CN102942208B - Method for easily and conveniently preparing carbon doped mesoporous ZnO Hamburg structure nanometer assembly - Google Patents
Method for easily and conveniently preparing carbon doped mesoporous ZnO Hamburg structure nanometer assembly Download PDFInfo
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- CN102942208B CN102942208B CN201210466728.4A CN201210466728A CN102942208B CN 102942208 B CN102942208 B CN 102942208B CN 201210466728 A CN201210466728 A CN 201210466728A CN 102942208 B CN102942208 B CN 102942208B
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Abstract
The invention discloses a method for easily and conveniently preparing a carbon doped mesoporous ZnO Hamburg structure nanometer assembly. The method comprises the following steps of: adding structure-directing agent glucose by taking ethylene glycol as a reaction solvent and inorganic salt zinc acetate of a transition metal and excess alkali source as reaction precursors, and performing induced polymerization and twin crystal polar field driving to realize self-assembly of the carbon doped ZnO nanoparticles, thereby obtaining high-quality and high-yield Hamburg type carbon doped mesoporous ZnO assembly. By using the Hamburg structure carbon doped mesoporous ZnO prepared by the invention, the diameter range of the assembly is 400-500 nm, the particle size of the ZnO nanoparticles is about 5.8 nm, and the mesoporous radius is averagely 7.6 nm. The Hamburg type carbon doped mesoporous ZnO prepared by the invention has the advantages of low product cost, easiness in control, high uniformity, high yield, high repeatability, suitability for large-scale production and the like.
Description
Technical field
The invention belongs to inorganic mesoporous technical field of material, particularly the method for the carbon-doped mesoporous ZnO of a kind of simple preparation hamburger structure nano assembly.
Background technology
Nano zine oxide (ZnO), as a kind of multifunctional semiconductor, has good conduction and thermal conductivity, chemical stability, non-migrating, fluorescence, absorption and scatters ultraviolet ability etc.It is at piezoelectric, optics, gas sensor, coating, there is important using value the aspects such as environmental improvement, in addition abundant raw materials, low price, nontoxic to environment, show especially boundless application prospect, the < of U.S. < physical chemistry > > magazine (2011, 115 13597 pages of volumes) and < < material wall bulletin > > magazine (2012, 68 90 pages of volumes) there is report.Mesoporous material is because having special aperture, larger pore volume, the abundant microtextures such as ion-exchange site, add that its specific surface area is large, adsorptive power forces it in fields such as heterogeneous catalyst, the energy, biotechnology, nano-device, water treatments, to be widely used, at the < of U.S. < hazardous material > > magazine (2010,181 204 pages of volumes), there is report.At present, the method that existing bibliographical information is prepared various mesoporous materials has: template, sol-gel method, sedimentation, thermal expansion gaseous diffusion process, structure directing method etc., wherein inorganic materials is also with mesoporous SiO
2, TiO
2in the majority with mesoporous carbon material, patent 200610011885.0,200410065441.6,200910050884.0 etc. discloses these synthetic methods.Meso-porous ZnO, because of Zn ion facile hydrolysis, is difficult to form as Si-O tridimensional network the same as Ti-O, so be difficult to obtain by traditional evaporation conduction self assembling process.< < JACS > > (2003,125 11299 pages of volumes) reported the cage shape polyhedron that utilizes vacuum thermal evaporation sedimentation making ZnO particle to assemble, because existing the gap of nano-scale to show the feature of meso-hole structure between particle.But the method temperature of reaction reaches 1150 ° of C, and is vacuum condition, high to plant and instrument requirement condition, control condition is harsh, production cost is high, is difficult to realize industrialization.
Summary of the invention
The object of the invention is for existing existing, control condition harsh, the production cost high weak point high to plant and instrument requirement condition of meso-porous ZnO of preparing, provide a kind of to plant and instrument less demanding, simple to operate easy to control, production cost is low, product homogeneity is high, can be mass, the method for the reproducible carbon-doped mesoporous ZnO of a kind of simple preparation hamburger structure nano assembly.
The present invention is achieved through the following technical solutions: the method for the carbon-doped mesoporous ZnO of a kind of simple preparation hamburger structure nano assembly, the ethylene glycol (EG) of take is reaction solvent, with the inorganic salt zinc acetate (Zn (Ac) of transition metal
22H
2o) and excessive alkali source (NaOH) be pre-reaction material, add structure directing agent glucose, by induced polymerization and twin polarity field, drive the ZnO nano particle self-assembly that has realized carbon (C) doping, thereby obtain the carbon-doped mesoporous ZnO assembly of hamburger type of high quality, high yield.
In the method for the described carbon-doped mesoporous ZnO of a kind of simple preparation hamburger structure nano assembly, the method for preparing carbon-doped mesoporous ZnO hamburger structure nano assembly comprises the following steps:
(1) Zn (OH)
4 2-the preparation of sol precursor
Get raw material zinc acetate (Zn (Ac)
22H
2o) and ethylene glycol (EG), be made into Zn
2+volumetric molar concentration is the colourless transparent solution A of 0.1～0.4M, carries out magnetic agitation under room temperature; Get sodium hydroxide (NaOH) and EG, be made into and take the solution B that NaOH volumetric molar concentration is 0.4～0.8M, solution B is dropwise added in solution A, through reaction, solution becomes gradually muddy and becomes clear again, treats that solution B drips end, taking 0.02～0.08M glucose is dissolved in wherein, continue to stir 10～20 minutes, solution becomes and connects diaphanous oyster white, and the mixed solution of gained is Zn (OH)
4 2-sol precursor;
(2) the preparation of carbon-doped mesoporous ZnO hamburger structure nano assembly
Mixed solution is transferred in reactor, and through 160～180 ° of C, after 12～24 hours, centrifuge washing, oven dry, obtain carbon-doped mesoporous ZnO hamburger structure nano assembly.
The doped meso-porous ZnO of hamburger structural carbon that adopts the present invention to prepare, its assembly diameter range is at 400～500nm, ZnO nano grain diameter size is about 5.8nm, mesoporous radius average out to 7.6nm, the advantage such as type carbon-doped mesoporous ZnO in hamburger prepared by the present invention has that product cost is low, easy to control, homogeneity is high, output is large, reproducible and applicable scale operation.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of carbon-doped mesoporous ZnO hamburger structure nano assembly of preparation in the embodiment 1 that surveys of the Dutch PW3040/60 of PHILIPS Co. type x-ray diffractometer, wherein: X-coordinate X is angle of diffraction (2 θ), and ordinate zou Y is relative diffracted intensity.Illustration is its little angle x-ray diffraction pattern.
The shape appearance figure of carbon-doped mesoporous ZnO hamburger structure nano assembly of preparation in the S-4800 of Tu2Shi HIT type field emission scanning electron microscope (FE-SEM) observation embodiment 1, illustration is its partial enlarged drawing.
Carbon-doped mesoporous ZnO hamburger structure nano assembly internal structure picture of preparation in the embodiment 1 that the JEM-2100F of Tu3Shi Jeol Ltd. type transmission electron microscope (TEM) observes.
The adsorption isothermal line of carbon-doped mesoporous ZnO hamburger structure nano assembly in the embodiment 1 that the ASAP of Tu4Shi Micromeritics Instrument Corp. U.S.A 2020 type physical adsorption appearances provide, illustration is its graph of pore diameter distribution.
Fig. 5 is the x ray photoelectron spectroscopic analysis figure (XPS) of C 1s in the structure nano assembly of carbon-doped mesoporous ZnO hamburger.
Fig. 6 is carbon-doped mesoporous ZnO hamburger structure nano assembly and each 50mg of business ZnO(in embodiment 1) adsorption effect comparison diagram to the Congo red solution of 30mL (100mg/L).
The meso-porous ZnO nanometer assembly shape appearance figure of preparation in the S-4800 of Tu7Shi HIT type field emission scanning electron microscope (FE-SEM) observation embodiment 2, product presents porous but without fixing exterior appearance, illustration is its partial enlarged drawing.
The carbon doping zinc oxide nanometer granule-morphology figure of preparation in the S-4800 of Tu8Shi HIT type field emission scanning electron microscope (FE-SEM) observation embodiment 3.The inhomogeneous pattern irregularity of product size.
Embodiment
Below by embodiment, the method for the carbon-doped mesoporous ZnO of a kind of simple preparation of the present invention hamburger structure nano assembly is made further and being illustrated.
Embodiment 1
Take 0.48g(2.2 * 10-3mol) Zn (Ac)
22H
2o is dissolved in 22mL ethylene glycol, obtains colourless transparent solution A, carries out magnetic agitation under room temperature; Get NaOH and ethylene glycol, be made into and take NaOH volumetric molar concentration as 0.6M, volume is the solution B of 10mL, solution B is dropwise added in solution A, and reaction for some time, solution becomes gradually muddy and becomes clear again, wait to drip and finish, take 0.2g glucose and be dissolved in wherein, continue to stir 15～20 minutes, solution is colloidal sol shape.Above-mentioned gained colloidal sol is transferred in 40mL reactor, through 160 ° of C, react after 24 hours, centrifuge washing, 60 ° of C are dried, and products obtained therefrom is done to X-ray diffraction, field emission scanning electron microscope, tem study, pore structure analysis, x ray photoelectron spectroscopic analysis and absorption property test.
For carbon-doped mesoporous ZnO hamburger structure nano assembly of preparing in the present embodiment, do X-ray diffraction analysis, result as shown in Figure 1, its X-coordinate X is angle of diffraction (2 θ), ordinate zou Y is relative diffracted intensity, in figure, all diffraction peaks can change into by face-centred cubic structure index the JCPDS in (100), (101), (002) and (102) etc. and international standard powder X-ray RD diffraction card, and 89-0511 is consistent.By formula, calculate known its size and be about 5.8nm.Illustration is its little angle x-ray diffraction pattern, is 1.468 ° locates at 2 θ angles, has the broadening peak that an intensity is not high, illustrate that it is mesoporous material, but the mesoporous degree of order is not high.
For carbon-doped mesoporous ZnO hamburger structure nano assembly of preparing in the present embodiment, do field emission scanning electron microscope analysis, the electromicroscopic photograph obtaining as shown in Figure 2, can find out the symmetrical configuration of hamburger shape ZnO, appearance and size is even, diameter is greatly about 400～500nm, rough, for small-particle forms.
For carbon-doped mesoporous ZnO hamburger structure nano assembly of preparing in the present embodiment, do tem study.As can be seen from Figure 3, carbon-doped mesoporous ZnO hamburger structure nano assembly integral body prepared by the present embodiment is to be piled up and formed by small-particle, and has the cave-shaped pore space structure of ant.
For carbon-doped mesoporous ZnO hamburger structure nano assembly of preparing in the present embodiment, do the test of N2 adsorption desorption, the information obtaining as shown in Figure 4, the sorption isotherm of sample belongs to IV type and has H3 hysteresis loop, and these can further prove that this sample is mesoporous material.Graph of pore diameter distribution in illustration more intuitively reality goes out sample and has narrower pore size distribution, and pore radius is about 7.6nm.In addition, the BET specific surface area of sample is 88m
2g
-1, be 20 times of bibliographical information business ZnO.
For carbon-doped mesoporous ZnO hamburger structure nano assembly of preparing in the present embodiment, do x ray photoelectron spectroscopic analysis.Fig. 5 has shown the wherein further swarming of C 1s power spectrum, by analyze known sample 283.3,284.8,286.2,288.6eV has peak (corresponding Zn-C key, C-C key, O-C-O complex body, C=O and C-O respectively) everywhere, and take C-C key and O-C-O complex body as main.The decolorizing carbon that image-stone China ink is described exists, and C successfully replaces part Zn position and a small amount of O position, realizes the doping of C.
Carbon-doped mesoporous ZnO hamburger structure nano assembly of preparing in the present embodiment is done to absorption property test, the information obtaining as shown in Figure 6, can find out that sample can remove water middle and high concentration organic pollutant (Congo red) at short notice, can reach fast balance, under the same terms, adsorptive capacity is 4 times of business ZnO.
Embodiment 2
Taking 0.48g(2.2 * 10-3mol) Zn (Ac) 22H2O is dissolved in 22mL ethylene glycol, obtains colourless transparent solution A, carries out magnetic agitation under room temperature; Get NaOH and EG, be made into and take NaOH volumetric molar concentration as 0.6M, the solution B that volume is 10mL, dropwise adds solution B in solution A, and reaction for some time, solution becomes gradually muddy and becomes clear again, waits to drip and finishes, and continues to stir 15～20 minutes, and solution is colloidal sol shape.Above-mentioned gained colloidal sol is transferred in 40mL reactor, through 160 ° of C, reacts after 24 hours, centrifuge washing, 60 ° of C are dried.
To in the present embodiment 2 preparation product do field emission scanning electron microscope analysis, the electromicroscopic photograph obtaining as shown in Figure 7, as can be seen from the figure, the meso-porous ZnO of preparing in the present embodiment is that particle is piled up and formed, present cavernous structure, but its overall dimensions is excessive, and without fixing pattern.Illustrate that from the side embodiment 1 is prepared in the process of sample, glucose is not only the carbon source that it provides carbon doping, more aspect the formation of hamburger profile and assembly dimensional homogeneity, is playing important guiding regulating effect.
Embodiment 3: take 0.48g(2.2 * 10-3mol) Zn (Ac) 22H2O is dissolved in 22mL water, obtains colourless transparent solution A, carries out magnetic agitation under room temperature; Get NaOH and be made into the aqueous solution B that volumetric molar concentration is 0.6M, volume is 10mL, and solution B is dropwise added in solution A, reaction for some time, solution becomes gradually muddy and becomes clear again, waits to drip and finishes, take 0.2g glucose and be dissolved in wherein, continue to stir 15～20 minutes, solution is colloidal sol shape.Above-mentioned gained colloidal sol is transferred in 40mL reactor, through 160 ° of C, reacts after 24 hours, centrifuge washing, 60 ° of C are dried.
Product to preparation in the present embodiment 3 is done field emission scanning electron microscope analysis, and as shown in Figure 8, as can be seen from the figure, the sample that the distilled water of take obtains as medium is irregular nano particle to the electromicroscopic photograph obtaining, without assembling sign.Also illustrate that alcohol system plays vital effect for the assembling of hamburger shape meso-porous ZnO.
XRD, FE-SEM, TEM, HRTEM, XPS, result and literature search that pore structure and absorption property are measured show: adopt the preparation-obtained carbon-doped mesoporous ZnO of the inventive method hamburger structure nano assembly, it is the sorbing material successfully synthesizing by current better simply single stage method, it is low that it has cost, output is high, appearance and size good uniformity, circulation ratio high, and merge mesoporous and carbon doping characteristic, it has filled up the blank in low temperature liquid phase single stage method synthesizing blender meso-porous ZnO field, batch production and further Application and Development for this kind of good adsorption performance material for water treatment can play certain pushing effect.
Claims (1)
1. the method for the carbon-doped mesoporous ZnO of simple preparation hamburger structure nano assembly, it is characterized in that preparing in the method for carbon-doped mesoporous ZnO hamburger structure nano assembly at this, the ethylene glycol (EG) of take is reaction solvent, inorganic salt zinc acetate and the excessive alkali source of transition metal of take is pre-reaction material, add structure directing agent glucose, by induced polymerization and twin polarity field, drive the ZnO nano particle self-assembly that realizes carbon (C) doping, obtain the carbon-doped mesoporous ZnO assembly of hamburger type, wherein, the method of preparing carbon-doped mesoporous ZnO hamburger structure nano assembly comprises the following steps:
(1) Zn (OH)
4 2-the preparation of sol precursor
Get raw material zinc acetate and ethylene glycol (EG), be made into Zn
2+volumetric molar concentration is the colourless transparent solution A of 0.1～0.4M, carries out magnetic agitation under room temperature; Get sodium hydroxide and EG, be made into and take the solution B that NaOH volumetric molar concentration is 0.4～0.8M, solution B is dropwise added in solution A, through reaction, solution becomes gradually muddy and becomes clear again, treats that solution B drips end, taking 0.02～0.08M glucose is dissolved in wherein, continue to stir 10～20 minutes, solution becomes and connects diaphanous oyster white, and the mixed solution of gained is Zn (OH)
4 2-sol precursor;
(2) the preparation of carbon-doped mesoporous ZnO hamburger structure nano assembly
Mixed solution is transferred in reactor, and through 160～180 ℃, after 12～24 hours, centrifuge washing, oven dry, obtain carbon-doped mesoporous ZnO hamburger structure nano assembly.
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Non-Patent Citations (4)
| Title |
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| "乙二醇溶剂中纳米氧化锌的制备";陈松;《光谱实验室》;20031130;第20卷(第6期);第937-940页 * |
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