CN117326590A - Three-phase coexisting monoclinic BiVO 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O nano sheet material and preparation method thereof - Google Patents
Three-phase coexisting monoclinic BiVO 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O nano sheet material and preparation method thereof Download PDFInfo
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000000463 material Substances 0.000 title claims abstract description 36
- 239000002135 nanosheet Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 13
- 238000003756 stirring Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000012153 distilled water Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims description 77
- 239000013078 crystal Substances 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 51
- 230000035484 reaction time Effects 0.000 claims description 47
- 239000002243 precursor Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002064 nanoplatelet Substances 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 10
- 239000000725 suspension Substances 0.000 abstract description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 abstract 2
- 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 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 25
- 238000010586 diagram Methods 0.000 description 22
- 230000001699 photocatalysis Effects 0.000 description 17
- 229910052797 bismuth Inorganic materials 0.000 description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 101100272667 Xenopus laevis ripply2.2 gene Proteins 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
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- 239000000693 micelle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Three-phase coexisting monoclinic BiVO 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 An O nanosheet material and method of making same comprising: bismuth nitrate pentahydrate and hexadecyl trimethyl ammonium bromide are dissolved in distilled water, stirred and reacted in a microwave reactor at 100 ℃ to obtain solution A; dissolving ammonium metavanadate in distilled water, and stirring until the ammonium metavanadate is completely dissolved to obtain a solution B; dropwise adding the solution A into a flask containing the solution B, and vigorously stirring to obtain a solution C; the solution C is reacted at 100 ℃ by adopting a microwave radiation method to obtain suspension, and then the suspension is centrifuged, washed and dried to obtain monoclinic BiVO 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 And (3) an O three-phase coexisting material.
Description
Technical Field
The target product of the invention is mainly applied to the field of photocatalytic materials, and particularly relates to a three-phase coexistence monoclinic BiVO 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O nano sheet material and a preparation method thereof.
Background
Bismuth vanadate (BiVO) 4 ) Is a typical n-type semiconductor material, has a band gap of 2.4eV, and has small forbidden bandwidth, excellent oxidation-reduction performance and photocatalysis performance, thereby bringing great attention to researchersTücks A，Beck H P.The photochromic effect of bismuth vanadate pigments：Investigations on the photochromic mechanism[J].Dyes and pigments，2007，72(2)：163-177)。BiVO 4 The material has important application in fields of photocatalytic degradation of pollutants, pigments, solar energy conversion, iron elastic materials and the like (Zhang Z, wang W, shang M, et al, photoataly degradation of rhodamine B and phenol by solution combustion synthesized BiVO) 4 photocatalyst[J].Catalysis communications，2010，11(11)：982-986)。BiVO 4 The crystal structure mainly comprises three crystal structures, namely a monoclinic phase, a tetragonal scheelite phase and a tetragonal zircon phase; in BiVO 4 In the crystal structure of (2) the 3d empty orbit of vanadium is coupled with the 2p of oxygen and the 6p orbit of bismuth, so that the conduction band of the boundary of the Brillouin zone is minimum, and the transition of electrons with low energy level can be directly facilitated; wherein, tetragonal phase BiVO 4 Has a band gap of 2.9eV, has good response to ultraviolet light, and is monoclinic phase BiVO 4 The band gap is 2.4eV, and has good response to ultraviolet light and visible light, thus having higher photocatalytic activity. Monoclinic phase and tetragonal white tungsten phase BiVO 4 Can mutually transform under 255 ℃ and when the tetragonal zircon phase BiVO 4 Heating to 400-500 ℃ and cooling to room temperature, and then converting into monoclinic BiVO 4 (Zhang X，Ai Z，Jia F，et al.Selective synthesis and visible-light photocatalytic activities of BiVO 4 with different crystalline phases[J].Materials Chemistry and Physics，2007，103(1)：162-167；M，/>S，Ivanda M，et al.Synthesis and characterisation of bismuth(III)vanadate[J].Journal of Molecular Structure，2005，744：535-540)。
Although monoclinic phase BiVO 4 Has excellent photocatalytic activity, but the problems of easy recombination of photo-generated electrons and holes and the like are still the constraint of BiVO 4 The main factor for improving the photocatalytic performance (Guo Xiaoyu. Bismuth vanadate and molybdic acidPreparation and performance [ D ] of bismuth-based heterostructure photocatalyst]University of gillin, 2016). For this purpose, doping (Piclli SK, furtak T E, brown L D, et al cobalt-phosphate (Co-Pi) catalyst modified Mo-doped BiVO 4 photoelectrodes for solar water oxidation[J].Energy&Environmental Science,2011,4: 5028-5034), cocatalyst loading (Zhang A, zhang J.Synthesis and characterization of Ag/BiVO 4 composite photocatalyst[J]Applied Surface Science,2010, 256: 3224-3227) and heterostructure formation (Wang W, huang X, wu S, et al preparation of p-n junction Cu) 2 O/BiVO 4 heterogeneous nanostructures with enhanced visible-light photocatalytic activity[J]Applied Catalysis B: environmental,2013, 134: 293-301), etc., provide a viable solution for improving the performance of these photocatalysts. Among them, the formation of heterojunction between different phases of the same material is a promising application method. The existence of the mixed phase can lead to higher photocatalytic activity, which is caused by the fact that the separation efficiency of electrons and holes is improved due to different valence and conduction band potentials between heterogeneous phases (Fan H, jiang T, li H, et al Effect of BiVO 4 crystalline phases on the photoinduced carriers behavior and photocatalytic activity[J].Journal of Physical Chemistry C，2012，116：2425-2430)。
According to the literature investigation result: biVO with different structures and phase compositions is prepared by adopting different methods 4 The material is favorable for promoting the promotion of the catalytic performance and the oxidation-reduction performance of the photocatalytic material. Currently synthesizing BiVO 4 The material can be prepared by coprecipitation, sonochemistry, solution-gel method, hydrothermal method, etc. (Ravidhas C, juliat Josephine A, sudhagar P, et al, facility synthesis of nanostructured monoclinic bismuth Vanadate by a co-precipitation method: structural, optical and photocatalytic properties [ J)]Materials Science in Semiconductor Processing,2015, 30: 343-351.). However, these methods generally require higher temperatures and require control of the pH of the reaction to regulate BiVO 4 The appearance of the product causes the problems of complex process, large energy consumption, long time consumption, instability and the like.
Disclosure of Invention
The invention aims to provide a three-phase coexisting monoclinic BiVO which is expected to solve the problem of easy recombination of electron-hole pairs of a single-phase photocatalytic material, has simple process operation, no need of acid and alkali, low energy consumption, short time and mildness and can be controllably prepared and applied to the field of photocatalysis 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O nano sheet material and a preparation method thereof.
The invention is realized by adopting the following scheme:
three-phase coexisting monoclinic BiVO 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The O nano sheet material and the preparation method thereof comprise the following steps:
first, 2.0615g of analytically pure Bi (NO 3 ) 3 ·5H 2 O and 1.5490g cetyl trimethylammonium bromide CTAB in a 250mL beaker, 115mL distilled water was added, and after stirring the solution for 15min on a magnetic stirrer at 800rpm, it was transferred to a 250mL round bottom flask; the round bottom flask is placed in a reactor with the brand name of 'Mei brand' PJ21C-AU, the equipment is a microwave reactor with a temperature control and reflux condensing device and a normal pressure reaction system, heating power is set to be 200-2000W, the frequency is 2450MHz, the heating temperature is 100 ℃, and the reaction precursor solution A is obtained after mixing for 60 min;
second, weighing 0.7457g NH 4 VO 3 Adding 85mL of distilled water into a 100mL beaker, and uniformly stirring for 15min by using a magnetic stirrer with the rotating speed of 800rpm to obtain a reaction precursor solution B;
thirdly, transferring the precursor solution B obtained in the second step into a 500mL round bottom flask, dropwise adding the precursor solution A obtained in the first step into the 500mL flask containing the precursor solution B under the condition of intense stirring, and continuing stirring for 10min after the dropwise adding is completed to obtain a mixed solution C;
fourthly, placing the mixed solution C obtained in the third step into a 'Mei brand' PJ21C-AU microwave reactor with an atmospheric reflux cooling device, setting the heating power to be 200-2000W, the frequency to be 2450MHz, the heating temperature to be 100 ℃, and the reaction time to be 30-130 min;
fifthly, after the reaction is finished, naturally cooling the product obtained in the round-bottomed flask, transferring the product into a centrifuge, centrifuging for 2min at a rotation speed of 5000rpm, removing supernatant and keeping a layer of product, washing the lower layer of product with distilled water and ethanol for 3-5 times respectively, then placing the washed product into an oven, adjusting the temperature of the oven to 70 ℃, and keeping the temperature for 24h to obtain the target three-phase coexisting nano-sheet material.
Monoclinic BiVO when the reaction time t=30 min 4 The strongest peak corresponds to hkl crystal plane indexSpace group is I2/a, unit cell parameter->Is->α=γ=90.0° and β= 90.38 °, the corresponding peak value is 35.4% of the total peak value, and the tetragonal scheelite type BiVO 4 The strongest peak corresponds to hkl crystal plane index (200), space group is I41/amd, unit cell parameter is +.>Is->α=β=γ=90.0°, the corresponding peak value is 36.2% of the total peak value, and, [ Bi 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The peak value corresponding to the O phase accounts for 28.4% of the total peak value; the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.20-1.89 mu m and the thickness of 20-130 nm.
Monoclinic BiVO when the reaction time t=50 min 4 The strongest peak corresponds to hkl crystal plane indexSpace group is I2/a, unit cell parameter->Is->Alpha = gamma = 90.0 deg. and beta = 90.38 deg., the corresponding peak value is 39.0% of the total peak value ratio, the tetragonal scheelite type BiVO 4 The strongest peak corresponds to hkl crystal plane index (200), space group is I41/amd, unit cell parameter is +.>Is->α=β=γ=90.0°, and the corresponding peak value is 39.0% of the total peak value ratio, [ Bi 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The peak value corresponding to the O phase accounts for 22.0% of the total peak value; the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.44-1.97 mu m and the thickness of 46-90 nm.
Monoclinic BiVO when the reaction time t=70 min 4 The characteristic peak of the peak corresponds to hkl crystal face indexSpace group is I2/a, unit cell parameter->Is->α=γ=90.0° and β= 90.38 °, the corresponding peak value is 43.2% of the total peak value, and the tetragonal scheelite type BiVO 4 The strongest peak corresponds to hkl crystal plane index (200), space group is I41/amd, unit cell parameter is +.>Is->α=β=γ=90.0°, the corresponding peak value being the total peak valueThe value ratio was 13.6% [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The peak value corresponding to the O phase accounts for 43.2% of the total peak value; the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.12-1.96 mu m and the thickness of 26-76 nm.
Monoclinic BiVO when the reaction time t=90 min 4 The strongest peak corresponds to hkl crystal plane indexSpace group is I2/a, unit cell parameter->Is->Alpha = gamma = 90.0 deg. and beta = 90.38 deg., the corresponding peak value is 39.5% of the total peak value, the tetragonal scheelite type BiVO 4 The strongest peak corresponds to hkl crystal plane index (200), space group is I41/amd, unit cell parameter is +.>Is->α=β=γ=90.0°, the corresponding peak value is 39.5% of the total peak value ratio, [ Bi 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The peak value corresponding to the O phase accounts for 21.0% of the total peak value; the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.40-2.01 mu m and the thickness of 43-141 nm.
Monoclinic BiVO when the reaction time t=130 min 4 The strongest peak corresponds to hkl crystal plane indexSpace group is I2/a, unit cell parameter->Is->α=γ=90.0° and β= 90.38 °, which isThe corresponding peak value accounts for 38.5% of the total peak value, and the tetragonal scheelite type BiVO 4 The strongest peak corresponds to hkl crystal plane index (200), space group is I41/amd, unit cell parameter is +.>Is->α=β=γ=90.0°, and the corresponding peak value is 38.5% of the total peak value ratio, [ Bi 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The peak value corresponding to the O phase accounts for 23.0% of the total peak value; the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.59-3.21 mu m and the thickness of 64-198 nm.
Compared with the prior art, the invention has the following beneficial technical effects:
(1)BiVO 4 is an n-type semiconductor material with narrow band gap, excellent oxidation-reduction performance and photocatalysis performance, and is widely applied to the fields of degrading organic pollutants, photoelectrochemical decomposing water, energy storage materials and the like;
(2) The microwave radiation method adopted by the patent has simple and convenient operation and concentrated energy, and is beneficial to improving the reaction rate and the monoclinic BiVO 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The synthesis efficiency of the O three-phase coexisting material;
(3) The three-phase coexisting monoclinic BiVO with regular appearance, small size and large specific surface area can be prepared by adopting the microwave radiation method related to the patent 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The preparation method of the O material is expected to become an effective strategy for solving the problem that the photocatalysis efficiency is difficult to improve caused by the easy recombination of single-phase electrons and holes, and the high-efficiency stable process characteristics have the potential of large-scale production and commercialization.
Three-phase coexisting monoclinic BiVO prepared by using method of the patent 4 Tetragonal scheeliteOre type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The O nano sheet material has larger specific surface area, regular morphology, high purity and small size; the patent is characterized in that the product is a three-phase coexisting material, the process is simple to operate, acid and alkali are not needed to be used, the energy consumption is low, the time is short, and the temperature is mild and controllable; the method solves the problem of single-phase BiVO 4 The research on the problem of electron-hole easy recombination and the improvement of the catalytic performance is necessary when the material is used as a photocatalytic material, has vivid scientificity, practicability and innovation, and is favorable for promoting BiVO 4 Research advances in the fields of photocatalysis, energy storage and the like.
The synthetic process mechanism of the method is as follows: microwave radiation is an electromagnetic radiation intermediate between infrared waves and radio waves. Unlike traditional heat source conducting heating from outside to inside, microwave radiation heating is bulk heating produced by dielectric loss of material in electromagnetic field, and has the features of high heat efficiency and no hysteresis. Can generate a large number of small bubbles under the disturbance of microwaves, which is BiVO 4 And [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The growth unit of O provides a nucleation medium. CTAB is a cationic surfactant with a long chain structure, and a macromolecular chain can be adsorbed and entangled with a product nucleus to form a micelle structure and inhibit aggregation of particles. The subsequent crystal growth process is based on the micelle template, and the three-phase coexisting monoclinic BiVO with regular appearance, small size and large specific surface area is formed by growth and assembly 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O product.
Drawings
FIG. 1 shows a three-phase co-existence monoclinic BiVO with a reaction time of 30min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 X bow line diffraction (XRD) pattern of O sample;
FIG. 2 is a plot of the ratio of phases in the XRD pattern of a sample at a reaction time of 30 minutes;
FIG. 3 is a table showing the proportions of the phases in the XRD pattern of the sample at a reaction time of 30min;
FIG. 4 is a sample 14-0133 phase tetragonal scheelite type BiVO 4 A crystal structure diagram of (2);
FIG. 5 shows sample 14-0688 phase monoclinic BiVO 4 A crystal structure diagram of (2);
FIG. 6 is a sample 48-575 phase [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 Crystal structure diagram of O;
FIG. 7 shows a three-phase co-existence monoclinic BiVO with a reaction time of 30min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 30 k-fold Scanning Electron Microscope (SEM) images of O samples;
FIG. 8 shows a three-phase co-existence monoclinic BiVO with a reaction time of 30min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 100 k-fold Scanning Electron Microscope (SEM) image of O samples;
FIG. 9 is a three-phase co-existence monoclinic BiVO 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 A synthetic morphology diagram of the O sample;
FIG. 10 shows a three-phase co-existence monoclinic BiVO with a reaction time of 50min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 X-ray diffraction (XRD) pattern of O sample;
FIG. 11 is a plot of the ratio of the phases in the XRD pattern of a sample at a reaction time of 50 minutes;
FIG. 12 is a table showing the proportions of the phases in the XRD pattern of the sample at a reaction time of 50min;
FIG. 13 shows a three-phase co-existence monoclinic BiVO with a reaction time of 50min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 13 k-fold Scanning Electron Microscope (SEM) images of O samples;
FIG. 14 shows a three-phase co-existence monoclinic BiVO with a reaction time of 50min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 25 k-fold Scanning Electron Microscope (SEM) images of O samples;
FIG. 15 shows a three-phase co-existence monoclinic BiVO with a reaction time of 70min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 X-ray diffraction (XRD) pattern of O sample;
FIG. 16 is a plot of the ratio of the phases in the XRD pattern of the sample at a reaction time of 70min;
FIG. 17 is a table showing the proportions of the phases in the XRD pattern of the sample at a reaction time of 70min;
FIG. 18 shows a three-phase co-existence monoclinic BiVO with a reaction time of 70min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 25 k-fold Scanning Electron Microscope (SEM) images of O samples;
FIG. 19 shows a three-phase co-existence monoclinic BiVO with a reaction time of 70min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 60 k-fold Scanning Electron Microscope (SEM) images of O samples;
FIG. 20 shows a three-phase co-existence monoclinic BiVO with a reaction time of 90min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 X-ray diffraction (XRD) pattern of O sample;
FIG. 21 is a graph showing the proportion of each phase in the XRD pattern of the sample at a reaction time of 90min;
FIG. 22 is a table showing the proportions of the phases in the XRD pattern of the sample at a reaction time of 90min;
FIG. 23 shows a three-phase co-existence monoclinic BiVO with a reaction time of 90min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 25 k-fold Scanning Electron Microscope (SEM) images of O samples;
FIG. 24 shows a three-phase co-existence monoclinic BiVO with a reaction time of 90min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 30 k-fold Scanning Electron Microscope (SEM) images of O samples;
FIG. 25 shows a three-phase co-existence monoclinic BiVO with a reaction time of 130min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 X bow line diffraction (XRD) pattern of O sample;
FIG. 26 is a plot of the ratio of the phases in the XRD pattern of the sample for a reaction time of 130min;
FIG. 27 is a table showing the proportions of the phases in the XRD pattern of the sample at a reaction time of 130min;
FIG. 28 shows a three-phase co-existence monoclinic BiVO with a reaction time of 130min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 50 k-fold Scanning Electron Microscope (SEM) images of O samples;
FIG. 29 shows a three-phase co-existence monoclinic BiVO with a reaction time of 130min 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 100 k-fold Scanning Electron Microscope (SEM) image of O samples.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
Example 1 preparation of three-phase Co-existing monoclinic BiVO Using microwave radiation technology 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O sample 1
2.0615g of analytically pure Bi (NO 3 ) 3 ·5H 2 O, 1.5490g cetyl trimethylammonium bromide CTAB in a 250mL beaker was added 115mL of distillationAfter stirring the water and the solution on a magnetic stirrer with the rotating speed of 800rpm for 15min, transferring the solution into a 250mL round bottom flask; the round bottom flask is placed in a reactor with the brand name of 'Mei brand' PJ21C-AU, the equipment is a microwave reactor with a temperature control and reflux condensing device and a normal pressure reaction system, heating power is 1000W, frequency is 2450MHz, heating temperature is 100 ℃, and reaction precursor solution A is obtained after mixing for 60 min; then, 0.7457g of NH was weighed 4 VO 3 Adding 85mL of distilled water into a 100mL beaker, and uniformly stirring for 15min by using a magnetic stirrer with the rotating speed of 800rpm to obtain a reaction precursor solution B; then transferring the precursor solution B obtained in the second step into a 500mL round bottom flask, dropwise adding the precursor solution A obtained in the first step into the 500mL flask containing the precursor solution B under the condition of intense stirring, and continuing stirring for 10min after the dropwise adding is completed to obtain a mixed solution C; placing the mixed solution C obtained in the third step into a 'Mei brand' PJ21C-AU microwave reactor with an atmospheric reflux cooling device, setting the heating power to be 1000W, the frequency to be 2450MHz, the heating temperature to be 100 ℃, and the reaction time to be 30min; after the reaction is finished, after the product obtained in the round-bottom flask is naturally cooled, transferring the product into a centrifuge, centrifuging for 2min at a rotation speed of 5000rpm, removing supernatant and keeping a layer of product, washing the lower layer of product with distilled water and ethanol for 3-5 times respectively, then placing the washed product into an oven, adjusting the temperature of the oven to 70 ℃, and keeping the temperature for 24h to obtain the target three-phase coexisting nano-sheet material.
X-ray diffraction results show that the phase of the product is tetragonal scheelite type BiVO 4 Monoclinic BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 In the O three-phase coexisting state, the XRD pattern of the resulting product with reaction time t=30min is as shown in fig. 1, with BiVO corresponding to tetragonal scheelite at 2θ= 18.319 °, 24.373 °, 30.677 °, 32.679 °, 39.527 ° and 48.402 ° 4 Is identical to the standard JCPDS card No. 14-0133 and corresponds to the (101), (200), (211), (112), (301) and (312) crystal planes respectively, the strongest peak corresponds to hkl crystal plane index (200), and its crystal structure is shown in FIG. 4The lattice spacing is 0.365nm, the space group is I41/amp, and the unit cell parameters areA kind of electronic device with high-pressure air-conditioning systemα=β=γ=90.0°, the corresponding peak to total peak ratio being 36.2% (fig. 2, 3); meanwhile, there are corresponding monoclinic BiVO at 2θ= 18.988 °, 28.586 °, 28.822 °, 28.947 °, 30.548 °, 42.464 ° and 53.310 ° 4 Is matched with the standard JCPDS card number 14-0688, and is respectively matched with (011),/or +>(121) The (040), (051) and (161) crystal planes correspond to each other, and the strongest peak corresponds to hkl crystal plane index +.>The crystal structure diagram is shown in FIG. 5, the lattice spacing is 0.309nm, the space group is I2/a, and the unit cell parameter +.>Is->α=γ=90.0° and β= 90.38 °, the corresponding peak value being 35.4% of the total peak value (fig. 2, 3); in addition, there are also the corresponding [ Bi ] at 2θ= 6.596 °, 10.995 °, 13.184 °, 19.756 ° and 42.823 ° 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The characteristic peak of O corresponds to the standard JCPDS card number 48-575, the crystal structure diagram is shown in figure 6, and the corresponding peak value accounts for 28.4 percent of the total peak value (figures 2 and 3).
Scanning electron microscope pictures (figures 7 and 8) show that the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.20-1.89 mu m and the thickness of 20-130 nm, the appearance schematic diagram is shown in figure 9, and the nano sheets are uniform in structure, uniform in distribution and good in dispersibility.
Example 2 preparation of three-phase Co-existing monoclinic System Using microwave radiation technologyBiVO 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O sample 2
2.0615g of analytically pure Bi (NO 3 ) 3 ·5H 2 O, 1.5490g cetyl trimethylammonium bromide CTAB in a 250mL beaker, 115mL distilled water was added, and after stirring the solution for 15min on a magnetic stirrer at 800rpm, it was transferred to a 250mL round bottom flask; the round bottom flask is placed in a reactor with the brand name of 'Mei brand' PJ21C-AU, the equipment is a microwave reactor with a temperature control and reflux condensing device and a normal pressure reaction system, heating power is 1000W, frequency is 2450MHz, heating temperature is 100 ℃, and reaction precursor solution A is obtained after mixing for 60 min; then, 0.7457g of NH was weighed 4 VO 3 Adding 85mL of distilled water into a 100mL beaker, and uniformly stirring for 15min by using a magnetic stirrer with the rotating speed of 800rpm to obtain a reaction precursor solution B; then transferring the precursor solution B obtained in the second step into a 500mL round bottom flask, dropwise adding the precursor solution A obtained in the first step into the 500mL flask containing the precursor solution B under the condition of intense stirring, and continuing stirring for 10min after the dropwise adding is completed to obtain a mixed solution C; placing the mixed solution C obtained in the third step into a 'Mei brand' PJ21C-AU microwave reactor with an atmospheric reflux cooling device, setting the heating power to be 1000W, the frequency to be 2450MHz, the heating temperature to be 100 ℃, and the reaction time to be 50min; after the reaction is finished, after the product obtained in the round-bottom flask is naturally cooled, transferring the product into a centrifuge, centrifuging for 2min at a rotation speed of 5000rpm, removing supernatant and keeping a layer of product, washing the lower layer of product with distilled water and ethanol for 3-5 times respectively, then placing the washed product into an oven, adjusting the temperature of the oven to 70 ℃, and keeping the temperature for 24h to obtain the target three-phase coexisting nano-sheet material.
X-ray diffraction results show that the phase of the product is tetragonal scheelite type BiVO 4 Monoclinic BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O three-phase coexisting state, reaction time t=50min of the obtained productAs shown in fig. 10, has an XRD pattern corresponding to tetragonal scheelite type BiVO at 2θ= 18.319 °, 24.373 °, 32.679 °, 34.714 °, 39.527 ° and 46.993 ° 4 Is identical to the standard JCPDS card No. 14-0133, and is respectively corresponding to (101), (200), (112), (220), (301) and (321) crystal faces, the strongest peak is correspondent to hkl crystal face index (200), its crystal structure diagram is shown in figure 4, lattice spacing is 0.365nm, space group is I41/amp, unit cell parameter isA kind of electronic device with high-pressure air-conditioning systemα=β=γ=90.0°, the corresponding peak to total peak ratio being 39.0% (fig. 11, 12); meanwhile, there are angles corresponding to monoclinic BiVO at 2θ= 18.669 °, 28.586 °, 28.822 °, 34.494 °, 39.782 ° and 46.711 ° 4 Is matched with the standard JCPDS card number 14-0688 and is respectively matched with (110),/for the standard JCPDS card number>(200) The (211) and (240) crystal planes correspond to each other, and the strongest peak corresponds to hkl crystal plane index +.>The crystal structure diagram is shown in FIG. 5, the lattice spacing is 0.309nm, the space group is I2/a, and the unit cell parameter +.>Is->α=γ=90.0° and β= 90.38 °, the corresponding peak to total peak ratio being 39.0% (fig. 11, 12); in addition, there are also the corresponding [ Bi ] at 2θ= 6.596 °, 10.995 °, 11.790 °, 13.184 ° and 42.823 ° 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The characteristic peak of O corresponds to the standard JCPDS card number 48-575, the crystal structure diagram is shown in figure 6, and the corresponding peak value accounts for 22.0% of the total peak value (figures 11 and 12).
Scanning electron microscope pictures (figures 13 and 14) show that the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.44-1.97 mu m and the thickness of 46-90 nm, the appearance schematic diagram is shown in figure 9, and the nano sheets are uniform in structure, uniform in distribution and good in dispersibility.
Example 3 preparation of three-phase Co-existing monoclinic BiVO Using microwave radiation technology 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O sample 3
2.0615g of analytically pure Bi (NO 3 ) 3 ·5H 2 O, 1.5490g cetyl trimethylammonium bromide CTAB in a 250mL beaker, 115mL distilled water was added, and after stirring the solution for 15min on a magnetic stirrer at 800rpm, it was transferred to a 250mL round bottom flask; the round bottom flask is placed in a reactor with the brand name of 'Mei brand' PJ21C-AU, the equipment is a microwave reactor with a temperature control and reflux condensing device and a normal pressure reaction system, heating power is 1000W, frequency is 2450MHz, heating temperature is 100 ℃, and reaction precursor solution A is obtained after mixing for 60 min; then, 0.7457g of NH was weighed 4 VO 3 Adding 85mL of distilled water into a 100mL beaker, and uniformly stirring for 15min by using a magnetic stirrer with the rotating speed of 800rpm to obtain a reaction precursor solution B; then transferring the precursor solution B obtained in the second step into a 500mL round bottom flask, dropwise adding the precursor solution A obtained in the first step into the 500mL flask containing the precursor solution B under the condition of intense stirring, and continuing stirring for 10min after the dropwise adding is completed to obtain a mixed solution C; placing the mixed solution C obtained in the third step into a 'Mei brand' PJ21C-AU microwave reactor with an atmospheric reflux cooling device, setting the heating power to be 1000W, the frequency to be 2450MHz, the heating temperature to be 100 ℃, and the reaction time to be 70min; after the reaction is finished, after the product obtained in the round-bottom flask is naturally cooled, transferring the product into a centrifuge, centrifuging for 2min at a rotation speed of 5000rpm, removing supernatant and keeping a layer of product, washing the lower layer of product with distilled water and ethanol for 3-5 times respectively, then placing the washed product into an oven, regulating the temperature of the oven to 70 ℃, and keeping the temperatureAnd obtaining the target three-phase coexisting nanosheet material after 24 hours.
X-ray diffraction results show that the phase of the product is tetragonal scheelite type BiVO 4 Monoclinic BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 As shown in fig. 15, the XRD patterns of the resultant product in the O three-phase coexistence state with the reaction time t=70min have the values corresponding to tetragonal scheelite type BiVO at 2θ= 18.319 °, 24.373 °, 30.677 °, 32.679 °, 39.527 °, 46.993 ° and 48.402 ° 4 Is identical to the standard JCPDS card No. 14-0133, and is respectively corresponding to (101), (200), (211), (112), (301), (321) and (312) crystal planes, the strongest peak is correspondent to hkl crystal plane index (200), its crystal structure diagram is shown in figure 4, lattice spacing is 0.365nm, space group is I41/amd, unit cell parameter isIs->α=β=γ=90.0°, the corresponding peak to total peak ratio being 13.6% (fig. 16, 17); meanwhile, there are corresponding monoclinic BiVO at 2θ= 18.669 °, 18.988 °, 28.822 °, 28.947 °, 30.548 °, 35.221 °, 39.782 ° and 47.305 ° 4 Is matched with the standard JCPDS card number 14-0688 and is respectively matched with (110), (011) and (10)>(121) The (040), (002), (211) and (042) crystal planes correspond, the strongest peak corresponds to hkl crystal plane index +.>The crystal structure diagram is shown in FIG. 5, the lattice spacing is 0.309nm, the space group is I2/a, and the unit cell parameter +.>Is->α=γ=90.0° and β= 90.38 °, which phase isThe corresponding peak to total peak ratio was 43.2% (fig. 16, 17); in addition, there are also the corresponding [ Bi ] at 2θ= 6.596 °, 10.995 °, 13.184 °, 19.756 ° and 42.823 ° 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The characteristic peak of O corresponds to the standard JCPDS card number 48-575, the crystal structure diagram is shown in figure 6, and the corresponding peak value accounts for 43.2% of the total peak value (figures 16 and 17).
Scanning electron microscope pictures (figures 18 and 19) show that the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.12-1.96 mu m and the thickness of 26-76 nm, the appearance schematic diagram is shown in figure 9, and the nano sheets are uniform in structure, uniform in distribution and good in dispersibility.
Example 4 preparation of three-phase Co-existing monoclinic BiVO Using microwave radiation technology 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O sample 4
2.0615g of analytically pure Bi (NO 3 ) 3 ·5H 2 O, 1.5490g cetyl trimethylammonium bromide CTAB in a 25mL beaker, 115mL distilled water was added, and after stirring the solution for 15min on a magnetic stirrer at 800rpm, it was transferred to a 250mL round bottom flask; the round bottom flask is placed in a reactor with the brand name of 'Mei brand' PJ21C-AU, the equipment is provided with a temperature control, reflux and condensation device, a microwave reactor of a normal pressure reaction system is provided with heating power of 1000W, frequency of 2450MHz and heating temperature of 100 ℃, and a reaction precursor solution A is obtained after mixing for 60 min; then, 0.7457g of NH was weighed 4 VO 3 Adding 85mL of distilled water into a 100mL beaker, and uniformly stirring for 15min by using a magnetic stirrer with the rotating speed of 800rpm to obtain a reaction precursor solution B; then transferring the precursor solution B obtained in the second step into a 500mL round bottom flask, dropwise adding the precursor solution A obtained in the first step into the 500mL flask containing the precursor solution B under the condition of intense stirring, and continuing stirring for 10min after the dropwise adding is completed to obtain a mixed solution C; placing the mixed solution C obtained in the third step into a 'Mei brand' PJ21C-AU microwave reactor with an atmospheric reflux cooling deviceSetting the heating power to 1000W, the frequency to 2450MHz, the heating temperature to 100 ℃ and the reaction time to 90min; after the reaction is finished, after the product obtained in the round-bottom flask is naturally cooled, transferring the product into a centrifuge, centrifuging for 2min at a rotation speed of 5000rpm, removing supernatant and keeping a layer of product, washing the lower layer of product with distilled water and ethanol for 3-5 times respectively, then placing the washed product into an oven, adjusting the temperature of the oven to 70 ℃, and keeping the temperature for 24h to obtain the target three-phase coexisting nano-sheet material.
X-ray diffraction results show that the phase of the product is tetragonal scheelite type BiVO 4 Monoclinic BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 As shown in fig. 20, the XRD patterns of the resultant product in the O three-phase coexistence state with the reaction time t=90 min have the values corresponding to tetragonal scheelite type BiVO at 2θ= 18.319 °, 24.373 °, 30.677 °, 32.679 °, 39.527 °, 46.993 ° and 48.402 ° 4 Is identical to the standard JCPDS card No. 14-0133, and is respectively corresponding to (101), (200), (211), (112), (301), (321) and (321) crystal faces, the strongest peak is correspondent to hkl crystal face index (200), its crystal structure diagram is shown in figure 4, lattice spacing is 0.365nm, space group is I41/amd, unit cell parameter isIs->α=β=γ=90.0°, the corresponding peak to total peak ratio being 39.5% (fig. 21, 22); meanwhile, there are angles corresponding to monoclinic BiVO at 2θ= 18.988 °, 28.822 °, 28.947 °, 30.548 °, 39.782 ° and 42.464 ° 4 Is matched with the standard JCPDS card number 14-0688, and is respectively matched with (011),/or +>(121) The (040), (211) and (051) crystal planes correspond, the strongest peak corresponds to hkl crystal plane index +.>Crystal junction thereofThe pattern is shown in FIG. 5, the lattice spacing is 0.309nm, the space group is I2/a, and the unit cell parameters areIs->α=γ=90.0° and β= 90.38 °, the corresponding peak to total peak ratio being 39.5% (fig. 21, 22); in addition, there are also the corresponding [ Bi ] at 2θ= 6.596 °, 10.995 °, 13.184 °, 19.756 ° and 42.823 ° 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The characteristic peak of O corresponds to the standard JCPDS card number 48-575, the crystal structure diagram is shown in figure 6, and the corresponding peak value accounts for 21.0% of the total peak value (figures 21 and 22).
Scanning electron microscope pictures (fig. 23 and 24) show that the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.40-2.01 mu m and the thickness of 43-141 nm, the appearance schematic diagram is shown in fig. 9, and the nano sheets are uniform in structure, uniform in distribution and good in dispersibility.
Example 5 preparation of three-phase Co-existing monoclinic BiVO Using microwave radiation technology 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O sample 5
2.0615g of analytically pure Bi (NO 3 ) 3 ·5H 2 O, 1.5490g cetyl trimethylammonium bromide CTAB in a 250mL beaker, 115mL distilled water was added, and after stirring the solution for 15min on a magnetic stirrer at 800rpm, it was transferred to a 250mL round bottom flask; the round bottom flask is placed in a reactor with the brand name of 'Mei brand' PJ21C-AU, the equipment is a microwave reactor with a temperature control and reflux condensing device and a normal pressure reaction system, heating power is 1000W, frequency is 2450MHz, heating temperature is 100 ℃, and reaction precursor solution A is obtained after mixing for 60 min; then, 0.7457g of NH was weighed 4 VO 3 Adding 85mL of distilled water into a 100mL beaker, and uniformly stirring for 15min by using a magnetic stirrer with the rotating speed of 800rpm to obtain a reaction precursor solution B; subsequently, the first and second heat exchangers are connected,transferring the precursor solution B obtained in the second step into a 500mL round bottom flask, dropwise adding the precursor solution A obtained in the first step into the 500mL flask containing the precursor solution B under the condition of intense stirring, and continuously stirring for 10min after the dropwise adding is completed to obtain a mixed solution C; placing the mixed solution C obtained in the third step into a 'Mei brand' PJ21C-AU microwave reactor with an atmospheric reflux cooling device, setting the heating power to be 1000W, the frequency to be 2450MHz, the heating temperature to be 100 ℃, and the reaction time to be 130min; after the reaction is finished, after the product obtained in the round-bottom flask is naturally cooled, transferring the product into a centrifuge, centrifuging for 2min at a rotation speed of 5000rpm, removing supernatant and keeping a layer of product, washing the lower layer of product with distilled water and ethanol for 3-5 times respectively, then placing the washed product into an oven, adjusting the temperature of the oven to 70 ℃, and keeping the temperature for 24h to obtain the target three-phase coexisting nano-sheet material.
X-ray diffraction results show that the phase of the product is tetragonal scheelite type BiVO 4 Monoclinic BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 As shown in fig. 25, the XRD patterns of the resultant product in the O three-phase coexistence state with the reaction time t=130 min have the values corresponding to tetragonal scheelite type BiVO at 2θ= 18.319 °, 24.373 °, 30.677 °, 32.679 °, 34.714 °, 48.402 ° and 49.931 ° 4 Is identical to the standard JCPDS card No. 14-0133, and is respectively corresponding to (101), (200), (211), (112), (220), (312) and (400) crystal faces, the strongest peak is correspondent to hkl crystal face index (200), its crystal structure diagram is shown in figure 4, lattice spacing is 0.365nm, space group is I41/amd, unit cell parameter isIs->α=β=γ=90.0°, the corresponding peak to total peak ratio being 38.5% (fig. 26, 27); meanwhile, there are corresponding monoclinic BiVO at 2θ= 18.669 °, 18.988 °, 28.586 °, 28.822 °, 28.947 °, 35.221 °, 39.782 ° and 42.464 ° 4 And (2) characteristic peaks ofThe standard JCPDS card number 14-0688 is matched with (110), (011) and (10)>(121) The (002), (211) and (240) crystal planes correspond to each other, and the strongest peak corresponds to hkl crystal plane index +.>The crystal structure diagram is shown in FIG. 5, the lattice spacing is 0.309nm, the space group is I2/a, and the unit cell parameter +.>Is->α=γ=90.0° and β= 90.38 °, the corresponding peak to total peak ratio being 38.5% (fig. 26, 27); in addition, there are also the corresponding [ Bi ] at 2θ= 6.596 °, 10.995 °, 11.790 °, 19.756 °, 24.992 ° and 42.823 ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The characteristic peak of O corresponds to the standard JCPDS card number 48-575, the crystal structure diagram is shown in figure 6, and the corresponding peak value accounts for 23.0% of the total peak value (figures 26 and 27).
Scanning electron microscope pictures (fig. 28 and 29) show that the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.59-3.21 mu m and the thickness of 64-198 nm, the appearance schematic diagram is shown in fig. 9, and the nano sheets are uniform in structure, uniform in distribution and good in dispersibility.
To demonstrate the effects achieved by the experimental procedures employed in examples 1-5 of the present invention, the products did not achieve the desired effects and innovations of examples 1-5 of the present invention without the use of the operations of examples 1-5.
Comparative example of example 1:
(Sun S，Wang W，Zhou L，et al.Efficient methylene blue removal over hydrothermally synthesized starlike BiVO 4 [J].Industrial&engineering Chemistry Research,2009, 48 (4): 1735-1739), sun et al use solvothermal synthesis of the desired product as follows: at room temperature, firstly weighing 0.2924g NH 4 VO 3 And 0.731g of EDTA, dissolved in 5mL of 2mol/L NaOH solution and 15mL of 2mol/L ammonia solution, respectively; next, 1.213g Bi (NO) 3 ) 3 ·5H 2 O, adding 5mL of 2mol/L nitric acid solution, and stirring for 10min; subsequently, the above three solutions were mixed, and 5mL of ethanol was added; finally, transferring the mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, and heating for 6 hours at 120 ℃; after the reaction is finished, washing with deionized water and ethanol; drying the washed product at 80 ℃ for 12 hours to obtain a target product; the method can not prepare BiVO with 14-0133 and 14-0688 phases 4 And 48-575 phase [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 And O three phases coexist, and the obtained product is a micron sheet with the size of 1-2 mu m.
The present invention patent is essentially different from the comparative example, and the present invention patent has vivid innovation.
Comparative example of example 2:
(Huo R，Yang X L，Liu Y Q，et al.Visible-light photocatalytic degradation of glyphosate over BiVO 4 prepared by different co-precipitation methods[J]materials Research Bulletin,2017, 88: 56-61), huo et al used the co-precipitation method to synthesize the target product as follows: at room temperature, 8.9850g Bi (NO 3 ) 3 ·5H 2 O, dissolve in 150mL 1.34mol/L glacial acetic acid solution; next, 2.1660g NH was weighed 4 VO 3 Added to 150mL of 0.5mol/L sodium hydroxide solution; then, the two solutions are quickly mixed under ultrasonic, the suspension is filtered, and the yellow precipitate is washed by distilled water and absolute ethyl alcohol and then is dried at 70 ℃; finally, calcining the dried product in air at 300-500 ℃ for 2 hours to obtain a target product; the method can not prepare BiVO with 14-0133 and 14-0688 phases 4 And 48-575 phase [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 And O three phases coexist, and the obtained product is nano particles with the size of 45-235 nm.
The present invention patent is essentially different from the comparative example, and the present invention patent has vivid innovation.
Comparative example of example 3:
(Khan I，Ali S，Mansha M，et al.Sonochemical assisted hydrothermal synthesis of pseudo-flower shaped Bismuth vanadate(BiVO 4 )and their solar-driven water splitting application[J]ultrasonics sonochemistry,2017, 36: 386-392), khan et al synthesized the target product by sonochemistry as follows: at room temperature, 4.85g Bi (NO 3 ) 3 ·5H 2 O and 1.82g V 2 O 5 Dissolved in 25mL of Teflon tube containing 1wt% SDS; secondly, treating for 2 hours by a pulse ultrasonic machine under the conditions of 10s of on/off period, 400W of power and 20kHz of frequency; then, taking out the pale yellow precipitate in the Teflon tube, and washing with deionized water; finally, transferring the washed precipitate into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and preserving for 4 hours at 90 ℃; after the reaction is finished, drying the obtained product at room temperature, and calcining at 550 ℃ for 4 hours to obtain a target product; the method can not prepare BiVO with 14-0133 and 14-0688 phases 4 And 48-575 phase [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O three phases coexist, and the resulting product is a micron flower with a size of 7 μm.
The present invention patent is essentially different from the comparative example, and the present invention patent has vivid innovation.
Claims (8)
1. Three-phase coexisting monoclinic BiVO 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The O nano sheet material and the preparation method thereof are characterized by comprising the following steps:
first, 2.0615g of analytically pure Bi (NO 3 ) 3 ·5H 2 O and 1.5490g cetyl trimethylammonium bromide CTAB in a 250mL beaker, 115mL distilled water was added and the solution was magnetically stirred at 800rpmStirring on a stirrer for 15min, and transferring into a 250mL round-bottom flask; the round bottom flask is placed in a reactor with the brand name of 'Mei brand' PJ21C-AU, the equipment is a microwave reactor with a temperature control and reflux condensing device and a normal pressure reaction system, heating power is set to be 200-2000W, the frequency is 2450MHz, the heating temperature is 100 ℃, and the reaction precursor solution A is obtained after mixing for 60 min;
second, weighing 0.7457g NH 4 VO 3 Adding 85mL of distilled water into a 100mL beaker, and uniformly stirring for 15min by using a magnetic stirrer with the rotating speed of 800rpm to obtain a reaction precursor solution B;
thirdly, transferring the precursor solution B obtained in the second step into a 500mL round bottom flask, dropwise adding the precursor solution A obtained in the first step into the 500mL flask containing the precursor solution B under the condition of intense stirring, and continuing stirring for 10min after the dropwise adding is completed to obtain a mixed solution C;
fourthly, placing the mixed solution C obtained in the third step into a 'Mei brand' PJ21C-AU microwave reactor with an atmospheric reflux cooling device, setting the heating power to be 200-2000W, the frequency to be 2450MHz, the heating temperature to be 100 ℃, and the reaction time to be 30-130 min;
fifthly, after the reaction is finished, naturally cooling the product obtained in the round-bottomed flask, transferring the product into a centrifuge, centrifuging for 2min at a rotation speed of 5000rpm, removing supernatant and keeping a layer of product, washing the lower layer of product with distilled water and ethanol for 3-5 times respectively, then placing the washed product into an oven, adjusting the temperature of the oven to 70 ℃, and keeping the temperature for 24h to obtain the target three-phase coexisting nano-sheet material.
2. The three-phase coexistence monoclinic BiVO of claim 1 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The method for O nano sheet material is characterized by comprising the following steps: the molar ratio of Bi to CTAB to V in the first and second steps is 2:2:3.
3. According to any one of claims 1-2The three-phase coexisting monoclinic BiVO 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O nanoplatelet materials.
4. A three-phase coexistence monoclinic BiVO according to claim 3 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O nanometer piece, its characterized in that: monoclinic BiVO when the reaction time t=30 min 4 The strongest peak corresponds to hkl crystal plane indexSpace group is I2/a, unit cell parameter->Is->α=γ=90.0° and β= 90.38 °, the corresponding peak value is 35.4% of the total peak value, and the tetragonal scheelite type BiVO 4 The strongest peak corresponds to hkl crystal plane index (200), space group is I41/amd, unit cell parameter is +.> Is->α=β=γ=90.0°, the corresponding peak value is 36.2% of the total peak value, and, [ Bi 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The peak value corresponding to the O phase accounts for 28.4% of the total peak value; the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.20-1.89 mu m and the thickness of 20-130 nm.
5. A three-phase coexistence monoclinic BiVO according to claim 3 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O nanometer piece, its characterized in that: monoclinic BiVO when the reaction time t=50 min 4 The strongest peak corresponds to hkl crystal plane indexSpace group is I2/a, unit cell parameter->Is->Alpha = gamma = 90.0 deg. and beta = 90.38 deg., the corresponding peak value is 39.0% of the total peak value ratio, the tetragonal scheelite type BiVO 4 The strongest peak corresponds to hkl crystal plane index (200), space group is I41/amd, unit cell parameter is +.> Is->α=β=γ=90.0°, and the corresponding peak value is 39.0% of the total peak value ratio, [ Bi 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The peak value corresponding to the O phase accounts for 22.0% of the total peak value; the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.44-1.97 mu m and the thickness of 46-90 nm.
6. A three-phase coexistence monoclinic BiVO according to claim 3 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O nanometer piece, its characterized in that: monoclinic BiVO when the reaction time t=70 min 4 The characteristic peak of the peak corresponds to hkl crystal face indexSpace group is I2/a, unit cell parameter->Is->α=γ=90.0° and β= 90.38 °, the corresponding peak value is 43.2% of the total peak value, and the tetragonal scheelite type BiVO 4 The strongest peak corresponds to hkl crystal plane index (200), space group is I41/amd, unit cell parameter is +.> Is->α=β=γ=90.0°, and the corresponding peak value is 13.6% of the total peak value, and [ Bi 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The peak value corresponding to the O phase accounts for 43.2% of the total peak value; the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.12-1.96 mu m and the thickness of 26-76 nm.
7. A three-phase coexistence monoclinic BiVO according to claim 3 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O nanometer piece, its characterized in that: monoclinic BiVO when the reaction time t=90 min 4 The strongest peak corresponds to hkl crystal plane indexSpace group is I2/a, unit cell parameter->Is->Alpha = gamma = 90.0 deg. and beta = 90.38 deg., the corresponding peak value is 39.5% of the total peak value, the tetragonal scheelite type BiVO 4 The strongest peak corresponds to hkl crystal plane index (200), space group is I41/amd, unit cell parameter is +.> Is->α=β=γ=90.0°, the corresponding peak value is 39.5% of the total peak value ratio, [ Bi 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The peak value corresponding to the O phase accounts for 21.0% of the total peak value; the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.40-2.01 mu m and the thickness of 43-141 nm.
8. A three-phase coexistence monoclinic BiVO according to claim 3 4 Tetragonal scheelite type BiVO 4 [ Bi ] 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 O nanometer piece, its characterized in that: monoclinic BiVO when the reaction time t=130 min 4 The strongest peak corresponds to hkl crystal plane indexSpace group is I2/a, unit cell parameter->Is->α=γ=90.0° and β= 90.38 °, the corresponding peak value is 38.5% of the total peak value, and the tetragonal scheelite type BiVO 4 The strongest peak corresponds to hkl crystal plane index (200), space group is I41/amd, unit cell parameter is +.> Is->α=β=γ=90.0°, and the corresponding peak value is 38.5% of the total peak value ratio, [ Bi 6 O 5 (OH) 3 ](NO 3 ) 5 ·3H 2 The peak value corresponding to the O phase accounts for 23.0% of the total peak value; the three-phase coexisting product is formed by stacking nano sheets with the particle size of 0.59-3.21 mu m and the thickness of 64-198 nm.
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