CN114146715A - 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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- CN114146715A CN114146715A CN202111528497.0A CN202111528497A CN114146715A CN 114146715 A CN114146715 A CN 114146715A CN 202111528497 A CN202111528497 A CN 202111528497A CN 114146715 A CN114146715 A CN 114146715A
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 119
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 88
- 239000000377 silicon dioxide Substances 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 38
- 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
- 229910052681 coesite Inorganic materials 0.000 claims description 23
- 229910052906 cristobalite Inorganic materials 0.000 claims description 23
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 23
- 239000011669 selenium Substances 0.000 claims description 23
- 229910052682 stishovite Inorganic materials 0.000 claims description 23
- 229910052905 tridymite Inorganic materials 0.000 claims description 23
- 229910016001 MoSe Inorganic materials 0.000 claims description 21
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 21
- 229910052711 selenium Inorganic materials 0.000 claims description 21
- 150000000703 Cerium Chemical class 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
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- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 6
- 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
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 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
- 239000002245 particle Substances 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 23
- 238000000926 separation method Methods 0.000 abstract description 19
- 239000001569 carbon dioxide Substances 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
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- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 description 20
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- 238000003756 stirring Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001816 cooling Methods 0.000 description 16
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 13
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 239000012265 solid product Substances 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000004312 hexamethylene tetramine Substances 0.000 description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 229910004619 Na2MoO4 Inorganic materials 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
- 230000035484 reaction time Effects 0.000 description 6
- 239000011684 sodium molybdate Substances 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 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
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011833 salt mixture Substances 0.000 description 4
- 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
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910021426 porous silicon Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 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
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 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
- 239000003463 adsorbent Substances 0.000 description 1
- 230000005540 biological transmission 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
- 239000003034 coal gas Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007274 generation of a signal involved in cell-cell signaling Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- -1 oxygen anions Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 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 vacancies2And MoSe2Hollow CeO rich in oxygen vacancies2And MoSe2Forming a heterojunction, hollow CeO rich in oxygen vacancies2The hollow structure is uniform, the specific surface area of the heterojunction composite material is improved, the adsorption capacity to carbon dioxide is strong, and the unique hollow structure can enable visible light to be in CeO2Multiple reflection in the hollow cavity, thereby improving the utilization efficiency of visible lightRate; 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 MoSe2With CeO2The 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, in particular to a heterojunction composite material and 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 sunlight2Formation of CO, CH4The greenhouse gas treatment of gas fuel is becoming the research focus of environmental chemistry. CeO (CeO)2Is 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 found2As an n-type semiconductor, the light absorption threshold is about 420nm, which is higher than the most commonly used TiO at present2(388 nm). At the same time, CeO2The 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 Ce4+The simple recombination of electron-hole pairs can be effectively inhibited under the excitation of light, and the photocatalysis efficiency is improved. Thus, CeO2Becomes a potential novel high-efficiency photocatalyst. However, CeO alone2For catalytic reduction of CO2The activity of (A) is not sufficiently high.
Disclosure of Invention
The invention aims to provide a heterojunction composite material, and a preparation method and application thereof2Reduction of CO and CH4Remarkably improve CO2Conversion, CO and CH4The 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 vacancies2And hollow CeO scattered in the oxygen-rich vacancy2MoSe of surface2Said MoSe2And oxygen-rich vacancy hollow CeO2A heterojunction structure is formed.
Preferably, the MoSe is2The mass fraction of (A) is 12.3-63.5%.
Preferably, the oxygen-rich vacancy hollow CeO2The particle size of the shell is 100-500 nm, and the thickness of the shell is 7-20 nm.
The invention provides a preparation method of the heterojunction composite material in the technical scheme, which comprises the following steps:
hollow CeO is formed2Mixing 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 CeO2The 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 SiO2@CeO2；
Subjecting the SiO2@CeO2Placing the mixture in a strong alkaline solution for silica removal treatment to obtain hollow CeO2。
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 2 hours;
the calcining temperature is 450-600 ℃, and the time is 100 min;
the concentration of the strong alkali solution is 3-5 mol/L.
Preferably, the hollow CeO2And 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 to 2.
Preferably, the temperature of the hydrothermal reaction is 180-200 ℃ and the time is 20-24 h.
Preferably, the calcining temperature is 450-550 ℃ and the calcining time is 30-40 min.
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 vacancies2And hollow CeO scattered in the oxygen-rich vacancy2MoSe of surface2Said MoSe2And oxygen-rich vacancy hollow CeO2A heterojunction structure is formed. The unique hollow structure in the heterojunction composite material provided by the invention can enable visible light to be in CeO2The 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 material2The hollow structure is uniform, the specific surface area of the heterojunction composite material is improved, and the hollow structure is used for CO2The adsorption capacity of the adsorbent is strong; introduction of oxygen vacancies is beneficial for CO2Trapping electrons, thereby facilitating the heterojunction composite to CO2The photocatalytic reduction process of (1). Introduced narrow bandgap semiconductor MoSe2With CeO2The 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 improved2Preparation of CO and CH4The 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 view of a non-porous SiO prepared in example 12、H-Vo-CeO2@MoSe2And SiO2@CeO2SEM picture of (1), H-CeO2And H-Vo-CeO2@MoSe2TEM image of (A) and H-Vo-CeO2@MoSe2In which a is SiO2SEM picture of (b) is H-Vo-CeO2@MoSe2SEM picture of (1), c is SiO2@CeO2SEM picture of (1), d is H-CeO2TEM image of (E) is H-Vo-CeO2@MoSe2In TEM image of (b), f is H-Vo-CeO2@MoSe2HRTEM image of (A);
FIG. 2 shows H-CeO prepared in example 12And H-Vo-CeO2@MoSe2And MoSe prepared in comparative example 12In which a is H-CeO2B is MoSe2And c is H-Vo-CeO2@MoSe2；
FIG. 3 shows H-CeO prepared in example 12@MoSe2And H-Vo-CeO2@MoSe2Wherein a is a heterojunction composite material precursor, and b is H-Vo-CeO2@MoSe2；
FIG. 4 shows H-CeO prepared in example 12And H-Vo-CeO2@MoSe2And MoSe prepared in comparative example 12Wherein a is H-CeO2B is MoSe2And c is H-Vo-CeO2@MoSe2；
FIG. 5 shows H-CeO prepared in example 12And H-Vo-CeO2@MoSe2And MoSe prepared in comparative example 12A characteristic detection map of (a);
FIG. 6 shows H-CeO prepared in example 12And H-Vo-CeO2@MoSe2And MoSe prepared in comparative example 12The catalytic performance test results under different reaction times are shown, wherein a is H-CeO2B is MoSe2And c is H-Vo-CeO2@MoSe2。
FIG. 7 shows H-CeO prepared in example 12MoSe prepared in comparative example 12And H-Vo-CeO prepared in examples 1 to 42@MoSe2And testing the photocatalytic performance at the reaction time of 4 h.
Detailed Description
The inventionA heterojunction composite material is provided, comprising oxygen-rich vacancy-rich hollow CeO2And hollow CeO scattered in the oxygen-rich vacancy2MoSe of surface2Said MoSe2And oxygen-rich vacancy hollow CeO2A heterojunction structure is formed.
In the present invention, the MoSe is2The mass fraction (b) of (c) is preferably 12.3 to 63.5%, more preferably 20 to 60%, and still more preferably 30 to 50%.
In the present invention, the oxygen-rich vacancy hollow CeO2The particle size of (A) is preferably 100 to 500nm, more preferably 200 to 400nm, and further preferably 200 to 300 nm; the oxygen-rich vacancy hollow CeO2The thickness of the shell layer(s) is preferably 7 to 20nm, more preferably 10 to 15nm, and still more preferably 10 to 12 nm.
The invention provides a preparation method of the heterojunction composite material in the technical scheme, which comprises the following steps:
hollow CeO is formed2Mixing 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 CeO2Mixing 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 CeO2The preparation method of (a) preferably comprises the steps of:
mixing nonporous silicon dioxide, polyvinylpyrrolidone, water, hexamethylenetetramine and water-soluble cerium salt, carrying out hydrothermal reaction, and calcining to obtain SiO2@CeO2；
Subjecting the SiO2@CeO2Placing the mixture in a strong alkaline solution for silica removal treatment to obtain hollow CeO2。
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 SiO2@CeO2。
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 ammonia water is preferably 30 to 35 wt%, more preferably 31 to 34 wt%, and even more preferably 32 wt%. In the invention, the volume ratio of the ammonia water to the tetraethoxysilane is preferably 4-5: 5-6, more preferably 4.2-4.8: 5.2 to 5.8, and more preferably 4.5 to 4.6: 5.5 to 5.6. In the invention, the volume ratio of the ammonia water to the ethanol is preferably 4-5: 70-80, more preferably 4.2-4.8: 72 to 78, and more preferably 4.5 to 4.6: 75-76. 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, preferably, the ammonia water and the ethanol are stirred and mixed for 20-40 min (more preferably 30min) at room temperature, and then the tetraethoxysilane is added for mixing. In the invention, the temperature of the hydrolysis reaction is preferably room temperature, and the time of the hydrolysis reaction is preferably 50-72 min, more preferably 60-70 min, and even more preferably 60-65 min. 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 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 invention, the particle size of the non-porous silicon dioxide is preferably 180-220 nm, and more preferably 190-210 nm.
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 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: 8-11, more preferably 1: 8.5 to 10.5, and more preferably 1: 9 to 10. In the present invention, the mass ratio of the non-porous silica to water is preferably 1: 65-1000, more preferably 1: 100 to 800, and 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 present 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 3 g/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 invention, the temperature of the hydrothermal reaction is preferably 95-100 ℃, more preferably 96-99 ℃, and further preferably 97-98 ℃; the time of the hydrothermal reaction is preferably 1.2-2.2 hours, more preferably 1.6-2 hours, and even more preferably 2 hours. After the hydrothermal reaction, the present invention preferably further comprises a post-treatment, soThe post-treatment comprises the following steps: 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 SiO2@CeO2And (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 invention, the calcination temperature is preferably 450-600 ℃, more preferably 500-600 ℃, and further preferably 550-600 ℃; the calcination time is preferably 60 to 120min, more preferably 90 to 110min, and further preferably 100 min.
To obtain SiO2@CeO2Then, the invention uses the SiO2@CeO2Placing the mixture in a strong alkaline solution for silica removal treatment to obtain hollow CeO2. In the present invention, the strong alkaline solution preferably includes a NaOH solution and/or a CaOH solution; the concentration of the strong alkali solution is preferably 3-5 mol/L, more preferably 3.5-4.5 mol/L, and further preferably 4 mol/L. The using amount of the strong alkali solution is not particularly limited, and SiO can be dissolved2@CeO2And (5) immersing. In the invention, the temperature of the silica removal treatment is preferably 60-80 ℃, more preferably 60-75 ℃, and further preferably 60-70 ℃. After the silica removal treatment, the present invention preferably further comprises a post-treatment comprising: cooling the reaction liquid obtained by the silica removal treatment to room temperature, carrying out solid-liquid separation, washing the obtained solid product, and drying to obtain hollow CeO2. 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,the solid-liquid separation method known to those skilled in the art may be used, specifically, centrifugal separation. In the present invention, the number of washing with water is preferably 1 to 5, and more preferably 2 to 3. 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 CeO2Then, the invention will use hollow CeO2Mixing 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 CeO2And selenium preferably in a mass ratio of 1: 0.45-0.5, 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 Na2MoO4(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 CeO2Mixing 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 CeO2And (4) mixing. In the invention, the molybdenum source and the water are preferably mixed by ultrasonic stirring; the ultrasonic stirring and mixing is not particularly limited, and the molybdenum source can be uniformly dispersed in water. In the invention, the selenium and the reducing agent are preferably mixed under stirring, and the mixing time is preferably 4-5 h, and more preferably 4.5 h. In the present invention, the molybdenum source dispersion, selenium-reducing agent mixture and hollowCeO2The mixing mode is preferably stirring mixing, and the stirring mixing time is preferably 1.5-2.5 h, and more preferably 2 h.
In the invention, the temperature of the hydrothermal reaction is preferably 180-200 ℃, more preferably 185-195 ℃, and further preferably 190 ℃; the time of the hydrothermal reaction is preferably 20 to 24 hours, more preferably 21 to 23 hours, and further preferably 22 hours. 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, washing the obtained solid product, and drying to obtain hollow CeO2. 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 number of washing with water is preferably 1 to 5, and more preferably 2 to 3. 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 invention, the calcination temperature is preferably 450-550 ℃, more preferably 480-520 ℃, and further preferably 500-510 ℃; the calcination time is preferably 30-40 min, more preferably 32-38 min, and further preferably 35-36 min; the calcination is preferably carried out in a rapid heating furnace, and the temperature of the rapid heating furnace is preferably raised from room temperature to the calcination temperature at a heating rate of 7-11 ℃/s, more preferably 9-10 ℃/s. In the present invention, during the calcination, the calcination is performed due to H2The 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 1 g: 4-6 MPa, more preferably 1 g: 5 MPa; the reaction temperature is preferably room temperature, and the reaction time is preferably 1-12 h, more preferably 6 h.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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 SiO2The preparation of (1): stirring 4.35mL of 32 wt% 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 pores2。
(2) Hollow CeO2The preparation of (1): 0.1g of nonporous SiO21g 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 added3)3Mixing the aqueous solution with 5mL of HMTA (0.5mol) to obtain a cerium salt mixture; adding the 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 a condenser pipeAdding water, introducing water for 30min, turning on a heating switch, reacting at 95 deg.C for 2h, cooling to room temperature, centrifuging, vacuum drying the obtained solid product at 60 deg.C to constant weight, calcining at 600 deg.C in air atmosphere for 100min to obtain SiO2@CeO2. Then SiO2@CeO2Placing 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 CeO2(abbreviation H-CeO)2)。
(3) Preparing a heterojunction composite material: adding 0.2mmol of Na2MoO4Adding 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 of Se in 10mL of hydrazine hydrate, and stirring for 5 hours at room temperature to obtain a selenium solution; mixing molybdenum source dispersion, selenium solution and 0.4mmol H-CeO2Stirring 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@MoSe2). Putting the precursor of the heterojunction composite material into a rapid heating furnace in H2Under 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@MoSe2Wherein, MoSe249.7%) by mass.
Example 2
A heterojunction composite material was prepared as in example 1, differing from example 1 only in that Na2MoO4The dosage of the (C) is 0.05mmol, and the heterojunction composite material (H-Vo-CeO for short) is obtained2@MoSe2Wherein, MoSe212.3%) was added.
Example 3
A heterojunction composite material was prepared as in example 1, differing from example 1 only in that Na2MoO4The dosage of the compound is 0.13mmol, and the heterojunction composite material (H-Vo-C for short) is obtainedeO2@MoSe2Wherein, MoSe233.4%) was added.
Example 4
A heterojunction composite material was prepared as in example 1, differing from example 1 only in that Na2MoO4The dosage of the (C) is 0.26mmol, and the heterojunction composite material (H-Vo-CeO for short) is obtained2@MoSe2Wherein, MoSe2Mass fraction of (d) 63.5%).
Comparative example 1
Adding 0.2mmol of Na2MoO4Adding 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 of Se in 10mL of hydrazine hydrate, and stirring for 5 hours at room temperature to obtain a 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 MoSe2。
FIG. 1 is a view of a non-porous SiO prepared in example 12、H-Vo-CeO2@MoSe2And SiO2@CeO2SEM picture of (1), H-CeO2And H-Vo-CeO2@MoSe2TEM image of (A) and H-Vo-CeO2@MoSe2In which a is SiO2SEM picture of (b) is H-Vo-CeO2@MoSe2SEM picture of (1), c is SiO2@CeO2SEM picture of (1), d is H-CeO2TEM image of (E) is H-Vo-CeO2@MoSe2In TEM image of (b), f is H-Vo-CeO2@MoSe2HRTEM of (g). As can be seen from a and c in FIG. 1, the non-porous SiO2(template) and SiO2@CeO2All are nano-spheres with uniform size, the average size is about 200nm, and no-hole SiO is adopted2Smooth surface, SiO2@CeO2The surface of the composite structure is relatively rough. As can be seen from b in FIG. 1, the final product H-Vo-CeO2@MoSe2Unique hollow shape of heterojunction, CeO2The surface is obviously coated with MoSe2And (3) slicing. At the same time, CeO with hollow structure2The appearance of (A) is not obviously changed, which indicates that the solvent is too hotProcess-to-hollow structure CeO2The morphology of (A) has no destructive effect. As can be seen from d in FIG. 1, the uniform hollow CeO is shown2Nanospheres, average size 200 nm. As can be seen from e in FIG. 1, the hollow CeO2Quilt MoSe2The laminated coating is covered, the hollow structure is not changed, and the size distribution is uniform. MoSe is clearly seen from f in FIG. 12Layer structure and lattice fringes of (1), H-Vo-CeO2@MoSe2Showing no more than four layers of the multilayer crystalline strip; MoSe2Was determined to be 1.56nm, much greater than its intrinsic (002) surface value of 0.64 nm; it is also apparent from region A that CeO2And MoSe2A heterostructure is formed at the interface of (a).
FIG. 2 shows H-CeO prepared in example 12And H-Vo-CeO2@MoSe2And MoSe prepared in comparative example 12In which a is H-CeO2B is MoSe2And c is H-Vo-CeO2@MoSe2. As can be seen from FIG. 2, the hollow CeO2The 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 structure2The morphology of (A) is destroyed and the hollow CeO2The structure did not collapse.
FIG. 3 shows H-CeO prepared in example 12@MoSe2And H-Vo-CeO2@MoSe2In which a is H-CeO2@MoSe2B is H-Vo-CeO2@MoSe2. The large peak of the transition metal Mo is evident from FIG. 3 and is found in H-CeO2@MoSe2At a g value of 1.98 no signal appears, at H2H-Vo-CeO subjected to atmosphere calcination treatment2@MoSe2The signal generation at the g value of 1.98 is obviously enhanced, which proves that the H-CeO2@MoSe2Carrying out H2The reduction treatment may be carried out in H-CeO2@MoSe2The 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 12And H-Vo-CeO2@MoSe2And MoSe prepared in comparative example 12Wherein a is H-CeO2B is MoSe2And c is H-Vo-CeO2@MoSe2. As can be seen from FIG. 4, the hollow CeO2、MoSe2And H-Vo-CeO2@MoSe2Respectively has a specific area of 157.395m2/g、59.9m2G and 226.2m2In terms of/g, hollow CeO2And MoSe2The specific surface area of the material is relatively small, and H-Vo-CeO2@MoSe2Has a large specific surface area.
FIG. 5 shows H-CeO prepared in example 12And H-Vo-CeO2@MoSe2And MoSe prepared in comparative example 12Detecting the profile. As can be seen from FIG. 5, H-Vo-CeO prepared in example 12@MoSe2The impedance of (2) is minimum, which means that the impedance of the material to the transmission of carriers is minimum, and the separation of photo-generated charges is facilitated.
Application example 1
15mg of H-Vo-CeO prepared in examples 1 to 4 and comparative examples 2 to 3 were added to each of the above solutions2@MoSe2H-CeO prepared in example 12And MoSe prepared in comparative example 12Independently 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 80kPa)2、MoSe2And H-Vo-CeO prepared in example 12@MoSe2CO and CH at different reaction times4Yield of (5) and H-Vo-CeO prepared in examples 2 to 42@MoSe2CO and CH at 4h of reaction4The results of the yield test are shown in FIGS. 6 to 7 and Table 1.
FIG. 6 shows H-CeO prepared in example 12And H-Vo-CeO2@MoSe2And MoSe prepared in comparative example 12The results of the catalytic performance test under different reaction times of (1), wherein a is H-CeO2B is MoSe2And c is H-Vo-CeO2@MoSe2。
FIG. 7 shows H-CeO prepared in example 12MoSe prepared in comparative example 12And H-Vo-CeO prepared in examples 1 to 42@MoSe2And testing the photocatalytic performance at the reaction time of 4 h.
TABLE 1H-Vo-CeO prepared in examples 1 to 4 and comparative examples 2 to 32@MoSe2H-CeO prepared in example 12And MoSe prepared in comparative example 12Photocatalytic performance test results of
As is clear from FIGS. 6 to 7 and Table 1, CeO was irradiated with visible light2、MoSe2And H-Vo-CeO2@MoSe2Photocatalytic CO2The main products of the reduction are two carbon-containing products, CO and CH4。CH4The reduction products of (a) involve more electron transfer and relative energy and are therefore more difficult to generate. H-CeO2More CO was detected in the photocatalytic reduction product but no CH4Is generated. H-Vo-CeO2@MoSe2Exhibit significantly enhanced photocatalytic CO2Reduction activity and concomitant CH4With the generation of MoSe2Increase in content of CO2The reducing performance of (a) is improved and then reduced. H-Vo-CeO2@MoSe2CH (A) of4Yields of (10.2. mu. mol) and CO (33.2. mu. mol) were the highest.
Photocatalytic reduction of CO for clearer analysis2CO and CH in the process4In the unit of every 0.5h for CO and CH4Analysis of the yield of (1), H-CeO prepared in example 12And H-Vo-CeO prepared in example 12@MoSe2And MoSe prepared in comparative example 12CO and CH formed4The yield is stable, and the phenomena of sharp increase and sharp decrease are not obvious in the reaction of 4 h; H-CeO2And MoSe2CO was generated under visible light irradiation, but CH was not detected during the entire test4；H-Vo-CeO2@MoSe2Catalytic reduction of CO2In the process, CH4And CO are both formed at the beginning of the reduction reaction, and, with the extension of the reduction reaction time, CO and CH4The content of (a) is continuously increasing. Thus, H-CeO2And MoSe2And contains oxygen vacancies andhollow heterojunction structure for lifting CeO2Photocatalytic reduction of CO2The 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 CeO2And hollow CeO scattered in the oxygen-rich vacancy2MoSe of surface2Said MoSe2And oxygen-rich vacancy hollow CeO2A heterojunction structure is formed.
2. The heterojunction composite material of claim 1, wherein the MoSe is2The mass fraction of (A) is 12.3-63.5%.
3. The heterojunction composite material of claim 1, wherein the oxygen-vacancy-rich hollow CeO2The particle size of the shell is 100-500 nm, and the thickness of the shell is 7-20 nm.
4. A method of preparing a heterojunction composite material as claimed in any of claims 1 to 3, comprising the steps of:
hollow CeO is formed2Mixing 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 preparing according to claim 4, wherein the hollow CeO2The preparation method comprises the following steps:
mixing non-porous silica, polyvinylpyrrolidone, water, and hexamethylene-tetramethleneMixing amine and water-soluble cerium salt, carrying out hydrothermal reaction and calcining to obtain SiO2@CeO2；
Subjecting the SiO2@CeO2Placing the mixture in a strong alkaline solution for silica removal treatment to obtain hollow CeO2。
6. The method according to claim 5, wherein the mass ratio of cerium in the non-porous silica and the water-soluble cerium salt is 1: 2171 to 2181;
the temperature of the hydrothermal reaction is 95-100 ℃, and the time is 100-120 min;
the calcining temperature is 450-600 ℃, and the time is 100 min;
the concentration of the strong alkali solution is 3-5 mol/L.
7. The method for preparing according to claim 4, wherein the hollow CeO2And 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 to 2.
8. The preparation method according to claim 4 or 7, wherein the temperature of the hydrothermal reaction is 180-200 ℃ and the time is 20-24 h.
9. The method according to claim 4, wherein the calcination is carried out at a temperature of 450 to 550 ℃ for 30 to 40 min.
10. Use of the heterojunction composite material of any one of claims 1 to 3 or the heterojunction composite material prepared by the preparation method of any one of claims 4 to 9 as a photocatalyst.
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