CN109916973A - A kind of Graphite alkene-MOFs composite material, its preparation and application - Google Patents
A kind of Graphite alkene-MOFs composite material, its preparation and application Download PDFInfo
- Publication number
- CN109916973A CN109916973A CN201910147932.1A CN201910147932A CN109916973A CN 109916973 A CN109916973 A CN 109916973A CN 201910147932 A CN201910147932 A CN 201910147932A CN 109916973 A CN109916973 A CN 109916973A
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- nanometer sheet
- graphene nanometer
- graphite alkene
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to nano material technology and electrochemical sensor fields, more particularly, to a kind of Graphite alkene-metal organic frame (MOFs) composite material, preparation method and application in electrochemical sensor.Wherein, the graphene is large stretch of graphene nanometer sheet of ball milling removing preparation, and the metal organic frame is dispersed on graphene nanometer sheet surface.The preparation method is as follows: (1) wet ball grinding removing, which prepares graphene nanometer sheet (2), combines organic ligand growth in situ metal organic frame on the surface of graphene in the abundant adsorbing metal ions in graphene nanometer sheet surface (3).Final acquisition stability and electric conductivity are good, Graphite alkene-metal organic frame compound with bigger serface and high porosity.The alkene of Graphite obtained by the present invention-metal organic frame compound electrochemical performance can be used for preparing highly sensitive electrochemical sensing platform.
Description
Technical field
The invention belongs to nano material technology and electrochemical sensor fields, more particularly, to a kind of Graphite alkene-
Metal organic frame (MOFs) composite material, preparation method and the application in electrochemical sensing field.
Background technique
In recent years, metal organic frame (Metal-organic frameworks, abbreviation MOFs) was because of its big hole
Rate and specific surface area, the advantages such as adjustable aperture and variable functional group have obtained extensively in electrochemical sensing field
Using.However, limiting its practical application and future development due to the unstability and poor electric conductivity of MOFs itself.
In order to solve this problem, MOFs is constructed into composite material with other materials to improve the stability of MOFs, absorption property and lead
Electrical property, it has also become the popular direction of research.So far, existing multiple material, which is reported, can be used for compound MOFs to improve its electrification
Learn performance, such as metallic/nanometer rods, quantum dot, conductive polymer polymer, carbon nanotube and porous carbon etc..
With the development that graphene is studied, graphene-based MOFs compound causes the extensive concern of people, synthesizes compound
Material can make up the disadvantage of material respectively, realize and have complementary advantages, effectively promotion sensing capabilities.However, existing graphene-based
MOFs compound mostly uses graphene oxide or redox graphene as base load MOFs, and this kind of graphenes are to utilize
The preparation of chemistry redox method, this method has the shortcomings that chemical reagent that are many intrinsic, such as using largely toxic, complicated
Preparation process and operating process present in risk.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of Graphite alkene-metal is organic
Frame composite material, preparation method and the application in electrochemical sensing field, by the way that Graphite alkene and MOFs is former
Position is compound, and graphene-based MOFs composite material is prepared at room temperature, thus solves existing graphene-based MOFs compound system
A large amount of toxic chemical reagent are used during standby, the technologies such as dangerous property are asked in complicated preparation process and operating process
Topic.
To achieve the above object, according to one aspect of the present invention, a kind of system of graphene-MOFs composite material is provided
Preparation Method includes the following steps:
(1) graphite powder is removed using wet ball grinding method, shearing force is occupied an leading position in ball milling stripping process, is obtained
Mixed system containing graphene nanometer sheet；
(2) institute is removed using gradient centrifugation to the mixed system containing graphene nanometer sheet that step (1) obtains
Graphite flake unstripped in mixed system is stated, graphene nanometer sheet solid is obtained；
(3) metal salt that will be dispersed in organic solvent is mixed with the graphene nanometer sheet that step (2) obtains, and stirring makes institute
The adsorption of metal ions in metal salt is stated in graphene nano on piece, obtains the graphene nanometer sheet of loaded metal ion；
(4) graphene nanometer sheet for the loaded metal ion that step (3) obtain is mixed with organic ligand, and in alkali source
Promote MOFs in the fabricated in situ on graphene nanometer sheet surface under booster action, finally obtains graphene-MOFs composite material.
Preferably, surfactant is also used during the wet ball grinding, for improving the stripping of graphite in mechanical milling process
From efficiency；The surfactant is anionic surfactant, cationic surfactant or nonionic surfactant.
Preferably, the surfactant is cetyl trimethylammonium bromide.
Preferably, the mass ratio of step (1) graphite powder and surfactant is 3:1 to 1:3.
Preferably, graphite powder is dispersed in ethanol water by step (1) carries out wet ball grinding, by controlling rotational speed of ball-mill
Ensure that shearing force is occupied an leading position in mechanical milling process, Ball-milling Time is not less than 12 hours.
Preferably, step (2) gradient centrifugation specifically: first pass through 500-2000 rpms of centrifugation 5-45
Unstripped complete graphite powder precipitating is taken out in minute initial gross separation, then passes through 8000-12000 rpms centrifugation 5-45 minutes
Further obtain graphene nanometer sheet solid.
Preferably, metal salt described in step (3) is Cu (NO3)2·3H2O、Ni(NO3)2·6H2O、Zn(NO3)2·
6H2O、Co(NO3)2·6H2One or more of O；The organic solvent is N,N-dimethylformamide, methanol or methanol
Aqueous solution.
Preferably, the mass ratio of step (3) metal salt and the graphene nanometer sheet is 10:1-20:1, described to stir
Mixing the time is 0.1 to 2 hours.
Preferably, step (4) organic ligand is Isosorbide-5-Nitrae-terephthalic acid (TPA), 1,3,5- trimesic acids and 2- methyl miaow
The one or more of azoles.
Preferably, the alkali source is triethylamine/n,N-Dimethylformamide mixed solution, and wherein triethylamine is described mixed
Closing the volumetric concentration in solution is 1%, and 1 to 10 milliliters of alkali sources are added in every gram of organic ligand.
Other side according to the invention provides a kind of electrochemical sensor of Graphite alkene/MOFs modification,
Including electrode and positioned at the active constituent of the electrode surface, the active constituent is graphene-made from the preparation method
MOFs composite material.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) present invention is using Graphite alkene as substrate, direct adsorbing metal ions, then adsorbs in graphene nano on piece
Metal ion site growth in situ MOFs, the presence of graphene can effectively reduce the reunion of MOFs, improve the dispersion of MOFs
Property, the MOFs for obtaining size and being evenly distributed, so that substantially increasing the property uniformity of composite material, stability and circulation makes
Use performance.
(2) graphene is prepared using wet ball grinding method, different from the graphene of oxidation-reduction method synthesis, avoided in synthesis
The use of harmful reagent, safer simplicity, and the potential volume production for realizing graphene.
(3) synthetic reaction of Graphite alkene/MOFs composite material of the present invention (20~30 DEG C) progress at room temperature,
And reaction time is short, greatly reduces cost, is conducive to large-scale production.
(4) Graphite alkene/MOFs compound produced by the present invention has good electrochemical reaction activity, based on its system
Standby highly sensitive electrochemical sensor, can for micro xanthine (XA), hypoxanthine (HXA), bisphenol-A (BPA) and
Parachlorophenol (CP) is detected, and is not needed excessive sample pre-treatments and is isolated and purified, and actual sample analysis is more suitable for.Base
In three times signal-to-noise ratio, the detection limit for XA, HXA, BPA and CP is respectively 0.0011,0.0073,0.0012 and 0.0019 milligram
Every liter.
(5) preparation method of Graphite alkene provided by the invention/MOFs modification electrochemical sensor is simple, cost
Low, the practical prospect as on-line monitoring is good, practical.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for the Graphite alkene that the method for embodiment 1 separates；
Fig. 2 is Graphite alkene/Cu-BTC scanning electron microscope (SEM) photograph of the method preparation of embodiment 1；
Fig. 3 is Graphite alkene/Cu-BTC transmission electron microscope picture of the method preparation of embodiment 1；
Fig. 4 is Graphite alkene/Cu-BTC (a) of the method preparation of embodiment 1, Graphite alkene prepared by comparative example 1
(b), Cu-BTC (d) XRD diagram of the Cu-BTC (c) and simulation that prepared by comparative example 2；
Fig. 5 is Graphite alkene/Cu-BTC thermogravimetric analysis figure of the method preparation of embodiment 1, wherein (a) is comparative example
1 ball milling removes graphene, is (b) Graphite alkene/Cu-BTC of embodiment 1, is (c) Cu-BTC of comparative example 2；
Fig. 6 is Graphite alkene/Cu-BTC of the method preparation of embodiment 1 and the nitrogen adsorption desorption song of Graphite alkene
Line, wherein curve a is Graphite alkene/Cu-BTC of embodiment 1, and curve b is the Graphite alkene of comparative example 1；
Fig. 7 be done with NADH probe calculate gained bare glassy carbon electrode and embodiment 1 method preparation Graphite alkene/
The heterogeneous electron transfer rate constant of Cu-BTC, wherein (a) is bare glassy carbon electrode, it is (b) the ball milling removing graphene of comparative example 1
Nano-sheet modified electrode, (c) be comparative example 2 Cu-BTC modified electrode, (d) the Graphite alkene of embodiment 1/Cu-BTC modification
Electrode；
Fig. 8 is with XA and HXA (a), and BPA (b) and CP (c) substance do differential pulse curve obtained by probe, wherein curve a
It is Graphite alkene/Cu-BTC modified electrode of embodiment 1, curve b is the ball milling removing graphene nanometer sheet modification of comparative example 1
Electrode, curve c are the Cu-BTC modified electrodes of comparative example 2, and curve d is bare glassy carbon electrode；
Fig. 9 is Graphite alkene/Cu-BTC modified electrode differential pulse voltammetry detection XA (a) of embodiment 1, HXA
(b), the response signal of BPA (c) and CP (d) compares figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of preparation methods of Graphite alkene-MOFs composite material, include the following steps:
(1) graphite powder is removed using wet ball grinding method, shearing force is occupied an leading position in ball milling stripping process, is obtained
Mixed system containing graphene nanometer sheet；
(2) institute is removed using gradient centrifugation to the mixed system containing graphene nanometer sheet that step (1) obtains
Graphite unstripped in mixed system is stated, graphene nanometer sheet solid is obtained；
(3) metal salt that will be dispersed in organic solvent is mixed with the graphene nanometer sheet that step (2) obtains, and stirring makes institute
The adsorption of metal ions in metal salt is stated in graphene nano on piece, obtains the graphene nanometer sheet of loaded metal ion；
(4) graphene nanometer sheet for the loaded metal ion that step (3) obtain is mixed with organic ligand, and in alkali source
The fabricated in situ for promoting graphene nanometer sheet surface MOFs under booster action, finally obtains graphene-MOFs composite material.
Theoretically, graphite Powder Particle Size is thinner, is more conducive to its wet ball grinding and removes to obtain graphene nanometer sheet.Comprehensively consider
Charge stripping efficiency and cost generally use medium-grained graphite powder, for example granularity mesh number is the graphite powder of 1200 mesh.
In some embodiments, surfactant is also used during the wet ball grinding, for improving stone in mechanical milling process
The charge stripping efficiency of ink；The surfactant is that anionic surfactant, cationic surfactant or non-ionic surface are living
Property agent, preferably cetyl trimethylammonium bromide.
In some embodiments, the mass ratio of the graphite powder and surfactant is 3:1 to 1:3.
In some embodiments, graphite powder is dispersed in ethanol water by step (1) carries out wet ball grinding, by controlling ball
Mill revolving speed ensures that shearing force is occupied an leading position in mechanical milling process, and Ball-milling Time is not less than 12 hours, and rotational speed of ball-mill is not less than 300
Rev/min.
In some embodiments, step (2) described gradient centrifugation specifically: step (2) the gradient centrifugation separation
Method specifically: it is heavy to first pass through the unstripped complete graphite powder of 500-2000 rpms of centrifugation initial gross separation in 5-45 minutes taking-up
It forms sediment, is then further centrifuged within centrifugation 5-45 minutes by 8000-12000 rpms and obtains graphene nanometer sheet solid.Then
It cleans the solid further to remove remaining surfactant, obtains final Graphite alkene nanometer after dry in baking oven
Piece.
In some embodiments, metal salt described in step (3) is Cu (NO3)2·3H2O、Ni(NO3)2·6H2O、Zn
(NO3)2·6H2O、Co(NO3)2·6H2One or more of O；The organic solvent is N,N-dimethylformamide, methanol
Or the aqueous solution of methanol.
In some embodiments, the mass ratio of step (3) metal salt and the graphene nanometer sheet is 10:1-20:1,
The mixing time is 0.1 to 2 hours, preferably 0.2 to 0.4 hour.The present invention is preparing graphene-MOFs composite material
When, after graphene nanometer sheet is made, a period of time is mixed in the organic solution of metal salt and graphene first, so that
Metal ion sufficiently adsorbs compound on graphene nanometer sheet surface, this absorption recombination time is for final graphene-obtained
The performance of MOFs composite material has large effect, finds suitable mixing time control between 0.1 to 2 hours in experiment
It is advisable, preferred stirring recombination time is 0.2 to 0.4 hour.
In some embodiments, step (4) organic ligand is Isosorbide-5-Nitrae-terephthalic acid (TPA), 1,3,5- trimesic acids and 2-
One of methylimidazole is a variety of.
In some embodiments, the alkali source is triethylamine/n,N-Dimethylformamide mixed solution, and wherein triethylamine exists
Volumetric concentration in the mixed solution is 1%, and 1 to 10 milliliters of alkali sources are added in every gram of organic ligand.
In some embodiments, step (4) specifically: by step (3) obtain graphene nanometer sheet and metal salt it is compound
System is mixed with organic ligand, and alkali source is then slowly added dropwise into system, promotes graphene nano under the booster action of alkali source
The fabricated in situ of piece surface MOFs controls the fabricated in situ time not shorter than 5 minutes, finally obtains graphite after being added dropwise to complete
Alkene-MOFs composite material.Synthesising reacting time in situ is longer in the step, and MOFs particle is bigger in obtained composite material,
The suitable reaction time is -90 minutes 5 minutes.
The present invention also provides a kind of electrochemical sensors of Graphite alkene/MOFs modification comprising electrode and is located at
The active constituent of the electrode surface, the active constituent are that graphene-MOFs made from preparation method of the present invention is compound
Material.The electrochemical sensor obtains as follows: graphene-MOFs composite material solid obtained has been dispersed in
In solvent, Graphite alkene/MOFs suspension is obtained；The suspension is coated in the electrode surface of electrochemical sensor, is waved
Graphite alkene/MOFs modification electrochemical sensor is obtained after hair organic solvent.Wherein organic solvent can use N, N- bis-
Methylformamide, water, ethyl alcohol or N-Methyl pyrrolidone.
Graphene is prepared different from chemistry redox method, physics stripping method is a kind of high-efficient simple, mild effective system
The method of standby graphene.Ball milling removing is a kind of physics stripping method.Ball-milling method has combined the high efficiency and gained of production
The good quality of graphene is a kind of method for preferably preparing graphene.Meanwhile compared to graphene oxide or oxygen reduction fossil
Black alkene, ball milling removing graphene are also proven to have more excellent electrochemical sensing activity.Pass through Graphite alkene and MOFs
In-situ reaction can provide a kind of more easy to avoid the operating process of use and the danger of reagent toxic in synthesis process
Safety prepares graphene-based MOFs method.Material after compound has had both the advantages of graphene and MOFs, can effectively apply
In building electrochemical sensing platform.
In the synthetic method of Graphite alkene-metal organic frame composite material of the present invention, the graphene is ball milling stripping
Large stretch of graphene nanometer sheet from preparation, the metal organic frame are dispersed on graphene nanometer sheet surface.Preparation side
Method is as follows: (1) wet ball grinding removing prepares graphene nanometer sheet；(2) in the abundant adsorbing metal ions in graphene nanometer sheet surface；
(3) organic ligand growth in situ metal organic frame on the surface of graphene is combined.Final acquisition stability and electric conductivity are good, tool
There is the Graphite of bigger serface and high porosity alkene-metal organic frame compound.
The present invention mixes a period of time by first carrying out metal salt with the graphene nanometer sheet that ball-milling method is removed, and makes
The metal ion obtained in metal salt sufficiently adsorbs on graphene nanometer sheet surface, then adds organic ligand and alkali source, makes
Metal organic frame is obtained in graphene nanometer sheet adsorption site fabricated in situ.This in-situ synthetic method can be by means of stone
The presence of black alkene effectively reduces the reunion of MOFs, improves the dispersibility of MOFs, the MOFs for obtaining size and being evenly distributed, thus
Substantially increase property uniformity, stability and the recycling performance of composite material.
The present invention realizes Graphite alkene-metal organic frame composite wood by adjusting synthesis thinking and synthesis technology
The room temperature of material synthesizes, and synthesis technology is simple.
The alkene of Graphite obtained by the present invention-metal organic frame compound electrochemical performance, can be used for preparing
Highly sensitive electrochemical sensing platform.
The electrode that electrochemical sensor of the present invention uses is conventional electrodes, such as usually used glass-carbon electrode.
In some embodiments, glass-carbon electrode includes glass-carbon electrode head, electrode jacket and copper rod shape conducting wire；The glass-carbon electrode
Head enclosed package is located at cylindrical shape electrode jacket center, the glass-carbon electrode head surface one inside the electrode jacket
End is in same plane with described electrode jacket one end, and the other end is connected with the copper rod shape conducting wire, and copper rod shape conducting wire extends to
The electrode jacket outer end.
Graphite alkene provided by the invention/MOFs modification electrochemical sensor, its preparation and application have following skill
Art advantage:
(1) preparation method is safe and simple
By wet ball grinding method, physics removes graphite powder and obtains graphene in ethanol/water mixed solution, is not related to having
The reagent of murder by poisoning and complicated dangerous experimental implementation.Meanwhile in gained graphene surface growth in situ at room temperature
MOFs, obtains the compound of uniform load MOFs on Graphite alkene, and method is easy.
(2) highly sensitive
Due to gained Graphite alkene/good electric conductivity of MOFs and electrochemical reaction activity, it is prepared for high sensitivity
Electrochemical sensor.Based on three times signal-to-noise ratio, the detection limit for XA, HXA, BPA and CP is respectively 0.0011,0.0073,
0.0012 and 0.0019 milligrams per liter.
(3) analysis speed is fast
Liquid-phase chromatography method detects a sample and needs or so half an hour, this sensor can directly examine sample simultaneously
It surveys, entire sample analysis time is about 2 minutes, meets the quick detection requirement in scene.
(4) practical
Sensor can detect simultaneously when detecting, and do not need excessive sample pre-treatments and isolate and purify, be more suitable for reality
The detection of border sample, and preparation method is simple, and at low cost, the practical prospect as on-line monitoring is good, practical.
Accordingly, with respect to detection methods such as traditional chromatography mass spectrometries, the electrochemical sensor of this method development is shown
The advantage highly sensitive, quick, environmental-friendly, easy to operate, accuracy is high, practical.
The following are embodiments:
Embodiment 1
A kind of preparation method of Graphite alkene/Cu-BTC composite material carries out in accordance with the following steps:
300 milligram of 1200 mesh graphite powder is dispersed in 30 milliliters with 300 milligrams of cetyl trimethylammonium bromide powder to contain
In the aqueous solution of 15% ethyl alcohol, control rotational speed of ball-mill is 300 rpms to guarantee that shearing force is occupied an leading position in mechanical milling process,
After ball-milling reaction 12 hours, remove to obtain graphene nanometer sheet mixed solution by ball milling.
Mixed solution is centrifuged the unstripped complete graphite powder precipitating of removal in 20 minutes at 2000 rpms.It is again that gained is molten
Liquid is centrifuged 20 minutes under 9000 rpms and obtains solid, cleans obtained solid repeatedly with ethyl alcohol and ultrapure water to remove residual
Cetyl trimethylammonium bromide, the finally forced air drying at 60 DEG C.
By 0.7 gram of Cu (NO3)2·3H2O is dispersed in 50 milliliters of DMF solutions, is subsequently added into 50 milligrams of Graphites
Alkene powder is directly added into 0.42 gram of H after stirring 0.5 hour3BTC.Then, 1 milliliter of triethylamine/DMF mixed solution is instilled
In the above mixed solution, wherein concentration of the triethylamine in the mixed solution is 1% (v/v), after persistently stirring 0.5 hour, is led to
It crosses and gained compound is collected by centrifugation, obtained solid ethyl alcohol and ultrapure water are washed 3 times repeatedly, forced air drying at most finally 30 DEG C
24 hours.Then desciccate is dispersed in n,N-Dimethylformamide with 2.0 milligrams every milliliter of concentration, obtains ball milling stone
Black alkene/Cu-BTC suspension.
A kind of preparation method of the electrochemical sensor of Graphite alkene/Cu-BTC composite material modification, according to following step
It is rapid to carry out:
Glass-carbon electrode is polishing to surface in smooth mirror surface with 0.05 micrometers alumina powder, then clear with ethyl alcohol and water ultrasound
It washes.Gained Graphite alkene/Cu-BTC compound dispersant liquid drop is coated in clean electrode surface, is done with volatilization under infrared lamp molten
Agent has just obtained Graphite alkene/Cu-BTC modification electrochemical sensing film.Glass-carbon electrode has purchased from the farsighted science and technology of Wuhan Grolsch
Limit company.Glass-carbon electrode head diameter is 3 millimeters, and length is 4 millimeters.Lagging material is polytetrafluoroethylene (PTFE).Copper rod shape conducting wire, diameter
It is 1 millimeter, one section connects with glass carbon phase, and the other end is stretched out by electrode jacket bottom.
Comparative example 1
A kind of Graphite alkene preparation method carries out in accordance with the following steps:
300 milligram of 1200 mesh graphite powder is dispersed in 30 milliliters with 300 milligrams of cetyl trimethylammonium bromide powder to contain
In the aqueous solution of 15% ethyl alcohol, control rotational speed of ball-mill is 300 rpms to guarantee that shearing force is occupied an leading position in mechanical milling process,
After ball-milling reaction 12 hours, remove to obtain graphene nanometer sheet mixed solution by ball milling.Mixed solution is at 2000 rpms
It is centrifuged the unstripped complete graphite powder precipitating of removal in 20 minutes.Acquired solution is centrifuged under 9000 rpms again 20 minutes
To solid, clean obtained solid repeatedly with ethyl alcohol and ultrapure water to remove remaining cetyl trimethylammonium bromide, finally in
Forced air drying at 60 DEG C.Then desciccate is dispersed in n,N-Dimethylformamide with 2.0 milligrams every milliliter of concentration, is obtained
To Graphite alkene suspension.
Comparative example 2
A kind of preparation method of Cu-BTC carries out in accordance with the following steps:
By 0.7 gram of Cu (NO3)2·3H2O is dispersed in 50 milliliters of DMF solutions, after stirring 0.5 hour, is directly added into
0.42 gram of H3BTC.Then, 1 milliliter of 1% (v/v) triethylamine/DMF is slowly dropped into the above mixed solution, persistently stirs 0.5
After hour, the compound as obtained by being collected by centrifugation washs obtained solid ethyl alcohol and ultrapure water 3 times, most finally 30 DEG C repeatedly
Lower forced air drying 24 hours.Then desciccate is dispersed in n,N-Dimethylformamide with 2.0 milligrams every milliliter of concentration,
Obtain Cu-BTC suspension.
Fig. 1 is the scanning electron microscope (SEM) photograph for the Graphite alkene that the method for embodiment 1 separates, from scanning electron microscope (SEM) photograph it can be seen that
Gained Graphite alkene is the graphene nanometer sheet that planar dimension reaches micron level, and micron level large scale is conducive to its conduct
The metal organic frame of supporting substrate surface in situ growth.
Fig. 2 is Graphite alkene/Cu-BTC scanning electron microscope (SEM) photograph of the method preparation of embodiment 1, as can be seen from the figure
It is about 30 nanometers of Cu-BTC nano particles that diameter is uniform-distribution with above graphene.
Fig. 3 is Graphite alkene/Cu-BTC transmission electron microscope picture of the method preparation of embodiment 1, as can be seen from the figure
The flaky structure of graphene, thereon uniform load Cu-BTC nano particle.
Fig. 4 is Graphite alkene/Cu-BTC (a) of the method preparation of embodiment 1, Graphite alkene prepared by comparative example 1
(b), Cu-BTC (d) XRD diagram of the Cu-BTC (c) and simulation that prepared by comparative example 2, successfully synthesize ball as we can see from the figure
Grind graphene/Cu-BTC compound.
Fig. 5 is Graphite alkene/Cu-BTC thermogravimetric analysis figure of the method preparation of embodiment 1, wherein (a) is comparative example
1 ball milling removes graphene, is (b) Graphite alkene/Cu-BTC of embodiment 1, is (c) Cu-BTC of comparative example 2, passes through meter
Calculation can obtain Cu-BTC and the weight fraction of Graphite alkene nanometer sheet respectively may be about 63.11% and 36.98%.
Fig. 6 is Graphite alkene/Cu-BTC of the method preparation of embodiment 1 and the nitrogen adsorption desorption song of Graphite alkene
Line, wherein curve a is Graphite alkene/Cu-BTC of embodiment 1, and curve b is the Graphite alkene of comparative example 1, can from figure
To find out that the introducing of Cu-BTC substantially increases adsorption capacity.
Fig. 7 is to make probe with nicotinamide adenine dinucleotide to calculate resulting heterogeneous electron turn by rotating disk electrode (r.d.e)
Rate constant is moved, wherein (a) is bare glassy carbon electrode, it is (b) the ball milling removing graphene nano sheet modified electrode of comparative example 1, (c)
It is the Cu-BTC modified electrode of comparative example 2, is (d) Graphite alkene/Cu-BTC modified electrode of embodiment 1, structure shows ball
Grinding graphene/Cu-BTC has optimal electro-catalysis ability.
Fig. 8 is with XA and HXA (a), and BPA (b) and CP (c) substance do differential pulse curve obtained by probe, wherein curve a
It is Graphite alkene/Cu-BTC modified electrode of embodiment 1, curve b is the ball milling removing graphene nanometer sheet modification of comparative example 1
Electrode, curve c are the Cu-BTC modified electrodes of comparative example 2, and curve d is bare glassy carbon electrode, and structure shows Graphite alkene/Cu-
BTC has optimal electrochemical reaction ability.
Fig. 9 is Graphite alkene/Cu-BTC modified electrode differential pulse voltammetry detection XA (a) of embodiment 1, HXA
(b), the response signal of BPA (c) and CP (d) compares figure.
Using common three-electrode system, using Graphite alkene/Cu-BTC modification electrochemical sensor probe as work
Make electrode, as reference electrode, platinum column electrode is used as to electrode saturated calomel electrode, connects electrochemical workstation and computer pair
Experimental data is acquired and records.
XA, HXA, BPA and CP are detected using the electrochemical sensor that above-mentioned preparation method is prepared.
Practical application: in the case where being sufficiently stirred, with the response of differential pulse voltammetry detection XA, HXA, BPA and CP
Signal.Medium is 10.0 milliliters, the phosphate buffer solution of 0.1 mole every liter of pH 7.0.Stirring lower enrichment 2 minutes, measurement
The peak current intensity of differential pulse voltammetry signal in response.It is constant that a kind of material concentration is to maintain in detection XA and HXA,
Change the concentration of determinand, as the result is shown without generating interference between XA and HXA, constructed sensor can be used for XA and HXA
While detect.
Electrochemical sensor is made in Graphite alkene/Cu-BTC of embodiment 1, various concentration pollutant is tested, to survey
Test result does linear fit, is based on three times signal-to-noise ratio, the detection limit for XA, HXA, BPA and CP is respectively 0.0011,
0.0073,0.0012 and 0.0019 milligrams per liter.It includes urine, blood plasma, purchase that the electrochemical probe of research and development, which is used for actual sample,
The detection of object receipt and industrial wastewater.Each sample is measured in parallel three times, and relative standard deviation (RSD) is below 5%, illustrates this
The favorable reproducibility of sensor.In order to verify the accuracy of the method, compareed with the measurement of the high performance liquid chromatography of comparative maturity,
High performance liquid chromatography measurement result and sensor measurement result relative error are below 9%, and (this deviation is generally in tolerance interval
It is interior), illustrate sensor accuracy height.
Graphite alkene/the MOFs of electrochemical sensor of the invention by glass-carbon electrode and modification in its surface is constituted, institute
The electrochemical sensor stated can be used for direct, quick, the highly sensitive and accuracy detection of XA, HXA, BPA and CP.With prepare stone
The comparison of black alkene/MOFs compound method, present invention shows high sensitivity, is simple to operate and friendly to environment, and what is synthesized answers
Closing object has excellent electrochemical sensing performance, can be used for constructing highly sensitive electrochemical sensing platform, has realization real-time
The prospect of on-line environmental monitoring.
Embodiment 2
A kind of preparation method of Graphite alkene/Co-BTC composite material carries out in accordance with the following steps:
300 milligram of 1200 mesh graphite powder is dispersed in 30 milliliters with 300 milligrams of cetyl trimethylammonium bromide powder to contain
In the aqueous solution of 15% ethyl alcohol, control rotational speed of ball-mill is 300 rpms to guarantee that shearing force is occupied an leading position in mechanical milling process,
After ball-milling reaction 12 hours, remove to obtain graphene nanometer sheet mixed solution by ball milling.
Mixed solution is centrifuged the unstripped complete graphite powder precipitating of removal in 20 minutes at 2000 rpms.It is again that gained is molten
Liquid is centrifuged 20 minutes under 9000 rpms and obtains solid, cleans obtained solid repeatedly with ethyl alcohol and ultrapure water to remove residual
Cetyl trimethylammonium bromide, the finally forced air drying at 60 DEG C.
By 0.85 gram of Co (NO3)2·6H2O is dispersed in 50 milliliters of DMF solutions, is subsequently added into 50 milligrams of Graphites
Alkene powder is directly added into 0.42 gram of H after stirring 0.5 hour3BTC.Then, 1 milliliter of 1% (v/v) triethylamine/DMF is slowly dripped
Enter in the above mixed solution, persistently stir 1.5 hours after, the compound as being collected by centrifugation obtained by, by obtained solid ethyl alcohol with
Ultrapure water washs 3 times repeatedly, forced air drying 24 hours at most finally 30 DEG C.Then it will be dried with 2.0 milligrams every milliliter of concentration
Product is dispersed in n,N-Dimethylformamide, obtains Graphite alkene/Co-BTC suspension.
Electrochemical sensor is made in Graphite alkene/Co-BTC prepared by embodiment 2, after tested, the sensor is accurate
Degree is high, and can be used for direct, the quick detection of XA, HXA, BPA and CP.
Embodiment 3
A kind of preparation method of Graphite alkene/Cu-BTC composite material carries out in accordance with the following steps:
300 milligram of 1200 mesh graphite powder is dispersed in 30 milliliters with 300 milligrams of cetyl trimethylammonium bromide powder to contain
In the aqueous solution of 15% ethyl alcohol, control rotational speed of ball-mill is 300 rpms to guarantee that shearing force is occupied an leading position in mechanical milling process,
After ball-milling reaction 12 hours, remove to obtain graphene nanometer sheet mixed solution by ball milling.
Mixed solution is centrifuged the unstripped complete graphite powder precipitating of removal in 20 minutes at 2000 rpms.It is again that gained is molten
Liquid is centrifuged 20 minutes under 9000 rpms and obtains solid, cleans obtained solid repeatedly with ethyl alcohol and ultrapure water to remove residual
Cetyl trimethylammonium bromide, the finally forced air drying at 60 DEG C.
By 0.7 gram of Cu (NO3)2·3H2O is dispersed in 50 milliliters of DMF solutions, is subsequently added into 50 milligrams of Graphites
Alkene powder is directly added into 0.42 gram of H after stirring 0.5 hour3BTC.Then, 1 milliliter of triethylamine/DMF mixed solution is instilled
In the above mixed solution, wherein concentration of the triethylamine in the mixed solution is that 1% (v/v) passes through after persistently stirring 1 hour
Gained compound is collected by centrifugation, obtained solid ethyl alcohol and ultrapure water are washed 3 times repeatedly, forced air drying 24 at most finally 30 DEG C
Hour.Then desciccate is dispersed in n,N-Dimethylformamide with 2.0 milligrams every milliliter of concentration, obtains Graphite
Alkene/Cu-BTC suspension.
Electrochemical sensor is made in Graphite alkene/Cu-BTC prepared by embodiment 3, after tested, the sensor is accurate
Degree is high, and can be used for direct, quick, the highly sensitive detection of XA, HXA, BPA and CP.
Embodiment 4
A kind of preparation method of Graphite alkene/Cu-BTC composite material carries out in accordance with the following steps:
300 milligram of 1200 mesh graphite powder is dispersed in 30 milliliters with 300 milligrams of cetyl trimethylammonium bromide powder to contain
In the aqueous solution of 15% ethyl alcohol, control rotational speed of ball-mill is 300 rpms to guarantee that shearing force is occupied an leading position in mechanical milling process,
After ball-milling reaction 12 hours, remove to obtain graphene nanometer sheet mixed solution by ball milling.
Mixed solution is centrifuged the unstripped complete graphite powder precipitating of removal in 20 minutes at 2000 rpms.It is again that gained is molten
Liquid is centrifuged 20 minutes under 9000 rpms and obtains solid, cleans obtained solid repeatedly with ethyl alcohol and ultrapure water to remove residual
Cetyl trimethylammonium bromide, the finally forced air drying at 60 DEG C.
By 0.7 gram of Cu (NO3)2·3H2O is dispersed in 50 milliliters of DMF solutions, is subsequently added into 50 milligrams of Graphites
Alkene powder is directly added into 0.42 gram of H after stirring 0.5 hour3BTC.Then, then, 1 milliliter of triethylamine/DMF mixing is molten
Drop enters in the above mixed solution, and wherein concentration of the triethylamine in the mixed solution is 1% (v/v), persistently stirs 1.5 hours
Afterwards, obtained solid ethyl alcohol and ultrapure water are washed drum at 3 times, most finally 30 DEG C by the compound as obtained by being collected by centrifugation repeatedly
It air-dries dry 24 hours.Then desciccate is dispersed in n,N-Dimethylformamide with 2.0 milligrams every milliliter of concentration, is obtained
Graphite alkene/Cu-BTC suspension.
Electrochemical sensor is made in Graphite alkene/Cu-BTC prepared by embodiment 4, after tested, the sensor is accurate
Degree is high, and can be used for direct, the quick detection of XA, HXA, BPA and CP.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of graphene-metal organic frame composite material preparation method, which comprises the steps of:
(1) graphite powder is removed using wet ball grinding method, shearing force is occupied an leading position in ball milling stripping process, is finally obtained
Mixed system containing graphene nanometer sheet；
(2) mixed system containing graphene nanometer sheet that step (1) obtains is mixed using gradient centrifugation removal is described
Unstripped complete graphite flake in zoarium system, obtains graphene nanometer sheet solid；
(3) metal salt that will be dispersed in organic solvent is mixed with the graphene nanometer sheet that step (2) obtains, and stirring makes the gold
Belong to the adsorption of metal ions in salt in graphene nano on piece, obtains the graphene nanometer sheet of loaded metal ion；
(4) graphene nanometer sheet for the loaded metal ion that step (3) obtain is mixed with organic ligand, and in the auxiliary of alkali source
Effect is lower to promote metal organic frame in the fabricated in situ on graphene nanometer sheet surface, and finally obtaining graphene-metal has machine frame
Frame composite material.
2. preparation method as described in claim 1, which is characterized in that also use surface-active during the wet ball grinding
Agent, for improving the charge stripping efficiency of graphite in mechanical milling process；The surfactant is anionic surfactant, cation form
Face activating agent or nonionic surfactant.
3. preparation method as claimed in claim 2, which is characterized in that the matter of step (1) graphite powder and surfactant
Amount is than being 3:1 to 1:3.
4. preparation method as described in claim 1, which is characterized in that graphite powder is dispersed in ethanol water by step (1)
Wet ball grinding is carried out, ensures that shearing force is occupied an leading position in mechanical milling process by controlling rotational speed of ball-mill, Ball-milling Time is not less than 12
Hour.
5. preparation method as described in claim 1, which is characterized in that step (2) described gradient centrifugation specifically: first
Unstripped complete graphite powder precipitating is removed by 500-2000 rpms of centrifugation initial gross separation in 5-45 minutes, is then passed through
8000-12000 rpms further obtains graphene nanometer sheet solid in centrifugation 5-45 minutes.
6. preparation method as described in claim 1, which is characterized in that metal salt described in step (3) is Cu (NO3)2·
3H2O、Ni(NO3)2·6H2O、Zn(NO3)2·6H2O、Co(NO3)2·6H2One or more of O；The organic solvent is
The aqueous solution of N,N-dimethylformamide, methanol or methanol.
7. preparation method as described in claim 1, which is characterized in that step (3) metal salt and the graphene nano
The mass ratio of piece is 10:1-20:1, and the mixing time is 0.1 to 2 hours.
8. preparation method as described in claim 1, which is characterized in that step (4) organic ligand is Isosorbide-5-Nitrae-terephthaldehyde
The one or more of acid, 1,3,5- trimesic acids and 2-methylimidazole.
9. preparation method as described in claim 1, which is characterized in that the alkali source is triethylamine/n,N-Dimethylformamide
Mixed solution, wherein volumetric concentration of the triethylamine in the mixed solution is 1%, and every gram of organic ligand is corresponding to be added
1 to 10 milliliters of alkali sources.
10. a kind of Graphite alkene-electrochemical sensor of metal organic frame modification, which is characterized in that it include electrode and
Positioned at the active constituent of the electrode surface, the active constituent is preparation method system as claimed in any one of claims 1 to 9
Graphene-metal organic frame the composite material obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910147932.1A CN109916973B (en) | 2019-02-28 | 2019-02-28 | Ball-milled graphene-MOFs composite material, and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910147932.1A CN109916973B (en) | 2019-02-28 | 2019-02-28 | Ball-milled graphene-MOFs composite material, and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109916973A true CN109916973A (en) | 2019-06-21 |
| CN109916973B CN109916973B (en) | 2020-05-19 |
Family
ID=66962653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910147932.1A Active CN109916973B (en) | 2019-02-28 | 2019-02-28 | Ball-milled graphene-MOFs composite material, and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109916973B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372879A (en) * | 2019-07-30 | 2019-10-25 | 南开大学 | A kind of metal-organic framework materials with purine electrochemical recognition function and preparation method thereof and its application |
| CN111751421A (en) * | 2020-07-14 | 2020-10-09 | 江西农业大学 | Electrochemical sensor for quickly and efficiently detecting lead ions |
| CN113171799A (en) * | 2021-04-19 | 2021-07-27 | 江苏国望高科纤维有限公司 | AZA/TiO2Nano composite material and preparation method and application thereof |
| CN113502057A (en) * | 2021-07-14 | 2021-10-15 | 华中科技大学 | Preparation method of thermal management coating based on organic metal framework composite material |
| CN114014311A (en) * | 2021-10-29 | 2022-02-08 | 广东极客亮技术有限公司 | Antibacterial and antiviral graphene and nano mirror aluminum composite material as well as preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432997A (en) * | 2013-08-30 | 2013-12-11 | 华南理工大学 | Cu-based organic skeleton-graphene oxide composite porous material and preparation method thereof |
| CN107490610A (en) * | 2017-09-05 | 2017-12-19 | 济南大学 | A kind of chiral MOF graphene hybrid materials and its preparation method and application |
| CN107703195A (en) * | 2017-08-16 | 2018-02-16 | 商丘师范学院 | A kind of preparation method of graphene metal organic frame composite modified electrode |
| CN108816284A (en) * | 2018-06-21 | 2018-11-16 | 阜阳师范学院 | A kind of NiCo metal organic framework nanosphere/graphene oxide composite material and its preparation method and application |
| CN109174187A (en) * | 2018-09-07 | 2019-01-11 | 常州大学 | A kind of preparation of the composite electrocatalyst of nickel based metal organic backbone |
-
2019
- 2019-02-28 CN CN201910147932.1A patent/CN109916973B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103432997A (en) * | 2013-08-30 | 2013-12-11 | 华南理工大学 | Cu-based organic skeleton-graphene oxide composite porous material and preparation method thereof |
| CN107703195A (en) * | 2017-08-16 | 2018-02-16 | 商丘师范学院 | A kind of preparation method of graphene metal organic frame composite modified electrode |
| CN107490610A (en) * | 2017-09-05 | 2017-12-19 | 济南大学 | A kind of chiral MOF graphene hybrid materials and its preparation method and application |
| CN108816284A (en) * | 2018-06-21 | 2018-11-16 | 阜阳师范学院 | A kind of NiCo metal organic framework nanosphere/graphene oxide composite material and its preparation method and application |
| CN109174187A (en) * | 2018-09-07 | 2019-01-11 | 常州大学 | A kind of preparation of the composite electrocatalyst of nickel based metal organic backbone |
Non-Patent Citations (2)
| Title |
|---|
| CAN WU 等: "Electrochemical Functionalization of N-Methyl-2-pyrrolidone-Exfoliated Graphene Nanosheets as Highly Sensitive Analytical Platform for Phenols", 《ANALYTICAL CHEMISTRY》 * |
| MIN MAO 等: "Facile and economical mass production of graphene dispersions and flakes", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110372879A (en) * | 2019-07-30 | 2019-10-25 | 南开大学 | A kind of metal-organic framework materials with purine electrochemical recognition function and preparation method thereof and its application |
| CN110372879B (en) * | 2019-07-30 | 2021-10-01 | 南开大学 | Metal-organic framework material with purine electrochemical recognition function and preparation method and application thereof |
| CN111751421A (en) * | 2020-07-14 | 2020-10-09 | 江西农业大学 | Electrochemical sensor for quickly and efficiently detecting lead ions |
| CN111751421B (en) * | 2020-07-14 | 2021-06-04 | 江西农业大学 | Electrochemical sensor for detecting lead ions |
| CN113171799A (en) * | 2021-04-19 | 2021-07-27 | 江苏国望高科纤维有限公司 | AZA/TiO2Nano composite material and preparation method and application thereof |
| CN113171799B (en) * | 2021-04-19 | 2023-05-05 | 江苏国望高科纤维有限公司 | AZA/TiO 2 Nanocomposite material, preparation method and application thereof |
| CN113502057A (en) * | 2021-07-14 | 2021-10-15 | 华中科技大学 | Preparation method of thermal management coating based on organic metal framework composite material |
| CN114014311A (en) * | 2021-10-29 | 2022-02-08 | 广东极客亮技术有限公司 | Antibacterial and antiviral graphene and nano mirror aluminum composite material as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109916973B (en) | 2020-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109916973A (en) | A kind of Graphite alkene-MOFs composite material, its preparation and application | |
| Chu et al. | Enhanced stripping voltammetric response of Hg2+, Cu2+, Pb2+ and Cd2+ by ZIF-8 and its electrochemical analytical application | |
| Zhou et al. | Enhanced electrochemical performance for sensing Pb (II) based on graphene oxide incorporated mesoporous MnFe2O4 nanocomposites | |
| Wang et al. | Magnetic Fe 3 O 4@ MOFs decorated graphene nanocomposites as novel electrochemical sensor for ultrasensitive detection of dopamine | |
| Wang et al. | Ultrathin two-dimension metal-organic framework nanosheets/multi-walled carbon nanotube composite films for the electrochemical detection of H2O2 | |
| Liu et al. | Nitrogen functionlized graphene quantum dots/3D bismuth oxyiodine hybrid hollow microspheres as remarkable photoelectrode for photoelectrochemical sensing of chlopyrifos | |
| Pan et al. | Nanocomposite based on graphene and intercalated covalent organic frameworks with hydrosulphonyl groups for electrochemical determination of heavy metal ions | |
| Cao et al. | Photoelectrochemical determination of malathion by using CuO modified with a metal-organic framework of type Cu-BTC | |
| Liu et al. | Facile preparation of well conductive 2D MOF for nonenzymatic detection of hydrogen peroxide: Relationship between electrocatalysis and metal center | |
| Liu et al. | Glycosyl/MOF-5-based carbon nanofibers for highly sensitive detection of anti-bacterial drug quercetin | |
| CN109884147A (en) | A kind of electrochemical method of walnut shell base Carbon Materials modified glassy carbon electrode detection trace heavy metal | |
| Kong et al. | Facile synthesis of reduced graphene oxide supported Pt-Pd nanocubes with enhanced electrocatalytic activity for chloramphenicol determination | |
| CN102267684B (en) | Metallic nano particle/ carbon composite material and preparation method and application thereof | |
| Li et al. | Fusiform-like metal-organic framework for enantioselective discrimination of tryptophan enantiomers | |
| CN109613090A (en) | Sea urchin type is Prussian blue-palladium core-shell structure load nitrogen-doped graphene nanocomposite and its electrode being prepared and application | |
| Zhou et al. | A novel electrochemical sensor based on AuPd/UiO-66-NH 2/GN composites for sensitive dopamine detection | |
| CN109187687B (en) | Preparation of conjugated organic microporous material modified electrode and application of modified electrode as peroxynitroso anion electrochemical sensor | |
| Jia et al. | Properties of Poly (sodium 4‐styrenesulfonate)‐Ionic Liquid Composite Film and Its Application in the Determination of Trace Metals Combined with Bismuth Film Electrode | |
| Dong et al. | Constructed 3D hierarchical porous wool-ball-like NiO-loaded AlOOH electrode materials for the determination of toxic metal ions | |
| CN107824797B (en) | Porous high-specific-surface-area bismuth nanoparticle modified nitrogen-doped carbon nanosheet material and preparation method and application thereof | |
| Tan et al. | UiO-66 derived nanoporous carbons/electrochemically reduced graphene oxide nanocomposites-based non-enzyme electrochemical sensor towards highly efficient determination of methyl parathion in food samples | |
| Dong et al. | POMs as active center for sensitively electrochemical detection of bisphenol A and acetaminophen | |
| Jiang et al. | Nitrogen, phosphorus co-doped hollow porous carbon microspheres as an oxidase-like electrochemical sensor for baicalin | |
| CN109828013B (en) | Metal organic framework material synthesized by electrochemical cathode and application of metal organic framework material in electrochemical detection of 2,4, 6-trichlorophenol in water | |
| CN103121108B (en) | Bi elementary substance nanostructured materials and preparation method and application thereof |
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 |