CN105502421A - Preparation method of zinc silicate hollow micron ball - Google Patents
Preparation method of zinc silicate hollow micron ball Download PDFInfo
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- CN105502421A CN105502421A CN201610015525.1A CN201610015525A CN105502421A CN 105502421 A CN105502421 A CN 105502421A CN 201610015525 A CN201610015525 A CN 201610015525A CN 105502421 A CN105502421 A CN 105502421A
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- Prior art keywords
- zinc
- zinc silicate
- preparation
- ball
- micron ball
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- 239000004110 Zinc silicate Substances 0.000 title claims abstract description 59
- 235000019352 zinc silicate Nutrition 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 title claims abstract 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004246 zinc acetate Substances 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract 2
- 239000004005 microsphere Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims 1
- 229910052984 zinc sulfide Inorganic materials 0.000 abstract description 32
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 abstract description 23
- 239000005083 Zinc sulfide Substances 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- ZOIVSVWBENBHNT-UHFFFAOYSA-N dizinc;silicate Chemical compound [Zn+2].[Zn+2].[O-][Si]([O-])([O-])[O-] ZOIVSVWBENBHNT-UHFFFAOYSA-N 0.000 description 44
- 239000000843 powder Substances 0.000 description 15
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- DHYOSSNHCWAKKV-UHFFFAOYSA-N [Si+4].[S-2].[Zn+2].[S-2].[S-2] Chemical compound [Si+4].[S-2].[Zn+2].[S-2].[S-2] DHYOSSNHCWAKKV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- ZHTHGKBAFPDEHL-UHFFFAOYSA-N silicic acid zinc Chemical compound [Zn].[Si](O)(O)(O)O ZHTHGKBAFPDEHL-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052844 willemite Inorganic materials 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical group [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000005049 combustion synthesis Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a preparation method of a zinc silicate hollow micron ball. The method includes the steps that firstly, a thiourea solution is added to a zinc acetate solution and mixed to be uniform, a hydrothermal reaction is conducted for 6-30 hours at the temperature of 100-220 DEG C, and a monodisperse zinc sulfide micron ball is obtained; the monodisperse zinc sulfide micron ball is dried, ethyl alcohol, ammonium hydroxide and ethyl orthosilicate are sequentially added while stirring is conducted, after stirring is ended, a monodisperse zinc sulfide@ silicon dioxide silicon core-shell structural ball is prepared, after drying is conducted, calcinations is conducted for 18-48 hours at the temperature of 800-1000 DEG C, and the zinc silicate hollow micron ball is obtained. According to the preparation method, the zinc silicate micron ball is prepared through a simple hydrothermal method, then the zinc silicate micron ball is coated with silicon dioxide, the zinc sulfide@ silicon dioxide silicon core-shell structural ball is obtained, finally calcination is conducted, and the zinc silicate hollow micron ball is obtained; the preparation method is novel, no surface active agent is needed in the reaction process, the purity of obtained particles is high, the size is controllable and uniform, and dispersity is good.
Description
Technical field
The present invention relates to zinc silicate, particularly relate to a kind of preparation method of zinc silicate hollow sub-microsphere; Belong to inorganic nanometer powder technical field of material.
Background technology
Inorganic fluorescent powder is a kind of important and luminescent material of cheapness, and thus its luminescent properties is studied widely at indicating meter and light-emitting device field.Zno-based ternary compound is a class multifunctional material, and chemical general formula is ZnM
2o
4or Zn
2mO
4, M is Al, Si, Ga, Fe, In, Sn, Sb, Ti, Mn, V, Cr etc.These compounds main are broadband semiconductor and typical phosphorescent light-emitting materials, and show the unexistent specific function of other common ternary compounds.
The molecular formula of zinc silicate is Zn
2siO
4, its band-gap energy is 5.5eV.Silicate aboundresources, with low cost, there is the good physical and chemical performance such as stronger environmental compatibility, more stable chemical property, stronger moisture resistance, be the emphasis that people study for a long time always.At present, silicate is widely used in every field, as material of construction and glass works etc. such as fluorescent material, mesopore molecular sieve, support of the catalyst, gas storage, gas delivery, medicament slow release, cement, concrete.
The property use of solid material is directly related with the spatial arrangement of composition material atom and the pattern of material etc., adopts simple, green, economic method controlledly synthesis functional silicate nano material in dimension and degree of crystallinity to be significant for its new using value of exploitation.Based on the constructional feature of silicate, oneself has synthesized many functional silicate materials at present, as there is high heat resistance, high strength, flame retardant resistance, high-wearing feature, the polymkeric substance of low-expansion superperformance and layered silicate organo-mineral complexing nano material, silicates mesoporous material etc.Wherein silicate (micro-) nano-hollow ball has the ability that the features such as aperture is adjustable, specific surface area large, hypotoxicity can improve its removal precious metal (as plumbous in divalence, bivalent chromium, ferric ion) due to it; Simultaneously because hollow structure specific surface area is large, its contact area with organic pollutant can be increased, thus raising catalytic performance; The zinc silicate micron ball of hollow structure can also as nano-reactor; In biosensor, hollow structure fully can contact with gas molecule to be measured relative to powder structure, thus improves its response sensitivity etc.; Zinc silicate hollow structure is also widely used in fields such as lithium ion battery, useful for drug delivery, fluorescent materials.
At present about the main preparation methods conventional solid synthesis method, combustion synthesis method, sol-gel method, microwave method, spray pyrolysis, chemical precipitation method, hydrothermal synthesis method etc. of zinc silicate.The various character of nano material and the size, size distribution, pattern, composition etc. of nanocrystal closely related.As can be seen here, by simple, green, economic method, regulation and control preparation is carried out to the zinc silicate nanometer material with ad hoc structure, pattern and size, have very important significance in materials synthesis chemical field and production application.
Summary of the invention
The object of the invention is to the defect overcoming the existence of existing technology of preparing, provide a kind of simple to operate, consume energy low, without the need to tensio-active agent, product postprocessing simple zinc silicate hollow sub-microsphere preparation method.
The present invention utilizes water (solvent) hot method preparing the advantage in novel material, on the basis of the ZnS micron ball of water heat transfer, coupled ion exchange process and Kinkendal Effect, easy calcination method is utilized to synthesize zinc silicate hollow sub-microsphere, gained hollow ball size uniform, its pattern and size control by reaction conditions.Up to now, yet there are no report with ion exchange method synthetic silicic acid zinc hollow sub-microsphere.
Object of the present invention is achieved through the following technical solutions:
A kind of preparation method of zinc silicate hollow sub-microsphere, it is characterized in that: joined by thiourea solution in zinc acetate solution, molar concentration rate is 3:1 ~ 1:2, is stirred to and mixes, be 100 ~ 220 DEG C of Water Under thermal response 6 ~ 30h in temperature, prepare monodisperse ZnS micron ball; Weigh the zinc sulfide powder of 0.02 ~ 0.1g after dry, under agitation add 10 ~ 40ml ethanol, the ammoniacal liquor of 1 ~ 5ml25%, 1 ~ 5ml tetraethoxy successively, after stirring 4 ~ 10h, prepare monodisperse ZnS silicon dixoide nucleocapsid structure ball; Weigh 0.01 ~ 0.1g zinc sulphide SiO 2 powder after dry and be placed in ceramic crucible, in the retort furnace of 800 ~ 1000 DEG C, calcine 18 ~ 48h, zinc silicate hollow sub-microsphere can be obtained;
For realizing object of the present invention further, the volumetric molar concentration choosing of described thiourea solution and zinc acetate solution is than being 2:1 ~ 1:1.
Described hydro-thermal reaction is carried out in teflon-lined autoclave.
Described hydrothermal temperature is preferably 180 ~ 220 DEG C, and the time of hydro-thermal reaction is preferably 8 ~ 20h.
Described coated silica be under agitation add ethanol, 25% ammoniacal liquor, tetraethoxy, its volume be respectively preferably 15 ~ 40ml, 2 ~ 4ml and 2 ~ 4ml.
The churning time of described coated silica is preferably 5 ~ 10h.
Described calcining temperature is preferably 850 ~ 1000 DEG C, and calcination time is preferably 18-48h.
Relative to prior art, tool of the present invention has the following advantages and beneficial effect:
(1) the present invention adopts hydrothermal method to prepare Zinc sulphide micron ball, simple to operate, and consume energy low, without the need to tensio-active agent, product postprocessing is simple.
(2) the present invention is on the basis of the ZnS micron ball of water heat transfer, coupled ion exchange process and Kinkendal Effect, utilizes easy calcination method to synthesize zinc silicate hollow sub-microsphere, belongs to pioneer invention.General water (solvent) hot method is difficult to the zinc silicate micron ball obtaining having hollow structure, the present invention first synthesizes the zinc sulphide structure of various pattern, then obtain the zinc silicate of the hollow structure of corresponding pattern by the method in the present invention, this preparation being zinc silicate provides new approach.
(3) gained rhombic system zinc silicate micron ball of the present invention, be hollow structure, gained particle purity is high, and size is controlled, even, good dispersity.
Accompanying drawing explanation
The X-ray diffractogram of the Zinc sulphide micron ball of Fig. 1 (a) prepared by embodiment 1;
The stereoscan photograph of the Zinc sulphide micron ball of Fig. 1 (b) prepared by embodiment 1.
The X-ray diffractogram of the zinc sulphide silicon dixoide nucleocapsid structure ball of Fig. 2 (a) prepared by embodiment 1;
The stereoscan photograph of the zinc sulphide silicon dixoide nucleocapsid structure ball of Fig. 2 (b) prepared by embodiment 1.
The X-ray diffractogram of the zinc silicate hollow sub-microsphere of Fig. 3 prepared by embodiment 1.
The stereoscan photograph of the zinc silicate hollow sub-microsphere of Fig. 4 prepared by embodiment 1.
The transmission electron microscope photo of the zinc silicate hollow sub-microsphere of Fig. 5 prepared by embodiment 1.
The stereoscan photograph of the zinc silicate hollow sub-microsphere of Fig. 6 prepared by embodiment 3.
Embodiment
For better understanding the present invention, below in conjunction with drawings and Examples, the invention will be further described, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
Slowly joined by 0.8mol/L thiourea solution in 0.4mol/L zinc acetate solution, the volume ratio of thiourea solution and zinc acetate solution is 1:1, is stirred to and mixes, and is 180 DEG C of Water Under thermal response 10h, prepares monodisperse ZnS micron ball in temperature; The X-ray diffractogram of gained Zinc sulphide micron ball and stereoscan photograph are respectively by shown in accompanying drawing 1 (a) He Fig. 1 (b).From Fig. 1 (a), the peak position of each diffraction peak and the upper diffraction peak of the standard card (JCPDSNo.77-2100) of Emission in Cubic ZnS match, and occur without dephasign peak, illustrate that product is pure Emission in Cubic ZnS.Can see that what ZnS micron ball was piled up by countless nano particle, diameter are the smooth surface of the solid sphere of 3-5 μm, ball by Fig. 1 (b).Weigh the zinc sulfide powder of 0.05g after dry, under agitation add 20ml ethanol, the ammoniacal liquor of 2ml25%, 2ml tetraethoxy successively, after stirring 6h, prepare monodisperse ZnS silicon dixoide nucleocapsid structure ball (ZnSSiO
2nucleocapsid structure ball).Fig. 2 (a) is ZnSSiO
2the XRD spectra of nucleocapsid structure ball, as can be seen from Fig., the ZnSSiO after coated
2nucleocapsid structure ball is still the peak of Emission in Cubic ZnS, just the strength ratio at peak coated before more weak, and more coarse, this may be the unbodied SiO on ZnS ball surface
2cause.Be SiO at a broad peak of about 22 °
2vitreous state phase peak.Fig. 2 (b) is ZnSSiO
2the stereoscan photograph of nucleocapsid structure ball, can find out, the surface of ZnS micron ball becomes coarse by smooth, has a lot of unbodied SiO
2be coated on above micron ball, large than before coated of the diameter of the ZnS micron ball after coated; Can also see there is a lot of unbodied SiO
2mixed and disorderly is scattered in side; SiO
2shell thickness can by change tetraethoxy amount or repeatedly repeat SiO
2coated process regulate.
Weigh 0.02g zinc sulphide SiO 2 powder after dry and be placed in ceramic crucible, in the retort furnace of 900 DEG C, calcine 24h, zinc silicate hollow sub-microsphere can be obtained.The X-ray diffractogram of gained zinc silicate hollow sub-microsphere as shown in Figure 3, can be seen, product is now Zn
2siO
4(JCPDSNo.37-1485) peak, there is no that other peaks exist, and this may be the prolongation along with the reaction times, zinc sulphide and SiO
2zn is transformed into completely by Kinkendal Effect (Kirkendalleffect)
2siO
4hollow sub-microsphere.The pattern of zinc silicate hollow sub-microsphere as shown in Figure 4, as can be seen from SEM photo, synthesized Zn
2siO
4micron ball becomes empty, some partial crushings.The diameter of ball is about 3 μm, and spherical shell is thinner, and its thickness is 100 ~ 300nm.Do tem analysis further to products therefrom, its result as shown in Figure 5.From the transmission electron microscope of sample, the product of gained is the Zn of hollow structure
2siO
4micron ball, and the surface of ball is formed by nano particle accumulation, and particle diameter is about 500nm.
Chinese invention patent 2006100404227 discloses composite hollow ball of radial solid matter willemite nano-wires formation and preparation method thereof, comprise the following steps: (1) first by carbonate and carbon dust by 2: 0.8 ~ 1.2 mol ratio mix mutually, on this mixture, cladding thickness is the zinc powder of 1 ~ 3mm again, (2) in argon atmospher, 3 ~ 7 minutes are incubated at first the mixture and silicon chip one that are covered with zinc powder being arised from 400 ~ 500 DEG C, again it is incubated 1 ~ 3 hour at 900 ~ 1100 DEG C in argon atmospher, the composite hollow ball that obtained radial solid matter willemite nano-wires is formed.Described carbonate is zinc carbonate or magnesiumcarbonate or manganous carbonate, and the described distance be covered with between the mixture of zinc powder and silicon chip is 6 ~ 10cm.But this technology needs high-temperature calcination in argon atmospher, preparation condition is harsh, and production cost is high, does not obtain complete empty highly purified zinc silicate micron ball simultaneously.As everyone knows, (micro-) nano-hollow ball, owing to having the features such as specific surface area is high, density is low, makes it have very high catalysis and absorption property.General water (solvent) hot method is difficult to the zinc silicate micron ball obtaining having hollow structure, the present invention utilizes simple method for calcinating to obtain zinc silicate hollow sub-microsphere, be first time ion exchange method synthetic silicic acid zinc hollow sub-microsphere, provide a kind of comparatively practical method preparing zinc silicate hollow structure.
Embodiment 2
Slowly joined by 0.8mol/L thiourea solution in 0.4mol/L zinc acetate solution, the volume ratio of thiourea solution and zinc acetate solution is 1.5:1, is stirred to and mixes, and is 180 DEG C of Water Under thermal response 12h, prepares monodisperse ZnS micron ball in temperature; Weigh the zinc sulfide powder of 0.1g after dry, under agitation add 40ml ethanol, the ammoniacal liquor of 4ml25%, 4ml tetraethoxy successively, after stirring 6h, prepare monodisperse ZnS silicon dixoide nucleocapsid structure ball.Weigh 0.02g zinc sulphide SiO 2 powder after dry and be placed in ceramic crucible, in the retort furnace of 900 DEG C, calcine 20h, zinc silicate hollow sub-microsphere can be obtained.X-ray diffractogram and the stereoscan photograph pattern of the present embodiment gained Zinc sulphide micron ball are similar to Fig. 1.The X-ray diffractogram of gained zinc silicate hollow sub-microsphere and the base peak (JCPDSNo.37-1485) of zinc silicate fit like a glove, and pattern is similar to shown in Fig. 4.
Embodiment 3
Slowly joined by 0.4mol/L thiourea solution in 0.2mol/L zinc acetate solution, the volume ratio of thiourea solution and zinc acetate solution is 1:1, is stirred to and mixes, and is 180 DEG C of Water Under thermal response 20h, prepares monodisperse ZnS micron ball in temperature; Weigh the zinc sulfide powder of 0.08g after dry, under agitation add 32ml ethanol, the ammoniacal liquor of 3.2ml25%, 3.2ml tetraethoxy successively, after stirring 10h, prepare monodisperse ZnS silicon dixoide nucleocapsid structure ball.Weigh 0.05g zinc sulphide SiO 2 powder after dry and be placed in ceramic crucible, in the retort furnace of 900 DEG C, calcine 48h, zinc silicate hollow sub-microsphere can be obtained.The X-ray diffractogram of gained zinc silicate hollow sub-microsphere and the base peak (JCPDSNo.37-1485) of zinc silicate fit like a glove, and pattern as shown in Figure 6.As can be seen from SEM photo, synthesized Zn
2siO
4micron ball becomes empty, some partial crushings.The diameter of ball is about 2 ~ 3 μm, and spherical shell is thinner, and its thickness is 300 ~ 500nm.
Embodiment 4
Slowly joined by 0.8mol/L thiourea solution in 0.4mol/L zinc acetate solution, the volume ratio of thiourea solution and zinc acetate solution is 2:1.5, is stirred to and mixes, and is 200 DEG C of Water Under thermal response 12h, prepares monodisperse ZnS micron ball in temperature; Weigh the zinc sulfide powder of 0.05g after dry, under agitation add 25ml ethanol, the ammoniacal liquor of 4ml25%, 4ml tetraethoxy successively, after stirring 8h, prepare monodisperse ZnS silicon dixoide nucleocapsid structure ball.Weigh 0.04g zinc sulphide SiO 2 powder after dry and be placed in ceramic crucible, in the retort furnace of 1000 DEG C, calcine 24h, zinc silicate hollow sub-microsphere can be obtained.Gained zinc silicate hollow sub-microsphere X-ray diffractogram as shown in Figure 3, the similar Fig. 5 of pattern.
Embodiment 5
Slowly joined by 0.4mol/L thiourea solution in 0.2mol/L zinc acetate solution, the volume ratio of thiourea solution and zinc acetate solution is 1.2:1, is stirred to and mixes, and is 220 DEG C of Water Under thermal response 10h, prepares monodisperse ZnS micron ball in temperature; Weigh the zinc sulfide powder of 0.05g after dry, under agitation add 20ml ethanol, the ammoniacal liquor of 2ml25%, 4ml tetraethoxy successively, after stirring 8h, prepare monodisperse ZnS silicon dixoide nucleocapsid structure ball.Weigh 0.10g zinc sulphide SiO 2 powder after dry and be placed in ceramic crucible, in the retort furnace of 1000 DEG C, calcine 20h, zinc silicate hollow sub-microsphere can be obtained.The X-ray diffractogram of gained zinc silicate hollow sub-microsphere and the base peak (JCPDSNo.37-1485) of zinc silicate fit like a glove.Pattern is as shown in Figure 4 similar.
The present invention is on the basis of the ZnS micron ball of water heat transfer, and coupled ion exchange process and Kinkendal Effect, utilize easy calcination method to synthesize zinc silicate hollow sub-microsphere, is the breakthrough of existing zinc silicate hollow sub-microsphere preparation method.General water (solvent) hot method is difficult to the zinc silicate micron ball obtaining having hollow structure, and the present invention first synthesizes the zinc sulphide structure of various pattern, then obtains the zinc silicate of the hollow structure of corresponding pattern by the method in the present invention.This preparation being zinc silicate provides new approach.
The present invention adopts hydrothermal method to prepare Zinc sulphide micron ball, only adopts water or alcohol to be solvent, simple to operate, consumes energy low, and pollute few, and reaction process is without the need to tensio-active agent, product postprocessing is simple, without the need to carrying out special processing to product.
Claims (8)
1. a preparation method for zinc silicate hollow sub-microsphere, is characterized in that comprising the steps:
1) join in zinc acetate solution by thiourea solution, control thiocarbamide and zinc acetate molar concentration rate are 3:1 ~ 1:2, are stirred to and mix, be 100 ~ 220 DEG C of Water Under thermal response 6 ~ 30h, prepare monodisperse ZnS micron ball in temperature;
2) monodisperse ZnS micron ball is dry, under agitation add ethanol, ammoniacal liquor and tetraethoxy successively, after stirring 4 ~ 10h, prepare monodisperse ZnS silicon dixoide nucleocapsid structure ball;
3) in 800 ~ 1000 DEG C, calcine 18-48h after the drying of monodisperse ZnS silicon dixoide nucleocapsid structure ball, obtain zinc silicate hollow sub-microsphere.
2. the preparation method of zinc silicate hollow sub-microsphere according to claim 1, is characterized in that: described hydro-thermal reaction is carried out in teflon-lined autoclave.
3. the preparation method of zinc silicate hollow sub-microsphere according to claim 1, is characterized in that: described hydrothermal temperature is 150 ~ 200 DEG C, and the time of hydro-thermal reaction is 10 ~ 20h.
4. the preparation method of zinc silicate hollow sub-microsphere according to claim 1, is characterized in that: according to every 0.1g monodisperse ZnS micron ball meter, add ethanol, ammoniacal liquor and tetraethoxy and be respectively 10 ~ 40ml, 1 ~ 5ml and 1 ~ 5ml.
5. the preparation method of zinc silicate hollow sub-microsphere according to claim 4, is characterized in that: the mass concentration of described ammoniacal liquor is 25%.
6. the preparation method of zinc silicate hollow sub-microsphere according to claim 1, is characterized in that: step (2) described churning time is 5 ~ 8h, and mixing speed is 300 ~ 600r/min.
7. the preparation method of zinc silicate hollow sub-microsphere according to claim 1, is characterized in that: described calcination time is 25 ~ 35h.
8. the preparation method of zinc silicate hollow sub-microsphere according to claim 1, is characterized in that: described calcining carries out in retort furnace.
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| CN114620737A (en) * | 2022-01-19 | 2022-06-14 | 中国科学院深圳先进技术研究院 | Hollow silicon dioxide and preparation method and application thereof |
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| CN106745197A (en) * | 2016-11-17 | 2017-05-31 | 新疆维吾尔自治区产品质量监督检验研究院 | ZnS micron balls and preparation method thereof |
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| CN112981501A (en) * | 2021-03-05 | 2021-06-18 | 赵琳琳 | Composite bright nickel plating solution |
| CN112981502A (en) * | 2021-03-05 | 2021-06-18 | 赵琳琳 | High-dispersion suspending agent for composite electroplating |
| CN112981501B (en) * | 2021-03-05 | 2024-03-01 | 惠州市荣安达化工有限公司 | Composite bright nickel plating solution |
| CN112981502B (en) * | 2021-03-05 | 2024-04-12 | 东莞市金稻田化工有限公司 | Suspending agent for high-dispersion composite electroplating |
| CN114620737A (en) * | 2022-01-19 | 2022-06-14 | 中国科学院深圳先进技术研究院 | Hollow silicon dioxide and preparation method and application thereof |
| CN114620737B (en) * | 2022-01-19 | 2023-09-15 | 深圳先进电子材料国际创新研究院 | Hollow silicon dioxide and preparation method and application thereof |
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