CN109569735A - A kind of bismuth series photocatalyst and its preparation method and application - Google Patents
A kind of bismuth series photocatalyst and its preparation method and application Download PDFInfo
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- CN109569735A CN109569735A CN201811443640.4A CN201811443640A CN109569735A CN 109569735 A CN109569735 A CN 109569735A CN 201811443640 A CN201811443640 A CN 201811443640A CN 109569735 A CN109569735 A CN 109569735A
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- bismuth
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- series photocatalyst
- photocatalyst
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- 150000001621 bismuth Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 48
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000001699 photocatalysis Effects 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229940006460 bromide ion Drugs 0.000 claims abstract description 7
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 110
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- 229910052797 bismuth Inorganic materials 0.000 claims description 35
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 34
- 229910052750 molybdenum Inorganic materials 0.000 claims description 25
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 24
- 230000001476 alcoholic effect Effects 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 239000011733 molybdenum Substances 0.000 claims description 24
- 238000001338 self-assembly Methods 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910001451 bismuth ion Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 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 4
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 30
- 239000003054 catalyst Substances 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 235000019441 ethanol Nutrition 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 31
- 239000001569 carbon dioxide Substances 0.000 description 29
- 239000013078 crystal Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000243 solution Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000010586 diagram Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000002356 single layer Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 7
- 238000010531 catalytic reduction reaction Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000011684 sodium molybdate Substances 0.000 description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 4
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical group Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 3
- 241000446313 Lamella Species 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 235000015393 sodium molybdate Nutrition 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001424 field-emission electron microscopy Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B01J35/39—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
-
- 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
- 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 invention belongs to photocatalyst technology field, in particular to a kind of bismuth series photocatalyst and its preparation method and application.Bismuth series photocatalyst provided by the invention includes bismuth molybdate and cetyl trimethylammonium bromide in chemical composition, and the bismuth molybdate is sheet, connects to form embroidery chondritic by intermolecular force；The cetyl trimethylammonium bromide is adsorbed on the surface of sheet bismuth molybdate by bromide ion；The bismuth series photocatalyst has hole.Catalyst provided by the invention has excellent catalytic properties, and in photocatalytic reduction of carbon oxide reaction, after reacting 4h, the production quantity of methanol can reach 30.4~106.5 μm of ol gcatal.‑1, the production quantity of ethyl alcohol can reach 8.7~45.4 μm of ol gcatal.‑1。
Description
Technical field
The invention belongs to photocatalyst technology fields, and in particular to a kind of bismuth series photocatalyst and preparation method thereof and answer
With.
Background technique
In recent years, ultra-thin two-dimensional layer semiconductor material attracts wide attention in photochemical catalyst field, such as: g-C3N4,
Transition metal dichalcogenide etc., main cause are ultra-thin two-dimensional layer materials, are conducive to photo-generated carrier and move from material internal
Material surface is moved on to, the recombination rate of electron hole pair can be greatly reduced, improves photocatalytic activity.In addition, studies have shown that Fermi
The spatial distribution of photo-generated carrier near energy level is concentrated mainly on the surface of material, this means that active light induced electron is empty
Cave is to the surface for being mainly derived from material.The material that semiconductor catalyst is prepared into ultra-thin stratiform can be greatly increased into specific surface
Product, to increase the number of active photo-generated carrier on the surface of the material.Therefore, different semiconductor catalysts is prepared into list
Layer or relatively thin two-dimensional layer material are the effective means for improving its photocatalysis performance.
In recent years bismuth based compound due to its forbidden bandwidth it is relatively narrow, meet the response condition in visible light region, stabilization, nothing
The advantages such as poison and the interest for causing numerous researchers.It is to improve its light that bismuth system multivariant oxide, which is prepared into ultra-thin stratiform nanometer sheet,
One of effective way of catalytic performance, therefore in research in recent years, report out that a variety of single layer Bi system multivariant oxide exists
The application of photocatalysis field.The single layer bismuth system's multivariant oxide prepared at present has preferable catalytic activity, but is used for photocatalysis
When carbon dioxide reduction reaction, catalytic effect is still undesirable.
Summary of the invention
The purpose of the present invention is to provide a kind of bismuth series photocatalyst and its preparation method and application, material provided by the invention
Material connects into 3D silk ball shape by intermolecular force by sheet bismuth molybdate, increases the specific surface area of material, improves material
As the catalytic activity of catalyst, and then improve the conversion ratio of carbon dioxide photo catalytic reduction reaction.
To achieve the goals above, the invention provides the following technical scheme:
It include bismuth molybdate and cetyl trimethyl bromination in chemical composition the present invention provides a kind of bismuth series photocatalyst
Ammonium, the bismuth molybdate are sheet, connect to form embroidery chondritic by intermolecular force；
The cetyl trimethylammonium bromide is adsorbed on the surface of sheet bismuth molybdate by bromide ion；
The bismuth series photocatalyst has hole.
Preferably, the volume > 0.14cm of the hole3·g-1；The specific surface area > 41m of the bismuth series photocatalyst2·
g-1；The average diameter of the bismuth series photocatalyst is 3~4 μm.
The present invention provides the preparation methods of bismuth series photocatalyst described in above-mentioned technical proposal, comprising the following steps:
There is provided includes bismuth source, molybdenum source, the reaction material liquid of cetyl trimethylammonium bromide and ethylene glycol；
The reaction material liquid is heated, obtains bismuth series photocatalyst through self assembly.
Preferably, in the reaction material liquid, the molar ratio of bismuth ion and molybdenum acid ion in molybdenum source is 2:1 in bismuth source.
Preferably, in the reaction material liquid, the molar ratio in cetyl trimethylammonium bromide and bismuth source is 1.8~2.5:5.
Preferably, the reaction material liquid provides as follows:
Bismuth source alcoholic solution is mixed with cetyl trimethylammonium bromide alcoholic solution, is then mixed again with molybdenum source alcoholic solution.
Preferably, in the alcoholic solution of the bismuth source, the concentration of bismuth ion is 0.045~0.055mmol/mL；
In the molybdenum source alcoholic solution, the concentration of molybdenum acid ion is 0.020~0.030mmol/mL.
Preferably, the bismuth source includes bismuth nitrate, and the molybdenum source includes sodium molybdate.
Preferably, the temperature of the self assembly is 120~180 DEG C, and the time of self assembly is 1.5~6h.
The present invention also provides prepare described in the bismuth series photocatalyst or above-mentioned technical proposal described in above-mentioned technical proposal
Application of the bismuth series photocatalyst that method is prepared in photocatalytic reduction of carbon oxide reaction.
Bismuth series photocatalyst provided by the invention, includes bismuth molybdate and cetyl trimethylammonium bromide in chemical composition,
The bismuth molybdate is sheet, connects to form embroidery chondritic by intermolecular force；The cetyl trimethyl bromination
Ammonium is adsorbed on the surface of sheet bismuth molybdate by bromide ion；The bismuth series photocatalyst has hole.Bismuth provided by the invention
In series photocatalyst, sheet bismuth molybdate have superthin structure, shorten photo-generated carrier from material internal be transferred to surface away from
From reducing transit time, to improve the separation rate of electron hole, be more advantageous to photo catalytic reduction CO2The progress of reaction,
Cetyl trimethylammonium bromide then can be by bromide ion strong adsorption on the surface of sheet bismuth molybdate, to make sheet bismuth molybdate
It is negatively charged, and 3D silk ball shape is formed by intermolecular force；And the 3D formed embroiders chondritic with hole, increases bismuth
The specific surface area of series catalysts further promotes the catalytic performance of catalyst.Embodiment shows that catalyst provided by the invention exists
In photocatalytic reduction of carbon oxide reaction, after reacting 4h, the production quantity of methanol can reach 30.4~106.5 μm of ol gcatal.-1,
The production quantity of ethyl alcohol is up to 8.7~45.4 μm of ol gcatal.-1。
Detailed description of the invention
Fig. 1 is the flow diagram of bismuth series photocatalyst preparation method provided by the invention；
Fig. 2 is the XRD diagram of 1~3 products obtained therefrom of the embodiment of the present invention 1~3 and comparative example；
Fig. 3 is the SEM figure and EDS figure of 1 products obtained therefrom of the embodiment of the present invention；
Fig. 4 is that the FESEM of 1 products obtained therefrom of the embodiment of the present invention 1~3 and comparative example schemes；
Fig. 5 is that the SEM of the products obtained therefrom of comparative example 2 and 3 of the present invention schemes；
Fig. 6 is the TEM figure, HRTEM figure and Mapping figure of 1 products obtained therefrom of the embodiment of the present invention；
Fig. 7 is the AFM figure and respective thickness measurement figure of 1 products obtained therefrom of the embodiment of the present invention 1,3 and comparative example；
Fig. 8 is 1~3 products obtained therefrom catalytic performance comparison diagram of the embodiment of the present invention 1~3 and comparative example；
Fig. 9 is that 1 products obtained therefrom of the embodiment of the present invention recycles catalytic performance comparison diagram；
Figure 10 is the SEM figure and XRD diagram after the circulation catalysis of 1 products obtained therefrom of the embodiment of the present invention.
Specific embodiment
It include bismuth molybdate and cetyl trimethyl bromination in chemical composition the present invention provides a kind of bismuth series photocatalyst
Ammonium, the bismuth molybdate are sheet, connect to form embroidery chondritic by intermolecular force；The cetyl trimethyl bromine
Change the surface that ammonium is adsorbed on sheet bismuth molybdate by bromide ion；The bismuth series photocatalyst has hole.
It include bismuth molybdate in bismuth series photocatalyst chemical composition provided by the invention, the bismuth molybdate is sheet, is passed through
Intermolecular force connects to form embroidery chondritic.In the present invention, bismuth molybdate with a thickness of 0.7~4.0nm, preferably 0.8
~3.7nm, more preferably 0.8~3.4mm.Bismuth molybdate is ultra-thin lamellar structure, contracting in bismuth series photocatalyst provided by the invention
Short photo-generated carrier is transferred to the distance on surface from material internal, transit time is reduced, to improve electron hole
Separation rate is more advantageous to photo catalytic reduction CO2The progress of reaction.
Bismuth system provided by the invention photocatalysis further includes cetyl trimethylammonium bromide (hereinafter referred to as CTAB), described
CTAB is adsorbed on the surface of sheet bismuth molybdate by bromide ion.In the present invention, the Br of CTAB-Ion strong adsorption is in single layer
The surface of bismuth molybdate, to keep single layer bismuth molybdate negatively charged.In self assembling process, the bismuth molybdate stacking of single layer is arranged by coulomb
Repulsion and CTA+The hydrophobic chain of ion blocks, and prevents from stacking and reunite, and then being formed, there is the 3D of hole to embroider chondritic, increase
The specific surface area of bismuth series catalysts further promotes the catalytic performance of catalyst.
In the present invention, the preferred > 0.14cm of the void content of the bismuth series photocatalyst3·g-1, more preferably 0.141
~0.20cm3·g-1；The preferred > 41m of specific surface area2·g-1, more preferably 41.5~72m2·g-1；Average diameter is 3~4 μm,
Preferably 3.2~3.8 μm, more preferably 3.5~3.6 μm.
The present invention provides the preparation methods of bismuth series photocatalyst described in above-mentioned technical proposal, comprising the following steps:
There is provided includes bismuth source, molybdenum source, the reaction material liquid of cetyl trimethylammonium bromide and ethylene glycol；
The reaction material liquid is heated, obtains bismuth series photocatalyst through self assembly.
It includes bismuth source, molybdenum source, the reaction material liquid of cetyl trimethylammonium bromide and ethylene glycol that the present invention, which provides,.In this hair
In bright, in the reaction material liquid, the molar ratio of bismuth ion and molybdenum acid ion in molybdenum source is preferably 2:1 in bismuth source；The CTAB
Molar ratio with bismuth source is preferably 1.8~2.5:5, more preferably 2:5.In the present invention, in the reaction material liquid, CTAB's is dense
Degree is preferably (4.8~5.2) × 10-3Mmol/L, more preferably (5.0~5.2) × 10-3mmol/L。
In the present invention, the reaction material liquid preferably provides as follows:
Bismuth source alcoholic solution is mixed with cetyl trimethylammonium bromide alcoholic solution, is then mixed again with molybdenum source alcoholic solution.
The present invention preferably mixes bismuth source alcoholic solution with cetyl trimethylammonium bromide alcoholic solution.In the present invention, institute
It states bismuth source alcoholic solution and preferably includes bismuth nitrate and ethylene glycol；The bismuth nitrate is preferably five nitric hydrate bismuths.In the present invention, institute
It states in the alcoholic solution of bismuth source, the concentration of bismuth ion is preferably 0.045~0.055mmol/mL, more preferably 0.045~
0.050mmol/mL is further preferably 0.050mmol/mL.The present invention does not have special want to the presentation mode of bismuth source alcoholic solution
It asks, after preferably mixing in bismuth source with ethylene glycol, stirs evenly.
In the present invention, the molybdenum source alcoholic solution preferably includes sodium molybdate and ethylene glycol；In the molybdenum source alcoholic solution, molybdic acid
The concentration of radical ion is preferably 0.020~0.030mmol/mL, more preferably 0.022~0.028mmol/mL, further preferably for
0.023~0.025mmol/mL.The present invention does not have particular/special requirement to the preparation method of the molybdenum source alcoholic solution, preferably by sodium molybdate
After being mixed with ethylene glycol, stir evenly.
The present invention is not special to bismuth source alcoholic solution and the hybrid mode of cetyl trimethylammonium bromide alcoholic solution
It is required that using mode well known to those skilled in the art.After mixing, acquired solution and molybdenum source after the present invention will preferably mix
Alcoholic solution mixing, obtains reaction material liquid.
In the present invention, the CTAB solution preferably includes CTAB and ethylene glycol, the amount ratio of the CTAB and ethylene glycol
Preferably 0.15~0.20g:40mL, more preferably 0.016~0.018g:40mL are further preferably 0.17g:40mL.The present invention couple
The preparation method of the CTAB solution does not have particular/special requirement to stir evenly after preferably mixing CTAB and ethylene glycol.
Further to promote each component evenly dispersed, mixed described in above-mentioned technical proposal of the present invention preferably under agitation
It carries out.The present invention does not have particular/special requirement to the speed of the stirring and time, and each component can be made fully dispersed.
After obtaining reaction material liquid, the present invention heats the reaction material liquid, obtains bismuth series photocatalyst through self assembly.
In the present invention, the temperature of the self assembly is preferably 120~180 DEG C, and more preferably 140~170 DEG C, further preferably for 150~
160℃；The time of self assembly is preferably 1.5~6h, more preferably 2~5h, is further preferably 3~4h.
The present invention heats reaction material liquid, in heating process, the bismuth of part CTAB and the offer of bismuth source in reaction material liquid
Ions binding, so that bismuth source be hindered to hydrolyze and assemble；Remaining CTAB then forms lameller micelles, as directed agents, promotes sheet
Bismuth molybdate generates；Under ethylene glycol existence condition, the sheet bismuth molybdate of generation is assembled by intermolecular force again, and formation has
The spherical bismuth molybdate of Three-dimensional embroidery.
The present invention also provides preparation sides described in bismuth series photocatalyst described in above-mentioned technical proposal or above-mentioned technical proposal
Application of the bismuth series photocatalyst that method is prepared in photocatalytic reduction of carbon oxide reaction.
In the present invention, application mode of the bismuth series photocatalyst in photocatalytic reduction of carbon oxide reaction is preferably wrapped
It includes:
Bismuth series photocatalyst is mixed with water, obtains catalyst aqueous solution；
Under vacuum conditions, carbon dioxide is passed through into the catalyst aqueous solution, successively carries out dark reaction and light is anti-
It answers, obtains methanol and ethyl alcohol.
The present invention mixes bismuth series photocatalyst with water, obtains catalyst aqueous solution.In the present invention, bismuth system light is urged
The amount ratio of agent and water be preferably (35~45) mg:100mL, more preferably (37~43) mg:100mL, further preferably for (39~
43)mg:100mL.In the present invention, the water is preferably deionized water.Mixing side of the present invention to bismuth series photocatalyst and water
Formula does not have particular/special requirement, using mode well known to those skilled in the art.
After obtaining catalyst aqueous solution, under vacuum conditions, carbon dioxide is passed through to the aqueous solution of catalyst by the present invention
In, dark reaction and light reaction are successively carried out, methanol and ethyl alcohol are obtained.In the present invention, the vacuum condition uses this field skill
Mode known to art personnel provides；The carbon dioxide is preferably ultrapure carbon dioxide, and the purity of the carbon dioxide is preferably
99.9%.The present invention does not have particular/special requirement to the mode that is passed through of the carbon dioxide, and carbon dioxide is preferably passed through catalyst water
The bottom of solution, so that carbon dioxide comes into full contact with catalyst.In the present invention, the carbon dioxide is passed through speed and is preferably
45~55mL/min, more preferably 48~52mL/min.The present invention preferably carries out above-mentioned restriction to the speed that is passed through of carbon dioxide,
Carbon dioxide can be made to come into full contact with catalyst, promote the reaction of carbon dioxide.In the present invention, carry out subsequent dark reaction and
During the entire process of light reaction, it is continually fed into carbon dioxide, to ensure the carbon dioxide in reaction system in saturation state.
In the present invention, after carbon dioxide to be passed through to the aqueous solution of catalyst, dark reaction is carried out.In the present invention, described
The temperature of dark reaction is preferably room temperature；The time of the dark reaction is preferably 0.5~1h, more preferably 0.6~0.8h.The present invention
There is no particular/special requirement to the concrete operations mode of the dark reaction, using mode well known to those skilled in the art.This hair
It is bright that carbon dioxide and the mixture of catalyst aqueous solution is made to carry out dark reaction, catalyst can be made to reach flat to the absorption of carbon dioxide
Weighing apparatus, and the solubility of the carbon dioxide in water is made to reach saturation state, in favor of the progress of photocatalytic reduction of carbon oxide reaction.
After dark reaction, the material after the dark reaction is carried out light reaction by the present invention.In the present invention, the light reaction is excellent
Be selected in that xenon lamp irradiation is lower to be carried out, the wavelength of the transmitting light of the xenon lamp preferably >=420nm.In embodiments of the present invention, the light
Reaction time is light application time, and the optical response time is preferably 3.5~4.5h, more preferably 4h.In the present invention, in light
According under the catalytic action with bismuth series photocatalyst, carbon dioxide is reduced, and generates methanol and ethyl alcohol.In the present invention, illumination is anti-
4h is answered, the yield of methanol reaches 30.4~79.2 μm of ol gcatal.-1；The yield of ethyl alcohol reaches 8.7~45.4 μm of ol
gcatal.-1。
In order to further illustrate the present invention, with reference to the accompanying drawings and examples to a kind of bismuth system photocatalysis provided by the invention
Agent and its preparation method and application is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
According to flow diagram shown in FIG. 1, bismuth series photocatalyst is prepared.Specifically: weighing 0.15g (0.4mmol)
CTAB is added in 40mL ethylene glycol, stirring to dissolution；It will be dissolved with 1mmol Bi (NO3)3·5H2The 20mL ethylene glycol solution of O is added
In CTAB solution, after stirring 0.5h, then will be dissolved with 0.5mmol Na2MoO4·2H2The 20mL ethylene glycol solution of O is slowly added into
It states in mixed solution, obtains reaction material liquid after stirring 10h.
Reaction material liquid is transferred in 100mL autoclave, after reacting 3h under the conditions of 160 DEG C, naturally cools to room
Temperature, centrifuged reaction product, then repeatedly washed with isopropanol, dry 10h under the conditions of 60 DEG C then to get single layer
Bi2MoO6The 3D being self-assembled into embroiders spheroidal material, is indicated with BM-3h.
The bismuth series photocatalyst 20mg being prepared is distributed in the water of 50g, the aqueous solution of bismuth molybdate is obtained, vacuumizes
Afterwards, it is continually fed into ultrapure carbon dioxide gas, carbon dioxide is passed into catalyst aqueous solution with the speed of 50mL/min, is passed through
Time is 300min；The reaction material liquid for being passed through carbon dioxide is placed in darkroom, 0.5h is stood；Then 4h is irradiated with xenon lamp, shone
During penetrating, at interval of 1h sample, using gas chromatograph in solution after reaction component and its content analyze.
Embodiment 2~3
Bismuth molybdate is prepared according to the method for embodiment 1, the difference is that the time of hydro-thermal is different, wherein embodiment 2
The hydro-thermal time is 1.5h, and gained sample is indicated with BM-1.5h, and the hydro-thermal time of embodiment 3 is 6h, and gained sample is with BM-6h table
Show.
According to the catalytic performance for testing products obtained therefrom shown in table 2.
Embodiment 4~5
Bismuth molybdate is prepared according to the method for embodiment 1, the difference is that the dosage of water is different when catalysis reaction, embodiment
Water is 30g in 4, and water is 40g in embodiment 5.
According to the catalytic performance for testing products obtained therefrom shown in table 2.
Comparative example 1
Bismuth molybdate is prepared according to the method for embodiment 1, the difference is that the time of hydro-thermal is 12h, products obtained therefrom name
For BM-12h.
Comparative example 2
Bismuth molybdate is prepared according to the method for embodiment 1, the difference is that not adding CTAB, product life in preparation process
Entitled BM- is without CTAB；
Comparative example 3
Bismuth molybdate is prepared according to the method for embodiment 1, the difference is that replacing with ethylene glycol solvent in preparation process
Water, product are named as BM- water.
1~3 raw material dosage of 1 Examples 1 to 5 of table and comparative example, preparation process and structure feature
Remarks: 3 product of comparative example is the sphere of particle agglomeration, not formed sheet.
2 Examples 1 to 5 carbon dioxide photo catalytic reduction reaction condition of table
| Test sample | 1 | 2 | 3 | 4 | 5 | To 1 | To 2 | To 3 |
| Sample quality/mg | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Water quality/g | 50 | 50 | 50 | 30 | 40 | 50 | 50 | 50 |
| Amount of carbon dioxide/L | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 |
| Dark reaction time/h | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Optical response time/h | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
Structure and performance characterization result
It is characterized using structure of the XRD technology to 1~3 products obtained therefrom of Examples 1 to 5 and comparative example, wherein embodiment 1
~3 and comparative example 1~3 characterization result it is as shown in Figure 2.By Fig. 2 test result it is found that except comparative example 2 (is marked with BM- without CTAB
Remember sample) outside, peak position appeared in the XRD spectrum of other samples matches with standard card PDF#21-0102, can be true
Determining Examples 1 to 3 and comparative example 1,3 gained test sample of comparative example is rhombic Bi2MoO6Material, cell parameter a=
15.91, b=15.8, c=17.19.Their XRD diagram go out peak position 2 θ=10.93 °, 23.52 °, 28.31 °, 32.53 °,
46.74 °, 55.58 ° correspond respectively to (002) in the crystal, (111), (131), (200), (202), (133) crystal face.
Pass through characterization result (corresponding test sample BM-1.5h, BM-3h, BM-6h of comparative example 1~3 and comparative example 1
And BM-12h) it is found that with the solvent heat time increase, it is seen that in preparation process crystal grain forming process.For BM-
The XRD diagram of 1.5h sample, the corresponding diffraction maximum of (200) crystal face is more sharp, and other crystallographic plane diffraction peaks all have biggish half
Peak width value illustrates during solvent heat, and when crystal growth has been initially formed (200) crystal face, and when other crystal faces are due to heating
Between it is shorter also unstable, and the X-ray diffraction peak position of BM-1.5h correspond to standard PDF card have minor shifts,
It may be that effect since crystallization time is shorter in synthesis process, between atom plays pendulum, lattice has distortion and becomes
Shape, each interplanar distance also have certain gap compared with the interplanar distance of standard；Compare in contrast, (131) crystal face in the XRD diagram of BM-3h
The diffraction peak intensity presented increases, and illustrates as extension (131) crystal face of hydro-thermal time is gradually perfect, and other crystal faces
It tends towards stability, can be good fit with standard card, wherein the corresponding diffraction peak intensity of (002) crystal face is very weak, show the material
(002) crystal face be exposed to outer, form layer structure.When generated time extends to 6h, by scheming it will be evident that BM-6h sample
(002), (131), (200), (202), the corresponding diffraction maximum of (133) crystal face becomes strong, and the diffraction of (111) crystal faces occurs
Peak shows the extension with the solvent heat time, each crystal face gradual perfection of crystal, and crystallinity is also continuously increased, and generated time prolongs
It is long to 12h when, the XRD diagram of BM-12h and BM-6h are essentially identical, further illustrate when the hydro-thermal time reaching 6h, crystal grain is basic
Significant change no longer occurs, the extension solvent heat time becomes smaller on the influence of the crystallinity of crystal.According to Scherrer formula D=k λ/β cos θ
(wherein D is crystallite dimension, and k is constant；λ is X-ray wavelength；β is diffraction peak width；θ is the angle of diffraction), it can analyze out
The crystallite dimension of BM-1.5h, BM-3h, BM-6h, BM-12h respectively may be about 30nm, 33nm, 76nm, 82nm, thus illustrate solvent
There is influence to material grains size in the time of heat.
The position of diffraction maximum and 1 resulting materials of Examples 1 to 3 and comparative example in the XRD spectra of 2 resulting materials of comparative example
The position of diffraction maximum is substantially the same, when illustrating to take water as a solvent, can also obtain rhombic Bi2MoO6Material, it was demonstrated that solvent
Change without influence product crystal phase composition.
It is different from the diffraction maximum position of other materials to go out peak position in the XRD spectra of 3 resulting materials of comparative example, in the angle of diffraction
2 θ are to have a sharp peak at 11.5 °, other diffraction maximums are corresponding with the information on standard card, but peak intensity is weaker and has partially
It moves, illustrates that comparative example 3 does not form rhombic Bi2MoO6Material can prove under conditions of no CTAB is participated in, difficult
To generate rectangle Bi2MoO6Material.
It is characterized using pattern of the electron microscope to 1 resulting materials of embodiment, as a result as shown in Fig. 3 (a).By Fig. 3
(a) it is found that embodiment 1 be prepared microscopic appearance uniformly, the sphere material of size uniformity.Other embodiments characterization result with
Embodiment 1 is close, has obtained morphological rules degree height, size uniformity, and disperse uniform sphere material.
Qualitative and quantitative analysis is carried out using element composition of the energy disperse spectroscopy to 1 resulting materials of embodiment, as a result such as Fig. 3 (b)
It is shown.By Fig. 3 (b) it is found that the material that embodiment 1 is prepared contains Bi, Mo, O, C, Br element, why contain C and Br,
It is because CTAB is interspersed in Bi in preparing sample2MoO6Between layers, stratified material self-assembled structures are become,
There is a small amount of CTAB that can not remove by washing.The ratio between atomicity of Bi and Mo should be theoretically 2:1, but measurement result is
9.77:3.50 is greater than 2:1, and illustrate may be due to being influenced by CTAB intercalation, and there are Mo defects for material internal.
Utilize the microstructure of 1 resulting materials of high power field emission microscopy observation Examples 1 to 3 and comparative example, such as Fig. 4
It is shown.In Fig. 4, (a-b), (c-d), (e-f), (g-h) shown silk ball for being followed successively by BM-1.5h, BM-3h, BM-6h, BM-12h
Shape material overall diagram and Local map, as seen from the figure, Examples 1 to 3 and 1 resulting materials of comparative example are that diameter is 3 μm or so
Chondritic is embroidered, is compared by observation, it can be seen that the size of silk ball can't occur obviously because of the variation of solvent heat time
Variation, silk ball structure is formed by countless sheet self assemblies, and with the variation of solvent heat time, the thickness of piece has occurred delicate
Variation.Using AFM, the lamellar spacing for measuring 1 resulting materials of embodiment is 0.8nm.Two wieners when the hydro-thermal time is 1.5h
Rice piece is relatively thin incomplete structure, and laminated structure becomes completely when the solvent heat time is extended for 3h, but thickness there is no
Significant change, when the solvent heat time is 6h, it can be seen that lamella thickeies, and when the hydro-thermal time is 12h, sheet becomes more smooth.
The structure of the resulting materials of embodiment 4 and 5 is same as Example 1, is specifically listed in Table 1 below.The above test result shows Bi2MoO6It is brilliant
In crystallization process, layered self-packaging structure constantly improve body with the increase of crystallization time, by Bao Bianhou, point of this and XRD
It is consistent to analyse result.
Using the pattern of the scanning electron microscope characterization resulting materials of comparative example 2 and 3, as a result as shown in Figure 5.In Fig. 5,
(a-b), (c-d) respectively corresponds the pattern of BM- water and BM- without CTAB, by test result it is found that solvent changes into synthesis process
Water, the bismuth molybdate material prepared under the conditions of other conditions are immovable are laminated structure mostly, but gained sphere material
Self assembly is in random state, and has a small amount of lamellar structure and unassembled；Illustrate that lamellar structure is the guiding role by CTAB
Caused by；In addition, irregular spherical shape is presented in resulting materials, illustrate that CTAB also plays certain lure during self assembly
Effect is led, but under conditions of no ethylene glycol makees solvent, spherical is by a small amount of random stacking self assembly of lamellar structure
At, for products obtained therefrom of the embodiment of the present invention, the lamellar structure of 3D silk ball material is less, and not compared with multiple hole knot
Structure, the result shows ethylene glycol to play the guiding work for making lamellar structure aggregate into silk ball shape in lamella self assembling process
With.It is not added CTAB in synthesis process, the BM- prepared under the conditions of other conditions are immovable is little particle group without CTAB material
Get together, form irregular spherical shape, this result shows that, CTAB can not only make bismuth molybdate formed lamellar structure, moreover it is possible to
It prevents from lamellar structure from stacking to reunite.
For further study the present invention material structure and composition, to the pattern and element of 1 resulting materials of embodiment
Distribution is further analyzed, shown in result figure 6.In Fig. 6, (a-b) is that the TEM of 1 resulting materials of embodiment schemes, and (c-d) is to implement
The HRTEM of 1 resulting materials of example schemes, and (e-j) is that the Mapping of 1 resulting materials of embodiment schemes.By Fig. 6 (a) it is found that 1 institute of embodiment
The silk ball shape that material is 3~4 μm of diameter is obtained, it is consistent with the result observed in SEM figure；In Fig. 6 (b) it is evident that spherical side
Edge shows lamellar structure, further demonstrates the 3D silk ball structure that the lamellar structure that material is 2D is self-assembled into.Fig. 6 (c-
D) scheme for the HRTEM of material, can be clearly seen that Bi in figure2MoO6The lattice structure and crystal face of material, through measuring lattice fringe
Be spaced about 0.315nm and 0.275nm, correspond respectively to (131) in X-ray diffractogram and (200) crystal face, illustrate the material
The crystalline condition of material is good.To investigate element and distribution situation in material, Mapping analysis is carried out to BM-3h, by Fig. 6 (e-
J) display is it is found that contain Bi, Mo, O, C, Br element, and be evenly distributed in material.The reason of wherein containing C and Br element sums up
For the use of directed agents CTAB in preparation process, since CTAB plays special adsorption, it is therefore prevented that stratiform Bi2MoO6Stacking, because
This material internal or surface still have a small amount of CTAB.
To investigate influence of the solvent heat time to two-dimensional slice structural thickness, by 1 gained Bi of embodiment2MoO6Material is 30
DEG C, power removes 10min under conditions of being 70W, carries out AFM Analysis (AFM) to the lamellar structure being scattered.As a result
As shown in fig. 7, the AFM two dimension that Fig. 7 (a and d), (b and e) and (c and f) respectively illustrates BM-3h, BM-6h, BM-12h material is flat
Face figure and corresponding thickness measurement.Wherein, the lamellar spacing of BM-3h is about 0.8nm, in reference standard PDF card
Normal Bi known to information2MoO6(020) interplanar distance of crystal is 0.809nm, while in the XRD spectrum of corresponding BM-3h sample
In almost without (020) crystal face diffraction maximum, it is outer to illustrate that (020) crystal face is exposed to, and exist in single layer state, and then demonstrate
BM-3h is the Bi of single layer2MoO6Material.By in thickness measure Fig. 7 (d) it is found that material surface is coarse zigzag, it is lesser
Sawtooth may be since, there are hole, biggish zigzag may be since the defect of material part causes between atom and atom
, the vacancy that Atomic Arrangement occurs makes surface lesser hole occur.The thickness of the two-dimensional slice structure of BM-6 obviously increases,
As shown in Fig. 7 (e), about 3.4nm is equivalent to 4 single-layer sheets and is superimposed.Lamella starts gradually to become smooth in figure, says
Defect on bright sheet layer material is gradually decreasing, while in the XRD spectrum of corresponding BM-6h sample, weaker (020) of appearance
The diffraction maximum of crystal face equally confirms that the stacking effect because of a small amount of (020) crystal face increases two-dimensional layer piece thickness.BM-12h's
Lamellar structure thickness is further increased compared with the sample of hydro-thermal BM-6h, as shown in Fig. 7 (f), about 3.8nm, and schistose surface becomes
It is more smooth, illustrate material after longer solvent heat, crystalline form is gradually improved.To sum up, it can be seen that material is in solvent
Crystallization process under heat condition: in solvent heat early period, crystal is mainly cross growth, forms the more sheet of relatively thin defect certainly
Assembled material；In the later period, with the extension of solvent heat time, crystal starts longitudinal growth, gradually increases lamellar spacing, surface
More smooth, this is consistent with the analysis result in XRD and SEM.
It is characterized using catalytic performance of the gas chromatograph to 1~3 resulting materials of Examples 1 to 3 and comparative example, it is qualitative
Analysis shows above-mentioned material as carbon dioxide photo catalytic reduction react in catalyst when, can react generation methanol and second
Alcohol.Specific test result is listed in table 2 and Fig. 8.Fig. 8 is that EXAMPLE Example 1~3 and 1~3 resulting materials of comparative example react 4h
Afterwards, in product methanol and ethanol content statistical chart, as seen from the figure, methanol production quantity is apparently higher than ethyl alcohol, and embodiment 1 is urged
Change effect is best, and the methanol of generation is most.From the point of view of methanol and the total production quantity of ethyl alcohol, the product of the embodiment of the present invention 1~3 is obvious
Higher than comparative example 1~3, illustrate that material catalytic efficiency provided by the invention is higher.
The stability that resulting materials are prepared for the characterization present invention, by Examples 1 to 5 resulting materials in identical photocatalysis item
Under part, 5 periods of recycling and reusing (4h light reaction is a cycle), the wherein circulation experiment result of 1 resulting materials of embodiment
As shown in figure 9, the methanol yield of 5 recycling, circulation experiment is respectively 106.51,89.5,88.54,85.12 and 86.78 μm of ol
gcatal.-1；Alcohol yied is respectively 10.26,37.77,38.97,40.36 and 38.41 μm of ol gcatal.-1, can from figure
To find out, methanol and ethyl alcohol gross production rate after recycling do not have significant change, but the selectivity of its methanol and ethyl alcohol occurs
Variation, methanol yield are more initially reduced, and alcohol yied increased, it may be possible to because during the reaction, material surface
CTAB is removed, and produces influence to the selectivity of product.Other embodiments test result is close with embodiment 1, concrete outcome
It is listed in Table 3 below.
After 5 circulation experiments, sem analysis is carried out to sample after the recovery, as shown in Figure 10 (a), it is micro- to observe its
Pattern is seen, significant change does not occur for structure；For the stability for further verifying material, and sample after the recovery is carried out
XRD analysis, as a result as described in Figure 10 (b), it can be seen that the diffraction maximum that each crystal face of resulting materials is recycled after recycling does not become
Weak or disappearance, illustrates the Bi of single layer2MoO6It is stabilized, further also demonstrates material provided by the invention with good steady
It is qualitative.
3 Examples 1 to 5 of table and comparative example 1~3 material catalytic performance characterization result (yield μm ol gcatal.-1)
By 3 test result of table it is found that material provided by the invention is applied to carbon dioxide photo catalytic reduction as catalyst
When reaction, more methanol and ethyl alcohol can be generated, improves titanium dioxide charcoal percent conversion.Moreover, material is repeatedly recycled, follow
Ring utilizes, and the generation total amount variation of methanol and ethyl alcohol less, illustrates that the catalytic performance of material is relatively stable, service life is longer.
As seen from the above embodiment, the stable structure of bismuth molybdate 3D silk ball material provided by the invention, catalytic performance is higher,
It is reacted suitable for carbon dioxide photo catalytic reduction.In addition, preparation method provided by the invention is simple, and it is easily-controllable, be conducive to batch
Production.
In bismuth molybdate 3D silk ball material structure provided by the invention carrier by inside to surface migration apart from it is short, spread when
Between it is short, Carrier recombination can be effectively prevented, and the stacking of stratified material, large specific surface area can be prevented, contacted more with reactant
Sufficiently, active site is more.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiments under the premise of without creativeness according to the present embodiment, these
Embodiment belongs to the scope of the present invention.
Claims (10)
- It include bismuth molybdate and cetyl trimethylammonium bromide, the bismuth molybdate in chemical composition 1. a kind of bismuth series photocatalyst For sheet, connect to form embroidery chondritic by intermolecular force；The cetyl trimethylammonium bromide is adsorbed on the surface of sheet bismuth molybdate by bromide ion；The bismuth series photocatalyst has hole.
- 2. bismuth series photocatalyst as described in claim 1, which is characterized in that the volume > 0.14cm of the hole3·g-1；Institute State the specific surface area > 41m of bismuth series photocatalyst2·g-1；The average diameter of the bismuth series photocatalyst is 3~4 μm.
- 3. the preparation method of bismuth series photocatalyst as claimed in claim 1 or 2, comprising the following steps:There is provided includes bismuth source, molybdenum source, the reaction material liquid of cetyl trimethylammonium bromide and ethylene glycol；The reaction material liquid is heated, obtains bismuth series photocatalyst through self assembly.
- 4. preparation method as claimed in claim 3, which is characterized in that in the reaction material liquid, bismuth ion and molybdenum source in bismuth source The molar ratio of middle molybdenum acid ion is 2:1.
- 5. preparation method as described in claim 3 or 4, which is characterized in that in the reaction material liquid, cetyl trimethyl bromine The molar ratio for changing ammonium and bismuth source is 1.8~2.5:5.
- 6. preparation method as claimed in claim 3, which is characterized in that the reaction material liquid provides as follows:Bismuth source alcoholic solution is mixed with cetyl trimethylammonium bromide alcoholic solution, is then mixed again with molybdenum source alcoholic solution.
- 7. preparation method as claimed in claim 6, which is characterized in that in the alcoholic solution of the bismuth source, the concentration of bismuth ion is 0.045~0.055mmol/mL；In the molybdenum source alcoholic solution, the concentration of molybdenum acid ion is 0.020~0.030mmol/mL.
- 8. preparation method as claimed in claim 3, which is characterized in that the bismuth source includes bismuth nitrate, and the molybdenum source includes molybdenum Sour sodium.
- 9. preparation method as claimed in claim 3, which is characterized in that the temperature of the self assembly is 120~180 DEG C, from group The time of dress is 1.5~6h.
- 10. any one of bismuth series photocatalyst of any of claims 1 or 2 or claim 3~9 preparation method are prepared into To bismuth series photocatalyst photocatalytic reduction of carbon oxide reaction in application.
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