25mL of n-hexane, followed by adding 0.119g of stearic acid, and the mixed solution was added into a photo-thermal catalytic reaction kettle. And (3) introducing nitrogen, purging for several times, and then filling hydrogen to 0.5MPa. When the temperature of the reaction kettle is raised to 80 ℃, a light source is turned on, the light source irradiates for two hours, reactants are collected and centrifugally filtered, and the supernatant is taken for further analysis.
Example 5
The preparation method of the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles comprises the following steps:
S1, taking 3gMIL-125, and mixing MIL-125 with a graphite phase carbon nitride precursor (melamine) according to a mass ratio of 3:1, and then placing the mixed solid in a tube furnace, heating to 550 ℃ at 5 ℃/min, and calcining for 4 hours to obtain light yellow powder.
S2, dispersing 0.2g of the yellow powder obtained in the step S1 in 50mL of deionized water by ultrasonic, adding a certain mass of potassium chloroplatinite into the solution to make the mass ratio of Pt relative to the yellow powder be 0.5wt%, and stirring the solution for 3h to uniformly mix the Pt and the yellow powder.
S3, then placing the mixed solution under a light source for light deposition for 120min. And then centrifugally separating the obtained suspension, washing the solid with ethanol for 3 times, washing with deionized water for 3 times to obtain a solid catalyst, and drying to obtain powder which is the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles.
The porous titanium dioxide-carbon nitride heterojunction composite material prepared according to the above steps was taken to disperse 0.05g in 25mL of n-hexane, followed by adding 0.119g of stearic acid, and the mixed solution was added into a photo-thermal catalytic reaction kettle. And (3) introducing nitrogen, purging for several times, and then filling hydrogen to 0.5MPa. When the temperature of the reaction kettle is raised to 80 ℃, a light source is turned on, the light source irradiates for two hours, reactants are collected and centrifugally filtered, and the supernatant is taken for further analysis.
Example 6
The preparation method of the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles comprises the following steps:
S1, taking 2.66gMIL-125, and mixing MIL-125 with a graphite phase carbon nitride precursor (melamine) according to a mass ratio of 2:1, and then placing the mixed solid in a tube furnace, heating to 550 ℃ at 5 ℃/min, and calcining for 4 hours to obtain light yellow powder.
S2, dispersing 0.2g of the yellow powder obtained in the step S1 in 50mL of deionized water by ultrasonic, adding a certain mass of potassium chloroplatinite into the solution to make the mass ratio of Pt relative to the yellow powder be 0.1wt%, and stirring the solution for 3h to uniformly mix the Pt and the yellow powder.
S3, then placing the mixed solution under a light source for light deposition for 120min. And then centrifugally separating the obtained suspension, washing the solid with ethanol for 3 times, washing with deionized water for 3 times to obtain a solid catalyst, and drying to obtain powder which is the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles.
The porous titanium dioxide-carbon nitride heterojunction composite material prepared according to the above steps was taken to disperse 0.05g in 25mL of n-hexane, followed by adding 0.119g of stearic acid, and the mixed solution was added into a photo-thermal catalytic reaction kettle. And (3) introducing nitrogen, purging for several times, and then filling hydrogen to 0.5MPa. When the temperature of the reaction kettle is raised to 80 ℃, a light source is turned on, the light source irradiates for two hours, reactants are collected and centrifugally filtered, and the supernatant is taken for further analysis.
Example 7
The preparation method of the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles comprises the following steps:
S1, taking 2.66gMIL-125, and mixing MIL-125 with a graphite phase carbon nitride precursor (melamine) according to a mass ratio of 2:1, and then placing the mixed solid in a tube furnace, heating to 550 ℃ at 5 ℃/min, and calcining for 4 hours to obtain light yellow powder.
S2, dispersing 0.2g of the yellow powder obtained in the step S1 in 50mL of deionized water by ultrasonic, adding a certain mass of potassium chloroplatinite into the solution to make the mass ratio of Pt relative to the yellow powder be 0.3wt%, and stirring the solution for 3h to uniformly mix the Pt and the yellow powder.
S3, then placing the mixed solution under a light source for light deposition for 120min. And then centrifugally separating the obtained suspension, washing the solid with ethanol for 3 times, washing with deionized water for 3 times to obtain a solid catalyst, and drying to obtain powder which is the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles.
The porous titanium dioxide-carbon nitride heterojunction composite material prepared according to the above steps was taken to disperse 0.05g in 25mL of n-hexane, followed by adding 0.119g of stearic acid, and the mixed solution was added into a photo-thermal catalytic reaction kettle. And (3) introducing nitrogen, purging for several times, and then filling hydrogen to 0.5MPa. When the temperature of the reaction kettle is raised to 80 ℃, a light source is turned on, the light source irradiates for two hours, reactants are collected and centrifugally filtered, and the supernatant is taken for further analysis.
Example 8
The preparation method of the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles comprises the following steps:
S1, taking 2.66gMIL-125, and mixing MIL-125 with a graphite phase carbon nitride precursor (melamine) according to a mass ratio of 2:1, and then placing the mixed solid in a tube furnace, heating to 550 ℃ at 5 ℃/min, and calcining for 4 hours to obtain light yellow powder.
S2, dispersing 0.2g of the yellow powder obtained in the step S1 in 50mL of deionized water by ultrasonic, adding a certain mass of potassium chloroplatinite into the solution to make the mass ratio of Pt relative to the yellow powder be 0.5wt%, and stirring the solution for 3h to uniformly mix the Pt and the yellow powder.
S3, then placing the mixed solution under a light source for light deposition for 120min. And then centrifugally separating the obtained suspension, washing the solid with ethanol for 3 times, washing with deionized water for 3 times to obtain a solid catalyst, and drying to obtain powder which is the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles.
The porous titanium dioxide-carbon nitride heterojunction composite material prepared according to the above steps was taken to disperse 0.05g in 25mL of n-hexane, followed by adding 0.119g of stearic acid, and the mixed solution was added into a photo-thermal catalytic reaction kettle. And (3) introducing nitrogen, purging for several times, and then filling hydrogen to 0.5MPa. When the temperature of the reaction kettle is raised to 80 ℃, a light source is turned on, the light source irradiates for two hours, reactants are collected and centrifugally filtered, and the supernatant is taken for further analysis.
Example 9
The preparation method of the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles comprises the following steps:
S1, taking 2.66gMIL-125, and mixing MIL-125 with a graphite phase carbon nitride precursor (melamine) according to a mass ratio of 2:1, and then placing the mixed solid in a tube furnace, heating to 550 ℃ at 5 ℃/min, and calcining for 4 hours to obtain light yellow powder.
S2, dispersing 0.2g of the yellow powder obtained in the step S1 in 50mL of deionized water by ultrasonic, adding a certain mass of potassium chloroplatinite into the solution to ensure that the mass ratio of Pt metal to the yellow powder is 0.7wt%, and stirring the solution for 3 hours to uniformly mix the Pt metal and the yellow powder.
S3, then placing the mixed solution under a light source for light deposition for 120min. And then centrifugally separating the obtained suspension, washing the solid with ethanol for 3 times, washing with deionized water for 3 times to obtain a solid catalyst, and drying to obtain powder which is the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles.
The porous titanium dioxide-carbon nitride heterojunction composite material prepared according to the above steps was taken to disperse 0.05g in 25mL of n-hexane, followed by adding 0.119g of stearic acid, and the mixed solution was added into a photo-thermal catalytic reaction kettle. And (3) introducing nitrogen, purging for several times, and then filling hydrogen to 0.5MPa. When the temperature of the reaction kettle is raised to 80 ℃, a light source is turned on, the light source irradiates for two hours, reactants are collected and centrifugally filtered, and the supernatant is taken for further analysis.
Example 10
The preparation method of the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles comprises the following steps:
S1, taking 2.66gMIL-125, and mixing MIL-125 with a graphite phase carbon nitride precursor (melamine) according to a mass ratio of 2:1, and then placing the mixed solid in a tube furnace, heating to 550 ℃ at 5 ℃/min, and calcining for 4 hours to obtain light yellow powder.
S2, dispersing 0.2g of the yellow powder obtained in the step S1 in 50mL of deionized water by ultrasonic, adding a certain mass of potassium chloroplatinite into the solution to ensure that the mass ratio of Pt metal to the yellow powder is 0.9wt%, and stirring the solution for 3 hours to uniformly mix the Pt metal and the yellow powder.
S3, then placing the mixed solution under a light source for light deposition for 120min. And then centrifugally separating the obtained suspension, washing the solid with ethanol for 3 times, washing with deionized water for 3 times to obtain a solid catalyst, and drying to obtain powder which is the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles.
The porous titanium dioxide-carbon nitride heterojunction composite material prepared according to the above steps was taken to disperse 0.05g in 25mL of n-hexane, followed by adding 0.119g of stearic acid, and the mixed solution was added into a photo-thermal catalytic reaction kettle. And (3) introducing nitrogen, purging for several times, and then filling hydrogen to 0.5MPa. When the temperature of the reaction kettle is raised to 80 ℃, a light source is turned on, the light source irradiates for two hours, reactants are collected and centrifugally filtered, and the supernatant is taken for further analysis.
Example 11
The preparation method of the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles comprises the following steps:
s1, taking 2.66gMIL-125, mixing MIL-125 with a graphite phase carbon nitride precursor (3-amino-1, 2,4 triazole) according to a mass ratio of 2:1, and then placing the mixed solid in a tube furnace, heating to 550 ℃ at 5 ℃/min, and calcining for 4 hours to obtain light yellow powder.
S2, dispersing 0.2g of the yellow powder obtained in the step S1 in 50mL of deionized water by ultrasonic, adding a certain mass of potassium chloroplatinite into the solution to ensure that the mass ratio of Pt metal to the yellow powder is 0.5wt%, and stirring the solution for 3 hours to uniformly mix the Pt metal and the yellow powder.
S3, then placing the mixed solution under a light source for light deposition for 120min. And then centrifugally separating the obtained suspension, washing the solid with ethanol for 3 times, washing with deionized water for 3 times to obtain a solid catalyst, and drying to obtain powder which is the porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles.
The porous titanium dioxide-carbon nitride heterojunction composite material prepared according to the above steps was taken to disperse 0.05g in 25mL of n-hexane, followed by adding 0.119g of stearic acid, and the mixed solution was added into a photo-thermal catalytic reaction kettle. And (3) introducing nitrogen, purging for several times, and then filling hydrogen to 0.5MPa. When the temperature of the reaction kettle is raised to 80 ℃, a light source is turned on, the light source irradiates for two hours, reactants are collected and centrifugally filtered, and the supernatant is taken for further analysis.
As shown in fig. 1, a scanning electron microscope picture of the porous titanium dioxide-carbon nitride heterojunction composite material is shown, and as shown in fig. 1 (b), the calcined and synthesized porous titanium dioxide nano particles are attached to carbon nitride.
As shown in fig. 2, an X-ray diffraction image of the porous titania-carbon nitride heterojunction composite material is shown, wherein xT-yC represents a mass ratio of the porous titania precursor to the carbon nitride precursor as X: and y. It was observed that as the ratio of porous titanium dioxide to carbon nitride increased, the intensity of the characteristic diffraction peak (27.4 °) attributed to Jin Gongxiang titanium dioxide increased and the intensity of the diffraction characteristic peaks (26.6 ° and 44.7 °) of carbon nitride decreased.
The following table shows the reaction results of examples 1 to 11:
Claims (10)
1. The preparation method of the porous heterojunction composite photocatalyst is characterized by comprising the following steps of:
(1) Mixing MIL-125 with a carbon nitride precursor, and then calcining the mixed solid;
(2) Dispersing the powder calcined in the step (1) in a solvent, adding a metal precursor solution, uniformly mixing, and performing photo-deposition treatment to obtain a suspension;
(3) And (3) centrifugally separating and drying the suspension to obtain the Pt/TiO 2-C3Nx heterojunction composite photocatalyst.
2. The method for preparing a porous heterojunction composite photocatalyst as claimed in claim 1, wherein in the step (1), the mass ratio of MILs-125 to carbon nitride precursor is 10:1-1:10.
3. The method for preparing a porous heterojunction composite photocatalyst as claimed in claim 1, wherein the carbon nitride precursor in the step (1) is at least one of melamine, urea, dicyandiamide or 3-amino-1, 2, 4-triazole.
4. The method for preparing a porous heterojunction composite photocatalyst as claimed in claim 1, wherein the temperature rising rate of calcination in the step (1) is 1 ℃/min-30 ℃/min.
5. The method for preparing a porous heterojunction composite photocatalyst as claimed in claim 1, wherein the calcination temperature in the step (1) is 300-600 ℃ and the calcination time is 10min-10h.
6. The method for preparing a porous heterojunction composite photocatalyst as claimed in claim 1, wherein the metal precursor in the step (2) is at least one of chloroplatinic acid, chloroplatinic acid hydrate, potassium chloroplatinate or other chloroplatinic acid soluble salts.
7. The method for preparing a porous heterojunction composite photocatalyst as claimed in claim 1, wherein the mass ratio of the metal to the calcined powder in the step (2) is 0.1wt% to 5wt%.
8. The method for preparing a porous heterojunction composite photocatalyst as claimed in claim 1, wherein the photo-deposition treatment time in the step (2) is 10min-300min.
9. The porous heterojunction composite photocatalyst prepared by the preparation method of any one of claims 1-8, wherein the catalyst is a porous titanium dioxide-carbon nitride heterojunction composite material loaded with platinum nano particles, and the specific surface area of the catalyst is greater than 50m 2/g.
10. Use of the porous heterojunction composite photocatalyst of claim 9 in photo-thermal synergistic catalytic fatty acid hydroconversion.
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