CN114146715B - Heterojunction composite material and preparation method and application thereof - Google Patents
Heterojunction composite material and preparation method and application thereof Download PDFInfo
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- CN114146715B CN114146715B CN202111528497.0A CN202111528497A CN114146715B CN 114146715 B CN114146715 B CN 114146715B CN 202111528497 A CN202111528497 A CN 202111528497A CN 114146715 B CN114146715 B CN 114146715B
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910016001 MoSe Inorganic materials 0.000 claims abstract description 104
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 36
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 26
- 229910052750 molybdenum Inorganic materials 0.000 claims description 26
- 239000011733 molybdenum Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 23
- 239000011669 selenium Substances 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- 229910052711 selenium Inorganic materials 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 19
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
- 150000000703 Cerium Chemical class 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
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- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 26
- 238000000926 separation method Methods 0.000 abstract description 19
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- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 13
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- 230000009467 reduction Effects 0.000 abstract description 9
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- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 3
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- 238000001179 sorption measurement Methods 0.000 abstract 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 33
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000010531 catalytic reduction reaction Methods 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 238000004458 analytical method Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 229910021426 porous silicon Inorganic materials 0.000 description 2
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- 238000005215 recombination Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
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Images
Classifications
-
- 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
-
- B01J35/39—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/057—Selenium or tellurium; Compounds thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention provides a heterojunction composite material and a preparation method and application thereof, and belongs to the technical field of catalysts. The heterojunction composite material provided by the invention comprises hollow CeO rich in oxygen vacancies 2 And MoSe 2 Hollow CeO rich in oxygen vacancies 2 And MoSe 2 Forming a heterojunction, hollow CeO rich in oxygen vacancies 2 The hollow structure is even, and the hollow structure is uniform,the specific surface area of the heterojunction composite material is increased, the adsorption capacity to carbon dioxide is strong, and the unique hollow structure can enable visible light to be in CeO 2 The hollow cavity is internally reflected for multiple times, so that the utilization efficiency of visible light is improved; the introduction of the oxygen vacancy is beneficial to the capture of electrons by carbon dioxide, and further the photocatalytic reduction process of the heterojunction composite material on the carbon dioxide is promoted. Introduced narrow bandgap semiconductor MoSe 2 With CeO 2 The heterojunction is formed, the absorption range of visible light and the separation efficiency of photon-generated carriers are increased, and the catalytic activity of the heterojunction composite material on reduction of carbon dioxide is improved.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a heterojunction composite material as well as a preparation method and application thereof.
Background
With the rapid development of the industry, the combustion of fossil fuels (coal, petroleum and natural gas) generates a large amount of carbon dioxide, the dynamic balance of the generation and conversion of the carbon dioxide is destroyed, and the concentration of the carbon dioxide rises sharply, so that a series of environmental problems such as global warming are caused. Therefore, how to reasonably utilize carbon dioxide is particularly important.
Catalytic reduction of CO by using semiconductor material using sunlight 2 Formation of CO, CH 4 The greenhouse gas treatment of gas fuel is gradually becoming a research hotspot of environmental chemistry. CeO (CeO) 2 Is an important functional rare earth oxide, has high chemical stability and crystal stability, and has wide application in the aspects of automobile exhaust purification and catalysis, advanced integrated circuits, solid fuel cells and the like. In recent years, ceO has been found 2 As an n-type semiconductor, the light absorption threshold is about 420 nm, which is higher than the most commonly used TiO at present 2 (388 nm). At the same time, ceO 2 The lattice oxygen anions are easy to be lost, and have a fast interface electron transfer reaction when being excited by light, ce is easy to absorb photons and change from 3 valence to 4 valence, and Ce 4＋ The simple recombination of electron-hole pairs can be effectively inhibited under the excitation of light, and the photocatalysis efficiency is improved. Thus, ceO 2 Becomes a potential novel high-efficiency photocatalyst. However, ceO alone 2 For catalytic reduction of CO 2 Is not sufficiently activeHigh.
Disclosure of Invention
The invention aims to provide a heterojunction composite material, and a preparation method and application thereof 2 Reduction of CO and CH 4 Remarkably improve CO 2 Conversion, CO and CH 4 The yield and selectivity of the heterojunction composite material are high, and the stability of the heterojunction composite material is excellent.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a heterojunction composite material, which comprises hollow CeO rich in oxygen vacancies 2 And hollow CeO dispersed in the oxygen-rich vacancy 2 MoSe of surface 2 Said MoSe 2 And oxygen-rich vacancy hollow CeO 2 A heterojunction structure is formed.
Preferably, the MoSe is 2 The mass fraction of (A) is 12.3 to 63.5%.
Preferably, the oxygen-rich vacancy hollow CeO 2 The particle size of the shell is 100 to 500nm, and the thickness of the shell is 7 to 20nm.
The invention provides a preparation method of the heterojunction composite material in the technical scheme, which comprises the following steps:
hollow CeO is formed 2 Mixing a molybdenum source, selenium, a reducing agent and water, and carrying out hydrothermal reaction to obtain a heterojunction composite material precursor;
and calcining the heterojunction composite material precursor in a hydrogen atmosphere to obtain the heterojunction composite material.
Preferably, the hollow CeO 2 The preparation method comprises the following steps:
mixing nonporous silicon dioxide, polyvinylpyrrolidone, water, hexamethylenetetramine and water-soluble cerium salt, carrying out hydrothermal reaction, and calcining to obtain SiO 2 @CeO 2 ；
Subjecting the SiO to 2 @CeO 2 Placing the mixture in a strong alkaline solution for silica removal treatment to obtain hollow CeO 2 。
Preferably, the mass ratio of the non-porous silica to the cerium in the water-soluble cerium salt is 1:2171 to 2181;
the temperature of the hydrothermal reaction is 95-100 ℃, and the time is 2h;
the calcining temperature is 450 to 600 ℃, and the time is 100min;
the concentration of the strong alkali solution is 3 to 5mol/L.
Preferably, the hollow CeO 2 And selenium in a mass ratio of 1:0.45 to 0.5;
the molar ratio of molybdenum to selenium in the molybdenum source is 1:2~3;
the reducing agent comprises hydrazine hydrate and/or sodium borohydride;
the molar ratio of the selenium to the reducing agent is 1:1~2.
Preferably, the temperature of the hydrothermal reaction is 180 to 200 ℃ and the time is 20 to 24h.
Preferably, the calcining temperature is 450 to 550 ℃, and the time is 30 to 40min.
The invention provides an application of the heterojunction composite material prepared by the preparation method in the technical scheme or the application of the heterojunction composite material prepared by the preparation method in the technical scheme as a photocatalyst.
The invention provides a heterojunction composite material, which comprises hollow CeO rich in oxygen vacancies 2 And hollow CeO dispersed in the oxygen-rich vacancy 2 MoSe of surface 2 Said MoSe 2 And oxygen-rich vacancy hollow CeO 2 A heterojunction structure is formed. The unique hollow structure in the heterojunction composite material provided by the invention can enable visible light to be in CeO 2 The hollow cavity is internally reflected for multiple times, so that the utilization efficiency of visible light is improved, and the photocatalyst has a good application prospect in the field of photocatalysis; ceO in heterojunction composite material 2 The hollow structure is uniform, the specific surface area of the heterojunction composite material is improved, and the hollow structure is used for CO 2 The adsorption capacity of the adsorbent is strong; introduction of oxygen vacancies is beneficial for CO 2 Trapping electrons, thereby facilitating the heterojunction composite to CO 2 The photocatalytic reduction process of (1). Introduced narrow bandgap semiconductor MoSe 2 With CeO 2 The heterojunction is formed, the absorption range of visible light and the separation efficiency of photon-generated carriers are increased, and the reduction of CO by the heterojunction composite material is improved 2 Preparation of CO and CH 4 The catalytic activity of (3).
The preparation method provided by the invention is simple to operate, wide in raw material source, low in cost, green and environment-friendly, and suitable for industrial production.
Drawings
FIG. 1 is a non-porous SiO prepared in example 1 2 、H-Vo-CeO 2 @MoSe 2 And SiO 2 @CeO 2 SEM picture of (1), H-CeO 2 And H-Vo-CeO 2 @MoSe 2 TEM image of (A) and H-Vo-CeO 2 @MoSe 2 HRTEM image of (1), wherein a is SiO 2 SEM picture of (b) is H-Vo-CeO 2 @MoSe 2 SEM picture of (1), c is SiO 2 @CeO 2 SEM picture of (1), d is H-CeO 2 TEM image of (e) is H-Vo-CeO 2 @MoSe 2 In TEM image of (b), f is H-Vo-CeO 2 @MoSe 2 HRTEM image of (A);
FIG. 2 shows H-CeO prepared in example 1 2 And H-Vo-CeO 2 @MoSe 2 And MoSe prepared in comparative example 1 2 In which a is H-CeO 2 B is MoSe 2 C is H-Vo-CeO 2 @MoSe 2 ；
FIG. 3 shows H-CeO prepared in example 1 2 @MoSe 2 And H-Vo-CeO 2 @MoSe 2 Wherein a is a heterojunction composite material precursor, and b is H-Vo-CeO 2 @MoSe 2 ；
FIG. 4 shows H-CeO prepared in example 1 2 And H-Vo-CeO 2 @MoSe 2 And MoSe prepared in comparative example 1 2 Wherein a is H-CeO 2 B is MoSe 2 And c is H-Vo-CeO 2 @MoSe 2 ；
FIG. 5 shows H-CeO prepared in example 1 2 And H-Vo-CeO 2 @MoSe 2 And MoSe prepared in comparative example 1 2 A characteristic detection map of (a);
FIG. 6 shows H-CeO prepared in example 1 2 And H-Vo-CeO 2 @MoSe 2 And MoSe prepared in comparative example 1 2 In different reactionsThe catalytic performance test result under time is shown, wherein a is H-CeO 2 B is MoSe 2 C is H-Vo-CeO 2 @MoSe 2 。
FIG. 7 shows H-CeO prepared in example 1 2 MoSe prepared in comparative example 1 2 And H-Vo-CeO prepared in example 1~4 2 @MoSe 2 And testing the photocatalytic performance at the reaction time of 4h.
Detailed Description
The invention provides a heterojunction composite material, which comprises oxygen-rich vacancy hollow CeO 2 And hollow CeO dispersed in the oxygen-rich vacancy 2 MoSe of surface 2 Said MoSe 2 And oxygen-rich vacancy hollow CeO 2 A heterojunction structure is formed.
In the present invention, the MoSe is 2 The mass fraction (b) is preferably from 12.3 to 63.5%, more preferably from 20 to 60%, and still more preferably from 30 to 50%.
In the present invention, the oxygen-rich vacancy hollow CeO 2 The particle size of (B) is preferably 100 to 500nm, more preferably 200 to 400nm, and still more preferably 200 to 300nm; the oxygen-rich vacancy hollow CeO 2 The thickness of the shell layer(s) is preferably 7 to 20nm, more preferably 10 to 15nm, and still more preferably 10 to 12nm.
The invention provides a preparation method of the heterojunction composite material in the technical scheme, which comprises the following steps:
hollow CeO is formed 2 Mixing a molybdenum source, selenium, a reducing agent and water, and carrying out hydrothermal reaction to obtain a heterojunction composite material precursor;
and calcining the heterojunction composite material precursor in a hydrogen atmosphere to obtain the heterojunction composite material.
The invention is to mix hollow CeO 2 Mixing the molybdenum source, selenium, a reducing agent and water, and carrying out hydrothermal reaction to obtain the heterojunction composite material precursor.
In the present invention, the hollow CeO 2 The preparation method of (a) preferably comprises the steps of:
mixing nonporous silicon dioxide, polyvinylpyrrolidone, water, hexamethylenetetramine and water-soluble cerium saltCalcining after hydrothermal reaction to obtain SiO 2 @CeO 2 ；
Subjecting the SiO 2 @CeO 2 Placing the mixture in a strong alkaline solution for silica removal treatment to obtain hollow CeO 2 。
The invention mixes the non-porous silicon dioxide, polyvinylpyrrolidone, water, hexamethylenetetramine and water-soluble cerium salt, carries out hydrothermal reaction and then calcines to obtain SiO 2 @CeO 2 。
In the present invention, the non-porous silica is preferably commercially available or self-made, which is well known to those skilled in the art. In the present invention, the method for preparing the non-porous silica preferably comprises the steps of: mixing ammonia water, ethanol and ethyl orthosilicate, and carrying out hydrolysis reaction to obtain nonporous silicon dioxide. In the present invention, the mass fraction of the aqueous ammonia is preferably 30 to 35wt%, more preferably 31 to 34wt%, and still more preferably 32wt%. In the present invention, the volume ratio of the ammonia water to the tetraethoxysilane is preferably 4~5:5~6, more preferably 4.2 to 4.8:5.2 to 5.8, and more preferably 4.5 to 4.6:5.5 to 5.6. In the present invention, the volume ratio of the ammonia water to the ethanol is preferably 4~5:70 to 80, more preferably 4.2 to 4.8:72 to 78, more preferably 4.5 to 4.6:75 to 76. In the present invention, the temperature of the mixing is preferably room temperature, and the mixing manner of the present invention is not particularly limited, and may be a mixing manner known to those skilled in the art, specifically, stirring and mixing; the speed and time of stirring and mixing are not specially limited, and the raw materials can be uniformly mixed; in the specific embodiment of the invention, ammonia water and ethanol are preferably stirred and mixed for 20 to 40min (more preferably 30 min) at room temperature, and then ethyl orthosilicate is added and mixed. In the present invention, the temperature of the hydrolysis reaction is preferably room temperature, and the time of the hydrolysis reaction is preferably 50 to 72min, more preferably 60 to 70min, and still more preferably 60 to 65min. After the hydrolysis reaction, the present invention preferably further comprises a post-treatment comprising: and carrying out solid-liquid separation on the reaction liquid obtained by the hydrolysis reaction, and sequentially washing, alcohol washing and drying the obtained solid product to obtain the non-porous silicon dioxide. The solid-liquid separation method of the present invention is not particularly limited, and a solid-liquid separation method known to those skilled in the art, specifically, centrifugal separation, may be employed. In the present invention, the alcohol washing alcohol preferably includes methanol and/or ethanol. In the invention, the drying mode is preferably vacuum drying, the drying temperature is preferably 60 to 80 ℃, more preferably 65 to 75 ℃, and even more preferably 70 ℃, the drying time is not particularly limited, and the drying is carried out until the weight is constant. In the present invention, the particle diameter of the non-porous silica is preferably 180 to 220nm, more preferably 190 to 210nm.
In the present invention, the water-soluble cerium salt preferably includes cerium nitrate and/or cerium acetate; the mass ratio of the non-porous silica to the cerium in the water-soluble cerium salt is preferably 1:2171 to 2181, more preferably 1:2171 to 2175, more preferably 1:2171 to 2173. In the present invention, the mass ratio of the non-porous silica to polyvinylpyrrolidone (PVP) is preferably 1:8 to 11, more preferably 1:8.5 to 10.5, and more preferably 1:9 to 10. In the present invention, the mass ratio of the nonporous silica to water is preferably 1: from 65 to 1000, more preferably from 1:100 to 800, more preferably 1:300 to 500. In the present invention, the mass ratio of cerium to hexamethylenetetramine in the water-soluble cerium salt is preferably 1:0.55 to 0.67, more preferably 1:0.58 to 0.65, more preferably 1:0.60 to 0.65. In the invention, the water-soluble cerium salt is preferably used in the form of a water-soluble cerium salt aqueous solution, and the concentration of the water-soluble cerium salt aqueous solution is preferably 1 to 4g/L, more preferably 1.5 to 3.5g/L, and further preferably 2 to 3g/L.
In the present invention, the order of mixing the non-porous silica, the polyvinylpyrrolidone, the water, the hexamethylenetetramine and the water-soluble cerium salt is preferably that the non-porous silica, the polyvinylpyrrolidone and the water are ultrasonically dispersed and mixed to obtain a mixed dispersion liquid; mixing water-soluble cerium salt and Hexamethylenetetramine (HMTA) to obtain a cerium salt mixture; mixing the mixed dispersion with a cerium salt mixture. The mixing mode of the invention is not particularly limited, and the mixing mode known to those skilled in the art can be adopted, such as stirring and mixing; the stirring and mixing speed and time are not particularly limited, and the raw materials can be uniformly mixed.
In the present invention, the temperature of the hydrothermal reaction is preferably 95 to 100 ℃, more preferably 96 to 99 ℃, and still more preferably 97 to 98 ℃; the hydrothermal reaction time is preferably 1.2 to 2.2h, more preferably 1.6 to 2h, and still more preferably 2h. After the hydrothermal reaction, the present invention preferably further comprises a post-treatment, which comprises: cooling the reaction liquid obtained by the hydrothermal reaction to room temperature, carrying out solid-liquid separation, and drying the obtained solid product to obtain SiO 2 @CeO 2 And (3) precursor. The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art may be used, specifically, natural cooling. The solid-liquid separation method of the present invention is not particularly limited, and a solid-liquid separation method known to those skilled in the art, specifically, centrifugal separation, may be employed. In the present invention, the drying method is preferably vacuum drying, the drying temperature is preferably 60 to 80 ℃, more preferably 65 to 75 ℃, and even more preferably 70 ℃, and the drying time is not particularly limited, and the drying may be performed until the weight is constant.
In the present invention, the temperature of the calcination is preferably 450 to 600 ℃, more preferably 500 to 600 ℃, and still more preferably 550 to 600 ℃; the calcination time is preferably 60 to 120min, more preferably 90 to 110min, and further preferably 100min.
To obtain SiO 2 @CeO 2 Then, the invention uses the SiO 2 @CeO 2 Placing the mixture in a strong alkaline solution for silica removal treatment to obtain hollow CeO 2 . In the present invention, the strong alkaline solution preferably includes a NaOH solution and/or a CaOH solution; the concentration of the alkali solution is preferably 3 to 5mol/L, more preferably 3.5 to 4.5mol/L, and even more preferably 4mol/L. The using amount of the strong alkali solution is not particularly limited, and SiO can be dissolved 2 @CeO 2 And (5) immersing. In the present invention, the temperature of the silica removal treatment is preferably 60 to 80 ℃, more preferably 60 to 75 ℃, and still more preferably 60 to 70 ℃. After the silica removal treatment, the present invention preferably further comprises a post-treatment comprising: oxidizing said dioxygenatedCooling the reaction liquid obtained by silicon treatment to room temperature, carrying out solid-liquid separation, washing the obtained solid product, and drying to obtain hollow CeO 2 . The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art, such as natural cooling, may be used. The solid-liquid separation method of the present invention is not particularly limited, and a solid-liquid separation method known to those skilled in the art, specifically, centrifugal separation, may be employed. In the present invention, the number of washing with water is preferably 1~5 times, more preferably 2~3 times. In the present invention, the drying method is preferably vacuum drying, the drying temperature is preferably 60 to 80 ℃, more preferably 65 to 75 ℃, and even more preferably 70 ℃, and the drying time is not particularly limited, and the drying may be performed until the weight is constant.
Hollow CeO 2 Then, the invention will use hollow CeO 2 Mixing the molybdenum source, selenium, a reducing agent and water, and carrying out hydrothermal reaction to obtain the heterojunction composite material precursor.
In the present invention, the hollow CeO 2 And selenium preferably in a mass ratio of 1:0.45 to 0.5, more preferably 1:0.46 to 0.49, and more preferably 1:0.47 to 0.48. In the present invention, the molybdenum source preferably includes Na 2 MoO 4 (ii) a The molar ratio of molybdenum to selenium in the molybdenum source is preferably 1:2~3, more preferably 1:2.2 to 2.8, and more preferably 1:2.4 to 2.5. In the present invention, the mass ratio of the molybdenum source to water is preferably 1:0.0001 to 0.002, preferably 1:0.0005 to 0.0001, more preferably 1:0.0006 to 0.0008. In the present invention, the reducing agent preferably includes hydrazine hydrate and/or sodium borohydride; the molar ratio of selenium to reducing agent is preferably 1:1~2, more preferably 1:1.2 to 1.8, and more preferably 1:1.4 to 1.5.
In the present invention, the hollow CeO 2 Mixing the molybdenum source, the selenium, the reducing agent and water, preferably mixing the molybdenum source and the water to obtain a molybdenum source dispersion liquid; mixing selenium with a reducing agent to obtain a selenium-reducing agent mixture; mixing the molybdenum source dispersion, the selenium-reducing agent mixture and the hollow CeO 2 And (4) mixing. In the invention, the molybdenum source and the water are preferably mixed by ultrasonic stirring; the invention is aboutThe ultrasonic stirring and mixing is not particularly limited, and the molybdenum source can be uniformly dispersed in water. In the present invention, the selenium and the reducing agent are preferably mixed under stirring, and the mixing time is preferably 4 to 5 hours, and more preferably 4.5 hours. In the present invention, the molybdenum source dispersion, the selenium-reducing agent mixture and the hollow CeO 2 The mixing mode is preferably stirring mixing, and the stirring mixing time is preferably 1.5 to 2.5 hours, and more preferably 2 hours.
In the invention, the temperature of the hydrothermal reaction is preferably 180 to 200 ℃, more preferably 185 to 195 ℃, and further preferably 190 ℃; the hydrothermal reaction time is preferably 20 to 24h, more preferably 21 to 23h, and further preferably 22h. After the hydrothermal reaction, the present invention preferably further comprises a post-treatment, wherein the post-treatment comprises: cooling the reaction liquid obtained by the hydrothermal reaction to room temperature, carrying out solid-liquid separation, washing the obtained solid product, and drying to obtain hollow CeO 2 . The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art may be used, specifically, natural cooling. The solid-liquid separation method of the present invention is not particularly limited, and a solid-liquid separation method known to those skilled in the art, specifically, centrifugal separation, may be used. In the present invention, the number of washing with water is preferably 1~5 times, more preferably 2~3 times. In the present invention, the drying method is preferably vacuum drying, the drying temperature is preferably 60 to 80 ℃, more preferably 65 to 75 ℃, and even more preferably 70 ℃, and the drying time is not particularly limited, and the drying may be performed until the weight is constant.
After the heterojunction composite material precursor is obtained, the heterojunction composite material precursor is calcined in a hydrogen atmosphere to obtain the heterojunction composite material. In the present invention, the temperature of the calcination is preferably 450 to 550 ℃, more preferably 480 to 520 ℃, and further preferably 500 to 510 ℃; the calcination time is preferably 30 to 40min, more preferably 32 to 38min, and further preferably 35 to 36min; the calcination is preferably carried out in a rapid-heating furnace, and the temperature rise rate of the temperature of the rapid-heating furnace from room temperature to the calcination temperature is preferably 7 to 11 ℃/s, more preferablyThe temperature is 9 to 10 ℃/s. In the present invention, during the calcination, the calcination is performed due to H 2 The crystal structure of the precursor of the heterojunction composite material is distorted to generate oxygen vacancies, and the heterojunction composite material rich in the oxygen vacancies is formed.
The invention provides an application of the heterojunction composite material prepared by the preparation method in the technical scheme or the application of the heterojunction composite material prepared by the preparation method in the technical scheme as a photocatalyst.
In the present invention, the heterojunction composite material is preferably used as a photocatalyst for preparing carbon monoxide and methane by reducing carbon dioxide.
In the present invention, the conditions for applying the heterojunction composite material in the preparation of carbon monoxide and methane by reducing carbon dioxide preferably include: the ratio of the mass of the heterojunction composite to the pressure of carbon dioxide is preferably 1g:4 to 6MPa, more preferably 1g:5MPa; the reaction temperature is preferably room temperature, and the reaction time is preferably 1 to 12h, more preferably 6h.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Non-porous SiO 2 The preparation of (1): stirring 4.35mL of 32wt% ammonia water and 74mL of ethanol with a magnetic stirrer at room temperature for 30min, adding 5.6mL of ethyl orthosilicate, stirring with the magnetic stirrer at room temperature for 1h to form an opal solution, centrifuging, washing the obtained solid product with water and ethanol in sequence, and vacuum drying at 60 ℃ to constant weight to obtain SiO without pores 2 。
(2) Hollow CeO 2 The preparation of (1): 0.1g of nonporous SiO 2 1g of PVP and 40mL of ultrapure water are ultrasonically dispersed uniformly to obtain a mixed dispersion liquid; 5mL of 0.5mol Ce (NO) solution was added 3 ) 3 Aqueous solutions and5mL of HMTA (0.5 mol) to obtain a cerium salt mixture; adding a cerium salt mixture into the mixed dispersion under the condition of rapid stirring at 1000rpm, then placing the mixture into a 250mL flask, turning on an oil bath stirrer switch, setting the heating temperature to 95 ℃, adjusting the stirring speed to 1000rpm, introducing water into a condensation tube, turning on the heating switch after 30min of water introduction, reacting for 2h at 95 ℃, then cooling to room temperature, centrifuging, drying the obtained solid product at 60 ℃ in vacuum to constant weight, and then calcining for 100min at 600 ℃ in an air atmosphere to obtain SiO 2 @CeO 2 . Then SiO 2 @CeO 2 Placing in NaOH solution with concentration of 3mol/L, removing silicon dioxide under oil bath condition of 60 ℃ for 6h, cooling to room temperature, centrifuging, washing the obtained solid product with water for 3 times, and vacuum drying at 60 ℃ to constant weight to obtain hollow CeO 2 (abbreviation H-CeO) 2 ）。
(3) Preparing a heterojunction composite material: adding 0.2mmol of Na 2 MoO 4 Adding the molybdenum source dispersion liquid into 50mL of deionized water, and carrying out ultrasonic stirring and mixing to obtain a molybdenum source dispersion liquid; dissolving 0.4mmol Se in 10 mL hydrazine hydrate, and stirring for 5h at room temperature to obtain selenium solution; mixing molybdenum source dispersion, selenium solution and 0.4mmol H-CeO 2 Stirring and mixing for 2H, placing in a reaction kettle, performing hydrothermal reaction at 200 ℃ for 24H, cooling to room temperature, centrifuging, washing the obtained solid product, and vacuum drying at 60 ℃ to constant weight to obtain heterojunction composite material precursor (H-CeO) 2 @MoSe 2 ). Putting the precursor of the heterojunction composite material into a rapid heating furnace in H 2 Under the condition, heating to 550 ℃ at the heating rate of 10 ℃/s, and then preserving heat and heating for 40min to obtain the heterojunction composite material (H-Vo-CeO for short) 2 @MoSe 2 Wherein, moSe 2 49.7%) by mass.
Example 2
A heterojunction composite material was prepared as in example 1, differing from example 1 only in that Na 2 MoO 4 The dosage of the (C) is 0.05mmol, and the heterojunction composite material (H-Vo-CeO for short) is obtained 2 @MoSe 2 Wherein, moSe 2 Mass ofFraction 12.3%).
Example 3
A heterojunction composite material was prepared as in example 1, differing from example 1 only in that Na 2 MoO 4 The dosage of (A) is 0.13mmol, and the heterojunction composite material (H-Vo-CeO for short) is obtained 2 @MoSe 2 Wherein, moSe 2 33.4%) was added.
Example 4
A heterojunction composite material was prepared as in example 1, differing from example 1 only in that Na 2 MoO 4 The dosage of the (C) is 0.26mmol, and the heterojunction composite material (H-Vo-CeO for short) is obtained 2 @MoSe 2 Wherein, moSe 2 Mass fraction of (d) 63.5%).
Comparative example 1
Adding 0.2mmol of Na 2 MoO 4 Adding the molybdenum source dispersion into 50mL of deionized water, and carrying out ultrasonic stirring and mixing to obtain a molybdenum source dispersion liquid; dissolving 0.4mmol Se in 10 mL hydrazine hydrate, and stirring for 5h at room temperature to obtain selenium solution; stirring and mixing the molybdenum source dispersion liquid and the selenium solution for 2h, then placing the mixture into a reaction kettle, carrying out hydrothermal reaction for 24h at the temperature of 200 ℃, cooling to room temperature, centrifuging, washing the obtained solid product with water, and carrying out vacuum drying at the temperature of 60 ℃ to constant weight to obtain MoSe 2 。
FIG. 1 is a non-porous SiO prepared in example 1 2 、H-Vo-CeO 2 @MoSe 2 And SiO 2 @CeO 2 SEM picture of (1), H-CeO 2 And H-Vo-CeO 2 @MoSe 2 TEM image of (A) and H-Vo-CeO 2 @MoSe 2 In which a is SiO 2 SEM picture of (b) is H-Vo-CeO 2 @MoSe 2 SEM picture of (1), c is SiO 2 @CeO 2 SEM picture of (1), d is H-CeO 2 TEM image of (e) is H-Vo-CeO 2 @MoSe 2 In TEM image of (b), f is H-Vo-CeO 2 @MoSe 2 HRTEM of (g). As can be seen from a and c in FIG. 1, the non-porous SiO 2 (template) and SiO 2 @CeO 2 All are nano-spheres with uniform size, the average size is about 200nm, and no-hole SiO is adopted 2 Smooth surface, siO 2 @CeO 2 The surface of the composite structure is relatively rough. As can be seen from b in FIG. 1, the final product H-Vo-CeO 2 @MoSe 2 Unique hollow shape of heterojunction, ceO 2 The surface is obviously coated with MoSe 2 And (3) slicing. At the same time, ceO with hollow structure 2 The shape change of the CeO is not obvious, which shows that the thermal process of the solvent is applied to the CeO with a hollow structure 2 The morphology of (A) has no destructive effect. As can be seen from d in FIG. 1, the uniform hollow CeO is shown 2 Nanospheres, average size 200 nm. As can be seen from e in FIG. 1, the hollow CeO 2 Quilt MoSe 2 The hollow structure is not changed and the size distribution is uniform by laminating and covering. MoSe is clearly seen from f in FIG. 1 2 Layer structure and lattice fringes of (1), H-Vo-CeO 2 @MoSe 2 Showing no more than four layers of the multilayer crystalline strip; moSe 2 Was determined to be 1.56nm, much greater than its intrinsic (002) surface value of 0.64nm; it is also apparent from region A that CeO 2 And MoSe 2 A heterostructure is formed at the interface of (a).
FIG. 2 shows H-CeO prepared in example 1 2 And H-Vo-CeO 2 @MoSe 2 And MoSe prepared in comparative example 1 2 In which a is H-CeO 2 B is MoSe 2 And c is H-Vo-CeO 2 @MoSe 2 . As can be seen from FIG. 2, the hollow CeO 2 The morphology of the CeO does not change obviously, which shows that the thermal process of the solvent can not be applied to the CeO with a hollow structure 2 The morphology of (A) is destroyed and the hollow CeO 2 The structure did not collapse.
FIG. 3 shows H-CeO prepared in example 1 2 @MoSe 2 And H-Vo-CeO 2 @MoSe 2 In which a is H-CeO 2 @MoSe 2 B is H-Vo-CeO 2 @MoSe 2 . The large peak of the transition metal Mo is evident from FIG. 3 and is found in H-CeO 2 @MoSe 2 At a g value of 1.98 no signal appears, at H 2 H-Vo-CeO after atmosphere calcination treatment 2 @MoSe 2 The signal generation at the g value of 1.98 is obviously enhanced, which proves that the H-CeO 2 @MoSe 2 Proceed with H 2 The reduction treatment may be carried out in H-CeO 2 @MoSe 2 The surface obtains more enriched oxygen vacancies, reduces the recombination rate of photo-generated electrons and photo-generated holes, and improves the light absorption capacity.
FIG. 4 shows H-CeO prepared in example 1 2 And H-Vo-CeO 2 @MoSe 2 And MoSe prepared in comparative example 1 2 In the BET diagram of (1), wherein a is H-CeO 2 B is MoSe 2 And c is H-Vo-CeO 2 @MoSe 2 . As can be seen from FIG. 4, the hollow CeO 2 、MoSe 2 And H-Vo-CeO 2 @MoSe 2 Are 157.395m 2 /g、59.9m 2 G and 226.2m 2 In terms of/g, hollow CeO 2 And MoSe 2 The specific surface area of the material is relatively small, and H-Vo-CeO 2 @MoSe 2 Has a large specific surface area.
FIG. 5 shows H-CeO prepared in example 1 2 And H-Vo-CeO 2 @MoSe 2 And MoSe prepared in comparative example 1 2 Detecting the profile. As can be seen from FIG. 5, H-Vo-CeO prepared in example 1 2 @MoSe 2 The impedance of (2) is minimum, which shows that the impedance of the device to the transmission of the carriers is minimum, and the device is favorable for the separation of the photo-generated charges.
Application example 1
15mg of H-Vo-CeO prepared in example 1~4 and comparative example 2~3, respectively 2 @MoSe 2 H-CeO prepared in example 1 2 And MoSe prepared in comparative example 1 2 Independently used as a catalyst for reducing carbon dioxide, and used for preparing carbon monoxide and methane, H-CeO under the conditions of visible light irradiation and room temperature by catalytic reduction of carbon dioxide (the pressure is 80 kPa) 2 、MoSe 2 And H-Vo-CeO prepared in example 1 2 @MoSe 2 CO and CH at different reaction times 4 Yield of (5) and H-Vo-CeO prepared in example 2~4 2 @MoSe 2 CO and CH at 4h of reaction 4 The results of the yield test of (a) are shown in FIG. 6~7 and Table 1.
FIG. 6 shows H-CeO prepared in example 1 2 And H-Vo-CeO 2 @MoSe 2 And MoSe prepared in comparative example 1 2 The results of the catalytic performance test under different reaction times of (1), wherein a is H-CeO 2 B is MoSe 2 And c is H-Vo-CeO 2 @MoSe 2 。
FIG. 7 shows H-CeO prepared in example 1 2 MoSe prepared in comparative example 1 2 And H-Vo-CeO prepared in example 1~4 2 @MoSe 2 And testing the photocatalytic performance at the reaction time of 4h.
TABLE 1H-Vo-CeO prepared in example 1~4 and comparative example 2~3 2 @MoSe 2 H-CeO prepared in example 1 2 And MoSe prepared in comparative example 1 2 Photocatalytic performance test results of
As can be seen from FIG. 6~7 and Table 1, ceO was irradiated under visible light 2 、MoSe 2 And H-Vo-CeO 2 @MoSe 2 Photocatalytic CO 2 The main products of the reduction are two carbon-containing products, CO and CH 4 。CH 4 The reduction products of (a) involve more electron transfer and relative energy and are therefore more difficult to generate. H-CeO 2 More CO was detected in the photocatalytic reduction product but no CH 4 Is generated. H-Vo-CeO 2 @MoSe 2 Exhibit significantly enhanced photocatalytic CO 2 Reduction activity and concomitant CH 4 With the generation of MoSe 2 Increase in content of CO 2 The reducing performance of (a) is improved and then reduced. H-Vo-CeO 2 @MoSe 2 CH (A) of 4 The yields of (10.2 μmol) and CO (33.2 μmol) were highest.
For clearer analysis of photocatalytic reduction of CO 2 CO and CH in the process 4 For CO and CH in units of every 0.5h 4 Yield analysis of (1), H-CeO prepared in example 1 2 And H-Vo-CeO prepared in example 1 2 @MoSe 2 And MoSe prepared in comparative example 1 2 CO and CH formed 4 The yield is stable, and the phenomena of sharp increase and sharp decrease are not obvious in the reaction of 4 h; H-CeO 2 And MoSe 2 CO was generated under visible light irradiation, but CH was not detected during the entire test period 4 ；H-Vo-CeO 2 @MoSe 2 Catalytic reduction of CO 2 In the process, CH 4 And CO are both formed at the beginning of the reduction reaction, and, with the time of the reduction reaction extended, CO and CH 4 The content of (a) is continuously increasing. Thus, H-CeO 2 And MoSe 2 For improving CeO by the composite and hollow heterojunction structure containing oxygen vacancy 2 Photocatalytic reduction of CO 2 The performance has extremely obvious promotion effect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A heterojunction composite material is characterized by comprising oxygen-rich vacancy hollow CeO 2 And hollow CeO dispersed in the oxygen-rich vacancy 2 MoSe of surface 2 Said MoSe 2 And oxygen-rich vacancy hollow CeO 2 A heterojunction structure is formed.
2. The heterojunction composite material of claim 1, wherein the MoSe is 2 The mass fraction of (B) is 12.3 to 63.5%.
3. The heterojunction composite material of claim 1, wherein the oxygen vacancy rich hollow CeO 2 The granularity of the shell is 100 to 500nm, and the thickness of the shell is 7 to 20nm.
4. A method of making the heterojunction composite of any of claims 1~3 comprising the steps of:
hollow CeO is formed 2 Mixing a molybdenum source, selenium, a reducing agent and water, and carrying out hydrothermal reaction to obtain a heterojunction composite material precursor;
and calcining the heterojunction composite material precursor in a hydrogen atmosphere to obtain the heterojunction composite material.
5. The method for producing a composite material according to claim 4, wherein the hollow CeO 2 The preparation method comprises the following steps:
mixing nonporous silicon dioxide, polyvinylpyrrolidone, water, hexamethylenetetramine and water-soluble cerium salt, carrying out hydrothermal reaction, and calcining to obtain SiO 2 @CeO 2 ；
Subjecting the SiO 2 @CeO 2 Placing the mixture in a strong alkaline solution for silica removal treatment to obtain hollow CeO 2 。
6. The preparation method according to claim 5, wherein the temperature of the hydrothermal reaction is 95 to 100 ℃ and the time is 100 to 120min;
the calcining temperature is 450 to 600 ℃, and the time is 100min;
the concentration of the strong alkali solution is 3 to 5mol/L.
7. The method for preparing according to claim 4, wherein the hollow CeO 2 And selenium in a mass ratio of 1:0.45 to 0.5;
the molar ratio of molybdenum to selenium in the molybdenum source is 1:2~3;
the reducing agent comprises hydrazine hydrate and/or sodium borohydride;
the molar ratio of the selenium to the reducing agent is 1:1~2.
8. The preparation method according to claim 4 or 7, wherein the hydrothermal reaction is carried out at a temperature of 180 to 200 ℃ for 20 to 24h.
9. The method for preparing the material according to claim 4, wherein the temperature of the calcination is 450 to 550 ℃, and the time is 30 to 40min.
10. Use of the heterojunction composite material of any one of claims 1~3 or the heterojunction composite material prepared by the method of manufacture of any one of claim 4~9 as a photocatalyst.
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