CN108452783B - Preparation method of nano two-dimensional material with fish-scale metal oxide grown on nanosheets - Google Patents

Preparation method of nano two-dimensional material with fish-scale metal oxide grown on nanosheets Download PDF

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CN108452783B
CN108452783B CN201810300463.8A CN201810300463A CN108452783B CN 108452783 B CN108452783 B CN 108452783B CN 201810300463 A CN201810300463 A CN 201810300463A CN 108452783 B CN108452783 B CN 108452783B
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ocn
nano
fish
carrying
nitrate hexahydrate
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CN108452783A (en
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张兰
丁青青
黄川辉
卢巧梅
陈晖�
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Fuzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character

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Abstract

The invention belongs to the technical field of nano materials, and belongs to a preparation method of a nano two-dimensional material with fish scale-shaped metal oxide grown on nanosheets. The method specifically comprises the following steps: preparing black solid ultrathin carbon nitrogen oxide nanosheet OCN from urea and glucose; carrying out ultrasonic treatment and stripping on OCN, and carrying out thermal reaction on the OCN, cobalt nitrate hexahydrate, hexamethylenetetramine, water and ethanol in an oil bath to obtain green precipitate; reacting the obtained precipitate for three hours at 300 ℃ in the air atmosphere to obtain a black powdery sample; then heating to 300 ℃ in a hydrogen atmosphere, and carrying out heat treatment for 3-5 h to obtain black magnetic Co/Co3O4Fish-imitated scaly two-dimensional nano material. The invention has low cost and simple process, and the prepared magnetic fish-imitating scaly nano material has high specific surface area, permanent porosity, good adsorption effect on phytohormone and good application prospect in the aspect of sample pretreatment.

Description

Preparation method of nano two-dimensional material with fish-scale metal oxide grown on nanosheets
Technical Field
The invention belongs to the technical field of nano materials, and belongs to a preparation method of a nano two-dimensional material with fish scale-shaped metal oxide grown on nanosheets.
Background
Solid Phase Extraction (SPE) is a sample pretreatment technology developed in the 70 s of the 20 th century. The basic principle is that a solid adsorbent is used for adsorbing a target object, the target object is separated from a sample matrix and an interfering object, and then the separation and enrichment of an object to be detected are realized through elution. Compared with liquid-liquid extraction (LLE), SPE has the advantages of less solvent consumption, short operation time, wide application range, high automation degree and the like. However, SPE also has the disadvantages of poor adsorbent selectivity, easy blockage of microporous structure, expensive commercial extraction column, etc.
In the aspect of PH pretreatment, the SPE technology has gradually replaced LLE and becomes a main method for purifying and enriching hormone. In SPE, the choice of adsorbent is crucial. At present, C18The Oasis series adsorbents (HLB-general type, MCX cationic type, MAX-anionic type), PVPP (polyvinyl polypyrrolidone), DEAE (diethylaminoethyl cross-linked dextran gel) all have application in the hormone purification process. Wherein, the C18 column is used for enriching the needed endogenous hormone and has the widest application; various Oasis adsorbents have dual mechanisms of reverse phase and ion exchange, so that the adsorbents have high selectivity; the PVPP can adsorb a large amount of pigments, glycosides and phenols in plants; DEAE can purify various hormones while maintaining the acid-base environment of the system. There are also few reports of the use of multiple SPE columns in series to improve purification enrichment.
Disclosure of Invention
The invention aims to provide a preparation method of a nano two-dimensional material with fish scale-shaped metal oxide grown on nano sheets. The invention has low cost and simple process, and the prepared magnetic fish-imitating scaly nano material has high specific surface area, permanent porosity, good adsorption effect on phytohormone and good application prospect in the aspect of sample pretreatment.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nano two-dimensional material with fish scale-like metal oxide grown on nano sheets comprises the following steps:
(1) uniformly mixing urea and glucose (mass ratio =10:1), putting into a crucible, heating to 550 ℃ in the air atmosphere of a tube furnace for 1h, then cooling to 200 ℃ for 20 min, and finally heating to 800 ℃ and then keeping for 1 h; finally, naturally cooling to room temperature; obtaining black solid ultrathin oxidized carbon nitrogen nano-sheet OCN.
(2) Carrying out ultrasonic and stripping on the OCN obtained in the step (1), and then carrying out thermal reaction on the OCN, cobalt nitrate hexahydrate, hexamethylenetetramine, water and ethanol at 90 ℃ in an oil bath (the molar ratio of the cobalt nitrate hexahydrate to the hexamethylenetetramine is 1: 2; the concentration of the dispersed OCN in an aqueous solution after the OCN is ultrasonically stripped is 2.5 mg/mL; and the mass ratio of the OCN to the cobalt nitrate hexahydrate is 1: 87); the ratio of the total water volume used in the experiment to the ethanol volume was 2:1, resulting in a green precipitate.
(3) And (3) reacting the material obtained in the step (2) for three hours at 300 ℃ in an air atmosphere to obtain a black powdery sample.
(4) Heating the material obtained in the step (3) to 300 ℃ at the speed of 5-10 ℃/min in a hydrogen atmosphere, and carrying out heat treatment for 3-5 h to obtain black magnetic Co/Co3O4Fish-imitated scaly two-dimensional nano material.
The synthesized material is used as an adsorbent for solid phase extraction, and is combined with HPLC-MS to be applied to the extraction of phytohormone.
The invention has the advantages that:
(1) the method has simple and economic design, and the prepared nano fish scale-shaped two-dimensional material has simple preparation process and good repeatability and controllability.
(2) The obtained fish-like scaly two-dimensional material has large specific surface area, and the enhancement effect of the hydrodynamics brought by the special fish-like structure in the solution on the enrichment capacity of the target object is obvious; containing Co/Co3O4The metal/metal oxide enables the material to have certain magnetism and is beneficial to separation, and the material can be effectively controlled in the sample detection process, so that the material has excellent effect on the pretreatment of the plant hormone. The synthesized two-dimensional material is applied to an SPE adsorbent, can effectively adsorb phytohormone under the optimal condition, and has low detection limit and wide linear range.
Drawings
FIG. 1 is a TEM image of an ultrathin oxidized carbon nitrogen nanosheet (OCN);
FIG. 2 is an SEM image of a fish-imitated scaly nano two-dimensional material;
FIG. 3 is a drawing showing the effective absorption of actual phytohormones from a fish-like scale-like nano two-dimensional material applied to solid phase extraction;
FIG. 4 is an eluent optimization diagram of the practical phytohormone sample of the fish-imitated scaly nano two-dimensional material applied to solid phase extraction.
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
Example 1
(1) Uniformly mixing urea and glucose (mass ratio =10:1, 10 g;1 g), putting into a crucible, heating to 550 ℃ in the air atmosphere of a tube furnace for 1h, then cooling to 200 ℃ for 20 min, and finally heating to 800 ℃ and then keeping for 1 h; finally, naturally cooling to room temperature; obtaining black solid ultrathin oxidized carbon nitrogen nano-sheet OCN.
(2) And (2) carrying out ultrasonic and stripping on the OCN obtained in the step (1), and then carrying out thermal reaction on the OCN, cobalt nitrate hexahydrate, hexamethylenetetramine, water and ethanol at 90 ℃ in an oil bath (0.87 g of the cobalt nitrate hexahydrate and 0.84 g of the hexamethylenetetramine are used, the concentration of the OCN dispersed in an aqueous solution after ultrasonic stripping is 2.5 mg/mL, the mass ratio of the OCN to the cobalt nitrate hexahydrate is 1:87, 4mL of deionized water and 4mL of ethanol), so as to obtain a green precipitate.
(3) And (3) reacting the material obtained in the step (2) for three hours at 300 ℃ in an air atmosphere to obtain a black powdery sample.
(4) Heating the material obtained in the step (3) to 300 ℃ at the speed of 5-10 ℃/min in a hydrogen atmosphere, and carrying out heat treatment for 3-5 h to obtain black magnetic Co/Co3O4Fish-imitated scaly two-dimensional nano material.
Application example 1
(1) The synthesized material is used as an adsorbent for solid phase extraction, and is combined with HPLC-MS to be applied to the extraction of phytohormone.
(2) Under a set chromatographic method, reverse phase C is applied18Chromatographic column, mobile phase A is 0.1% formic acid water; b is acetonitrile containing 0.1% formic acid, the sample amount is 10 μ L, the flow rate is 1.0 mL/min, and the extraction time, extraction temperature and analysis time are optimizedThe analysis temperature, ion concentration, etc., and measuring phytohormones such as auxin, gibberellin, cytokinin, abscisic acid, etc.
(3) The phytohormone is detected under the conditions of extraction time of 60min, elution time of 10min and gradient elution.
Fig. 3 is a comparative graph of the optimization of the adsorbent dosage.
FIG. 4 shows the optimization of the elution solvent conditions, comparing methanol, acetonitrile, isopropanol, methanol with formic acid and acetonitrile, and it can be seen that the acetonitrile with acid is the best.
Wherein FIG. 1 is a TEM (transmission electron microscope) image of an ultrathin oxidized carbon nitrogen nanosheet (OCN), from which it can be clearly found that OCN is a wrinkled two-dimensional sheet consisting of folded and folded sheets.
Wherein, FIG. 2 is an SEM (scanning electron microscope) image of the fish scale-like nano two-dimensional material, and the figure shows that the shape of fish scales is well grown on an OCN template.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (3)

1. The application of the nano two-dimensional material of the fish scale-shaped metal grown on the nano sheets in the extraction of the plant hormones is characterized in that: the preparation method of the material comprises the following steps:
(1) uniformly mixing urea and glucose, putting into a crucible, heating to 550 ℃ in the air atmosphere of a tube furnace, keeping for 1h, then cooling to 200 ℃ and keeping for 20 min, and finally heating to 800 ℃ and keeping for 1 h; finally, naturally cooling to room temperature; obtaining black solid ultrathin oxidized carbon nitrogen nanosheet OCN;
(2) carrying out ultrasonic treatment and stripping on the OCN obtained in the step (1), and then carrying out thermal reaction on the OCN, cobalt nitrate hexahydrate, hexamethylenetetramine, water and ethanol at 90 ℃ in an oil bath to obtain green precipitate;
(3) reacting the precipitate obtained in the step (2) for three hours at 300 ℃ in an air atmosphere to obtain black powder;
(4) heating the powder obtained in the step (3) to 300 ℃ at the speed of 5-10 ℃/min in a hydrogen atmosphere, and carrying out heat treatment for 3-5 h to obtain black magnetic Co/Co3O4Fish-imitated scaly two-dimensional nano material.
2. Use according to claim 1, characterized in that: the mass ratio of urea to glucose in the step (1) is 10: 1.
3. Use according to claim 1, characterized in that: cobalt nitrate hexahydrate was used: the molar ratio of the hexamethylene tetramine is 1: 2; after OCN ultrasonic stripping, the concentration of the OCN dispersed in the water solution is 2.5 mg/mL, and the volume ratio of water to ethanol is 2:1 in an experiment; the mass ratio of OCN to cobalt nitrate hexahydrate is 1: 87.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN104391062A (en) * 2014-10-31 2015-03-04 厦门大学 Method for preparing g-C3N4 coating on solid-phase microextraction head
CN106582651A (en) * 2017-01-10 2017-04-26 武汉大学 Preparation method for porous carrier-loaded nano-cobalt catalyst
CN106622324A (en) * 2016-12-07 2017-05-10 福建医科大学 Graphite-phase nitrogen carbide nanosheet/cobaltosic oxide nanosheet composite nanomaterial of scale-shaped structure and preparation method and application thereof
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Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
CN104391062A (en) * 2014-10-31 2015-03-04 厦门大学 Method for preparing g-C3N4 coating on solid-phase microextraction head
CN106315574B (en) * 2015-06-29 2018-03-27 徐海波 Graphene oxide quantum dot and the material formed with class graphene-structured thing and preparation method
CN106622324A (en) * 2016-12-07 2017-05-10 福建医科大学 Graphite-phase nitrogen carbide nanosheet/cobaltosic oxide nanosheet composite nanomaterial of scale-shaped structure and preparation method and application thereof
CN106582651A (en) * 2017-01-10 2017-04-26 武汉大学 Preparation method for porous carrier-loaded nano-cobalt catalyst

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Title
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