CN108176364A - The preparation method of cobalt/carbon nano-composite material derived from a kind of metal organic framework - Google Patents
The preparation method of cobalt/carbon nano-composite material derived from a kind of metal organic framework Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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Abstract
The present invention provides a kind of preparation methods of cobalt/carbon nano-composite material derived from metal organic framework, preparation process is by 4,4 biphenyl dicarboxylic acids or 1,3,5 benzenetricarboxylic acids are dissolved in the aqueous solution containing potassium hydroxide or sodium hydroxide, the aqueous solution of soluble metal cobalt salt is added in, after carrying out mixing reaction under room temperature, cobalt-based metal organic framework presoma is obtained after centrifuge washing, drying.Then cobalt/the carbon nano-composite material is obtained after obtained presoma is calcined under nitrogen or argon gas atmosphere.The preparation of cobalt-based metal organic framework precursor that the present invention uses has the advantages that ambient operation, saves energy consumption, water as solvent, environmental-friendly, and magnetic cobalt/the carbon nano-composite material synthesized has excellent selective adsorption capacity for triphenylmethane dye, can also carry out simple and quick separation using magnetic.
Description
Technical field
The present invention relates to the preparing technical fields of cobalt/carbon nano-composite material, and particularly one kind is with metal organic framework material
The method for expecting to prepare cobalt/carbon nano-composite material for presoma.
Background technology
Cobalt/carbon nano-composite material is obtaining more and more extensive concern in recent decades, because their application is spread
The various fields such as sensing, microwave absorption, ultracapacitor, absorption, catalysis.The conventional synthesis technology of cobalt/carbon nano-composite material
Including chemical vapour deposition technique, arc discharge method, plasma evaporation method etc..However, these synthetic technologys have complex process,
The shortcomings of synthesis condition is harsh, of high cost, cumbersome limits their large-scale production and application.
Metal-organic framework materials typically refer to metal ion or metal atomic cluster and organic ligand by being self-assembly of
One kind there is the crystalline material of periodic network structure and porous character.In recent years, to contain cobalt-based metal-organic framework materials
For presoma, cobalt/carbon nano-composite material can be obtained by the straightforward procedure calcined in inert gas.In the prior art,
The preparation of the nano tube supported nanometer cobalt catalyst of a kind of magnetic reported such as the Chinese patent that Authorization Notice No. is CN 103816905B
In this method, the metal organic framework product Co-MOF of cobalt is prepared for first with solvent-thermal method for method, and wherein reaction temperature is
80-180 DEG C, reaction time 8-120h, reaction reagent is methanol, ethyl alcohol, n,N-Dimethylformamide (DMF).Then by Co-
MOF is calcined in tube furnace and is obtained carbon nanotube loaded nanometer cobalt catalyst.Such as the China of 106410224 A of Publication No. CN
A kind of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst of patent report and preparation method thereof, in this method, at 160 degree
Under conditions of 72h, hydro-thermal is prepared for [Co (O-BDC) (bbp)] precursor, and it is nano combined can to obtain cobalt carbon pores shape through high-temperature calcination
Object.A kind of metallic framework organic compound derivatization magnetic carbon as 104841402 A Chinese patents of Publication No. CN are reported is received
Rice material and application thereof, in this method, using methanol or DMF as solvent, under conditions of room temperature, be prepared for a series of iron content or
The MOF precursors of cobalt.However, in the above-mentioned methods, the preparation of metal organic framework presoma needs to have using methanol, DMF etc.
The reaction conditions such as poison harmful organic solvent, higher reaction temperature or longer reaction time, are unfavorable for the big of MOF precursors
Technical scale metaplasia is produced.
Invention content
The shortcomings that in order to overcome the prior art, the purpose of the present invention is to provide one kind to be derived from metal organic framework with insufficient
Cobalt/carbon nano-composite material preparation method, in this method, in the preparation process of metal organic framework presoma, using water as
Reaction dissolvent is not needed to using the organic solvents such as methanol, ethyl alcohol, DMF, and can react at normal temperatures, the reaction time is short, behaviour
Make simple.In addition, gained cobalt/carbon nano-composite material has excellent selective absorption performance to triphenylmethane dye,
And it can realize simple and quick separation using magnetism.
To achieve the above object, the present invention provides cobalt/carbon nano-composite material derived from a kind of metal-organic framework materials
Preparation method, it is as follows including step：
(1) preparation of cobalt-based metal organic framework presoma：By 1,3,5- benzenetricarboxylic acids (1,3,5-H3) or 4,4 ' BTC-
Biphenyl dicarboxylic acid (4,4 '-H2BPDC) be dissolved in alkaline aqueous solution, add in the aqueous solution of soluble metal cobalt salt, under room temperature into
Row is mixed, and then obtains cobalt-based metal organic framework presoma after centrifuge washing, drying；
(2) preparation of cobalt/carbon nano-composite material：After the presoma heating that step (1) is obtained under protective atmosphere into
Row calcining, obtains the cobalt/carbon nano-composite material after cooling.
In the step (1), the alkaline aqueous solution is sodium hydroxide or the aqueous solution of potassium hydroxide；The 1,3,5- benzene
The amount ratio of the substance of tricarboxylic acid and sodium hydroxide or potassium hydroxide is 1:3；4,4 '-the biphenyl dicarboxylic acid and sodium hydroxide or hydrogen
The amount ratio of the substance of potassium oxide is 1:2.
In the step (1), the soluble cobalt is cobaltous sulfate, cobalt nitrate, cobalt chloride or cobalt acetate；The 1,3,5-
The amount ratio of the substance of benzenetricarboxylic acid and Cobalt salts is 2:3；The amount ratio of the substance of the 4,4 '-biphenyl dicarboxylic acid and Cobalt salts
It is 1:1.
In the step (1), the mixing speed is 400~1000r/min, and mixing time is 0.5~24 hour, centrifugation
The rotating speed of washing is 5000~10000r/min, and drying temperature is 60~80 DEG C, and the time is 4~8 hours.
In the step (2), the protective atmosphere is nitrogen or argon gas.
In the step (2), the heating rate is 1~15 DEG C/min, and calcination time is 1~24 hour, calcination temperature
It is 500~1000 DEG C.
Magnetic cobalt/carbon composite obtained by above-mentioned preparation method, the metal organic framework presoma are [Co (BPDC)
(H2O)2]·H2O or [NaCo3(BTC)2(μ3-OH)](μ2-H2O)4(H2O)7·1.5H2On。
Magnetic cobalt/carbon composite obtained by the present invention is made of carbon and carbon-coated cobalt nano-particle, cobalt nanometer
A diameter of 5~the 100nm of grain.
Compared with prior art, the advantage of the invention is that：
(1) present invention is in the preparation process of cobalt-based metal organic framework precursor, using water as solvent, does not need to use first
The organic solvents such as alcohol, ethyl alcohol, DMF, and do not need to the reaction conditions such as hydro-thermal solvent heat.
(2) preparation method of magnetic cobalt/carbon composite of the present invention, it is easy to operate, it is easily controllable, be conducive to extensive life
Productionization.
(3) cobalt/carbon nano-composite material of the present invention has the selective absorption performance of excellent triphenylmethane dye,
And it is easily removed using magnetism.
Description of the drawings
Fig. 1 is the XRD diagram that the XRD diagram of 1 precursor of (a) embodiment and (b) simulate Co-BPDC.
Fig. 2 is the XRD diagram that the XRD diagram of 2 precursor of (a) embodiment and (b) simulate Co-BTC.
Fig. 3 is (a) embodiment 1 and the XRD diagram of 2 cobalts of (b) embodiment/carbon composite.
Fig. 4 is that the SEM of 2 cobalts of embodiment/carbon nano-composite material schemes.
Fig. 5 is the hysteresis graph of 2 cobalts of embodiment/carbon nano-composite material.
Fig. 6 for 2 product of embodiment adsorb (a) acid fuchsin, (b) malachite green, (c) basic fuchsin, (d) acid fuchsin-
The purple of methylene blue mixed solution, (e) malachite green-rhodamine B mixed solution and (f) basic fuchsin-methyl orange mixed solution
Outer visible absorbance curve.
Specific embodiment
Here is that in conjunction with specific embodiments, the present invention is further explained.These embodiments are merely to illustrate the present invention, but not
For limiting the scope of the invention.
Embodiment 1
The preparation method of cobalt/carbon composite, specifically includes following steps derived from a kind of metal organic framework：
(1) 0.484g 4,4 '-biphenyl dicarboxylic acid and 0.224g KOH are dissolved in wiring solution-forming in 25mL water, by 0.582g
Cobalt nitrate hexahydrate is dissolved in wiring solution-forming in 25mL water, then both solution are carried out room temperature and are mixed 0.5 hour, mixing speed
For 500r/min, centrifuge washing is then carried out under the rotating speed of 8000r/min, is placed into baking oven, 70 DEG C of dryings 5 hours obtain
To cobalt-based metal organic framework presoma；
(2) presoma that step (1) obtains is put into quartz boat, with nitrogen as protection gas in tube furnace, with 5
DEG C/heating rate of min, 900 degree are heated to, is kept for 3 hours start to cool down, is taken out after being cooled to room temperature and obtains black
Cobalt/carbon nano-composite material.
Fig. 1 is X-ray powder diffraction (XRD) figure of cobalt-based metal organic framework precursor that the present embodiment is prepared
Spectrum, it is consistent with the XRD spectrum that Co-BPDC is simulated in Fig. 1 b.
Fig. 3 a are the XRD spectrum of cobalt/carbon nano-composite material that the present embodiment is prepared.26 ° of peak is typical in figure
Graphitized carbon (002) crystallographic plane diffraction peak, other three apparent diffraction maximums can index turn to the diffraction of cubic phase metal Co
Peak.
Embodiment 2
(1) 1,3,5- benzenetricarboxylic acids of 0.414g and 0.24g NaOH are dissolved in wiring solution-forming in 50mL water, by 0.714g six
Water cobalt chloride is dissolved in wiring solution-forming in 50mL water, then both solution are carried out room temperature and are mixed 1 hour, and mixing speed is
Then 800r/min carries out centrifuge washing under the rotating speed of 10000r/min, places into baking oven, 80 DEG C of dryings 5 hours obtain
Co-BTC presomas；
(2) presoma that step (1) obtains is put into quartz boat, with nitrogen as protection gas in tube furnace, with 5
DEG C/heating rate of min, 800 degree are heated to, is kept for 3 hours start to cool down, is taken out after being cooled to room temperature and obtains the magnetic of black
Property cobalt/carbon composite.
Fig. 2 is X-ray powder diffraction (XRD) figure of cobalt-based metal organic framework precursor that the present embodiment is prepared
Spectrum, from figure 2 it can be seen that consistent with the XRD spectrum that Co-BTC is simulated in Fig. 2 b.
Fig. 3 b are the XRD spectrum of cobalt/carbon nano-composite material that the present embodiment is prepared.26 ° of peak is typical in figure
Graphitized carbon (002) crystallographic plane diffraction peak, other three apparent diffraction maximums can index turn to the diffraction of cubic phase metal Co
Peak.
Fig. 4 is scanning electron microscope (SEM) collection of illustrative plates of cobalt/carbon nano-composite material that the present embodiment is prepared.It is shown in figure
Cobalt/carbon sample is made of micron bar, and a large amount of cobalt nano-particle of the Dispersion on surface of these micron bars.
Fig. 5 is the B-H loop collection of illustrative plates of cobalt/carbon nano-composite material that the present embodiment is prepared, and shows cobalt/carbon nanometer
The saturation magnetization of composite material is 74.75emu/g, is easy to Magnetic Isolation.
Embodiment 3
0.582g cobalt nitrate hexahydrates are changed to tetra- water acetic acids of 0.498g by the specific experiment step of the present embodiment with embodiment 1
Cobalt.
Embodiment 4
0.714g CoCL2 6H2Os are changed to seven water sulfuric acid of 0.562g by the specific experiment step of the present embodiment with embodiment 2
Cobalt.
Embodiment 5
A concentration of 100mg/ of 30mL are added in using cobalt/carbon nano-composite material that 3mg embodiments 2 are prepared as adsorbent
In the acid fuchsine solution of L, after adsorbing different time sections, adsorbent is removed with magnet, utilizes ultraviolet-visible absorption spectroscopy instrument
Acid fuchsin aqueous solution after test absorption.The ultravioletvisible absorption of 2 product of embodiment absorption acid fuchsin is shown in Fig. 6 a
Spectrum.It can be seen from the figure that with the extension of adsorption time, characteristic absorption peak (542nm) intensity of acid fuchsin disappears substantially
It loses, it is fine that this illustrates that cobalt/carbon nano-composite material that embodiment 2 is prepared has the acid fuchsin molecule in aqueous solution
Adsorption capacity.
Embodiment 6
A concentration of 50mg/L of 30mL are added in using cobalt/carbon nano-composite material that 3mg embodiments 2 are prepared as adsorbent
Malachite green solution in, adsorb different time sections after, adsorbent is removed with magnet, utilize ultraviolet-visible absorption spectroscopy instrument survey
Malachite green aqueous solution after examination absorption.The ultraviolet-visible absorption spectroscopy that embodiment 2 adsorbs malachite green is shown in Fig. 6 b.From
It can be seen from the figure that, with the extension of adsorption time, characteristic absorption peak (616nm) intensity of malachite green disappears substantially, this says
Cobalt/carbon nano-composite material that bright embodiment 2 is prepared has absorption well for the malachite green molecule in aqueous solution
Ability.
Embodiment 7
A concentration of 50mg/L of 30mL are added in using cobalt/carbon nano-composite material that 3mg embodiments 2 are prepared as adsorbent
Basic Fuchsin in Aqueous Solution in, adsorb different time sections after, adsorbent is removed with magnet, utilize ultraviolet-visible absorption spectroscopy instrument survey
Basic fuchsin aqueous solution after examination absorption.The ultravioletvisible absorption light of 2 product of embodiment absorption basic fuchsin is shown in Fig. 6 c
Spectrum.It can be seen from the figure that with the extension of adsorption time, absorption peak (542nm) intensity of basic fuchsin disappears substantially, this says
Cobalt/carbon nano-composite material that bright embodiment 2 is prepared has absorption well for the basic fuchsin molecule in aqueous solution
Ability.
Embodiment 8
30mL acid fuchsins are added in using cobalt/carbon nano-composite material that 3mg embodiments 2 are prepared as adsorbent
In the mixed solution of (100mg/L) and methylene blue (20mg/L), after adsorbing 300min, adsorbent is removed with magnet, is utilized
Aqueous solution after the test absorption of ultraviolet-visible absorption spectroscopy instrument.2 product of embodiment absorption acid fuchsin and Asia is shown in Fig. 6 d
Ultraviolet-visible absorption spectroscopy after methyl blue mixed solution.It can be seen from the figure that after absorption 300min, only methylene blue
Characteristic absorption peak (664nm), and the absorption peak (542nm) of acid fuchsin disappears substantially, this illustrates what embodiment 2 was prepared
Cobalt/carbon nano-composite material has good selective adsorption capacity for the acid fuchsin molecule in mixed dye solution.
Embodiment 9
30mL malachite greens are added in using cobalt/carbon nano-composite material that 3mg embodiments 2 are prepared as adsorbent
In the mixed dye solution of (50mg/L) and rhodamine B (20mg/L), after adsorbing 300min, adsorbent is removed with magnet, profit
With the aqueous solution after the test absorption of ultraviolet-visible absorption spectroscopy instrument.It is molten that 2 product of embodiment absorption mixed dye is shown in Fig. 6 e
Ultraviolet-visible absorption spectroscopy after liquid.It can be seen from the figure that after absorption 300min, the only characteristic absorption peak of rhodamine B
(554nm), and the absorption peak (616nm) of malachite green disappears substantially, this illustrates that cobalt/carbon nanometer that embodiment 2 is prepared is answered
Condensation material has good selective adsorption capacity for the malachite green molecule in mixed dye solution.
Embodiment 10
30mL basic fuchsins are added in using cobalt/carbon nano-composite material that 3mg embodiments 2 are prepared as adsorbent
In (50mg/L) and the mixed solution of methyl orange (20mg/L), after adsorbing 300min, adsorbent is removed with magnet, utilization is ultraviolet
Aqueous solution after the test absorption of visible absorption spectra instrument.After 2 product of embodiment absorption mixed dye solution is shown in Fig. 6 f
Ultraviolet-visible absorption spectroscopy.It can be seen from the figure that after absorption 300min, the only characteristic absorption peak (462nm) of methyl orange, and
The absorption peak (542nm) of basic fuchsin disappears substantially, this illustrate cobalt/carbon nano-composite material that embodiment 2 is prepared for
Basic fuchsin molecule in mixed dye solution has good selective adsorption capacity.
Claims (8)
1. the preparation method of cobalt/carbon nano-composite material derived from a kind of metal organic framework, which is characterized in that including following step
Suddenly：
(1) by 1,3,5- benzenetricarboxylic acid or 4,4 '-biphenyl dicarboxylic acid is dissolved in alkaline aqueous solution, adds in soluble metal cobalt salt
Aqueous solution, be mixed under room temperature, then through centrifuge washing, it is dry after obtain cobalt-based metal organic framework presoma；
(2) presoma for obtaining step (1) is calcined under protective atmosphere, and the cobalt/carbon nanometer is obtained after cooling and is answered
Condensation material.
2. preparation method as described in claim 1, which is characterized in that in the step (1), the alkaline aqueous solution is hydrogen-oxygen
Change the aqueous solution of sodium or potassium hydroxide；The amount of the 1,3,5- benzenetricarboxylic acids and the substance of sodium hydroxide or potassium hydroxide ratio is 1:
3；The amount ratio of the substance of the 4,4 '-biphenyl dicarboxylic acid and sodium hydroxide or potassium hydroxide is 1:2.
3. preparation method as described in claim 1, which is characterized in that in the step (1), the soluble metal cobalt salt is
Cobaltous sulfate, cobalt acetate, cobalt nitrate or cobalt chloride；The amount ratio of the substance of the 1,3,5- benzenetricarboxylic acids and Cobalt salts is 2:3；Institute
The amount ratio for stating the substance of 4,4 '-biphenyl dicarboxylic acid and Cobalt salts is 1:1.
4. preparation method as described in claim 1, which is characterized in that in the step (1), the mixing speed for 400~
1000r/min, mixing time are 0.5~24 hour, and the rotating speed of centrifuge washing is 5000~10000r/min, drying temperature 60
~80 DEG C, the time is 4~8 hours.
5. preparation method as described in claim 1, which is characterized in that in the step (2), the protective atmosphere for nitrogen or
Person's argon gas；The heating rate of the calcining is 1~15 DEG C/min, and calcination time is 1~24 hour, calcination temperature for 500~
1000℃。
6. preparation method as described in claim 1, which is characterized in that step (1) obtained presoma is [Co (BPDC)
(H2O)2]·H2O or { [NaCo3(BTC)2(μ3-OH)](μ2-H2O)4(H2O)7·1.5H2O}n。
7. preparation method as described in claim 1, which is characterized in that obtained cobalt/carbon composite is by carbon and carbon coating
Cobalt nano-particle composition, a diameter of 5~100nm of cobalt nano-particle.
8. the purposes of cobalt/carbon nano-composite material made from the preparation method as described in any in claim 1~7, as triphen
The adsorbent of methylmethane class dyestuff.
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| CN110694578A (en) * | 2019-09-23 | 2020-01-17 | 五邑大学 | Co-C-N composite material and preparation method and application thereof |
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| CN111569875A (en) * | 2020-04-15 | 2020-08-25 | 江苏大学 | Copper/porous carbon nanorod material, preparation method and application |
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