CN106986374A - A kind of high specific surface area and mesoporous zinc-oxide nano cluster and preparation method thereof - Google Patents
A kind of high specific surface area and mesoporous zinc-oxide nano cluster and preparation method thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 84
- 229960001296 zinc oxide Drugs 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 122
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 79
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 48
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 27
- 239000011780 sodium chloride Substances 0.000 claims abstract description 27
- 229960002668 sodium chloride Drugs 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000006193 liquid solution Substances 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 2
- 238000012377 drug delivery Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 24
- 239000003643 water by type Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 6
- 241000209094 Oryza Species 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- -1 nanometer rods Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- IJRVLVIFMRWJRQ-UHFFFAOYSA-N nitric acid zinc Chemical compound [Zn].O[N+]([O-])=O IJRVLVIFMRWJRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- 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
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of high specific surface area and mesoporous zinc-oxide nano cluster and preparation method thereof, it is characterized in that the mesoporous zinc-oxide nano cluster obtained is formed by the assembling accumulation of yardstick is 35 nanometers, wall thickness is 12 nanometers hallow nanoparticles, with the characteristic such as specific surface area is high and photocatalysis performance is excellent.Its preparation process is：（1）Deionized water and ethylene glycol solution are mixed and obtain ethylene glycol and water mixed solution；（2）Under rapid mixing conditions, zinc nitrate, sodium hydroxide, sodium-chloride water solution are added to ethylene glycol and water mixed solution, the reaction precursor liquid solution for preparing mesoporous zinc-oxide nano cluster is obtained；（3）Reaction precursor liquid solution was reacted after 1 10 hours under stirring at room temperature, is centrifuged at a high speed and is cleaned by ultrasonic, drying and calcining obtains mesoporous zinc-oxide nano cluster powder.The high specific surface area and mesoporous zinc-oxide nano cluster that the present invention is obtained has important application value in terms of photocatalytic degradation, drug delivery, antibacterial, environmental improvement and protection.
Description
Technical field
The high specific surface area and mesoporous zinc oxide formed is accumulated the present invention relates to a kind of assembled by hollow zinc oxide nano-particle
Nano-cluster and preparation method thereof.
Background technology
As a kind of important functional oxide semiconductor, zinc oxide not only has unique physicochemical property and good life
Thing compatibility, and there is larger energy gap (3.37 eV) and exciton bind energy (60 meV), these characteristics at room temperature
Make it in photocatalysis contaminant degradation, photocatalysis hydrogen production, solar cell, antibiotic and sterilizing, drug delivery, environmental improvement, air-sensitive
Many aspects such as sensing, photoelectric device have important application value and wide application prospect.Therefore, in recent years people not
With substantial amounts of trial and effort has been done in the nano zinc oxide material control synthesis of appearance structure, hydro-thermal method, liquid phase are developed and have sunk
A variety of nano zinc oxide material preparation sides such as shallow lake method, sol-gel process, Hydrolyze method, chemical vapor deposition (CVD), high-temperature calcination
Method, has synthesized that nano particle, nanometer rods, nano wire, nanobelt, nanotube, nanometer sheet etc. be one-dimensional, two dimensional oxidation zinc nano material
And the three-dimensional zinc oxide micro-nano hierarchy constructed by nano particle, nanometer sheet, nanometer rods etc. for elementary cell assembling.Many institutes
It is known, many performances of nano zinc oxide material, using closely related with its specific surface area.Obviously, high-specific surface area oxygen is constructed
Changing zinc nanostructured has highly important scientific meaning and practical value.However, compared with commercial Zinc oxide powder material（Than
Surface area is 4-5 meters squared per grams）, the larger specific surface area of zinc oxide nano-particle（10-40 meters squared per grams）, higher ratio table
The factors such as face energy, stronger surface polarity are easy to cause its own to reunite, and then limit giving full play to for its nano effect.
Therefore, people are that template has successfully constructed a series of different scales, different wall with polystyrene spheres, silica, carbon ball etc.
Zinc oxide micron hollow ball；Calcining basic zinc carbonate microballoon is used to be prepared for be made up of Zinc oxide nano sheet, aperture for 20-
50 nanometers, specific surface area be about 30 meters squared per grams mesoporous ZnO microsphere.As far as we know, although people are by constructing sky
The heart, meso-hole structure effectively increase the specific surface area, stability and catalytic activity of Zinc oxide powder material, but use has been reported at present
The technology of preparing in road, people are still difficult to synthesize the Zinc oxide powder material that specific surface area is more than 50 meters squared per grams, and existing oxygen
Change zinc is hollow, mesoporous microsphere prepares method and usually requires complicated cumbersome reactions steps, higher reaction temperature or longer reaction
Time.Therefore, there is provided a kind of easy, quick, nothing for the weak point of the invention for existing Zinc oxide powder material preparation technology
The preparation method of high specific surface area and mesoporous zinc-oxide nano cluster is prepared under template, room temperature condition.
The content of the invention
The technical problem to be solved in the present invention is to overcome existing specific area Zinc oxide powder material preparation technology deficiency
Place there is provided it is a kind of it is easy, quick, without the technology of preparing that mesoporous zinc-oxide nano cluster is prepared under template, room temperature condition.The present invention's
Accumulation is formed, catalytic activity height, the Jie of specific surface area greatly are assembled by hollow zinc oxide nano-particle another object is that preparing
Hole zinc-oxide nano cluster, is constructed, practical application is provided in terms of antibiotic and sterilizing for photocatalysis contaminant degradation, gas sensing device
Material base.
In the present invention high specific surface area and mesoporous zinc-oxide nano cluster be using zinc nitrate be zinc source, sodium hydroxide as precipitating reagent,
Prepared using liquid-phase precipitation method in ethylene glycol and water mixed solution, its preparation process includes step in detail below：
（1）A certain amount of deionized water is added in ethylene glycol solution, ethylene glycol and water mixed solution is uniformly mixing to obtain；
（2）Under agitation, to step（1）Zinc nitrate, hydrogen-oxygen are sequentially added in the ethylene glycol of acquisition and the mixed solution of water
Change sodium, sodium chloride, obtain the reaction precursor liquid solution for preparing high specific surface area and mesoporous zinc-oxide nano cluster, wherein, zinc nitrate, hydrogen
Sodium oxide molybdena, the concentration of sodium chloride are respectively 0.01-0.30 mol/Ls, 0.05-1.5 mol/Ls, 0.005-0.05 mol/Ls；
（3）By step（2）In reaction precursor liquid solution react under stirring at room temperature 1-10 hours, milky high-ratio surface is made
The mesoporous zinc-oxide nano cluster colloidal solution of product；
（4）After question response terminates, mesoporous zinc-oxide nano cluster colloidal solution is centrifuged with supercentrifuge, in rotating speed
After 5000-14000 revs/min centrifuges 10-100 minutes, colourless solution in centrifuge tube is removed, white precipitate product is obtained；
（5）It is cleaned by ultrasonic step with deionized water or absolute alcohol（4）The precipitated product of acquisition, and done in 50-200 degree baking ovens
It is dry 1-10 hours, obtain mesoporous zinc-oxide nano cluster powder.
Beneficial effects of the present invention：
（1）High specific surface area and mesoporous zinc-oxide nano cluster is prepared under conditions of room temperature, without template the invention provides a kind of
Method, it is characterised in that mesoporous zinc-oxide nano cluster is in ethylene glycol and water mixed solution, using zinc nitrate as zinc source, hydroxide
Sodium makees precipitating reagent, is prepared using liquid-phase precipitation method；
（2）The mesoporous zinc-oxide nano cluster that this method is obtained is by yardstick is 3-5 nanometers, wall thickness is 1-2 nanometers hollow Nano
Particle assembling accumulates what is formed, and its pore size is 2-5 nanometers, and specific surface area is up to 160 meters squared per grams, far above current business
With（4-5 meters squared per grams）The zinc oxide nano-powder material reported for work with document（10-40 meters squared per grams）；
（3）The mesoporous zinc-oxide nano cluster that this method is obtained has yield height, monodispersity is good, nano-cluster yardstick is adjustable, hot steady
Qualitative good the features such as, appearance structure change does not occur in 200 degrees Celsius of calcinings for a long time；
（4）The mesoporous zinc-oxide nano cluster that this method is obtained has excellent photocatalytic degradation characteristic and can recycled for multiple times；
（5）The present invention is raw materials used abundant and cheap and easy to get, and high specific surface area and mesoporous zinc-oxide nano cluster yield is high and prepares work
Skill is simple and easy to do, experimental repeatability is good, it is easy to prepared by magnanimity, low cost, large-scale production, is adapted to industrialization large-scale production,
Be content with very little following commercial applications demand.
Brief description of the drawings
Fig. 1 is the light shot after with the naked eye observing obtained mesoporous zinc-oxide nano cluster colloidal solution and powder with digital camera
Photo is learned, wherein, Fig. 1 a are the optical photographs of mesoporous zinc-oxide nano cluster colloidal solution, and solution colour is milky, and Fig. 1 b are
The mesoporous zinc-oxide nano cluster powder photo obtained after centrifugal drying, it can be seen that mesoporous zinc-oxide nano cluster after drying and grinding
For white powder；
Fig. 2 is with multiple transmission electron microscopes shot after JEOL-1400 transmission electron microscope observings to the mesoporous zinc-oxide nano cluster of acquisition
（TEM）One of photo, wherein, wherein, Fig. 2 a are mesoporous zinc-oxide nano cluster low power TEM image, and Fig. 2 b are mesoporous zinc oxide nano
Rice cluster high power TEM image, TEM results show that product is accumulated by the hollow beads that yardstick is 3-5 nanometers, wall thickness is 1-2 nanometers
The monodisperse mesoporous zinc-oxide nano cluster formed；
Fig. 3 is after obtained mesoporous zinc-oxide nano cluster is evenly spread on slide, with Bruker D8-Advance types X-
X ray diffractometer x carries out testing the X-ray diffraction of acquisition to it（XRD）Collection of illustrative plates, wherein, ordinate is relative intensity, abscissa
For the angle of diffraction, XRD data displays, all X-ray diffraction peak peak positions of product and zinc oxide standard spectrogram（JCPDS cards No.36-
1451）It coincide, illustrates that obtained mesoporous zinc-oxide nano cluster has wurtzite structure；
Fig. 4 is to use Japan Shimadzu UV-3101PC types ultraviolet-visible-near infrared spectrometer（UV-Vis-NIR）To oxygen
Change the light absorbs spectrogram obtained after zinc nanoparticles are tested, wherein, ordinate is absorption intensity, and abscissa is light wave ripple
It is long.It can be seen that mesoporous zinc-oxide nano cluster has significant exciton absorption peak in 340 nanometers；
Fig. 5 is the mesoporous zinc oxide automatically tested with TriStar II 3020 than surface and lacunarity analysis instrument under 77 K
Isothermal nitrogen adsorption-desorption curve of nano-cluster, wherein, mesoporous zinc-oxide nano cluster is in 200 degrees Celsius of vacuum conditions before measurement
4 hours degassing process of lower progress, as a result show, the pore size of the mesoporous zinc-oxide nano cluster obtained in the present invention is received for 2-5
Rice, its specific surface area is 160 meters squared per grams, far above current commercialization（4-5 meters squared per grams）The zinc oxide nano reported for work with document
Rice powder body material（10-40 meters squared per grams）；
Fig. 6 is with PLS-SXE300C xenon lamps（300W）Make mesoporous zinc-oxide nano cluster pair under the conditions of the irradiation of simulated solar radiant
Dyestuff contaminant rhodamine B（Rh B）The experimental result of catalytic degradation, wherein, Fig. 6 a are rhodamine Bs in Photocatalytic Degradation Process
Solution colour changes, and Fig. 6 b are the optical absorption maps of residual rhodamine B in solution, and Fig. 6 c are photocatalysis effect figures, and Fig. 6 d are to be situated between
Hole zinc-oxide nano cluster is circulated in degradation results, circulation experiment to rhodamine B keeps light application time to be 50 minutes, and rhodamine B is dense
Spend for 0.01 mmoles/liter, as a result show, the mesoporous zinc-oxide nano cluster of acquisition under the conditions of solar irradiation there is excellent light to urge
Change degradation characteristic and stability, the reusable edible in photocatalytic degradation；
It in ethylene glycol and water volume ratio is 80 that Fig. 7, which is,:In 20 mixed solution, in zinc nitrate and naoh concentration different condition
Under, the transmission electron microscope photo of obtained mesoporous zinc-oxide nano cluster, wherein, the concentration difference of zinc nitrate and sodium hydroxide in Fig. 7 a
For 0.01 mol/L and 0.05 mol/L, the concentration of zinc nitrate and sodium hydroxide is respectively 0.1 mol/L and 0.5 in Fig. 7 b
The concentration of zinc nitrate and sodium hydroxide is respectively zinc nitrate in 0.2 mol/L and 1.0 mol/Ls, Fig. 7 d in mol/L, Fig. 7 c
Concentration with sodium hydroxide be respectively in 0.3 mol/L and 1.5 mol/Ls, figure all scales be 100 nanometers；
Fig. 8 is that in the ethylene glycol mixed solution different from water volume ratio, constant bar is kept in zinc nitrate and naoh concentration
Under part, the transmission electron microscope photo of obtained zinc oxide nano-particle, wherein, ethylene glycol and water volume ratio are 85 in Fig. 8 a:15, figure
Ethylene glycol and water volume ratio are 80 in 8b:Ethylene glycol and water volume ratio are 75 in 20, Fig. 8 c:Ethylene glycol and water body in 25, Fig. 8 d
Product is than being 60:Ethylene glycol and water volume ratio are 50 in 40, Fig. 8 e:Ethylene glycol and water volume ratio are 40 in 50, Fig. 8 f:60, Fig. 8 g
Middle ethylene glycol is 30 with water volume ratio:Ethylene glycol and water volume ratio are 20 in 70, Fig. 8 h:Ethylene glycol and water volume in 80, Fig. 8 i
Than for 10:Ethylene glycol and water volume ratio are 0 in 90, Fig. 8 j:In 100, i.e. pure water solution, all scales are 200 to receive in figure
Rice；
It in ethylene glycol and water volume ratio is 80 that Fig. 9, which is,:It is 0.05 mol/L keeping nitric acid zinc concentration in 20 mixed solution
Under the conditions of, the transmission electron microscope photo of obtained zinc oxide nano-particle under naoh concentration different condition, wherein, hydrogen in Fig. 9 a
The concentration of sodium oxide molybdena is 0.1 mol/L, and the concentration of sodium hydroxide is the dense of sodium hydroxide in 0.2 mol/L, Fig. 9 c in Fig. 9 b
Spend for 0.5 mol/L, the concentration of sodium hydroxide is that all scales are 100 nanometers in 1 mol/L, figure in Fig. 9 d.
Embodiment
From market, purchase prepares ethylene glycol, zinc nitrate, hydrogen-oxygen that high specific surface area and mesoporous zinc-oxide nano cluster is used first
Change sodium, sodium chloride；Then zinc nitrate, sodium hydroxide, sodium-chloride water solution are prepared with 18 megaohms of deionized waters, wherein, zinc nitrate,
Sodium hydroxide, sodium-chloride water solution concentration are respectively 4 mol/Ls, 10 mol/Ls, 2 mol/Ls；
Present disclosure is described in further detail with reference to specific embodiment, but the invention is not restricted to be exemplified below
Specific examples；
Embodiment 1
It is prepared by high specific surface area and mesoporous zinc-oxide nano cluster
6 ml deionized waters are added in 32 milliliters of ethylene glycol solutions first, obtain ethylene glycol after stirring mixes with water
Solution；Then under rapid mixing conditions（800 revs/min）, 0.5 milliliter 4 is sequentially added to the mixed solution of ethylene glycol and water
Mol/L zinc nitrate aqueous solution, 1 milliliter of 10 mol/L sodium hydrate aqueous solution, 0.5 milliliter of 2 mol/L sodium-chloride water solution,
Obtain and prepare the reaction precursor liquid solution of high specific surface area and mesoporous zinc-oxide nano cluster, wherein, ethylene glycol and water in presoma
Volume ratio is 80:20, zinc nitrate, sodium hydroxide, the concentration of sodium chloride are respectively 0.05 mol/L, 0.25 mol/L, 0.025
Mol/L；Finally the reaction precursor liquid solution prepared is reacted 1 hour under stirring at room temperature, color as shown in Figure 1a is obtained
For milky mesoporous zinc-oxide nano cluster colloidal solution；After question response terminates, mesoporous zinc-oxide nano cluster colloidal solution is used
Supercentrifuge is centrifuged, and after the centrifugation 10 minutes of 10000 revs/min of rotating speed, is removed colourless solution in centrifuge tube, is obtained white
Color precipitated product；The white precipitate product of acquisition is cleaned by ultrasonic 3-5 times with deionized water or absolute alcohol, and in 200 degree of bakings
Dried 2 hours in case, the mesoporous zinc-oxide nano cluster powder as shown in Fig. 1 b, Fig. 2 is made；
Embodiment 2
It is prepared by the high specific surface area and mesoporous zinc-oxide nano cluster of different scale
Take 4 parts 32 milliliters of ethylene glycol solution to be respectively added in 4 50 milliliters of centrifuge tubes first, and be labeled as A, B, C, D, with
Quickly stirring afterwards（800 revs/min）Under the conditions of 7.2 ml deionized waters added into centrifuge tube A successively, rub for 0.1 milliliter 4
That/liter zinc nitrate aqueous solution, 0.2 milliliter of 10 mol/L sodium hydrate aqueous solution, 0.5 milliliter of 2 mol/L sodium-chloride water solution；
4.5 ml deionized waters, 1 milliliter of 4 mol/L zinc nitrate aqueous solution, 2 milliliter of 10 mol/L hydroxide are added into centrifuge tube B
Sodium water solution, 0.5 milliliter of 2 mol/L sodium-chloride water solution；1.5 ml deionized waters are added into centrifuge tube C, are rubbed for 2 milliliter 4
That/liter zinc nitrate aqueous solution, 4 milliliter of 10 mol/L sodium hydrate aqueous solution, 0.5 milliliter of 2 mol/L sodium-chloride water solution；To
Added in centrifuge tube D 6 milliliter of 10 mol/L sodium hydrate aqueous solution, 1.5 milliliter of 8 mol/L zinc nitrate aqueous solution, 0.5 milliliter
2 mol/L sodium-chloride water solutions；Acquisition prepares the reaction precursor of the high specific surface area and mesoporous zinc-oxide nano cluster of different scale respectively
Liquid solution, wherein, the volume ratio of ethylene glycol and water is 80 in A, B, C, D presoma:Zinc nitrate, hydroxide in 20, A presomas
Sodium, the concentration of sodium chloride are respectively zinc nitrate, hydrogen in 0.01 mol/L, 0.05 mol/L, 0.025 mol/L, precursor B
Sodium oxide molybdena, the concentration of sodium chloride be respectively zinc nitrate in 0.1 mol/L, 0.5 mol/L, 0.025 mol/L, C presomas,
Sodium hydroxide, the concentration of sodium chloride are respectively nitric acid in 0.2 mol/L, 1.0 mol/Ls, 0.025 mol/L, D presomas
Zinc, sodium hydroxide, the concentration of sodium chloride are respectively 0.3 mol/L, 1.5 mol/Ls, 0.025 mol/L；Finally match somebody with somebody above-mentioned
The reaction precursor liquid solution made reacts 5 hours under stirring at room temperature, and acquisition color is milky mesoporous zinc-oxide nano cluster
Colloidal solution；After question response terminates, mesoporous zinc-oxide nano cluster colloidal solution is centrifuged with supercentrifuge, in rotating speed
After 5000-14000 revs/min centrifuges 10 minutes, colourless solution in centrifuge tube is removed, white precipitate product is obtained；Use deionization
Water or absolute alcohol are cleaned by ultrasonic 3-5 times to the white precipitate product of acquisition, and different scale high-ratio surface as shown in Figure 7 is made
The mesoporous zinc-oxide nano cluster of product；
Embodiment 3
High specific surface area and mesoporous zinc-oxide nano cluster is prepared in the ethylene glycol mixed solution different from water volume ratio
Take in 4 50 milliliters of centrifuge tubes and be respectively labeled as A, B, C, D, then quickly stirring（800 revs/min）Under the conditions of successively
Add 34 milliliters of ethylene glycol into centrifuge tube A, 4 ml deionized waters, 0.5 milliliter of 4 mol/L zinc nitrate aqueous solution, 1 milliliter 10
Mol/L sodium hydrate aqueous solution, 0.5 milliliter of 2 mol/L sodium-chloride water solution；32 milliliters of second two are added into centrifuge tube B
Alcohol, 6 ml deionized waters, 0.5 milliliter of 4 mol/L zinc nitrate aqueous solution, 1 milliliter of 10 mol/L sodium hydrate aqueous solution, 0.5
2 mol/L sodium-chloride water solutions of milliliter；30 milliliters of ethylene glycol are added into centrifuge tube C, 8 ml deionized waters, are rubbed for 0.5 milliliter 4
That/liter zinc nitrate aqueous solution, 1 milliliter of 10 mol/L sodium hydrate aqueous solution, 0.5 milliliter of 2 mol/L sodium-chloride water solution；To
Add 24 milliliters of ethylene glycol in centrifuge tube D, 14 ml deionized waters, 0.5 milliliter of 4 mol/L zinc nitrate aqueous solution, 1 milliliter 10
Mol/L sodium hydrate aqueous solution, 0.5 milliliter of 2 mol/L sodium-chloride water solution；Obtain ethylene glycol different from water volume ratio
The reaction precursor liquid solution of mesoporous zinc-oxide nano cluster is prepared, wherein, the volume score of ethylene glycol and water in A, B, C, D presoma
Wei 85:15、80:20、75:25、60:40, in presoma zinc nitrate, sodium hydroxide, the concentration of sodium chloride be 0.05 mole/
Liter, 0.25 mol/L, 0.025 mol/L；The above-mentioned reaction precursor liquid solution prepared is finally reacted 1 under stirring at room temperature
Hour, acquisition color is milky mesoporous zinc-oxide nano cluster colloidal solution；After question response terminates, by mesoporous zinc-oxide nano
Cluster colloidal solution is centrifuged with supercentrifuge, after the centrifugation 10 minutes of 10000 revs/min of rotating speed, removes nothing in centrifuge tube
Color solution, obtains white precipitate product；3-5 is cleaned by ultrasonic to the white precipitate product of acquisition with deionized water or absolute alcohol
It is secondary, high specific surface area and mesoporous zinc-oxide nano cluster as shown in Figure 8 is made；
Embodiment 4
High specific surface area and mesoporous zinc-oxide nano cluster is prepared under naoh concentration different condition
Take in 4 50 milliliters of centrifuge tubes and be respectively labeled as A, B, C, D, then quickly stirring（800 revs/min）Under the conditions of successively
32 milliliters of ethylene glycol, 6.6 ml deionized waters, 0.5 milliliter of 4 mol/L zinc nitrate aqueous solution, 0.4 milli are added into centrifuge tube A
Rise 10 mol/L sodium hydrate aqueous solutions, 0.5 milliliter of 2 mol/L sodium-chloride water solution；32 milliliters of second are added into centrifuge tube B
Glycol, 6.2 ml deionized waters, 0.5 milliliter of 4 mol/L zinc nitrate aqueous solution, 0.8 milliliter of 10 mol/L sodium hydroxide are water-soluble
Liquid, 0.5 milliliter of 2 mol/L sodium-chloride water solution；32 milliliters of ethylene glycol, 5 ml deionized waters, 0.5 are added into centrifuge tube C
4 mol/L zinc nitrate aqueous solutions of milliliter, 2 milliliter of 10 mol/L sodium hydrate aqueous solution, 0.5 milliliter of 2 mol/L sodium chloride water
Solution；32 milliliters of ethylene glycol, 3 ml deionized waters, 0.5 milliliter of 4 mol/L zinc nitrate aqueous solution, 4 are added into centrifuge tube D
10 mol/L sodium hydrate aqueous solutions of milliliter, 0.5 milliliter of 2 mol/L sodium-chloride water solution；Acquisition prepares mesoporous zinc oxide nano
The reaction precursor liquid solution of rice cluster, wherein, naoh concentration is respectively 0.1 mol/L, 0.2 rubbed in A, B, C, D presoma
You/liter, the mol/L of 0.5 mol/L 1, zinc nitrate, the concentration of sodium chloride are 0.05 mol/L, 0.025 mol/L；Finally
The above-mentioned reaction precursor liquid solution prepared is reacted 1 hour under stirring at room temperature, acquisition color is milky mesoporous oxidation
Zinc nano-cluster colloidal solution；After question response terminates, mesoporous zinc-oxide nano cluster colloidal solution is centrifuged with supercentrifuge,
After the centrifugation 10 minutes of 10000 revs/min of rotating speed, colourless solution in centrifuge tube is removed, white precipitate product is obtained；Use deionization
Water or absolute alcohol are cleaned by ultrasonic 3-5 times to the white precipitate product of acquisition, and high specific surface area and mesoporous oxygen as shown in Figure 9 is made
Change zinc nano-cluster.
Obviously, those skilled in the art can be to the mesoporous zinc-oxide nano of the present invention with high-specific surface area
Cluster and preparation method thereof carries out various changes and modification without departing from the spirit and scope of the present invention.So, if the present invention
These modifications and variations belong within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to include these
Including change and modification.
Claims (2)
1. a kind of high specific surface area and mesoporous zinc-oxide nano cluster, it is characterised in that：
（1）In the present invention described mesoporous zinc-oxide nano cluster be by yardstick be 3-5 nanometers, wall thickness be that 1-2 nanometers hollow receives
Rice corpuscles, which is assembled, accumulates what is formed, and its pore size is 2-5 nanometers, and specific surface area is 160 meters squared per grams, higher than commercialization and
The zinc oxide nano-powder material reported for work；
（2）The mesoporous zinc-oxide nano cluster obtained has yield height, monodispersity is good, nano-cluster yardstick is adjustable, heat endurance is good
The features such as, appearance structure change does not occur in 200 degrees Celsius of calcinings for a long time；
（3）The mesoporous zinc-oxide nano cluster obtained not only has excellent photocatalytic degradation characteristic but also can recycled for multiple times.
2. the preparation method of the high specific surface area and mesoporous zinc-oxide nano cluster described in claim 1, it is characterized in that including following step
Suddenly：
（1）Deionized water and ethylene glycol solution are mixed and obtain ethylene glycol and water mixed solution；
（2）Under agitation, to step（1）Zinc nitrate, hydrogen-oxygen are added successively in the ethylene glycol of acquisition and the mixed solution of water
Change sodium, sodium-chloride water solution, obtain the reaction precursor liquid solution for preparing high specific surface area and mesoporous zinc-oxide nano cluster, wherein, nitre
Sour zinc, the concentration of sodium hydroxide are respectively 0.01-0.30 mol/Ls, 0.05-1.5 mol/Ls, 0.005-0.05 mol/Ls；
（3）By step（2）In reaction precursor liquid solution react under stirring at room temperature 1-10 hours, milky high-ratio surface is made
The mesoporous zinc-oxide nano cluster colloidal solution of product；
（4）After question response terminates, by mesoporous zinc-oxide nano cluster colloidal solution in 5000-14000 revs/min of centrifugation 10- of rotating speed
After 100 minutes, colourless solution in centrifuge tube is removed, white precipitate product is obtained；
（6）It is cleaned by ultrasonic the white precipitate product obtained with deionized water or absolute alcohol, and is dried in 50-200 degree baking ovens
1-10 hours, obtain high specific surface area and mesoporous zinc-oxide nano cluster powder.
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