CN103877961B - A kind of charcoal base zinc oxide nanosphere composite and preparation method thereof - Google Patents
A kind of charcoal base zinc oxide nanosphere composite and preparation method thereof Download PDFInfo
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- CN103877961B CN103877961B CN201410077963.1A CN201410077963A CN103877961B CN 103877961 B CN103877961 B CN 103877961B CN 201410077963 A CN201410077963 A CN 201410077963A CN 103877961 B CN103877961 B CN 103877961B
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Abstract
The present invention relates to a kind of charcoal base zinc oxide nanosphere composite, the chondritic be made up of go to mineralize carbon based material and Zinc oxide nano sheet, the diameter of its zinc oxide nanosphere is 4-10um.Technical scheme method of operating of the present invention is simple, and without the need to high-temperature calcination, specific surface and the reactivity of synthesized carbon based material zinc oxide nanosphere composite improve greatly, and then improve the performances such as its photocatalysis.
Description
Technical field
The present invention relates to a kind of charcoal base zinc oxide nanosphere composite and preparation method thereof, belong to field of material preparation.
Background technology
ZnO is II-VI race's direct band gap semiconductor material with wide forbidden band, and energy gap is 3.37eV, and exciton binding energy is 60meV, has possessed the supremacy clause launching blue light or black light simultaneously.At present, ZnO is widely applied in microelectronics, solar cell window material, microsensor etc., and is also day by day paid attention in photocatalysis, degradating organic dye and sewage disposal etc.But due to poor surface adsorption property and less specific area, there is serious photoetch problem in single zinc oxide material, thus greatly reduces its photocatalysis performance.Research shows, ZnO chondritic has higher photocatalysis performance.In addition, for the pulverous Zinc oxide catalytic be suspended in reaction system, be separated and reclaim very difficult.Therefore utilize certain solids to do carrier, by catalyst immobilization, and to improve its catalytic effect be that zinc oxide utilizes one of problem demanding prompt solution.
Up to now, someone to have attempted with zeolite, quartz glass substrate, aluminium flake, sand etc. as carrier, adopts sol-gel process or coprecipitation to make zinc oxide load on it, prepares composite photo-catalyst.Because active carbon has the character that other materials cannot replace, as large in specific area, pore structure is flourishing, thermal conductivity is high, wearability is good, the composites of activated carbon supported zinc oxide demonstrates higher photocatalysis performance.This mainly has higher specific area and flourishing pore structure due to active carbon, and absorption property is stronger.By zinc oxide appendix in activated carbon surface, not only increase the specific surface of composite, also obtain specificity photocatalysis property by interaction stronger between itself and carrier, thus improve zinc oxide utilization rate.
At present, the preparation of charcoal base zinc oxide composite mainly contains microemulsion method and infusion process.Although these methods can be successfully surperficial in porous charcoal sill by nano granular of zinc oxide appendix, in preparation process, need high-temperature calcination, add material preparation cost.In addition porous active charcoal material surface appendix zinc oxide is mainly based on nano particle, and the two-dimensional nanostructures such as nanotube are less, still has certain limit to the raising of its specific area.If can in carbon based material surface direct growth, appendix zinc oxide two dimension, three nanostructureds, can greatly improve its specific area and reactivity.But due to carbon based material complicated component, surface irregularity, exists numerous avtive spot, make the growth fraction of zinc oxide ordered nano-structure more difficult.So, seek directly to seem particularly important in the synthetic method of carbon based material superficial growth zinc oxide two dimension, 3-D nano, structure.
Summary of the invention
For above-mentioned defect, the present invention, by suitably processing carbon based material, adopts hydro-thermal method success at carbon based material surface making ZnO nanosphere composite.
To achieve these goals, the present invention adopts following technical scheme:
A kind of charcoal base zinc oxide nanosphere composite, the chondritic be made up of go to mineralize carbon based material and Zinc oxide nano sheet, the diameter of its zinc oxide nanosphere is 4-10um.
The present invention also provides the preparation method of above-mentioned charcoal base zinc oxide nanosphere composite, immerses in mixed solution by carbon based material after going Mineralization process, after water-bath synthesis.
In above-mentioned preparation method, described carbon based material comprises the steps: through going Mineralization process
1) hydrofluoric acid solution and hydrochloric acid solution is prepared respectively;
2) take in the input of the carbon based material after screening hydrofluoric acid solution and heat, filter, and use deionized water rinsing;
3) by step 2) gained carbon based material drops into condensing reflux in hydrochloric acid, and filter, and use deionized water boiling washing, to Cl-being detected;
4) step 3) gained carbon based material is put into ethanol respectively, NaOH solution soaks 4-8h.
In step 1), described hydrofluoric acid mass fraction is 20-30%, preferably 25%; Described hydrochloric acid mass fraction is 15-45%, preferably 15%.
In step 2) in, described heating-up temperature is 50-90 DEG C, preferably 80 DEG C, time 1-3h.
In step 3), described condensing reflux temperature is 50-90 DEG C, preferably 80 DEG C, time 1-3h.
In step 4), described NaOH solution is 0.05-0.2mol/L, preferred 0.08-0.12mol/L.
In above-mentioned preparation method, described carbon based material is selected from the one in semicoke, active carbocoal, active carbon.
In above-mentioned preparation method, described mixed solution by zinc nitrate and hexamethylenetetramine formulated in proportion.
Wherein, described zinc nitrate concentration is 0.01-0.3mol/L, preferred 0.05-0.2mol/L, further preferred 0.1mol/L.
Described zinc nitrate and hexamethylenetetramine mol ratio are 0.2-5:1, preferred 0.5-1.5:1, further preferred 1:1;
Described water-bath synthesis condition is: temperature 70-100 DEG C, preferred 80-95 DEG C; Time 1-5h, preferred 2-4h.
It should be noted that going Mineralization carbon based material to drop into before mixed solution, needing first mixed solution is warming up to required bath temperature, then add Mineralization carbon based material and carry out water-bath synthetic reaction.
Adopt technical scheme of the present invention, can effectively solve carbon based material complicated component, surface irregularity, there is the defect of numerous avtive spot, by the process to carbon based material, select suitable water bath condition, greatly improve specific area and the reactivity of carbon based material zinc oxide composite, thus improve its utilization ratio in photocatalysis etc.Whole technical process is simple, does not need HTHP, the harsh conditions such as microwave, does not need special installation and have the high feature of production efficiency, being beneficial to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the SEM(SEM of the semicoke substrate making ZnO nanosphere of embodiment 1) macrograph.
Fig. 2 is the SEM(SEM of the semicoke substrate making ZnO nanosphere of embodiment 1) high power photo.
Detailed description of the invention
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1 semicoke substrate making ZnO nanosphere
Step one, semicoke, through removing Mineralization, comprise the steps:
1) preparing mass fraction is respectively the hydrofluoric acid of 25% and the hydrochloric acid of 15%;
2) take the semicoke after 10g screening, drop in the hydrofluoric acid of 20mL, at 80 DEG C, heat 2h, filter, and use deionized water rinsing;
3) by step 2) gained semicoke drops in the hydrochloric acid of 20mL, and condensing reflux 2h at 80 DEG C, filters, and uses deionized water boiling washing, to Cl-being detected;
4) step 3) gained semicoke is put into ethanol, 0.1mol/LNaOH solution soaks 6h.
Step 2, water-bath synthesis
1) 0.1mol/L zinc nitrate and 0.1mol/L hexamethylenetetramine solution is prepared respectively, respectively get 15mL to add in the water heating kettle of 50mL polytetrafluoroethylene (PTFE) and form mixed solution, and mixed solution is heated to 95 DEG C, again the semicoke after process is immersed in mixed solution, thermostatic drying chamber clock is put into after sealing, Hydrothermal Synthesis 4h, obtain semicoke substrate ZnO nano ball, its electron scanning micrograph as illustrated in fig. 1 and 2.
Embodiment 2 active carbocoal substrate making ZnO nanosphere
According to the method making ZnO nanosphere of embodiment 1, difference is:
1) semicoke substrate is replaced with active carbocoal;
2) when semicoke goes to mineralize, hydrochloric acid solution mass fraction is 30%;
3) hydrothermal temperature is set to 60 DEG C.
Embodiment 3 absorbent charcoal based end making ZnO nanosphere
According to the method making ZnO nanosphere of embodiment 1, difference is:
1) semicoke substrate is replaced with active carbon;
2) when active carbon goes to mineralize, hydrochloric acid solution mass fraction is 45%.
3) the hydro-thermal reaction time is set to 2h.
Through detecting above-described embodiment 1-3 gained nano material, due to the carbon based material successful load in surface ZnO nano chondritic, the ZnO nano Particle Phase ratio with traditional, can improve its surface area and absorption property, thus improve its Photocatalytic Degradation Property.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (3)
1. a charcoal base zinc oxide nanosphere composite, is characterized in that, the chondritic be made up of go to mineralize carbon based material and Zinc oxide nano sheet, and the diameter of its zinc oxide nanosphere is 4-10 μm; The preparation method of the described carbon based material that goes to mineralize comprises the steps:
1) hydrofluoric acid solution and hydrochloric acid solution is prepared respectively;
2) heat in the carbon based material input hydrofluoric acid solution after screening, filter, and use deionized water rinsing; Described carbon based material is selected from the one in semicoke, active carbocoal, active carbon;
3) by step 2) gained carbon based material drops into condensing reflux in hydrochloric acid, and filter, and use deionized water boiling washing, to Cl being detected
-;
4) by step 3) gained carbon based material puts into ethanol respectively, NaOH solution soaks 4-8h;
In step 2) in, described heating-up temperature is 50-90 DEG C;
In step 3) in, described condensing reflux temperature is 50-90 DEG C.
2. the preparation method of charcoal base zinc oxide nanosphere composite described in claim 1, is characterized in that, immerse in mixed solution by carbon based material after going Mineralization process, after water-bath synthesis;
Described carbon based material comprises the steps: through going Mineralization process
1) hydrofluoric acid solution and hydrochloric acid solution is prepared respectively;
2) heat in the carbon based material input hydrofluoric acid solution after screening, filter, and use deionized water rinsing; Described carbon based material is selected from the one in semicoke, active carbocoal, active carbon;
3) by step 2) gained carbon based material drops into condensing reflux in hydrochloric acid, and filter, and use deionized water boiling washing, to Cl being detected
-;
4) by step 3) gained carbon based material puts into ethanol respectively, NaOH solution soaks 4-8h;
In step 2) in, described heating-up temperature is 50-90 DEG C, time 1-3h;
In step 3) in, described condensing reflux temperature is 50-90 DEG C, time 1-3h;
Described water-bath synthesis condition is: temperature 70-90 DEG C; Time 1-5h;
Described mixed solution by zinc nitrate and hexamethylenetetramine formulated in proportion; Wherein said zinc nitrate concentration is 0.01-0.3mol/L; Described zinc nitrate and hexamethylenetetramine mol ratio are 0.2-5:1.
3. preparation method according to claim 2, is characterized in that, going Mineralization carbon based material to drop into before mixed solution, first mixed solution is warming up to required bath temperature, then adds Mineralization carbon based material and carry out water-bath synthetic reaction.
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| CN111974374A (en) * | 2020-08-20 | 2020-11-24 | 昆明理工大学 | Preparation method of biochar modified nano ZnO composite powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1724138A (en) * | 2005-06-22 | 2006-01-25 | 中山大学 | Porous carbon adsorbing agent containing nano zinc oxide micropartical and its preparation process and application |
| CN103145113A (en) * | 2011-12-07 | 2013-06-12 | 中国科学院合肥物质科学研究院 | Micro-nano structure zinc oxide-carbon composite pellet and preparation method thereof |
| CN103535376A (en) * | 2013-09-15 | 2014-01-29 | 浙江理工大学 | Preparation method of nanometer zinc oxide-bamboo charcoal composite particle with antibacterial and adsorption functions |
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| CN1724138A (en) * | 2005-06-22 | 2006-01-25 | 中山大学 | Porous carbon adsorbing agent containing nano zinc oxide micropartical and its preparation process and application |
| CN103145113A (en) * | 2011-12-07 | 2013-06-12 | 中国科学院合肥物质科学研究院 | Micro-nano structure zinc oxide-carbon composite pellet and preparation method thereof |
| CN103535376A (en) * | 2013-09-15 | 2014-01-29 | 浙江理工大学 | Preparation method of nanometer zinc oxide-bamboo charcoal composite particle with antibacterial and adsorption functions |
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