CN104667898A - Preparation method of eucalyptus-based porous carbon-silicon dioxide solid-phase extraction column - Google Patents
Preparation method of eucalyptus-based porous carbon-silicon dioxide solid-phase extraction column Download PDFInfo
- Publication number
- CN104667898A CN104667898A CN201510060603.5A CN201510060603A CN104667898A CN 104667898 A CN104667898 A CN 104667898A CN 201510060603 A CN201510060603 A CN 201510060603A CN 104667898 A CN104667898 A CN 104667898A
- Authority
- CN
- China
- Prior art keywords
- eucalyptus
- porous carbon
- base porous
- phase extraction
- silica
- 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
Abstract
The invention discloses a preparation method of a eucalyptus-based porous carbon-silicon dioxide solid-phase extraction column. The method comprises the following steps: (1) adding zinc chloride to a eucalyptus rod, activating, washing, drying and grinding under a hydrothermal condition, adding sodium hydroxide, fully mixing evenly, forming a column form, putting into an atmosphere furnace, protecting with nitrogen, firing at high temperature, naturally cooling, taking out, washing off sodium hydroxide with hydrochloric acid, and drying to obtain eucalyptus-based porous carbon; (2) adding mixed acid to the porous carbon, activating, washing off excessive mixed acid and drying for later use; and (3) mixing the porous carbon with silicon dioxide evenly, packing to a polyethylene solid-phase extraction pipe, adding to a sieve plate, and compacting, so as to prepare the eucalyptus-based porous carbon-silicon dioxide solid-phase extraction column. The eucalyptus-based porous carbon-silicon dioxide solid-phase extraction column is low in cost, available, convenient to operate, simple in technological process, good in repeatability, small in pollution and the like, and has strong practicability.
Description
Technical field
The present invention relates to the preparing technical field of solid-phase extraction column, particularly relate to a kind of preparation method of eucalyptus base porous carbon-Silica solid phase extraction column.
Background technology
The filler great majority of the solid-phase extraction column of current use are: silica filler, polymer filler, aluminium oxide, active carbon, diatomite etc.But it is complicated mostly to there is preparation, the shortcoming that cost is high.
Along with the minimizing of the mineral resources such as oil, coal, the utilization of biomass resource more and more comes into one's own.Under the guiding of national policy, the nearest Two decades years in my district plants eucalyptus energetically, and growth is fast, aboundresources.It is a kind of economic function woods, and according to incompletely statistics, within 2011, whole district's eucalyptus area has reached to more than 180 ten thousand hm
2, account for 1/4 of the artificial Commercial Forests area of the whole district, Eucalyptus Wood output accounts for 2/3 of whole district's timber yield, and its area and output all rank first in the country.Eucalyptus is mainly processed as master with timber, prefabricated board, building slab, papermaking and paper pulp etc. at present.After transporting a large amount of trunks, leave the residues such as a large amount of branches and leaves, branch, sawdust, bark, how to process these residues? improve resource utilization, increase the income of self-employed tree cultivator and enterprise.Therefore, if they are converted into porous carbon, develop a kind of efficient small-sized solid-phase extraction column, these resources will be utilized more fully, and bring larger income to agriculture and forestry.
Summary of the invention
The invention provides a kind of preparation method of eucalyptus base porous carbon-Silica solid phase extraction column.The present invention with the eucalyptus discarded object of a large amount of cheapnesss for raw material, simple course of reaction is utilized to prepare eucalyptus base porous carbon-Silica solid phase extraction column, not only for heavy metal ion, there is good adsorption effect, for industrial wastewater dyestuff, also there is all well and good effect.
The present invention adopts following technical scheme:
The concrete steps of the preparation method of eucalyptus base porous carbon-Silica solid phase extraction column of the present invention are as follows:
(1) preparation of eucalyptus base porous carbon:
With eucalyptus bar for raw material, add zinc chloride and change in advance, under the condition of hydro-thermal, activate 1-3 hour, washing, dry, pulverize, obtain preactivated eucalyptus bar powder; In preactivated eucalyptus bar powder, add NaOH, fully mix, make column; Eucalyptus powder column is put into atmosphere furnace, nitrogen protection, at high temperature calcination; Naturally cool, take out, wash away NaOH with hydrochloric acid, dry, obtain eucalyptus base porous carbon;
(2) activation of eucalyptus base porous carbon:
In eucalyptus base porous carbon prepared by step (1), add nitration mixture, it is activated, make hole, eucalyptus Quito carbon surface increase carboxyl, oh group, improve adsorbance; Wash away unnecessary nitration mixture, dry, stand-by;
(3) preparation of eucalyptus base porous carbon-Silica solid phase extraction column:
Eucalyptus base porous carbon after step (2) activation is mixed with silica and mixes, install in polyethylene solid phase extraction tube, add upper sieve plate, compacting, obtained eucalyptus base porous carbon-Silica solid phase extraction column.
In step (1), the weight ratio of eucalyptus bar and zinc chloride is 0.5 ~ 2:1; The temperature of hydro-thermal is 100 ~ 200 degree; Particle diameter after pulverizing is 5mm; 0.5 ~ 2:1 with the weight ratio of NaOH in preactivated eucalyptus bar powder; The temperature and time of high temperature sintering is 600-1100 degree respectively, 2h.
In step (2), described nitration mixture is made up of sulfuric acid, nitric acid, and the w/v of eucalyptus base porous carbon and nitration mixture is 0.5-2:1mg/ml; Soak time is 4-8h.
In step (3), the preparation method of described silica is as follows: often add 10-20ml ethanol in the reactor, and correspondence adds 100-1000ul water, 100-1000ul ammoniacal liquor, after stirring, adds 200-700ul TEOS, room temperature reaction 5-12h, after reaction terminates, centrifugal 5 minutes, get lower sediment, ultrasonic disperse in ethanol, centrifugal again, 4 times repeatedly, by lower sediment N
2dry up, obtain silica.
In step (3), the eucalyptus base porous carbon after activation with the ratio of silica is: the corresponding 0.005-0.2g silica of eucalyptus base porous carbon after every 0.005-0.2g activates.
Porous carbon and the full and uniform blended rear filling of silica have successfully been prepared eucalyptus base porous carbon-Silica solid phase extraction column by the present invention, the raw materials of this solid-phase extraction column is easy to get, and eucalyptus base porous carbon mixes fully with silica, mutual support, have certain gap, the super large surface area based on porous carbon has the adsorption capacity of super large.
Good effect of the present invention is as follows:
Compared with traditional filler, have the following advantages:
(1) prepare that the raw material sources of porous carbon extensively, cheap are easy to get, technique is simple, pollution-free.
(2) method of silica is simple, ripe.
(3) the solid-phase extraction column cost prepared by is low, and adsorbance is large.
(4) fairly simple, easy to operate, the favorable reproducibility of preparation technology and pollute little, cheaper.Be applicable to marketing, benefit from the numerous common people.
(5) preparation technology of eucalyptus base porous carbon-Silica solid phase extraction column of the present invention is simple, and raw material sources are extensive, and required laboratory apparatus is also fairly simple, may be used for large-scale production.
(6) adsorb object to be combined closely by complexing and physisorption power porous carbon, be conducive to realizing absorption object good absorption, adopt organic solvent or diluted acid wash-out, detect.
(7) eucalyptus base porous carbon-Silica solid phase extraction column of preparing of the method, makes full use of local characteristic resource, traditional discarded object is become useful product, improves the added value of agricultural product.
Accompanying drawing explanation
Fig. 1 is the Raman spectrogram of the eucalyptus base porous carbon prepared under different temperatures.
Fig. 2 is the XRD spectra of the eucalyptus base porous carbon prepared under different temperatures.
Detailed description of the invention
The following examples describe in further detail of the present invention.
Embodiment 1
The concrete steps of the preparation method of eucalyptus base porous carbon-Silica solid phase extraction column of the present invention are as follows:
(1) preparation of eucalyptus base porous carbon:
With eucalyptus bar for raw material, add zinc chloride and change in advance, under the condition of hydro-thermal, activate 1 hour, washing, dry, pulverize, obtain preactivated eucalyptus bar powder; In preactivated eucalyptus bar powder, add NaOH, fully mix, make column; Eucalyptus powder column is put into atmosphere furnace, nitrogen protection, at high temperature calcination; Naturally cool, take out, wash away NaOH with hydrochloric acid, dry, obtain eucalyptus base porous carbon;
(2) activation of eucalyptus base porous carbon:
In eucalyptus base porous carbon prepared by step (1), add nitration mixture, it is activated, make hole, eucalyptus Quito carbon surface increase carboxyl, oh group, improve adsorbance; Wash away unnecessary nitration mixture, dry, stand-by;
(3) preparation of eucalyptus base porous carbon-Silica solid phase extraction column:
Eucalyptus base porous carbon after step (2) activation is mixed with silica and mixes, install in polyethylene solid phase extraction tube, add upper sieve plate, compacting, obtained eucalyptus base porous carbon-Silica solid phase extraction column.
In step (1), the weight ratio of eucalyptus bar and zinc chloride is 0.5:1; The temperature of hydro-thermal is 100 degree; Particle diameter after pulverizing is 5mm; 0.5:1 with the weight ratio of NaOH in preactivated eucalyptus bar powder; The temperature and time of high temperature sintering is 600 degree respectively, 2h.
In step (2), described nitration mixture is made up of sulfuric acid, nitric acid, and the w/v of eucalyptus base porous carbon and nitration mixture is 0.5:1mg/ml; Soak time is 4h.
In step (3), the preparation method of described silica is as follows: often add 10ml ethanol in the reactor, and correspondence adds 100ul water, 100ul ammoniacal liquor, after stirring, adds 200ul TEOS, room temperature reaction 5h, after reaction terminates, centrifugal 5 minutes, get lower sediment, ultrasonic disperse in ethanol, centrifugal again, 4 times repeatedly, by lower sediment N
2dry up, obtain silica.
In step (3), the eucalyptus base porous carbon after activation with the ratio of silica is: the corresponding 0.005g silica of eucalyptus base porous carbon after every 0.005g activates.
Embodiment 2
The concrete steps of the preparation method of eucalyptus base porous carbon-Silica solid phase extraction column of the present invention are as follows:
(1) preparation of eucalyptus base porous carbon:
With eucalyptus bar for raw material, add zinc chloride and change in advance, under the condition of hydro-thermal, activate 3 hours, washing, dry, pulverize, obtain preactivated eucalyptus bar powder; In preactivated eucalyptus bar powder, add NaOH, fully mix, make column; Eucalyptus powder column is put into atmosphere furnace, nitrogen protection, at high temperature calcination; Naturally cool, take out, wash away NaOH with hydrochloric acid, dry, obtain eucalyptus base porous carbon;
(2) activation of eucalyptus base porous carbon:
In eucalyptus base porous carbon prepared by step (1), add nitration mixture, it is activated, make hole, eucalyptus Quito carbon surface increase carboxyl, oh group, improve adsorbance; Wash away unnecessary nitration mixture, dry, stand-by;
(3) preparation of eucalyptus base porous carbon-Silica solid phase extraction column:
Eucalyptus base porous carbon after step (2) activation is mixed with silica and mixes, install in polyethylene solid phase extraction tube, add upper sieve plate, compacting, obtained eucalyptus base porous carbon-Silica solid phase extraction column.
In step (1), the weight ratio of eucalyptus bar and zinc chloride is 2:1; The temperature of hydro-thermal is 200 degree; Particle diameter after pulverizing is 5mm; 2:1 with the weight ratio of NaOH in preactivated eucalyptus bar powder; The temperature and time of high temperature sintering is 1100 degree respectively, 2h.
In step (2), described nitration mixture is made up of sulfuric acid, nitric acid, the w/v 2:1mg/ml of eucalyptus base porous carbon and nitration mixture; Soak time is 8h.
In step (3), the preparation method of described silica is as follows: often add 20ml ethanol in the reactor, and correspondence adds 1000ul water, 1000ul ammoniacal liquor, after stirring, adds 700ul TEOS, room temperature reaction 12h, after reaction terminates, centrifugal 5 minutes, get lower sediment, ultrasonic disperse in ethanol, centrifugal again, 4 times repeatedly, by lower sediment N
2dry up, obtain silica.
In step (3), the eucalyptus base porous carbon after activation with the ratio of silica is: the corresponding 0.005g silica of eucalyptus base porous carbon after every 0.2g activates.
Embodiment 3
The concrete steps of the preparation method of eucalyptus base porous carbon-Silica solid phase extraction column of the present invention are as follows:
(1) preparation of eucalyptus base porous carbon:
With eucalyptus bar for raw material, add zinc chloride and change in advance, under the condition of hydro-thermal, activate 2 hours, washing, dry, pulverize, obtain preactivated eucalyptus bar powder; In preactivated eucalyptus bar powder, add NaOH, fully mix, make column; Eucalyptus powder column is put into atmosphere furnace, nitrogen protection, at high temperature calcination; Naturally cool, take out, wash away NaOH with hydrochloric acid, dry, obtain eucalyptus base porous carbon;
(2) activation of eucalyptus base porous carbon:
In eucalyptus base porous carbon prepared by step (1), add nitration mixture, it is activated, make hole, eucalyptus Quito carbon surface increase carboxyl, oh group, improve adsorbance; Wash away unnecessary nitration mixture, dry, stand-by;
(3) preparation of eucalyptus base porous carbon-Silica solid phase extraction column:
Eucalyptus base porous carbon after step (2) activation is mixed with silica and mixes, install in polyethylene solid phase extraction tube, add upper sieve plate, compacting, obtained eucalyptus base porous carbon-Silica solid phase extraction column.
In step (1), the weight ratio of eucalyptus bar and zinc chloride is 1:1; The temperature of hydro-thermal is 150 degree; Particle diameter after pulverizing is 5mm; 1:1 with the weight ratio of NaOH in preactivated eucalyptus bar powder; The temperature and time of high temperature sintering is 900 degree respectively, 2h.
In step (2), described nitration mixture is made up of sulfuric acid, nitric acid, the w/v 1:1mg/ml of eucalyptus base porous carbon and nitration mixture; Soak time is 6h.
In step (3), the preparation method of described silica is as follows: often add 15ml ethanol in the reactor, and correspondence adds 500ul water, 500ul ammoniacal liquor, after stirring, adds 400ul TEOS, room temperature reaction 9h, after reaction terminates, centrifugal 5 minutes, get lower sediment, ultrasonic disperse in ethanol, centrifugal again, 4 times repeatedly, by lower sediment N
2dry up, obtain silica.
In step (3), the eucalyptus base porous carbon after activation with the ratio of silica is: the corresponding 0.2g silica of eucalyptus base porous carbon after every 0.005g activates.
Adopt Raman spectrometer to the sign of porous carbon in experiment, as shown in Figure 1, along with the rising of temperature, the ratio of ID/IG is more and more less, and peak degree of separation is more and more higher, demonstrates its graphited porous carbon of the more and more higher acquisition of degree of graphitization.
As shown in Figure 2, X diffraction curve has 2 diffraction maximums at 24 ° and 44 ° of places, correspond respectively to (002), (101) crystal face of graphite, their intensity significantly increases along with the rising of temperature, simultaneously, 002 crystal face, along with temperature is gradually to 26.5 ° of skews, proves graphited raising further.
Porous carbon synthesized by the present invention is by specific surface instrument measurement the specific area, and result shows, specific area is at 1200-2000m
2/ g, illustrates larger specific area.
Lead ion is selected to be the object assessing solid-phase extraction column, from the capacity of pillar, the conditions such as adsorption flow rate, elution flow rate, repeatability are investigated, result shows: this product demonstrates adsorption capacity comparatively large (80-200mg/L), favorable reproducibility (3-5 time) and pollutes the advantages such as little, there is very strong practicality, improve the added value of agricultural product.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (5)
1. a preparation method for eucalyptus base porous carbon-Silica solid phase extraction column, is characterized in that: the concrete steps of described method are as follows:
(1) preparation of eucalyptus base porous carbon:
With eucalyptus bar for raw material, add zinc chloride and change in advance, under the condition of hydro-thermal, activate 1-3 hour, washing, dry, pulverize, obtain preactivated eucalyptus bar powder; In preactivated eucalyptus bar powder, add NaOH, fully mix, make column; Eucalyptus powder column is put into atmosphere furnace, nitrogen protection, at high temperature calcination; Naturally cool, take out, wash away NaOH with hydrochloric acid, dry, obtain eucalyptus base porous carbon;
(2) activation of eucalyptus base porous carbon:
In eucalyptus base porous carbon prepared by step (1), add nitration mixture, it is activated, make hole, eucalyptus Quito carbon surface increase carboxyl, oh group, improve adsorbance; Wash away unnecessary nitration mixture, dry, stand-by;
(3) preparation of eucalyptus base porous carbon-Silica solid phase extraction column:
Eucalyptus base porous carbon after step (2) activation is mixed with silica and mixes, install in polyethylene solid phase extraction tube, add upper sieve plate, compacting, obtained eucalyptus base porous carbon-Silica solid phase extraction column.
2. the preparation method of eucalyptus base porous carbon-Silica solid phase extraction column as claimed in claim 1, it is characterized in that: in step (1), the weight ratio of eucalyptus bar and zinc chloride is 0.5 ~ 2:1; The temperature of hydro-thermal is 100 ~ 200 degree; Particle diameter after pulverizing is 5mm; 0.5 ~ 2:1 with the weight ratio of NaOH in preactivated eucalyptus bar powder; The temperature and time of high temperature sintering is 600-1100 degree respectively, 2h.
3. the preparation method of eucalyptus base porous carbon-Silica solid phase extraction column as claimed in claim 1, it is characterized in that: in step (2), described nitration mixture is made up of sulfuric acid, nitric acid, and the w/v of eucalyptus base porous carbon and nitration mixture is 0.5-2:1mg/ml; Soak time is 4-8h.
4. the preparation method of eucalyptus base porous carbon-Silica solid phase extraction column as claimed in claim 1, it is characterized in that: in step (3), the preparation method of described silica is as follows: often add 10-20ml ethanol in the reactor, correspondence adds 100-1000ul water, 100-1000ul ammoniacal liquor, after stirring, add 200-700ul TEOS, room temperature reaction 5-12h, after reaction terminates, centrifugal 5 minutes, get lower sediment, ultrasonic disperse is in ethanol, more centrifugal, 4 times repeatedly, by lower sediment N
2dry up, obtain silica.
5. the preparation method of eucalyptus base porous carbon-Silica solid phase extraction column as claimed in claim 1, it is characterized in that: in step (3), the eucalyptus base porous carbon after activation with the ratio of silica is: the corresponding 0.005-0.2g silica of eucalyptus base porous carbon after every 0.005-0.2g activates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510060603.5A CN104667898B (en) | 2015-02-06 | 2015-02-06 | A kind of preparation method of eucalyptus base porous carbon-Silica solid phase extraction column |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510060603.5A CN104667898B (en) | 2015-02-06 | 2015-02-06 | A kind of preparation method of eucalyptus base porous carbon-Silica solid phase extraction column |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104667898A true CN104667898A (en) | 2015-06-03 |
| CN104667898B CN104667898B (en) | 2018-12-25 |
Family
ID=53303797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510060603.5A Expired - Fee Related CN104667898B (en) | 2015-02-06 | 2015-02-06 | A kind of preparation method of eucalyptus base porous carbon-Silica solid phase extraction column |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104667898B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107175090A (en) * | 2017-05-31 | 2017-09-19 | 中国科学院南京土壤研究所 | A kind of porous carbon solid-phase micro-extraction coating and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483500A (en) * | 2003-08-19 | 2004-03-24 | 中国进出口商品检验技术研究所 | Column for purifying pesticide residue and purification method thereof |
| CN1803242A (en) * | 2005-11-29 | 2006-07-19 | 林黎明 | Solid phase dispersion microwave extraction method of sample residues matrix and extraction stuffing and solvent |
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| CN101785990A (en) * | 2010-02-09 | 2010-07-28 | 乐山师范学院 | Method for preparing activated carbon-silicon dioxide mixed adsorbing material by using silicon tetrachloride |
-
2015
- 2015-02-06 CN CN201510060603.5A patent/CN104667898B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483500A (en) * | 2003-08-19 | 2004-03-24 | 中国进出口商品检验技术研究所 | Column for purifying pesticide residue and purification method thereof |
| CN1803242A (en) * | 2005-11-29 | 2006-07-19 | 林黎明 | Solid phase dispersion microwave extraction method of sample residues matrix and extraction stuffing and solvent |
| CN101785990A (en) * | 2010-02-09 | 2010-07-28 | 乐山师范学院 | Method for preparing activated carbon-silicon dioxide mixed adsorbing material by using silicon tetrachloride |
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
Non-Patent Citations (2)
| Title |
|---|
| W.RUDZISKI等: "Studies of properties of complex carbon-silica adsorbents", 《FRESENIUS JOURNAL OF ANALYTICAL CHEMISTRY》 * |
| 王应红等: "活性炭-二氧化硅双功能吸附材料对姜黄素的吸附", 《林产化学与工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107175090A (en) * | 2017-05-31 | 2017-09-19 | 中国科学院南京土壤研究所 | A kind of porous carbon solid-phase micro-extraction coating and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104667898B (en) | 2018-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103044970B (en) | Preparation method of wet-process Maya-blue-like dye | |
| CN103131285B (en) | A kind of Photothermal conversion composition and preparation method thereof | |
| CN105664847A (en) | Method for preparing high-specific surface area porous carbon material based on oil tea seed husk and application thereof | |
| CN107128899A (en) | A kind of preparation method of spherical nitrogen-doped carbon nano material | |
| CN106881071A (en) | A kind of preparation method of modified activated carbon/diatomite adsorbant | |
| CN107774294A (en) | A kind of novel photochemical catalyst K g C3N4And its prepare and apply | |
| CN105586036A (en) | Preparation method of nitrogen-doped fluorescent carbon dots | |
| CN104071787A (en) | Preparation method of biomass-based active carbon | |
| CN110813233A (en) | Method for adsorbing heavy metal ions in soil by coconut shell charcoal | |
| CN102674346A (en) | Process for preparing high-specific surface area composite pore structure coal-based activated carbon by using low dosage of KOH | |
| CN101376114B (en) | Method for preparing metal or metallic oxide/carbon composite material | |
| CN103706338B (en) | A kind of mud adsorbent removed for organic dye pollutant and preparation method thereof | |
| CN101942281B (en) | Organic binding agent for back aluminum paste of silicon-based solar battery and preparation method thereof | |
| CN106430304A (en) | Preparation method of high-specific surface and high-temperature-resistant ceria-zirconia solid solution | |
| CN101936832B (en) | New method for particle size analysis of ferruginous cemented mud rock | |
| CN106753662A (en) | A kind of preparation technology of biomass granule fuel reducing agent | |
| CN110357063B (en) | Carbon nanotube/porous carbon nanocomposite and preparation method and application thereof | |
| Khan et al. | Eriobotrya japonica assisted green synthesis of g‐C3N4 nanocomposites and its exceptional photoactivities for doxycycline and rhodamine B degradation with mechanism insight | |
| CN104667898A (en) | Preparation method of eucalyptus-based porous carbon-silicon dioxide solid-phase extraction column | |
| CN105060287B (en) | A kind of preparation method of graphene net material that is that ultracapacitor is connected with each other and rolling | |
| CN104399493A (en) | Anthemia-shaped NiS/ZnS visible light photocatalyst and preparation method thereof | |
| Huang et al. | Application of metallic nanoparticle-biochars with ionic liquids for thermal transfer fluids | |
| CN103301812A (en) | Magnetic core-shell microspheres, and preparation method and use thereof | |
| CN102897722A (en) | Alpha-In2Se3 nano-grade flower-ball solvothermal synthesizing method | |
| CN109847716B (en) | Natural mineral-based uranium extraction adsorbent from seawater and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20181225 Termination date: 20210206 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |