CN103127919A - Method for preparing titanium-based graphene coating for solid phase microextraction - Google Patents
Method for preparing titanium-based graphene coating for solid phase microextraction Download PDFInfo
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Abstract
The invention discloses a method for preparing a titanium-based graphene coating for solid phase microextraction. The method comprises five steps. According to the method, a silanization agent serves as an intermediate carrier, graphene is modified on the surface of a metal titanium wire, a coating which has a multi-layer sheet graphene structure is formed on the titanium-based surface, and the material can be applied to the extraction head in the solid phase microextraction technology. The method is advanced in thought, clear in concept, simple and convenient in coating preparation, the thickness is controllable, and the obtained coating is uniform, stable and high-temperature resistant. According to the solid phase microextraction head, trace phthalate in different water samples such as running water, underground water and lake water can be extracted at high efficiency, the corresponding detection limit can be 0.030mu g/L, the reproducibility is 2.2-12.6 percent, the marked recovery rate is 73.8-104.5 percent, and the repeated extraction frequency exceeds 200 times. The method has wide application prospects in the technical field of analytical chemistry and environmental analysis.
Description
Technical field
The present invention relates to a kind of preparation method of the multi-layer graphene structure solid-phase micro-extraction coating based on the titanium silk, relate in particular to a kind of titanium foundation stone China ink ene coatings preparation method for SPME, belong to analytical chemistry and environmental analysis technical field.
Background technology
Solid phase micro-extraction technique (SPME) is the novel Sample Pretreatment Technique that last century, the nineties grew up, and treasury is got, concentrated and resolve in one.After Canadian Pawliszyn research group succeeded in developing, Supelco company released commercial SPME device in 1993.SPME is after releasing, in short time decades, obtained very large application aspect sample pre-treatments, and successfully realized and the on-line coupling of gas-chromatography (GC), liquid chromatogram (HPLC), greatly shortened the pre-treatment time and improved extraction efficiency.The selection of extracting head coating and load are the cores of SPME, mainly follow the principle of " similar compatibility ", and it is selective similar to GC to extractibility.Although SPME is a kind of pretreatment technology of very attractive, due to present commercial SPME coating and few, limited its scope of application.Sensitivity, the degree of accuracy and range of application etc. to extraction ability, solvent resistance, heat endurance, reappearance and the subsequent analysis method of SPME also need be investigated accordingly.
In recent years, due to the larger specific area of carbon nanomaterial, the characteristics such as superior absorption property and stable chemical nature make it be widely used aspect sample pre-treatments.Graphene is one of representative of carbon nanomaterial, is the basic material of nearly all material with carbon element, has larger specific area (2630m
2/ g), remarkable heat endurance, chemical stability and superelevation mechanical strength.Condensed ring structure and hydrophobicity make Graphene to the absorption of compound with benzene ring structure.
The selection of extracting head matrix is also an important content of SPME.Fiber material relatively more commonly used has quartz fibre and stainless steel wire etc. at present.Quartz fibre rich surface hydroxyl be very beneficial for the bonding of micro-extraction coat layer, but quartz fibre material itself is more crisp, easily fractures in extraction process, this has just limited the service life of quartz fibre.The stainless steel wire the adsorbed hydroxyl content is not enough, and is unfavorable for the generation of chemical bonding.The present invention chooses the titanium silk as the matrix of SPME.The titanium silk also has a small amount of metallic element and its common titanium alloy that forms except contained titanium elements own.Compare with pure titanium silk, titanium alloy wire toughness is better.And there is one deck titanium oxide film on titanium silk surface, and under alkali condition, the titanyl key easily breaks to form the titanium hydroxyl bond, for the load that extracts coating provides possibility.
Summary of the invention
1, purpose: the purpose of this invention is to provide a kind of titanium foundation stone China ink ene coatings preparation method for SPME.The method has overcome the deficiencies in the prior art, is the preparation method of a kind of technique titanium foundation stone China ink ene coatings advanced, easy and simple to handle.
2, technical scheme: the present invention is a kind of titanium foundation stone China ink ene coatings preparation method for SPME, and it comprises the steps:
Step 1) get a segment length be the titanium silk of 10-15cm as the solid phase micro-extracting head matrix, carry out ultrasonic cleaning with organic solvent, after the titanium silk is taken out, use washed with de-ionized water, natural drying in air;
Step 2) under water bath condition, the titanium silk is inserted carry out the hydroxylating processing in the alkaline hydrogen sodium hydroxide solution, make the surperficial titanium oxide film of titanium silk form fine and close hydroxyl, make it be conducive to bonding with follow-up silylating reagent, successively clean with hydrochloric acid, methyl alcohol and deionized water after the titanium silk takes out, remove the free hydroxide ion in surface;
Step 3) immerses the titanium silk carries out silanization processing 12h in silylating reagent;
Step 4) is with N, and N '-dimethyl formamide is dispersant, and N, N '-dicyclohexylcarbodiimide be as crosslinking agent, and with carboxylated graphene powder mixing, obtain adhesive carrier carboxylated Graphene coating turbid solution;
Step 5) shifts out the titanium silk from the silylating reagent of described step 3), put at once baking oven and carry out the stable processing of drying; After having dried by the fire, the titanium silk is inserted in the adhesive carrier carboxylated Graphene coating turbid solution of described step 4), under 70 ℃ of water bath condition, it is surperficial that the condensation of carboxylated Graphene by carboxyl and silylating reagent amino is bonded to the titanium silk.After adhering to cated titanium silk and extracting out, in air drying, repeatedly carry out above step repeatedly from turbid solution, until coating layer thickness reaches desired thickness, be generally 19-21 μ m.The solid-phase micro-extraction coating that above step obtains is titanium base carboxylated Graphene coating.The titanium base carboxylated Graphene coating for preparing is packed in a preprepared stainless steel hollow sleeve (sleeve pipe away from an end of extraction coating with gas chromatographic sample introduction pad end-blocking), be cured processing, carboxylated Graphene coating after processing is reduced 12h with hydrazine under alkali condition, obtain titanium foundation stone China ink ene coatings, this coating is carried out burin-in process again, namely completes the whole preparation of described solid-phase micro-extraction coating.
Wherein, the organic solvent described in step 1) is selected from least a in acetone, methyl alcohol, carrene, acetonitrile etc.; The ultrasonic cleaning time is every kind of organic solvent at least 5 minutes;
Wherein, step 2) the alkaline concentration of sodium hydroxide solution described in is 1mol/L, and the processing time is 1-2h, and required bath temperature is 70 ℃;
Wherein, in step 3), described silylating reagent is that the 3-propyl-triethoxysilicane is dissolved in toluene, and its volume ratio is 1:9;
Wherein, in step 4), described with N, N '-dimethyl formamide (DMF) is dispersant, N, N '-dicyclohexylcarbodiimide (DCC) is as crosslinking agent, and with carboxylated graphene powder mixing, between the three, ratio used is DMF:DCC: the carboxylated Graphene is 5mL:0.1mg:0.1mg.
Wherein, the internal diameter of the described preprepared stainless steel hollow sleeve of step 5) is 709 ± 5 μ m;
Wherein, in the described curing schedule of step 5), under vacuum condition, temperature is 70 ℃, and the time is 2h; In described aging step, temperature is 280 ℃, and the time is 1h, and carries out under the helium protection.
Wherein, step 5) described " reducing 12h with hydrazine under alkali condition; obtain titanium foundation stone China ink ene coatings ", its detailed process is: the ammoniacal liquor of 1mL28% and the hydrazine solution of 1mL35% are dissolved in the ammoniacal liquor mixed solution that obtains hydrazine in the 10mL pure water, the titanium base carboxylated Graphene coating that obtains is reduced 12h in this mixed solution, obtain titanium foundation stone China ink ene coatings under 70 ° of C conditions.
The coating structure of said method gained SPME as shown in Figure 2, wherein, A is the titanium silk, B is the 3-propyl-triethoxysilicane, C is grapheme material.
The following describes above-mentioned preparation method's principle: Graphene is one of representative of carbon nanomaterial, is the basic material of nearly all graphite material, has larger specific area (2630m
2/ g), remarkable heat endurance, chemical stability and superelevation mechanical strength.Condensed ring structure and hydrophobicity make Graphene be difficult for and fixedly combine, this method adopts the method for covalent bonding, the carboxyl effect of shrinking of amino and carboxylated Graphene by the 3-propyl-triethoxysilicane will firmly be combined in fixedly phase surface with the Graphene of carboxyl functional group.The adhesive kind of using is a lot, as a kind of common fat-soluble condensing agent N, is generally solid under N '-dicyclohexylcarbodiimide, normal temperature, and under heating condition, dissolving gradually can be used for that between amino and carboxyl, dehydrating condensation forms peptide bond etc.In the incomplete polymerizing curable stage, it has good adhesive performance, can be used for firmly adsorbing the carboxylated grapheme material.After solidifying fully, it can form the outer absorbent coating with functionalization.So repeat several times, obtain having the SPME coating of certain thickness multilayer carboxylated graphene-structured, and form grapheme material under the hydrazine reducing agent effect.
The method utilizes silylating reagent as intermediate carrier, is difficult to the Graphene coating of load in the finishing of Titanium silk, for the preparation of novel solid phase micro extraction head.Silylating reagent used is the 3-propyl-triethoxysilicane.Outside functional coating Graphene by with the repeatedly reaction of 3-propyl-triethoxysilicane, form the coating with multilayer chip graphene-structured, be used for extraction water body low pole or nonpolar phthalate compound.The method thinking advanced person, definite conception, coating prepare easy, thickness is controlled, the gained coating evenly, stable, energy is high temperature resistant, can be used for efficient extraction water body Trace Phthalate Esters, corresponding detectability can reach 0.030 μ g/L, the extraction reappearance is 2.2～12.6%, and adding the external standard rate of recovery is 73.8～104.5%, and the re-extract access times are over 200 times.
3, advantage and effect: compared with prior art, have following beneficial effect based on solid-phase micro-extraction coating with multi-layer graphene structure of titanium silk and preparation method thereof under the present invention:
(1) the matrix used titanium silk of the present invention is the alloy that contains Determination of multiple metal elements, and it is stronger that toughness compares to quartz fibre, is conducive to long-term use.Titanium silk surface titanyl key is easily taken exercise under alkali condition and is formed the titanium hydroxyl, is convenient to the chemical bonding with grapheme material;
(2) compare with the mono-layer graphite ene coatings, the gap space between the Graphene coating adjacent two layers coating with sandwich construction that the present invention is prepared is conducive to the absorption of analyte, thereby improves extraction efficiency;
(3) sandwich construction Graphene coating production of the present invention is simple, easy and simple to handle, and grapheme material is high temperature resistant, and adsorptivity is strong, so range of application is more extensive.
Description of drawings
Fig. 1 is the preparation flow schematic diagram of titanium base Graphene solid-phase micro-extraction coating
Fig. 2 is the schematic cross-section of titanium base Graphene solid-phase micro-extraction coating, and wherein, A is the titanium silk, and B is the 3-propyl-triethoxysilicane, and C is grapheme material
Fig. 3 is the side schematic view of titanium base Graphene solid-phase micro-extraction coating, and wherein, A is the titanium silk, and C is grapheme material
Fig. 4 be titanium base Graphene solid-phase micro-extraction coating at 70 ℃, pH=6, under the KCl%=20% condition, extraction is 40 minutes, 280 ℃ of total ion chromatograms that the GC-MS that resolved 5 minutes analyzes.wherein 1, repefral, 2, diethyl phthalate, 3, dipropyl phthalate, 4, diisobutyl phthalate, 5, dibutyl phthalate, 6, two (the 2-methoxyl group second) esters of phthalic acid, 7, phthalic acid two (4-methyl-2-amyl group) ester, 8, phthalic acid two (2-ethyoxyl) ethyl ester, 9, diamyl phthalate, 10, DHP, 11, butyl benzyl phthalate, 12, phthalic acid two (2-butoxyethyl group) ester, 13, dicyclohexyl phthalate, 14, phthalic acid (2-ethylhexyl) ester, 15, di-n-octyl phthalate
Fig. 5 is titanium base Graphene solid-phase micro-extraction coating and commercialization PDMS coating effect of extracting comparison diagram, 1, repefral, 2, diethyl phthalate, 3, dipropyl phthalate, 4, diisobutyl phthalate, 5, dibutyl phthalate, 6, two (the 2-methoxyl group second) esters of phthalic acid, 7, phthalic acid two (4-methyl-2-amyl group) ester, 8, phthalic acid two (2-ethyoxyl) ethyl ester, 9, diamyl phthalate, 10, DHP, 11, butyl benzyl phthalate, 12, phthalic acid two (2-butoxyethyl group) ester, 13, dicyclohexyl phthalate, 14, phthalic acid (2-ethylhexyl) ester, 15, di-n-octyl phthalate
The specific embodiment
The present invention is further elaborated below in conjunction with instantiation, but the present invention is not limited to this a kind of example.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.The described dispersant N that uses of lower routine embodiment, N '-dimethyl formamide and binding agent N, N '-dicyclohexylcarbodiimide be all available from U.S. TEDIA company, and production code member is (DS1451-002) and (Q5G6N-RL).
Embodiment 1
See Fig. 1---Fig. 3, get the long titanium silk of one section 10cm, successively remove surface contaminants at 5mL acetone, methyl alcohol and deionized water for ultrasonic 5min.Under 70 ℃ of water bath condition, immerse hydroxylating processing 1h in the 1mol/L sodium hydroxide solution after taking out, put into immediately 120 ℃ of baking ovens and react 30min.After taking out, the titanium silk successively uses 1mol/L hydrochloric acid solution, the free hydroxide ion of methyl alcohol and washed with de-ionized water surface.After drying, the toluene solution 12h that the titanium silk is immersed 10% 3-propyl-triethoxysilicane carries out silanization to be processed.Under ultrasound condition, 0.1mg carboxylated Graphene is joined 5mL N, in N '-dimethyl formamide, add subsequently 0.1mg N, N '-dicyclohexylcarbodiimide fully mixes.The titanium silk is shifted out from the silylating reagent agent, put at once baking oven and carry out the stable processing of drying; After having dried by the fire, the titanium silk is inserted in carboxylated Graphene coating turbid solution, under 70 ℃ of water bath condition, it is surperficial that the condensation of carboxylated Graphene by carboxyl and silylating reagent amino is bonded to the titanium silk.After adhering to cated titanium silk and extracting out, in air drying, repeatedly carry out above step repeatedly from turbid solution, until coating layer thickness reaches 20 μ m left and right.The solid-phase micro-extraction coating that above step obtains is titanium base carboxylated Graphene coating.The titanium base carboxylated Graphene coating for preparing is packed in a preprepared stainless steel hollow sleeve (sleeve pipe away from an end of extraction coating with gas chromatographic sample introduction pad end-blocking), lower 70 ℃ of vacuum condition is cured and processes 2h, the hydrazine solution that carboxylated Graphene coating after processing is contained the ammoniacal liquor of 1mL28% and 1mL35% at 10mL reduces 12h, obtain titanium foundation stone China ink ene coatings, this coating is carried out burin-in process 1h at 280 ℃, namely completes the whole preparation of described solid-phase micro-extraction coating.
the methanol solution of 15 kinds of phthalic acid esters of preparation 0.05mg/L, 15 kinds of phthalic acid esters specifically refer to: repefral, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, DHP, di-n-octyl phthalate, phthalic acid (2-ethylhexyl) ester, dicyclohexyl phthalate, butyl benzyl phthalate, two (the 2-methoxyl group second) esters of phthalic acid, phthalic acid two (4-methyl-2-amyl group) ester, phthalic acid two (2-ethyoxyl) ethyl ester, phthalic acid two (2-butoxyethyl group) ester.Above-mentioned standard liquid is got 16 μ L be dissolved in pure water, be mixed with 15 kinds of phthalic acid mixed solutions of 8mL0.1 μ g/L.Get this embodiment gained titanium base Graphene solid phase micro-extracting head, after 280 ℃ of aging 15min, under 70 ℃ of water bath condition, immerse in the solution of above-mentioned phthalic acid ester, 400r/min rotating speed, potassium chloride concentration are under 20% condition, extraction 40min; Extracting head after extraction is directly inserted the GC mouth, through 280 ℃ of parsing 5min, carry out GC-MS and analyze, obtain result as shown in Figure 4.As seen from the figure, titanium base Graphene solid-phase micro-extraction coating has effect of extracting preferably to phthalic acid ester.Repeat above-mentioned experiment three times, relative standard deviation is 2.2～12.6% as a result, and stability is relatively good.Recovery of standard addition can reach 73.8～104.5%, satisfies the requirement of conventional analysis.
Titanium base Graphene solid-phase micro-extraction coating and commercial solid-phase micro-extraction coating PDMS with preparation compares according to above experimental program:
1) PDMS that the 100 μ m of use commercialization SPME are thick is after 280 ℃ of aging 30min, and under 70 ℃ of water bath condition, in the solution of the phthalic acid ester of immersion 8mL0.1 μ g/L, 400r/min rotating speed, potassium chloride concentration are under 20% condition, extraction 40min; Extracting head after extraction is directly inserted the GC mouth, through 280 ℃ of parsing 5min, carry out GC-MS and analyze, obtain result as shown in Figure 5.
2) extract under the same conditions with titanium base Graphene solid-phase micro-extraction coating the phthalic acid ester solution for preparing, then carry out GC-MS and analyze, obtain result as shown in Figure 5.
By shown in Figure 5, the effect of extracting of the titanium base Graphene micro-extraction coat layer that embodiment 1 is prepared is better than the effect of extracting of the thick PDMS of commercial 100 μ m.The average extraction efficiency of titanium foundation stone China ink ene coatings is 3.6-10.1 times of commercialization PDMS coating extraction efficiency.
Claims (8)
1. titanium foundation stone China ink ene coatings preparation method who is used for SPME, it is characterized in that: it comprises the steps:
Step 1) get a segment length be the titanium silk of 10-15cm as the solid phase micro-extracting head matrix, carry out ultrasonic cleaning with organic solvent, after the titanium silk is taken out, use washed with de-ionized water, natural drying in air;
Step 2) under water bath condition, the titanium silk is inserted carry out the hydroxylating processing in the alkaline hydrogen sodium hydroxide solution, make the surperficial titanium oxide film of titanium silk form fine and close hydroxyl, make it be conducive to bonding with follow-up silylating reagent, successively clean with hydrochloric acid, methyl alcohol and deionized water after the titanium silk takes out, remove the free hydroxide ion in surface;
Step 3) immerses the titanium silk carries out silanization processing 12h in silylating reagent;
Step 4) is with N, and N '-dimethyl formamide is dispersant, and N, N '-dicyclohexylcarbodiimide be as crosslinking agent, and with carboxylated graphene powder mixing, obtain adhesive carrier carboxylated Graphene coating turbid solution;
Step 5) shifts out the titanium silk from the silylating reagent of described step 3), put at once baking oven and carry out the stable processing of drying; After having dried by the fire, the titanium silk is inserted in the adhesive carrier carboxylated Graphene coating turbid solution of described step 4), under 70 ℃ of water bath condition, it is surperficial that the condensation of carboxylated Graphene by carboxyl and silylating reagent amino is bonded to the titanium silk; After adhering to cated titanium silk and extracting out, in air drying, repeatedly carry out above step repeatedly, until coating layer thickness reaches desired thickness 19-21 μ m from turbid solution; The solid-phase micro-extraction coating that above step obtains is titanium base carboxylated Graphene coating, the titanium base carboxylated Graphene coating for preparing is packed in a preprepared stainless steel hollow sleeve, sleeve pipe away from an end of extraction coating with gas chromatographic sample introduction pad end-blocking, be cured processing, carboxylated Graphene coating after processing is reduced 12h with hydrazine under alkali condition, obtain titanium foundation stone China ink ene coatings, this coating is carried out burin-in process again, namely completes the whole preparation of described solid-phase micro-extraction coating.
2. a kind of titanium foundation stone China ink ene coatings preparation method for SPME according to claim 1 is characterized in that: the organic solvent described in step 1) is selected from least a in acetone, methyl alcohol, carrene, acetonitrile; The ultrasonic cleaning time is every kind of organic solvent at least 5 minutes.
3. a kind of titanium foundation stone China ink ene coatings preparation method for SPME according to claim 1, is characterized in that: step 2) described in alkaline concentration of sodium hydroxide solution be 1mol/L, the processing time is 1-2h, required bath temperature is 70 ℃.
4. a kind of titanium foundation stone China ink ene coatings preparation method for SPME according to claim 1, it is characterized in that: the silylating reagent described in step 3) is that the 3-propyl-triethoxysilicane is dissolved in toluene, its volume ratio is 1:9.
5. a kind of titanium foundation stone China ink ene coatings preparation method for SPME according to claim 1, it is characterized in that: described in step 4) with N, N '-dimethyl formamide is that DMF is dispersant, N, N '-dicyclohexylcarbodiimide is that DCC is as crosslinking agent, and with carboxylated graphene powder mixing, between the three, ratio used is DMF:DCC: the carboxylated Graphene is 5mL:0.1mg:0.1mg.
6. a kind of titanium foundation stone China ink ene coatings preparation method for SPME according to claim 1, it is characterized in that: the internal diameter of the described preprepared stainless steel hollow sleeve of step 5) is 709 ± 5 μ m.
7. a kind of titanium foundation stone China ink ene coatings preparation method for SPME according to claim 1, it is characterized in that: in the described curing schedule of step 5), under vacuum condition, temperature is 70 ℃, and the time is 2h; In described aging step, temperature is 280 ℃, and the time is 1h, and carries out under the helium protection.
8. a kind of titanium foundation stone China ink ene coatings preparation method for SPME according to claim 1, it is characterized in that: step 5) described " reducing 12h with hydrazine under alkali condition; obtain titanium foundation stone China ink ene coatings ", its detailed process is: the ammoniacal liquor of 1mL28% and the hydrazine solution of 1mL35% are dissolved in the ammoniacal liquor mixed solution that obtains hydrazine in the 10mL pure water, the titanium base carboxylated Graphene coating that obtains is reduced 12h in this mixed solution, obtain titanium foundation stone China ink ene coatings under 70 ° of C conditions.
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Cited By (10)
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| CN103638693A (en) * | 2013-10-23 | 2014-03-19 | 大连理工大学 | Preparation method of in-tube solid-phase micro-extraction column |
| CN104437441A (en) * | 2014-11-03 | 2015-03-25 | 济南大学 | Method for preparing solid phase micro-extraction fiber of graphene coating |
| EP3053688A1 (en) * | 2015-02-06 | 2016-08-10 | Agie Charmilles SA | Graphene electrode |
| CN106622183A (en) * | 2016-11-15 | 2017-05-10 | 沈阳师范大学 | Novel solid-phase microextraction fiber preparation method and solid-phase microextraction fiber |
| CN109292754A (en) * | 2018-08-07 | 2019-02-01 | 济南大学 | A kind of preparation method of polyethyleneimine-modified graphene aerogel |
| CN109364901A (en) * | 2018-12-06 | 2019-02-22 | 福州大学 | The solid-phase micro-extraction coating fiber and application of a kind of carboxylated porous oxidation carbon-nitrogen nano-material and its preparation |
| CN111569848A (en) * | 2020-06-15 | 2020-08-25 | 甘肃政法大学 | Preparation method of solid-phase micro-extraction fiber with reduced graphene oxide as coating material |
| CN111665110A (en) * | 2020-06-24 | 2020-09-15 | 青岛菲灿新材料科技服务有限责任公司 | graphene-Co3O4Solid phase micro-extraction probe and preparation method thereof |
| CN113059808A (en) * | 2021-04-12 | 2021-07-02 | 华东理工大学 | Method for selectively processing 3D printing model by functionalized digital light |
| CN114990683A (en) * | 2022-06-06 | 2022-09-02 | 华北电力大学（保定） | Graphene coating stainless steel array microporous fiber and preparation method thereof |
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| CN103638693A (en) * | 2013-10-23 | 2014-03-19 | 大连理工大学 | Preparation method of in-tube solid-phase micro-extraction column |
| CN103638693B (en) * | 2013-10-23 | 2015-08-19 | 大连理工大学 | A kind of preparation method of in-tube solid-phase micro-extraction column |
| CN104437441A (en) * | 2014-11-03 | 2015-03-25 | 济南大学 | Method for preparing solid phase micro-extraction fiber of graphene coating |
| EP3053688A1 (en) * | 2015-02-06 | 2016-08-10 | Agie Charmilles SA | Graphene electrode |
| CN106622183A (en) * | 2016-11-15 | 2017-05-10 | 沈阳师范大学 | Novel solid-phase microextraction fiber preparation method and solid-phase microextraction fiber |
| CN109292754A (en) * | 2018-08-07 | 2019-02-01 | 济南大学 | A kind of preparation method of polyethyleneimine-modified graphene aerogel |
| CN109364901A (en) * | 2018-12-06 | 2019-02-22 | 福州大学 | The solid-phase micro-extraction coating fiber and application of a kind of carboxylated porous oxidation carbon-nitrogen nano-material and its preparation |
| CN111569848A (en) * | 2020-06-15 | 2020-08-25 | 甘肃政法大学 | Preparation method of solid-phase micro-extraction fiber with reduced graphene oxide as coating material |
| CN111665110A (en) * | 2020-06-24 | 2020-09-15 | 青岛菲灿新材料科技服务有限责任公司 | graphene-Co3O4Solid phase micro-extraction probe and preparation method thereof |
| CN113059808A (en) * | 2021-04-12 | 2021-07-02 | 华东理工大学 | Method for selectively processing 3D printing model by functionalized digital light |
| CN114990683A (en) * | 2022-06-06 | 2022-09-02 | 华北电力大学（保定） | Graphene coating stainless steel array microporous fiber and preparation method thereof |
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Application publication date: 20130605 |