CN108525615A - A kind of preparation and its application of the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam - Google Patents
A kind of preparation and its application of the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam Download PDFInfo
- Publication number
- CN108525615A CN108525615A CN201810198254.7A CN201810198254A CN108525615A CN 108525615 A CN108525615 A CN 108525615A CN 201810198254 A CN201810198254 A CN 201810198254A CN 108525615 A CN108525615 A CN 108525615A
- Authority
- CN
- China
- Prior art keywords
- foam
- doped graphene
- based nitrogen
- dyestuff
- aeroge
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The present invention relates to the preparations and its application of a kind of Ni-based nitrogen-doped graphene aeroge of three-dimensional foam.The preparation method is that：Graphene oxide is prepared using improved Hummers methods, it will be added to the self-assembling reaction for carrying out graphene in the mixed liquor of graphene oxide, nitrogen source, reducing agent, crosslinking agent after nickel foam is cleaned and etching, the Ni-based nitrogen-doped graphene aeroge of foam obtained after the graphene hydrogel of generation is freeze-dried again.The composite catalyst is added in waste water from dyestuff with high salt, the dyestuff that the aeroge that can degrade adsorbs above realizes innoxious degradation.The catalyst of the present invention has many advantages, such as that high catalytic efficiency, reusability are good, particularly pertinent is to overcome that Conventional nano/micron-scale Co catalysts are not easily recycled, graphene aerogel mechanical strength is low, waste water from dyestuff with high salt is also easy to produce the technical problems such as highly toxic halogenated organic by-product when free-radical oxidation is degraded, and can be applied to dye wastewater treatment field with high salt.
Description
Technical field
The present invention relates to a kind of composite catalyzing material applied to dye wastewater treatment technology field with high salt, more particularly to
The preparation and its application in handling waste water from dyestuff with high salt of a kind of Ni-based nitrogen-doped graphene aeroge of three-dimensional foam.
Background technology
Waste water from dyestuff with high salt（Salinity is more than 1%）Belong to difficult for biological degradation, very harmful industrial wastewater.Transition metals cobalt
The single peroxosulphuric hydrogen potassium of catalysis can generate the Strong oxdiatives species such as sulphuric acid free radical, hydroxyl radical free radical, to most difficult to degrade
Organic pollution realizes efficient degradation.However, when waste water from dyestuff with high salt using the technical finesse, the chlorion in waste water can be caught
It obtains sulphuric acid free radical and hydroxyl radical free radical generates the lower chlorine radical of activity, cause dyestuff mineralising efficiency low.Even more serious
It is that chlorine radical is easily reacted with dye molecule and in-between catabolite, generates the even carcinogenic halogenated organic of toxicity bigger
By-product, this seriously constrains scale application of the technology in waste water from dyestuff with high salt（Ruixia Y., et al.
Effects of chloride ion on degradation of Acid Orange 7 by sulfate radical-
based advanced oxidation process: Implications for formation of chlorinated
aromatic compounds [J]. J. Hazard. Mater., 2011,96: 173-179.）.
In addition, there is also secondary pollution problems for traditional ionic Co catalysts.In recent years, Chinese patent CN
106694052 A（It is catalyzed the cellulose base composite catalyst and preparation method thereof of persulfate degradation of dye methyl orange）, China
102583692 B of patent CN（The method for the treatment of organic pollutants in water by catalyzing persulfate through heterogeneous copper oxide）Deng preparation
Go out nanoscale or micron-sized different-phase catalyst.Although these catalyst can realize effective degradation of organic pollution,
Need complex processes, the cost recovery such as filtering, centrifugation, dry higher when recycling.
Invention content
The invention reside in overcoming in background technology, there are Conventional nano/micron-scale Co catalysts to be not easily recycled, graphene
The low problem of aeroge mechanical strength, and a kind of Ni-based nitrogen-doped graphene aeroge of three-dimensional foam is provided and preparation method thereof.
The Ni-based nitrogen-doped graphene aerogel catalyst of the three-dimensional foam have high catalytic efficiency, reusability is good, way of recycling is simple
The advantages that list and big mechanical strength, particularly pertinent is that the catalyst overcomes Conventional nano/micron-scale Co catalysts and is not easy
Recycling, graphene aerogel mechanical strength is low, waste water from dyestuff with high salt be also easy to produce when free-radical oxidation is degraded it is highly toxic organic
The technical problems such as halogenated by-products.It is with high salt in processing that the present invention also provides a kind of Ni-based nitrogen-doped graphene aeroges of three-dimensional foam
Application in waste water from dyestuff.
The present invention solves the problems, such as that it can reach by following technical solution：
A kind of Ni-based nitrogen-doped graphene aeroge of three-dimensional foam, component and proportioning are as follows by weight percentage：Graphite oxide
4.0~10.9 % of alkene, nitrogen source 8.3~21.7%, crosslinking agent 1.7~5.4%, reducing agent 8.3~10.9%, nickel foam 51.1~
77.7%。。
Further, the nitrogen source is at least one of urea, ammonium hydroxide, melamine, and the crosslinking agent is four boron
At least one of sour sodium, polyvinyl alcohol, the reducing agent are ascorbic acid, sodium hydrogensulfite, sodium borohydride, hydroquinone
At least one of.
The invention also discloses a kind of preparation methods of the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam, including following step
Suddenly：
（1）Graphene oxide is added in distilled water in proportion, ultrasonic agitation dispersion；
（2）In proportion in step（1）Graphene oxide solution in nitrogen source, crosslinking agent and reducing agent is added, ultrasonic agitation is uniform；
（3）Pretreated nickel foam is immersed into step（2）Mixed liquor in, then it is above-mentioned mixed liquor is anti-under the conditions of 90 DEG C
Answer 12 h；
（4）After the completion of reaction, the Ni-based nitrogen-doped graphene hydrogel of foam is obtained, is drawn off going to clean wash with distilled water
Matter, then be freeze-dried, obtain the Ni-based nitrogen-doped graphene aeroge of foam.
Further, the nickel foam preprocess method is as follows：
（1）Nickel foam is put into acetone solvent, ultrasound 10 minutes, to remove the micro greasy dirt on nickel foam substrate, to increase
Add the hydrophily of matrix；
（2）It will be cleaned by ultrasonic 10 minutes through treated nickel foam distilled water；
（3）Nickel foam after distilled water is cleaned by ultrasonic, with the salt acid etch 15 minutes of 6.0 mol/L, to remove matrix surface
Oxide layer and nickel foam surface layer formed micro-rough surface, to enhance its binding force with graphene；
（4）Nickel foam after HCl treatment is cleaned by ultrasonic 15 minutes with distilled water, then for several times with distilled water flushing；
（5）The nickel foam of above-mentioned processing is placed in 60 DEG C of 3 h of drying in baking oven.
Further, the preparation method of the graphene oxide includes the following steps：
（1）The graphite powder for sequentially adding 1 g is added in conical flask（1200 mesh）With the concentrated sulfuric acid of 23 mL, ice bath simultaneously stirs
10 min；
（2）It is slowly added to the potassium permanganate of 3 g into above-mentioned flask, flask is placed in 35 DEG C of water-baths and stirs 2 h；
（3）50 mL distilled water are added into flask, flask is placed in 95 DEG C of water-baths and stir 15 min；
（4）Mixed liquor in flask is transferred in the beaker equipped with 150 mL distilled water, hydrogen peroxide is added dropwise（Mass concentration
It is 30%）, stirred when being added dropwise, until solution becomes yellow from brown；
（5）Said mixture is filtered, then with the HCl of 50 mL（Mass concentration 10%）Dialysis 3 times, to remove impurity；
（6）Above-mentioned solution is filtered, filter residue is freeze-dried at -40 DEG C, obtains graphene oxide.
Further, a concentration of 0.5 ~ 2 g/L of the graphene oxide, nitrogen concentration are 1 ~ 4 g/L, and crosslinker concentration is
0.2 ~ 1 g/L, reductant concentration are 1 ~ 2 g/L, and freeze-drying temperature is -40 DEG C, and sublimation drying is 12 h.
The invention also discloses a kind of Ni-based nitrogen-doped graphene aeroges of three-dimensional foam in handling waste water from dyestuff with high salt
Application.
Further, the application process includes the following steps：
（1）The Ni-based nitrogen-doped graphene aeroge of foam is added in waste water from dyestuff with high salt and is stirred, in certain temperature item
Dye molecule is set to be adsorbed on graphene aerogel surface completely under part；
（2）The Ni-based nitrogen-doped graphene aeroge of foam is taken out, removes surface salt ion wash with distilled water；
（3）The Ni-based nitrogen-doped graphene aeroge of foam is added in the solution containing single peroxosulphuric hydrogen potassium, sulfuric acid is generated
The Strong oxdiatives species such as free radical and hydroxyl radical free radical, come the dyestuff for graphene aerogel adsorption of degrading.
Further, the step（1）Described in waste water from dyestuff with high salt in sodium chloride concentration be 10 ~ 50 g/L, dyestuff
The molar concentration rate of a concentration of 0.1 ~ 0.5 mmol/L, single peroxosulphuric hydrogen potassium and dyestuff is（10~50）：1；The step（1）
Middle adsorption temp condition is 30 ~ 50 DEG C, and adsorption time is 30 ~ 90 min；Step（3）Degradation temperature condition is 10 ~ 40 DEG C, drop
The solution time is 30 ~ 60 min.
The present invention can have the advantages that compared with above-mentioned background technology：The present invention using mechanical performance it is excellent,
Chemical stability is strong, high temperature resistant, electric conductivity are strong, the nickel foam of porosity and large specific surface area is as nitrogen-doped graphene aeroge
Template, the mechanical strength and catalytic performance of nitrogen-doped graphene aeroge can be improved.The Ni-based N doping of prepared foam
Graphene aerogel is non-metal catalyst, not will produce the secondary pollution problem of cobalt loss, this macroscopic view composite Nano catalysis
Agent also has the advantages that large specific surface area, high catalytic efficiency, easy to be recycled.
Provided by the present invention to be catalyzed single peroxosulphuric hydrogen potassium using the Ni-based nitrogen-doped graphene aeroge of foam, degradation is high
The method of salt dyestuff waste water, also has the advantages that：Prepared composite catalyst large specific surface area, absorption property is strong,
The separation of dye molecule and salt ion in waste water from dyestuff with high salt can be realized with efficient absorption dye molecule；It is prepared compound to urge
Agent catalytic performance is strong, can be catalyzed single peroxosulphuric hydrogen potassium and generate a large amount of sulphuric acid free radical and hydroxyl radical free radical, realize dye
Expect the degradation of molecule.
Description of the drawings
Attached drawing 1 be in inventive embodiments 1 the Ni-based nitrogen-doped graphene aeroge of foam to the adsorption effect figure of acid orange 7；
Attached drawing 2 is that the Ni-based nitrogen-doped graphene aerogel catalyst of foam recycles five times to acid orange 7 in inventive embodiments 1
The adsorption effect figure；
Attached drawing 3 be in inventive embodiments 2 the Ni-based nitrogen-doped graphene aeroge of foam to the adsorption effect figure of methyl orange.
Specific implementation mode：
The invention will be further described below in conjunction with the accompanying drawings and the specific embodiments：
Embodiment 1
Using urea as nitrogen source, sodium tetraborate is crosslinking agent, and ascorbic acid is reducing agent, prepares the Ni-based nitrogen-doped graphene gas of foam
Gel（Graphene oxide 4.0%, nitrogen source 8.3%, crosslinking agent 1.7%, reducing agent 8.3%, nickel foam 77.7%）, handle salinity
（NaCl）For the acid orange 7 of 20 g/L（A concentration of 0.2 mmol/L）Waste water.The tool of the Ni-based nitrogen-doped graphene aeroge of foam
Body method of preparation and use is as follows：
（1）The pretreatment of nickel foam
By nickel foam（2 cm×4 cm×0.6 cm）It immerses in acetone, ultrasound 10 minutes is micro- on nickel foam substrate to remove
Greasy dirt is measured, to increase the hydrophily of matrix；Will be 10 minutes through treated nickel foam distilled water ultrasound, then with 6.0
The salt acid etch of mol/L 15 minutes, to remove the oxide layer of matrix surface and form the surface of micro-rough on nickel foam surface layer,
To enhance its binding force with graphene；Nickel foam after HCl treatment is cleaned by ultrasonic 15 minutes with distilled water, then with steaming
Distilled water is rinsed for several times, and the nickel foam of above-mentioned processing is finally placed in baking oven 60 DEG C of dryings 3 hours.
（2）The preparation of graphene oxide
The graphite powder for sequentially adding 1 g is added in conical flask（1200 mesh）With the concentrated sulfuric acid of 23 mL, ice bath simultaneously stirs 10
min；It is slowly added to the potassium permanganate of 3 g into flask, flask is placed in 35 DEG C of water-baths and stirs 2 h；Add into flask
Enter 50 mL distilled water, flask is placed in 95 DEG C of water-baths and stirs 15 min；Mixed liquor in flask is transferred to and is equipped with
In the beaker of 150 mL distilled water, hydrogen peroxide is added dropwise（Mass concentration is 30%）, stirred when being added dropwise, until solution is by palm fibre
Discoloration is yellow；Said mixture is filtered, then with the HCl of 50 mL（Mass concentration 10%）Dialysis 3 times, to remove impurity elimination
Matter；Above-mentioned solution is filtered, filter residue is freeze-dried under the conditions of -40 DEG C, obtains graphene oxide.
（3）The preparation of the Ni-based N doping graphene oxide of foam
By graphene oxide（25 mg）It is added in the distilled water of 50 mL, 1 h is stirred by ultrasonic, obtains finely dispersed graphene
Suspension；0.05 g urea, 0.01 g sodium tetraborates, 0.05 g ascorbic acid, ultrasonic agitation 1 are added in above-mentioned suspension
h；Pretreated nickel foam is immersed into above-mentioned mixed liquor, mixed liquor is reacted into 12 h under the conditions of 90 DEG C, it is Ni-based to obtain foam
Nitrogen-doped graphene hydrogel；The Ni-based nitrogen-doped graphene hydrogel of foam is taken out and is cleaned multiple times with distilled water and is cleaned
Matter finally carries out 12 h of freeze-drying under the conditions of -40 DEG C, obtains the Ni-based nitrogen-doped graphene aeroge of foam.
（4）The innoxious degradation of acid orange 7 high-salt wastewater
Dyestuff is acid orange 7 in selected waste water from dyestuff with high salt, and a concentration of 50 mg/L, NaCl concentration is 20 g/L.Using biography
The single peroxosulphuric hydrogen potassium of cobalt ions catalysis of system come degrade the waste water when, degradation efficiency is low, and chlorophenol is produced in degradation process
The even carcinogenic halogenated organic by-product of a variety of high toxicities such as class, chlorobenzene class.
Using the specific mistake of the prepared Ni-based nitrogen-doped graphene aeroge catalytic degradation acid orange 7 high-salt wastewater of foam
Journey is as follows：The Ni-based nitrogen-doped graphene aeroge of foam is added to acid orange 7 waste water（100 mL）In and stir, setting absorption
Temperature is respectively 40 DEG C, and absorbance is measured by sampling at regular intervals and calculates dyestuff in the Ni-based nitrogen-doped graphene gas of foam
The adsorbance of gel surface.As shown in Fig. 1, acid orange 7 is all adsorbed on graphene aerogel after 70 min in solution
Surface.The Ni-based nitrogen-doped graphene aeroge of foam is taken out from solution, surface salt ion is removed with distilled water flushing；Then
It is added to containing single peroxosulphuric hydrogen potassium（5 mmol/L）Solution in and be stirred, react 60 min after acid orange 7 it is complete
Degradation.It is detected and is found using microcoulomb method, halogenated organic by-product is not generated in degradation process.
When by carrying out reuse again after the Ni-based nitrogen-doped graphene aeroge use of above-mentioned foam, it is washed with distilled water to remove
It after impurity, reuses 5 times, nickel foam absorption and degradation efficiency have no and be substantially reduced（See attached drawing 2）。
Embodiment 2
Using ammonium hydroxide as nitrogen source, polyvinyl alcohol is crosslinking agent, and sodium hydrogensulfite is reducing agent, prepares the Ni-based nitrogen-doped graphene of foam
Aeroge（10.9 % of graphene oxide, nitrogen source 21.7%, crosslinking agent 5.4%, reducing agent 10.9%, nickel foam 51.1%）, handle salt
Degree（NaCl）For the methyl orange of 30 g/L（A concentration of 0.2 mmol/L）Waste water.The tool of the Ni-based nitrogen-doped graphene aeroge of foam
Body method of preparation and use is as follows：
（1）Nickel foam is carried out according to the method for embodiment 1（2 cm×5 cm×0.6 cm）Pretreatment；
（2）The preparation of graphene oxide is carried out according to the method for embodiment 1；
（3）The preparation of the Ni-based N doping graphene oxide of foam.
By graphene oxide（100 mg）It is added in the distilled water of 100 mL, 1 h is stirred by ultrasonic, obtains finely dispersed
Graphene suspension；0.2 g ammonium hydroxide, 0.05 g polyvinyl alcohol, 0.1 g sodium hydrogensulfites are added in above-mentioned suspension, ultrasound
Stir 1 h；Above-mentioned mixed liquor is reacted into 12 h under the conditions of 90 DEG C, obtains the Ni-based nitrogen-doped graphene hydrogel of foam；It will bubble
The Ni-based nitrogen-doped graphene hydrogel of foam takes out and removal impurity is cleaned multiple times with distilled water, is finally freezed under the conditions of -40 DEG C
Dry 12 h, obtain the Ni-based nitrogen-doped graphene aeroge of foam.
Using the specific mistake of the prepared Ni-based nitrogen-doped graphene aeroge catalytic degradation methyl orange high-salt wastewater of foam
Journey is as follows：The Ni-based nitrogen-doped graphene aeroge of foam is added to Methyl Orange in Wastewater（100 mL）In, it is stirred under the conditions of 30 DEG C
Dye molecule is all adsorbed on graphene aerogel surface after mixing 80 min（See attached drawing 3）；By the Ni-based nitrogen-doped graphene of foam
Aeroge takes out, and removes surface salt ion wash with distilled water；By the Ni-based nitrogen-doped graphene aeroge of foam be added to containing
Single peroxosulphuric hydrogen potassium（10 mmol/L）Solution in, stir 60 min after, graphene aerogel absorption methyl orange by whole
Degradation.It is detected and is found using microcoulomb method, halogenated organic by-product is not generated in degradation process.
Claims (10)
1. a kind of Ni-based nitrogen-doped graphene aeroge of three-dimensional foam, component and proportioning are as follows by weight percentage：Aoxidize stone
4.0~10.9 % of black alkene, nitrogen source 8.3~21.7%, crosslinking agent 1.7~5.4%, reducing agent 8.3~10.9%, nickel foam 51.1~
77.7%。
2. the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam according to claim 1, it is characterised in that：The nitrogen source
For at least one of urea, ammonium hydroxide, melamine, the crosslinking agent is at least one of sodium tetraborate, polyvinyl alcohol,
The reducing agent is at least one of ascorbic acid, sodium hydrogensulfite, sodium borohydride, hydroquinone.
3. a kind of preparation method of the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam according to claim 1, feature
It is：Include the following steps：
（1）Graphene oxide is added in distilled water in proportion, ultrasonic agitation dispersion；
（2）In proportion in step（1）Graphene oxide solution in nitrogen source, crosslinking agent and reducing agent is added, ultrasonic agitation is uniform；
（3）Pretreated nickel foam is immersed into step（2）Mixed liquor in, then it is above-mentioned mixed liquor is anti-under the conditions of 90 DEG C
Answer 12 h；
（4）After the completion of reaction, the Ni-based nitrogen-doped graphene hydrogel of foam is obtained, is drawn off going to clean wash with distilled water
Matter, then be freeze-dried, obtain the Ni-based nitrogen-doped graphene aeroge of foam.
4. the preparation method of the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam according to claim 3, feature exist
In：The nickel foam preprocess method is as follows：
（1）Nickel foam is put into acetone solvent, ultrasound 10 minutes, to remove the micro greasy dirt on nickel foam substrate, to increase
Add the hydrophily of matrix；
（2）It will be cleaned by ultrasonic 10 minutes through treated nickel foam distilled water；
（3）Nickel foam after distilled water is cleaned by ultrasonic, with the salt acid etch 15 minutes of 6.0 mol/L, to remove matrix surface
Oxide layer and nickel foam surface layer formed micro-rough surface, to enhance its binding force with graphene；
（4）Nickel foam after HCl treatment is cleaned by ultrasonic 15 minutes with distilled water, then for several times with distilled water flushing；
（5）The nickel foam of above-mentioned processing is placed in 60 DEG C of 3 h of drying in baking oven.
5. the preparation method of the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam according to claim 3, feature exist
In：The preparation method of the graphene oxide includes the following steps：
（1）The concentrated sulfuric acid of the graphite powder and 23 mL of 1200 mesh for sequentially adding 1 g is added in conical flask, ice bath simultaneously stirs
10 min；
（2）It is slowly added to the potassium permanganate of 3 g into above-mentioned flask, flask is placed in 35 DEG C of water-baths and stirs 2 h；
（3）50 mL distilled water are added into flask, flask is placed in 95 DEG C of water-baths and stir 15 min；
（4）Mixed liquor in flask is transferred in the beaker equipped with 150 mL distilled water, hydrogen peroxide, dioxygen water quality is added dropwise
A concentration of 30% is measured, is stirred when being added dropwise, until solution becomes yellow from brown；
（5）Said mixture is filtered, then with the HCl of 50 mL, HCl mass concentrations 10%, dialysis 3 times, to remove impurity elimination
Matter；
（6）Above-mentioned solution is filtered, filter residue is freeze-dried at -40 DEG C, obtains graphene oxide.
6. the preparation method of the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam according to claim 3, feature exist
In：A concentration of 0.5 ~ 2 g/L of graphene oxide, nitrogen concentration are 1 ~ 4 g/L, and crosslinker concentration is 0.2 ~ 1 g/L, reduction
Agent concentration is 1 ~ 2 g/L, and freeze-drying temperature is -40 DEG C, and sublimation drying is 12 h.
7. a kind of Ni-based nitrogen-doped graphene aeroge of three-dimensional foam described in claim 1 is in handling waste water from dyestuff with high salt
Using.
8. the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam according to claim 7 is in handling waste water from dyestuff with high salt
Using,
It is characterized in that：The application process includes the following steps：
（1）The Ni-based nitrogen-doped graphene aeroge of foam is added in waste water from dyestuff with high salt and is stirred, in certain temperature item
Dye molecule is set to be adsorbed on graphene aerogel surface completely under part；
（2）The Ni-based nitrogen-doped graphene aeroge of foam is taken out, removes surface salt ion wash with distilled water；
（3）The Ni-based nitrogen-doped graphene aeroge of foam is added in the solution containing single peroxosulphuric hydrogen potassium, sulfuric acid is generated
The Strong oxdiatives species such as free radical and hydroxyl radical free radical, come the dyestuff for graphene aerogel adsorption of degrading.
9. the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam according to claim 8 is in handling waste water from dyestuff with high salt
Using, it is characterised in that：The step（1）Described in waste water from dyestuff with high salt in sodium chloride concentration be 10 ~ 50 g/L, dyestuff is dense
It is 0.1 ~ 0.5 mmol/L to spend, and the molar concentration rate of single peroxosulphuric hydrogen potassium and dyestuff is 10 ~ 50：1.
10. the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam according to claim 8 is in handling waste water from dyestuff with high salt
Application, it is characterised in that：The step（1）Middle adsorption temp condition is 30 ~ 50 DEG C, and adsorption time is 30 ~ 90 min；Step
Suddenly（3）Degradation temperature condition is 10 ~ 40 DEG C, and degradation time is 30 ~ 60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810198254.7A CN108525615B (en) | 2018-03-12 | 2018-03-12 | Preparation and application of three-dimensional foam nickel-based nitrogen-doped graphene aerogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810198254.7A CN108525615B (en) | 2018-03-12 | 2018-03-12 | Preparation and application of three-dimensional foam nickel-based nitrogen-doped graphene aerogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108525615A true CN108525615A (en) | 2018-09-14 |
| CN108525615B CN108525615B (en) | 2020-08-25 |
Family
ID=63483473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810198254.7A Expired - Fee Related CN108525615B (en) | 2018-03-12 | 2018-03-12 | Preparation and application of three-dimensional foam nickel-based nitrogen-doped graphene aerogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108525615B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109331502A (en) * | 2018-11-07 | 2019-02-15 | 湖北文理学院 | A kind of Ni-based three-dimensional grapheme stirring rod of foam |
| CN110060876A (en) * | 2019-04-22 | 2019-07-26 | 杭州电子科技大学 | A kind of preparation method of NGA@PEDOT material and the super capacitor for dragonfly shape miniature drone |
| CN110240149A (en) * | 2019-06-27 | 2019-09-17 | 中素新科技有限公司 | The production method of graphene |
| CN110841642A (en) * | 2019-12-03 | 2020-02-28 | 哈尔滨工业大学 | Preparation method of ultra-small ferroferric oxide compact coated three-dimensional reduced graphene oxide Fenton catalyst |
| CN112886028A (en) * | 2019-11-29 | 2021-06-01 | 中国科学院大连化学物理研究所 | Self-supporting porous air electrode material and preparation and application thereof |
| CN113201755A (en) * | 2021-04-01 | 2021-08-03 | 南京工业大学 | Preparation method of monatomic aerogel electrocatalyst |
| CN113600160A (en) * | 2021-08-05 | 2021-11-05 | 厦门大学 | TiO with photocatalytic function2Preparation of nanowire/graphene aerogel |
| CN115367858A (en) * | 2022-08-16 | 2022-11-22 | 华侨大学 | Water treatment method for promoting monopersulfate thermal activation system to degrade paracetamol and cooperatively controlling generation of chlorinated organic byproducts |
| CN115458759A (en) * | 2022-10-26 | 2022-12-09 | 哈尔滨工业大学 | Preparation method and application of nitrogen-doped graphene oxygen reduction catalyst with high specific surface area |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
| US20150030968A1 (en) * | 2012-03-09 | 2015-01-29 | Basf Se | Aerogel based on doped graphene |
| CN105000548A (en) * | 2014-04-22 | 2015-10-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of novel three-dimensional nitrogen doped graphene composite material system |
| CN105938908A (en) * | 2016-06-12 | 2016-09-14 | 江苏大学 | Nitrogen-doped three-dimensional graphene catalyst and preparation method thereof |
| CN106757283A (en) * | 2015-11-25 | 2017-05-31 | 常德力元新材料有限责任公司 | Foam metal-graphene composite material and preparation method thereof |
| CN107528052A (en) * | 2017-08-16 | 2017-12-29 | 南京师范大学 | Graphene derived from a kind of double-network hydrogel/tin-nickel alloy composite and its preparation method and application |
| CN107697905A (en) * | 2017-10-30 | 2018-02-16 | 山西大学 | A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge |
-
2018
- 2018-03-12 CN CN201810198254.7A patent/CN108525615B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150030968A1 (en) * | 2012-03-09 | 2015-01-29 | Basf Se | Aerogel based on doped graphene |
| EP2687483A1 (en) * | 2012-07-16 | 2014-01-22 | Basf Se | Graphene containing nitrogen and optionally iron and/or cobalt |
| CN102874796A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Nitrogen mixed grapheme hydrogel or aerogel and preparation method thereof |
| CN105000548A (en) * | 2014-04-22 | 2015-10-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of novel three-dimensional nitrogen doped graphene composite material system |
| CN106757283A (en) * | 2015-11-25 | 2017-05-31 | 常德力元新材料有限责任公司 | Foam metal-graphene composite material and preparation method thereof |
| CN105938908A (en) * | 2016-06-12 | 2016-09-14 | 江苏大学 | Nitrogen-doped three-dimensional graphene catalyst and preparation method thereof |
| CN107528052A (en) * | 2017-08-16 | 2017-12-29 | 南京师范大学 | Graphene derived from a kind of double-network hydrogel/tin-nickel alloy composite and its preparation method and application |
| CN107697905A (en) * | 2017-10-30 | 2018-02-16 | 山西大学 | A kind of preparation method of three-dimensional nitrogen-doped graphene aeroge |
Non-Patent Citations (2)
| Title |
|---|
| FAZE WANG ET AL.: "Nickel skeleton three-dimensional nitrogen doped graphene nanosheets/nanoscrolls as promising supercapacitor electrodes", 《NANOTECHNOLOGY》 * |
| 周雪君，时鹏辉，姚伟峰: "掺氮石墨烯的制备及其催化性能研究", 《上海电力学院学报》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109331502B (en) * | 2018-11-07 | 2024-01-23 | 湖北文理学院 | Foam nickel-based three-dimensional graphene stirring rod |
| CN109331502A (en) * | 2018-11-07 | 2019-02-15 | 湖北文理学院 | A kind of Ni-based three-dimensional grapheme stirring rod of foam |
| CN110060876A (en) * | 2019-04-22 | 2019-07-26 | 杭州电子科技大学 | A kind of preparation method of NGA@PEDOT material and the super capacitor for dragonfly shape miniature drone |
| CN110240149A (en) * | 2019-06-27 | 2019-09-17 | 中素新科技有限公司 | The production method of graphene |
| CN110240149B (en) * | 2019-06-27 | 2021-04-02 | 中素新科技有限公司 | Production method of graphene |
| CN112886028B (en) * | 2019-11-29 | 2022-03-08 | 中国科学院大连化学物理研究所 | Self-supporting porous air electrode material and preparation and application thereof |
| CN112886028A (en) * | 2019-11-29 | 2021-06-01 | 中国科学院大连化学物理研究所 | Self-supporting porous air electrode material and preparation and application thereof |
| CN110841642B (en) * | 2019-12-03 | 2022-07-15 | 哈尔滨工业大学 | Preparation method of ultra-small ferroferric oxide compact coated three-dimensional reduced graphene oxide Fenton catalyst |
| CN110841642A (en) * | 2019-12-03 | 2020-02-28 | 哈尔滨工业大学 | Preparation method of ultra-small ferroferric oxide compact coated three-dimensional reduced graphene oxide Fenton catalyst |
| CN113201755A (en) * | 2021-04-01 | 2021-08-03 | 南京工业大学 | Preparation method of monatomic aerogel electrocatalyst |
| CN113201755B (en) * | 2021-04-01 | 2022-08-30 | 南京工业大学 | Preparation method of monatomic aerogel electrocatalyst |
| CN113600160A (en) * | 2021-08-05 | 2021-11-05 | 厦门大学 | TiO with photocatalytic function2Preparation of nanowire/graphene aerogel |
| CN115367858A (en) * | 2022-08-16 | 2022-11-22 | 华侨大学 | Water treatment method for promoting monopersulfate thermal activation system to degrade paracetamol and cooperatively controlling generation of chlorinated organic byproducts |
| CN115367858B (en) * | 2022-08-16 | 2023-11-21 | 华侨大学 | Water treatment method for promoting degradation of paracetamol by monopersulfate heat activation system and cooperatively controlling generation of chlorinated organic byproducts |
| CN115458759A (en) * | 2022-10-26 | 2022-12-09 | 哈尔滨工业大学 | Preparation method and application of nitrogen-doped graphene oxygen reduction catalyst with high specific surface area |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108525615B (en) | 2020-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108525615A (en) | A kind of preparation and its application of the Ni-based nitrogen-doped graphene aeroge of three-dimensional foam | |
| CN102000573A (en) | Modified activated carbon and application thereof | |
| CN108970608B (en) | Supported noble metal catalyst with coating structure, preparation method thereof and application thereof in Cu (II) liquid-phase catalytic reduction | |
| CN101298049B (en) | Method for preparing Pd/foamed metal catalyst for hydrogenolysis dechlorination | |
| CN108855083A (en) | A method of sulfa drugs in water removal is removed with modified zeolite activation Peracetic acid | |
| CN106362754A (en) | Iron sodium bismuthate-graphene visible-light-driven Fenton-like composite catalyst used for removing nonyl phenol and preparation method thereof | |
| CN110420641A (en) | A kind of method of three-dimensional support type cobalt hydroxide prepared and its handle phenolic waste water for being catalyzed persulfate | |
| CN106345466A (en) | Method for preparing hydroxylation graphene oxide-magnesium titanate/silver molybdate composite materials | |
| CN104841451A (en) | Preparation of Cu doped MnO2 mesoporous material and application of material in Fenton-like water treatment advanced oxidation technology | |
| CN113134347A (en) | Preparation method and application of heteroatom porous carbon | |
| Xing et al. | Motion-based phenol detection and degradation using 3D hierarchical AA-NiMn-CLDHs@ HNTs-Ag nanomotors | |
| CN113600150B (en) | Method for preparing magnetic super-crosslinked polymer from vacuum residue | |
| CN108927223A (en) | A kind of method and its application preparing cyclodextrin@ferroferric oxide/carbon nanotube complex | |
| CN107051480A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN1266052C (en) | Preparing composite iron powder by aluminium magnesium alloy for degrading organics contained halogen in water | |
| CN112517041B (en) | Solid-phase Fenton-like catalyst and preparation method and application thereof | |
| Mamba et al. | Application of Carbon Nanotube‐Polymer Composites and Carbon Nanotube‐Semiconductor Hybrids in Water Treatment | |
| Kuo et al. | Application of cuprous oxide synthesized from copper-containing waste liquid to treat aqueous reactive dye | |
| CN107008389A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| Zhao et al. | Efficient degradation of organophosphorus herbicide by free‐standing 3D reduced graphene oxide supported nFe3O4 catalytic‐activated persulfate | |
| CN112076750A (en) | Preparation of ferroferric oxide modified carbon nanotube reduced graphene oxide compound and application of ferroferric oxide modified carbon nanotube reduced graphene oxide compound in removal of tetrabromobisphenol A in water | |
| CN107008377A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008289A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008354A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008376A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200825 |