CN103623823B - Composite microsphere with carbon sphere nucleus and CuO shell and preparation method and application thereof - Google Patents
Composite microsphere with carbon sphere nucleus and CuO shell and preparation method and application thereof Download PDFInfo
- Publication number
- CN103623823B CN103623823B CN201310662396.1A CN201310662396A CN103623823B CN 103623823 B CN103623823 B CN 103623823B CN 201310662396 A CN201310662396 A CN 201310662396A CN 103623823 B CN103623823 B CN 103623823B
- Authority
- CN
- China
- Prior art keywords
- carbon ball
- cuo
- shell
- complex microsphere
- shell type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 84
- 239000004005 microsphere Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000002131 composite material Substances 0.000 title abstract description 6
- 229920002472 Starch Polymers 0.000 claims abstract description 31
- 235000019698 starch Nutrition 0.000 claims abstract description 31
- 239000008107 starch Substances 0.000 claims abstract description 31
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000011258 core-shell material Substances 0.000 claims description 38
- 239000002351 wastewater Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 12
- 229940012189 methyl orange Drugs 0.000 claims description 12
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims description 11
- 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 claims description 11
- 229940043267 rhodamine b Drugs 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001592 potato starch Polymers 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 2
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 239000002078 nanoshell Substances 0.000 claims 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 87
- 238000000034 method Methods 0.000 abstract description 28
- 239000002245 particle Substances 0.000 abstract description 6
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000008213 purified water Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 230000008569 process Effects 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 229960004643 cupric oxide Drugs 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 229920001661 Chitosan Polymers 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920002261 Corn starch Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000008120 corn starch Substances 0.000 description 5
- 229940099112 cornstarch Drugs 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000004237 Crocus Nutrition 0.000 description 1
- 241000596148 Crocus Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229920002752 Konjac Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 235000010485 konjac Nutrition 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a composite microsphere with a carbon sphere nucleus and a CuO shell. A carbon sphere is used as the nucleus, a shell layer consisting of CuO nanometer particles is used as the shell layer of the composite microsphere, the shell thickness is not smaller than 5 nm, and the nucleus diameter is smaller than 300 nm. The diameter of the prepared composite microsphere with the carbon sphere nucleus and the CuO shell is 200 nm to 1 micron. The carbon sphere is used as the nucleus. First, natural starch is dissolved, and then, a starch solution is poured in an autoclave to carry out hydro-thermal synthesis, thereby forming a polyhydroxy carbon sphere. Finally, a copper source is directly added to the water solution of the polyhydroxy carbon sphere to further carry out hydro-thermal synthesis, a copper oxide precursor reacts with the hydroxy of the carbon sphere, and the composite microsphere with the carbon sphere nucleus and the CuO shell is finally obtained through the subsequent processing of centrifugal, washing and drying. According to the obtained method, the carbon sphere is used as the nucleus, CuO is coated on the surface of the nucleus to form the shell layer, and the particle size is uniformly distributed and is at a submicron grade, so that the CuO photocatalyst performance can be improved. The method has great significance in a water treatment method for organic pollutants in purified water.
Description
Technical field
The invention belongs to technical field of composite materials, be raw material in particular to a kind of native starch, prepared the carbon ball of uniform particle diameter by Hydrothermal Synthesis, then add the further Hydrothermal Synthesis in copper source and prepare the preparation method that can be used for the carbon ball CuO core-shell type complex microsphere processing organic pollutants.
Background technology
The Bohai Sea is the unique type semienclosed inland sea of China, for Tianjin, Hebei, Shandong and Liaoning San Sheng mono-city institute around, its exchange of seawater ability, marine ecosystems are more fragile, large-scale regionl development brings larger pressure to Marine Environment of Bohai Sea, thus adverse effect is caused to the marine eco-environment, huge Lu Yuan effluent pressure is the main cause causing Bohai environment to worsen, the major pollutants of land source emission are chemical oxygen consumption (COC), petroleum-type, organic pollution, inorganic nitrogen and phosphate etc., what be especially worth people to pay close attention to is, organic pollution has half volatile, the characteristic of biological high enrichment, to the marine eco-environment, there is height harmfulness.
Many patents are about the process of research organic wastewater, such as: patent publication No. is the method that patent reports chitosan magnetic adsorbent removal sulfonic-group-containing dye in alkaline waste water of CN102107980A, first, shitosan is dissolved in ferric chloride in aqueous solution, solid can be separated out after adding ethanol, the solid of separating out after filtration, mix with Nanometer Magnetite after washing, cross-linking reaction is carried out again with crosslinking agent glutaraldehyde water solution, namely chitosan magnetic adsorbent is obtained, then the chitosan magnetic adsorbent obtained is joined warp in the alkaline waste water solution containing sulfonic group dyestuff, stir, magnetic separation, dry the chitosan magnetic adsorbent obtaining absorbing dye, finally, the chitosan magnetic adsorbent of absorbing dye is joined in the aqueous solution containing desorbing agent, chitosan magnetic adsorbent and dyestuff can be obtained to recycle through stirring, filtering.The patent publication No. load Er that has been the patent research of CN102078807A
3+: YAlO
3/ TiO
2photochemical catalyst degrade to the degradation effect of organic pollution under visible light illumination, by the conversion luminescence agent Er containing rare earth Er
3+: YAlO
3be doped to TiO
2in powder, and both bonds are carried on spheric active carbon surface, both expand TiO
2optical absorption edge, saved the energy, achieved TiO again
2recycling, greatly reduce use cost.The patent publication No. technique that to be the patent research of 101343135 adopt electrodialysis and rectifying to combine removes the method for the formic acid of low concentration in water, acetic acid or its mixture, the present invention can remove the organic acid in water by electrodialysis process, and can reach by distillation concentrated acid solution the object reclaiming high concentrated acid.Patent publication No. is that the patent of CN102942281A adopts secondary flocculation sediment-secondary membrane separation-evaporation and concentration process integration route processing, during the condensed water of the light phase waste water of centrifuge and one-level UF membrane is adopted and flocculation sediment-evaporation-UF membrane process integration route process, waste water after process, its COD reaches country-level water discharge standard.The patent No. be 200610129857 patent micro-oxygen bioremediation of there was reported energy-conservation odorless the organic matter in waste water is degraded, while removal COD, reduce the colourity of waste water and improve the biodegradability of hardly degraded organic substance waste water, in addition, the patent No. be 03155006 patent be investigated the organic wastewater that the process of high speed electrolytic oxidizing treatment contains aminopolycanboxylic acid.In sum, at present, also there are the following problems: (1) complicated process of preparation for the method for process organic wastewater, and postprocessing working procedures is various, is unfavorable for industrial applications; (2) energy consumption is high, is unfavorable for economize energy; (3) process organic limitednumber, the scope of application is narrow; (4) treatment process cost is high, is unfavorable for industrialization promotion.Photocatalytic Oxidation With Semiconductors technology has outstanding advantage and very strong potential using value as a kind of method for treating water in process organic wastewater, Photocatalytic Oxidation With Semiconductors technology is widely used in the degraded of Organic Pollutants In Water, photocatalytic oxidation is because of under the irradiation of sunshine or ultraviolet light, organic pollution in energy photocatalytic degradation water, make it be degraded to nontoxic Small molecular, do not cause the advantages such as secondary pollution to become the method for the eliminating organic pollutant of current most application prospect to environment.Therefore, prepare photochemical catalyst that Cheap highly effective, technique simply processes organic wastewater and become the primary difficult problem that needs at present overcome.
Summary of the invention
The object of the invention is to overcome the shortcoming existed in prior art, provide one with carbon ball for core, CuO nano particle is the carbon ball CuO core-shell type complex microsphere of complex microsphere shell.The preparation method of this complex microsphere is for core with carbon ball, first native starch is dissolved, then starch solution is put into autoclave and carry out Hydrothermal Synthesis, thus form polyhydroxy carbon ball, finally direct aqueous solution copper source being added above-mentioned polyhydroxy carbon ball, further Hydrothermal Synthesis, the presoma of cupric oxide and the hydroxyl reaction of carbon ball, again through centrifugal, washing, dry subsequent treatment, finally obtain carbon ball CuO core-shell type complex microsphere; The carbon ball of gained is core, and CuO is coated on its surface and forms shell, even particle size distribution, and particle diameter at submicron order, thus can improve the method for CuO photocatalysis performance, significant to the method for the water treatment of purification organic pollutants.
Object of the present invention is achieved through the following technical solutions:
A kind of carbon ball CuO core-shell type complex microsphere, with carbon ball for core, the complex microsphere shell that shell is made up of CuO nano particle, shell is thick is >=5nm; Nuclear diameter is <300nm, and the diameter of prepared carbon ball CuO core-shell type complex microsphere is 200nm ~ 1 μm.
The preparation method of described carbon ball CuO core-shell type complex microsphere, specifically comprises the steps:
(1) preparation of starch solution: native starch is dissolved in distilled water, room temperature-100 DEG C stirs 0.5 ~ 24 hour, naturally cools to room temperature, is mixed with the starch solution that concentration is 1 ~ 50mg/mL;
(2) preparation of polyhydroxy carbon ball: pour in autoclave by the starch solution prepared by step 1, at 120-180 DEG C of Water Under thermal response 6-24h, naturally cools to room temperature, namely obtains carbon ball solution;
(3) again copper source is directly joined in above-mentioned carbon ball solution, every mL carbon ball solution adds 0.001-1g copper source, after stirring, Hydrothermal Synthesis 6-48h is carried out further at 120-200 DEG C, naturally cool to room temperature, again through centrifugal, washing, 60-120 DEG C dry 8-24h subsequent treatment, finally obtain carbon ball CuO core-shell type complex microsphere powder;
In step 1, described native starch is cereal starch, potato starch or bean starch.
In step 3, described copper source is copper sulphate, copper nitrate, copper chloride or Schweinfurt green.
The preferred value of the starch solution concentration in described step (1) is 10 ~ 25mg/mL.
The preferred value of the copper source addition in described step (3) is that every mL carbon ball solution adds 0.01-0.05g copper source.
The application of described carbon ball CuO core-shell type complex microsphere, for the degraded of the organic pollution in waste water, wherein said organic pollution is specially methyl orange, methyl blue or rhodamine B.
Reaction mechanism of the present invention is:
When starch solution polycondensation reaction will occur and carbonization through hydro-thermal reaction, form polyhydroxy carbon ball particle structure, when adding the further hydro-thermal reaction in copper source, the presoma Kocide SD and polyhydroxy carbon ball that generate cupric oxide are carried out condensation reaction dry out, finally obtain carbon ball CuO core-shell type complex microsphere.
The present invention compared with prior art tool has the following advantages and effect:
(1) the present invention adopts starch to be that core has obvious superiority.The remarkable advantages such as native starch has biodegradable, good biocompatibility, and non-toxic and raw material sources are extensive, cheap.
(2) micro-structural of carbon ball CuO core-shell type complex microsphere prepared of the present invention as: the diameter of complex microsphere and shell is thick can by regulating the control such as mass ratio, the concentration in copper source, the temperature and time of hydro-thermal reaction of carbon ball and cupric oxide, simple to operate.
(3) the present invention utilizes carbon ball for core, and the complex microsphere of cupric oxide prepared by shell has good visible light absorption, under simulated solar irradiation, irradiate methyl orange solution, and the degradation rate of methyl orange, up to 97.3%, is conducive to making full use of sunshine, economize energy.
(4) the carbon ball that prepared by the present invention is core, and the cupric oxide photocatalytic degradation efficiency of the complex microsphere of cupric oxide prepared by shell in waste water treatment applications field relative to the hollow structure of bibliographical information is high by about 15%, and better effects if, is with a wide range of applications.
(5) present invention process process is simple, environmental friendliness, instrument and equipment are cheap, has good feasibility.
(6) the carbon ball CuO core-shell type complex microsphere prepared by the present invention has good degradation effect to the organic pollution in waste water, and organic degradation rate reaches more than 95%.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph (SEM) of the polyhydroxy carbon ball obtained in embodiment 4.
Fig. 2 is the stereoscan photograph (SEM) of the carbon ball CuO core-shell type complex microsphere obtained in embodiment 5
Detailed description of the invention
Below in conjunction with embodiment, further detailed description is done to the present invention, but embodiments of the present invention are not limited thereto.
The method of testing of carbon ball CuO core-shell type complex microsphere absorption property of the present invention for: obtained carbon ball CuO core-shell type complex microsphere powder is joined in the simulative organic wastewater solution of methyl orange/methyl blue/rhodamine B, in photocatalytic reaction device, adsorb 30min make it to reach adsorption equilibrium, the absorbance recording now methyl orange/methyl blue/rhodamine B solution is A
0, under the irradiation of simulated solar irradiation, react 2-12h, finally, the absorbance of methyl orange/methyl blue/rhodamine B is A
n, record the absorbance changes delta A=A of methyl orange/methyl blue/rhodamine B before and after reaction
0-A
n, then the degradation rate of methyl orange/methyl blue/rhodamine B is η=Δ A/A
0* 100%.
Embodiment 1
120mg potato starch is dissolved in 120mL distilled water, 2h is dissolved under stirring at 100 DEG C, naturally cool to room temperature, then obtained starch solution is poured in autoclave, Hydrothermal Synthesis 12h is carried out at 180 DEG C, naturally cool to room temperature, the diameter of gained carbon ball is 200nm, and add 0.1793g copper nitrate, stirred at ambient temperature is even, further at 180 DEG C of hydro-thermal reaction 10h, naturally cool to room temperature, through centrifugal, washing, at 80 DEG C of dry 10h, namely obtain the carbon ball CuO core-shell type complex microsphere that diameter is 300nm, shell is thick is about 50nm.
Weigh 10mg carbon ball CuO core-shell type complex microsphere, add the methyl orange solution that 10mL concentration is 10mg/L, in camera bellows, stir 30min make it to reach adsorption equilibrium, then, under simulated solar irradiation, irradiate 6h, the degradation rate being recorded methyl orange by ultraviolet-uisible spectrophotometer is 65%.
Embodiment 2
1200mg potato starch is dissolved in 120mL distilled water, 5h is dissolved at 100 DEG C, naturally cool to room temperature, then obtained starch solution is poured in autoclave, Hydrothermal Synthesis 16h is carried out at 170 DEG C, naturally cool to room temperature, the diameter of gained carbon ball is 280nm, and add 1.3424g copper nitrate, stirred at ambient temperature is even, further at 180 DEG C of hydro-thermal reaction 24h, naturally cool to room temperature, through centrifugal, washing, at 100 DEG C of dry 8h, namely obtain the carbon ball CuO core-shell type complex microsphere that diameter is 330nm, shell is thick is about 25nm.
Weigh 10mg carbon ball CuO core-shell type complex microsphere, add the methyl orange solution that 10mL concentration is 10mg/L, in camera bellows, stir 30min make it to reach adsorption equilibrium, then, under simulated solar irradiation, irradiate 6h, the degradation rate being recorded methyl orange by ultraviolet-uisible spectrophotometer is 97.2%.
Embodiment 3
1200mg konjak starch is dissolved in 150mL distilled water, at room temperature dissolve 24h, then obtained starch solution is poured in autoclave, Hydrothermal Synthesis 48h is carried out at 120 DEG C, naturally cool to room temperature, the diameter of gained carbon ball is 880nm, add 7.5120g copper nitrate, stirred at ambient temperature is even, further at 200 DEG C of hydro-thermal reaction 24h, naturally cools to room temperature, through centrifugal, washing, at 60 DEG C of dry 24h, namely obtain the carbon ball CuO core-shell type complex microsphere that diameter is 1000nm, shell is thick is about 60nm.
Weigh 10mg carbon ball CuO core-shell type complex microsphere, add the methyl blue solution that 10mL concentration is 10mg/L, in camera bellows, stir 30min make it to reach adsorption equilibrium, then, under simulated solar irradiation, irradiate 10h, the degradation rate being recorded methyl blue by ultraviolet-uisible spectrophotometer is 93.6%.
Embodiment 4
2400mg cornstarch is dissolved in 150mL distilled water, 3h is dissolved at 100 DEG C, then obtained starch solution is poured in autoclave, Hydrothermal Synthesis 16h is carried out at 150 DEG C, naturally cool to room temperature, (as shown in Figure 1, the diameter of the polyhydroxy carbon ball prepared by cornstarch is about 100-150nm) add 0.5378g Schweinfurt green, stirred at ambient temperature is even, further at 180 DEG C of hydro-thermal reaction 12h, naturally cool to room temperature, through centrifugal, washing, at 120 DEG C of dry 6h, namely the carbon ball CuO core-shell type complex microsphere that diameter is 220nm is obtained, shell is thick is about 35nm.
Weigh 10mg carbon ball CuO core-shell type complex microsphere, add the methyl blue solution that 10mL concentration is 15mg/L, in camera bellows, stir 30min make it to reach adsorption equilibrium, then, under simulated solar irradiation, irradiate 2h, the degradation rate being recorded methyl blue by ultraviolet-uisible spectrophotometer is 83.2%.
Embodiment 5
5000mg cornstarch is dissolved in 100mL distilled water, dissolves 10h at 100 DEG C, then obtained starch solution is poured in autoclave, Hydrothermal Synthesis 16h is carried out at 160 DEG C, naturally cool to room temperature, the diameter of gained carbon ball is 160nm, adds 1.7524g Schweinfurt green, stirred at ambient temperature is even, further at 120 DEG C of hydro-thermal reaction 48h, naturally cool to room temperature, through centrifugal, washing, at 90 DEG C of dry 10h, namely obtain carbon ball CuO core-shell type complex microsphere.As shown in Figure 2, the polyhydroxy carbon ball obtained by cornstarch is the diameter of carbon ball CuO core-shell type complex microsphere prepared by core is about 200-300nm, and shell is thick is 20-70nm.
Weigh 10mg carbon ball CuO core-shell type complex microsphere, add the rhodamine B solution that 10mL concentration is 10mg/L, in camera bellows, stir 30min make it to reach adsorption equilibrium, then, under simulated solar irradiation, irradiate 6h, (at pre-irradiation, methyl orange is obvious crocus, after illumination 6h, the aqueous solution of methyl orange is colourless substantially) degradation rate that records rhodamine B by ultraviolet-uisible spectrophotometer is 97.3%.
Embodiment 6
3000mg cornstarch is dissolved in 120mL distilled water, 5h is dissolved at 100 DEG C, then obtained starch solution is poured in autoclave, Hydrothermal Synthesis 16h is carried out at 160 DEG C, naturally cool to room temperature, the diameter of gained carbon ball is 280nm, add 0.7524g Schweinfurt green, stirred at ambient temperature is even, further at 160 DEG C of hydro-thermal reaction 20h, naturally cools to room temperature, through centrifugal, washing, at 90 DEG C of dry 10h, namely obtain the carbon ball CuO core-shell type complex microsphere that diameter is 300nm, shell is thick is about 10nm.
Weigh 10mg carbon ball CuO core-shell type complex microsphere, add the rhodamine B solution that 10mL concentration is 15mg/L, in camera bellows, stir 30min make it to reach adsorption equilibrium, then, under simulated solar irradiation, irradiate 0.5h, the degradation rate being recorded rhodamine B by ultraviolet-uisible spectrophotometer is 29.8%.
From embodiment 2 and embodiment 6, the hydrothermal temperature of carbon ball and the hydro-thermal time suitable time can obtain the homogeneous carbon ball of domain size distribution, add copper source further, select suitable hydrothermal temperature and hydro-thermal time can obtain the carbon ball CuO core-shell type complex microsphere of complete crystallization, and the ratio in carbon ball and copper source will ensure that the surface of the cupric oxide generated is exposed to the absorption increased organic pollution and improves degradation rate as far as possible, therefore, its photocatalytic degradation effect is better, and organic degradation rate can reach more than 90%.
Claims (7)
1. a carbon ball CuO core-shell type complex microsphere, is characterized by this complex microsphere with carbon ball for core, the complex microsphere shell that shell is made up of CuO nano particle, and shell is thick is >=5nm; Nuclear diameter is <300nm, and the diameter of prepared carbon ball CuO core-shell type complex microsphere is 200nm ~ 1 μm.
2. the preparation method of carbon ball CuO core-shell type complex microsphere as claimed in claim 1, is characterized by and comprise the steps:
(1) preparation of starch solution: native starch is dissolved in distilled water, room temperature-100 DEG C stirs 0.5 ~ 24 hour, naturally cools to room temperature, is mixed with the starch solution that concentration is 1 ~ 50mg/mL;
(2) preparation of polyhydroxy carbon ball: pour in autoclave by the starch solution prepared by step 1, at 120-180 DEG C of Water Under thermal response 6-24h, naturally cools to room temperature, namely obtains carbon ball solution;
(3) again copper source is directly joined in above-mentioned carbon ball solution, every mL carbon ball solution adds 0.001-0.05g copper source, after stirring, Hydrothermal Synthesis 6-48h is carried out further at 120-200 DEG C, naturally cool to room temperature, again through centrifugal, washing, 60-120 DEG C dry 8-24h subsequent treatment, finally obtain carbon ball CuO core-shell type complex microsphere powder.
3. the preparation method of carbon ball CuO core-shell type complex microsphere as claimed in claim 2, it is characterized by step 1, described native starch is cereal starch, potato starch or bean starch.
4. the preparation method of carbon ball CuO core-shell type complex microsphere as claimed in claim 2, it is characterized by step 3, described copper source is copper sulphate, copper nitrate, copper chloride or Schweinfurt green.
5. the preparation method of carbon ball CuO core-shell type complex microsphere as claimed in claim 2, the preferred value that it is characterized by the starch solution concentration in described step (1) is 10 ~ 25mg/mL.
6. the preparation method of carbon ball CuO core-shell type complex microsphere as claimed in claim 2, the preferred value that it is characterized by the copper source addition in described step (3) is that every mL carbon ball solution adds 0.01-0.05g copper source.
7. the application of carbon ball CuO core-shell type complex microsphere as claimed in claim 1, it is characterized by the degraded for the organic pollution in waste water, wherein said organic pollution is specially methyl orange, methyl blue or rhodamine B.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310662396.1A CN103623823B (en) | 2013-12-06 | 2013-12-06 | Composite microsphere with carbon sphere nucleus and CuO shell and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310662396.1A CN103623823B (en) | 2013-12-06 | 2013-12-06 | Composite microsphere with carbon sphere nucleus and CuO shell and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103623823A CN103623823A (en) | 2014-03-12 |
CN103623823B true CN103623823B (en) | 2015-06-10 |
Family
ID=50205487
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310662396.1A Expired - Fee Related CN103623823B (en) | 2013-12-06 | 2013-12-06 | Composite microsphere with carbon sphere nucleus and CuO shell and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103623823B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106749465A (en) * | 2016-11-30 | 2017-05-31 | 湖北芳通药业股份有限公司 | A kind of process for refining of 17 ɑ hydroxyl progesterones |
CN107051459A (en) * | 2017-03-30 | 2017-08-18 | 常州大学 | A kind of preparation method of hud typed cupric oxide/bronzing catalyst |
CN110237675B (en) * | 2019-07-17 | 2021-06-11 | 烟台大学 | Preparation method and application of high-activity fluorine fixing agent |
CN113045318B (en) * | 2021-05-11 | 2022-08-12 | 西北工业大学 | Submicron carbide ceramic hollow microsphere and preparation method thereof |
CN113830749A (en) * | 2021-09-24 | 2021-12-24 | 吉林大学 | Method for preparing core-shell structure metal oxide and core-shell structure metal oxide |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102464304A (en) * | 2010-11-12 | 2012-05-23 | 中国科学院过程工程研究所 | Multi-shell-layer metal oxide hollow ball and preparation method thereof |
CN102580525A (en) * | 2012-03-21 | 2012-07-18 | 河北工业大学 | Method for using activated carbon load copper oxide composite catalyst to absorb nitrogenous oxide |
CN102600857A (en) * | 2012-03-01 | 2012-07-25 | 浙江大学 | Preparation method of carbon ball-loaded CuO-BiVO4 heterojunction compound photocatalyst |
CN103230790A (en) * | 2013-04-10 | 2013-08-07 | 武汉理工大学 | A visible light catalyst of compound carbon sphere / indium oxyhydroxide and a preparation method thereof |
-
2013
- 2013-12-06 CN CN201310662396.1A patent/CN103623823B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102464304A (en) * | 2010-11-12 | 2012-05-23 | 中国科学院过程工程研究所 | Multi-shell-layer metal oxide hollow ball and preparation method thereof |
CN102600857A (en) * | 2012-03-01 | 2012-07-25 | 浙江大学 | Preparation method of carbon ball-loaded CuO-BiVO4 heterojunction compound photocatalyst |
CN102580525A (en) * | 2012-03-21 | 2012-07-18 | 河北工业大学 | Method for using activated carbon load copper oxide composite catalyst to absorb nitrogenous oxide |
CN103230790A (en) * | 2013-04-10 | 2013-08-07 | 武汉理工大学 | A visible light catalyst of compound carbon sphere / indium oxyhydroxide and a preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN103623823A (en) | 2014-03-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104959141B (en) | A kind of loaded Cu/Cu2The redox graphene of O photochemical catalysts/amorphous carbon composite and its preparation method and application | |
Shao et al. | An all-in-one strategy for the adsorption of heavy metal ions and photodegradation of organic pollutants using steel slag-derived calcium silicate hydrate | |
CN103623823B (en) | Composite microsphere with carbon sphere nucleus and CuO shell and preparation method and application thereof | |
CN103433060B (en) | Core-shell TiO2/ZnIn2S4 composite photocatalyst and preparation method and application thereof | |
Li et al. | Recent developments in functional nanocomposite photocatalysts for wastewater treatment: a review | |
Zhang et al. | Facile preparation of high-performance hydrochar/TiO2 heterojunction visible light photocatalyst for treating Cr (VI)-polluted water | |
Zhao et al. | Advances in template prepared nano‐oxides and their applications: polluted water treatment, energy, sensing and biomedical drug delivery | |
Meng et al. | Sonocatalytic degradation of Rhodamine B in the presence of C60 and CdS coupled TiO2 particles | |
CN103599802A (en) | Preparation method of silver phosphate/graphene nanocomposite | |
CN106311206A (en) | Titanium dioxide/graphene composite nanometer photocatalyst, method for preparing same and application of titanium dioxide/graphene composite nanometer photocatalyst | |
CN112718009B (en) | PDI/MOF heterojunction photocatalyst and preparation method and use method thereof | |
CN110776049A (en) | Method for treating organic wastewater by activating peroxymonosulfate with functionalized zirconium-based metal organic framework/protonated carbon nitride composite material | |
Sun et al. | Effective removal of nanoplastics from water by cellulose/MgAl layered double hydroxides composite beads | |
CN113731395B (en) | Zinc stannate photocatalyst rich in oxygen vacancies, preparation method and application | |
CN109046450B (en) | BiOCl/(BiO)2CO3Preparation method and application of loaded cellulose acetate/fibroin hybrid membrane | |
CN108654642B (en) | Efficient composite photocatalyst Ag with visible light response2Preparation method of O/alpha-FeOOH | |
CN109647349B (en) | Modified ferroferric oxide nano compound for removing heavy metal ions and organic matters in industrial wastewater and preparation method thereof | |
Zhang et al. | Construction of precious metal-loaded BiOI semiconductor materials with improved photocatalytic activity for microcystin-LR degradation | |
CN112619671A (en) | Binary composite nano catalyst and preparation method and application thereof | |
Su et al. | Fabrication of magnetic Fe3O4@ SiO2@ Bi2O2CO3/rGO composite for enhancing its photocatalytic performance for organic dyes and recyclability | |
Zhang et al. | Carbon nano-onions (CNOs)/TiO 2 composite preparation and its photocatalytic performance under visible light irradiation | |
Yuan et al. | Agricultural bamboo leaf waste as carbon precursor for the preparation of Cu-Al/biomass fiber adsorption and its application in the removal of ammonia nitrogen pollutants from domestic wastewater | |
CN109092360A (en) | A kind of preparation method of the nano hybridization gel mould for catalytic degradation organic matter | |
Li et al. | Progress of Copper‐based Nanocatalysts in Advanced Oxidation Degraded Organic Pollutants | |
CN111203245B (en) | Composite photocatalyst for efficiently degrading ciprofloxacin and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150610 |
|
CF01 | Termination of patent right due to non-payment of annual fee |