CN108906005A - A kind of graphene silica gel solid phase extraction material and preparation method thereof - Google Patents
A kind of graphene silica gel solid phase extraction material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of graphene silica gel solid phase extraction materials and preparation method thereof, and including graphene aerogel, the silica matrix being filled in graphene aerogel, preparation method is that D1 prepares graphene aerogel；The annealing of D2 graphene aerogel；Filling gel matrix in D3 graphene aerogel.Silica matrix is fixed in graphene aerogel by this method, it does not need using other polymer support materials, graphene aerogel has excellent absorbent-type, more silica matrix can be adsorbed, its column capacity is higher, graphene aerogel capillarity protrusion, can absorb target substance faster, keep detection sensitiveer quick.
Description
Technical field
The present invention relates to silica gel solid phase extraction techniques fields, and in particular to a kind of graphene silica gel solid phase extraction material and its
Preparation method.
Background technique
Solid Phase Extraction（Abbreviation SPE）It is the sample pre-treatments skill to grow up since 19th century the mid-80
Art, it is established on the basis of traditional liquid-liquid extraction, and similar mix of conjugate interaction and is widely used at present principle
HPLC, GC in stationary phase rudimentary knowledge have gradually developed, most of SPE is used to handling liquid samples, extraction, concentration
With purification half volatile therein and fixedness compound, main purpose is to reduce sample substrate interference, and it is sensitive to improve detection
Degree, SPE can also be applied on solid sample, but must first be processed into liquid.Solid-phase adsorbent common at present includes silicon
Gel matrix, high molecular polymer matrix, absorbent-type solid-phase adsorbent, mixed type solid-phase adsorbent.Silica matrix Solid Phase Extraction is small
Column higher cost, when carry out method exploitation, needs the help of professional, inconvenient to use.
Summary of the invention
To overcome the deficiency, the purpose of the present invention is to provide a kind of graphene silica gel solid phase extraction material and its preparations
Method.
The technical solution adopted by the present invention to solve the technical problems is：A kind of graphene silica gel solid phase extraction material, packet
The silica matrix for including graphene aerogel, being filled in graphene aerogel.
Specifically, silica matrix one kind selected from the following：Octadecyl silane（Sealing end）, octyl bonded silica
Glue, octadecyl silane（It is uncapped）, silica gel bonded cyano（CN）, silica gel bonded amino（NH 2 ）, silica gel bonded N-
Propyl ethylenediamine（PSA）, silica gel bonded quaternary ammonium salt functional group（SAX）, silica gel bonded carboxyl（COOH）, silica gel bonded propane sulfonic acid
（PRS）, silica gel bonded benzene sulfonic acid functional group（SCX）, non-bonded silica gel（Silica）, silica gel bonded glycol-based（Diol）.
A kind of preparation method of graphene silica gel solid phase extraction material, including：
D1 prepares graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphene oxide water that concentration is 5mg/mL
Solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, it is mixed
Liquid instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain the second mixed dispersion liquid, be transferred into tube furnace, in water
It closes under hydrazine atmosphere, is heated to 80-90 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining the first hydrogel, it is saturating with 20% water-alcohol solution
6h is analysed, after refrigerator freezing, then is freeze-dried with freeze dryer, obtains graphene aerogel, when freeze-drying, freeze dryer keeps 10Pa
Vacuum degree below, freeze-drying process 24-48h；
The annealing of D2 graphene aerogel
Graphene aerogel is placed in tube furnace and anneals, and is carried out in a manner of vacuumizing-filling the water nitrogen gas displacement 3 times, in nitrogen
It is warming up to 800-900 DEG C with the speed of 5 DEG C/min under gas atmosphere, and after keeping 5-10h, then room is down to the speed of 5 DEG C/min
Temperature, the graphene aerogel after being annealed；
Filling gel matrix in D3 graphene aerogel
Nanometer silica gel matrix is added in 20% ethyl alcohol, ultrasonic disperse, obtains silica matrix dispersion liquid, it will by being prepared in D2
Graphene aerogel after annealing is impregnated in silica matrix dispersion liquid, after fully absorbing, is taken out, under atmospheric pressure at room,
Place for 24 hours, after ethyl alcohol volatilization, then place it in 30-40 DEG C of vacuum drying oven it is dry for 24 hours, obtain filled with silica matrix
Graphene aerogel.
Specifically, the concentration of the suspension of the nanometer silica gel matrix is 30-40g/mL
Specifically, when the ultrasonic disperse, supersonic frequency 20-25kHz.
The invention has the advantages that：Silica matrix is fixed in graphene aerogel by this method, does not need to make
With other polymer support materials, graphene aerogel has excellent absorbent-type, can adsorb more silica matrix,
Column capacity is higher, and graphene aerogel capillarity protrusion can absorb target substance faster, keeps detection sensitiveer fast
It is prompt.
Specific embodiment
The present invention is described in further detail now.
Embodiment one
A kind of graphene silica gel solid phase extraction material, including graphene aerogel, the silica gel base being filled in graphene aerogel
Matter.
Specifically, the silica matrix selects octadecyl silane（Sealing end）, it is primarily adapted for use in adsorption sample matrix
Middle nonpolarity or moderately polar object, for example barbiturate, caffeine, drug, dyestuff, aromatic oil, fungicide, remove
Careless agent, pesticide, phthalic acid ester, surfactant, fat-soluble vitamin etc..
A kind of preparation method of graphene silica gel solid phase extraction material, including：
D1 prepares graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphene oxide water that concentration is 5mg/mL
Solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, it is mixed
Liquid instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain the second mixed dispersion liquid, be transferred into tube furnace, in water
It closes under hydrazine atmosphere, is heated to 90 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining the first hydrogel, be dialysed with 20% water-alcohol solution
6h after refrigerator freezing, then is freeze-dried with freeze dryer, obtains graphene aerogel, when freeze-drying, freeze dryer keep 10Pa with
Under vacuum degree, freeze-drying process 48h；
The annealing of D2 graphene aerogel
Graphene aerogel is placed in tube furnace and anneals, and is carried out in a manner of vacuumizing-filling the water nitrogen gas displacement 3 times, in nitrogen
800 DEG C are warming up to the speed of 5 DEG C/min under gas atmosphere, and after keeping 5h, then room temperature is down to the speed of 5 DEG C/min, obtained
Graphene aerogel after annealing；
Filling gel matrix in D3 graphene aerogel
Nanometer silica gel matrix is added in 20% ethyl alcohol, ultrasonic disperse, obtains silica matrix dispersion liquid, it will by being prepared in D2
Graphene aerogel after annealing is impregnated in silica matrix dispersion liquid, after fully absorbing, is taken out, under atmospheric pressure at room,
Place for 24 hours, after ethyl alcohol volatilization, then place it in 30 DEG C of vacuum drying oven it is dry for 24 hours, obtain the stone filled with silica matrix
Black alkene aeroge.
Specifically, the concentration of the suspension of the nanometer silica gel matrix is 30g/mL
Specifically, when the ultrasonic disperse, supersonic frequency 20-25kHz.
Embodiment two
A kind of graphene silica gel solid phase extraction material, including graphene aerogel, the silica gel base being filled in graphene aerogel
Matter.
Specifically, the silica matrix selects octyl bonded silica gel, relies primarily on the interaction of nonpolar carbochain, but
It is since the carbochain of octyl is shorter than the carbochain of octadecyl, so octyl bonded silica gel is to the non-polar compound in sample substrate
Adsorption capacity be markedly less than octadecyl silane, facilitate the sample too strong to non-polar compound absorption property and carry out
Elution, be mainly used in blood, urine, in body fluid and blood plasma drug and metabolic components extraction, it is fat-soluble in blood plasma and
The extraction of water soluble vitamin and for the desalination of large biological molecule sample etc..
A kind of preparation method of graphene silica gel solid phase extraction material, including：
D1 prepares graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphene oxide water that concentration is 5mg/mL
Solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, it is mixed
Liquid instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain the second mixed dispersion liquid, be transferred into tube furnace, in water
It closes under hydrazine atmosphere, is heated to 80 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining the first hydrogel, be dialysed with 20% water-alcohol solution
6h after refrigerator freezing, then is freeze-dried with freeze dryer, obtains graphene aerogel, when freeze-drying, freeze dryer keep 10Pa with
Under vacuum degree, freeze-drying process is for 24 hours；
The annealing of D2 graphene aerogel
Graphene aerogel is placed in tube furnace and anneals, and is carried out in a manner of vacuumizing-filling the water nitrogen gas displacement 3 times, in nitrogen
820 DEG C are warming up to the speed of 5 DEG C/min under gas atmosphere, and after keeping 6h, then room temperature is down to the speed of 5 DEG C/min, obtained
Graphene aerogel after annealing；
Filling gel matrix in D3 graphene aerogel
Nanometer silica gel matrix is added in 20% ethyl alcohol, ultrasonic disperse, obtains silica matrix dispersion liquid, it will by being prepared in D2
Graphene aerogel after annealing is impregnated in silica matrix dispersion liquid, after fully absorbing, is taken out, under atmospheric pressure at room,
Place for 24 hours, after ethyl alcohol volatilization, then place it in 32 DEG C of vacuum drying oven it is dry for 24 hours, obtain the stone filled with silica matrix
Black alkene aeroge.
Specifically, the concentration of the suspension of the nanometer silica gel matrix is 40g/mL
Specifically, when the ultrasonic disperse, supersonic frequency 20-25kHz.
Embodiment three
A kind of graphene silica gel solid phase extraction material, including graphene aerogel, the silica gel base being filled in graphene aerogel
Matter.
Specifically, the silica matrix selects octadecyl silane（It is uncapped）, physics, chemical property and sealing end
Octadecyl silane it is similar, but due to uncapped C18 bonded silica gel surface have more silanol functional group,
Additional polar interaction is made it have, compared with the octadecyl silane of sealing end, to the adsorptivity of alkali compounds
It can be enhanced, the polar form and nonpolar compound being mainly used in adsorption sample matrix.
A kind of preparation method of graphene silica gel solid phase extraction material, including：
D1 prepares graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphene oxide water that concentration is 5mg/mL
Solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, it is mixed
Liquid instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain the second mixed dispersion liquid, be transferred into tube furnace, in water
It closes under hydrazine atmosphere, is heated to 82 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining the first hydrogel, be dialysed with 20% water-alcohol solution
6h after refrigerator freezing, then is freeze-dried with freeze dryer, obtains graphene aerogel, when freeze-drying, freeze dryer keep 10Pa with
Under vacuum degree, freeze-drying process 28h；
The annealing of D2 graphene aerogel
Graphene aerogel is placed in tube furnace and anneals, and is carried out in a manner of vacuumizing-filling the water nitrogen gas displacement 3 times, in nitrogen
840 DEG C are warming up to the speed of 5 DEG C/min under gas atmosphere, and after keeping 6h, then room temperature is down to the speed of 5 DEG C/min, obtained
Graphene aerogel after annealing；
Filling gel matrix in D3 graphene aerogel
Nanometer silica gel matrix is added in 20% ethyl alcohol, ultrasonic disperse, obtains silica matrix dispersion liquid, it will by being prepared in D2
Graphene aerogel after annealing is impregnated in silica matrix dispersion liquid, after fully absorbing, is taken out, under atmospheric pressure at room,
Place for 24 hours, after ethyl alcohol volatilization, then place it in 35 DEG C of vacuum drying oven it is dry for 24 hours, obtain the stone filled with silica matrix
Black alkene aeroge.
Specifically, the concentration of the suspension of the nanometer silica gel matrix is 34g/mL
Specifically, when the ultrasonic disperse, supersonic frequency 20-25kHz.
Example IV
A kind of graphene silica gel solid phase extraction material, including graphene aerogel, the silica gel base being filled in graphene aerogel
Matter.
Specifically, the silica matrix is selected from silica gel bonded cyano（CN）, amino bonded silica gel is using silica gel as matrix
Amino solid-phase adsorbent, since it is with polar stationary phase and weak anion exchanger, amino bonded silica gel has double
Recast is used, and amino bonded silica gel is mainly used in the separation of isomer, it can also be used to remove sulfonate radical strong anion.
A kind of preparation method of graphene silica gel solid phase extraction material, including：
D1 prepares graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphene oxide water that concentration is 5mg/mL
Solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, it is mixed
Liquid instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain the second mixed dispersion liquid, be transferred into tube furnace, in water
It closes under hydrazine atmosphere, is heated to 84 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining the first hydrogel, be dialysed with 20% water-alcohol solution
6h after refrigerator freezing, then is freeze-dried with freeze dryer, obtains graphene aerogel, when freeze-drying, freeze dryer keep 10Pa with
Under vacuum degree, freeze-drying process 30h；
The annealing of D2 graphene aerogel
Graphene aerogel is placed in tube furnace and anneals, and is carried out in a manner of vacuumizing-filling the water nitrogen gas displacement 3 times, in nitrogen
860 DEG C are warming up to the speed of 5 DEG C/min under gas atmosphere, and after keeping 8h, then room temperature is down to the speed of 5 DEG C/min, obtained
Graphene aerogel after annealing；
Filling gel matrix in D3 graphene aerogel
Nanometer silica gel matrix is added in 20% ethyl alcohol, ultrasonic disperse, obtains silica matrix dispersion liquid, it will by being prepared in D2
Graphene aerogel after annealing is impregnated in silica matrix dispersion liquid, after fully absorbing, is taken out, under atmospheric pressure at room,
Place for 24 hours, after ethyl alcohol volatilization, then place it in 36 DEG C of vacuum drying oven it is dry for 24 hours, obtain the stone filled with silica matrix
Black alkene aeroge.
Specifically, the concentration of the suspension of the nanometer silica gel matrix is 36g/mL
Specifically, when the ultrasonic disperse, supersonic frequency 20-25kHz.
Embodiment five
A kind of graphene silica gel solid phase extraction material, including graphene aerogel, the silica gel base being filled in graphene aerogel
Matter.
Specifically, the silica matrix selects silica gel bonded N- propyl ethylenediamine（PSA）, PSA bonded silica gel and amino are solid
The absorption property of phase adsorbent is quite similar, is at present in the most widely used solid-phase adsorbent of every field, due to N- propyl
Ethylenediamine amino containing there are two, the pKa value of two amino is respectively 10.9 and 10.1, its ion-exchange capacity is made to compare amino bonded
Silica gel is stronger, and chelation can be generated between PSA bonded silica gel and metal ion, so can be used in adsorption sample matrix
Metal ion, pigment, organic acid etc..
A kind of preparation method of graphene silica gel solid phase extraction material, including：
D1 prepares graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphene oxide water that concentration is 5mg/mL
Solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, it is mixed
Liquid instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain the second mixed dispersion liquid, be transferred into tube furnace, in water
It closes under hydrazine atmosphere, is heated to 88 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining the first hydrogel, be dialysed with 20% water-alcohol solution
6h after refrigerator freezing, then is freeze-dried with freeze dryer, obtains graphene aerogel, when freeze-drying, freeze dryer keep 10Pa with
Under vacuum degree, freeze-drying process 44h；
The annealing of D2 graphene aerogel
Graphene aerogel is placed in tube furnace and anneals, and is carried out in a manner of vacuumizing-filling the water nitrogen gas displacement 3 times, in nitrogen
900 DEG C are warming up to the speed of 5 DEG C/min under gas atmosphere, and after keeping 10h, then room temperature is down to the speed of 5 DEG C/min, obtained
Graphene aerogel after annealing；
Filling gel matrix in D3 graphene aerogel
Nanometer silica gel matrix is added in 20% ethyl alcohol, ultrasonic disperse, obtains silica matrix dispersion liquid, it will by being prepared in D2
Graphene aerogel after annealing is impregnated in silica matrix dispersion liquid, after fully absorbing, is taken out, under atmospheric pressure at room,
Place for 24 hours, after ethyl alcohol volatilization, then place it in 38 DEG C of vacuum drying oven it is dry for 24 hours, obtain the stone filled with silica matrix
Black alkene aeroge.
Specifically, the concentration of the suspension of the nanometer silica gel matrix is 38g/mL
Specifically, when the ultrasonic disperse, supersonic frequency 20-25kHz.
Embodiment six
A kind of graphene silica gel solid phase extraction material, including graphene aerogel, the silica gel base being filled in graphene aerogel
Matter.
Specifically, the silica matrix selects silica gel bonded quaternary ammonium salt functional group（SAX）, quaternary ammonium salt bonded silica gel is with silicon
Glue exchanges solid-phase adsorbent as a kind of strong anion of matrix, and the functional groups such as quaternary ammonium salt are bonded on silica gel, are made it have
Extremely strong strong anion switching performance can be used for extracting and purify negatively charged target from water and nonaqueous phase sample substrate
Object is most suitable for extracting weakly acidic object；It can also be used to remove some strong anions in sample substrate, such as organic
Acid, sulfonate radical, inorganic ions and nucleotide etc.；It can also be used for the desalination of some large biological molecules.
A kind of preparation method of graphene silica gel solid phase extraction material, including：
D1 prepares graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphene oxide water that concentration is 5mg/mL
Solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, it is mixed
Liquid instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain the second mixed dispersion liquid, be transferred into tube furnace, in water
It closes under hydrazine atmosphere, is heated to 88 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining the first hydrogel, be dialysed with 20% water-alcohol solution
6h after refrigerator freezing, then is freeze-dried with freeze dryer, obtains graphene aerogel, when freeze-drying, freeze dryer keep 10Pa with
Under vacuum degree, freeze-drying process 45h；
The annealing of D2 graphene aerogel
Graphene aerogel is placed in tube furnace and anneals, and is carried out in a manner of vacuumizing-filling the water nitrogen gas displacement 3 times, in nitrogen
900 DEG C are warming up to the speed of 5 DEG C/min under gas atmosphere, and after keeping 10h, then room temperature is down to the speed of 5 DEG C/min, obtained
Graphene aerogel after annealing；
Filling gel matrix in D3 graphene aerogel
Nanometer silica gel matrix is added in 20% ethyl alcohol, ultrasonic disperse, obtains silica matrix dispersion liquid, it will by being prepared in D2
Graphene aerogel after annealing is impregnated in silica matrix dispersion liquid, after fully absorbing, is taken out, under atmospheric pressure at room,
Place for 24 hours, after ethyl alcohol volatilization, then place it in 40 DEG C of vacuum drying oven it is dry for 24 hours, obtain the stone filled with silica matrix
Black alkene aeroge.
Specifically, the concentration of the suspension of the nanometer silica gel matrix is 40g/mL
Specifically, when the ultrasonic disperse, supersonic frequency 20-25kHz.
The present invention is not limited to the embodiment, anyone should learn that the structure made under the inspiration of the present invention becomes
Change, the technical schemes that are same or similar to the present invention are fallen within the scope of protection of the present invention.
Technology not described in detail in the present invention, shape, construction portion are well-known technique.
Claims (8)
1. a kind of graphene silica gel solid phase extraction material, it is characterised in that：Including graphene aerogel, it is filled in graphene airsetting
Silica matrix in glue.
2. a kind of graphene silica gel solid phase extraction material according to claim 1, it is characterised in that：The silica matrix choosing
From one kind below：Octadecyl silane (sealing end), octyl bonded silica gel, octadecyl silane (uncapped), silicon
Glue is bonded cyano (CN), silica gel bonded amino (NH 2), silica gel bonded N- propyl ethylenediamine (PSA), silica gel bonded quaternary ammonium salt official
It can group (SAX), silica gel bonded carboxyl (COOH), silica gel bonded propane sulfonic acid (PRS), silica gel bonded benzene sulfonic acid functional group (SCX), not
Bonded silica gel (Silica), silica gel bonded glycol-based (Diol).
3. a kind of preparation method of graphene silica gel solid phase extraction material, it is characterised in that：Including：
D1 prepares graphene aerogel；
The annealing of D2 graphene aerogel；
Filling gel matrix in D3 graphene aerogel.
4. a kind of preparation method of graphene silica gel solid phase extraction material according to claim 3, it is characterised in that：To going
Large scale graphene oxide is added in ionized water, ultrasonic disperse 1h prepares the graphene oxide water solution that concentration is 5mg/mL, then
The mass ratio of addition carbon nanotube, ultrasonic disperse 30min, graphene oxide and carbon nanotube is 1:1, mixed liquor is obtained, to mixed
It closes and instills two drop ammonium hydroxide in liquid, stir 30min, obtain the second mixed dispersion liquid, be transferred into tube furnace, in hydrazine hydrate atmosphere
Under, it is heated to 80-90 DEG C, keeps for 24 hours, carrying out hydro-thermal reaction, obtaining the first hydrogel, with 20% water-alcohol solution dialysis 6h, ice
It after case freezing, then is freeze-dried with freeze dryer, obtains graphene aerogel.
5. a kind of preparation method of graphene silica gel solid phase extraction material according to claim 3, it is characterised in that：It is described
Graphene aerogel annealing process is：Graphene aerogel is placed in tube furnace and anneals, in a manner of vacuumizing-fill the water nitrogen into
Row gas displacement 3 times, it is warming up to 800-900 DEG C with the speed of 5 DEG C/min in a nitrogen atmosphere, and after keeping 5-10h, then with 5
DEG C/speed of min is down to room temperature, the graphene aerogel after being annealed.
6. a kind of preparation method of graphene silica gel solid phase extraction material according to claim 3, it is characterised in that：Graphite
The technique of filling gel matrix is in alkene aeroge, and nanometer silica gel matrix is added in 20% ethyl alcohol, and ultrasonic disperse obtains
Graphene aerogel after annealing is impregnated in preparing in D2 in silica matrix dispersion liquid, fills by silica matrix dispersion liquid
After point absorbing, takes out, under atmospheric pressure at room, place for 24 hours, after ethyl alcohol volatilization, then place it in 30-40 DEG C of vacuum drying oven
Drying for 24 hours, obtains the graphene aerogel filled with silica matrix.
7. a kind of preparation method of graphene silica gel solid phase extraction material according to claim 3, it is characterised in that：It is described
The concentration of the suspension of nanometer silica gel matrix is 30-40g/mL.
8. a kind of preparation method of graphene silica gel solid phase extraction material according to claim 6, it is characterised in that：It is described
When ultrasonic disperse, supersonic frequency 20-25kHz.
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| CN109870061A (en) * | 2019-03-27 | 2019-06-11 | 山东星火科学技术研究院 | A kind of phase change energy storage device and preparation method thereof |
| CN110404519A (en) * | 2019-09-04 | 2019-11-05 | 安徽省聚科石墨烯科技股份公司 | A kind of graphene aerogel adsorbent detected for phenylurea analog herbicide in water |
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