CN102872888B - BiPO4 nanorod and preparation method and application thereof - Google Patents
BiPO4 nanorod and preparation method and application thereof Download PDFInfo
- Publication number
- CN102872888B CN102872888B CN201210369293.1A CN201210369293A CN102872888B CN 102872888 B CN102872888 B CN 102872888B CN 201210369293 A CN201210369293 A CN 201210369293A CN 102872888 B CN102872888 B CN 102872888B
- Authority
- CN
- China
- Prior art keywords
- preparation
- bipo
- bipo4
- reaction
- nanorod
- 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.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a BiPO4 nanorod and a preparation method and application thereof. The preparation method of the BiPO4 nanorod includes the steps: adding Bi(NO3)3 5H2O and NaH2PO4 2H2O into deionized water for reaction so as to obtain precipitate, namely the BiPO4 nanorod. BiPO4 which is prepared by the method and of monoclinic-phase monazite and hexagonal mixed crystal structures has fine ultraviolet light catalytic activity, and MB (methylene blue) liquid phase degradation rate of the BiPO4 reaches degradation activity of BiPO4 prepared by a hydrothermal method; and the whole preparation method is low in raw material cost, simple in process, low in preparation temperature and suitable for industrialized mass production and has extremely high practical value and application prospect, and product cost is effectively reduced.
Description
Technical field
The present invention relates to a kind of BiPO
4nanometer rods and preparation method thereof and application, belong to catalysis material technical field.
Background technology
Photocatalysis has important prospect in the depollution of environment and using energy source, is the focus of physio-chemical study.Due to TiO
2based on photochemical catalyst there are the restraining factors such as light induced electron-hole-recombination rate is high, absorption spectrum is narrow, to the progress of its modification not making a breakthrough property.At present, seek novel, efficient compound oxide photocatalyst and cause certain concern.The advantages such as wherein nonmetal oxyacid hydrochlorate has Stability Analysis of Structures, good crystallinity as novel photocatalyst, electronics-hole-recombination rate is low, photoetch is little, inductive effect is large compare the potential class photochemical catalyst of tool.BiPO
4be a kind of functional material widely, be widely used in radioactive element, the selective catalytic oxidation of alkane, the modifications of glass such as Fen Li Mei, plutonium, neptunium, uranium, previous work proves BiPO
4there is good ultraviolet catalytic active.BiPO
4there are three kinds of crystal phase structures: six side's phases, monoclinic phase monazite and monoclinic phase, structure is comparatively stablized with photocatalytic activity it is preferred that monoclinic phase monazite structure.BiPO
4preparation method mainly contains four classes: (one) is solid phase preparation, high-temperature molten salt method or fused salt pulling method; (2) be vapor deposition method; (3) be ultrasound wave irradiation method; (4) be hydro-thermal method.That wherein prepared by method () is the BiPO that bulk has laser and nonlinear optical properties
4crystal, is not suitable for doing photocatalyst material and uses; The precursors of method (two) is Bi [Se
2p (OiPr)
2]
3, be not conventional chemical reagent, and reaction needs the hot environment that reduces pressure in a vacuum furnace; Method (three), though possess the advantage that reaction temperature is low, the reaction time is short, can only prepare the BiPO with six side's phase structures
4; Method (four) can prepare the less BiPO of size
4nanometer rods, regulation and control reaction temperature and initial thing ratio can prepare three kinds of crystal phase structures, but the method preparation amount very little, need high temperature and high pressure environment, the practical application for this catalyst has significant limitation.
Summary of the invention
The object of this invention is to provide a kind of BiPO
4nanometer rods and preparation method thereof and application, solving transformation environment in traditional preparation methods, high temperature, shortcoming that single preparation amount is few, is BiPO
4suitability for industrialized production and practical application set up good technical foundation, the BiPO with monoclinic phase monazite and six side's phase duplex grain structures (ratio is about 5:1) provided by the invention
4there is good ultraviolet catalytic active.
A kind of BiPO provided by the present invention
4the preparation method of nanometer rods, comprises the steps:
By Bi (NO
3)
35H
2o and NaH
2pO
42H
2o adds in deionized water and reacts, and gained sediment is described BiPO
4nanometer rods.
In above-mentioned preparation method, Bi (NO
3)
35H
2o and NaH
2pO
42H
2the molfraction ratio of O can be 1:(1 ~ 10), specifically can be 1:1,1:1.5,1:2,1:4,1:5,1:6,1:7 or 1:10.
In above-mentioned preparation method, the pH value range of described reaction is between 1.0 ~ 7.0, and is not 7.0.
In above-mentioned preparation method, the time of described reaction can be 24 ~ 72h, and the temperature of reaction is 70 ~ 100 DEG C.
In above-mentioned preparation method, the ratio of solvent of described reaction can be: Bi (NO described in every 1mol
3)
35H
2o needs deionized water described in (24 ~ 360) L, specifically can be 24L, 36L, 72L, 120L, 180L or 240L.
Present invention also offers BiPO prepared by said method
4nanometer rods and the application as photochemical catalyst thereof.
The BiPO with monoclinic phase monazite and six side's phase duplex grain structures utilizing method of the present invention to prepare
4there is good ultraviolet catalytic active, hydro-thermal method is reached to MB liquid phase degradation rate and prepares BiPO
4degrading activity; In whole preparation method, raw material is inexpensive, technique is simple, preparation temperature is low, effectively reduces product cost, is applicable to industrialized production, has very high practical value and application prospect.
Accompanying drawing explanation
Fig. 1 is BiPO prepared by embodiment 1
4xRD.
Fig. 2 is BiPO prepared by embodiment 2
4xRD.
Fig. 3 is BiPO prepared by embodiment 3
4xRD.
Fig. 4 is BiPO prepared by embodiment 4
4tEM, wherein ratio of solvent is 180.
Fig. 5 is BiPO prepared by embodiment 4
4xRD, wherein ratio of solvent is 180.
Fig. 6 is BiPO prepared by embodiment 5
4the curve of the MB of photocatalytic degradation under ultraviolet light.
Detailed description of the invention
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The initial thing of reaction used in the following embodiment of the present invention is the pure Bi (NO of commercially available analysis
3)
35H
2o, NaH
2pO
42H
2o, the HNO of adjust ph
3be commercially available with NaOH, HNO
3mass percentage to be 68%, NaOH pure for analyzing, deionized water is self-control.
Adopt BiPO prepared by JEM2100 transmission electron microscope observing
4granule-morphology and size, beam voltage is 100kV.With German Bruker D8Advance type X-ray diffractometer (Cu target K
αray, tube voltage 40kV, tube current 20mA), test preparation BiPO
4crystal formation.
Embodiment 1, regulation and control reaction time prepare BiPO
4nanometer rods
Weigh 24.3g(50mmol) Bi (NO
3)
35H
2the NaH of O and 7.8g (50mmol)
2pO
42H
2o, adds the there-necked flask of 5.0L, measures 3.6L deionized water and joins in there-necked flask, then magneton is loaded there-necked flask.Spherical condensation tube is received on there-necked flask one osculum, and the temperature sensor of electric heating cover is inserted in reactant liquor from another osculum of there-necked flask, the large mouth stopper jam-pack in the middle of there-necked flask.Magnetic agitation knob on adjustment electric heating cover is to 800r/min, and the temperature arranging electric heating cover temperature control panel is 100 DEG C.After heating about 30min, reactant liquor comes to life.From reactant liquor boiling, the timing control reaction time is respectively 24h, 36h, 48h, 60h and 72h(and does 5 groups of tests altogether), stop heating at the end of reaction and stir, supernatant liquor is outwelled after at room temperature leaving standstill cooling by reactant liquor, and bottom white depositions is transferred in 500ml beaker.Add the target product of 500ml deionized water and stirring washing preparation, after standing a period of time after lower leaf on cleaning solution obviously, supernatant liquor is outwelled (washing 3 times altogether).Finally, the beaker filling target product is put into drying box dry 12h at 120 DEG C, and final white pressed powder is the BiPO of preparation
4.
As seen from Figure 1, when the reaction time is 24h, the BiPO of preparation
4all peaks are pure phase monoclinic phase monazite structure (space group P2
1/ n, JPCDS 15-0767), without any dephasign, lattice paprmeter is a=6.752, b=6.933, c=6.468, β=103.7 °, 2 θ be 19.3 °, 21.5 °, 25.6 °, 27.4 °, 29.4 °, 31.5 °, 37.1 ° diffraction maximum respectively corresponding monoclinic phase (011), (-111), (111), (200, (120), (012) and (-212) crystal face, also have some assorted peaks in figure, owing to there is the foreign ion formation such as some sodium.Along with the prolongation in reaction time, six side's phase structure (space group P3 are there are
121/n, JPCDS 15-0766 and JPCDS 45-1370) crystal face is respectively the characteristic peak 20.1 ° of (101), and the amount of six side's phase structures is very small, almost negligible.
Embodiment 2, regulation and control Bi
3+/ PO
4 3-ratio prepares BiPO
4nanometer rods
Weigh 24.3g(50mmol) Bi (NO
3)
35H
2the NaH of O and 39.0g (250mmol)
2pO
42H
2o, Bi
3+/ PO
4 3-mol ratio is that 1:5(fixes Bi (NO
3)
35H
2o consumption is 50mmol, regulation and control Bi
3+/ PO
4 3-molar ratio is respectively 1:1,1:1.5,1:2,1:4,1:5,1:6,1:7 and 1:10 and does 8 groups of tests altogether, weighs NaH according to ratio difference
2pO
42H
2the amount of O is respectively 7.8g, 11.7g, 15.6g, 31.2g, 46.8g, 54.6g and 78.0g), add the there-necked flask of 5.0L, measure 3.6L deionized water and join in there-necked flask, then magneton is loaded there-necked flask.Spherical condensation tube is received on there-necked flask one osculum, and the temperature sensor of electric heating cover is inserted in reactant liquor from another osculum of there-necked flask, the large mouth stopper jam-pack in the middle of there-necked flask.Magnetic agitation knob on adjustment electric heating cover is to 800r/min, and the temperature arranging electric heating cover temperature control panel is 100 DEG C.After heating about 30min, reactant liquor comes to life.From reactant liquor boiling, timing controls the reaction time is 48h, and stop heating at the end of reaction and stir, supernatant liquor is outwelled after at room temperature leaving standstill cooling by reactant liquor, and bottom white depositions is transferred in 500ml beaker.Add the target product of 500ml deionized water and stirring washing preparation, after standing a period of time after lower leaf on cleaning solution obviously, supernatant liquor is outwelled (washing 3 times altogether).Finally, the beaker filling target product is put into drying box dry 12h at 120 DEG C, and final white pressed powder is the BiPO of preparation
4.
As seen from Figure 2, at Bi
3+/ PO
4 3-the BiPO prepared when ratio is 1:1 ~ 1:2
4for pure phase monoclinic phase monazite structure (space group P2
1/ n, JPCDS 15-0767).The BiPO prepared when ratio is 1:4
4in there are six side's phase structure (space group P3
121/n, JPCDS 45-1370) crystal face be respectively (100), (101) and (200) characteristic peak 14.6 °, 20.1 ° and 29.5 °, along with PO
4 3-the increase gradually of ratio, the characteristic peak of six side's phase structures strengthens gradually, and the characteristic peak 21.3 ° of monoclinic phase monazite structure surface (-111), (200), (120), 27.1 °, 29.1 ° weaken gradually.At Bi
3+/ PO
4 3-ratio is in the change procedure of 1:4 ~ 1:7, along with PO
4 3-biPO prepared by the raising of ratio
4in catalyst, the composition of six side's phase structures increases gradually, works as Bi
3+/ PO
4 3-when ratio is 1:5, monoclinic phase monazite structure and six side's phase structure ratios are 5:1.
Embodiment 3, regulation and control reacting liquid pH value prepare BiPO
4nanometer rods
Weigh 24.3g(50mmol) Bi (NO
3)
35H
2the NaH of O and 39.0g (250mmol)
2pO
42H
2o, Bi
3+/ PO
4 3-mol ratio is 1:5, adds the there-necked flask of 5.0L, measures 3.6L deionized water and joins in there-necked flask, then magneton is loaded there-necked flask.Regulate magnetic agitation knob on electric heating cover to 800r/min, be 2.2 by the pH value of pHSJ-4A type pH meter measurement reaction mixture at ambient temperature, use dense HNO
3regulate reaction mixture pH value to be 1.0 and 1.5, with the NaOH solution of 1.0mol/L regulate the pH value of reaction mixture be 3.0,5.0 and 7.0(do 6 groups of tests altogether).After reacting liquid pH value is adjusted to appropriate value, spherical condensation tube is received on there-necked flask one osculum, the temperature sensor of electric heating cover is inserted in reactant liquor from another osculum of there-necked flask, the large mouth stopper jam-pack in the middle of there-necked flask.The temperature arranging electric heating cover temperature control panel is 100 DEG C.After heating about 30min, reactant liquor comes to life.From reactant liquor boiling, timing controls the reaction time is 48h, and stop heating at the end of reaction and stir, supernatant liquor is outwelled after at room temperature leaving standstill cooling by reactant liquor, and bottom white depositions is transferred in 500ml beaker.Add the target product of 500ml deionized water and stirring washing preparation, after standing a period of time after lower leaf on cleaning solution obviously, supernatant liquor is outwelled (washing 3 times altogether).Finally, the beaker filling target product is put into drying box dry 12h at 120 DEG C, and final white pressed powder is the BiPO of preparation
4.
As seen from Figure 3, the BiPO prepared under pH is 1.0 and 1.5 conditions
4for pure phase monoclinic phase monazite structure (space group P2
1/ n, JPCDS 15-0767).Occur six side's phase structures when pH value is 2.2, along with the raising of pH, six side's phase constituents also increase gradually; The BiPO prepared when pH is 5.0
4the composition of six side's phase structures is greater than the composition of monoclinic phase monazite structure; The product prepared when pH is 7.0 has not been BiPO
4, be alkali formula bismuth phosphate Bi
3o (PO
4)
2oH.
Embodiment 4, adjusting solvent are than preparation BiPO
4nanometer rods
Weigh 4.85g(10mmol) Bi (NO
3)
35H
2the NaH of O and 7.8g (50mmol)
2pO
42H
2o, adds the there-necked flask of 5.0L, measures 3.6L deionized water and joins in there-necked flask, now deionized water volume L and Bi
3+the ratio of molal quantity mol be called for short ratio of solvent be 360(adjusting solvent than 240,180,120,72,36,24 differences, Bi (NO
3)
35H
2o and NaH
2pO
42H
2o weighed amount is respectively 7.29g and 11.7g, 9.70g and 15.6g, 14.55g and 23.4g, 48.6g and 78.0g, 72.9g and 117.0g, does 7 groups of tests altogether), Bi
3+/ PO
4 3-mol ratio is constant is 1:5.Then magneton is loaded there-necked flask, spherical condensation tube is received on there-necked flask one osculum, the temperature sensor of electric heating cover is inserted in reactant liquor from another osculum of there-necked flask, the large mouth stopper jam-pack in the middle of there-necked flask.Magnetic agitation knob on adjustment electric heating cover is to 800r/min, and the temperature arranging electric heating cover temperature control panel is 100 DEG C.After heating about 30min, reactant liquor comes to life.From reactant liquor boiling, the timing control reaction time is respectively 48h, stops heating and stir at the end of reaction, and supernatant liquor is outwelled after at room temperature leaving standstill and cooling by reactant liquor, and bottom white depositions is transferred in 500ml beaker.Add the target product of 500ml deionized water and stirring washing preparation, after standing a period of time after lower leaf on cleaning solution obviously, supernatant liquor is outwelled (washing 3 times altogether).Finally, the beaker filling target product is put into drying box dry 12h at 120 DEG C, and final white pressed powder is the BiPO of preparation
4.
As seen from Figure 4, the BiPO prepared under this condition
4the diameter of nanometer rods is less than 90nm, and length is no more than 400nm.
Embodiment 5, BiPO
4the ultraviolet catalytic activity rating of nanometer rods
The BiPO that the present embodiment is used
4for product prepared by embodiment 4, ratio of solvent is wherein 180.
Measure 50mg BiPO
4photochemical catalyst and 100ml concentration are 1.0 × 10
-5methylene blue dye (MB) aqueous solution of mol/L mixes in the beaker of 150ml, and first ultrasonic 10min, stirs 10min, make BiPO in dark room conditions
4in MB solution, reach adsorption-desorption balance and be uniformly dispersed.Then be positioned in the ultraviolet light evaluating apparatus of 254nm and carry out activity rating, light intensity when wherein stablizing is 0.9mW/cm
2, sample 1 time (every sub-sampling 4.0ml) every 5min, centrifugal 10min under the rotating speed of 12000r/min, get supernatant liquor Hitachi U-3010 ultraviolet-visible spectrophotometer and measure MB residual concentration, calculate the degradation rate of MB, compare preparation BiPO
4ultraviolet catalytic active.
Above-mentioned test is parallel carries out 3 times, the result of its catalytic degradation as shown in Figure 6, as shown in Figure 6, by 3 parallel laboratory test results, BiPO prepared by the present invention
4be very controlled, and stability is fine.
Claims (3)
1. a BiPO
4the preparation method of nanometer rods, comprises the steps:
In atmospheric conditions, by Bi (NO
3)
35H
2o and NaH
2pO
42H
2o adds in deionized water and carries out boiling reflux reaction, and gained sediment is described BiPO
4nanometer rods;
Bi (NO
3)
35H
2o and NaH
2pO
42H
2the molfraction of O is than being 1:(1 ~ 10);
The pH value of described reaction is between 1.0 ~ 7.0, and is not 7.0;
The time of described reaction is 24 ~ 72h, and the temperature of reaction is 100 DEG C;
The ratio of solvent of described reaction is Bi (NO described in every 1mol
3)
35H
2o needs (24 ~ 360) L deionized water.
2. the BiPO for preparing of method described in claim 1
4nanometer rods.
3. BiPO according to claim 1
4nanometer rods is as the application in photochemical catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210369293.1A CN102872888B (en) | 2012-09-27 | 2012-09-27 | BiPO4 nanorod and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210369293.1A CN102872888B (en) | 2012-09-27 | 2012-09-27 | BiPO4 nanorod and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102872888A CN102872888A (en) | 2013-01-16 |
| CN102872888B true CN102872888B (en) | 2015-01-14 |
Family
ID=47474533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210369293.1A Expired - Fee Related CN102872888B (en) | 2012-09-27 | 2012-09-27 | BiPO4 nanorod and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102872888B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103111315A (en) * | 2013-03-15 | 2013-05-22 | 南开大学 | Preparation method of bismuth phosphate (BiPO4) photocatalysts differing in structure |
| CN103386317B (en) * | 2013-08-14 | 2015-05-20 | 福州大学 | Bismuth phosphate compound graphene oxide photocatalyst as well as preparation method and application thereof |
| CN103754934B (en) * | 2013-10-11 | 2015-10-07 | 合肥学院 | Ultrasonic liquid phase synthesis BiPO4Method for preparing micro-nano powder |
| CN103586055A (en) * | 2013-11-26 | 2014-02-19 | 中国科学院福建物质结构研究所 | Application of bismuth phosphate compound serving as catalyst for photochemical water splitting hydrogen production |
| CN104150457B (en) * | 2014-07-16 | 2016-04-27 | 河南师范大学 | The biomimetic synthesis method of the controlled prism-shaped bismuth phosphate photocatalyst of size |
| CN104492467A (en) * | 2014-11-27 | 2015-04-08 | 陕西科技大学 | Bismuth phosphate nano crystal cluster as well as preparation method and application thereof |
| CN105498815A (en) * | 2015-12-07 | 2016-04-20 | 扬州天辰精细化工有限公司 | Preparation method of rod-like bismuth phosphate loaded biomass carbon aerogel material |
| CN106215960B (en) * | 2016-07-11 | 2019-06-18 | 华南理工大学 | A kind of efficient composite photo-catalyst Fe-TiO2/BiPO4And preparation method thereof |
| CN107597155B (en) * | 2017-09-27 | 2020-04-28 | 大连民族大学 | One-pot synthesis of visible-light-responsive photocatalyst BiPO4/WO3Preparation method of nanosheet |
| CN110075883A (en) * | 2019-05-30 | 2019-08-02 | 江汉大学 | A kind of BiPO4The preparation method of nano-photocatalyst |
| CN110227520B (en) * | 2019-07-05 | 2022-03-18 | 宿州学院 | Copper-doped bismuth phosphate composite material, preparation method and application thereof |
| CN110227518B (en) * | 2019-07-05 | 2022-03-18 | 宿州学院 | Copper-zinc co-doped bismuth phosphate composite material, preparation method and application thereof |
| CN111185207A (en) * | 2020-01-20 | 2020-05-22 | 西安理工大学 | Ag/BiPO4Preparation method of nano composite photocatalyst |
| CN113231087B (en) * | 2021-05-08 | 2022-07-22 | 江南大学 | Method for preparing hydrogen peroxide by mixed crystal bismuth phosphate-based sacrificial agent-free photocatalysis |
-
2012
- 2012-09-27 CN CN201210369293.1A patent/CN102872888B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 磷酸铋纳米棒的可控合成及其光催化性能;刘艳芳等;《物理化学学报》;20111223;第28卷(第3期);654-660 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102872888A (en) | 2013-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102872888B (en) | BiPO4 nanorod and preparation method and application thereof | |
| Bridson et al. | Synthesis and crystal structure of maricite and sodium iron (III) hydroxyphosphate | |
| Birgisson et al. | Formation mechanisms of nanocrystalline MnO2 polymorphs under hydrothermal conditions | |
| Jensen et al. | Mechanisms for iron oxide formation under hydrothermal conditions: an in situ total scattering study | |
| Ardanova et al. | Isomorphous substitutions of rare earth elements for calcium in synthetic hydroxyapatites | |
| Ding et al. | Oxygen vacancy effect on photoluminescence properties of self-activated yttrium tungstate | |
| Sardar et al. | Nanocrystalline cerium− bismuth oxides: synthesis, structural characterization, and redox properties | |
| CN104108753A (en) | Preparation for visible-light responsible BiVO4 catalyst | |
| CN102380367B (en) | Control synthetic method of high-visible-light-activity mixed crystal type BiVO4 photocatalysts | |
| Lanfredi et al. | K-and Cu-doped CaTiO3-based nanostructured hollow spheres as alternative catalysts to produce fatty acid ethyl esters as potential biodiesel | |
| CN102616849A (en) | Method for directly synthesizing M-phase vanadium dioxide nano particles by liquid phase method | |
| Carta et al. | NiFe2O4 nanoparticles dispersed in an aerogel silica matrix: an X-ray absorption study | |
| CN102173458A (en) | Preparation method of bismuth ferrite nano powder | |
| CN108636398A (en) | A kind of preparation method of vanadium doping strontium titanates nano-photocatalyst material | |
| Li et al. | Synthesis and characterization of yellow pigments (Li0. 4RE0. 6Al0. 6) 1/2MoO4–BiVO4 with high NIR reflectance | |
| CN103058265A (en) | Preparation method of mesoporous nano flake zinc oxide powder with high specific surface area | |
| CN102173459B (en) | Method for preparing yttrium ferrite nanometer powder by using microwaves | |
| CN104475142A (en) | Visible-light-response doped sodium tantalum oxide and preparation method thereof | |
| CN104192890A (en) | Method for preparing carbon-dope zinc oxide nanopillars | |
| Rahman et al. | Toward sustainable energy: photocatalysis of Cr-doped TiO 2: 2. Effect of defect disorder | |
| CN107352521B (en) | A kind of threadiness phosphatization tin compound and preparation method thereof | |
| CN103043722A (en) | Method for transforming vanadium dioxide from B phase to doped M phase | |
| CN101219375A (en) | Process for producing composite photocatalysis material containing rare earth element | |
| CN104591302B (en) | A kind of calcium-titanium ore type nano material and preparation method thereof | |
| Jermolovicius et al. | Greening the green ethylene with microwaves |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150114 Termination date: 20210927 |