CN113398994B - Keggin type heteropolyacid indissolvable salt heterojunction catalyst and preparation method and application thereof - Google Patents

Keggin type heteropolyacid indissolvable salt heterojunction catalyst and preparation method and application thereof Download PDF

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CN113398994B
CN113398994B CN202110710498.0A CN202110710498A CN113398994B CN 113398994 B CN113398994 B CN 113398994B CN 202110710498 A CN202110710498 A CN 202110710498A CN 113398994 B CN113398994 B CN 113398994B
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salt
heteropoly acid
keggin type
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keggin
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CN113398994A (en
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刘季铨
薛岗林
杨鹏
赵瑞雪
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NORTHWEST UNIVERSITY
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
    • B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
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    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B01J35/39—
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/027—Preparation from water
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The application discloses a Keggin type heteropoly acid insoluble salt heterojunction catalyst and a preparation method and application thereof, and belongs to the technical field of preparation of polyacid composite materials. The preparation method of the catalyst comprises the steps of adding Keggin type heteropoly acid indissolvable salt, bismuth precursor salt and an organic solvent (organic-water mixed solvent) into a closed container, reacting at 150-250 ℃, and drying to obtain the Keggin type heteropoly acid indissolvable salt heterojunction catalyst. The preparation method has the advantages of simple preparation process, controllable conditions, stable composite structure and lower cost; the prepared Keggin type heteropolyacid indissolvable salt heterojunction material has good photocatalysis performance, and can be used for photocatalysis nitrogen reduction, oxygen reduction and the like.

Description

Keggin type heteropolyacid indissolvable salt heterojunction catalyst and preparation method and application thereof
Technical Field
The application belongs to the technical field of polyacid composite materials, and particularly relates to a Keggin type heteropolyacid insoluble salt heterojunction catalyst, and a preparation method and application thereof.
Background
In the context of energy, environment and climate crisis caused by exhaustion of fossil energy and emission of greenhouse gases, compounds with economic added values (such as ammonia, hydrogen peroxide and the like) are synthesized by taking renewable light energy as driving force from a large number of available small molecules (such as nitrogen, oxygen and water) in the environment so as to meet the demands of daily chemical products. However, the synthetic route has the problems of low photocatalysis efficiency (short service life of photo-generated carriers and narrow photo-response range), high difficulty in generating high-value products, high industrial production cost and the like. Therefore, the application has high efficiency and high selectivity, and is a main target of chemical engineering upgrading in renewable energy systems.
Photocatalytic nitrogen reduction was first described by Schrauzer et al 1977 in Fe doped TiO 2 Upper realization (G.N.Schrauzer, T.D.Guth, J.Am.Chem.Soc.1977,99 (22), 7189-7193). Because the radius of Bi atoms is large, the Bi-O structure formed by hybridization of f orbit electrons and O2p electrons has a proper energy level structure, and is favorable for absorbing ultraviolet light and visible light. Meanwhile, bismuth-based materials are easy to form oxygen defect structures so as to be beneficial to adsorbing substrate gas molecules. In addition, bismuth-based materials have conductivity over common oxides, such as TiO 2 . The bismuth-based semiconductor photocatalysts that have been developed so far have Bi 2 O 2 CO 3 (J.Colloid Interface Sci.2021,583,499-509；ACS Appl.Mater.Interfaces 2018,10(30),25321-25328.)、Bi 5 O 7 I(ACS Appl.Mater.Interfaces 2016,8(41),27661-27668.)Bi 5 O 7 Br(Adv.Mater.2017,29(31),1701774)、Bi 3 O 4 Br(Adv.Mater.2019,31(28),1807576)、BiOBr(J.Am.Chem.Soc.2015,137(19),6393-6399；J.Mater.Sci.2019,54(13),9397-9413；Nano Lett.2018,18(11),7372-7377；CN111408363A)、BiOI(J.Colloid Interface Sci.2019,539,563-574.)、BiOCl(Nanoscale 2016,8(4),1986-1993.ACS Appl.Energy Mater.2019,2(12),8394-8398.)、Bi 2 WO 6 (RSC Advances 2017,7 (79), 50040-50043;ACS Sustainable Chem.Eng.2018,6 (9), 11190-11195; catal. Sci. Technology.2019; chem. Eur. J.2021,414 (15), 128827) and Bi 2 MoO 6 (chem. Eur. J.2016,22 (52), 18722-18728), and the like. However, the photo-generated electron-hole of the single bismuth-based photocatalyst is easily recombined, resulting in a decrease in photocatalytic activity thereof. Research shows that the compound semiconductor can effectively promote the photo-generated electricityThe separation efficiency of the sub-hole pairs and the widened light response range can improve the performance of the photocatalyst.
Polyacids are polyoxometalate metal complexes (POMs) that are very similar to semiconducting metal oxides in both structural and photochemical properties. Their LUMO-HOMO level differences are comparable to the forbidden band width of semiconductors. The excited states formed when they are excited by light have very strong redox properties. In addition, they possess excellent electron carrying and releasing capabilities ("electron library" properties) and reversible multi-electron redox properties. In the photocatalytic reaction, a two-electron or multi-electron reduction process is promoted. However, the polyacid spectrum response range of a single component is narrow, the photo-generated carriers are easy to compound, the chemical adsorption to nitrogen is weak, and the photocatalytic nitrogen reduction performance is not obvious. It has been reported that the polyacid-based composite catalyst has SiW 12 /K-C 3 N 4 (Appl.Catal.,B 2018,239,260-267)、rGO@POMs(ACS Appl.Mater.Interfaces 2019,11(41),37927-37938)、ZIF-67@PMo 12-x V x (ChemSusChem 2020,13 (10), 2769-2778) and P 2 W 17 M/V-g-C 3 N 4 (Inorg.Chem.Front.2019,6(11),3315-3326)。
Besides nitrogen reduction, bismuth-based photocatalysts for preparing hydrogen peroxide by photocatalytic oxygen reduction mainly comprise BiVO 4 (ACS Catalysis 2016,6 (8), 4976-4982;Appl.Catal.B 2020,272,119003;J.Am.Chem.Soc.2020,142 (19), 8641-8648.) and Bi/Bi 2 O 2-x CO 3 (chem. Eng. J.2019,363, 374-382.). Meanwhile, research based on polyacid composite photocatalyst mainly comprises immobilizing the absent Keggin type polyacid on functionalized g-C through covalent bond 3 N 4 (Nano Energy 2017,35,405-414；Catal.Sci.Technol.2018,8(6),1686-1695；CN 110052280A)。
Therefore, the bismuth-based material with proper forbidden bandwidth, ultraviolet-visible light wide wavelength range response and high oxygen defect density is compounded with the quasi-semiconductor polyacid with 'electron library' and reversible multi-electron redox properties, so that the spectral response and absorption efficiency can be effectively improved, the separation of photo-generated carriers (electrons-holes) can be promoted, and the gas substrate can be increasedChemisorption of molecules, and the like. However, it is difficult to form a complex of the polyacid and the bismuth-based photocatalyst, and it is necessary to introduce a polymer having tackiness such as SiW 9 Co 3 /PDA/Bi 2 WO 6 (J.Mater.Chem.A 2020,8(32),16590-16598)。
Disclosure of Invention
In order to remedy the defects of the soluble polyacid, the method adopts indissolvable polyacrylate (Keggin type heteropolyacid indissolvable salt) and forms a heterojunction catalyst by growing bismuth-based materials on the surface of the insoluble polyacid, so that the photocatalytic performance of the insoluble polyacid is improved. The method of the application is an interfacial growth method, and is different from the direct addition of Cs salt to PMo-containing material 12 O 40 Bi of (2) 2 O 3 Formation of Cs in aqueous suspension 3 PMo 12 O 40 /Bi 2 O 3 A composite structure. The preparation method has the advantages of simple preparation process, controllable conditions, stable composite structure and lower cost; the prepared Keggin type polyacid indissolvable salt heterojunction material has good photocatalytic performance, and can be used for photocatalytic nitrogen reduction, oxygen reduction and the like.
In order to achieve the technical purpose, the application adopts the following technical scheme:
keggin-type heteropolyacid insoluble salt heterojunction catalyst with structural general formula of Keggin-POMs@BiMO x Wherein bismuth-based material BiMOx is Bi 2 O 3 、Bi 2 O 2 CO 3 、Bi 2 MoO 6 、Bi 2 WO 6 、BiVO 4 Bismuth oxyhalide BiO with different oxyhalide ratios m X n And (x=f, cl, br, I) and the like.
In another aspect of the application, the preparation method of the Keggin type heteropoly acid insoluble salt heterojunction catalyst is provided, keggin type heteropoly acid insoluble salt is dispersed in bismuth precursor salt solution, and after the reaction at 150-250 ℃, the Keggin type heteropoly acid insoluble salt heterojunction catalyst is obtained after washing and drying.
The Keggin type heteropoly acid (polyoxometallate, POMs) is a metal-oxygen cluster structure formed by transition metal (such as W, mo, V, nb, ta) and oxygen. Wherein, is saturated KegThe general formula of gin-type heteropolyacid anions can be expressed as [ AM ] 12 O 40 ] n- A is P, si, ge, as; m is Mo or W; the general formula of the transition metal substituted Keggin type heteropolyacid anion can be expressed as [ AM ] 1 x M 2 12-x O 40 ] n- A is P, si, ge, as; m is M 1 V, co, cu, fe, mn, ti, ru, ce, x is 1-3; m is M 2 Is Mo or W.
The Keggin type heteropoly acid insoluble salt is saturated Keggin type heteropoly acid anions and transition metal substituted Keggin type heteropoly acid anions and metal large cations (such as Cs) + 、Ag + Isophyton) to form a poorly soluble salt; or insoluble salts formed by hexacoordination chelate formed by metals Ru and Ir and nitrogen, sulfur and phosphorus and saturated Keggin type heteropolyacid anions or transition metal substituted Keggin type heteropolyacid anions; or insoluble salt formed by quaternary ammonium salt, imidazole salt and Keggin type heteropolyacid anions or transition metal substituted Keggin type heteropolyacid anions.
The bismuth salt precursor is a sulfate containing metallic bismuth (Bi 2 (SO 4 ) 3 ) Nitrate (Bi (NO) 3 ) 3 ) And halides (BiX) 3 (x=f, cl, br, I)), and the like. In preparing bismuth-based materials, the bismuth salt precursor salts described above, and salt species forming lamellar structure materials with bismuth trivalent ions, e.g. Bi, should be included 2 WO 6 Desired meta-tungstate, bi formation 2 MoO 6 The desired meta-molybdate, the halide required to form bismuth oxyhalide, etc.
The molar ratio of the Keggin type heteropoly acid insoluble salt to the bismuth precursor salt is 0.01:1-5:1.
The solvent of the bismuth precursor salt solution is an organic solvent or an organic-water mixed solvent. In the solvothermal synthesis, the ratio of water to organic solvent in the mixed solvent is not more than 1:1. Organic solvents are commonly used organic monohydric alcohols (e.g., ethanol), dihydric alcohols (e.g., ethylene glycol), and trihydric alcohols (e.g., glycerol). The mixed solvent comprises water, acetonitrile, N-dimethylformamide, dimethyl sulfoxide and the like.
In another aspect of the application, the application of the Keggin-type heteropolyacid indissolvable salt heterojunction catalyst in photocatalytic nitrogen and oxygen reduction is also provided.
The reduction reaction pressure is usually one atmosphere, and can be carried out under high pressure, the pressure is within 10Mpa, and the reaction temperature is in the range of 0-100 ℃. The nitrogen reduction and oxygen reduction reactions are carried out in pure water without electrolyte, and the catalyst can be suspended in a reaction system or coated on a substrate carrier (such as a quartz plate) which does not absorb visible light and ultraviolet light to form a film. The photocatalytic reaction can be carried out in a reaction kettle containing quartz or sapphire window sheets, and can also be carried out in a full mixed flow reaction kettle or a fixed bed reactor containing quartz or sapphire window sheets. The reaction gas enters the reactor through bubbling or is carried out in a form of gas-liquid two-phase mixture. The photocatalytic reaction is carried out in the ultraviolet-visible range, and the light source includes sunlight or an artificial light source (such as a xenon lamp, a tungsten lamp, a mercury lamp, etc.).
The beneficial effects of the application are as follows: (1) The method has the advantages of simple preparation process, low cost and easily available raw materials. (2) The prepared Keggin type heteropoly acid indissolvable salt heterojunction catalyst is characterized in that bismuth-based materials grow on the surface of Keggin type heteropoly acid indissolvable salt to form a compound similar to a core-shell structure. (3) The prepared Keggin type heteropoly acid indissolvable salt heterojunction catalyst has a light response range from ultraviolet to visible light and has a higher oxygen defect position. (4) The prepared Keggin type heteropolyacid indissolvable salt heterojunction catalyst has good photocatalytic activity and is suitable for preparing ammonia by nitrogen reduction and preparing hydrogen peroxide by oxygen reduction. (5) The prepared Keggin type heteropoly acid indissolvable salt heterojunction catalyst has excellent stability, the Keggin type heteropoly acid indissolvable salt and bismuth-based material have strong acting force, and the part where component loss or destruction occurs in the photocatalysis process is relatively small.
Drawings
FIG. 1 is a schematic illustration of the preparation of hydrogen peroxide by photocatalytic oxygen reduction using a heterojunction catalyst in accordance with the present application; wherein, 1: [ Ru (bpy) 3 ] 2.5 SiFe(OH 2 )W 11 O 39 @δ-Bi 2 O 3 ，2：Cs 3 PW 12 O 40 @δ-Bi 2 O 3 ，3：δ-Bi 2 O 3 ，4：Cs 3 PW 12 O 40 ；
FIG. 2 is a schematic illustration of the photocatalytic nitrogen reduction of the heterojunction catalyst of the present application to produce ammonia; wherein, 1: [ Ru (bpy) 3 ] 1.5 PMo 12 O 40 @Bi 2 MoO 6 ，2：Bi 2 MoO 6 ，3：[Ru(bpy) 3 ] 1.5 PMo 12 O 40 。
Detailed Description
The following description of the present application will be made more complete and clear in view of the detailed description of the application, which is to be taken in conjunction with the accompanying drawings that illustrate only some, but not all, of the embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The present embodiment provides a Cs 3 PW 12 O 40 @δ-Bi 2 O 3 The preparation method of the heterojunction catalyst comprises the following steps: 20mg Cs 3 PW 12 O 40 Powder, dispersed in 20mL of an ethylene glycol-water mixed solution (V Ethylene glycol :V Water and its preparation method =4:1). After 15min of ultrasound, 970mg Bi (NO) was added 3 ) 3 ·5H 2 O, stir at room temperature for 1h. The mixture was transferred to a closed reaction vessel and reacted thermally with stirring at 150℃for 4h. Then the sample taken out is washed three times by ultrapure water and absolute ethyl alcohol respectively, and then dried at room temperature to obtain Cs 3 PW 12 O 40 @δ-Bi 2 O 3 Heterojunction catalysts.
Example 2
The present embodiment provides a [ Ru (bpy) 3 ] 2.5 SiFe(OH 2 )W 11 O 39 @δ-Bi 2 O 3 The preparation method of the heterojunction catalyst comprises the following steps: 40mg of [ Ru (bpy) 3 ] 2.5 SiFe(OH 2 )W 11 O 39 Powder, dispersed in 20mL of an ethylene glycol-water mixed solution (V Ethylene glycol :V Water and its preparation method =3:1). After 15min of ultrasound, 490mg Bi (NO) was added 3 ) 3 ·5H 2 O, stir at room temperature for 1h. The mixture was transferred to a closed reaction vessel and reacted thermally with stirring at 170℃for 4h. Then the sample is washed three times with ultrapure water and absolute ethanol, and dried at room temperature to obtain [ Ru (bpy) 3 ] 2.5 SiFe(OH 2 )W 11 O 39 @δ-Bi 2 O 3 Heterojunction catalysts.
Example 3
The present embodiment provides an Ag 4 SiMo 12 O 40 @δ-Bi 2 O 3 The preparation method of the heterojunction catalyst comprises the following steps: 250mg of Ag 4 SiMo 12 O 40 The powder was dispersed in 20mL of ethylene glycol. After 15min of ultrasound, 17.8mg Bi was added 2 (SO 4 ) 3 Stir at room temperature for 1h. The mixture was transferred to a closed reaction vessel and reacted thermally with stirring at 190℃for 4h. Then the sample taken out is washed three times by ultrapure water and absolute ethyl alcohol respectively, and dried at room temperature to obtain Ag 4 SiMo 12 O 40 @δ-Bi 2 O 3 Heterojunction catalysts.
Example 4
The present embodiment provides a [ Ru (bpy) 3 ] 1.5 PMo 12 O 40 @Bi 2 MoO 6 The preparation method of the heterojunction catalyst comprises the following steps: 900mg [ Ru (bpy) 3 ] 1.5 PMo 12 O 40 The powder was dispersed in 20mL glycerol. After 15min of ultrasound, 98mg Bi (NO) was added 3 ) 3 ·5H 2 O and 4.8g Na 2 MoO 4 ·2H 2 O was stirred at room temperature for 1h. The mixture was transferred to a closed reaction vessel and reacted under stirring at 200℃for 2 hours. Then the sample is washed three times with ultrapure water and absolute ethanol, and dried at room temperature to obtain [ Ru (bpy) 3 ] 1.5 PMo 12 O 40 @Bi 2 MoO 6 Heterojunction catalysts.
Example 5
The present embodiment provides an Ag 5 PW 10 V 2 O 40 @Bi 2 MoO 6 The preparation method of the heterojunction catalyst comprises the following steps: 10mg of Ag 5 PW 10 V 2 O 40 Powder, dispersed in 20mL glycol-water mixed solution (V Ethylene glycol :V Water and its preparation method =3:1). After 15min of ultrasound, 49mg Bi (NO) was added 3 ) 3 ·5H 2 O and 2.4g Na 2 MoO 4 ·2H 2 O was stirred at room temperature for 1h. The mixture was transferred to a closed reaction vessel and reacted under stirring at 200℃for 2 hours. Then the sample taken out is washed three times by ultrapure water and absolute ethyl alcohol respectively, and dried at room temperature to obtain Ag 5 PW 10 V 2 O 40 @Bi 2 MoO 6 Heterojunction catalysts.
Example 6
The present embodiment provides a Cs 5 PW 10 V 2 O 40 @Bi 2 WO 6 The preparation method of the heterojunction catalyst comprises the following steps: 3.2g Cs 5 PW 10 V 2 O 40 The powder was dispersed in 20mL glycerol. After 15min of ultrasound, 12.5mg Bi (NO) was added 3 ) 3 ·5H 2 O and 0.83g Na 2 WO 4 ·2H 2 O was stirred at room temperature for 1h. The mixture was transferred to a closed reaction vessel and reacted under stirring at 250℃for 2 hours. Then the sample taken out is washed three times by ultrapure water and absolute ethyl alcohol respectively, and then dried at room temperature to obtain Cs 5 PW 10 V 2 O 40 @Bi 2 WO 6 Heterojunction catalysts.
Example 7
The present embodiment provides a [ Ru (bpy) 3 ] 3 SiW 9 O 37 Co 3 (H 2 O) 3 The preparation method of the @ BiOBr heterojunction catalyst comprises the following steps: 80mg [ Ru (bpy) 3 ] 3 SiW 9 O 37 Co 3 (H 2 O) 3 Powder, dispersed in 40mL of an ethylene glycol-water mixed solution (V Ethylene glycol :V Water and its preparation method =1:1). After 15min of ultrasound, 1.45g Bi (NO) was added 3 ) 3 ·5H 2 O and 0.31g NaBr were stirred at room temperatureAnd 1h. The mixture was transferred to a closed reaction vessel and reacted under stirring at 180℃for 12 hours. Then the sample is washed three times with ultrapure water and absolute ethanol, and dried at room temperature to obtain [ Ru (bpy) 3 ] 3 SiW 9 O 37 Co 3 (H 2 O) 3 @ BiOBr heterojunction catalyst.
Example 8 comparative experiments
Similar to the synthesis of example 1, except that Bi (NO 3 ) 3 ·5H 2 O is dispersed in the mixed solvent and thermally reacted for 4 hours at 180 ℃. Then the sample taken out is washed three times by ultrapure water and absolute ethyl alcohol respectively, and then is dried at room temperature to obtain delta-Bi 2 O 3 Heterojunction catalysts.
Example 9 photocatalytic oxygen reduction experiments
Ru (bpy) prepared in example 2 3 ] 2.5 SiFe(OH 2 )W 11 O 39 @δ-Bi 2 O 3 (0.1 g) was dispersed in 100mL of ultrapure water. After introducing oxygen and stirring for 30min, the light source 300W (lambda) was turned on>420 nm). The reaction temperature is controlled at 20 ℃, samples are taken every 30min, and the activity of catalyzing the reduction of oxygen into hydrogen peroxide is examined.
Cs prepared in example 1 3 PW 12 O 40 @δ-Bi 2 O 3 Dispersed in 100mL of ultrapure water. After oxygen was introduced and stirred for 30min, the light source 300W was turned on (220<λ<800 nm). The reaction temperature is controlled at 20 ℃, samples are taken every 30min, and the activity of catalyzing the reduction of oxygen into hydrogen peroxide is examined and examined.
delta-Bi prepared in example 8 2 O 3 Dispersed in 100mL of ultrapure water. After introducing oxygen and stirring for 30min, the light source 300W (lambda) was turned on>420 nm). The reaction temperature is controlled at 20 ℃, samples are taken every 30min, and the activity of catalyzing the reduction of oxygen into hydrogen peroxide is examined and examined.
Cs is processed by 3 PW 12 O 40 Dispersed in 100mL of ultrapure water. After oxygen was introduced and stirred for 30min, the light source 300W was turned on (220<λ<800 nm). The reaction temperature is controlled at 20 ℃, samples are taken every 30min, and the catalytic oxygen reduction of the samples is examined and inspected to obtain dioxygenActivity of water.
As shown in FIG. 1, the Keggin type heteropoly acid insoluble salt heterojunction catalysts obtained in the embodiments 1 and 2 of the application have good photocatalytic activity and are superior to Keggin type heteropoly acid insoluble salt Cs 3 PW 12 O 40 And the single component bismuth-based photocatalytic material delta-Bi prepared in example 8 2 O 3 。
Example 10 photocatalytic nitrogen reduction experiments
Ru (bpy) prepared in example 4 3 ] 1.5 PMo 12 O 40 @Bi 2 MoO 6 (0.1 g) was dispersed in 100mL of ultrapure water. After introducing nitrogen and stirring for 30min, the light source 300W was turned on (220<λ<800 nm). The reaction temperature is controlled at 20 ℃, samples are taken every 30min, and the activity of catalyzing nitrogen to reduce into ammonia is examined and examined.
Bi is mixed with 2 MoO 6 (0.1 g) was dispersed in 100mL of ultrapure water. After introducing nitrogen and stirring for 30min, the light source 300W was turned on (220<λ<800 nm). The reaction temperature is controlled at 20 ℃, samples are taken every 30min, and the activity of catalyzing nitrogen to reduce into ammonia is examined and examined.
Will [ Ru (bpy) 3 ] 1.5 PMo 12 O 40 (0.1 g) was dispersed in 100mL of ultrapure water. After introducing nitrogen and stirring for 30min, the light source 300W was turned on (220<λ<800 nm). The reaction temperature is controlled at 20 ℃, samples are taken every 30min, and the activity of catalyzing nitrogen to reduce into ammonia is examined and examined.
As shown in FIG. 2, the [ Ru (bpy) ] prepared by the present application 3 ] 1.5 PMo 12 O 40 @Bi 2 MoO 6 Photocatalytic activity higher than Bi 2 MoO 6 And [ Ru (bpy) 3 ] 1.5 PMo 12 O 40 。
Although embodiments of the present application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the application, the scope of which is defined in the appended claims and their equivalents.

Claims (3)

1. The preparation method of the Keggin type heteropoly acid insoluble salt heterojunction catalyst is characterized in that Keggin type heteropoly acid insoluble salt is dispersed in bismuth-containing precursor salt solution, reacted at 150-250 ℃, washed and dried to obtain the Keggin type heteropoly acid insoluble salt heterojunction catalyst;
the Keggin type heteropoly acid comprises saturated Keggin type heteropoly acid and transition metal substituted Keggin type heteropoly acid;
the anionic general formula of the Keggin type heteropolyacid is [ AM ] 12 O 40 ] n- A is P, si, ge, as; m is Mo or W;
the anion general formula of the transition metal substituted Keggin type heteropolyacid is [ AM ] 1 x M 2 12-x O 40 ] n- A is P, si, ge, as, M 1 V, co, fe, ru, x is 1-3, M 2 Is Mo or W;
the Keggin type heteropolyacid insoluble salt is as follows:
insoluble salt formed by saturated Keggin type heteropoly acid anions or transition metal substituted Keggin type heteropoly acid anions and metal large cations;
metal Ru 2+ 、Ir 2+ Insoluble salts formed by hexacoordination chelate formed by nitrogen, sulfur and phosphorus and saturated Keggin type heteropoly acid anions or transition metal substituted Keggin type heteropoly acid anions;
insoluble salt formed by quaternary ammonium salt, imidazole salt and saturated Keggin type heteropoly acid anions or transition metal substituted Keggin type heteropoly acid anions;
the bismuth precursor salt comprises sulfate, nitrate or halide of metallic bismuth and salt which forms lamellar structure material with bismuth trivalent ion;
bismuth-based materials forming heterojunction structures with Keggin-type heteropoly acid insoluble salts comprise Bi 2 O 3 、Bi 2 O 2 CO 3 、Bi 2 MoO 6 、Bi 2 WO 6 Or BiVO 4 And bismuth oxyhalide BiO with different oxyhalide ratios m X n X is F, cl, br or I;
the prepared Keggin type heteropoly acid indissolvable salt heterojunction catalyst is a compound formed by growing bismuth-based materials on the surface of Keggin type heteropoly acid indissolvable salt to form a core-shell structure.
2. The Keggin-type heteropoly acid insoluble salt heterojunction catalyst prepared by the preparation method as claimed in claim 1, which is characterized in that the structural general formula is Keggin-POMs@BiMO x Wherein BiMO is x Is a bismuth-based photocatalytic material.
3. The application of the Keggin type heteropoly acid insoluble salt heterojunction catalyst in photocatalysis as claimed in claim 2, which is characterized by comprising photocatalysis nitrogen reduction and photocatalysis oxygen reduction.
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