CN103877961A - Carbon-based zinc oxide nanosphere composite material and preparation method thereof - Google Patents
Carbon-based zinc oxide nanosphere composite material and preparation method thereof Download PDFInfo
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- CN103877961A CN103877961A CN201410077963.1A CN201410077963A CN103877961A CN 103877961 A CN103877961 A CN 103877961A CN 201410077963 A CN201410077963 A CN 201410077963A CN 103877961 A CN103877961 A CN 103877961A
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Abstract
The invention relates to a carbon-based zinc oxide nanosphere composite material and a preparation method thereof. The composite material is in a spherical structure consisting of a demineralized carbon-based material and a zinc oxide nanosheet, wherein the diameter of a zinc oxide nanosphere is 4-10 microns. According to the technical scheme, an operation method is simple, the high-temperature calcination is omitted, the specific surface and reaction activity of the synthesized carbon-based zinc oxide nanosphere composite material are greatly increased, and then the performance such as photocatalysis are improved.
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 family 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 of transmitting blue light or black light simultaneously.At present, ZnO is widely applied at aspects such as microelectronics, solar cell window material, microsensors, and is also day by day paid attention at aspects such as photocatalysis, degradating organic dye and sewage disposals.But due to poor surface adsorption property and less specific area, there is serious photoetch problem in single zinc oxide material, thereby greatly reduced its photocatalysis performance.Research shows, ZnO chondritic has higher photocatalysis performance.In addition,, for the pulverous Zinc oxide catalytic being suspended in reaction system, separate 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 has 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 etc., the composites of activated carbon supported zinc oxide demonstrates higher photocatalysis performance.This is mainly that absorption property is stronger because active carbon has higher specific area and flourishing pore structure.Zinc oxide appendix, in activated carbon surface, is not only improved to the specific surface of composite, also can obtain specificity photocatalysis property compared with strong interaction by between itself and carrier, thereby improved 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 by nano granular of zinc oxide appendix in porous charcoal sill surface, in preparation process, need high-temperature calcination, increased material preparation cost.In addition porous active charcoal material surface appendix zinc oxide is mainly taking nano particle as main, and the two-dimensional nanostructures such as nanotube are less, and the raising of its specific area is still had to certain limit.If can be 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,, there are numerous avtive spots in surface irregularity, makes 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 carbon based material is suitably processed, 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 being formed by 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, carbon based material is immersed in mixed solution after going mineral materialization to process, after water-bath is synthetic.
In above-mentioned preparation method, described carbon based material is through going the processing of mineral materialization to comprise following steps:
1) prepare respectively hydrofluoric acid solution and hydrochloric acid solution;
2) take in the carbon based material input hydrofluoric acid solution after screening 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 respectively to ethanol, 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, and time 1-3h.
In step 3), described condensing reflux temperature is 50-90 DEG C, preferably 80 DEG C, and time 1-3h.
In step 4), described NaOH solution is 0.05-0.2mol/L, preferably 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 is formulated in proportion by zinc nitrate and hexamethylenetetramine.
Wherein, described zinc nitrate concentration is 0.01-0.3mol/L, preferably 0.05-0.2mol/L, further preferred 0.1mol/L.
Described zinc nitrate and hexamethylenetetramine mol ratio are 0.2-5:1, preferably 0.5-1.5:1, further preferred 1:1;
Described water-bath synthesis condition is: temperature 70-100 DEG C, preferably 80-95 DEG C; Time 1-5h, preferably 2-4h.
It should be noted that going mineral materialization carbon based material to drop into before mixed solution, need first mixed solution is warming up to required bath temperature, then add mineral materialization 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 spots, by the processing to carbon based material, select suitable water bath condition, greatly improve specific area and the reactivity of carbon based material zinc oxide composite, thereby improve its utilization ratio at aspects such as photocatalysis.Whole technical process is simple, does not need the harsh conditions such as HTHP, microwave, does not need special installation and has the advantages that production efficiency is high, is beneficial to suitability for industrialized production.
Brief description of the drawings
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 are used for illustrating the present invention, but are not used for limiting the scope of the invention.
1) preparing respectively mass fraction is 25% hydrofluoric acid and 15% hydrochloric acid;
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/L NaOH solution soaks 6h.
Step 2, water-bath are synthesized
1) prepare respectively 0.1mol/L zinc nitrate and 0.1mol/L hexamethylenetetramine solution, respectively get in the water heating kettle that 15mL adds 50mL polytetrafluoroethylene (PTFE) and form mixed solution, and mixed solution is heated to 95 DEG C, again semicoke after treatment is immersed in mixed solution, after sealing, put into thermostatic drying chamber clock, Hydrothermal Synthesis 4h, obtains semicoke substrate ZnO nano ball, and its electron scanning micrograph as illustrated in fig. 1 and 2.
Embodiment 2 active carbocoal substrate making ZnO nanospheres
According to the method making ZnO nanosphere of embodiment 1, difference is:
1) semicoke substrate is replaced with to active carbocoal;
2) when semicoke goes to mineralize, hydrochloric acid solution mass fraction is 30%;
3) hydrothermal temperature is made as 60 DEG C.
Making ZnO nanosphere of the absorbent charcoal based end of embodiment 3
According to the method making ZnO nanosphere of embodiment 1, difference is:
1) semicoke substrate is replaced with to active carbon;
2) when active carbon goes to mineralize, hydrochloric acid solution mass fraction is 45%.
3) the hydro-thermal reaction time is made as 2h.
Through above-described embodiment 1-3 gained nano material is detected, due to the successful load in carbon based material surface ZnO nano chondritic, the ZnO nano Particle Phase ratio with traditional, can improve its surface area and absorption property, thereby improves 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 (10)
1. a charcoal base zinc oxide nanosphere composite, is characterized in that, the chondritic being formed by go to mineralize carbon based material and Zinc oxide nano sheet, and the diameter of its zinc oxide nanosphere is 4-10um.
2. the preparation method of charcoal base zinc oxide nanosphere composite described in claim 1, is characterized in that, carbon based material is immersed in mixed solution after going mineral materialization to process, after water-bath is synthetic.
3. preparation method according to claim 2, is characterized in that, described carbon based material is through going the processing of mineral materialization to comprise following steps:
1) prepare respectively hydrofluoric acid solution and hydrochloric acid solution;
2) carbon based material after screening is dropped in hydrofluoric acid solution and heated, 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 respectively to ethanol, NaOH solution soaks 4-8h.
4. preparation method according to claim 3, is characterized in that, in step 2) in, described heating-up temperature is 50-90 DEG C, time 1-3h.
5. preparation method according to claim 3, is characterized in that, in step 3), described condensing reflux temperature is 50-90 DEG C, time 1-3h.
6. preparation method according to claim 2, is characterized in that, described carbon based material is selected from the one in semicoke, active carbocoal, active carbon.
7. preparation method according to claim 2, is characterized in that, described mixed solution is formulated in proportion by zinc nitrate and hexamethylenetetramine; Wherein said zinc nitrate concentration is 0.01-0.3mol/L.
8. preparation method according to claim 7, is characterized in that, described zinc nitrate and hexamethylenetetramine mol ratio are 0.2-5:1.
9. preparation method according to claim 2, is characterized in that, described water-bath synthesis condition is: temperature 70-90 DEG C; Time 1-5h.
10. preparation method according to claim 2, is characterized in that, going mineral materialization carbon based material to drop into before mixed solution, first mixed solution is warming up to required bath temperature, then adds mineral materialization carbon based material and carry out water-bath synthetic reaction.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109526983A (en) * | 2018-12-29 | 2019-03-29 | 中国科学院兰州化学物理研究所 | A method of hydridization antibacterial agent is prepared using oil shale semi-coke |
| 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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| 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 |
| WO2013050570A1 (en) * | 2011-10-05 | 2013-04-11 | Lightlab Sweden Ab | Method for manufacturing nanostructures and cathode for field emission lighting arrangement |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2013050570A1 (en) * | 2011-10-05 | 2013-04-11 | Lightlab Sweden Ab | Method for manufacturing nanostructures and cathode for field emission lighting arrangement |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109526983A (en) * | 2018-12-29 | 2019-03-29 | 中国科学院兰州化学物理研究所 | A method of hydridization antibacterial agent is prepared using oil shale semi-coke |
| CN109526983B (en) * | 2018-12-29 | 2021-07-13 | 中国科学院兰州化学物理研究所 | Method for preparing hybrid antibacterial agent by using oil shale semicoke |
| 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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