CN111203261A - Specific three-layer stacked ternary composite catalyst and preparation method and application thereof - Google Patents
Specific three-layer stacked ternary composite catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 239000011206 ternary composite Substances 0.000 title abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 34
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 241000446313 Lamella Species 0.000 claims abstract description 5
- 230000020477 pH reduction Effects 0.000 claims abstract description 5
- 230000001737 promoting effect Effects 0.000 claims abstract description 5
- 239000011343 solid material Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 18
- 238000006731 degradation reaction Methods 0.000 claims description 18
- 235000015393 sodium molybdate Nutrition 0.000 claims description 18
- 239000011684 sodium molybdate Substances 0.000 claims description 18
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 18
- 239000006228 supernatant Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000015556 catabolic process Effects 0.000 claims description 16
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 16
- 238000005303 weighing Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- 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 description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- 229940043267 rhodamine b Drugs 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 238000011156 evaluation Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 6
- 238000000527 sonication Methods 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000002372 labelling Methods 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- 230000006798 recombination Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention relates to a specific three-layer stacked ternary composite catalyst, a preparation method and an application thereof, wherein the ternary composite catalyst is TiO2‑MoS2‑C3N4Wherein, MoS2Supported on TiO2On the (001) plane of (C), and layer C3N4Then is randomly attached to the MoS2Layer or TiO2(001) On the layer. The invention utilizes MoS2Replacing expensive noble metal, increasing contact area of the two in a two-dimensional layered structure, greatly promoting separation of electron hole pairs, and finally adding a lamella C formed after acidification treatment in an ultrasonic mode3N4To obtain the TiO stacked layer by layer2‑MoS2‑C3N4A three-way composite catalyst. TiO prepared by the invention2‑MoS2‑C3N4Is a multilayer stacked structure, the great contact area of the catalyst effectively improves the photocatalytic performance of the catalyst, and TiO is independently used2Or C3N42-3 times of the catalyst.
Description
Technical Field
The invention relates to a specific three-layer stacked ternary composite catalyst, a preparation method and application thereof, wherein (001) TiO is formed by controlling the preparation process2-MoS2On the basis of C3N4And exhibits a reduced rhodamine degradation under simulated sunlight conditions compared to the use of C alone3N4The catalytic efficiency is 2-4 times higher when the catalyst is used.
Background
In the current era, environmental pollution and energy crisis are two major problems which need to be solved urgently by researchers, and photocatalysis can prepare clean energy-hydrogen by decomposing water and can also degrade organic pollutants, so that the method is a novel technology with high efficiency, green and environmental protection, namely TiO2The most widely used catalyst among them. However, TiO2The photocatalytic efficiency is always limited by higher photogenerated electron and hole recombination rate and visible light nonresponsive characteristic, so TiO with high quantum efficiency and visible light response is developed2Is an important direction for the development of the field of photocatalysis
Recently, a large proportion of anatase TiO crystals exposing high energy (001) crystal planes2Is the focus of research, especially 2-dimensional layered anatase TiO2It has a great amount of reactive active sites, is a promising photocatalytic material, but is TiO excited by light2The generated electrons and holes are easily recombined, so that a noble metal is usually supported as a promoter to accelerate the separation of electron-hole pairs. Obviously, noble metals are expensive and are compatible with 2-dimensional TiO2Has a small contact surfaceThe wide use of such catalysts is greatly limited. The invention adopts two-dimensional MoS2To replace noble metals and compound C3N4To further improve the electron-hole separation efficiency and visible light response. In the preparation of the three-way composite catalyst, 2-dimensional layered TiO with exposed (001) crystal face is synthesized firstly2Then through a second hydrothermal reaction on the layered TiO2Upper load 2-dimensional MoS2Layer, finally, the prepared layer C is added3N4Ultrasonic dispersion and calcination under nitrogen to form the composite catalyst.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a specific three-layer stacked three-way composite catalyst.
Yet another object of the present invention is to: provides a preparation method of the specific three-layer stacked three-way composite catalyst product.
Yet another object of the present invention is to: provides an application of the product.
The purpose of the invention is realized by the following scheme: a specific three-layer stacked three-element composite catalyst is TiO2-MoS2-C3N4Wherein, MoS2Supported on TiO2On the (001) plane of (C), and layer C3N4Then is randomly attached to the MoS2Layer or TiO2(001) On the layer.
The invention also provides a preparation method of the specific three-layer stacked ternary composite catalyst, which utilizes MoS2Replacing expensive noble metal, increasing contact area of the two in a two-dimensional layered structure, greatly promoting separation of electron hole pairs, and finally adding a lamella C formed after acidification treatment in an ultrasonic mode3N4To obtain the TiO stacked layer by layer2-MoS2-C3N4The three-way composite catalyst comprises the following steps:
(1) taking 10ml of tetrabutyl titanate, putting the tetrabutyl titanate into a polytetrafluoroethylene beaker, stirring, weighing 1-5 ml of hydrofluoric acid, dropwise adding the hydrofluoric acid into the beaker, and continuously stirring for 30min, transferring the mixture into a 50ml hydrothermal kettle, preserving heat in a 200 ℃ oven for 24 hours, removing supernatant after the reaction is finished, washing the solid material with absolute ethyl alcohol and deionized water for multiple times, drying at 80 ℃ overnight, finally putting the solid material into a muffle furnace, calcining at 600 ℃ for 2 hours to remove fluorine atoms on the surface, wherein the obtained catalyst is marked as (001) -TiO2；
(2) Taking (001) -TiO2Putting 200mg of the mixture into a beaker, adding 20ml of deionized water, respectively weighing 0.1-0.03 g of sodium molybdate and adding thiourea of which the mass is 2 times that of the sodium molybdate into the solution, uniformly stirring the solution, then transferring the solution into a 50ml hydrothermal kettle, preserving the temperature for 24 hours at 200 ℃, removing supernatant after the reaction is finished, washing the solid material with absolute ethyl alcohol and deionized water for multiple times, drying the solid material at 80 ℃ overnight, and marking the obtained catalyst as TiO2-MoS2；
(3) A certain amount of melamine is taken into a crucible and calcined at a certain temperature and a certain heating rate to prepare C3N4Placing the mixture into concentrated hydrochloric acid for 2 hours, then carrying out ultrasonic treatment for 2 hours, washing the mixture for multiple times by using deionized water until the mixture is neutral, and drying the mixture at 80 ℃ overnight;
(4) taking TiO2-MoS2And C3N4In deionized water, the C3N4And TiO2-MoS2The mass ratio of (1: 0) to (1: 1), carrying out ultrasonic treatment for 5 hours, filtering, drying at 80 ℃ overnight, and finally calcining the dried sample for 2 hours in a nitrogen atmosphere to obtain a catalyst labeled as TiO2-MoS2-C3N4。
The invention provides application of a specific three-layer stacked ternary composite catalyst in degrading rhodamine under the condition of simulating sunlight.
The performance evaluation of the prepared catalyst is carried out in a photoreactor, and the specific process is as follows:
the reaction substrate is 15mg/L rhodamine B (RhB) solution, 50mg of catalyst is added into a quartz reaction tube with 100ml of RhB, the light source is a 300W mercury lamp, no filter is added, and the distance between the lamp and the reaction tube is 10 cm.
Firstly, placing a reaction tube in a reactor, stirring for 30min in the dark state to ensure that the catalyst is saturated by adsorption, then opening a mercury lamp, taking 5ml of solution every 20min, centrifuging at high speed, sucking supernatant liquid, placing the supernatant liquid in a cuvette, and detecting the absorbance of a substrate in an ultraviolet-visible spectrophotometer, wherein the detection wavelength is 552 nm.
Degradation rate simulation was performed using a pseudo first order kinetic equation:
co is the initial concentration of RhB, mol/L
t is the reaction time, min
C is the RhB concentration in the solution after the reaction time t, mol/L
k is the reaction rate, min-1
When degrading rhodamine, compared with TiO2Photoresponse under ultraviolet light only and C3N4Degradation efficiency of 20% only in 30min under simulated sunlight, TiO2-MoS2-C3N4The ternary composite catalyst shows excellent photoresponse and degradation efficiency is higher than that of C3N4The height is 2-4 times higher. The invention can prepare the TiO stacked layer by layer2-MoS2-C3N4Three-way composite catalyst for researching layered anatase TiO with large-proportion high-energy (001) crystal face exposed2Crystal face effect of (1) and (C)3N4The multi-element composition of the composite material has certain reference value.
TiO2-MoS2-C3N4Using MoS2Replacing expensive noble metal, increasing contact area of the two in a two-dimensional layered structure, greatly promoting separation of electron hole pairs, and finally adding a lamella C formed after acidification treatment in an ultrasonic mode3N4To obtain the TiO stacked layer by layer2-MoS2-C3N4A three-way composite catalyst. When degrading rhodamine, compared with TiO2Photoresponse under ultraviolet light only and C3N4Degradation efficiency of 20% only in 30min under simulated sunlight, TiO2-MoS2-C3N4The ternary composite catalyst shows excellent photoresponse and degradation efficiency is higher than that of C3N4The height is 2-4 times higher. The invention can prepare the TiO stacked layer by layer2-MoS2-C3N4Three-way composite catalyst for researching layered anatase TiO with large-proportion high-energy (001) crystal face exposed2Crystal face effect of (1) and (C)3N4The multi-element composition of the composite material has certain reference value.
The invention has the following advantages:
the invention uses MoS2The catalyst can replace noble metal as a cocatalyst, thereby effectively reducing the cost in large-scale use. Use of C in the invention3N4The composite material is used for forming a 'heterojunction' structure, and the separation efficiency of electron-hole pairs is further improved. TiO prepared by the invention2-MoS2-C3N4Is a multilayer stacked structure, the great contact area of the catalyst effectively improves the photocatalytic performance of the catalyst, and TiO is independently used2Or C3N42-3 times of the catalyst.
Detailed Description
The following examples illustrate the invention in detail: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and an operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
Example 1:
a specific three-layer stacked ternary composite catalyst using MoS2Replacing expensive noble metal, increasing contact area of the two in a two-dimensional layered structure, greatly promoting separation of electron hole pairs, and finally adding a lamella C formed after acidification treatment in an ultrasonic mode3N4To obtain the TiO stacked layer by layer2-MoS2-C3N4Three-way composite catalyst of, wherein, MoS2Supported on TiO2On the (001) plane of (C), and layer C3N4Then is randomly attached to the MoS2Layer or TiO2(001) On a layer as followsThe preparation method comprises the following steps:
(1) putting 10ml of tetrabutyl titanate in a polytetrafluoroethylene beaker, stirring, weighing 1.2ml of hydrofluoric acid, dropwise adding the hydrofluoric acid into the beaker, continuously stirring for 30min, transferring the stirred tetrabutyl titanate into a 50ml hydrothermal kettle after uniform stirring, keeping the temperature in a 200 ℃ oven for 24 h, removing supernatant after the reaction is finished, washing the solid material with absolute ethyl alcohol and deionized water for multiple times, drying the solid material at 80 ℃ overnight, finally putting the solid material into a muffle furnace, controlling the temperature rise speed to be 3 ℃, calcining the solid material at 600 ℃ for 2h to remove fluorine atoms on the surface, and marking the obtained catalyst as 1.2-TiO2；
(2) Taking 1.2-TiO2Putting 200mg into a beaker, adding 20ml of deionized water to obtain a solution, respectively weighing 30mg of sodium molybdate and 60mg of sodium molybdate, adding the sodium molybdate and the 60mg of sodium molybdate into the solution, uniformly stirring, transferring the solution into a 50ml hydrothermal kettle, preserving the temperature for 24 hours at 200 ℃, removing supernatant after the reaction is finished, washing the solid material with absolute ethyl alcohol and deionized water for multiple times, drying the solid material at 80 ℃ overnight, and marking the obtained catalyst as 1.2TiO2-MoS2；
(3) Placing 2g melamine in a crucible, calcining at 550 deg.C for 2h at a temperature rise rate of 5 deg.C, placing in concentrated hydrochloric acid for 2h, performing ultrasonic treatment for 2h, washing with deionized water for several times to neutrality, drying at 80 deg.C overnight, and marking as C3N4；
(4) 100mg of 1.2TiO are taken2-MoS2And 50mg of C3N4After 5 hours of sonication in deionized water, filtration and drying at 80 ℃ overnight, the dried sample was calcined at 500 ℃ under nitrogen for 2 hours, and the catalyst obtained was labeled 1.2TiO2--0.03MoS2-0.05C3N4。
The prepared photocatalyst sample is subjected to catalytic performance evaluation by the experimental conditions, and the degradation rate of rhodamine B within 40min is measured to be 76.5%, and the degradation efficiency k is 0.04753min-1。
Example 2:
a specific three-layer stacked ternary composite catalyst is prepared by the following steps:
the method comprises the following steps:
(1) putting 10ml of tetrabutyl titanate in a polytetrafluoroethylene beaker, stirring, weighing 2.4ml of hydrofluoric acid, dropwise adding the hydrofluoric acid into the beaker, continuously stirring for 30min, transferring the mixture into a hydrothermal kettle after uniformly stirring, keeping the temperature in a 200 ℃ oven for 24 hours, removing supernatant after the reaction is finished, washing the solid material with absolute ethyl alcohol and deionized water for multiple times, drying the solid material at 80 ℃ overnight, and finally putting the solid material in a muffle furnace, wherein the temperature rising speed is controlled to be 3 ℃. Calcining at 600 ℃ for 2h to remove surface fluorine atoms, and marking the obtained catalyst as 2.4-TiO2；
(2) Taking 2.4-TiO2Putting 200mg into a beaker, adding 20ml of deionized water to obtain a solution, respectively weighing 30mg of sodium molybdate and 60mg of thiourea, adding the sodium molybdate and the thiourea into the solution, uniformly stirring, transferring the solution into a 50ml hydrothermal kettle, preserving the temperature for 24 hours at 200 ℃, removing supernatant after the reaction is finished, washing the solid material with absolute ethyl alcohol and deionized water for multiple times, drying the solid material at 80 ℃ overnight, and marking the obtained catalyst as 2.4TiO2-MoS2；
(3) Placing 2g melamine in a crucible, calcining at 550 deg.C for 2h at a temperature rise rate of 5 deg.C, placing in concentrated hydrochloric acid for 2h, performing ultrasonic treatment for 2h, washing with deionized water for several times to neutrality, drying at 80 deg.C overnight, and marking as C3N4；
(4) 100mg of 2.4TiO are taken2-MoS2And 50mg of C3N4After 5 hours of sonication in deionized water, filtered and dried at 80 ℃ overnight, the dried sample was calcined at 500 ℃ under nitrogen for 2 hours, and the resulting catalyst was labeled 2.4TiO2-0.03MoS2-0.05C3N4。
The prepared photocatalyst sample is subjected to catalytic performance evaluation by the experimental conditions, and the degradation rate of rhodamine B within 40min is 86.6%, and the degradation efficiency k is 0.06311min-1。
Example 3:
a specific three-layer stacked ternary composite catalyst is prepared by the following steps:
(1) taking 10ml of tetrabutyl titanate, placing the tetrabutyl titanate in a polytetrafluoroethylene beaker, andstirring, weighing 2.4ml of hydrofluoric acid, dropwise adding the hydrofluoric acid into a beaker, continuously stirring for 30min, transferring the mixture into a hydrothermal kettle after uniform stirring, keeping the temperature in a 200 ℃ oven for 24 hours, removing supernatant after the reaction is finished, washing solid materials for multiple times by using absolute ethyl alcohol and deionized water, drying the solid materials at 80 ℃ overnight, finally putting the solid materials into a muffle furnace, controlling the temperature rise speed to be 3 ℃, calcining the solid materials at 600 ℃ for 2 hours to remove fluorine atoms on the surface, and marking the obtained catalyst as 2.4-TiO2；
(2) Taking (001) -TiO2Putting 200mg into a beaker, adding 20ml of deionized water to obtain a solution, respectively weighing 15mg of sodium molybdate and 30mg of thiourea, adding the sodium molybdate and the thiourea into the solution, uniformly stirring, transferring the solution into a 50ml hydrothermal kettle, preserving the temperature at 200 ℃ for 24 hours, removing supernatant after the reaction is finished, washing the solid material with absolute ethyl alcohol and deionized water for multiple times, drying the solid material at 80 ℃ overnight, and marking the obtained catalyst as 2.4TiO2-MoS2；
(3) Placing 2g melamine in a crucible, calcining at 550 deg.C for 2h at a temperature rise rate of 5 deg.C, placing in concentrated hydrochloric acid for 2h, performing ultrasonic treatment for 2h, washing with deionized water for several times to neutrality, drying at 80 deg.C overnight, and marking as C3N4；
(4) 100mg of 2.4TiO are taken2-MoS2And 50mg of C3N4After 5 hours of sonication in deionized water, filtration and drying at 80 ℃ overnight, the dried sample was calcined at 500 ℃ under nitrogen for 2 hours, and the catalyst obtained was labeled 2.4TiO2-0.015MoS2-0.05C3N4。
The monolithic TiO to be prepared2The sample of the photocatalyst is subjected to catalytic performance evaluation by the experimental conditions, and the degradation rate of rhodamine B within 40min is 69.5%, and the degradation efficiency k is 0.03796min-1。
Example 4:
catalyst C3N4The preparation method comprises the following steps:
(1) putting 2g of melamine into a crucible, calcining for 2h at 550 ℃ at the temperature rise speed of 5 ℃, putting the melamine into concentrated hydrochloric acid for 2h, then carrying out ultrasonic treatment for 2h, washing the melamine to be neutral for many times by using deionized water, and drying the melamine overnight at 80 ℃;
(2) finally, the dried sample is calcined for 2 hours at 500 ℃ in a nitrogen atmosphere, and the obtained catalyst is marked as C3N4。
The obtained monolithic form C3N4The sample of the photocatalyst is subjected to catalytic performance evaluation by the experimental conditions, and the degradation rate of rhodamine B within 40min is 41%, and the degradation efficiency k is 0.01642min-1。
Claims (6)
1. A specific three-layer stacked three-element composite catalyst is TiO2-MoS2-C3N4Characterized in that MoS2Supported on TiO2On the (001) plane of (C), and layer C3N4Then is randomly attached to the MoS2Layer or TiO2(001) On the layer.
2. The method for preparing the specific three-layer stacked three-way composite catalyst according to claim 1, wherein MoS is utilized2Replacing expensive noble metal, increasing contact area of the two in a two-dimensional layered structure, greatly promoting separation of electron hole pairs, and finally adding a lamella C formed after acidification treatment in an ultrasonic mode3N4To obtain the TiO stacked layer by layer2-MoS2-C3N4The three-way composite catalyst comprises the following steps:
(1) putting 10ml of tetrabutyl titanate in a polytetrafluoroethylene beaker, stirring, weighing 1-5 ml of hydrofluoric acid, dropwise adding the hydrofluoric acid into the beaker, continuously stirring for 30min, transferring the beaker to a 50ml hydrothermal kettle, keeping the temperature in a 200 ℃ oven for 24 hours, removing supernatant after the reaction is finished, washing a solid material for multiple times by using absolute ethyl alcohol and deionized water, drying the solid material at 80 ℃ overnight, finally putting the solid material into a muffle furnace, calcining the solid material at 600 ℃ for 2 hours to remove fluorine atoms on the surface, and marking the obtained catalyst as (001) -TiO2；
(2) Taking (001) -TiO2200mg was placed in a beaker and 20ml of deionized water was addedRespectively weighing 0.1-0.03 g of sodium molybdate and thiourea with the added mass being 2 times of that of the sodium molybdate, adding the sodium molybdate and the thiourea into the solution, uniformly stirring, transferring the solution into a 50ml hydrothermal kettle, preserving the temperature for 24 hours at 200 ℃, removing supernatant after the reaction is finished, washing the solid material with absolute ethyl alcohol and deionized water for multiple times, drying the solid material at 80 ℃ overnight, and marking the obtained catalyst as TiO2-MoS2；
(3) A certain amount of melamine is taken into a crucible and calcined at a certain temperature and a certain heating rate to prepare C3N4Placing the mixture into concentrated hydrochloric acid for 2 hours, then carrying out ultrasonic treatment for 2 hours, washing the mixture for multiple times by using deionized water until the mixture is neutral, and drying the mixture at 80 ℃ overnight;
(4) taking TiO2-MoS2And C3N4In deionized water, the C3N4And TiO2-MoS2The mass ratio of (1: 0) to (1: 1), carrying out ultrasonic treatment for 5 hours, filtering, drying at 80 ℃ overnight, and finally calcining the dried sample for 2 hours in a nitrogen atmosphere to obtain a catalyst labeled as TiO2-MoS2-C3N4。
3. The method for preparing the specific three-layer stacked three-way composite catalyst according to claim 2, comprising the following steps:
(1) putting 10ml of tetrabutyl titanate in a polytetrafluoroethylene beaker, stirring, weighing 1.2ml of hydrofluoric acid, dropwise adding the hydrofluoric acid into the beaker, continuously stirring for 30min, transferring the stirred tetrabutyl titanate into a 50ml hydrothermal kettle after uniform stirring, keeping the temperature in a 200 ℃ oven for 24 h, removing supernatant after the reaction is finished, washing the solid material with absolute ethyl alcohol and deionized water for multiple times, drying the solid material at 80 ℃ overnight, finally putting the solid material into a muffle furnace, controlling the temperature rise speed to be 3 ℃, calcining the solid material at 600 ℃ for 2h to remove fluorine atoms on the surface, and marking the obtained catalyst as 1.2-TiO2；
(2) Taking 1.2-TiO2Putting 200mg into a beaker, adding 20ml of deionized water to obtain a solution, respectively weighing 30mg of sodium molybdate and 60mg of sodium molybdate, adding the solution into the solution, stirring the solution uniformly, transferring the solution into a 50ml hydrothermal kettle, preserving the temperature at 200 ℃ for 24 hours, and removing the upper part after the reaction is finishedWashing the solid material with anhydrous ethanol and deionized water, drying at 80 deg.C overnight, and labeling the obtained catalyst as 1.2TiO2-MoS2；
(3) Placing 2g melamine in a crucible, calcining at 550 deg.C for 2h at a temperature rise rate of 5 deg.C, placing in concentrated hydrochloric acid for 2h, performing ultrasonic treatment for 2h, washing with deionized water for several times to neutrality, drying at 80 deg.C overnight, and marking as C3N4；
(4) 100mg of 1.2TiO are taken2-MoS2And 50mg of C3N4After 5 hours of sonication in deionized water, filtration and drying at 80 ℃ overnight, the dried sample was calcined at 500 ℃ under nitrogen for 2 hours, and the catalyst obtained was labeled 1.2TiO2--0.03MoS2-0.05C3N4。
The prepared photocatalyst sample is subjected to catalytic performance evaluation by the experimental conditions, and the degradation rate of rhodamine B within 40min is measured to be 76.5%, and the degradation efficiency k is 0.04753min-1。
4. The method for preparing the specific three-layer stacked three-way composite catalyst according to claim 2, comprising the following steps:
(1) putting 10ml of tetrabutyl titanate in a polytetrafluoroethylene beaker, stirring, weighing 2.4ml of hydrofluoric acid, dropwise adding the hydrofluoric acid into the beaker, continuously stirring for 30min, transferring the mixture into a hydrothermal kettle after uniformly stirring, keeping the temperature in a 200 ℃ oven for 24 hours, removing supernatant after the reaction is finished, washing the solid material with absolute ethyl alcohol and deionized water for multiple times, drying the solid material at 80 ℃ overnight, and finally putting the solid material in a muffle furnace, wherein the temperature rising speed is controlled to be 3 ℃. Calcining at 600 ℃ for 2h to remove surface fluorine atoms, and marking the obtained catalyst as 2.4-TiO2；
(2) Taking 2.4-TiO2Putting 200mg into a beaker, adding 20ml of deionized water to obtain a solution, respectively weighing 30mg of sodium molybdate and 60mg of thiourea, adding the solution into the solution, uniformly stirring, transferring the solution into a 50ml hydrothermal kettle, preserving the temperature at 200 ℃ for 24 hours, removing supernatant after the reaction is finished, and adding absolute ethyl alcohol and deionized waterWashing the solid material with water several times, drying overnight at 80 ℃ and labelling the catalyst as 2.4TiO2-MoS2；
(3) Placing 2g melamine in a crucible, calcining at 550 deg.C for 2h at a temperature rise rate of 5 deg.C, placing in concentrated hydrochloric acid for 2h, performing ultrasonic treatment for 2h, washing with deionized water for several times to neutrality, drying at 80 deg.C overnight, and marking as C3N4；
(4) 100mg of 2.4TiO are taken2-MoS2And 50mg of C3N4After 5 hours of sonication in deionized water, filtered and dried at 80 ℃ overnight, the dried sample was calcined at 500 ℃ under nitrogen for 2 hours, and the resulting catalyst was labeled 2.4TiO2-0.03MoS2-0.05C3N4。
The prepared photocatalyst sample is subjected to catalytic performance evaluation by the experimental conditions, and the degradation rate of rhodamine B within 40min is 86.6%, and the degradation efficiency k is 0.06311min-1。
5. The method for preparing the specific three-layer stacked three-way composite catalyst according to claim 2, comprising the following steps:
(1) putting 10ml of tetrabutyl titanate in a polytetrafluoroethylene beaker, stirring, weighing 2.4ml of hydrofluoric acid, dropwise adding the hydrofluoric acid into the beaker, continuously stirring for 30min, transferring the stirred solution to a hydrothermal kettle after uniform stirring, keeping the temperature in a 200 ℃ oven for 24 h, removing supernatant after the reaction is finished, washing solid materials for multiple times by using absolute ethyl alcohol and deionized water, drying the solid materials at 80 ℃ overnight, finally putting the dried solid materials into a muffle furnace, controlling the temperature rise speed to be 3 ℃, calcining the solid materials for 2h at 600 ℃ to remove fluorine atoms on the surface, and marking the obtained catalyst as 2.4-TiO2；
(2) Taking 2.4-TiO2Putting 200mg into a beaker, adding 20ml of deionized water to obtain a solution, respectively weighing 15mg of sodium molybdate and 30mg of thiourea, adding the sodium molybdate and the thiourea into the solution, uniformly stirring, transferring the solution into a 50ml hydrothermal kettle, preserving the temperature at 200 ℃ for 24 hours, removing supernatant after the reaction is finished, washing the solid material with absolute ethyl alcohol and deionized water for multiple times, and drying the solid material at 80 ℃ overnightThe catalyst obtained is labelled 2.4TiO2-MoS2；
(3) Placing 2g melamine in a crucible, calcining at 550 deg.C for 2h at a temperature rise rate of 5 deg.C, placing in concentrated hydrochloric acid for 2h, performing ultrasonic treatment for 2h, washing with deionized water for several times to neutrality, drying at 80 deg.C overnight, and marking as C3N4；
(4) 100mg of 2.4TiO are taken2-MoS2And 50mg of C3N4After 5 hours of sonication in deionized water, filtration and drying at 80 ℃ overnight, the dried sample was calcined at 500 ℃ under nitrogen for 2 hours, and the catalyst obtained was labeled 2.4TiO2-0.015MoS2-0.05C3N4。
6. The application of the specific three-layer stacked three-way composite catalyst according to claim 1 in degrading rhodamine.
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