CN104291314A - Preparation method of mesoporous imprinted carbon nanospheres - Google Patents
Preparation method of mesoporous imprinted carbon nanospheres Download PDFInfo
- Publication number
- CN104291314A CN104291314A CN201410499699.0A CN201410499699A CN104291314A CN 104291314 A CN104291314 A CN 104291314A CN 201410499699 A CN201410499699 A CN 201410499699A CN 104291314 A CN104291314 A CN 104291314A
- Authority
- CN
- China
- Prior art keywords
- mesoporous
- drying
- nanometer ball
- carbon nanometer
- nano carbon
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 7
- 229910052799 carbon Inorganic materials 0.000 title abstract description 7
- 239000002077 nanosphere Substances 0.000 title abstract 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 44
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000002444 silanisation Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 13
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 238000009826 distribution Methods 0.000 claims abstract description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 241000143432 Daldinia concentrica Species 0.000 claims description 45
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 45
- 238000001035 drying Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000005119 centrifugation Methods 0.000 claims description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 230000004048 modification Effects 0.000 claims description 19
- 238000012986 modification Methods 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229960001866 silicon dioxide Drugs 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000006884 silylation reaction Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- 241000628997 Flos Species 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 239000003738 black carbon Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- -1 γ-(methacryloxypropyl) propyl Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 229910014033 C-OH Inorganic materials 0.000 claims description 2
- 229910014570 C—OH Inorganic materials 0.000 claims description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 241000237502 Ostreidae Species 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 2
- 229950004394 ditiocarb Drugs 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000002932 luster Substances 0.000 claims description 2
- 238000006011 modification reaction Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000020636 oyster Nutrition 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000012876 topography Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 2
- 230000000274 adsorptive effect Effects 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
本发明涉及一种介孔印迹碳纳米球的制备方法，是以葡萄糖为碳源、二氧化硅为介孔模板，经水热合成制备介孔碳纳米球，经硅烷化修饰改性、表面接枝、交联反应、洗涤除去二苯并噻吩，制成介孔印迹碳纳米球，此制备方法工艺先进合理，数据翔实精确，产物形貌好，为黑色圆形颗粒，颗粒直径≤250nm，产物纯度达98%，介孔形貌良好，孔径分布集中于3-5nm，印迹效果明显，对二苯并噻吩的吸附在20min时达到平衡，饱和吸附量为134.08mg/g，是十分理想的介孔印迹碳纳米球的制备方法。
The invention relates to a method for preparing mesoporous imprinted carbon nanospheres, which uses glucose as a carbon source and silicon dioxide as a mesoporous template to prepare mesoporous carbon nanospheres through hydrothermal synthesis, modified by silanization, surface contact branching, cross-linking reaction, and washing to remove dibenzothiophene to make mesoporous imprinted carbon nanospheres. This preparation method has advanced and reasonable technology, detailed and accurate data, and good product appearance. The purity reaches 98%, the mesopore shape is good, the pore size distribution is concentrated in 3-5nm, and the imprinting effect is obvious. The adsorption of dibenzothiophene reaches equilibrium in 20 minutes, and the saturated adsorption capacity is 134.08mg/g, which is a very ideal medium. A method for preparing hole-imprinted carbon nanospheres.
Description
Technical field
The present invention relates to a kind of preparation method of mesoporous trace Nano carbon balls, belong to the technical field of carbon-organic composite material surface chemical modification and application.
Background technology
Containing S-contained substances such as thiophene, mercaptan, thioethers in fuel oil, can discharge oxysulfide in combustion, cause the environmental problem such as haze, acid rain, it is very important for carrying out deep removal to S-contained substance in oil product.
Conventional desulfurizing oil technology completes under the reaction conditions of high temperature, high pressure, high energy consumption, heavily contaminated, be difficult to realize deep desulfuration, surface molecule print adsorption desulfurize is a kind of novel oil product deep desulfuration technology, reaction conditions is gentle, energy consumption is low, cost is low, renewable, pollution is few, there is the advantage of efficient specific recognition absorption, while realizing deep desulfuration, also can obtain high value added product, there is great researching value and application prospect.
Surface molecule print adsorption desulfurize, produces trace hole in stromal surface, the size of target molecule, configuration, Chemical recognition site is marked in solid substrate, obtains the efficient selective to target molecule and adsorptive power.
Meso-porous carbon material has that electrical and thermal conductivity performance, chemical stability are good, the advantage of acid and alkali-resistance, there is abundant meso-hole structure, add the specific surface area for trace, can effectively improve and the consistency of reaction solvent and surfactivity in printing process, improve imprinting effect, strengthening absorption property, is a kind of substrate material well preparing surface molecule print sorbing material.
Graft modification modification, the trace polymerization on mesoporous carbon nanometer ball surface are new technologies, in application parameter, detection sign, all need further research.
Summary of the invention
Goal of the invention
The object of the invention is the practical situation for background technology, employing glucose is carbon source, silicon-dioxide is mesoporous template, through Hydrothermal Synthesis polymer microballoon, high temperature cabonization removing silicon-dioxide obtains mesoporous carbon nanometer ball, surface modification, grafting, trace polymerization, make mesoporous trace Nano carbon balls, to increase substantially adsorption desulfurize effect.
Technical scheme
The chemical substance material that the present invention uses is: glucose, silicon-dioxide, dibenzothiophene, Ethylene glycol dimethacrylate, α-methacrylic acid, chloroform, dehydrated alcohol, anhydrous methanol, glacial acetic acid, p-(chloromethyl) phenyltrimethoxysila,e, Thiocarb, sulfuric acid, nitric acid, toluene, deionized water, nitrogen, and it is as follows that its combination prepares consumption: with gram, milliliter, centimetre
3for measure unit
Preparation method is as follows:
(1) mesoporous carbon nanometer ball is prepared
1. prepare D/W, take glucose 3.168g ± 0.001g, measure deionized water 40mL ± 0.001mL, add in beaker, stir 5min, become the D/W of 0.4mol/L;
2. get D/W 40mL ± 0.01mL, silicon-dioxide 0.2g ± 0.01g is placed in polytetrafluoroethylcontainer container, container is placed in ultrasonic disperse instrument and carries out dispersing and dissolving, become oyster white clarification mixed solution;
3. the polytetrafluoroethylcontainer container filling mixed solution is put into reactor, and airtight, then puts into process furnace and heat, Heating temperature 180 DEG C ± 2 DEG C, heat-up time 1440min; Mixed solution carries out hydrothermal synthesis reaction in a kettle., and reaction formula is as follows:
In formula: C-OH: surface has the Nano carbon balls of hydrogen-oxygen functional group
4. stop heating, in reactor, solution cools to 25 DEG C with the furnace, obtains brown cloudy solution;
5. centrifugation, is placed in brown cloudy solution in centrifuge tube and is separated, obtain floss;
6. washing, suction filtration, add floss in beaker, add deionized water 100mL, agitator treating, then carry out suction filtration with millipore filtration, retains filter cake;
7. vacuum-drying, is placed in quartz container by filter cake, and be then placed in vacuum drying oven dry, drying temperature 55 DEG C, vacuum tightness 10Pa, time of drying, 1440min, obtained brown ceramic powder;
8. dried brown ceramic powder is placed in sintering oven, carries out sintering carbonization, sintering temperature 800 DEG C ± 2 DEG C, and input nitrogen protection, nitrogen input speed 100cm
3/ min, sintering time 120min, become black carbon nanometer ball after sintering;
9. black carbon nanometer ball is positioned in beaker, adds hydrofluoric acid 40mL ± 0.001mL, soak 20min, removing silicon-dioxide; Then use deionized water 1000mL agitator treating, after suction filtration, obtain filter cake;
10. vacuum-drying, is placed in vacuum drying oven dry, drying temperature 55 DEG C, vacuum tightness 10Pa by filter cake, time of drying, 1440min, obtained mesoporous carbon nanometer ball after drying;
(2) silylation modification modification mesoporous carbon nanometer ball
Silylation modification modification mesoporous carbon nanometer ball carries out on there-necked flask, electric heater, completes under heating, water cycle condensation, magnetic agitation;
1. take mesoporous carbon nanometer ball 0.3g ± 0.001g, add in there-necked flask; By dehydrated alcohol 45mL ± 0.01mL, deionized water 15mL ± 0.001mL, γ-(methacryloxypropyl) propyl trimethoxy silicane 1mL ± 0.001mL adds in there-necked flask; Place and stir magneton;
2. then drip glacial acetic acid 1.3mL ± 0.001mL, rate of addition 0.1mL/min, regulate pH ≈ 5, in alkalescence;
3. opening electric heater, temperature rises to 65 DEG C ± 2 DEG C, stirs magneton and stirs;
4. heated and stirred 120min, carries out modification reaction; Reaction formula is as follows:
In formula: C-C
9h
17o
5si: silanization mesoporous carbon nanometer ball; CH
3oH: anhydrous methanol
5. after modification, modified-reaction, close electric heater, stop heated and stirred, make it be cooled to 25 DEG C with bottle, obtain modification solution;
6. modification solution is placed in centrifuge tube and carries out centrifugation, rotating speed 8000r/min, centrifugation 10min, after centrifugation, obtain silanization mesoporous carbon nanometer ball;
7. wash, be separated, silanization mesoporous carbon nanometer ball is placed in beaker, adds dehydrated alcohol 100mL, agitator treating, then carry out centrifugation, retain throw out; Absolute ethanol washing, centrifugation repeat three times;
8. throw out is carried out vacuum-drying, drying temperature 55 DEG C, vacuum tightness 10Pa, time of drying, 720min, obtained silanization mesoporous carbon nanometer ball after drying;
(3) silanization mesoporous carbon nanometer ball surface grafting α-methacrylic acid
Silanization mesoporous carbon nanometer ball surface grafting α-methacrylic acid carries out in there-necked flask, completes in heating, ultrasonic disperse process;
1. take silanization mesoporous carbon nanometer ball 0.2g ± 0.001g, be placed in there-necked flask, add deionized water 15mL ± 0.001mL, α-methacrylic acid 1mL ± 0.001mL, ammonium persulphate 0.132g ± 0.001g; Then there-necked flask is placed in ultrasonic disperse instrument and carries out ultrasonic disperse, ultrasonic frequency 40kHz, jitter time 20min; Nitrogen is inputted, nitrogen input speed 10cm in ultrasonic disperse process
3/ min;
2. open ultrasonic disperse instrument well heater, Heating temperature 70 DEG C ± 2 DEG C, and carry out water cycle condensation, reaction times 1440min, reaction formula is as follows:
In formula: C-C
13h
23o
7si: the mesoporous carbon nanometer ball of grafting polymethyl acrylic acid
3., after cooling, product is transferred in centrifuge tube, carries out centrifugation, after centrifugation, retain solid product;
4. wash, be separated, wash with dehydrated alcohol, then carry out centrifugation, removing surface aggregate thing impurity, washing separation repeats three times;
5. vacuum-drying, the mesoporous carbon nanometer ball of the grafting polymethyl acrylic acid after washing being separated carries out vacuum-drying, drying temperature 55 DEG C, vacuum tightness 10Pa, and time of drying, 720min, obtained the mesoporous carbon nanometer ball of surface grafting methacrylic acid;
(4) mesoporous trace Nano carbon balls is prepared
Prepare mesoporous trace Nano carbon balls to carry out on there-necked flask, electric heater, complete under heating, water cycle condensation, magnetic agitation;
1. dibenzothiophene 0.111g ± 0.001g, chloroform 10mL ± 0.001mL are added in there-necked flask, stir and make it dissolve;
2. there-necked flask is placed on electric heater, adds the mesoporous carbon nanometer ball 0.1g ± 0.001g of grafted methacrylic acid, stir 30min, dibenzothiophene and methacrylic acid are fully acted on;
3. add linking agent Ethylene glycol dimethacrylate 3mL ± 0.001mL, start heating, Heating temperature 50 DEG C ± 2 DEG C, water cycle condensation reaction 600min, reaction formula is as follows:
In formula: C-C
35h
45sO
11si: containing the mesoporous trace Nano carbon balls of dibenzothiophene
4. after reaction, wash, then carry out centrifugation with the mixing solutions of dehydrated alcohol 90mL, acetic acid 10mL, washing, centrifugation repeat three times, with the dibenzothiophene on eluted polymer surface;
5. after centrifugation, outwell supernatant liquor, leave sedimentable matter, be i.e. mesoporous trace Nano carbon balls;
6. mesoporous trace Nano carbon balls is placed in vacuum drying oven dry, drying temperature 55 DEG C, vacuum tightness 10Pa, time of drying 720min;
7. dried mesoporous trace Nano carbon balls is placed in beaker, adds normal hexane 200mL, agitator treating 5min; Washing removing dibenzothiophene molecule, obtains mesoporous trace Nano carbon balls black solid;
8. black solid is placed in vacuum drying oven dry, drying temperature 55 DEG C, vacuum tightness 10Pa, time of drying 720min; End product is obtained: mesoporous trace Nano carbon balls after drying;
(5) detect, analyze, characterize
The color and luster of mesoporous trace Nano carbon balls of preparation, pattern, structure, chemical physics performance are detected, analyze, characterized;
Morphology analysis is carried out with field emission scanning electron microscope;
With transmission electron microscope to its internal structure, Analysis of Surface Topography;
Specific surface area and pore analysis is carried out with BET analyser;
With FTIR spectrum analyser, its surface functional group is analyzed;
Thermal stability analysis is carried out with thermogravimetric analyzer;
Carry out absorption with gas chromatograph to measure;
Conclusion: mesoporous trace Nano carbon balls is black powder particle, particle diameter≤250nm, product purity 98%, the mesoporous pattern of product is good, and pore size distribution concentrates on 3-5nm, and imprinting effect is obvious, to dibenzothiophene be adsorbed on 20min time reach balance, saturated extent of adsorption is 134.08mg/g;
(6) product storage
Be stored in the Glass Containers of amber transparent to the mesoporous trace Nano carbon balls of preparation, airtight lucifuge stores, and is placed in drying, clean environment, and sun-proof, moistureproof, anti-acid-alkali salt corrodes, storing temp 20 DEG C, relative humidity≤10%.
Beneficial effect
The present invention has obvious advance compared with background technology, take glucose as carbon source, silicon-dioxide is mesoporous template, mesoporous carbon nanometer ball is prepared through Hydrothermal Synthesis, through silylation modification modification, surface grafting, crosslinking reaction, washing removing dibenzothiophene, make mesoporous trace Nano carbon balls, this preparation method's technique is advanced, reaction conditions is gentle, rational technology, product morphology is well regular, for the spherical powder granule of black, particle diameter≤250nm, product purity reaches 98%, have and enrich meso-hole structure, mesoporous pattern is good, pore size distribution concentrates on 3-5nm, trace mesoporous carbon nanometer ball imprinting effect is obvious, good to dibenzothiophene specific recognition adsorptive power, balance is reached when 20min, saturated extent of adsorption is 134.08mg/g, can in specific recognition, catch absorption, single-minded response, high efficiency separation field is applied.
Accompanying drawing explanation
Fig. 1 mesoporous carbon nanometer ball preparing processes figure
Fig. 2 mesoporous trace Nano carbon balls end product preparing processes figure
Fig. 3 mesoporous carbon nanometer ball amplifies 150,000 times of scanning electron microscope shape appearance figures
Fig. 4 mesoporous carbon nanometer ball amplifies 200,000 times of transmission electron microscope shape appearance figures
Fig. 5 mesoporous trace Nano carbon balls N2 adsorption test graph of pore diameter distribution
Fig. 6 mesoporous trace Nano carbon balls Static Adsorption graphic representation
Shown in figure, list of numerals is as follows:
1, process furnace, 2, reactor, 3, polytetrafluoroethylcontainer container, 4, mixing solutions, 5, kettle cover, 6, container cover, 7, automatically controlled, 8, first display screen, 9, first pilot lamp, 10, first power switch, 11, first Heating temperature modulator, 12, first heat-up time modulator, 13, furnace chamber, 14, worktable, 15, electric heater, 16, second display screen, 17, second pilot lamp, 18, second source switch, 19, mixing control device, 20, second Heating temperature modulator, 21, second heat-up time modulator, 22, heating jacket, 23, there-necked flask, 24, addition funnel, 25, control valve, 26, agitator, 27, water cycle prolong, 28, water inlet pipe, 29, rising pipe, 30, air outlet, 31, mixed solution.
Embodiment
Below in conjunction with accompanying drawing, the present invention will be further described:
Shown in Fig. 1, be mesoporous carbon nanometer ball preparing processes figure, each position wants correct, and proportioning according to quantity, operates according to the order of sequence.
The value of the chemical substance needed for preparation determines by the scope pre-set, with gram, milliliter, centimetre
3for measure unit.
The preparation of mesoporous carbon nanometer ball is carried out in a kettle., completes under Hydrothermal Synthesis state;
Process furnace 1 is vertical, is worktable 14, worktable 14 is put reactor 2, and sealed by kettle cover 5 at process furnace 1 inner bottom part, in reactor 2, put polytetrafluoroethylcontainer container 3, is mixing solutions 4, and is sealed by container cover 6 in polytetrafluoroethylcontainer container 3; Process furnace 1 bottom is automatically controlled 7, and automatically controlled 7 is provided with the first display screen 8, first pilot lamp 9, first power switch 10, first temperature regulator 11, first modulator heat-up time 12.
Shown in Fig. 2, be mesoporous trace Nano carbon balls end product preparing processes figure, each position wants correct, and proportioning according to quantity, operates according to the order of sequence.
The preparation of mesoporous trace Nano carbon balls is carried out in there-necked flask, completes under heating, water cycle condensation, whipped state;
Electric heater is vertical, and electric heater 15 is provided with second display screen 16, second pilot lamp 17, second source switch 18, mixing control device 19, second Heating temperature modulator 20, second controller heat-up time 21; Be heating jacket 22 on electric heater 15 top, in heating jacket 22, put there-necked flask 23, set gradually addition funnel 24 and control valve 25, agitator 26, water cycle prolong 27 and water inlet pipe 28, rising pipe 29, air outlet 30 on there-necked flask 23 top from left to right; It is mixed solution 31 in there-necked flask 23.
Shown in Fig. 3, for mesoporous trace Nano carbon balls amplifies 150,000 times of scanning electron microscope shape appearance figures, known in figure: porous trace Nano carbon balls is regular spherical, particle diameter≤250nm.
Shown in Fig. 4, for porous trace Nano carbon balls amplifies 200,000 times of transmission electron microscope shape appearance figures, known in figure: mesoporous trace Nano carbon balls has loose internal structure, surface irregularity, is covered with hole.
Shown in Fig. 5, for mesoporous trace Nano carbon balls N2 adsorption test graph of pore diameter distribution, ordinate zou is pore volume between unit aperture region, X-coordinate is aperture, known in figure: the pore size distribution of mesoporous trace Nano carbon balls concentrates on 3-5nm, pore size distribution is concentrated, and belongs to mesoporous material.
Shown in Fig. 6, for mesoporous trace Nano carbon balls Static Adsorption graphic representation, ordinate zou is adsorptive capacity, X-coordinate is adsorption time, known in figure: the time that the absorption of mesoporous trace Nano carbon balls to dibenzothiophene reaches balance is 20min, and maximal absorptive capacity is 134.08mg/g.
Claims (3)
1. the preparation method of a mesoporous trace Nano carbon balls, it is characterized in that: the chemical substance material of use is: glucose, silicon-dioxide, dibenzothiophene, Ethylene glycol dimethacrylate, α-methacrylic acid, chloroform, dehydrated alcohol, anhydrous methanol, glacial acetic acid, p-(chloromethyl) phenyltrimethoxysila,e, Thiocarb, sulfuric acid, nitric acid, toluene, deionized water, nitrogen, it is as follows that its combination prepares consumption: with gram, milliliter, centimetre
3for measure unit
Preparation method is as follows:
(1) mesoporous carbon nanometer ball is prepared
1. prepare D/W, take glucose 3.168g ± 0.001g, measure deionized water 40mL ± 0.001mL, add in beaker, stir 5min, become the D/W of 0.4mol/L;
2. get D/W 40mL ± 0.01mL, silicon-dioxide 0.2g ± 0.01g is placed in polytetrafluoroethylcontainer container, container is placed in ultrasonic disperse instrument and carries out dispersing and dissolving, become oyster white clarification mixed solution;
3. the polytetrafluoroethylcontainer container filling mixed solution is put into reactor, and airtight, then puts into process furnace and heat, Heating temperature 180 DEG C ± 2 DEG C, heat-up time 1440min; Mixed solution carries out hydrothermal synthesis reaction in a kettle., and reaction formula is as follows:
In formula: C-OH: surface has the Nano carbon balls of hydrogen-oxygen functional group
4. stop heating, in reactor, solution cools to 25 DEG C with the furnace, obtains brown cloudy solution;
5. centrifugation, is placed in brown cloudy solution in centrifuge tube and is separated, obtain floss;
6. washing, suction filtration, add floss in beaker, add deionized water 100mL, agitator treating, then carry out suction filtration with millipore filtration, retains filter cake;
7. vacuum-drying, is placed in quartz container by filter cake, and be then placed in vacuum drying oven dry, drying temperature 55 DEG C, vacuum tightness 10Pa, time of drying, 1440min, obtained brown ceramic powder;
8. dried brown ceramic powder is placed in sintering oven, carries out sintering carbonization, sintering temperature 800 DEG C ± 2 DEG C, and input nitrogen protection, nitrogen input speed 100cm
3/ min, sintering time 120min, become black carbon nanometer ball after sintering;
9. black carbon nanometer ball is positioned in beaker, adds hydrofluoric acid 40mL ± 0.001mL, soak 20min, removing silicon-dioxide; Then use deionized water 1000mL agitator treating, after suction filtration, obtain filter cake;
10. vacuum-drying, is placed in vacuum drying oven dry, drying temperature 55 DEG C, vacuum tightness 10Pa by filter cake, time of drying, 1440min, obtained mesoporous carbon nanometer ball after drying;
(2) silylation modification modification mesoporous carbon nanometer ball
Silylation modification modification mesoporous carbon nanometer ball carries out on there-necked flask, electric heater, completes under heating, water cycle condensation, magnetic agitation;
1. take mesoporous carbon nanometer ball 0.3g ± 0.001g, add in there-necked flask; By dehydrated alcohol 45mL ± 0.01mL, deionized water 15mL ± 0.001mL, γ-(methacryloxypropyl) propyl trimethoxy silicane 1mL ± 0.001mL adds in there-necked flask; Place and stir magneton;
2. then drip glacial acetic acid 1.3mL ± 0.001mL, rate of addition 0.1mL/min, regulate pH ≈ 5, in alkalescence;
3. opening electric heater, temperature rises to 65 DEG C ± 2 DEG C, stirs magneton and stirs;
4. heated and stirred 120min, carries out modification reaction; Reaction formula is as follows:
In formula: C-C
9h
17o
5si: silanization mesoporous carbon nanometer ball; CH
3oH: anhydrous methanol
5. after modification, modified-reaction, close electric heater, stop heated and stirred, make it be cooled to 25 DEG C with bottle, obtain modification solution;
6. modification solution is placed in centrifuge tube and carries out centrifugation, rotating speed 8000r/min, centrifugation 10min, after centrifugation, obtain silanization mesoporous carbon nanometer ball;
7. wash, be separated, silanization mesoporous carbon nanometer ball is placed in beaker, adds dehydrated alcohol 100mL, agitator treating, then carry out centrifugation, retain throw out; Absolute ethanol washing, centrifugation repeat three times;
8. throw out is carried out vacuum-drying, drying temperature 55 DEG C, vacuum tightness 10Pa, time of drying, 720min, obtained silanization mesoporous carbon nanometer ball after drying;
(3) silanization mesoporous carbon nanometer ball surface grafting α-methacrylic acid
Silanization mesoporous carbon nanometer ball surface grafting α-methacrylic acid carries out in there-necked flask, completes in heating, ultrasonic disperse process;
1. take silanization mesoporous carbon nanometer ball 0.2g ± 0.001g, be placed in there-necked flask, add deionized water 15mL ± 0.001mL, α-methacrylic acid 1mL ± 0.001mL, ammonium persulphate 0.132g ± 0.001g; Then there-necked flask is placed in ultrasonic disperse instrument and carries out ultrasonic disperse, ultrasonic frequency 40kHz, jitter time 20min; Nitrogen is inputted, nitrogen input speed 10cm in ultrasonic disperse process
3/ min;
2. open ultrasonic disperse instrument well heater, Heating temperature 70 DEG C ± 2 DEG C, and carry out water cycle condensation, reaction times 1440min, reaction formula is as follows:
In formula: C-C
13h
23o
7si: the mesoporous carbon nanometer ball of grafting polymethyl acrylic acid
3., after cooling, product is transferred in centrifuge tube, carries out centrifugation, after centrifugation, retain solid product;
4. wash, be separated, wash with dehydrated alcohol, then carry out centrifugation, removing surface aggregate thing impurity, washing separation repeats three times;
5. vacuum-drying, the mesoporous carbon nanometer ball of the grafting polymethyl acrylic acid after washing being separated carries out vacuum-drying, drying temperature 55 DEG C, vacuum tightness 10Pa, and time of drying, 720min, obtained the mesoporous carbon nanometer ball of surface grafting methacrylic acid;
(4) mesoporous trace Nano carbon balls is prepared
Prepare mesoporous trace Nano carbon balls to carry out on there-necked flask, electric heater, complete under heating, water cycle condensation, magnetic agitation;
1. dibenzothiophene 0.111g ± 0.001g, chloroform 10mL ± 0.001mL are added in there-necked flask, stir and make it dissolve;
2. there-necked flask is placed on electric heater, adds the mesoporous carbon nanometer ball 0.1g ± 0.001g of grafted methacrylic acid, stir 30min, dibenzothiophene and methacrylic acid are fully acted on;
3. add linking agent Ethylene glycol dimethacrylate 3mL ± 0.001mL, start heating, Heating temperature 50 DEG C ± 2 DEG C, water cycle condensation reaction 600min, reaction formula is as follows:
In formula: C-C
35h
45sO
11si: containing the mesoporous trace Nano carbon balls of dibenzothiophene
4. after reaction, wash, then carry out centrifugation with the mixing solutions of dehydrated alcohol 90mL, acetic acid 10mL, washing, centrifugation repeat three times, with the dibenzothiophene on eluted polymer surface;
5. after centrifugation, outwell supernatant liquor, leave sedimentable matter, be i.e. mesoporous trace Nano carbon balls;
6. mesoporous trace Nano carbon balls is placed in vacuum drying oven dry, drying temperature 55 DEG C, vacuum tightness 10Pa, time of drying 720min;
7. dried mesoporous trace Nano carbon balls is placed in beaker, adds normal hexane 200mL, agitator treating 5min; Washing removing dibenzothiophene molecule, obtains mesoporous trace Nano carbon balls black solid;
8. black solid is placed in vacuum drying oven dry, drying temperature 55 DEG C, vacuum tightness 10Pa, time of drying 720min; End product is obtained: mesoporous trace Nano carbon balls after drying;
(5) detect, analyze, characterize
The color and luster of mesoporous trace Nano carbon balls of preparation, pattern, structure, chemical physics performance are detected, analyze, characterized;
Morphology analysis is carried out with field emission scanning electron microscope;
With transmission electron microscope to its internal structure, Analysis of Surface Topography;
Specific surface area and pore analysis is carried out with BET analyser;
With FTIR spectrum analyser, its surface functional group is analyzed;
Thermal stability analysis is carried out with thermogravimetric analyzer;
Carry out absorption with gas chromatograph to measure;
Conclusion: mesoporous trace Nano carbon balls is black powder particle, particle diameter≤250nm, product purity 98%, the mesoporous pattern of product is good, and pore size distribution concentrates on 3-5nm, and imprinting effect is obvious, to dibenzothiophene be adsorbed on 20min time reach balance, saturated extent of adsorption is 134.08mg/g;
(6) product storage
Be stored in the Glass Containers of amber transparent to the mesoporous trace Nano carbon balls of preparation, airtight lucifuge stores, and is placed in drying, clean environment, and sun-proof, moistureproof, anti-acid-alkali salt corrodes, storing temp 20 DEG C, relative humidity≤10%.
2. the preparation method of a kind of mesoporous trace Nano carbon balls according to claim 1, is characterized in that: the preparation of mesoporous carbon nanometer ball is carried out in a kettle., completes under Hydrothermal Synthesis state;
Process furnace (1) is for vertical, be worktable (14) at process furnace (1) inner bottom part, worktable (14) is put reactor (2), and sealed by kettle cover (5), polytetrafluoroethylcontainer container (3) is put in reactor (2), be mixing solutions (4) in polytetrafluoroethylcontainer container 3, and sealed by container cover (6); Process furnace (1) bottom is automatically controlled (7), and automatically controlled (7) are provided with the first display screen (8), the first pilot lamp (9), the first power switch (10), the first temperature regulator (11), the first modulator heat-up time (12).
3. the preparation method of a kind of mesoporous trace Nano carbon balls according to claim 1, is characterized in that: the preparation of mesoporous trace Nano carbon balls is carried out in there-necked flask, completes under heating, water cycle condensation, whipped state;
Electric heater is vertical, and electric heater (15) is provided with second display screen (16), the second pilot lamp (17), second source switch (18), mixing control device (19), the second Heating temperature modulator (20), the second controller heat-up time (21); Be heating jacket (22) on electric heater (15) top, in heating jacket (22), put there-necked flask (23), set gradually addition funnel (24) and control valve (25), agitator (26), water cycle prolong (27) and water inlet pipe (28), rising pipe (29), air outlet (30) on there-necked flask (23) top from left to right; Be mixed solution (31) in there-necked flask (23).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410499699.0A CN104291314B (en) | 2014-09-26 | 2014-09-26 | A kind of preparation method of mesoporous imprinted carbon nanosphere |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410499699.0A CN104291314B (en) | 2014-09-26 | 2014-09-26 | A kind of preparation method of mesoporous imprinted carbon nanosphere |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104291314A true CN104291314A (en) | 2015-01-21 |
| CN104291314B CN104291314B (en) | 2016-03-23 |
Family
ID=52311308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410499699.0A Active CN104291314B (en) | 2014-09-26 | 2014-09-26 | A kind of preparation method of mesoporous imprinted carbon nanosphere |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104291314B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109589808A (en) * | 2018-12-27 | 2019-04-09 | 太原理工大学 | A kind of preparation method of carbon based surfaces molecular engram two dimension composite membrane |
| CN110711568A (en) * | 2019-11-25 | 2020-01-21 | 太原理工大学 | A kind of hydrophilic bifunctional monomer imprinted adsorption material and preparation method thereof |
| CN111085118A (en) * | 2019-12-09 | 2020-05-01 | 太原理工大学 | Preparation method of polydopamine modified polyether sulfone imprinted composite membrane |
| CN111268814A (en) * | 2020-01-07 | 2020-06-12 | 昆明理工大学 | An anthracycline antibiotic wastewater treatment method combining porous carbon nanosphere-based surface molecularly imprinted filter material and ultrafiltration molecularly imprinted membrane |
| CN113443851A (en) * | 2021-06-23 | 2021-09-28 | 贵州石博士科技股份有限公司 | Composite solid nano-based early strength agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030219828A1 (en) * | 2000-08-21 | 2003-11-27 | Singh Waheguru Pal | Imprinting large molecular weight compounds in polymer composites |
| CN101845125A (en) * | 2010-03-29 | 2010-09-29 | 太原理工大学 | Method for preparing molecular imprinted polymer on surface of carbon microspheres |
| CN103332671A (en) * | 2013-06-18 | 2013-10-02 | 太原理工大学 | Porous imprinting carbon nano-sphere preparation method |
-
2014
- 2014-09-26 CN CN201410499699.0A patent/CN104291314B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030219828A1 (en) * | 2000-08-21 | 2003-11-27 | Singh Waheguru Pal | Imprinting large molecular weight compounds in polymer composites |
| CN101845125A (en) * | 2010-03-29 | 2010-09-29 | 太原理工大学 | Method for preparing molecular imprinted polymer on surface of carbon microspheres |
| CN103332671A (en) * | 2013-06-18 | 2013-10-02 | 太原理工大学 | Porous imprinting carbon nano-sphere preparation method |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109589808A (en) * | 2018-12-27 | 2019-04-09 | 太原理工大学 | A kind of preparation method of carbon based surfaces molecular engram two dimension composite membrane |
| CN110711568A (en) * | 2019-11-25 | 2020-01-21 | 太原理工大学 | A kind of hydrophilic bifunctional monomer imprinted adsorption material and preparation method thereof |
| CN110711568B (en) * | 2019-11-25 | 2022-04-08 | 太原理工大学 | Hydrophilic bifunctional monomer imprinting adsorption material and preparation method thereof |
| CN111085118A (en) * | 2019-12-09 | 2020-05-01 | 太原理工大学 | Preparation method of polydopamine modified polyether sulfone imprinted composite membrane |
| CN111085118B (en) * | 2019-12-09 | 2022-02-25 | 太原理工大学 | Preparation method of polydopamine modified polyether sulfone imprinted composite membrane |
| CN111268814A (en) * | 2020-01-07 | 2020-06-12 | 昆明理工大学 | An anthracycline antibiotic wastewater treatment method combining porous carbon nanosphere-based surface molecularly imprinted filter material and ultrafiltration molecularly imprinted membrane |
| CN111268814B (en) * | 2020-01-07 | 2022-05-24 | 昆明理工大学 | An anthracycline antibiotic wastewater treatment method combining porous carbon nanosphere-based surface molecularly imprinted filter material and ultrafiltration molecularly imprinted membrane |
| CN113443851A (en) * | 2021-06-23 | 2021-09-28 | 贵州石博士科技股份有限公司 | Composite solid nano-based early strength agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104291314B (en) | 2016-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103332671B (en) | A kind of preparation method of porous trace Nano carbon balls | |
| CN104291314A (en) | Preparation method of mesoporous imprinted carbon nanospheres | |
| CN103709340B (en) | The method of Powdered Activated Carbon surface grafting NIPA | |
| CN104312215B (en) | A kind of surface graft modification method of silicon-dioxide | |
| CN105664847B (en) | A kind of preparation and application of the porous carbon materials of the high-specific surface area based on tea seed shell base | |
| CN103506119B (en) | Method for rapidly preparing carbon nanotube-loaded cuprous oxide photocatalyst | |
| CN106732410A (en) | A kind of preparation method of amino modified silicon substrate carbon dioxide absorber | |
| CN107556472B (en) | The covalent organic porous polymer material of hollow/solid controllable spherical of one kind, Preparation method and use | |
| CN105597724A (en) | Method for preparing magnetic-biochar-supported photocatalyst | |
| CN105854801A (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
| CN106672942B (en) | A kind of preparation method of porous carbon nanotube | |
| CN104828802A (en) | Synthetic method and application of mesoporous carbon material high-effectively adsorbing tetracycline | |
| CN106334530A (en) | Method for preparing porous compound desulfurizer for removing organic sulfide | |
| CN102516581A (en) | Preparation method of imprinted carbon microspheres | |
| CN101531835A (en) | Wollastonite powder surface wet modification method assisted by microwave | |
| CN111346609A (en) | Adsorbing material for heavy metal dye-containing wastewater and preparation method thereof | |
| Liang et al. | Using recycled coffee grounds for the synthesis of ZIF-8@ BC to remove Congo red in water | |
| CN102260542B (en) | Preparation method of a three-dimensional ordered macroporous iron oxide desulfurizer | |
| CN110560001A (en) | Preparation method and application of Fe-MOFs nano material containing ionic liquid | |
| CN105457681A (en) | Preparation method of ZnO/graphene oxide composite photocatalysis material | |
| CN105854898A (en) | Preparation method of cellulose-based core-shell CdS/ZnO (cadmium-sulfur/zinc oxide) photocatalyst | |
| CN105797677A (en) | Preparation method of highly-hydrophobic silicon dioxide aerogel | |
| CN103143318A (en) | Preparation method for siliceous earth/FeOOH composite materials in micro-nano structure | |
| CN101845125B (en) | A method for preparing molecularly imprinted polymers on the surface of carbon microspheres | |
| CN103599781B (en) | A kind of preparation method of core-shell type carbon-coated nano-copper catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 |