CN114939406A - Bi2MoO6 photocatalyst and preparation method and application thereof - Google Patents
Bi2MoO6 photocatalyst and preparation method and application thereof Download PDFInfo
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- CN114939406A CN114939406A CN202210296208.7A CN202210296208A CN114939406A CN 114939406 A CN114939406 A CN 114939406A CN 202210296208 A CN202210296208 A CN 202210296208A CN 114939406 A CN114939406 A CN 114939406A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 52
- 229910002900 Bi2MoO6 Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 36
- 150000001336 alkenes Chemical class 0.000 claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- 229940015043 glyoxal Drugs 0.000 claims description 11
- 150000001621 bismuth Chemical class 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 150000002751 molybdenum Chemical class 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 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 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 claims description 3
- 229940036358 bismuth subcarbonate Drugs 0.000 claims description 3
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 3
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 claims description 3
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 3
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 3
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000002057 nanoflower Substances 0.000 claims description 2
- NPNPBXVQJSIOBJ-UHFFFAOYSA-M oxobismuthanyl perchlorate Chemical compound [Bi+]=O.[O-]Cl(=O)(=O)=O NPNPBXVQJSIOBJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001338 self-assembly Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 238000009777 vacuum freeze-drying Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 7
- 230000004913 activation Effects 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 49
- 239000007789 gas Substances 0.000 description 12
- 238000007146 photocatalysis Methods 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- VDQDGCAHVVNVDM-UHFFFAOYSA-K bismuth;triperchlorate Chemical compound [Bi+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O VDQDGCAHVVNVDM-UHFFFAOYSA-K 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
The invention discloses a Bi2MoO6 photocatalyst and a preparation method and application thereof. The synthesis method is simple and efficient, the cost is low, and the prepared Bi2MoO6 photocatalyst not only has an electron aggregation effect at an oxygen vacancy, but also can adsorb carbon dioxide and reduce the activation energy of the reaction; in addition, Bi alkene and Bi with oxygen vacancy 2 MoO 6 The ohmic contact between the catalyst and the catalyst can realize nearly zero-resistance charge transfer, and the catalyst can effectively improve the separation of carriers andthe method has the advantages of high transfer efficiency, good photocatalytic carbon dioxide reduction performance, contribution to realizing strategic targets of carbon peak reaching and carbon neutralization proposed by China and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of energy environment and nano material preparation, and particularly relates to a Bi2MoO6 photocatalyst and a preparation method and application thereof.
Background
The photocatalysis technology is a green and sustainable energy regeneration process by converting carbon dioxide and water into valuable hydrocarbon through artificial photocatalysis by utilizing solar energy and oxidizing and reducing the carbon dioxide into hydrocarbon fuel, and is vital to environmental protection. By utilizing the photocatalysis technology to oxidize and reduce the carbon dioxide into other hydrocarbon products, the concentration of the carbon dioxide in the atmosphere can be reduced, and a novel energy storage mode is provided. The carbon monoxide and the methane and other hydrocarbon fuels can be used as one or more high-added-value chemical fuels, and have a plurality of advantages compared with the traditional fossil fuel. For example, the cleaning and pollution-free cleaning agent has the advantages of being clean, free of pollution, easy to obtain raw materials, low in price, high in energy density and the like.
However, the traditional photocatalytic material has low solar energy utilization rate, difficult carrier separation and higher carbon dioxide activation energy, and hinders the catalytic reaction; in addition, conventional photocatalytic materials lack high active sites and low charge transfer efficiency. Therefore, practical application of carbon dioxide photo-reduction requires designing a catalyst which can reduce the carbon dioxide reduction activation energy and can effectively realize the mass transfer of charges.
Oxygen-vacancy-bearing catalysts can, on the one hand, capture more electrons as charge separation centers. On the other hand, the catalyst with oxygen vacancy can generate local polarization phenomenon, and adsorb more carbon dioxide, thereby reducing the activation energy of the carbon dioxide and enabling the reaction to be easier to perform. Bi alkene and Bi with oxygen vacancy 2 MoO 6 Due to the strong interaction of the built-in electric field in the middle of the ohmic contact, the charge can be transferred by nearly zero resistance, the separation and transfer of current carriers are well realized, and the photocatalytic performance is improved in energy efficiency.
Disclosure of Invention
The invention mainly aims to overcome the defects of the background technology and provides a preparation method of a Bi2MoO6 photocatalyst. The material has the functions of adsorbing carbon dioxide and reducing the activation energy of the carbon dioxide, can effectively realize the capture of charges and the separation of carriers, and has high photocatalytic carbon dioxide reduction performance, long cycle service life and wide application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a Bi2MoO6 photocatalyst comprises the following steps:
(1) crushing large-size Bi balls by a cell crusher, adding deionized water for centrifugal washing for a plurality of times, and finally taking 1/4 supernatant to obtain Bi alkene;
(2) putting bismuth salt into a container, adding a reducing solvent, and stirring until the bismuth salt and the reducing solvent are uniformly mixed to obtain a solution A;
(3) putting the molybdenum salt into a reaction kettle, adding a reducing solvent, and stirring until the mixture is uniformly mixed to obtain a solution B;
(4) dropwise adding the solution A into the solution B under continuous stirring, and then stirring and reacting for a certain time to obtain a solution C;
(5) and (2) adding a reducing solvent, glyoxal and the Bi alkene synthesized in the step (1) into the solution C, stirring and mixing uniformly, placing the reaction kettle in an oven, heating and preserving heat, and washing, centrifuging and drying a product after the reaction is finished to obtain the photocatalyst.
Preferably, the diameter of the large-sized Bi sphere is 5-10 microns.
Preferably, in the step (2), the bismuth salt is one or more selected from bismuth oxide perchlorate, bismuth nitrate, bismuth sulfate, bismuth acetate, bismuth subcarbonate or bismuth trichloride; the molar mass of the bismuth salt is 0.1-2 mmol. More preferably, the molar mass of the bismuth salt is 0.6 to 0.8 mmol.
Preferably, in the step (3), the molybdenum salt is one or more selected from sodium molybdate, copper molybdate, iron molybdate, zinc molybdate, ammonium molybdate or cobalt molybdate; the mass of the molybdenum salt is 0.2-4 mmol. More preferably, the molar mass of the molybdenum salt is 1.2 to 1.6 mmol.
Preferably, in the step (2) and the step (3), the reducing solvent is one or more selected from the group consisting of ethylene glycol, ethanol, methanol, formic acid, benzyl alcohol, isopropanol, formaldehyde, hydrazine hydrate, glucose solution and sodium borohydride solution; the volume of the reducing solvent in the step (2) and the step (3) is 5-50 mL. Further preferably, the volume of the reducing solvent is 5-10 mL.
Preferably, in the step (5), the reducing solvent is one or more selected from ethylene glycol, ethanol, methanol, formic acid, benzyl alcohol, isopropanol, formaldehyde, hydrazine hydrate, glucose solution or sodium borohydride solution; in the step (5), the volume of the reducing solvent is 20-60mL, the volume of the glyoxal is 0.1-1mL, and the volume of the Bi alkene is 0.1-1 mL. More preferably, the volume of the reducing solvent in the step (5) is 30-40 mL, the volume of the glyoxal is 0.4-0.6mL, and the volume of the Bi alkene is 0.4-0.6 mL.
Preferably, the stirring time in steps (2) to (5) is 1 to 4 hours.
Preferably, the temperature of the oven in the step (5) is 100-.
In addition, the invention also claims the Bi2MoO6 photocatalyst prepared by the method and the application of the Bi2MoO6 photocatalyst in the photocatalytic reduction of carbon dioxide.
Preferably, the specific method of the application is as follows: under the irradiation of visible light, Bi2MoO6 is used as a photocatalyst to catalyze the reduction of carbon dioxide to generate combustible fuel.
Preferably, the combustible fuel is one or more of carbon monoxide, methane, methanol, formaldehyde, formic acid, ethanol and ethane.
Compared with the prior art, the invention has the following beneficial effects:
(1) the Bi2MoO6 photocatalyst provided by the invention is a nanoflower self-assembled by nanosheets, the specific surface area is large, the number of active sites of photocatalytic reaction is large, and the contact between the nanosheets is beneficial to shortening the transfer distance of charges and prolonging the service life of the charges, so that the photocatalytic carbon dioxide reduction performance is further improved.
(2) The oxygen vacancy of the Bi2MoO6 photocatalyst provided by the invention can capture more electrons on one hand and serve as a charge separation center, and the efficient separation of charges is realized, so that the service life of the charges is prolonged. On the other hand, the catalyst with oxygen vacancy can generate local polarization phenomenon and adsorb more carbon dioxide, thereby reducing the activation energy of carbon dioxide and enabling the reaction to be easier to carry out.
(3) In addition, the Bi alkene and Bi with oxygen vacancy of the invention 2 MoO 6 Due to the strong interaction of the built-in electric field in the middle of the ohmic contact, the charge can be transferred almost to zero resistance, the separation and transfer of carriers are well realized, and the photocatalytic carbon dioxide reduction performance is improved in energy efficiency.
Drawings
FIG. 1 is a field emission scanning electron microscope photograph of a Bi2MoO6 photocatalyst prepared in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following is only illustrative of the present invention and is not to be construed as limiting the invention.
The terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
Example 1
A preparation method of a Bi2MoO6 photocatalyst comprises the following steps:
(1) firstly, crushing large-size Bi balls by a cell crusher, then adding deionized water for centrifugal washing for a plurality of times, and finally taking 1/4 supernatant to obtain Bi alkene;
(2) putting 0.4mmol of bismuth sulfate into a container, adding 10mL of ethanol, and stirring until the mixture is uniformly mixed to obtain a solution A;
(3) putting 0.8mmol of zinc molybdate into a reaction kettle, adding 10mL of ethanol, and stirring until the mixture is uniformly mixed to obtain a solution B;
(4) dropwise adding the solution A into the solution B under continuous stirring, and then stirring and reacting for 1 hour to obtain a solution C;
(5) and (3) adding 30mL of isopropanol, 0.4mL of glyoxal and 0.6mL of Bi alkene synthesized in the step (1) into the solution C, stirring and mixing for 1 hour, placing the reaction kettle in an oven, preserving the temperature at 180 ℃ for 12 hours, washing the product for 3 times by using ethanol and deionized water respectively after the reaction is finished, centrifuging and drying to obtain the photocatalyst.
The performance of the Bi2MoO6 photocatalyst described in example 1 was evaluated as follows: weighing 50mg of photocatalyst, adding 10mL of deionized water into a reaction vessel, performing ultrasonic treatment for half an hour to uniformly spread a sample at the bottom of the reactor, and drying for 5 hours at 60 ℃; the air in the reaction system was removed by introducing nitrogen gas for 60 minutes. Carbon dioxide and water are used as raw materials, and the reaction is carried out under the irradiation of a 300W xenon lamp (lambda is more than 420nm), and the distance between a reactor and a light source is 1 cm.
The content of generated gas was measured by gas chromatography with 1mL of gas per hour. Through measurement, the rates of the visible light photocatalysis carbon dioxide of the photocatalyst in the embodiment for reducing and generating carbon monoxide and methanol respectively reach 88.62 mu mol/h/g and 1.89 mu mol/h/g.
Example 2
A preparation method of a Bi2MoO6 photocatalyst comprises the following steps:
(1) crushing large-size Bi balls by a cell crusher, adding deionized water for centrifugal washing for a plurality of times, and finally taking 1/4 supernatant to obtain Bi alkene;
(2) putting 0.65mmol of bismuth nitrate into a container, adding 5mL of ethylene glycol, and stirring until the mixture is uniformly mixed to obtain a solution A;
(3) putting 1.3mmol of sodium molybdate into a reaction kettle, adding 5mL of ethylene glycol, and stirring until the mixture is uniformly mixed to obtain a solution B;
(4) dropwise adding the solution A into the solution B under continuous stirring, and then stirring and reacting for 1 hour to obtain a solution C;
(5) and (2) adding 30mL of ethanol, 0.5mL of glyoxal and 0.5mL of Bi alkene synthesized in the step (1) into the solution C, stirring and mixing for 1 hour, placing the reaction kettle in an oven, preserving the temperature at 160 ℃ for 20 hours, washing the product for 3 times by using ethanol and deionized water respectively after the reaction is finished, centrifuging and drying to obtain the photocatalyst.
The performance of the Bi2MoO6 photocatalyst described in example 2 was evaluated as follows: weighing 50mg of photocatalyst, adding 10mL of deionized water into a reaction vessel, performing ultrasonic treatment for half an hour to uniformly spread a sample at the bottom of the reactor, and drying at 60 ℃ for 5 hours; the air in the reaction system was removed by introducing nitrogen gas for 45 minutes. Carbon dioxide and water are used as raw materials, and the reaction is carried out under the irradiation of a 300W xenon lamp (lambda is more than 420nm), and the distance between a reactor and a light source is 1 cm.
The content of generated gas was measured by gas chromatography with 1mL of gas per hour. Through determination, the rate of the photocatalyst in the embodiment for generating carbon monoxide through reduction of the visible light photocatalysis carbon dioxide reaches 169.93 mu mol/h/g, and the rate of the photocatalyst for generating methane through reduction of the visible light photocatalysis carbon dioxide reaches 4.65 mu mol/h/g.
Example 3
A preparation method of a Bi2MoO6 photocatalyst comprises the following steps:
(1) crushing large-size Bi balls by a cell crusher, adding deionized water for centrifugal washing for a plurality of times, and finally taking 1/4 supernatant to obtain Bi alkene;
(2) putting 1.5mmol of bismuth acetate into a container, adding 20mL of methanol, and stirring until the mixture is uniformly mixed to obtain a solution A;
(3) putting 3mmol of ammonium molybdate into a reaction kettle, adding 20mL of 50% glucose solution, and stirring until the solution is uniformly mixed to obtain a solution B;
(4) dropwise adding the solution A into the solution B under continuous stirring, and then stirring and reacting for 2 hours to obtain a solution C;
(5) and (2) adding 40mL of benzyl alcohol, 0.3mL of glyoxal and 0.8mL of Bi alkene synthesized in the step (1) into the solution C, stirring and mixing for 1 hour, placing the reaction kettle in an oven, preserving heat for 16 hours at 140 ℃, washing the product for 3 times by using ethanol and deionized water after the reaction is finished, centrifuging and drying to obtain the photocatalyst.
The performance of the Bi2MoO6 photocatalyst described in example 3 was evaluated as follows: weighing 50mg of photocatalyst, adding 10mL of deionized water into a reaction vessel, performing ultrasonic treatment for half an hour to uniformly spread a sample at the bottom of the reactor, and drying for 5 hours at 60 ℃; the air in the reaction system was removed by introducing nitrogen gas for 45 minutes. Carbon dioxide and water are used as raw materials, and the reaction is carried out under the irradiation of a 300W xenon lamp (lambda is more than 420nm), and the distance between a reactor and a light source is 1 cm.
The content of generated gas was measured by gas chromatography taking 1mL of gas per hour. Through determination, the rates of the visible light photocatalysis carbon dioxide of the photocatalyst in the embodiment for reducing and generating carbon monoxide and methane respectively reach 68.28 mu mol/h/g and 0.92 mu mol/h/g.
Example 4
A preparation method of a Bi2MoO6 photocatalyst comprises the following steps:
(1) crushing large-size Bi balls by a cell crusher, adding deionized water for centrifugal washing for a plurality of times, and finally taking 1/4 supernatant to obtain Bi alkene;
(2) putting 0.8mmol of bismuth trichloride into a container, adding 15mL of formaldehyde, and stirring until the mixture is uniformly mixed to obtain a solution A;
(3) placing 1.6mmol of cobalt molybdate in a reaction kettle, adding a mixed solution of 15mL of ethanol and 5mL of 20% sodium borohydride, and stirring until the mixture is uniformly mixed to obtain a solution B;
(4) dropwise adding the solution A into the solution B under continuous stirring, and then stirring and reacting for 1 hour to obtain a solution C;
(5) and (2) adding 30mL of ethylene glycol, 0.8mL of glyoxal and 0.2mL of Bi alkene synthesized in the step (1) into the solution C, stirring and mixing for 4 hours, placing the reaction kettle in an oven, keeping the temperature at 100 ℃ for 8 hours, washing the product for 3 times by using ethanol and deionized water after the reaction is finished, centrifuging and drying to obtain the photocatalyst.
The performance of the Bi2MoO6 photocatalyst described in example 4 was evaluated as follows: weighing 50mg of photocatalyst, adding 10mL of deionized water into a reaction vessel, performing ultrasonic treatment for half an hour to uniformly spread a sample at the bottom of the reactor, and drying for 5 hours at 60 ℃; the air in the reaction system was removed by introducing nitrogen for 45 minutes. Carbon dioxide and water are used as raw materials, and the reaction is carried out under the irradiation of a 300W xenon lamp (lambda is more than 420nm), and the distance between a reactor and a light source is 1 cm.
The content of generated gas was measured by gas chromatography with 1mL of gas per hour. Through measurement, the rates of the photocatalyst of the embodiment for generating carbon monoxide and methanol through the reduction of carbon dioxide by visible light photocatalysis respectively reach 93.31 mu mol/h/g and 1.88 mu mol/h/g.
Example 5
A preparation method of a Bi2MoO6 photocatalyst comprises the following steps:
(1) crushing large-size Bi balls by a cell crusher, adding deionized water for centrifugal washing for a plurality of times, and finally taking 1/4 supernatant to obtain Bi alkene;
(2) putting 2mmol of bismuth perchlorate oxide into a container, adding 20mL of formic acid, and stirring until the mixture is uniformly mixed to obtain a solution A;
(3) putting 4mmol of iron molybdate into a reaction kettle, adding 20mL of formic acid, and stirring until the mixture is uniformly mixed to obtain a solution B;
(4) dropwise adding the solution A into the solution B under continuous stirring, and then stirring and reacting for 2 hours to obtain a solution C;
(5) and (3) adding 20mL of isopropanol, 1mL of glyoxal and 1mL of Bi alkene synthesized in the step (1) into the solution C, stirring and mixing for 4 hours, placing the reaction kettle in an oven, preserving the temperature for 18 hours at 140 ℃, washing the product for 3 times by using ethanol and deionized water after the reaction is finished, centrifuging and drying to obtain the photocatalyst.
The performance of the Bi2MoO6 photocatalyst described in example 5 was evaluated as follows: weighing 50mg of photocatalyst, adding 10mL of deionized water into a reaction vessel, performing ultrasonic treatment for half an hour to uniformly spread a sample at the bottom of the reactor, and drying for 5 hours at 60 ℃; the air in the reaction system was removed by introducing nitrogen for 45 minutes. Carbon dioxide and water are used as raw materials, and the reaction is carried out under the irradiation of a 300W xenon lamp (lambda is more than 420nm), and the distance between a reactor and a light source is 1 cm.
The content of generated gas was measured by gas chromatography with 1mL of gas per hour. Through measurement, the rate of generating carbon monoxide by the visible light photocatalysis carbon dioxide of the photocatalyst in the embodiment reaches 142.88 mu mol/h/g.
Example 6
A preparation method of a Bi2MoO6 photocatalyst comprises the following steps:
(1) crushing large-size Bi balls by a cell crusher, adding deionized water for centrifugal washing for a plurality of times, and finally taking 1/4 supernatant to obtain Bi alkene;
(2) putting 0.1mmol of bismuth subcarbonate into a container, adding 5mL of ethylene glycol, and stirring until the mixture is uniformly mixed to obtain a solution A;
(3) putting 0.2mmol of sodium molybdate into a reaction kettle, adding 5mL of ethanol, and stirring until the mixture is uniformly mixed to obtain a solution B;
(4) dropwise adding the solution A into the solution B under continuous stirring, and then stirring and reacting for 1 hour to obtain a solution C;
(5) and (2) adding 20mL of benzyl alcohol, 0.2mL of glyoxal and 0.4mL of Bi alkene synthesized in the step (1) into the solution C, stirring and mixing for 2 hours, placing the reaction kettle in an oven, preserving the temperature for 4 hours at 180 ℃, washing the product for 3 times by using ethanol and deionized water after the reaction is finished, centrifuging and drying to obtain the photocatalyst.
The performance of the Bi2MoO6 photocatalyst described in example 6 was evaluated as follows: weighing 50mg of photocatalyst, adding 10mL of deionized water into a reaction vessel, performing ultrasonic treatment for half an hour to uniformly spread a sample at the bottom of the reactor, and drying for 5 hours at 60 ℃; the air in the reaction system was removed by introducing nitrogen for 45 minutes. Carbon dioxide and water are used as raw materials, and the reaction is carried out under the irradiation of a 300W xenon lamp (lambda is more than 420nm), and the distance between a reactor and a light source is 1 cm.
The content of generated gas was measured by gas chromatography with 1mL of gas per hour. Through determination, the rate of the photocatalyst in the embodiment for generating carbon monoxide through reduction of the visible light photocatalysis carbon dioxide reaches 129.63 mu mol/h/g, and the rate of the photocatalyst for generating methane through reduction of the visible light photocatalysis carbon dioxide reaches 3.08 mu mol/h/g.
The above description describes a preferred embodiment of the present invention and should not be taken as limiting the scope of the invention as claimed. Any modification, equivalent replacement and improvement without departing from the principle and spirit of the present invention shall be considered to be within the protection scope of the present claims.
Claims (10)
1. A preparation method of a Bi2MoO6 photocatalyst is characterized by comprising the following steps:
(1) firstly, crushing large-size Bi spheres by a cell crusher, adding deionized water for centrifugal washing for several times, and finally taking 1/4 supernatant to obtain Bi alkene;
(2) putting bismuth salt into a container, adding a reducing solvent, and stirring until the bismuth salt and the reducing solvent are uniformly mixed to obtain a solution A;
(3) putting the molybdenum salt into a reaction kettle, adding a reducing solvent, and stirring until the mixture is uniformly mixed to obtain a solution B;
(4) dropwise adding the solution A into the solution B under continuous stirring, and then stirring and reacting for a certain time to obtain a solution C;
(5) and (2) adding a reducing solvent, glyoxal and the Bi alkene synthesized in the step (1) into the solution C, stirring and mixing uniformly, placing the reaction kettle in an oven, heating and preserving heat, and washing, centrifuging and drying a product after the reaction is finished to obtain the photocatalyst.
2. The preparation method according to claim 1, wherein in the step (2), the bismuth salt is one or more selected from bismuth oxide perchlorate, bismuth nitrate, bismuth sulfate, bismuth acetate, bismuth subcarbonate, and bismuth trichloride; the molar mass of the bismuth salt is 0.1-2 mmol.
3. The method according to claim 1, wherein in the step (3), the molybdenum salt is one or more selected from sodium molybdate, copper molybdate, iron molybdate, zinc molybdate, ammonium molybdate, or cobalt molybdate; the mass of the molybdenum salt is 0.2-4 mmol.
4. The method according to claim 1, wherein in the step (2) and the step (3), the reducing solvent is one or more selected from the group consisting of ethylene glycol, ethanol, methanol, formic acid, benzyl alcohol, isopropyl alcohol, formaldehyde, hydrazine hydrate, a glucose solution, and a sodium borohydride solution; the volume of the reducing solvent in the step (2) and the step (3) is 5-50 mL.
5. The method according to claim 1, wherein in the step (5), the reducing solvent is one or more selected from the group consisting of ethylene glycol, ethanol, methanol, formic acid, benzyl alcohol, isopropyl alcohol, formaldehyde, hydrazine hydrate, glucose solution, and sodium borohydride solution; in the step (5), the volume of the reducing solvent is 20-60mL, the volume of the glyoxal is 0.1-1mL, and the volume of the Bi alkene is 0.1-1 mL.
6. The production method according to claim 1, wherein the stirring time in steps (2) to (5) is 1 to 4 hours.
7. The preparation method according to claim 1, wherein the temperature of the oven in the step (5) is 100-180 ℃, the holding time is 4-20 hours, the washing solution used for washing is one or more of deionized water or absolute ethyl alcohol, and the drying method is vacuum drying or freeze drying.
8. The Bi2MoO6 photocatalyst prepared by the method of any one of claims 1-7, wherein the photocatalyst is in a nanoflower shape formed by self-assembly of nanosheets.
9. Use of the Bi2MoO6 photocatalyst of claim 8 in photocatalytic reduction of carbon dioxide.
10. The application of claim 9, wherein the specific method of the application is as follows: under the irradiation of visible light, Bi2MoO6 is used as a photocatalyst to catalyze the reduction of carbon dioxide to generate combustible fuel.
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| CN105126821A (en) * | 2015-08-14 | 2015-12-09 | 南昌航空大学 | Flower-like Bi2MoO6 preparation and applications of flower-like Bi2MoO6 in photocatalytic reduction of CO2 |
| WO2019128245A1 (en) * | 2017-12-26 | 2019-07-04 | 深圳大学 | Bismuthene nanosheet and preparation method therefor |
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