CN105540641A - Method for preparing flower-like microspheric magnesium doped zinc oxide material - Google Patents
Method for preparing flower-like microspheric magnesium doped zinc oxide material Download PDFInfo
- Publication number
- CN105540641A CN105540641A CN201610067244.0A CN201610067244A CN105540641A CN 105540641 A CN105540641 A CN 105540641A CN 201610067244 A CN201610067244 A CN 201610067244A CN 105540641 A CN105540641 A CN 105540641A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- zinc oxide
- flower
- gained
- doped zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- 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
- C01P2004/32—Spheres
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The method discloses a method for preparing a flower-like microspheric magnesium doped zinc oxide material, wherein the method uses solvothermal synthesis, and belongs to the technical field of inorganic chemistry and material synthesis. The molar ratio of doped magnesium and zinc is 0.1 percent to 4 percent; the method comprises the steps of mixing zinc acetate, magnesium acetate and nitrilotriacetic acid according to a certain molar ratio; dissolving the mixture into a mixed liquid of ethylene glycol and acetone; placing the mixture into a reaction still for performing solvothermal synthesis reaction; washing a solvothermal product and performing suction filtration; dissolving organic impurities by using a dimethylformamide solution; performing vacuum drying and annealing process to obtain the flower-like microspheric magnesium doped zinc oxide. The method has the advantages of simple process, low cost, high repeatability and environmental friendliness; toxic reagents are not used during the preparation process. The prepared magnesium doped zinc oxide is in a flower-like microspheric structure which is formed by assembling nanorods. The magnesium doped zinc oxide is high in crystallinity, good in dispersity and big in surface area, and has wide application prospects in fields such as photocatalysis, sensors and new energy resources.
Description
Technical field
The invention belongs to technical field of semiconductor material preparation, relate to the preparation of photoelectric material, sensor material, be specifically related to a kind of preparation method of magnesium doped zinc oxide material of flower-like microsphere.
Background technology
Zinc oxide is a kind of multifunctional semiconductor material, because it has the characteristics such as good optics, piezoelectricity, photosensitive, air-sensitive, photochemical catalysis, conductance, make it can be widely used in solar cell, piezoelectric transducer, gas sensor, photodiode, ultraviolet light detector, semiconductor laser etc.In order to improve further it electricity, light, magnetic aspect performance, different impurity elements can be mixed.In zinc oxide, mix magnesium, can energy gap be regulated, realize energy band engineering.In theory by regulating the content of magnesium to realize Zn
1-xmg
xenergy gap continuously adjustabe between 3.37 ~ 7.8eV of O (ZMO).When in ZMO crystal, Mg content is less, magnesium atom enters in ZMO lattice and instead of part zinc atom, and the crystalline structure of ZMO is identical with ZnO, is hexagonal wurtzite structure, but the increase of the molar percentage along with magnesium, crystalline structure can change the cubic structure of MgO into.Research shows that the doping molar percentage of magnesium is when 0 ~ 40% range, the energy gap of ZMO can be made to regulate effectively continuously and crystalline structure (T.Makino identical with ZnO between 3.3eV to 4eV, Y.Segawa, M.Kawasaki, AppliedPhysicsLetters, 1998,78,123).Due to Mg
2+with Zn
2+ionic radius difference little, be respectively
with
replace doping difficulty little, within the scope of certain x can with the lattice match of zinc oxide.The ZMO that this band gap is adjustable can be used as the barrier layer of Zinc oxide based semiconductor quantum well, heterojunction and superstructure, thus realize electricity and optical property can the novel semi-conductor photoelectric device of cutting, may obtain covering the photoelectric device such as semiconductor laser, detector of blue light to ultraviolet spectral region.In sun power Window layer, relative pure zinc oxide, magnesium doping zinc-oxide film can realize band gap broadening, while enhancing is to ultraviolet absorption, the increase of band gap can cause heterojunction boundary potential barrier to increase, and reduces current carrier in heterojunction and then wears probability, reduce reverse saturation current, make open circuit voltage become large, improve the quality of battery heterojunction, improve the spectral response in shortwave district.In addition, the doping of magnesium can make the resistance of zinc oxide material increase, and can reduce vertically moving of light induced electron further, reduces the phenomenon of photoelectric current short circuit, strengthens the external fan-out capability of photoelectric current.The people such as ZiqingDuan are at Cu
2o-Mg
xzn
1-xin the research of O heterojunction solar battery, pure zinc oxide is replaced to do Window layer with magnesium doping zinc-oxide, find that the electricity conversion of solar cell is improved (Z.Duan, A.DuPasquier, Y.Lu, Y.XuandE.Garfunkel, SolarEnergyMaterialsandSolarCells, 2012,96,292.).In addition, its characteristics of luminescence can be changed by magnesium-doped, at short wavelength's nano luminescent device and nano photoelectronic devices field, there is application prospect and scientific research value.
The Measures compare preparing magnesium doping zinc-oxide is at present many.Systematic study ZMO alloy is Japanese A.Ohtomo research group the earliest.Their ZMO alloy firm (A.Ohtomo, M.Kawasaki, T.Koida, etal., Appl.Phys.Lett., 1998,72 (19): 2466.) that utilized pulsed laser deposition to prepare.The people such as W.I.Park are with metal organic chemical vapor deposition (MOCVD) legal system standby ZMO film (W.I.Park, G.C.Yi, H.M.Jang, Appl.Phys.Lett., 2001,79:2022.), the molecular beam epitaxy such as T.Takagi has prepared ZMO film (T.Takagi, T.Tanaka, H.Fujita, etal., J.Appl.Phys., 2003,42:401.).Y.W.Heo report uses MBE technology to prepare ZMO nanometer rod (Y.W.Heo, M.Kaufman, K.Pruessner, etal., Solid-StateElecortnics, 2003,47:2263.).The high pressure pulse laser deposition such as M.Loernz has prepared ZMO nano-wire array (M.Loernz, E.M.Kaidashev, A.Rahm, etal., Appl.Phys.Lett., 2005,86:143113.).The people such as WonIPark are with gas phase epitaxy of metal organic compound legal system standby ZMO rod (WonIPark, SungJinAn, JiaLong, etal., J.Phys.Chem.B., 2004.108:15457-15460.).Zhejiang University Zhi Mingjia etc. have prepared the ZMO nano wire of different-shape with thermal evaporation.These research methods need expensive plant and instrument and harsher experiment condition mostly.
And solvent-thermal method has simple to operate, cost is low, and the product purity of preparation is high, grain development is complete, is evenly distributed, and particle agglomeration is less, the advantage such as chemical constitution and morphology controllable.One of solvent-thermal process Research Characteristics is that research system is generally in imperfect nonequilibrium situations, avoids the interference of water, be conducive to the homogeneous reaction under non-aqueous conditions during reaction.Organic complex is adopted to prepare the research report of magnesium doped zinc oxide nano structure under having no solvent thermal reaction condition at present.The invention provides a kind of hot legal system of simple solvent that adopts for the method for the magnesium doping zinc-oxide of flower-like microsphere structure.
Summary of the invention
The object of the present invention is to provide that a kind of technique is simple, cost is low, repeatability is high, and the preparation method of the magnesium doped zinc oxide material of composition environmental protection and morphology controllable, using zinc acetate, magnesium acetate as Zn
2+source, Mg
2+source, with nitrilotriacetic acid(NTA) by certain mixed in molar ratio, is dissolved in the mixed liquid be made up of ethylene glycol and acetone, then is placed in reactor solvent-thermal process magnesium zinc-organic chelate.After reaction terminates, be cooled to room temperature, then use ethanol and washing with acetone, suction filtration obtains organic chelate pressed powder, then uses other organic impurities in dimethyl formamide dissolved powders, to improve product purity grade.Then vacuum-drying, removes volatile acetone and moisture, finally by anneal, inner complex is degraded and generates metal oxide.
The technical scheme that the present invention realizes above-mentioned purpose is specially:
A preparation method for the magnesium doped zinc oxide material of flower-like microsphere, comprises the steps:
(1) in ethylene glycol, add acetone, mix, form mixed solvent;
(2) in mixed solvent, add zinc acetate, stir and make it fully dissolve;
(3) add magnesium acetate again, stir and make it fully dissolve;
(4) add nitrilotriacetic acid(NTA) again, stir, obtain reaction soln;
(5) step (4) gained reaction soln is placed in reactor, naturally cools to room temperature 180 ~ 200 DEG C of isothermal reactions after 6 ~ 12 hours, obtain solvent thermal product;
(6) the solvent thermal product dehydrated alcohol of step (5) gained, acetone and deionized water are washed 2 ~ 5 times respectively, suction filtration obtains solid;
(7) by the solid product of step (6) gained in 200ml dimethyl formamide 40 ~ 60 DEG C stir suction filtration after 0.5 ~ 2 hour, vacuum-drying 12 ~ 48 hours at then placing it in 50 ~ 80 DEG C;
(8) by step (7) dried solid 400 ~ 550 DEG C of cycle annealings 1 ~ 2 hour in atmosphere, then naturally cool to room temperature, obtain final product.
Further, the concentration of zinc acetate in reaction soln is 0.05 ~ 0.1mol/L, and the concentration of nitrilotriacetic acid(NTA) in reaction soln is 0.067 ~ 0.133mol/L, and the mol ratio of magnesium acetate and zinc acetate is 0.1% ~ 4%, and the volume ratio of ethylene glycol and acetone is 10:1.
Further, the volume of described reaction soln accounts for 60 ~ 80% of reactor volume.
In a preference of the present invention, described zinc acetate concentration is 0.067mol/L, the mol ratio of magnesium acetate and zinc acetate is 4%, nitrilotriacetic acid(NTA) concentration is 0.1mol/L, solvent thermal reaction temperature is 200 DEG C, 12 hours reaction times, and solvent thermal product dehydrated alcohol, acetone and deionized water wash 3 times respectively, the solid product that suction filtration obtains in 200ml dimethyl formamide 40 DEG C stir suction filtration after 1 hour, vacuum-drying 24 hours at then placing it in 60 DEG C; Finally carry out anneal, annealing temperature is 500 DEG C, annealing time 1 hour.
The reagent that the present invention participates in reacting is analytical pure, commercially available.
For the structure of the standby material of institute system, pattern, composition and optical property, X-ray diffraction analysis (XRD), scanning electron microscope analysis (SEM) have been carried out to prepared sample, energy dispersion X-ray spectroscopic analysis (EDS), X-ray photoelectron spectroscopic analysis (XPS), UV-Vis spectra (UV-Vis) is analyzed.The magnesium doped zinc oxide material be prepared from according to method disclosed by the invention, from the magnesium doping zinc-oxide to the known product of its XRD figure spectrum analysis being wurtzite, good crystallinity.Its low power and high power SEM display, the magnesium doping zinc-oxide flower-like microsphere diameter 2 ~ 10 μm of preparation, the nanometer rod being 200nm ~ 900nm by radius assembles.UV-Vis absorption spectrum show sample has obvious energy of absorption edge at 388nm place, pure zinc oxide energy of absorption edge of comparing blue shift.The energy gap of zinc oxide is added after confirming magnesium doping.
Beneficial effect of the present invention is:
(1) the magnesium doping zinc-oxide prepared by the present invention presents a kind of special flower-like microsphere structure assembled by nanometer rod, degree of crystallinity is high, good dispersity, has large surface-area, is with a wide range of applications in fields such as photochemical catalysis, sensor and new forms of energy.
(2) method technique of the present invention is simple, and cost is low, and repeatability is high, does not use toxic reagent in preparation process, environmentally friendly.
(3) method of the present invention only needs anneal in air, avoids the use of shielding gas, is conducive to saving cost.
Accompanying drawing explanation
The X-ray diffractogram of the magnesium doping zinc-oxide that Fig. 1 embodiment 1 is obtained.
The low power scanning electron microscope (SEM) photograph of the magnesium doping zinc-oxide that Fig. 2 embodiment 1 is obtained.
The high power scanning electron microscope (SEM) photograph of the magnesium doping zinc-oxide that Fig. 3 embodiment 1 is obtained.
The energy spectrogram of the magnesium doping zinc-oxide that Fig. 4 embodiment 1 is obtained.
The Zn2pX X-ray photoelectron spectroscopy X areal map of the magnesium doping zinc-oxide that Fig. 5 embodiment 1 is obtained.
The Mg2sX X-ray photoelectron spectroscopy X areal map of the magnesium doping zinc-oxide that Fig. 6 embodiment 1 is obtained.
The O1sX X-ray photoelectron spectroscopy X areal map of the magnesium doping zinc-oxide that Fig. 7 embodiment 1 is obtained.
The uv-visible absorption spectroscopy figure of the magnesium doping zinc-oxide that Fig. 8 embodiment 1 is obtained.
Embodiment
For a better understanding of the present invention, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
The hydrothermal method preparation process of magnesium doped zinc oxide material is as follows:
(1) in 60ml ethylene glycol, add 6ml acetone, mix, form mixed solvent;
(2) in mixed solvent, add zinc acetate, make acetic acid zinc concentration be 0.067mol/L, stir and make it fully dissolve;
(3) add magnesium acetate again, make the concentration of magnesium acetate be 0.00268mol/L, stir and make it fully dissolve;
(4) add nitrilotriacetic acid(NTA) again, the concentration making nitrilotriacetic acid(NTA) is 0.1mol/L, stirs, obtains reaction soln;
(5) get appropriate step (4) gained reaction soln and be placed in reactor, make the volume of reaction soln account for 60% of reactor volume, naturally cool to room temperature 200 DEG C of isothermal reactions after 12 hours, obtain solvent thermal product;
(6) the solvent thermal product dehydrated alcohol of step (5) gained, acetone and deionized water are washed 3 times respectively, suction filtration obtains solid;
(7) by the solid product of step (6) gained in 200ml dimethyl formamide 40 DEG C stir suction filtration after 1 hour, the solid product obtained vacuum-drying 24 hours at 60 DEG C;
(8) by the solid product of step (7) gained 500 DEG C of cycle annealings 1 hour in atmosphere, then naturally cool to room temperature, obtain final product.
The XRD figure spectrum of the magnesium doping zinc-oxide of the present embodiment gained is shown in Fig. 1, and low power scanning electron microscope (SEM) photograph is shown in Fig. 2, and high power scanning electron microscope (SEM) photograph is shown in Fig. 3; Fig. 4 can be seen by spectrogram; Fig. 5 to 7 is shown in by XPS collection of illustrative plates, and uv-visible absorption spectroscopy figure is shown in Fig. 8.
The XRD figure spectrum that embodiment 1 prepares sample is listed in Fig. 1.(100), (002), (101) in corresponding zinc oxide wurtzite structure standard card (JCPDSCard:36-1451) in position of each characteristic diffraction peak of sample, (102), (110) and the crystal plane direction such as (103), (112).
The low power scanning electron microscope (SEM) photograph of Fig. 2 can find out that the product that reaction generates is micro-sphere structure, its diameter 2 ~ 10 μm.
It is that 200nm ~ 900nm nanometer rod assembles by radius that the high power scanning electron microscope (SEM) photograph of Fig. 3 shows the flower-like microsphere generated.
In the product of the power spectrum graphs open-birth one-tenth of Fig. 4, the percentage composition of zinc, magnesium, oxygen is respectively 46.04%, 1.85%, 52.11%.
Fig. 5,6,7 shows Zn2p respectively, the x-ray photoelectron power spectrum region collection of illustrative plates of Mg2s, O1s, and the element further illustrating sample is formed.As can be seen from the figure, Zn2p track is at 1020.42eV (2p
3/2) and 1042.33eV (2p
1/2) two place's characteristic peaks, this and Zn
2+in conjunction with energy characteristic peak positions coincide; In conjunction with the characteristic peak corresponding Mg2s track spectrogram that can be positioned at 87.83eV place, with Mg
2+in conjunction with energy characteristic peak positions coincide; In conjunction with the characteristic peak corresponding O1s track spectrogram that can be positioned at 530.47eV place, with O
2-in conjunction with energy characteristic peak positions coincide.Therefore, in the target product synthesized in this experiment, the valence state of zinc, magnesium, oxygen element is respectively+1 ,+2 ,-2.Also demonstrate magnesium to be doped in zinc oxide lattice simultaneously.
Fig. 8 is the optical absorption figure that embodiment 1 prepares the pure zinc oxide of sample and preparation, and wave spectrum wavelength region is from 200nm to 800nm.Can find that from figure embodiment 1 is prepared sample and had obvious energy of absorption edge at 388nm, have obvious blue shift compared with the energy of absorption edge 402nm place of pure zinc oxide sample.Further demonstrate that magnesium is doped in zinc oxide, add its energy gap.
Embodiment 2
The hydrothermal method preparation process of magnesium doped zinc oxide material is as follows:
(1) in 60ml ethylene glycol, add 6ml acetone, mix, form mixed solvent;
(2) in mixed solvent, add zinc acetate, make acetic acid zinc concentration be 0.083mol/L, stir and make it fully dissolve;
(3) add magnesium acetate again, make the concentration of magnesium acetate be 0.00166mol/L, stir and make it fully dissolve;
(4) add nitrilotriacetic acid(NTA) again, the concentration making nitrilotriacetic acid(NTA) is 0.1mol/L, stirs, obtains reaction soln;
(5) get appropriate step (4) gained reaction soln and be placed in reactor, make the volume of reaction soln account for 80% of reactor volume, naturally cool to room temperature 200 DEG C of isothermal reactions after 6 hours, obtain solvent thermal product;
(6) the solvent thermal product dehydrated alcohol of step (5) gained, acetone and deionized water are washed 3 times respectively, suction filtration obtains solid;
(7) by the solid product of step (6) gained in 200ml dimethyl formamide 40 DEG C stir 1 hour, suction filtration, the solid product obtained vacuum-drying 24 hours at 60 DEG C;
(8) by the solid product of step (7) gained 500 DEG C of cycle annealings 1 hour in atmosphere, then naturally cool to room temperature, obtain final product.
Embodiment 3
The hydrothermal method preparation process of magnesium doped zinc oxide material is as follows:
(1) in 60ml ethylene glycol, add 6ml acetone, mix, form mixed solvent;
(2) in mixed solvent, add zinc acetate, make acetic acid zinc concentration be 0.05mol/L, stir and make it fully dissolve;
(3) add magnesium acetate again, make the concentration of magnesium acetate be 0.001mol/L, stir and make it fully dissolve;
(4) add nitrilotriacetic acid(NTA) again, the concentration making nitrilotriacetic acid(NTA) is 0.133mol/L, stirs, obtains reaction soln;
(5) get appropriate step (4) gained reaction soln and be placed in reactor, make the volume of reaction soln account for 80% of reactor volume, naturally cool to room temperature 180 DEG C of isothermal reactions after 12 hours, obtain solvent thermal product;
(6) the solvent thermal product dehydrated alcohol of step (5) gained, acetone and deionized water are washed 3 times respectively, suction filtration obtains solid;
(7) by the solid product of step (6) gained in 200ml dimethyl formamide 40 DEG C stir 1 hour, suction filtration, the solid product obtained vacuum-drying 24 hours at 80 DEG C;
(8) by the solid product of step (7) gained 550 DEG C of cycle annealings 1 hour in atmosphere, then naturally cool to room temperature, obtain final product.
Embodiment 4
The hydrothermal method preparation process of magnesium doped zinc oxide material is as follows:
(1) in 60ml ethylene glycol, add 6ml acetone, mix;
(2) in mixed solvent, add zinc acetate, make acetic acid zinc concentration be 0.1mol/L, stir and make it fully dissolve;
(3) add magnesium acetate again, make the concentration of magnesium acetate be 0.004mol/L, stir and make it fully dissolve;
(4) add nitrilotriacetic acid(NTA) again, the concentration making nitrilotriacetic acid(NTA) is 0.133mol/L, stirs, obtains reaction soln;
(5) get appropriate step (4) gained reaction soln and be placed in reactor, make the volume of reaction soln account for 60% of reactor volume, naturally cool to room temperature 200 DEG C of isothermal reactions after 12 hours, obtain solvent thermal product;
(6) the solvent thermal product dehydrated alcohol of step (5) gained, acetone and deionized water are washed 3 times respectively, suction filtration obtains solid;
(7) by the solid product of step (6) gained in 200ml dimethyl formamide 40 DEG C stir 1 hour, suction filtration, the solid product obtained vacuum-drying 24 hours at 80 DEG C;
(8) by the solid product of step (7) gained 550 DEG C of cycle annealings 1 hour in atmosphere, then naturally cool to room temperature, obtain final product.
Embodiment 5
The hydrothermal method preparation process of magnesium doped zinc oxide material is as follows:
(1) in 60ml ethylene glycol, add 6ml acetone, mix, form mixed solvent;
(2) in mixed solvent, add zinc acetate, make acetic acid zinc concentration be 0.067mol/L, stir and make it fully dissolve;
(3) add magnesium acetate again, make the concentration of magnesium acetate be 0.00201mol/L, stir and make it fully dissolve;
(4) add nitrilotriacetic acid(NTA) again, the concentration making nitrilotriacetic acid(NTA) is 0.1mol/L, stirs, obtains reaction soln;
(5) get appropriate step (4) gained reaction soln and be placed in reactor, make the volume of reaction soln account for 60% of reactor volume, naturally cool to room temperature 200 DEG C of isothermal reactions after 12 hours, obtain solvent thermal product;
(6) the solvent thermal product dehydrated alcohol of step (5) gained, acetone and deionized water are washed 3 times respectively, suction filtration obtains solid;
(7) by the solid product of step (6) gained in 200ml dimethyl formamide 40 DEG C stir 1 hour, suction filtration, the solid product obtained vacuum-drying 24 hours at 60 DEG C;
(8) by the solid product of step (7) gained 450 DEG C of cycle annealings 2 hours in atmosphere, then naturally cool to room temperature, obtain final product.
Embodiment 6
The hydrothermal method preparation process of magnesium doped zinc oxide material is as follows:
(1) in 60ml ethylene glycol, add 6ml acetone, mix, form mixed solvent;
(2) in mixed solvent, add zinc acetate, make acetic acid zinc concentration be 0.067mol/L, stir and make it fully dissolve;
(3) add magnesium acetate again, make the concentration of magnesium acetate be 0.00201mol/L, stir and make it fully dissolve;
(4) add nitrilotriacetic acid(NTA) again, the concentration making nitrilotriacetic acid(NTA) is 0.067mol/L, stirs, obtains reaction soln;
(5) get appropriate step (4) gained reaction soln and be placed in reactor, make the volume of reaction soln account for 60% of reactor volume, naturally cool to room temperature 200 DEG C of isothermal reactions after 6 hours, obtain solvent thermal product;
(6) the solvent thermal product dehydrated alcohol of step (5) gained, acetone and deionized water are washed 3 times respectively, suction filtration obtains solid;
(7) by the solid product of step (6) gained in 200ml dimethyl formamide 40 DEG C stir 1 hour, suction filtration, the solid product obtained vacuum-drying 24 hours at 60 DEG C;
(8) by the solid product of step (7) gained 550 DEG C of cycle annealings 1 hour in atmosphere, then naturally cool to room temperature, obtain final product.
Embodiment 7
The hydrothermal method preparation process of magnesium doped zinc oxide material is as follows:
(1) in 60ml ethylene glycol, add 6ml acetone, mix, form mixed solvent;
(2) in mixed solvent, add zinc acetate, make acetic acid zinc concentration be 0.05mol/L, stir and make it fully dissolve;
(3) add magnesium acetate again, make the concentration of magnesium acetate be 0.00005mol/L, stir and make it fully dissolve;
(4) add nitrilotriacetic acid(NTA) again, the concentration making nitrilotriacetic acid(NTA) is 0.067mol/L, stirs, obtains reaction soln;
(5) get appropriate step (4) gained reaction soln and be placed in reactor, make the volume of reaction soln account for 60% of reactor volume, naturally cool to room temperature 200 DEG C of isothermal reactions after 6 hours, obtain solvent thermal product;
(6) the solvent thermal product dehydrated alcohol of step (5) gained, acetone and deionized water are washed 3 times respectively, suction filtration obtains solid;
(7) by the solid product of step (6) gained in 200ml dimethyl formamide 40 DEG C stir 1 hour, suction filtration, the solid product obtained vacuum-drying 24 hours at 80 DEG C;
(8) by the solid product of step (7) gained 400 DEG C of cycle annealings 2 hours in atmosphere, then naturally cool to room temperature, obtain final product.
Embodiment 8
The hydrothermal method preparation process of magnesium doped zinc oxide material is as follows:
(1) in 60ml ethylene glycol, add 6ml acetone, mix, form mixed solvent;
(2) in mixed solvent, add zinc acetate, make acetic acid zinc concentration be 0.05mol/L, stir and make it fully dissolve;
(3) add magnesium acetate again, make the concentration of magnesium acetate be 0.0005mol/L, stir and make it fully dissolve;
(4) add nitrilotriacetic acid(NTA) again, the concentration making nitrilotriacetic acid(NTA) is 0.1mol/L, stirs, obtains reaction soln;
(5) get appropriate step (4) gained reaction soln and be placed in reactor, make the volume of reaction soln account for 60% of reactor volume, naturally cool to room temperature 190 DEG C of isothermal reactions after 12 hours, obtain solvent thermal product;
(6) the solvent thermal product dehydrated alcohol of step (5) gained, acetone and deionized water are washed 3 times respectively, suction filtration obtains solid;
(7) by the solid product of step (6) gained in 200ml dimethyl formamide 40 DEG C stir 1 hour, suction filtration, the solid product obtained vacuum-drying 24 hours at 80 DEG C;
(8) by the solid product of step (7) gained 500 DEG C of cycle annealings 2 hours in atmosphere, then naturally cool to room temperature, obtain final product.
Claims (4)
1. a preparation method for the magnesium doped zinc oxide material of flower-like microsphere, is characterized in that, comprise the steps:
(1) in ethylene glycol, add acetone, mix, form mixed solvent;
(2) in mixed solvent, add zinc acetate, stir and make it fully dissolve;
(3) add magnesium acetate again, stir and make it fully dissolve;
(4) add nitrilotriacetic acid(NTA) again, stir, obtain reaction soln;
(5) step (4) gained reaction soln is placed in reactor, naturally cools to room temperature 180 ~ 200 DEG C of isothermal reactions after 6 ~ 12 hours, obtain solvent thermal product;
(6) the solvent thermal product dehydrated alcohol of step (5) gained, acetone and deionized water are washed 2 ~ 5 times respectively, suction filtration obtains solid;
(7) by the solid product of step (6) gained in 200ml dimethyl formamide 40 ~ 60 DEG C stir suction filtration after 0.5 ~ 2 hour, vacuum-drying 12 ~ 48 hours at then placing it in 50 ~ 80 DEG C;
(8) by the solid product of step (7) gained 400 ~ 550 DEG C of cycle annealings 1 ~ 2 hour in atmosphere, then naturally cool to room temperature, obtain final product.
2. the preparation method of the magnesium doped zinc oxide material of flower-like microsphere according to claim 1, is characterized in that, in step (1), the volume ratio of ethylene glycol and acetone is 10:1.
3. the preparation method of the magnesium doped zinc oxide material of flower-like microsphere according to claim 1, it is characterized in that, the concentration of zinc acetate in reaction soln is 0.05 ~ 0.1mol/L, the concentration of nitrilotriacetic acid(NTA) in reaction soln is 0.067 ~ 0.133mol/L, and the mol ratio of magnesium acetate and zinc acetate is 0.1% ~ 4%.
4. the preparation method of the magnesium doped zinc oxide material of flower-like microsphere according to claim 1, is characterized in that, the volume of reaction soln accounts for 60 ~ 80% of reactor volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610067244.0A CN105540641B (en) | 2016-01-30 | 2016-01-30 | A kind of preparation method of the mg-doped zinc oxide material of flower-like microsphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610067244.0A CN105540641B (en) | 2016-01-30 | 2016-01-30 | A kind of preparation method of the mg-doped zinc oxide material of flower-like microsphere |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105540641A true CN105540641A (en) | 2016-05-04 |
| CN105540641B CN105540641B (en) | 2017-08-15 |
Family
ID=55820276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610067244.0A Expired - Fee Related CN105540641B (en) | 2016-01-30 | 2016-01-30 | A kind of preparation method of the mg-doped zinc oxide material of flower-like microsphere |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105540641B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106564928A (en) * | 2016-10-20 | 2017-04-19 | 上海电机学院 | CBD production method of Mg-doped ZnO nanorods |
| CN108295860A (en) * | 2018-02-08 | 2018-07-20 | 陕西科技大学 | A kind of preparation method and applications of stainless (steel) wire load bismuth oxide nanometer sheet |
| CN108479747A (en) * | 2018-04-16 | 2018-09-04 | 陕西科技大学 | The method that solvent-thermal method prepares stainless (steel) wire load bismuth oxide nanosheet photocatalyst |
| CN108906025A (en) * | 2018-08-01 | 2018-11-30 | 安徽锦华氧化锌有限公司 | A kind of preparation method of rare earth doped modified nano zinc oxide-graphene composite photocatalyst material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249284A (en) * | 2011-05-13 | 2011-11-23 | 陕西师范大学 | Preparation method for micrometer barium-doped zinc oxide |
| CN104495928A (en) * | 2015-01-09 | 2015-04-08 | 中国科学院上海硅酸盐研究所 | Preparation method of vanadium dioxide/zinc oxide nano composite powder |
| CN104907036A (en) * | 2015-05-15 | 2015-09-16 | 燕山大学 | Graded dandelion-flower-shaped ZnO-Al2O3 compound and preparation method therefor |
-
2016
- 2016-01-30 CN CN201610067244.0A patent/CN105540641B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249284A (en) * | 2011-05-13 | 2011-11-23 | 陕西师范大学 | Preparation method for micrometer barium-doped zinc oxide |
| CN104495928A (en) * | 2015-01-09 | 2015-04-08 | 中国科学院上海硅酸盐研究所 | Preparation method of vanadium dioxide/zinc oxide nano composite powder |
| CN104907036A (en) * | 2015-05-15 | 2015-09-16 | 燕山大学 | Graded dandelion-flower-shaped ZnO-Al2O3 compound and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| NADIA ABDEL AAL ET AL.: ""Novel synthesis, optical, and photoluminescence properties of MgxZn1-xO nanoflowers"", 《J SOL-GEL SCI TECHNOL》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106564928A (en) * | 2016-10-20 | 2017-04-19 | 上海电机学院 | CBD production method of Mg-doped ZnO nanorods |
| CN108295860A (en) * | 2018-02-08 | 2018-07-20 | 陕西科技大学 | A kind of preparation method and applications of stainless (steel) wire load bismuth oxide nanometer sheet |
| CN108479747A (en) * | 2018-04-16 | 2018-09-04 | 陕西科技大学 | The method that solvent-thermal method prepares stainless (steel) wire load bismuth oxide nanosheet photocatalyst |
| CN108906025A (en) * | 2018-08-01 | 2018-11-30 | 安徽锦华氧化锌有限公司 | A kind of preparation method of rare earth doped modified nano zinc oxide-graphene composite photocatalyst material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105540641B (en) | 2017-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lv et al. | Generalized colloidal synthesis of high-quality, two-dimensional cesium lead halide perovskite nanosheets and their applications in photodetectors | |
| Bhaumik et al. | Copper oxide based nanostructures for improved solar cell efficiency | |
| Mazhdi et al. | The effects of gadolinium doping on the structural, morphological, optical, and photoluminescence properties of zinc oxide nanoparticles prepared by co-precipitation method | |
| Kumar et al. | Efficient UV photodetectors based on Ni-doped ZnS nanoparticles prepared by facial chemical reduction method | |
| Shi et al. | Thickness tunable Cu 2 ZnSnSe 4 nanosheets | |
| Chand et al. | Effect of Cr and Fe doping on the structural and optical properties of ZnO nanostructures | |
| Kaur et al. | Structural, morphological and optical properties of Eu-N co-doped zinc oxide nanoparticles synthesized using co-precipitation technique | |
| Jin et al. | Solution synthesis of pure 2H CuFeO 2 at low temperatures | |
| CN105540641A (en) | Method for preparing flower-like microspheric magnesium doped zinc oxide material | |
| Hajimazdarani et al. | Enhanced optical properties and photodetection behavior of ZnS thin film deposited by electron beam evaporation upon doping with europium oxide | |
| JP2018140934A (en) | Sodium- or antimony-doped nanoparticles | |
| KR20120100568A (en) | Copper indium selenide nanoparticles and preparing method of the same | |
| Colak et al. | Tm-doped ZnO nanorods as a TCO for PV applications | |
| Kumar et al. | Thermo-optical correlation for room temperature synthesis: cold-sintered lead halides | |
| Zhu et al. | Synthesis of water-soluble antimony sulfide quantum dots and their photoelectric properties | |
| Thakur et al. | Recent advances in BaZrS3 perovskites: synthesis, properties, and future trends | |
| Dekhil et al. | Investigation on microstructural and optical properties of CuSbS 2 nanoparticles synthesized by hydrothermal technique | |
| Vallejo et al. | Synthesis and characterization of nanoparticles of CZTSe by microwave-assited chemical synthesis | |
| Senthil et al. | Improved performance of ZnO thin film solar cells by doping magnesium ions | |
| Vahidshad et al. | Synthesis and characterization of copper indium sulfide chalcopyrite structure with hot injection method | |
| Al-Agel et al. | Solution processed ZnO rectangular prism as an effective photoanode material for dye sensitized solar cells | |
| Saini et al. | ZnO-CdS powder nanocomposite: synthesis, structural and optical characterization | |
| Echresh et al. | High photocurrent gain in NiO thin film/M-doped ZnO nanorods (M= Ag, Cd and Ni) heterojunction based ultraviolet photodiodes | |
| Shim et al. | Hydrothermal synthesis of CuInSe2 nanoparticles in acetic acid | |
| Singh et al. | Unmediated one-step synthesis of novel ZnSO for photovoltaic and electronic applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170815 Termination date: 20200130 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |