CN108525635A - A kind of preparation method and applications of the magnetic nitrogen-doped carbon nanometer pipe based on MOF - Google Patents
A kind of preparation method and applications of the magnetic nitrogen-doped carbon nanometer pipe based on MOF Download PDFInfo
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- CN108525635A CN108525635A CN201810371860.4A CN201810371860A CN108525635A CN 108525635 A CN108525635 A CN 108525635A CN 201810371860 A CN201810371860 A CN 201810371860A CN 108525635 A CN108525635 A CN 108525635A
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- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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- 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
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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
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Abstract
The magnetic nitrogen-doped carbon nanometer pipe material based on MOF and the preparation method and application thereof that the invention discloses a kind of as sorbing material, which is formed by MOF high-temperature calcinations；Wherein, while retaining MOF appearances, carbon nanotube of the Surface Creation containing a large amount of free N elements.Using MOF as template, direct high-temperature calcination forms the magnetic carbon material of gained of the invention.Compared with MOF sorbing materials, carbon material environmental stability is stronger, and using the strong conjugate surface of carbon nanotube, it is pi-conjugated can to form π with object；Relative to business carbon nano tube, which has very strong magnetism, can simplify the detection process of object by MSPE methods.Preparation process of the present invention is simple, and there is gained magnetism nitrogen-doped carbon nano material higher magnetism, large specific surface area, superpower environmental stability can be specifically bound with object, and there is good application prospect in the fields such as content of Microcystin in detecting lake water.
Description
Technical field
The preparation method and applications of the present invention relates to a kind of magnetic nitrogen-doped carbon nanometer pipe based on MOF.
Background technology
Algae is biology most ancient on a kind of earth, their morphological differences is big, simple in structure, typically in ocean
Kind analogy fresh water species class it is more.The nutrition of algae, modes of reproduction are varied, they can rapid growth under suitable conditions,
And water surface is gathered under the action of the buoyancy and hydrographic factor of itself, the macroscopic algae solution of people is formed, i.e., " red tide "
(Red tide) or " wawter bloom " (Water-bloom)." red tide " or " wawter bloom " is some toxiferous algae classes, its hair mostly
It is raw to cause high risks to environment and culture fishery, it is considered as worldwide public hazards.Chemical analysis is the normal of algae toxin detection
With method, there is higher sensitivity.It includes high performance liquid chromatography (HPLC), capillary electrophoresis (CE), thin layer color
Spectrometry (TLC) and high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) etc..In recent years, by
In the advantages such as highly selective and highly sensitive of HPLC-MS/MS, it is made to be increasingly becoming the routine side of algae toxin analysis detection
Method.But with the continuous expansion of algae toxin pollution range, the actual sample type analyzed is needed to become increasingly complex, algae toxin
Content it is also lower and lower, therefore before in instrument, sample introduction is analyzed, need to carry out a degree of sample pre-treatments, it is dry to reduce
It disturbs, improve sensitivity of analytical method, reduce the pollution of instrument, ensure the reliable of analysis result.
Solid Phase Extraction (SPE) is the common pre-treating method of algae toxin separation and concentration, it results from 20th century 70
Mid-nineties 90 is currently used for sample cleanup, the most commonly used method based on solid-phase adsorbent of analyte enrichment method.SPE
Have many advantages, such as that easy to operate, solvent consumption is few, but it also has extraction pillar to be easy to block, operating process take it is longer etc.
Disadvantage.In order to overcome these disadvantages, and some Solid Phase Extraction new technologies are derived.The solid-phase adsorbent of magnetization
（MSPE）Just it is being widely used in the separation and concentration of object.This method is substantially the improvement of tradition dSPE methods, than
Traditional dSPE methods more quickly with simply.In MSPE methods, by permanent magnet generate externally-applied magnetic field help,
So that the separation of the solid-phase adsorbent and sample solution of magnetization becomes simpler.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to synthesize a kind of novel magnetic by calcination method for the first time
Property nitrogen-doped carbon nanometer pipe sorbing material, and applied to detection lake water in Microcystin content.Magnetic nitrogen-doped carbon nanometer
Pipe has up to 400 g/m as sorbing material3Specific surface area；In organic solution and strong acid（pH=1）Highly basic（pH=14）In
Structure still holding is stablized, thermal stability is good；It is easy preparation etc., meanwhile, additional is that CNTs provides magnetic particle, after convenient
Continuous concentration and separation.
To achieve the goals above, the technical solution adopted by the present invention is：
A kind of magnetic nitrogen-doped carbon nanometer pipe material as sorbing material be by easily prepared MOF (ZIF-67) calcinings and
At under hydrogen reducing, Co ions are exposed to surface, and material is made to have larger magnetism；While retaining MOF appearances, table
Face generates the carbon nanotube containing a large amount of free N elements.
The magnetic nitrogen-doped carbon nanometer pipe as sorbing material is by MOF, dinectly bruning forms in tube furnace；
It includes the following steps：
1）The preparation of MOF
(a):1.5 g-2.5 g organic ligands are dissolved in 20-40 mL methanol/ethanol mixed solutions（v:v=1:1-50:1）,
Ultrasonic dissolution；1.5 g-2.5 g of metal salt separately are taken, ultrasonic dissolution is in 20-40 mL methanol/ethanol mixed solutions（v:v=1:1-
50:1）In； (b):Two parts of clear solutions are mixed, stir 5-25 s energetically, then stand 15-30 h at room temperature；(c):Instead
After the completion of answering, products therefrom ultra-pure water and absolute methanol are respectively washed 3 times successively, 3- is centrifuged under the rotating speed of 3000-8000 rpm
5 min, products therefrom are dried in vacuum overnight at 30-70 DEG C, obtain MOF crystal；
2）The preparation of magnetic nitrogen-doped carbon nanometer pipe material
(a):0.1-5.0 g MOF are placed in and is warming up to 200-400 DEG C with the speed of 1-5 DEG C/min in tube furnace and protects
1-3 h are held, then is warming up to 650-950 DEG C with the speed of 1-5 DEG C/min and keeps 2-6 h, finally with 1-5 DEG C/min
Speed be down to room temperature（Calcination process keeps H2/ Ar atmosphere）, you can obtain final product.Product is collected with magnet to centrifuge tube
In, kept dry.
Step 1）'s（a）Middle organic ligand includes one or more in 2-methylimidazole, terephthalic acid (TPA).Metal salt packet
It includes one or more in cabaltous nitrate hexahydrate, six chloride hydrate zinc.
Step 1）'s（a）Middle methanol/ethanol mixed solution is methanol and ethyl alcohol by volume 1:1-50:1 mixes.
Using：The novel magnetic nitrogen-doped carbon nanometer pipe material of gained is used to detect the content of Microcystin in lake water.
It is an advantage of the invention that：1）The method of the present invention design is simple, economical, the novel magnetic nitrogen-doped carbon nanometer pipe of preparation
With larger specific surface area, it can quickly detect the content of Microcystin in lake water, still keep good after being repeated 5 times
Adsorption capacity and reproducibility provide possibility for the merchandized handling of the material.2）Composite material of the present invention is in water phase and organic
It is stabilized in phase, and there is good thermal stability, structural stability and resistance to acid and alkali, can realized and be used repeatedly,
Use cost can be greatly reduced.3）The present invention proposes the MOF dinectly brunings magnetic nitrogen-doped carbon nanometer pipe material is made.By
Easily prepared MOF is calcined, and under hydrogen reducing, Co metal ions are exposed to surface, and material is made to have larger magnetism；
While retaining MOF appearances, carbon nanotube of the Surface Creation containing a large amount of free N elements greatly expands functionalization
The type of carbon nanomaterial.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of magnetic nitrogen-doped carbon nanometer pipe material.
Fig. 2 is adsorption time curve graph of the magnetic nitrogen-doped carbon nanometer pipe material of present invention gained to Microcystin.
Fig. 3 is that the magnetic nitrogen-doped carbon nanometer pipe material of present invention gained extracts Microcystin and directly into standard items
Comparison diagram, a are chromatographic isolation of the mixed mark of 3 kinds of Microcystins after magnetic N doping graphitic carbon material is enriched with elution step
Figure, b are the chromatogram of the direct loading separation of the mixed mark of 3 kinds of Microcystins.
Specific implementation mode
The present invention is described in more detail for embodiment below in conjunction with the accompanying drawings, it should be pointed out that embodiment described below
It is intended to be convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1：
A kind of synthetic method of magnetism nitrogen-doped carbon nanometer pipe material comprising following steps：
The preparation of 1.1 ZIF-67：
(a):By 1.5 g 2-methylimidazoles（2-MeIm）It is dissolved in 20mL methanol/ethanol mixed solutions（v:v=1:1）, ultrasonic molten
Solution；Separately take cabaltous nitrate hexahydrate（Co(NO3)2·6H2O）1.5 g, ultrasonic dissolution is in 20mL methanol/ethanol mixed solutions（v:v=
1:1）In； (b):Two parts of clear solutions are mixed, 5 s is stirred energetically, then stands 15 h at room temperature；(c):Reaction is completed
Afterwards, products therefrom ultra-pure water and absolute methanol are respectively washed 3 times successively, 3min, products therefrom is centrifuged under the rotating speed of 3000 rpm
It is dried in vacuum overnight at 30 DEG C, obtains the ZIF-67 crystal of purple.
The preparation of 1.2 magnetic nitrogen-doped carbon nanometer pipe materials：
(a):0.1g ZIF-67 are placed in tube furnace and is warming up to 200 DEG C with the speed of 1 DEG C/min and keeps 1 h, then
It is warming up to 650 DEG C with the speed of 1 DEG C/min and keeps 2h, room temperature is finally down to the speed of 1 DEG C/min（It is calcined
Journey keeps H2/ Ar gaseous mixture atmosphere）, you can obtain final product.Product is collected with magnet into centrifuge tube, kept dry.
It can be found by Fig. 1：Carbon nanotube after calcining, which remains unchanged, maintains the type looks of ZIF-67, while end occurs in edge
Hold the carbon nanotube containing Co elements.
Embodiment 2：
A kind of synthetic method of magnetism nitrogen-doped carbon nanometer pipe material comprising following steps：
The preparation of 1.1 carboxylated ZIF-67：
(a):By 1.0g terephthalic acid (TPA)s（H2BDC）With 1.5 g 2-methylimidazoles（2-MeIm）It is dissolved in 30 mL methanol/ethanols
Mixed solution（v:v=25:1）, ultrasonic dissolution；Separately take cabaltous nitrate hexahydrate（Co(NO3)2·6H2O）2.0g, ultrasonic dissolution exist
30mL methanol/ethanol mixed solutions（v:v=25:1）In； (b):Two parts of clear solutions are mixed, stir 15 s energetically, then
100 DEG C of 10 h of reaction；(c):After the completion of reaction, products therefrom ultra-pure water and absolute methanol are respectively washed 3 times successively, 5000
4 min are centrifuged under the rotating speed of rpm, products therefrom is dried in vacuum overnight at 50 DEG C, and the carboxylated ZIF-67 for obtaining purple is brilliant
Body.
The preparation of 1.2 magnetic nitrogen-doped carbon nanometer pipe materials：
(a):2.0 g ZIF-67 are placed in tube furnace and are warming up to 300 DEG C and 2 h of holding with the speed of 3 DEG C/min,
750 DEG C being warming up to the speed of 3 DEG C/min again and keeping 4 h, room temperature is finally down to the speed of 3 DEG C/min（Calcining
Process keeps H2/ Ar gaseous mixture atmosphere）, you can obtain final product.Product is collected with magnet into centrifuge tube, kept dry.
Embodiment 3：
A kind of synthetic method of magnetism nitrogen-doped carbon nanometer pipe material comprising following steps：
The preparation of 1.1 ZIF-67@ZIF-8 bimetallics MOF：
(a):By 2.5 g 2-methylimidazoles（2-MeIm）It is dissolved in 40 mL methanol/ethanol mixed solutions（v:v=50：1）, ultrasound
Dissolving；Separately take cabaltous nitrate hexahydrate（Co(NO3)2·6H2O）1.5 g and six chloride hydrate zinc（Zn(Cl)2·6H2O）0.8 g surpasses
Sound is dissolved in 40 mL methanol/ethanol mixed solutions（v:v=50：1）In； (b):Two parts of clear solutions are mixed, are stirred energetically
Then 25 s stand 30 h at room temperature；(c):After the completion of reaction, products therefrom is respectively washed 3 successively with ultra-pure water and absolute methanol
It is secondary, 5 min are centrifuged under the rotating speed of 8000 rpm, products therefrom is dried in vacuum overnight at 70 DEG C, obtains the ZIF- of lilac
67@ZIF-8 bimetallic MOF crystal.
The preparation of 1.2 magnetic nitrogen-doped carbon nanometer pipe materials：
(a):5.0 g ZIF-67 are placed in tube furnace and is warming up to 400 DEG C with the speed of 5 DEG C/min and keeps 3 h, then
It is warming up to 950 DEG C with the speed of 5 DEG C/min and keeps 6 h, room temperature is finally down to the speed of 5 DEG C/min（Calcination process
Keep H2/ Ar gaseous mixture atmosphere）, you can obtain final product.Product is collected with magnet into centrifuge tube, kept dry.
Application example
The material that embodiment 1 is synthesized detects the microcystin in lake water as Magnetic solid phases fiber material in conjunction with HPLC-MS
The content of element, is as follows：
Adsorption time is tested：The magnetic nitrogen-doped carbon nanometer pipe material for weighing the above-mentioned preparations of 1.0 mg respectively, adds it to
It is 25 ng mL containing Microcystins Concentration-1, volume be 50 mL different centrifuge tubes in, adsorb 0- under room temperature
150 min stop absorption at 1,5,20,40,60,90,120,150 min；Material is isolated with magnet, eluant, eluent is added
Elute 10 min.Take eluent Accela efficient liquid phases system and TSQ Quantum Access Max triple quadrupole bars
Mass spectrometry analyzer detects the content of Microcystin, and as can be seen from Figure 2 absorption tends to be saturated after 90 min, so
The optimal adsorption time is 90 min.Simultaneously we measure under the adsorption time of 90 min, using the material carry out extraction and
Directly compared into mixed mark.As a result show that three kinds of standard algae toxin sample rate of recovery after enrichment are very high（Such as Fig. 3 institutes
Show）, by calculating enriching and recovering rate all 90% or more, and reproducibility is very good.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (5)
1. a kind of preparation method of the magnetic nitrogen-doped carbon nanometer pipe based on MOF, which is characterized in that the magnetism nitrogen-doped carbon is received
Mitron is by MOF, dinectly bruning forms in tube furnace comprising following steps：
1）The preparation of MOF
(a):1.5 g-2.5 g organic ligands are dissolved in 20-40 mL methanol/ethanol mixed solutions, ultrasonic dissolution；Separately take gold
Belong to 1.5 g-2.5 g of salt, ultrasonic dissolution is in 20-40 mL methanol/ethanol mixed solutions； (b):Two parts of clear solutions are mixed
It closes, stirs 5-25 s energetically, then stand 15-30 h at room temperature；(c):After the completion of reaction, by products therefrom ultra-pure water and
Absolute methanol is respectively washed 3 times successively, and 3-5 min are centrifuged under the rotating speed of 3000-8000 rpm, and products therefrom is true at 30-70 DEG C
Sky is dried overnight, and obtains MOF crystal；
2）The preparation of magnetic nitrogen-doped carbon nanometer pipe material
(a):0.1-5.0 g MOF are placed in and is warming up to 200-400 DEG C with the speed of 1-5 DEG C/min in tube furnace and protects
1-3 h are held, then is warming up to 650-950 DEG C with the speed of 1-5 DEG C/min and keeps 2-6 h, finally with 1-5 DEG C/min
Speed be down to room temperature, calcination process keeps H2/ Ar gaseous mixture atmosphere, obtains final product, and product is collected with magnet to centrifugation
Guan Zhong, kept dry.
2. preparation method according to claim 1, which is characterized in that step 1）'s（a）Middle organic ligand includes：2- methyl
It is one or more in imidazoles, terephthalic acid (TPA).
3. preparation method according to claim 1, which is characterized in that step 1）'s（a）Middle metal salt includes：Six hydration nitre
It is one or more in sour cobalt, six chloride hydrate zinc.
4. preparation method according to claim 1, which is characterized in that step 1）'s（a）Middle methanol/ethanol mixed solution is
Methanol and ethyl alcohol by volume 1:1-50:1 mixes.
5. the application of magnetic nitrogen-doped carbon nanometer pipe, feature made from the preparation method as described in claim 1-4 is any exist
In the magnetic nitrogen-doped carbon nanometer pipe material of gained is used to detect the content of Microcystin in lake water.
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Cited By (19)
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| CN109616333A (en) * | 2018-12-07 | 2019-04-12 | 武汉工程大学 | A kind of nitrogen-doped carbon nanometer pipe/cobaltosic oxide composite material and preparation method thereof |
| CN109663577A (en) * | 2019-01-31 | 2019-04-23 | 沈阳工业大学 | The preparation method of the nitrogen co-doped cobaltosic oxide of carbon |
| CN109678225A (en) * | 2018-12-10 | 2019-04-26 | 沈阳化工大学 | A kind of preparation method and applications of the electric Fenton film of carbon nanotube integration |
| CN109822110A (en) * | 2019-04-09 | 2019-05-31 | 安徽大学 | A kind of preparation method of the nano combined absorbing material of Zn@MWCNTs |
| CN110354884A (en) * | 2019-06-27 | 2019-10-22 | 华南师范大学 | A kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC and its preparation method and application |
| CN110694578A (en) * | 2019-09-23 | 2020-01-17 | 五邑大学 | Co-C-N composite material and preparation method and application thereof |
| CN110918075A (en) * | 2019-12-17 | 2020-03-27 | 中国科学院兰州化学物理研究所 | Preparation and application of metal organic framework magnetic nano porous carbon material |
| CN111036184A (en) * | 2020-01-03 | 2020-04-21 | 福州大学 | Preparation of hydroxylated magnetic nitrogen-doped carbon nano-tube based on MOF and application of hydroxylated magnetic nitrogen-doped carbon nano-tube in detection of auxin content in tea |
| CN111250131A (en) * | 2020-01-16 | 2020-06-09 | 辽宁大学 | Co3ZnC/Co @ NGC magnetic wave-absorbing material and preparation method and application thereof |
| CN111547701A (en) * | 2020-05-12 | 2020-08-18 | 湖南垚恒环境科技有限公司 | Magnetic cobalt nanoparticle confinement nitrogen-doped porous carbon material and preparation method thereof |
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| CN111672474A (en) * | 2020-06-28 | 2020-09-18 | 福州大学 | Magnetic nitrogen-doped carbon oxide nanotube material and preparation method and application thereof |
| CN111760555A (en) * | 2020-06-08 | 2020-10-13 | 天津科技大学 | Preparation method and application of ZIF-based low-temperature adsorption material |
| CN112264074A (en) * | 2020-11-04 | 2021-01-26 | 天津大学 | Nitrogen-doped carbon nanosheet-loaded Fe-based catalyst and preparation method and application thereof |
| CN112827495A (en) * | 2021-01-05 | 2021-05-25 | 北京科技大学 | Preparation method of heat storage/catalysis integrated material |
| CN114713259A (en) * | 2022-04-02 | 2022-07-08 | 中山大学 | Preparation of cobalt-carbon-nitrogen hollow polyhedral catalyst and application of cobalt-carbon-nitrogen hollow polyhedral catalyst in degradation of emerging pollutants |
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| CN109822110A (en) * | 2019-04-09 | 2019-05-31 | 安徽大学 | A kind of preparation method of the nano combined absorbing material of Zn@MWCNTs |
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Application publication date: 20180914 |