CN113828291B - Composite photocatalyst with full spectrum absorption characteristic and preparation method thereof - Google Patents
Composite photocatalyst with full spectrum absorption characteristic and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 37
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 20
- 238000001228 spectrum Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002135 nanosheet Substances 0.000 claims abstract description 41
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 16
- 239000012498 ultrapure water Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 12
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- 238000000151 deposition Methods 0.000 claims abstract description 8
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- 239000012467 final product Substances 0.000 claims abstract description 3
- 239000011669 selenium Substances 0.000 claims description 33
- 229910052593 corundum Inorganic materials 0.000 claims description 22
- 239000010431 corundum Substances 0.000 claims description 22
- 229910052797 bismuth Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
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- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- CJCPHQCRIACCIF-UHFFFAOYSA-L disodium;dioxido-oxo-selanylidene-$l^{6}-sulfane Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=[Se] CJCPHQCRIACCIF-UHFFFAOYSA-L 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000032900 absorption of visible light Effects 0.000 abstract description 2
- 238000000862 absorption spectrum Methods 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
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- 239000004408 titanium dioxide Substances 0.000 description 6
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- 238000006243 chemical reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012212 insulator Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 239000012159 carrier gas Substances 0.000 description 2
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- 230000031700 light absorption Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
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- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- 238000002256 photodeposition Methods 0.000 description 1
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Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
Abstract
The invention discloses a composite photocatalyst with full spectrum absorption characteristic, which comprises TiO 2 、g‑C 3 N 4 And Bi (Bi) 2 Se 3 . The invention also discloses a preparation method thereof, which comprises the steps of firstly preparing TiO 2 Dispersing nanosheets and dicyandiamide in ultrapure water by ultrasonic, stirring and heating until moisture is evaporated, and roasting the obtained product at high temperature to obtain TiO 2 @g‑C 3 N 4 Composite nanosheets; then preparing Bi by adopting a liquid phase deposition method or a solid phase sintering method 2 Se 3 And is deposited in situ on TiO 2 @g‑C 3 N 4 And (3) obtaining the final product on the surface of the composite nano sheet. The composite photocatalyst material prepared by the method has excellent photocatalytic performance and good optical stability. g-C using different coating thicknesses 3 N 4 To improve TiO 2 With Bi 2 Se 3 Not only promotes the absorption of visible light, but also provides more active sites; with Bi 2 Se 3 The combination of the (2) not only expands the absorption spectrum of the photocatalyst to the near infrared region, but also strengthens the separation and transportation efficiency of the photo-generated electrons and holes, and the photocatalysis efficiency is greatly improved.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a composite photocatalyst with full spectrum absorption characteristic and a preparation method thereof.
Background
Bi of graphene-like layered structure 2 Se 3 Because of its simple band structure, the energy fluctuation body band gap, which is much larger than room temperature, is considered as one of the most promising topological insulator materials. The topological insulator is a novel quantum state discovered in recent years, and has great application prospect in the aspects of energy non-consumption transmission, spintronics, quantum computers and the like. The novel quantum surface state of the topological insulator can realize high-migration and non-dissipation electrical transmission, thereby creating a perfect conductive channel. Although Bi of narrow band gap 2 Se 3 (0.3 eV) TiO may be used 2 The spectral absorption range of (2) is expanded to the near infrared region, but the improvement of the whole photocatalytic performance is not obvious. This is due to Bi 2 Se 3 Cannot be combined with TiO 2 The band gap of the (B) is matched to form a type II band edge connection, which is not beneficial to separation and transportation of photo-generated charges. Therefore, based on the energy band structure theory, the patent is characterized in Bi 2 Se 3 With TiO 2 The design between the two is added with a g-C 3 N 4 And the band gap connecting layer is used as a matching transition between the band gap connecting layer and the band gap connecting layer. g-C 3 N 4 As a visible light photocatalyst with excellent performance, the catalyst not only has a suitable oxidation-reduction potential (CB: -0.52eV; VB:1.88 eV), but also has a good oxidation-reduction potential with Bi 2 Se 3 The Fermi energy level connection between the two can play a role in band edge reforming. In the multilayer composite heterostructure, each unit layer has the functions of mutual influence, g-C 3 N 4 Not only as TiO 2 With Bi 2 Se 3 The band gap transition layer between the two layers can be used as a sensitization layer of visible light; and topology insulator Bi 2 Se 3 The heterogeneous interface and topological surface state of the near infrared absorbing layer serve as near infrared absorbing layers, and the rapid separation and transportation of photo-generated charges are promoted.
Although topological insulator Bi 2 Se 3 There have been few reports on the related photocatalysts of (a), but most cases have not added an energy band transition layer, and Bi has not been considered 2 Se 3 The problem of matching with the substrate, while increasing the light absorption, is that the carrier transport efficiency is not ideal, resulting in an overall photocatalytic efficiency that is not high. In addition, these processes generally involve organic solvents and harmful by-products, and in most cases these reaction processes are very difficult to control and the yields are not high.
Disclosure of Invention
The invention aims to: the invention aims to provide a composite photocatalyst with full spectrum absorption characteristic, which not only has excellent photocatalytic performance, but also has excellent stability, and a preparation method thereof.
The technical scheme is as follows: the composite photocatalyst with full spectrum absorption characteristic comprises TiO 2 、g-C 3 N 4 And Bi (Bi) 2 Se 3 The method comprises the steps of carrying out a first treatment on the surface of the The TiO 2 With Bi 2 Se 3 The mass ratio of (2) is 100:1-9; the g-C 3 N 4 In TiO 2 The thickness of the coating on the surface of the nano sheet is 1-5 nm.
The preparation method of the composite photocatalyst with full spectrum absorption characteristic comprises the following steps:
(1) TiO is mixed with 2 Dispersing nanosheets and dicyandiamide in ultrapure water by ultrasonic, stirring and heating until moisture is evaporated, and roasting the obtained product at high temperature to obtain TiO 2 @g-C 3 N 4 Composite nanosheets;
(2) Preparation of Bi by employing liquid deposition method or solid phase sintering method 2 Se 3 And is deposited in situ on TiO 2 @g-C 3 N 4 On the surface of the composite nano-sheet, the final product is obtained。
Further, in the step (1), the high temperature is 530-580 ℃, and the roasting time is 2-3h.
Further, in the step (2), the specific steps of the liquid phase deposition method are as follows:
(11) Bismuth nitrate pentahydrate, aminotriacetic acid and ascorbic acid are firstly prepared into bismuth chelating solution, and then TiO is prepared 2 @g-C 3 N 4 The composite nano-sheet is ultrasonically dispersed in the nano-sheet;
(12) Under the condition of stirring, taking a certain amount of ammonia water, adjusting the pH value of the solution to 9, and adding a sodium selenosulfate solution with a stoichiometric ratio;
(13) Maintaining the temperature of the solution at 55-85deg.C, and stirring at the temperature for 30-120min;
(14) Respectively cleaning the solid precipitate for several times by using absolute ethyl alcohol and ultrapure water under the condition of ultrasound until the pH value is neutral;
(15) The washed product was placed in a vacuum drying oven and dried in vacuum.
Further, in the step (11), the mass ratio of the bismuth nitrate pentahydrate, the aminotriacetic acid and the ascorbic acid is 2:2:1.
Further, in the step (15), the temperature of the vacuum drying is 70-80 ℃ and the drying time is 24-30h.
Further, in the step (2), the specific steps of the solid-phase sintering method are as follows:
(21) TiO is firstly put into 2 @g-C 3 N 4 Uniformly dispersing the composite nano-sheet, nano-selenium powder and nano-bismuth powder, and mechanically grinding;
(22) Placing the ground mixed powder material into a corundum crucible, and placing the corundum crucible into a tube furnace protected by inert gas;
(23) Under the protection of inert gas, sintering at high temperature, wherein the heating rate is 5 ℃/min, continuously preserving heat, and then naturally cooling to room temperature.
Further, in the step (21), the molar ratio of the nano selenium powder to the nano bismuth powder is 3:2; the sum of the mass of the nano selenium powder and the nano bismuth powder is TiO 2 @g-C 3 N 4 1 to 10 percent of composite nano-sheet.
Further, in the step (21), the grinding time is 30-120min.
Further, in the step (23), the high temperature is 650-950 ℃, the sintering time is 15-20h, and the heat preservation time is 15-20h.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
1. the process flow is simple, no complex equipment is needed, the cost of raw materials is low, no pollution is caused to the environment, and the yield of the photocatalyst is at the gram level;
2. the g-C can be controlled by adjusting the addition amount of dicyandiamide 3 N 4 Is a coating thickness of (2);
3. the invention innovatively utilizes g-C with different coating thicknesses 3 N 4 To improve TiO 2 With Bi 2 Se 3 Not only promotes the absorption of visible light, but also provides more active sites;
4. with Bi 2 Se 3 The combination of the (2) not only expands the absorption spectrum of the photocatalyst to the near infrared region, but also strengthens the separation and transportation efficiency of the photo-generated electrons and holes, and the photocatalysis efficiency is greatly improved.
5. Can be prepared by adjusting Bi 2 Se 3 With TiO 2 To optimize the photocatalytic performance.
6. By adjusting g-C 3 N 4 The thickness of the coating layer is used for optimizing the photocatalytic performance, and the preparation method has certain universality;
7. the composite photocatalyst material prepared by the method has excellent photocatalytic performance and good optical stability.
Drawings
FIG. 1 is a graph showing the photocatalytic hydrogen production performance for 5 hours for a nanocomposite prepared according to the scheme of example 1 as a photocatalyst;
FIG. 2 shows a nanocomposite prepared according to the scheme of example 1 as a photocatalystTiO for use 2 TEM image of the nanoplatelets;
FIG. 3 is a TEM image of a nanocomposite prepared according to the scheme of example 1 as a photocatalyst;
FIG. 4 is a graph showing the spectral absorption contrast of nanocomposite prepared according to the scheme of example 1 as a photocatalyst.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
Firstly, dispersing 1.0g of titanium dioxide nanosheets and 1.0g of dicyandiamide in 100ml of ultrapure water in an ultrasonic manner, continuing to heat and stir at 90 ℃ until moisture is evaporated to dryness, placing the obtained mixed powder into a corundum boat, covering a corundum cover, and then placing the corundum boat into an electric furnace for roasting for 3 hours at 550 ℃ to obtain TiO 2 @g-C 3 N 4 Composite nanosheets; the resulting TiO is then 2 @g-C 3 N 4 The composite nano-sheet is dispersed in 100ml bismuth chelate liquid (bismuth nitrate 0.01 mol.l) -1 ) Ammonia was added dropwise until ph=9 and 0.1mol·l was added again -1 Na of (2) 2 SeSO 3 7ml of solution, continuously stirring for 90min at 75 ℃, obtaining a product by adopting a centrifugal mode after the reaction is finished, and ultrasonically cleaning the product for a plurality of times by using absolute ethyl alcohol and ultrapure water until the pH value in the centrifugal cleaning liquid is neutral; finally, the resulting product was dried in a vacuum oven at 70℃for 24h. After the drying is finished, the TiO is obtained 2 @g-C 3 N 4 @Bi 2 Se 3 A composite photocatalyst material.
Example 2
Firstly, dispersing 1.0g of titanium dioxide nanosheets and 1.0g of dicyandiamide in 100ml of ultrapure water in an ultrasonic manner, continuing to heat and stir at 90 ℃ until moisture is evaporated to dryness, placing the obtained mixed powder into a corundum boat, covering a corundum cover, and then placing the corundum boat into an electric furnace for roasting for 3 hours at 550 ℃ to obtain TiO 2 @g-C 3 N 4 Composite nanosheets; the resulting TiO is then 2 @g-C 3 N 4 The composite nano-sheet is dispersed in 100ml bismuth chelate liquid (bismuth nitrate 0.005 mol.l) -1 ) Ammonia was added dropwise until ph=9 and 0.1mol·l was added again -1 Na of (2) 2 SeSO 3 3.5ml of solution, continuously stirring for 90min at 75 ℃, obtaining a product by adopting a centrifugal mode after the reaction is finished, and ultrasonically cleaning the product for a plurality of times by using absolute ethanol and ultrapure water until the pH value in the centrifugal cleaning liquid is neutral; finally, the resulting product was dried in a vacuum oven at 70℃for 24h. After the drying is finished, the TiO is obtained 2 @g-C 3 N 4 @Bi 2 Se 3 A composite photocatalyst material.
According to the method of example 1, example 2 is different in Bi 2 Se 3 With TiO 2 The mass ratio of (3): 100, while in the preparation of example 1, bi 2 Se 3 With TiO 2 The mass ratio of (2) is 6:100.
example 3
Firstly, dispersing 1.0g of titanium dioxide nanosheets and 0.5g of dicyandiamide in 100ml of ultrapure water in an ultrasonic manner, continuing to heat and stir at 90 ℃ until moisture is evaporated to dryness, placing the obtained mixed powder into a corundum boat, covering a corundum cover, and then placing the corundum boat into an electric furnace for roasting for 3 hours at 550 ℃ to obtain TiO 2 @g-C 3 N 4 Composite nanosheets; the resulting TiO is then 2 @g-C 3 N 4 The composite nano-sheet is dispersed in 100ml bismuth chelate liquid (bismuth nitrate 0.01 mol.l) -1 ) Ammonia was added dropwise until ph=9 and 0.1mol·l was added again -1 Na of (2) 2 SeSO 3 7ml of solution, continuously stirring for 90min at 75 ℃, obtaining a product by adopting a centrifugal mode after the reaction is finished, and ultrasonically cleaning the product for a plurality of times by using absolute ethyl alcohol and ultrapure water until the pH value in the centrifugal cleaning liquid is neutral; finally, the resulting product was dried in a vacuum oven at 70℃for 24h. After the drying is finished, the TiO is obtained 2 @g-C 3 N 4 @Bi 2 Se 3 A composite photocatalyst material.
According to the method of example 1, example 3 is different from g-C 3 N 4 In TiO 2 The coating thickness of the nanosheet surface layer is 3-5 nm, while in the preparation process of example 1, g-C 3 N 4 In TiO 2 The coating thickness of the nano sheet surface layer is 8-10 nm.
Example 4
Firstly, dispersing 1.0g of titanium dioxide nanosheets and 1.0g of dicyandiamide in 100ml of ultrapure water in an ultrasonic manner, continuing to heat and stir at 90 ℃ until moisture is evaporated to dryness, placing the obtained mixed powder into a corundum boat, covering a corundum cover, and then placing the corundum boat into an electric furnace for roasting for 3 hours at 550 ℃ to obtain TiO 2 @g-C 3 N 4 Composite nanosheets; the resulting TiO is then 2 @g-C 3 N 4 The composite nano-sheet is dispersed in 100ml bismuth chelate liquid (bismuth nitrate 0.01 mol.l) -1 ) Ammonia was added dropwise until ph=9 and 0.1mol·l was added again -1 Na of (2) 2 SeSO 3 7ml of solution, continuously stirring for 90min at 85 ℃, obtaining a product by adopting a centrifugal mode after the reaction is finished, and ultrasonically cleaning the product for a plurality of times by using absolute ethyl alcohol and ultrapure water until the pH value in the centrifugal cleaning liquid is neutral; finally, the resulting product was dried in a vacuum oven at 70℃for 24h. After the drying is finished, the TiO is obtained 2 @g-C 3 N 4 @Bi 2 Se 3 A composite photocatalyst material.
According to the method of example 1, example 4 is different in Bi 2 Se 3 The deposition temperature of (2) was 85℃and Bi was used in the preparation of example 1 2 Se 3 The deposition temperature of (2) was 75 ℃.
Example 5
Firstly, dispersing 1.0g of titanium dioxide nanosheets and 1.0g of dicyandiamide in 100ml of ultrapure water in an ultrasonic manner, continuing to heat and stir at 90 ℃ until moisture is evaporated to dryness, placing the obtained mixed powder into a corundum boat, covering a corundum cover, and then placing the corundum boat into an electric furnace for roasting for 3 hours at 550 ℃ to obtain TiO 2 @g-C 3 N 4 Composite nanosheets; the resulting TiO is then 2 @g-C 3 N 4 Uniformly mixing the composite nano-sheet 24h with 0.053g of nano-selenium powder and 0.209g of nano-bismuth powder, continuously grinding for 30min, and placing the obtained mixed powder into a tube furnace for high-temperature roasting at 650 ℃ for 15h under the protection of high-purity argon. After the roasting is completed, tiO is obtained 2 @g-C 3 N 4 @Bi 2 Se 3 A composite photocatalyst material.
According to the method of example 1, example 5 is different in Bi 2 Se 3 Is prepared by a direct solid phase sintering method, and Bi is used in the preparation process of the example 1 2 Se 3 Is prepared by adopting a liquid phase deposition method.
Example 6
Firstly, dispersing 1.0g of titanium dioxide nanosheets and 1.0g of dicyandiamide in 100ml of ultrapure water in an ultrasonic manner, continuing to heat and stir at 90 ℃ until moisture is evaporated to dryness, placing the obtained mixed powder into a corundum boat, covering a corundum cover, and then placing the corundum boat into an electric furnace for roasting for 3 hours at 550 ℃ to obtain TiO 2 @g-C 3 N 4 Composite nanosheets; the resulting TiO is then 2 @g-C 3 N 4 Uniformly mixing the composite nano-sheet 24h with 0.053g of nano-selenium powder and 0.209g of nano-bismuth powder, continuously grinding for 30min, and placing the obtained mixed powder into a tube furnace for high-temperature roasting at 650 ℃ for 24h under the protection of high-purity argon. After the roasting is completed, tiO is obtained 2 @g-C 3 N 4 @Bi 2 Se 3 A composite photocatalyst material.
According to the method of example 5, example 6 is different in Bi 2 Se 3 The sintering time of (2) was 24h, while in the preparation of example 5, bi was 2 Se 3 The sintering time of (2) was 15h.
The test of the photocatalytic hydrogen production performance comprises the following specific steps:
the photocatalytic water splitting performance is tested on a Beijing Porphy Labsolar-III AG on-line photocatalytic system, the model of a light source is PLS-SXE300, and an AM 1.5G optical filter is provided, and the intensity of the light filter is equivalent to that of sunlight. Before testing, 5mg of photocatalyst is dispersed in a mixed solution containing 70ml of ultrapure water and 30ml of methanol, and is subjected to ultrasonic treatment for 30min to ensure uniform dispersion of the catalyst, the distance between a light source and a liquid level is about 10cm, and the irradiation area is about 10cm 2 . The whole photocatalysis process is carried out at room temperature, and the whole process is filled with glycol cooling liquid (-5 ℃) to eliminate the heat of the light sourceIs a function of (a) and (b). Platinum is loaded on the surface of the catalyst by an in-situ photo-deposition method, namely, a certain amount of converted chloroplatinic acid solution (the mass ratio of the platinum to the catalyst is 3%) is added into the mixed solution. The carrier gas of the whole system is high-purity argon, and the flow rate is 6.0 ml.min -1 Calibrated with Beijing seven-star CS200 flow rate controller. After the photocatalyst generates hydrogen under illumination, the hydrogen is carried into gas chromatograph by carrier gas after a certain time, and on-line qualitative and quantitative detection is carried out. The gas chromatograph is GC9790, zhejiang Fuli production, the detector is a heat conduction pool, and the detector is matched withMolecular sieves.
The performance test results of the composite photocatalyst material are shown in fig. 1 (example 1), and the graph clearly shows that the photocatalyst provided by the invention has excellent photocatalytic hydrogen production performance, reaching 45 mmol.g -1 ·h -1 。
As shown in fig. 4, via Bi 2 Se 3 Modified TiO 2 The light absorption range of the nano sheet is expanded from ultraviolet light wave band to near infrared wave band, and the nano sheet has the characteristic of full spectrum absorption.
Claims (10)
1. A composite photocatalyst with full spectrum absorption characteristic is characterized by comprising TiO 2 、g-C 3 N 4 And Bi (Bi) 2 Se 3 The method comprises the steps of carrying out a first treatment on the surface of the The TiO 2 With Bi 2 Se 3 The mass ratio of (2) is 100:1-9; the g-C 3 N 4 In TiO 2 The thickness of the coating on the surface of the nano sheet is 1-5 nm.
2. A method for preparing the composite photocatalyst with full spectrum absorption characteristic as claimed in claim 1, comprising the steps of:
(1) TiO is mixed with 2 Dispersing nanosheets and dicyandiamide in ultrapure water by ultrasonic, stirring and heating until moisture is evaporated, and roasting the obtained product at high temperature to obtain TiO 2 @g-C 3 N 4 Composite nanosheets;
(2) Preparation of Bi by employing liquid deposition method or solid phase sintering method 2 Se 3 And is deposited in situ on TiO 2 @g-C 3 N 4 And (3) obtaining the final product on the surface of the composite nano sheet.
3. The method for preparing a composite photocatalyst having full spectrum absorption characteristics according to claim 2, wherein in the step (1), the high temperature is 530-580 ℃ and the calcination time is 2-3h.
4. The method for preparing a composite photocatalyst having full spectrum absorption characteristics according to claim 2, wherein in step (2), the specific steps of the liquid phase deposition method are as follows:
(11) Bismuth nitrate pentahydrate, aminotriacetic acid and ascorbic acid are firstly prepared into bismuth chelating solution, and then TiO is prepared 2 @g-C 3 N 4 The composite nano-sheet is ultrasonically dispersed in the nano-sheet;
(12) Under the condition of stirring, taking a certain amount of ammonia water, adjusting the pH value of the solution to 9, and adding a sodium selenosulfate solution with a stoichiometric ratio;
(13) Maintaining the temperature of the solution at 55-85deg.C, and stirring at the temperature for 30-120min;
(14) Respectively cleaning the solid precipitate for several times by using absolute ethyl alcohol and ultrapure water under the condition of ultrasound until the pH value is neutral;
(15) The washed product was placed in a vacuum drying oven and dried in vacuum.
5. The method for preparing a composite photocatalyst having full spectrum absorption characteristics according to claim 4, wherein in the step (11), the mass ratio of bismuth nitrate pentahydrate, aminotriacetic acid and ascorbic acid is 2:2:1.
6. The method for preparing a composite photocatalyst having full spectrum absorption characteristics according to claim 4, wherein in the step (15), the vacuum drying temperature is 70-80 ℃ and the drying time is 24-30h.
7. The method for preparing a composite photocatalyst having full spectrum absorption characteristics according to claim 2, wherein in step (2), the specific steps of the solid phase sintering method are as follows:
(21) TiO is firstly put into 2 @g-C 3 N 4 Uniformly dispersing the composite nano-sheet, nano-selenium powder and nano-bismuth powder, and mechanically grinding;
(22) Placing the ground mixed powder material into a corundum crucible, and placing the corundum crucible into a tube furnace protected by inert gas;
(23) Under the protection of inert gas, sintering at high temperature, wherein the heating rate is 5 ℃/min, continuously preserving heat, and then naturally cooling to room temperature.
8. The method for preparing a composite photocatalyst with full spectrum absorption characteristics according to claim 7, wherein in the step (21), the molar ratio of the nano selenium powder to the nano bismuth powder is 3:2; the sum of the mass of the nano selenium powder and the nano bismuth powder is TiO 2 @g-C 3 N 4 1 to 10 percent of composite nano-sheet.
9. The method for preparing a composite photocatalyst having full spectrum absorption characteristics according to claim 7, wherein in step (21), the grinding time is 30 to 120min.
10. The method for preparing a composite photocatalyst having full spectrum absorption characteristics according to claim 7, wherein in the step (23), the high temperature is 650-950 ℃, the sintering time is 15-20h, and the holding time is 15-20h.
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