CN114892272A - Preparation method of oxygen-rich vacancy bismuth molybdate single crystal nanorod - Google Patents
Preparation method of oxygen-rich vacancy bismuth molybdate single crystal nanorod Download PDFInfo
- Publication number
- CN114892272A CN114892272A CN202210477657.1A CN202210477657A CN114892272A CN 114892272 A CN114892272 A CN 114892272A CN 202210477657 A CN202210477657 A CN 202210477657A CN 114892272 A CN114892272 A CN 114892272A
- Authority
- CN
- China
- Prior art keywords
- bismuth
- molybdate
- oxygen
- single crystal
- bismuth molybdate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 title claims abstract description 115
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 61
- 239000001301 oxygen Substances 0.000 title claims abstract description 61
- 239000002073 nanorod Substances 0.000 title claims abstract description 58
- 239000013078 crystal Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims abstract description 38
- 229930195725 Mannitol Natural products 0.000 claims abstract description 38
- 235000010355 mannitol Nutrition 0.000 claims abstract description 38
- 239000000594 mannitol Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 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 abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000011684 sodium molybdate Substances 0.000 claims description 22
- 235000015393 sodium molybdate Nutrition 0.000 claims description 22
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 21
- 230000001699 photocatalysis Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006862 quantum yield reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 56
- 230000000052 comparative effect Effects 0.000 description 28
- 229910052797 bismuth Inorganic materials 0.000 description 21
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- -1 bismuth oxyhalide Chemical class 0.000 description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 description 15
- 239000002135 nanosheet Substances 0.000 description 13
- 229910021529 ammonia Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002107 nanodisc Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 238000009620 Haber process Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000804 electron spin resonance spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229960003316 potassium mercuric iodide Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/32—Titanates; Germanates; Molybdates; Tungstates
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
-
- 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 relates to a preparation method of an oxygen-rich vacancy bismuth molybdate single crystal nanorod. The method comprises the following steps: (1) respectively dissolving bismuth nitrate and molybdate in a mannitol solution, then dripping the molybdate solution into the bismuth nitrate solution while stirring, and adjusting the pH of the system to be 2-6 to obtain a bismuth molybdate precursor; (2) and (2) adding the bismuth molybdate precursor obtained in the step (1) into a reaction kettle, carrying out hydrothermal reaction, and centrifuging, washing and drying the obtained precipitate to obtain the oxygen-rich vacancy bismuth molybdate single crystal nanorod. The bismuth molybdate single crystal nanorod prepared by the invention has the diameter of 4-12 nm, the length of 8-50 nm, the specific surface area of 78.3m2/g, a large number of oxygen vacancies, high photocatalytic nitrogen fixation activity and a nitrogen fixation rate of 182.4 mu mol g ‑1 h ‑1 The apparent quantum yield of 420nm reaches 2.78%, and the method has great application value in the fields of energy, environment and the like.
Description
Technical Field
The invention relates to a preparation method of an oxygen-rich vacancy bismuth molybdate single crystal nanorod, and belongs to the technical field of nanomaterials and photocatalysis.
Background
Ammonia is used as a key component for chemical product synthesis, and influences the global economic development. Because of the low ammonia production efficiency of plant nitrogen fixation, artificial nitrogen fixation is developed from the beginning of the 19 th century. Currently, industrial ammonia synthesis employs the Haber-Bosch process, i.e., via N 2 And H 2 Reacting at high temperature (300-550 ℃) and high pressure (15-25 MPa) to generate ammonia. The method has high energy consumption, occupies 1-2% of energy consumption every year all over the world, discharges about 1% of carbon dioxide all over the world, and has great harm to the environment. The photocatalysis nitrogen fixation technology can utilize clean solar energy as a driving force to ensure that N is 2 And H 2 The O directly reacts to produce ammonia under illumination, is sustainable and pollution-free, and shows great application potential.
Bismuth-containing compounds, such as bismuth oxyhalide, bismuth oxycarbonate, bismuth molybdate, bismuth tungstate, etc., having appropriate band structures, being susceptible to formation of oxygen vacancies, adsorption and activation of N 2 Strong capability and excellent photocatalytic nitrogen fixation activity. Bismuth molybdate has relatively high stability and conduction band edge, and shows greater application potential. Hitherto, methods for forming oxygen vacancies in bismuth molybdate have only included alkali etching treatment, sodium borohydride and electrochemical reduction, solvothermal synthesis in ethylene glycol, induction of surface bromine doping, and the like. In view of the practical availability and the different distribution of oxygen vacancies in bismuth molybdate, there is a need to develop a new, simple, and more efficient process. Mannitol is a commonly used structure inducer in bismuth oxyhalide synthesis, but is less useful for preparing other bismuth-containing compounds, particularly for generating oxygen vacancies, and as a polyol, mannitol should be reducing at high temperatures, so it is necessary to explore its ability to generate oxygen vacancies in bismuth molybdate.
Chinese patent document CN104525186A discloses a spherical bismuth molybdate nanocomposite with a heterostructure, and a preparation method and application thereof. According to the method, the nano bismuth oxide microspheres are etched by subacid mannitol under the hydrothermal action of high temperature and high pressure, so that the bismuth oxide on the spherical surface is slowly dissolved, and bismuth oxygen ions are ionized. The molybdate ions in the solution react with the bismuth oxide ions dissociated by etching to generate Bi 3.64 Mo 0.36 O 6.55 And (4) a crystal nucleus. Subsequently, excess molybdate ions in the liquid phase continue to react with Bi 3.64 Mo 0.36 O 6.55 Bi reacted to rearrange its crystal structure and convert it into another crystal phase 2 MoO 6 . However, the bismuth molybdate synthesized by the method is Bi 3.64 Mo 0.36 O 6.55 /Bi 2 MoO 6 The heterogeneous structure can not obtain bismuth molybdate single crystals, and has small specific surface area and still unsatisfactory photocatalytic activity. In addition, the morphology of bismuth molybdate mainly comprises nano-sheets, nano-discs and multilevel structures, and the construction units of the multilevel structures are usually single-crystal nano-sheets or nano-discs, which shows that the common single-crystal structures of bismuth molybdate are nano-sheets or nano-discs, and rare one-dimensional single-crystal nanobelts and nano-rods, although the one-dimensional structures are favorable for the migration of photo-generated charges along one-dimensional direction, thereby improving the separation.
Therefore, the development of a method for preparing oxygen-rich vacancy bismuth molybdate single crystal nanorods, which has a simple preparation process and low cost and is easy for industrial production, is urgently needed to improve the photocatalytic nitrogen fixation activity of bismuth molybdate and realize large-scale production, so that the current increasingly serious energy and environmental problems are relieved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an oxygen-rich vacancy bismuth molybdate single crystal nanorod. According to the method, the bismuth molybdate nanorod which contains a large number of oxygen vacancies and is 4-12 nm in diameter and 8-50 nm in length is prepared in the mannitol aqueous solution through a hydrothermal method, the operation is simple, the cost is low, the industrial batch production is easy to realize, and the existing large number of oxygen vacancies and the single crystal nanorod structure can obviously improve the photocatalytic nitrogen fixation activity of the material.
The technical scheme of the invention is as follows:
a preparation method of oxygen-rich vacancy bismuth molybdate single crystal nanorods comprises the following steps:
(1) respectively dissolving bismuth nitrate and molybdate in a mannitol solution, then dripping the molybdate solution into the bismuth nitrate solution while stirring, and adjusting the pH of the system to be 2-6 to obtain a bismuth molybdate precursor;
(2) and (2) adding the bismuth molybdate precursor obtained in the step (1) into a reaction kettle, carrying out hydrothermal reaction, and centrifuging, washing and drying the obtained precipitate to obtain the oxygen-rich vacancy bismuth molybdate single crystal nanorod.
Preferably, in step (1), the molybdate salt is sodium molybdate.
Preferably, in step (1), the molar ratio of bismuth nitrate to molybdate salt is 2: 1.
according to the invention, in the step (1), the concentration of the mannitol solution is preferably 0.1-0.8 mol/L.
Further preferably, the concentration of the mannitol solution is 0.2 mol/L.
According to the invention, in the step (1), the molar mass-to-volume ratio of the bismuth nitrate to the mannitol solution is (1-20): 150 in mmol/L; the molar mass-volume ratio of the sodium molybdate to the mannitol solution is (1-20): 300 in mmol/L.
More preferably, the molar weight of the bismuth nitrate is 2mmol, the molar weight of the sodium molybdate is 1mmol, and the volume of the mannitol is 30 mL.
Preferably, in the step (1), the pH of the system is adjusted by a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.5-1.5 mol/L.
More preferably, the concentration of the sodium hydroxide solution is 1mol/L, and the pH of the system is adjusted to be 3.
According to the preferable selection of the method, in the step (2), the hydrothermal reaction is carried out under the conditions that the reaction temperature is 120-180 ℃ and the reaction time is 6-48 h.
Further preferably, the hydrothermal reaction is carried out at the reaction temperature of 160 ℃ for 12-24 h.
The invention has the technical characteristics that:
the invention discovers that the bismuth molybdate synthesized in the mannitol aqueous solution by a hydrothermal method is in a single crystal nanorod shape, and the bismuth molybdate synthesized in pure water is in a nanosheet shape. Compared with a two-dimensional bismuth molybdate nano-plate, the bismuth molybdate nano-rod has larger specific surface area, and contains a large number of oxygen vacancies under the action of mannitol solution, so that the photocatalytic nitrogen fixation activity of the bismuth molybdate is effectively improved.
In addition, the invention also discovers that the oxygen vacancy content in the synthesized bismuth molybdate single-crystal nanorod is increased and then decreased along with the increase of the pH value of the precursor, and reaches the maximum value when the pH value is 3; the length and the diameter of the single crystal nanorod are gradually increased along with the increase of the pH value of the precursor, and the specific surface area is gradually reduced; the change trend of the photocatalytic nitrogen fixation activity of the product along with the increase of pH is consistent with the change of the oxygen vacancy content, which shows the decisive influence of the oxygen vacancy content on the photocatalytic activity. Therefore, the pH of the precursor is strictly controlled.
The invention has the following beneficial effects:
1. the diameter of the bismuth molybdate single crystal nanorod prepared by the method is 4-12 nm, the length of the nanorod is 8-50 nm, and the specific surface area of the nanorod reaches 78.3m 2 The nitrogen fixing rate reaches 182.4 mu mol g -1 h -1 The apparent quantum yield of 420nm reaches 2.78%, and the method has great application value in the fields of energy, environment and the like.
2. According to the invention, mannitol and the pH value of an adjusting system are added to regulate and control bismuth molybdate to form a crystal phase structure, and then hydrothermal treatment is carried out, so that the obtained bismuth molybdate is a single crystal nanorod. The specific surface area of the obtained product is obviously improved, the photocatalytic activity is obviously increased, the operation process is simple, the cost is low, and the industrial batch production is easy to realize.
Drawings
Fig. 1 is a TEM photograph of bismuth molybdates prepared in example 1, example 2, example 3 and comparative example 1.
In the figure: a. b and c are TEM photographs of the bismuth molybdate single-crystal nanorods of example 1, example 2 and example 3, respectively; d is a TEM photograph of the bismuth molybdate nanosheet of comparative example 1.
Fig. 2 is an optical photograph of the bismuth molybdates prepared in example 1 and comparative example 1.
In the figure: a is an optical photograph of the bismuth molybdate nanorods prepared in example 1; b is an optical photograph of the bismuth molybdate nanosheet prepared in comparative example 1.
Fig. 3 is an X-ray diffraction pattern of the bismuth molybdates prepared in example 1, example 3 and comparative example 1.
In the figure: the ordinate represents diffraction intensity, and the abscissa represents diffraction angle (2 θ).
Fig. 4 is an electron paramagnetic resonance spectrum of the bismuth molybdates prepared in example 1 and comparative example 1.
Fig. 5 is an ultraviolet-visible diffuse reflectance spectrum of the bismuth molybdates prepared in example 1, example 2, example 3 and comparative example 1.
Fig. 6 is a fluorescence spectrum of the bismuth molybdates prepared in example 1 and comparative example 1.
FIG. 7 is a graph showing N values of bismuth molybdates prepared in example 1 and comparative example 1 2 Adsorption and desorption isotherms.
Fig. 8 is a graph showing visible-light catalytic nitrogen fixation curves of the bismuth molybdates prepared in example 1, example 2, example 3 and comparative example 1.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Bismuth nitrate pentahydrate was purchased from Shanghai Allantin Biochemical technology, Inc. under the designation B110814;
sodium molybdate dihydrate was purchased from Shanghai Allan Biotechnology Ltd, cat # S104867;
mannitol was purchased from national pharmaceutical group chemical agents limited, cat # 63008818;
sodium hydroxide was purchased from national pharmaceutical group chemical agents limited, cat # 10019764.
In the following examples, TEM photographs were obtained by observation with a Hitachi HT-7700 type transmission electron microscope; n is a radical of 2 The adsorption and desorption isotherm is determined by an SSA-7000 type full-automatic specific surface area and pore size analyzer of Piaude instruments, China, and the specific surface area is calculated by a BET method; electron paramagnetic resonance spectroscopy was performed on a BrukerA300-10/12 spectrometer.
The visible light catalysis nitrogen fixation uses a teaching gold source CEL-HXF300-T3 type xenon lamp (300-W) and a CEL-UVIRCUT420 cut-off filter (the wavelength is more than 420nm) as a visible light source, the reaction temperature of a circulating cooling water system is controlled to be 20 ℃, and the generated ammonia is measured by a Nessler reagent method.
The principle of the Nessler reagent method for determining the ammonia concentration is as follows:
the alkaline solution of potassium mercuric iodide reacts with ammonia to generate a light yellowish-brown colloidal compound, the chromaticity of the compound is in direct proportion to the content of ammonia nitrogen, the absorbance of the compound in the wavelength range of 410-425 nm can be measured by using standard ammonium chloride solutions with different concentrations, a standard curve of the concentration and the absorbance is made, and the ammonia content of the reaction solution is calculated according to the made standard curve and the measured absorbance of the reaction solution.
Example 1
A preparation method of oxygen-rich vacancy bismuth molybdate single crystal nanorods comprises the following steps:
(1) respectively dissolving 2mmol of bismuth nitrate and 1mmol of sodium molybdate in mannitol solution with the concentration of 0.2mol/L and the volume of 30mL, slowly dropping the sodium molybdate solution into the bismuth nitrate solution while magnetically stirring, and adjusting the pH value of the system to 3 by using 1mol/L sodium hydroxide solution to obtain the bismuth molybdate precursor.
(2) And (2) adding the bismuth molybdate precursor obtained in the step (1) into a polytetrafluoroethylene reaction kettle lining with the volume of 80mL, placing the polytetrafluoroethylene reaction kettle lining into a constant-temperature blast oven, carrying out hydrothermal reaction for 12 hours at 160 ℃, and centrifuging, washing and drying the obtained precipitate to obtain the oxygen-rich vacancy bismuth molybdate single crystal nanorod.
Example 2
A preparation method of oxygen-rich vacancy bismuth molybdate single crystal nanorods comprises the following steps:
(1) respectively dissolving 2mmol of bismuth nitrate and 1mmol of sodium molybdate in mannitol solution with the concentration of 0.2mol/L and the volume of 30mL, slowly dropping the sodium molybdate solution into the bismuth nitrate solution while magnetically stirring, and adjusting the pH value of the system to 2 by using 1mol/L sodium hydroxide solution to obtain the bismuth molybdate precursor.
(2) And (2) adding the bismuth molybdate precursor obtained in the step (1) into a polytetrafluoroethylene reaction kettle lining with the volume of 80mL, placing the polytetrafluoroethylene reaction kettle lining into a constant-temperature air-blast oven for hydrothermal reaction at 160 ℃ for 12 hours, and centrifuging, washing and drying the obtained precipitate to obtain the oxygen-rich vacancy bismuth molybdate single crystal nanorod.
Example 3
A preparation method of oxygen-rich vacancy bismuth molybdate single crystal nanorods comprises the following steps:
(1) respectively dissolving 2mmol of bismuth nitrate and 1mmol of sodium molybdate in a mannitol solution with the concentration of 0.2mol/L and the volume of 30mL, slowly dropping the sodium molybdate solution into the bismuth nitrate solution while magnetically stirring, and adjusting the pH value of the system to 6 by using a 1mol/L sodium hydroxide solution to obtain a bismuth molybdate precursor.
(2) And (2) adding the bismuth molybdate precursor obtained in the step (1) into a lining of a reaction kettle made of 80mL of polytetrafluoroethylene, placing the lining into a constant-temperature air-blast oven for hydrothermal reaction at 160 ℃ for 12 hours, and centrifuging, washing and drying the obtained precipitate to obtain the oxygen-rich vacancy bismuth molybdate single crystal nanorod.
Example 4
A preparation method of oxygen-rich vacancy bismuth molybdate single crystal nanorods comprises the following steps:
(1) respectively dissolving 4mmol of bismuth nitrate and 2mmol of sodium molybdate in a mannitol solution with the concentration of 0.2mol/L and the volume of 30mL, slowly dropping the sodium molybdate solution into the bismuth nitrate solution while magnetically stirring, and adjusting the pH value of the system to 3 by using a 1mol/L sodium hydroxide solution to obtain a bismuth molybdate precursor.
(2) And (2) adding the bismuth molybdate precursor obtained in the step (1) into a polytetrafluoroethylene reaction kettle lining with the volume of 80mL, placing the polytetrafluoroethylene reaction kettle lining into a constant-temperature air-blast oven for hydrothermal reaction at 160 ℃ for 12 hours, and centrifuging, washing and drying the obtained precipitate to obtain the oxygen-rich vacancy bismuth molybdate single crystal nanorod.
Example 5
A preparation method of oxygen-rich vacancy bismuth molybdate single crystal nanorods comprises the following steps:
(1) respectively dissolving 2mmol of bismuth nitrate and 1mmol of sodium molybdate in mannitol solution with the concentration of 0.1mol/L and the volume of 30mL, slowly dropping the sodium molybdate solution into the bismuth nitrate solution while magnetically stirring, and adjusting the pH value of the system to 3 by using 1mol/L sodium hydroxide solution to obtain the bismuth molybdate precursor.
(2) And (2) adding the bismuth molybdate precursor obtained in the step (1) into a polytetrafluoroethylene reaction kettle lining with the volume of 80mL, placing the polytetrafluoroethylene reaction kettle lining into a constant-temperature air-blast oven for hydrothermal reaction at 160 ℃ for 12 hours, and centrifuging, washing and drying the obtained precipitate to obtain the oxygen-rich vacancy bismuth molybdate single crystal nanorod.
Example 6
A preparation method of oxygen-rich vacancy bismuth molybdate single crystal nanorods comprises the following steps:
(1) respectively dissolving 2mmol of bismuth nitrate and 1mmol of sodium molybdate in mannitol solution with the concentration of 0.2mol/L and the volume of 30mL, slowly dropping the sodium molybdate solution into the bismuth nitrate solution while magnetically stirring, and adjusting the pH value of the system to 3 by using 1mol/L sodium hydroxide solution to obtain the bismuth molybdate precursor.
(2) And (2) adding the bismuth molybdate precursor obtained in the step (1) into a polytetrafluoroethylene reaction kettle lining with the volume of 80mL, placing the polytetrafluoroethylene reaction kettle lining into a constant-temperature air-blast oven for hydrothermal reaction at 180 ℃ for 12 hours, and centrifuging, washing and drying the obtained precipitate to obtain the oxygen-rich vacancy bismuth molybdate single crystal nanorod.
Example 7
A preparation method of oxygen-rich vacancy bismuth molybdate single crystal nanorods comprises the following steps:
(1) respectively dissolving 2mmol of bismuth nitrate and 1mmol of sodium molybdate in mannitol solution with the concentration of 0.2mol/L and the volume of 30mL, slowly dropping the sodium molybdate solution into the bismuth nitrate solution while magnetically stirring, and adjusting the pH value of the system to 3 by using 1mol/L sodium hydroxide solution to obtain the bismuth molybdate precursor.
(2) And (2) adding the bismuth molybdate precursor obtained in the step (1) into a polytetrafluoroethylene reaction kettle lining with the volume of 80mL, placing the polytetrafluoroethylene reaction kettle lining into a constant-temperature air-blast oven for hydrothermal reaction at 160 ℃ for 24 hours, and centrifuging, washing and drying the obtained precipitate to obtain the oxygen-rich vacancy bismuth molybdate single crystal nanorod.
Comparative example 1
A preparation method of bismuth molybdate nano-sheets comprises the following steps:
(1) respectively dissolving 2mmol of bismuth nitrate and 1mmol of sodium molybdate in 30mL of deionized water, slowly dropping the sodium molybdate solution into the bismuth nitrate solution, and adjusting the pH value of the precursor to 3 by using 1mol/L of sodium hydroxide solution to obtain the precursor.
(2) And (2) adding the bismuth molybdate precursor obtained in the step (1) into a polytetrafluoroethylene reaction kettle lining with the volume of 80mL, placing the polytetrafluoroethylene reaction kettle lining into a constant-temperature air-blast oven for hydrothermal reaction at 160 ℃ for 12 hours, and centrifuging, washing and drying the obtained precipitate to obtain the bismuth molybdate nanosheet.
TEM photographs of the bismuth molybdate prepared in mannitol in example 1, example 2 and example 3 of the present invention and the bismuth molybdate prepared in ultra pure water in comparative example 1 are shown in fig. 1.
As can be seen from FIG. 1, the morphologies of the bismuth molybdates in example 1, example 2 and example 3 are the nanorods shown in FIG. 1a, FIG. 1b and FIG. 1c, respectively; the morphology in comparative example 1 is shown in fig. 1d as irregular nanosheets, indicating that mannitol solution can regulate the morphology of bismuth molybdate. Comparing the TEM images of example 1, example 2 and example 3, it can be seen that the particle size and rod length at the same scale are example 2 > example 1 > example 3, indicating that the rod length and particle size of the bismuth molybdate nanorods synthesized in the mannitol solution gradually increase with the increase of the pH of the precursor.
Optical photographs of the bismuth molybdates prepared in inventive example 1 and comparative example 1 are shown in fig. 2.
As can be seen from FIG. 2, the color of the bismuth molybdate synthesized in the mannitol solution was clearly darkened, indicating that a large number of oxygen vacancies were formed.
The X-ray diffraction patterns of the bismuth molybdates prepared in inventive example 1, example 3 and comparative example 1 are shown in fig. 3.
As can be seen from fig. 3, example 1 and comparative example 1 have typical bismuth molybdate peaks. The peak of example 1 was significantly weakened, indicating that the introduction of a large number of oxygen vacancies resulted in a decrease in the crystallinity thereof, and that it was shifted to a low-angle direction, indicating that the interlayer spacing thereof was enlarged. The peak of example 3 is stronger than that of example 1, which shows that when the pH of the precursor is 3-6, the oxygen vacancy in the bismuth molybdate nanorod is gradually reduced with the increase of the pH, so that the crystallinity is enhanced, and the diffraction peak is shifted to a high angle, so that the interlayer spacing becomes smaller.
The electron paramagnetic resonance spectra of the bismuth molybdates prepared in inventive example 1 and comparative example 1 are shown in fig. 4.
As can be seen from fig. 4, the bismuth molybdate nanorods prepared in example 1 have stronger EPR signals than the bismuth molybdate nanosheets prepared in comparative example 1, indicating that more electrons are trapped by oxygen vacancies, which indicates that the bismuth molybdate prepared in a mannitol solution in example 1 has a large number of oxygen vacancies, which is much higher than the oxygen vacancy content of bismuth molybdate synthesized in ultra-pure water.
Fig. 5 shows solid uv-vis diffuse reflectance spectra of the bismuth molybdates prepared in inventive example 1, example 2, example 3 and comparative example 1.
As can be seen from fig. 5, the visible light absorption performance of the bismuth molybdate synthesized in the mannitol solution is significantly enhanced compared with that of the bismuth molybdate synthesized in ultra-pure water, and the bismuth molybdate also has significant absorption for low-energy long-wavelength light after 600nm, indicating that the formation of oxygen vacancies enhances the visible light absorption performance.
The fluorescence spectra of the bismuth molybdates prepared in inventive example 1 and comparative example 1 are shown in fig. 6.
As can be seen from fig. 6, the fluorescence peak of the oxygen-rich vacancy bismuth molybdate nanorod synthesized in the mannitol solution is obviously weakened compared with that of the bismuth molybdate synthesized in ultra-pure water, which indicates that the photo-generated charge recombination efficiency of the oxygen-rich vacancy bismuth molybdate is low and the photocatalytic performance is better.
N of bismuth molybdates prepared according to inventive example 1 and comparative example 1 2 The adsorption and desorption isotherms are shown in fig. 7.
As can be seen from fig. 7, both the bismuth molybdate prepared in the comparative example and the bismuth molybdate prepared in example 1 have type IV isotherms, and exhibit hysteresis loops of types H3 and H2, respectively, i.e., mesoporous structures. The specific surface area of the bismuth molybdate nanosheet prepared in the comparative example was 16.7m 2 (per gram), the specific surface area of the bismuth molybdate nanorods prepared in example 1 is 68.9m 2 (g), the specific surface areas of examples 2 to 7 were 78.3m, respectively 2 /g、55.8m 2 /g、43.6m 2 /g、52.3m 2 /g、54.6m 2 G and 49.7m 2 Thus, mannitol not only can generate a large number of oxygen vacancies in bismuth molybdate, but also can improve the specific surface area of the bismuth molybdate material.
Test example 1
The bismuth molybdate prepared in the embodiments 1-3 and the comparative example 1 is applied to visible light catalysis nitrogen fixation, and the specific steps are as follows:
40mg of the bismuth molybdate powders prepared in examples 1 to 3 and comparative example 1 were ultrasonically dispersed in 80mL of deionized water, respectively, and the suspension was transferred to a nitrogen fixation reaction vessel. Bubbling with high-purity nitrogen in the dark for 30min, illuminating with 300-W xenon lamp (wavelength greater than 420nm) for 80min (introducing nitrogen all the time), taking out 4mL of reaction solution from the reactor every 20min by using an injector, centrifuging the reaction solution in a centrifuge at 10000rpm to separate supernatant and photocatalyst, taking out the supernatant, and determining the ammonia concentration by using a Nessler reagent method.
The visible light catalysis nitrogen fixation curves of the bismuth molybdates prepared in the embodiments 1-3 and the comparative example 1 are shown in fig. 8.
As can be seen from FIG. 8, the nitrogen fixation rates of the oxygen-rich vacancy-enriched bismuth molybdate nanorods prepared in example 1, example 2 and example 3 were 182.4. mu. mol g -1 h -1 、95.5μmol g -1 h -1 And 147.7. mu. mol g -1 h -1 Comparative example 1 the nitrogen fixation rate of the bismuth molybdate nanosheet was 1.7. mu. mol g -1 h -1 The nitrogen fixation rates of the oxygen-rich vacancy bismuth molybdate nanorods prepared in example 1, example 2 and example 3 are 107, 56 and 87 times of those of the bismuth molybdate nanosheets of comparative example 1, respectively.
The data show that the oxygen-rich vacancy bismuth molybdate nanorod prepared in the mannitol solution has higher photocatalytic activity and higher industrial application value.
It is obvious that the above examples of the present invention are only simple applications of increasing the content of oxygen vacancies in bismuth molybdate and improving the activity of photocatalyst by synthesizing an oxygen vacancy-rich bismuth molybdate nanorod with a mannitol solution, and are given as examples for clearly illustrating the broad scope of the present invention, and are not intended to limit the application fields and embodiments of the present invention. Other variations should be made in specific cases for specific applications of each photocatalyst. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of oxygen-rich vacancy bismuth molybdate single crystal nanorods is characterized by comprising the following steps:
(1) respectively dissolving bismuth nitrate and molybdate in a mannitol solution, then dripping the molybdate solution into the bismuth nitrate solution while stirring, and adjusting the pH of the system to be 2-6 to obtain a bismuth molybdate precursor;
(2) and (2) adding the bismuth molybdate precursor obtained in the step (1) into a reaction kettle, carrying out hydrothermal reaction, and centrifuging, washing and drying the obtained precipitate to obtain the oxygen-rich vacancy bismuth molybdate single crystal nanorod.
2. The method for preparing an oxygen-rich vacancy bismuth molybdate single crystal nanorod according to claim 1, wherein in the step (1), the molybdate salt is sodium molybdate.
3. The method for preparing oxygen-rich vacancy bismuth molybdate single crystal nanorods of claim 1, wherein in step (1), the molar ratio of bismuth nitrate to molybdate salt is 2: 1.
4. the method for preparing the oxygen-rich vacancy bismuth molybdate single crystal nanorod according to claim 1, wherein in the step (1), the concentration of the mannitol solution is 0.1-0.8 mol/L.
5. The method for preparing oxygen-rich vacancy bismuth molybdate single crystal nanorods of claim 4, wherein the concentration of the mannitol solution is 0.2 mol/L.
6. The method for preparing the oxygen-rich vacancy bismuth molybdate single crystal nanorod according to claim 1, wherein in the step (1), the molar mass-to-volume ratio of bismuth nitrate to a mannitol solution is (1-20): 150 in mmol/L; the molar mass-volume ratio of the sodium molybdate to the mannitol solution is (1-20): 300 in mmol/L.
7. The method for preparing oxygen-rich vacancy bismuth molybdate single crystal nanorods of claim 6, wherein the molar mass of bismuth nitrate is 2mmol, the molar mass of sodium molybdate is 1mmol, and the volume of mannitol is 30 mL.
8. The method for preparing the oxygen-rich vacancy bismuth molybdate single crystal nanorod according to claim 1, wherein in the step (1), the pH of the system is adjusted through a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is 0.5-1.5 mol/L.
9. The method for preparing oxygen-rich vacancy bismuth molybdate single crystal nanorods of claim 1, wherein the concentration of the sodium hydroxide solution is 1mol/L, and the pH of the adjusting system is 3.
10. The method for preparing the oxygen-rich vacancy bismuth molybdate single crystal nanorod according to claim 1, wherein in the step (2), the hydrothermal reaction is carried out at the reaction temperature of 150-180 ℃ for 6-48 h;
further preferably, the hydrothermal reaction is carried out at the reaction temperature of 160 ℃ for 12-24 h.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210477657.1A CN114892272B (en) | 2022-05-05 | 2022-05-05 | Preparation method of oxygen-enriched vacancy bismuth molybdate monocrystal nanorod |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210477657.1A CN114892272B (en) | 2022-05-05 | 2022-05-05 | Preparation method of oxygen-enriched vacancy bismuth molybdate monocrystal nanorod |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114892272A true CN114892272A (en) | 2022-08-12 |
CN114892272B CN114892272B (en) | 2024-03-29 |
Family
ID=82719111
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210477657.1A Active CN114892272B (en) | 2022-05-05 | 2022-05-05 | Preparation method of oxygen-enriched vacancy bismuth molybdate monocrystal nanorod |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114892272B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105731541A (en) * | 2016-01-15 | 2016-07-06 | 武汉工程大学 | Gamma-bismuth molybdate crystal nanosheets and preparation method thereof |
CN109865513A (en) * | 2017-12-05 | 2019-06-11 | 中国科学院金属研究所 | A kind of bismuth molybdate material and its preparation method and application of richness surface Lacking oxygen |
CN112844372A (en) * | 2021-02-20 | 2021-05-28 | 辽宁大学 | Oxygen vacancy-containing bismuth molybdate thermal catalyst and preparation method and application thereof |
-
2022
- 2022-05-05 CN CN202210477657.1A patent/CN114892272B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105731541A (en) * | 2016-01-15 | 2016-07-06 | 武汉工程大学 | Gamma-bismuth molybdate crystal nanosheets and preparation method thereof |
CN109865513A (en) * | 2017-12-05 | 2019-06-11 | 中国科学院金属研究所 | A kind of bismuth molybdate material and its preparation method and application of richness surface Lacking oxygen |
CN112844372A (en) * | 2021-02-20 | 2021-05-28 | 辽宁大学 | Oxygen vacancy-containing bismuth molybdate thermal catalyst and preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
LIWU ZHANG,ET AL.: "Controllable synthesis of Bi2MoO6 and effect of morphology and variation in local structure on photocatalytic activities", 《APPLIED CATALYSIS B: ENVIRONMENTAL》, vol. 98, pages 138 - 146, XP027134696 * |
YONGXING XING,ET AL.: "Mannitol-assisted synthesis of ultrathin Bi2MoO6 architectures: excellent selective adsorption and photocatalytic performance", 《J NANOPART RES》, vol. 21, pages 1 - 14 * |
Also Published As
Publication number | Publication date |
---|---|
CN114892272B (en) | 2024-03-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108722384B (en) | Oxygen-enriched vacancy titanium dioxide nanoflower and preparation method thereof | |
CN105289693B (en) | A kind of Zn0.5Co0.5Fe2O4/g‑C3N4The preparation method of composite photo-catalyst | |
CN111333117A (en) | Preparation of cupronickel type structure CuFeO2Method for preparing biochar composite material | |
CN111924865B (en) | Crystal face selective growth boehmite and preparation method thereof | |
Yan et al. | Study on micro-nanocrystalline structure control and performance of ZnWO 4 photocatalysts | |
CN112516997B (en) | CeO 2 /MnO 2 Method for preparing nano-rod | |
CN106558695A (en) | A kind of nickel cobalt aluminum complex hydroxide, nickel cobalt aluminium composite oxide and preparation method thereof | |
CN112076741B (en) | CeO (CeO) 2 /Bi 2 O 4 Composite visible light catalyst and preparation method thereof | |
CN110407245B (en) | Method for preparing flaky and spherical cuprous oxide nanoparticles by one-pot method | |
CN114308073B (en) | Preparation method and application of composite catalyst | |
CN112642427B (en) | Metal M doped titanium dioxide photocatalyst and application thereof in photocatalytic nitrogen fixation | |
CN106925300A (en) | One kind synthesis CeO2The method of/CdS hetero-junctions | |
CN107126953B (en) | Bismuth/non-stoichiometric ratio Oriviris compound nano composite material and preparation method and application thereof | |
Jiang et al. | Solvothermal synthesis of TiO2/Bi2WO6 heterojunction photocatalyst with optimized interface structure and enabled photocatalytic performance | |
CN114892272B (en) | Preparation method of oxygen-enriched vacancy bismuth molybdate monocrystal nanorod | |
CN115557529B (en) | Cadmium sulfide coated rubidium tungsten bronze composite nano powder and preparation method and application thereof | |
Song et al. | Synthesis of different shapes ZnFe2O4–BiOCl nanocomposites for photocatalytic reduction of CO2 in cyclohexanol | |
CN111266114A (en) | Metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst and preparation method and application thereof | |
US11623210B2 (en) | Method for preparing silicate/carbon composite from attapulgite, and use of silicate/carbon composite | |
CN112058257B (en) | Rare earth Tb doped bismuth vanadate photocatalyst and preparation method thereof | |
CN112547077B (en) | Broad-spectral-response sillenite-based efficient photocatalyst and preparation method thereof | |
CN105036216B (en) | A kind of sodium manganese water-purifying material and its preparation method and application | |
CN113856668A (en) | Bi/BiVO4Preparation method of composite heterojunction photocatalytic material | |
CN109987640B (en) | Preparation of nano α -Fe2O3Method (2) | |
CN116328777B (en) | Preparation method of magnetic zinc oxide@zinc ferrite photocatalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |