CN105694810B - A kind of method that CuO/ porous carbon composite wave-suction materials are prepared for template with ZIF 67 - Google Patents
A kind of method that CuO/ porous carbon composite wave-suction materials are prepared for template with ZIF 67 Download PDFInfo
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- CN105694810B CN105694810B CN201610268827.XA CN201610268827A CN105694810B CN 105694810 B CN105694810 B CN 105694810B CN 201610268827 A CN201610268827 A CN 201610268827A CN 105694810 B CN105694810 B CN 105694810B
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Abstract
The invention discloses a kind of method for preparing CuO/ porous carbon composite wave-suction materials with ZIF 67 for template, comprise the following steps：The powder of precipitation method synthesis metal organic framework ZIF 67；The powder of ZIF 67 is placed under nitrogen and calcined, the material after calcining is dissolved in HF solution, obtains removing metal Co product, is marked as NPC；NPC is dissolved in Cu (NO3)2In solution, upper solution is removed after reaction, will be calcined again in nitrogen at 300 DEG C~600 DEG C after obtained solids drying process, that is, obtain the porous carbon composite wave-suction material that CuO inlays.Preparation method of the present invention has that technique is simple, production cost is low, subsequent treatment is easy and the advantages of without complicated synthesis device, is mass produced suitable for industrialization.
Description
Technical field
The present invention relates to a kind of the composite wave-absorbing material that CuO inlays porous carbon is prepared by template of metal organic framework ZIF-67
The method of material, belong to microwave absorbing material technical field.
Background technology
With the continuous development of electromagnetic wave technology, novel wave-absorbing material is gradually to lightweight, minimal thickness, broadband, strong absorption
Direction is developed, and in recent years, due to the advantage such as carbon material density is small, electromagnetic attenuation ability is strong, carbon-based material is as lightweight suction ripple material
Material has obtained the extensive concern of people.Cobalt-based imidazate metal-organic framework materials (ZIF-67) have higher heat endurance,
Also have the advantages that specific surface area is big, porosity is high, preparation technology is simple in addition, suitable for batch production, use it as predecessor
Gained carbon material has higher graphitization property, possesses the essential condition for developing into lightweight microwave absorbing material.
Cupric oxide (CuO) is a kind of P-type semiconductor, has narrower energy gap (1.2eV), due to its unique performance
And its extensive potential application, obtained in the application such as optoelectronic switch, anode material, catalysis, optoelectronic pole and gas sensor
Extensive concern.In recent years, CuO composite as microwave absorbing material by numerous studies.For example, Zen et al. passes through in sky
The method that Cu- carbon fibers are calcined in gas is prepared for CuO- carbon fibre composites, it is found that the compound is in matching thickness
It is -29.6dB (Zeng J, Xu J, Tao P, et that its reflection loss, which is optimal value, when 1.8mm, 7.8GHz
al.Ferromagnetic and microwave absorption properties of copper oxide-carbon
Fiber composites.Journal of Alloys and Compounds, 2009,487 (1)：304-308.).Zhao etc.
People is prepared for Ni-CuO core-shell structures by two-step hydrothermal route method, and the composite construction is in relatively low matching thickness
Under (1.7mm), reflection loss RL values are optimal for -62.2dB.Test proves that CuO has relatively low dielectric constant values, in Ni-
Existing interface enhances interfacial polarization between Ni and CuO in CuO compounds, improves the microwave absorbing property (Biao of material
Zhao, Gang Shao, Bingbing Fan, Wanyu Zhao and Rui Zhang, Facile synthesis and
enhanced microwave absorption properties of novel hierarchical
heterostructures based on a Ni microsphere-CuO nano-rice core-shell
Composite.Phys.Chem.Chem.Phys., 2015,17,6044-6052).In addition dielectric constant relatively low CuO (ε ' ≈
4) impedance matching of composite is also improved.Therefore, CuO also can improve the impedance of carbon material as a kind of impedance matching agent
Matching properties.
The content of the invention
Goal of the invention：The technical problems to be solved by the invention are to provide one kind using metal organic framework ZIF-67 as template
The method that CuO inlays porous carbon composite wave-suction material is prepared, the preparation method technique is simple, production cost is low.
In order to solve the above technical problems, the technical solution adopted in the present invention is：
A kind of method that CuO/ porous carbon composite wave-suction materials are prepared using ZIF-67 as template, comprises the following steps：
Step 1, precipitation method synthesis metal organic framework ZIF-67 powder；
Step 2, the ZIF-67 powder of step 1 is placed under nitrogen and calcined, organic macromolecule is carbonized, by the thing after calcining
Matter is dissolved in HF solution, is obtained removing metal Co product, is marked as NPC；
Step 3, the product NPC of step 2 is dissolved in Cu (NO3)2In solution, upper solution is removed after reaction, by what is obtained
Solids drying process, it is placed under nitrogen and calcines again after drying, that is, obtain the porous carbon composite wave-suction material that CuO inlays；Wherein,
The calcining heat is 300 DEG C~600 DEG C.
Wherein, in step 2, for every 1mgZIF-67 powder, the volume of required HF solution is 0.5mL.
Wherein, in step 2, the mass percentage concentration of the HF solution is 10%.
Wherein, in step 2, the calcining heat is 700 DEG C, calcination time 5h.
Wherein, in step 3, for every 1mgNPC, required Cu (NO3)2The volume of solution is 100mL.
Wherein, in step 3, the Cu (NO3)2The concentration of solution is 0.4mol/L.
Wherein, in step 3, the drying temperature is 60 DEG C, drying time 24h.
Wherein, in step 3, the calcination time is 3h.
The principle of preparation method of the present invention：Impregnating porous carbon by simple copper nitrate, (porous carbon is pure NPC, is passed through
The metal Co that HF is removed in Co@NPC is obtained) method obtain the mixture of porous carbon load copper nitrate, then mixture is existed
Calcining obtains the porous carbon complex (CuO NPC) that CuO inlays under suitable condition.
Beneficial effect：Complicated preparation method, equipment requirement height and cost be present compared to existing carbon microwave receptor material
The problems such as big, preparation method of the present invention have that technique is simple, production cost is low, subsequent treatment is easy and set without complicated synthesis
The advantages of standby, mass produced suitable for industrialization.
Brief description of the drawings
Fig. 1 is the X-ray diffraction that the CuO that the embodiment of the present invention 1,2,3 is prepared inlays porous carbon composite wave-suction material
Collection of illustrative plates；
Fig. 2 is the NPC of the gained of the embodiment of the present invention 1 SEM pictures；
Fig. 3 is the SEM pictures that the CuO that the embodiment of the present invention 1 is prepared inlays porous carbon composite wave-suction material；
Fig. 4 is the reflection loss collection of illustrative plates that the CuO that the embodiment of the present invention 1 is prepared inlays porous carbon composite wave-suction material；
Fig. 5 is the reflection loss collection of illustrative plates that the CuO that the embodiment of the present invention 2 is prepared inlays porous carbon composite wave-suction material；
Fig. 6 is the reflection loss collection of illustrative plates that the CuO that the embodiment of the present invention 3 is prepared inlays porous carbon composite wave-suction material.
Embodiment
Technical scheme is described further below in conjunction with accompanying drawing, but the scope of protection of present invention is simultaneously
It is not limited to this.
Embodiment 1
The present invention prepares the method that CuO inlays porous carbon composite wave-suction material by template of metal organic framework ZIF-67,
Specifically comprise the following steps：
Step 1, (Nagy L.Torad, Ming Hu, Shinsuke Ishihara, Hiroaki according to the literature
Sukegawa, Alexis A.Belik, Masataka Imura, Katsuhiko Ariga, Yoshio Sakka, and
Yusuke Yamauchi, Direct Synthesis of MOF-Derived Nanoporous Carbon with
Magnetic Co Nanoparticles toward Effi cient Water Treatment.Small, 2014,10,
2096-2107) precipitation method synthesis metal organic framework ZIF-67 powder：Weigh 2.63g methylimidazoles and be placed in 100mLA beakers
In, then toward 30mL methanol and 10mL distilled water is sequentially added in A beakers, stir to material and be completely dissolved；Into 100mLB beakers
Add 600mg polyvinylpyrrolidones and 520mg CoCl2·6H2O, then toward addition 40mL methanol in B beakers, stirring 5min is extremely
Material is completely dissolved, and ageing 24h is sealed with preservative film；Material in A beakers and B beakers is mixed, by mixture after reaction 24h
Expect that the precipitation of bottom is put into vacuum drying chamber at 60 DEG C after centrifuging and methanol washs and dry 5h, ground after drying
Grind to obtain purple ZIF-67 powder；
Step 2, take 100mgZIF-67 powder to be put into tube furnace under nitrogen atmosphere and calcine 5h in 700 DEG C, after calcining
Material is dissolved in 50mL 10wt% HF solution, agitator treating more than 3 times, is obtained removing metal Co product, is marked
For NPC；Wherein, tube furnace heating rate is 1 DEG C/min；
Step 3,100mgNPC powder is taken to be dissolved in the Cu (N0 that 100mL concentration is 0.4mol/L3)23h is stirred in solution, it is quiet
Put and treat powder drop, go upper solution, obtained solids is dried in vacuo 24h at 60 DEG C, obtain bearing in mesopore orbit
The porous carbon of copper nitrate is carried, the porous carbon dust for having loaded copper nitrate is put into N in tube furnace23h is calcined in 300 DEG C under atmosphere,
The porous carbon composite wave-suction material that CuO inlays is obtained, is S-300 by the Product Labeling of gained.
Embodiment 2
Step 1, with embodiment 1；
Step 2, with embodiment 1；
Step 3,100mgNPC powder is taken to be dissolved in the Cu (NO that 100mL concentration is 0.4mol/L3)23h is stirred in solution, it is quiet
Put and treat powder drop, go upper solution, obtained solids is dried in vacuo 24h at 60 DEG C, obtain bearing in mesopore orbit
The porous carbon of copper nitrate is carried, the porous carbon dust for having loaded copper nitrate is put into N in tube furnace23h is calcined in 450 DEG C under atmosphere,
The porous carbon composite wave-suction material that CuO inlays is obtained, is S-450 by the Product Labeling of gained.
Embodiment 3
Step 1, with embodiment 1；
Step 2, with embodiment 1；
Step 3, it is 0.4mol/L Cu (NO to take 100mgNPC powder to be dissolved in 100mL concentration3)23h is stirred in solution, it is quiet
Put and treat powder drop, go upper solution, obtained solids is dried in vacuo 24h at 60 DEG C, obtain bearing in mesopore orbit
The porous carbon of copper nitrate is carried, the porous carbon dust for having loaded copper nitrate is put into N in tube furnace23h is calcined in 600 DEG C under atmosphere,
The porous carbon composite wave-suction material that CuO inlays is obtained, is S-600 by the Product Labeling of gained.
Fig. 1 is the X ray diffracting spectrum that the CuO that embodiment 1,2,3 is prepared inlays porous carbon composite wave-suction material, from
Fig. 1 can be seen that the NPC that embodiment 1,2,3 obtains and occur graphitized carbon (002) crystallographic plane diffraction peak at 2 θ=30.55 °,
It is CuO that 1300 DEG C of embodiment, which calcines obtained product S-300 principal phases, and 2450 DEG C of embodiment calcines obtained product S-450 principal phases
For Cu, in addition with Cu2O and CuO diffraction maximum is present, and when calcining heat is 600 DEG C, 3600 DEG C of embodiment calcines what is obtained
The oxide diffraction maximum of copper is very weak in product S-600 samples, basic only surplus Cu diffraction maximum, and the valence state of Cu based products with
Calcining heat is raised and gradually reduced.
Fig. 2 is the NPC of the gained of embodiment 1 SEM photograph, figure it is seen that the NPC granulateds prepared by embodiment 1
Looks are granatohedron.
Fig. 3 is the SEM photograph that the CuO that embodiment 1 is prepared inlays porous carbon composite wave-suction material, can from Fig. 3
Go out, compared to Fig. 2 NPC pattern, the granatohedron that CuO inlays porous carbon composite wave-suction material has certain contraction, whole
The change of bodily form looks is little.
Fig. 4 is the reflection loss collection of illustrative plates for the product S-300 that embodiment 1 is prepared, from fig. 4, it can be seen that product S-300
Excellent microwave absorbing property is shown, is 11GHz in frequency, when matching thickness is 2mm, optimal RL values can reach -27dB,
Frequency bandwidths of the RL less than -10dB is 3.5GHz, and when matching thickness is 1-5mm, frequency of the RL values less than -10dB can cover
3-13GHz。
Fig. 5 is the reflection loss collection of illustrative plates for the product S-450 that embodiment 2 is prepared, from fig. 5, it can be seen that product S-450
Under best match frequency 16.5GHz, best match thickness 1mm, optimal RL values can only achieve -7dB.
Fig. 6 is the reflection loss collection of illustrative plates for the product S-600 that embodiment 3 is prepared, from fig. 6, it can be seen that product S-600
Poor absorbent properties are shown, the result shows CuO insertion can greatly improve porous carbon microwave absorbing material
Absorbing property, and the microwave absorbing property that CuO is reduced to sample after Ni metal significantly reduces.
The method that the present invention prepares composite wave-suction material is that what is obtained is compound by inside electromagnetic wave transparent material insertion wave absorbing agent duct
After absorbing material and paraffin proportioning under relatively low coating layer thickness, excellent lightweight broad-band microwave absorbing property has been embodied, and
Grain is uniformly dispersed, and does not reunite, can be as practical lightweight broad-band electromagnetic wave absorption material.Preparation method of the present invention overcomes
Tradition prepares the complicated technology of porous carbon/magnetic nanoparticle material, and preparation method technique of the present invention is simple, production cost is low,
It is easy to industrialized production.
Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and is not to the present invention
The restriction of embodiment.For those of ordinary skill in the field, it can also be made on the basis of the above description
Its various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.And these belong to this hair
Among the obvious changes or variations that bright spirit is extended out is still in protection scope of the present invention.
Claims (8)
- A kind of 1. method that CuO/ porous carbon composite wave-suction materials are prepared using ZIF-67 as template, it is characterised in that including as follows Step：Step 1, precipitation method synthesis metal organic framework ZIF-67 powder；Step 2, the ZIF-67 powder of step 1 is placed under nitrogen and calcined, the material after calcining is dissolved in HF solution, obtained Metal Co product is removed, is marked as NPC；Step 3, the product NPC of step 2 is dissolved in Cu (NO3)2In solution, upper solution is removed after reaction, the solid that will be obtained Calcined again in nitrogen at 300 DEG C~600 DEG C after thing drying process, that is, obtain the porous carbon composite wave-suction material that CuO inlays.
- 2. the method according to claim 1 that CuO/ porous carbon composite wave-suction materials are prepared using ZIF-67 as template, it is special Sign is：In step 2, for every 1mgZIF-67 powder, the volume of required HF solution is 0.5mL.
- 3. the method according to claim 1 that CuO/ porous carbon composite wave-suction materials are prepared using ZIF-67 as template, it is special Sign is：In step 2, the mass percentage concentration of the HF solution is 10%.
- 4. the method according to claim 1 that CuO/ porous carbon composite wave-suction materials are prepared using ZIF-67 as template, it is special Sign is：In step 2, the calcining heat is 700 DEG C, calcination time 5h.
- 5. the method according to claim 1 that CuO/ porous carbon composite wave-suction materials are prepared using ZIF-67 as template, it is special Sign is：In step 3, for every 1mgNPC, required Cu (NO3)2The volume of solution is 100mL.
- 6. the method according to claim 1 that CuO/ porous carbon composite wave-suction materials are prepared using ZIF-67 as template, it is special Sign is：In step 3, the Cu (NO3)2The concentration of solution is 0.4mol/L.
- 7. the method according to claim 1 that CuO/ porous carbon composite wave-suction materials are prepared using ZIF-67 as template, it is special Sign is：In step 3, the drying temperature is 60 DEG C, drying time 24h.
- 8. the method according to claim 1 that CuO/ porous carbon composite wave-suction materials are prepared using ZIF-67 as template, it is special Sign is：In step 3, the calcination time is 3h.
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| CN109772463B (en) * | 2019-03-19 | 2020-05-26 | 中南大学 | Catalyst ZIF-67-Me/CuO for CO reduction and low-temperature denitrationxAnd preparation method and application thereof |
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