CN107963671A - Support type composite and its preparation method and application - Google Patents
Support type composite and its preparation method and application Download PDFInfo
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- CN107963671A CN107963671A CN201711388977.5A CN201711388977A CN107963671A CN 107963671 A CN107963671 A CN 107963671A CN 201711388977 A CN201711388977 A CN 201711388977A CN 107963671 A CN107963671 A CN 107963671A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention discloses a kind of support type composite and its preparation method and application, to protonate carbonitride as nanometer bridge, is loaded on graphite alkenyl nanometer materials and obtains the composite material, its step is：（1）Under ultrasound, the water slurry of graphene oxide is prepared using oxidation graphite solid；（2）It is uniform to add protonation carbonitride ultrasound into the water slurry of graphene oxide；（3）Add FeCl3·6H2O and polyvinylpyrrolidone are to step（2）Stirred evenly in the suspension；（4）It is rapid to carry out hydro-thermal reaction；（5）The nanocomposite is obtained after washing, drying.The nanocomposite is a kind of one pot of hydro-thermal assemble method for synchronously being reduced and being protonated carbonitride self-assembling technique synchronous with graphene using science integration nano-metal-oxide growth in situ and graphene oxide, synthesis step is simple, efficient, it is easy to largely prepare, is particularly suitable for application as the electrochemical catalysis detecting and analysis of nitrite.
Description
Technical field
The present invention relates to a kind of functionalization graphene nano material and its preparation method and application, particularly one kind can be made
For electrochemical sensing material protonation carbonitride as the support type composite of nanometer bridge and its preparation
Method, belongs to field of material preparation.
Background technology
With the continuous improvement of economic level, environmental problem is also into the puzzlement in for people's lives.In daily life, it is empty
Gas and water, food are the necessitys of human survival, and there are a large amount of harmful substances in water and food, therefore for wherein nuisance
The detection of matter is necessary.Nitrite is widely used in agricultural, industry, food manufacturing, therefore to the essence of its content
Really quick detection becomes prevention and eliminates the most important thing of harm.
Electrochemical sensor detection technique, can be converted into electric signal intuitively by the chemical reaction occurred in electrode surface
Show, play the role of sensing, its high sensitivity to particular chemicals.Relative to other existing detection means, electrification
Learning sensor has obvious superiority.Common bare electrode can not meet need of the people to high sensitivity detection many kinds of substance
Ask, in electrode face finish different activities material to improve catalytic effect of the electrode for particular chemicals so that sensor
It is overall more sensitive.Since the introducing of nano material can greatly improve the performance of electrochemical sensor.Build novel nano material
Expecting the electrochemical sensor of modification has become the research hotspot of this area.
Graphene（Graphene）, as new two-dimension nano materials, possess high conductivity, wide electrochemical window, most
Possess good chemical stability in number electrolyte and the advantages of surface easily regenerates, this is provided to seek preferable nanostructured
Important channel.Carbonitride（g-C3N4）Possess higher chemical stability.g-C3N4It is by three s-triazine or s-triazine structure
The laminated structure that unit is polymerized by amino group.C3N4With a large amount of Cation adsorption sites.But it is in terms of electrochemistry
Application it is less, this is because the shortcomings of material scatter is poor, size is larger, electric conductivity is poor, seriously limits it in electricity
The application of chemical aspect.And the carbonitride Jing Guo nitric acid treatment is expressed as H-C3N4, there is small size, and there is certain conduction
Property, composite substrate can be coupled as with graphene.
Bloodstone（Fe2O3）, as a kind of band gap（Eg=2.2 eV）Relatively narrow n-type metal oxide semiconductor material, by
It is low, non-toxic in cost, it is readily produced and is had been a great concern the characteristics of storage.Catalyst, fuel, magnetic material,
Possess in gas sensor, biology sensor and lithium ion battery extensively using and by research on deeply process.Graphene, H-C3N4
With Fe2O3Synergistic effect can assign the new characteristic of material and cause material has for different demands different potentially should
With.And in the prior art, structure trielement composite material generally requires the technique of complexity, has wasted largely manpower, material resources, and three
It is useless higher.Thus, realize that multicomponent mixture structure nanosensor also becomes most important at present and most challenges using simple technique
One of work.（1. L. Cui, T. Pu, Y. Liu, X. He, Electrochim. Acta 88 (2013) 559-
564. 2. J. Jiang, W. Fan, X. Du, Biosens. Bioelectron. 51 (2014) 343-348）.
But in the above-mentioned methods, synthesis step is cumbersome, it is necessary to multistep complex operations, it is difficult to which industrialization is extensive raw
Production, and the three wastes are more.
The content of the invention
The present invention is for the deficiencies of existing in the prior art cumbersome, complicated, the three wastes are larger, there is provided one kind protonation nitrogen
Change the support type composite of carbon as nanometer bridge and preparation method thereof.
Realizing the technical solution of the object of the invention is：Support type composite, to protonate nitrogen
Change carbon as nanometer bridge, loaded on graphite alkenyl nanometer materials and obtain the composite material.
The preparation method of above-mentioned support type composite, includes the following steps：（1）Under ultrasound, use
Oxidation graphite solid prepares the water slurry of graphene oxide；（2）Add protonation carbonitride（H-C3N4）Arrive graphene oxide
Ultrasound is uniform in water slurry；（3）Add FeCl3·6H2O and polyvinylpyrrolidone（PVP）To step（2）The suspension
In stir evenly；（4）It is rapid to carry out hydro-thermal reaction；（5）The nanocomposite is obtained after washing, drying.
Further, step（1）In, oxidation graphite solid uses improved Hummers methods with native graphite
It is prepared by powder；Ultrasonic time is 1 ~ 24 h.
Further, step（1）In, the ratio of graphite oxide and water is 1:1~1:4 mg/ml.
Further, step（2）In, step（1）Described in graphite oxide and protonation carbonitride ratio be 5:1~1:2
mg/mg；Ultrasonic time is 0.1 ~ 4 h.
Further, step（3）In, step（1）Described in graphite oxide and FeCl3·6H2The ratio of O is 1:1~1:40
mg/mg；Step（1）Described in graphite oxide and PVP ratio be 1:1~1:40 mg/mg；Mixing time is 10 ~ 60 min.
Further, step（4）In, hydrothermal temperature is 120 ~ 200 DEG C；The hydro-thermal reaction time is 6 ~ 24 h.
Application of the above-mentioned support type composite as the electrochemical sensor used in nitrite.
Compared with prior art, it is an advantage of the invention that：
（1）Preparation method of the present invention avoids cumbersome multicomponent material synthesis step, it is only necessary to after being stirred,
It can be synthesized using one pot of Hydrothermal Synthesiss technology.
（2）For the present invention as long as by routine operations such as simple centrifuge washing, filterings, technique is simple, environmentally protective.
（3）Functionalization graphene nano hybridization sensing material prepared by the present invention can easily be reacted by adjusting
Temperature and burden control Fe2O3In H-C3N4With the load capacity and size on graphene, and then adjust hybrid material catalytic
Energy.
（4）The present invention preparation method close to Green Chemistry requirement, it is easily controllable, be conducive to industrialized mass production.
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Brief description of the drawings
Fig. 1 is support type composite of the protonation carbonitride of the invention prepared as nanometer bridge
Preparation process schematic diagram.
Fig. 2 is the Principle of Process schematic diagram of support type composite prepared by the present invention.
Fig. 3 is the infrared spectrogram of the nano combined sensing material synthesized in the embodiment of the present invention 1.
Fig. 4 is the TEM photos of the nano combined sensing material synthesized in the embodiment of the present invention 1.
Fig. 5 is the XRD diagram of the nano combined sensing material synthesized in the embodiment of the present invention 1.
Fig. 6 is the nano combined sensing material modified glassy carbon electrode pair of functionalization graphene in invention embodiment 1
In the i-t curves of nitrite.
Embodiment
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings, the present embodiment is with the technology of the present invention side
Implemented under the premise of case, give detailed embodiment and specific operating process, but protection scope of the present invention is unlimited
In following embodiments.
As depicted in figs. 1 and 2, support type graphene-based nanometer of the protonation carbonitride of the present invention as nanometer bridge
The preparation method of composite material, this method comprise the following steps：
Step 1, prepare carbonitride；
Step 2, prepare protonation carbonitride；
Step 3, use improved Hummers methods to prepare oxidation graphite solid with natural graphite powder；
Under step 4, ultrasound, the water slurry of graphene oxide is prepared using oxidation graphite solid；The ratio of graphite oxide and water is
1:1~1:4 mg/ml；Ultrasonic time is 1 ~ 24 h.
Step 5, the protonation carbonitride that will be prepared in step 2（H-C3N4）It is added in the suspension of step 4 and ultrasound is equal
It is even；Graphite oxide and H-C3N4Ratio be 5:1~1:2 mg/mg；Ultrasonic time is 0.1 ~ 4 h.
Step 6, add FeCl3·6H2O and polyvinylpyrrolidone（PVP）Stirred evenly into the suspension of step 5；Oxygen
Graphite and FeCl3·6H2The ratio of O is 1:1~1:40 mg/mg；The ratio of graphite oxide and PVP are 1:1~1:40 mg/mg；Stirring
Time is 10 ~ 60 min.
Step 7, by the suspension of step 6 carry out rapidly hydro-thermal reaction；Hydrothermal temperature is 120 ~ 200 DEG C；During reaction
Between be 6 ~ 24 h.
The nanocomposite is obtained after step 8, washing, drying.
Wherein, the structural formula of carbonitride is as follows：
。
Embodiment 1
The first step, is weighed 5 g melamines in crucible, is calcined in Muffle furnace using temperature programming：P1T=350 DEG C,
t=10 min；P2T=550 DEG C, the min of t=240, natural cooling after the completion of reaction, obtains yellow blocks of solid.It is ground into
Powder is up to g-C3N4;
Second step, weighs g-C3N4100 mg add 10 mL HNO in 50 mL round-bottomed flasks3（65 wt%）, 80 DEG C are condensed back to
Flow, react 5 h under magnetic agitation.Room temperature cools down after reaction, and NaHCO is added dropwise into reaction solution3In solution and solution is to weak
It is acid.Decompression filters, and is washed 3 times using ethanol afterwards for several times with deionized water washing, 70 DEG C of 12 h of vacuum drying, pulverize
Up to acidifying g-C3N4（H-C3N4）.
3rd step, the preparation of oxidation graphite solid；
At 80 DEG C, 20 g native graphites are pre-oxidized with the 30 mL concentrated sulfuric acids, 10 g potassium peroxydisulfates and 10 g phosphorus pentoxides
Afterwards, pH=7 are washed to, air drying is stand-by overnight；
The 460 mL concentrated sulfuric acids are cooled to 0 DEG C or so, then the 20 g graphite pre-oxidized is added thereto, is slowly added into 60
G potassium permanganate so that system temperature is no more than 20 DEG C, and 35 DEG C are warming up to after addition, after stirring 2 h, and it is in batches slow
It is slow to add 920 mL deionized waters so that system temperature is no more than 98 DEG C, is stirred for after 15 minutes, adds 2.8 L deionizations
30 % hydrogen peroxide of water and 50 mL.Obtained glassy yellow suspension is depressurized and is filtered, washing.Until there is no sulfuric acid in filtrate
Radical ion, and when being in neutrality, product is dried in 60 DEG C of vacuum, obtains oxidation graphite solid；
25 mg graphite oxides powder under ultrasound, are loaded round-bottomed flask, add 50 mL water by the 4th step, after 1.5 h of ultrasound,
Obtain graphene oxide（GO）Suspension；
40 mg prepared in the first step are protonated carbonitride by the 5th step（H-C3N4）It is added in the suspension of step 4 and surpasses
0.5 h of sound is uniformly mixed；
6th step, takes 250 mg FeCl3·6H2O and 250 mg polyvinylpyrrolidones（PVP）After being dissolved in 30 ml water,
The solution is added to and stirs 30 min in the suspension of the 5th step and is uniformly mixed；
7th step, hydro-thermal reaction is carried out rapidly by the suspension of the 6th step；Reaction temperature is 160 DEG C；Reaction time is 12 h.
8th step, by the crude product that the 7th step obtains through filtering, washing, after dry, graphene is obtained after washing, drying
Nanocomposite.
The graphene nanocomposite material（The nano combined sensing material of functionalization graphene）Infrared spectrum as shown in figure 3, card
The bright nano-hybrid material successfully synthesizes.
The TEM figures of the nano combined sensing material of functionalization graphene are as shown in Figure 4, it was demonstrated that the nano-hybrid material has succeeded
Synthesis.
The XRD diagram of the nano combined sensing material of functionalization graphene is as shown in Figure 5；
The nano combined sensing material modified glassy carbon electrode of functionalization graphene for nitrite i-t curves as shown in fig. 6, card
The bright nano-hybrid material there is good electro-catalysis to respond nitrite.H-C3N4Substantial amounts of defective bit is conducive to Fe2O3's
Growth, significantly improves chemical property.The range of linearity of detection is：25 nmol/L -3000 μm of ol/L, detection are limited to
18.43 nmol/L。
Embodiment 2
The first to three step, with step 1 in embodiment 1 to three.
25 mg graphite oxides powder under ultrasonic, loaded round-bottomed flask, add 25 mL water, 24 h of ultrasound by the 4th step
Afterwards, graphene oxide is obtained（GO）Suspension；
5 mg prepared in the first step are protonated carbonitride by the 5th step（H-C3N4）It is added in the suspension of step 4 and surpasses
0.1 h of sound is uniformly mixed；
6th step, takes 25 mg FeCl3·6H2O and 25 mg polyvinylpyrrolidones（PVP）, will after being dissolved in 30 ml water
The solution, which is added to, to be stirred 60 min in the suspension of the 5th step and is uniformly mixed；
7th step, hydro-thermal reaction is carried out rapidly by the suspension of the 6th step；Reaction temperature is 160 DEG C；Reaction time is 24 h.
8th step, with step 8 in embodiment 1.
Embodiment 3
The first to three step, with step 1 in embodiment 1 to three.
25 mg graphite oxides powder under ultrasonic, loaded round-bottomed flask, add 100 mL water, 1 h of ultrasound by the 4th step
Afterwards, graphene oxide is obtained（GO）Suspension；
50 mg prepared in the first step are protonated carbonitride by the 5th step（H-C3N4）It is added in the suspension of step 4 and surpasses
4 h of sound is uniformly mixed；
6th step, takes 50 mg FeCl3·6H2O and 50 mg polyvinylpyrrolidones（PVP）, will after being dissolved in 30 ml water
The solution, which is added to, to be stirred 50 min in the suspension of the 5th step and is uniformly mixed；
7th step, hydro-thermal reaction is carried out rapidly by the suspension of the 6th step；Reaction temperature is 160 DEG C；Reaction time is 15 h.
8th step, with step 8 in embodiment 1.
Embodiment 4
The first to three step, with step 1 in embodiment 1 to three.
25 mg graphite oxides powder under ultrasonic, loaded round-bottomed flask, add 80 mL water, 1 h of ultrasound by the 4th step
Afterwards, graphene oxide is obtained（GO）Suspension；
40 mg prepared in the first step are protonated carbonitride by the 5th step（H-C3N4）It is added in the suspension of step 4 and surpasses
4 h of sound is uniformly mixed；
6th step, takes 25 mg FeCl3·6H2O and 25 mg polyvinylpyrrolidones（PVP）, will after being dissolved in 30 ml water
The solution, which is added to, to be stirred 10 min in the suspension of the 5th step and is uniformly mixed；
7th step, hydro-thermal reaction is carried out rapidly by the suspension of the 6th step；Reaction temperature is 120 DEG C；Reaction time is 15 h.
8th step, with step 8 in embodiment 1.
Embodiment 6
The first to three step, with step 1 in embodiment 1 to three.
25 mg graphite oxides powder under ultrasonic, loaded round-bottomed flask, add 25 mL water, 12 h of ultrasound by the 4th step
Afterwards, graphene oxide is obtained（GO）Suspension；
15 mg prepared in the first step are protonated carbonitride by the 5th step（H-C3N4）It is added in the suspension of step 4 and surpasses
2 h of sound is uniformly mixed；
6th step, takes 30 mg FeCl3·6H2O and 30 mg polyvinylpyrrolidones（PVP）, will after being dissolved in 30 ml water
The solution, which is added to, to be stirred 50 min in the suspension of the 5th step and is uniformly mixed；
7th step, hydro-thermal reaction is carried out rapidly by the suspension of the 6th step；Reaction temperature is 160 DEG C；Reaction time is 20 h.
8th step, with step 8 in embodiment 1.
Embodiment 7
First to fourth step, with step 1 in embodiment 1 to four.
5 mg prepared in the first step are protonated carbonitride by the 5th step（H-C3N4）It is added in the suspension of step 4 simultaneously
0.5 h of ultrasound is uniformly mixed；
6th step, with step 6 in embodiment 1.；
7th step, hydro-thermal reaction is carried out rapidly by the suspension of the 6th step；Reaction temperature is 120 DEG C；Reaction time is 12 h.
8th step, with step 8 in embodiment 1.
Embodiment 8
First to fourth step, with step 1 in embodiment 1 to four.
50 mg prepared in the first step are protonated carbonitride by the 5th step（H-C3N4）It is added in the suspension of step 4
And 4 h of ultrasound are uniformly mixed；
6th step, with step 6 in embodiment 1.；
7th step, hydro-thermal reaction is carried out rapidly by the suspension of the 6th step；Reaction temperature is 200 DEG C；Reaction time is 12 h.
8th step, with step 8 in embodiment 1.
Embodiment 9
The first to five step, with step 1 in embodiment 1 to five.
6th step, takes 1000 mg FeCl3·6H2O and 1000 mg polyvinylpyrrolidones（PVP）It is dissolved in 30 ml water
In after, which is added to and stirs 30 min in the suspension of the 5th step and is uniformly mixed；
7th step, hydro-thermal reaction is carried out rapidly by the suspension of the 6th step；Reaction temperature is 200 DEG C；Reaction time is 6 h.
8th step, with step 8 in embodiment 1.
Embodiment 10
The first to five step, with step 1 in embodiment 1 to five.
6th step, takes 500 mg FeCl3·6H2O and 1000 mg polyvinylpyrrolidones（PVP）It is dissolved in 30 ml water
Afterwards, which is added to and stirs 20 min in the suspension of the 5th step and be uniformly mixed；
7th step, hydro-thermal reaction is carried out rapidly by the suspension of the 6th step；Reaction temperature is 160 DEG C；Reaction time is 10 h.
8th step, with step 8 in embodiment 1.
The invention avoids cumbersome multicomponent material synthesis step, it is only necessary to after being stirred, utilizes one pot of hydro-thermal
Synthetic technology can synthesize.The preparation of the nanocomposite is a kind of science integration nano-metal-oxide growth in situ, oxygen
Graphite alkene synchronously reduces and one pot of hydro-thermal assemble method of protonation carbonitride self-assembling technique synchronous with graphene.Synthesis
Afterwards, as long as passing through the routine operations such as simple centrifuge washing, filtering, you can be prepared.The functionalization that at the same time prepared by the present invention
Graphene nano hydridization sensing material can be easily by adjusting reaction temperature and burden control Fe2O3In protonation nitrogen
Change carbon and load capacity and size on graphene, and then adjust the catalytic performance of hybrid material.The present invention preparation method close to
The requirement of Green Chemistry, it is easily controllable, be conducive to industrialized mass production.
Claims (10)
1. support type composite, it is characterised in that to protonate carbonitride as nanometer bridge, loaded
The composite material is obtained on to graphite alkenyl nanometer materials.
2. the preparation method of support type composite, includes the following steps：（1）Under ultrasound, using oxidation stone
Black solid prepares the water slurry of graphene oxide；（2）Protonation carbonitride is added into the water slurry of graphene oxide to surpass
Sound is uniform；（3）Add FeCl3·6H2O and polyvinylpyrrolidone are to step（2）Stirred evenly in the suspension；（4）Rapidly
Carry out hydro-thermal reaction；（5）The nanocomposite is obtained after washing, drying.
3. preparation method as claimed in claim 2, it is characterised in that step（1）In, oxidation graphite solid is used using improvement
Hummers methods afterwards are prepared with natural graphite powder；Ultrasonic time is 1 ~ 24 h.
4. preparation method as claimed in claim 2, it is characterised in that step（1）In, the ratio of graphite oxide and water is 1:1~1:
4 mg/ml。
5. preparation method as claimed in claim 2, it is characterised in that step（2）In, step（1）Described in graphite oxide
Ratio with protonation carbonitride is 5:1~1:2 mg/mg；Ultrasonic time is 0.1 ~ 4 h.
6. preparation method as claimed in claim 2, it is characterised in that step（3）In, step（1）Described in graphite oxide
And FeCl3·6H2The ratio of O is 1:1~1:40 mg/mg.
7. preparation method as claimed in claim 2, it is characterised in that step（3）In, step（1）Described in graphite oxide
Ratio with PVP is 1:1~1:40 mg/mg.
8. preparation method as claimed in claim 2, it is characterised in that step（3）In, mixing time is 10 ~ 60 min.
9. preparation method as claimed in claim 2, it is characterised in that step（4）In, hydrothermal temperature is 120 ~ 200
℃；The hydro-thermal reaction time is 6 ~ 24 h.
10. electrochemical sensor of the support type composite as claimed in claim 1 as nitrite
Application.
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| CN109279691A (en) * | 2018-10-18 | 2019-01-29 | 哈尔滨工业大学 | A kind of electrochemical appliance preparing hydrogen peroxide and application |
| CN109358100A (en) * | 2018-08-23 | 2019-02-19 | 南京大学盐城环保技术与工程研究院 | Ethanol amine and the graphene-based nano combined sensing material of Nano silver grain difunctionalization support type and preparation method thereof |
| CN110316724A (en) * | 2019-06-21 | 2019-10-11 | 浙江工商大学 | A kind of three-dimensional modified graphene aeroge and its preparation and the application in water process |
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| CN109019556A (en) * | 2018-08-07 | 2018-12-18 | 中国石油大学(北京) | It is a kind of to load the preparation method and gained carbon material for having the carbon material of metal oxide |
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| CN109279691A (en) * | 2018-10-18 | 2019-01-29 | 哈尔滨工业大学 | A kind of electrochemical appliance preparing hydrogen peroxide and application |
| CN110316724A (en) * | 2019-06-21 | 2019-10-11 | 浙江工商大学 | A kind of three-dimensional modified graphene aeroge and its preparation and the application in water process |
| CN110316724B (en) * | 2019-06-21 | 2020-12-11 | 浙江工商大学 | Three-dimensional modified graphene aerogel, preparation thereof and application thereof in water treatment |
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