CN106353286B - A kind of preparation method and applications of ionic liquid-carbon nanobelts - Google Patents
A kind of preparation method and applications of ionic liquid-carbon nanobelts Download PDFInfo
- Publication number
- CN106353286B CN106353286B CN201610644258.4A CN201610644258A CN106353286B CN 106353286 B CN106353286 B CN 106353286B CN 201610644258 A CN201610644258 A CN 201610644258A CN 106353286 B CN106353286 B CN 106353286B
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- sulphion
- carbon nanobelts
- carbon
- fluorescence
- 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.)
- Active
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 122
- 239000002127 nanobelt Substances 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007864 aqueous solution Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002608 ionic liquid Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000012452 mother liquor Substances 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 17
- 230000005284 excitation Effects 0.000 claims abstract description 15
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001917 fluorescence detection Methods 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 5
- 230000036647 reaction Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 11
- 230000000171 quenching effect Effects 0.000 abstract description 6
- 238000010791 quenching Methods 0.000 abstract description 5
- 238000011896 sensitive detection Methods 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- -1 CH3COO- Chemical class 0.000 description 1
- 201000010374 Down Syndrome Diseases 0.000 description 1
- 206010016654 Fibrosis Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 208000003443 Unconsciousness Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000007882 cirrhosis Effects 0.000 description 1
- 208000019425 cirrhosis of liver Diseases 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002284 excitation--emission spectrum Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/17—Nanostrips, nanoribbons or nanobelts, i.e. solid nanofibres with two significantly differing dimensions between 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Immunology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Pathology (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a kind of preparation methods of ionic liquid-carbon nanobelts, by DC power supply, using graphite rod as electrode, and ionic liquid [BMIM] PF6Two-phase system with water is electrolyte solution, applies potential electrolysis graphite rod, after cell reaction, product obtains ionic liquid-carbon nanobelts mother liquor after separating-purifying.It also discloses a kind of using ionic liquid-carbon nanobelts fluorescence detection sulphion method, the fluorescent quenching of ionic liquid-carbon nanobelts is acted on using sulphion, realizes the selective Sensitive Detection to sulphion in aqueous solution.Ionic liquid-carbon nanobelts prepared by the present invention capable of emitting blue-fluorescence under the excitation of ultraviolet light, the addition of sulphion then can be such that its blue-fluorescence is quenched, when sulphion concentration is 0.1~300 μM, ionic liquid-carbon nanobelts fluorescence intensity reduces percentage and sulphion concentration is in a linear relationship, detection is limited to 85nM, therefore can realize the Sensitive Detection to sulphion.
Description
Technical field
The invention belongs to carbon nanomaterial technical fields, and in particular to a kind of preparation method of ionic liquid-carbon nanobelts
And its application.
Background technique
Sulphion concentration is critically important environmental index, because to can result in humans and animals in higher concentrations dead for sulphion
It dies.Moreover, sulphion can stimulate mucous membrane, in addition to nervous system play the role of one it is extreme, cause people unconscious and breathe
Paralysis.In addition, the content of sulphion and various diseases, as Alzheimer's disease, Down syndrome, cirrhosis are related.Therefore,
Developing one kind, quickly, in sensitive detection aqueous solution the method for sulphion plays an important role safely guarantee human health.
Low-dimensional carbon nanomaterial is research hotspot in recent years, and low-dimensional carbon nanomaterial and block materials have dramatically different
Physicochemical properties, and due to quantum confined effect and edge effect show special photoluminescent property and electric property and by
Research extensively.Carbon nanobelts are the materials different from other carbon allotrope properties as quasi- one-dimensional carbon nano material.According to
The arrangement mode of edge carbons is different, and there are mainly two types of structure, the carbon nanobelts (Zigzag) of serrated boundary for carbon nanobelts
And the carbon nanobelts (Armchair) on handrail type boundary.Zigzag type carbon nanobelts can be used as conductor, and Armchair type carbon is received
Rice band can be used as semiconductor.Although carbon nanobelts are relatively new materials, various excellent characteristics and extensive research
Achievement makes it in various fields, from electronic product to automobile industry, all has potential application.
The technology for being typically prepared carbon nanobelts mainly has photoetching process, chemical method, chemical vapour deposition technique etc..Currently, synthesis
The method of carbon nanobelts includes that chemical synthesis, shearing graphene film are received at graphene ribbon, ultrasonic graphene, chemical oxidation treatment carbon
Mitron.But these methods usually require the equipment of higher cost and complexity and limit its mass production and practical application.
Ionic liquid (IL) is due to excellent property, such as insignificant vapour pressure, the electrochemical window that thermal stability is good, wide
Mouth, low viscosity, excellent ionic conductivity and recuperability, referred to as " the green substitute " of conventional solvent.These characteristics make
Ionic liquid is obtained to play an important role in terms of liquid/liquid extraction, electrochemistry, chemical synthesis and catalysis.The high dielectric of ionic liquid is normal
Number can hinder to accumulate between nano material because of model ylid bloom action, and nano material is uniformly dispersed.Ionic liquid and carbon
The gel compound that nanobelt is formed, referred to as " Buckie gel ".These materials are general in capacitor, sensor and driver
In.
Lu etc. uses water soluble ion liquid [BMIM] BF4, by an one-step electrochemistry method in [BMIM] BF4It is mixed with water
In homogeneous system electrolytic graphite rod be prepared for fluorescence carbon nanobelts, nano particle and graphene (ACS Nano.2009,3,
2367-2375), mechanism study proves removing gained appearance of nano material and size by anion BF4 -Special adsorption control.So
And it is easy to exist simultaneously two kinds of carbon material products in product, and [BMIM] BF4For water soluble ion liquid, formed homogeneously with water
System is electrolysed graphite fast speed, the more difficult regulation of product structure uniformity.It is larger such as to prepare gained carbon nanobelts caliber, about
10nm。
So far, the electrolytic graphite rod in hydrophobic ionic liquid-water two-phase system prepares the research for the carbon material that shines
It does not have been reported that also.In addition, the luminous fluorescents carbon material such as carbon dots, graphene quantum dot, luminous carbon nanobelts, is based on coordination or quiet more
Electro ultrafiltration detection cation, with sulphion selective response and can directly carry out sulphion detection luminous carbon material it is current
Also there is not document report.
Summary of the invention
The present invention provides a kind of preparation method and applications of ionic liquid-carbon nanobelts, using an one-step electrochemistry method
Ionic liquid-carbon nanobelts are synthesized, the fluorescent quenching of ionic liquid-carbon nanobelts is acted on using sulphion, is realized to water-soluble
The selective Sensitive Detection of sulphion in liquid.
A kind of preparation method of ionic liquid-carbon nanobelts, passes through DC power supply, using graphite rod as electrode, ionic liquid
[BMIM]PF6Two-phase system with water is electrolyte solution, applies potential electrolysis graphite rod, after cell reaction, product warp
After separating-purifying, ionic liquid-carbon nanobelts mother liquor is obtained.
Ionic liquid prepared by the present invention-carbon nanobelts length is 35~45nm, and width is 3~7nm.High-resolution transmission electricity
Clearly lattice line, good crystallinity can be seen in mirror.Emit blue-fluorescence, maximum excitation wavelength under 365nm ultraviolet light
For 340nm, maximum emission wavelength 425nm, when being excited with 330~380nm excitation wavelength, fluorescent emission peak position is omited
Micro- red shift.
Ionic liquid [BMIM] PF6Volume ratio with water is 2:3~1:4.In the present invention, [BMIM] PF6For hydrophobicity
Ionic liquid constitutes mutual exclusive two-phase system with water.Ionic liquid has high ionic conductivity, and removes in graphite
PF in journey6 -Special adsorption will effectively facilitate the removing of graphite.However, when ionic liquid concentration is more lower, system electricity
Very little is flowed, carbon material peeling rate is extremely slow, and when ionic liquid concentration increases, system electric current will be increased rapidly.However, working as ion
When strength of fluid is excessively high, system electric current crosses senior general and electrochemical workstation is caused to damage.Therefore, comprehensively considering can quickly, effectively
Structure uniformly luminous carbon material is obtained, and does not allow to easily cause apparatus damage, the present invention [BMIM] PF6Volume ratio with water is 2/
3~1/4.
The complementary compatible heterogeneous medium of hydrophobic ionic liquid and water composition that the present invention selects, one side water is that green is molten
Agent, ionic liquid, which will not volatilize, generates pollution, which is better than hydrophobic ionic liquid-organic solvent system.Another party
Face hydrophobic ionic liquid and carbon material have π-π effect, in conjunction with the carbon material separated after, due to the mutual not phase with water phase
The phenomenon that capacitive, carbon material is combined with each other in water phase or stacks generation reunion, will greatly be inhibited, and be conducive to stablize institute
Carbon material is obtained, structure uniformly luminous carbon material is made.
There are three stage, the expansions of electrochemical oxidation, intercalation and graphite anode during electrochemical stripping.First rank
Section, there is the induction period before removing sign, and electrolyte solution becomes yellow from colourless, then becomes dark-brown；Second stage, can
To see that graphite anode expands；The thin slice of phase III, expansion are peeled off from anode, form " black wash " with electrolyte.BF6 -Oxidation
Current potential is higher than water, therefore can be oxidized in anode surface water and generate hydroxyl and oxygen radical, BF6 -Play a part of inserting agent.It applies
The decomposition voltage added is too low, is not enough to aoxidize water and generates hydroxyl and oxygen radical, to crack graphite rod, and overtension, then can
A large amount of large stretch of graphite are peeled off, carbon nanobelts can not be formed, and decomposition voltage span is smaller, be conducive to obtain the uniform carbon of structure
Material.Preferably, the application voltage is 7~8V.
With the progress of electrolysis, a large amount of carbon nanobelts are peeled off, and the reaction time is too long, may pass through π-between carbon nanobelts
π effect is reunited, preferably, the time of the cell reaction is 3~4h.
The product process for separation and purification are as follows: reaction product revolving speed be 12000rpm centrifuge in centrifugation 10~
Then 20min is that the rufous supernatant of collection is filtered by vacuum in 0.22 μm of filter membrane with aperture, gained filtrate be from
Sub- liquid-carbon nanobelts mother liquor.
There is N, P, F in spectrum entirely through x-ray photoelectron spectroscopy map analysis in ionic liquid-carbon nanobelts prepared by the present invention
Characteristic peak, it was demonstrated that ionic liquid [BMIM] PF6Successfully it has been combined on carbon nanobelts.
Ionic liquid-carbon nanobelts fluorescence detection sulphion method is utilized the present invention also provides a kind of, comprising: ion
Liquid-carbon nanobelts mother liquor obtains ionic liquid-carbon nanobelts aqueous solution, measures its fluorescence intensity after water dilutes and adjusts pH
Value, is separately added into a series of sulphion aqueous solution of known concentrations thereto, after reacted, measures its fluorescence intensity level again,
For the percentage reduced using fluorescence intensity as ordinate, sulphion concentration is abscissa, working curve is drawn, then by unknown concentration
Sulphion aqueous solution be added in the ionic liquid-carbon nanobelts aqueous solution, fluorescence intensity level is measured, according to working curve
Sulfite ion concentration is calculated, the ionic liquid-carbon nanobelts mother liquor is prepared by the above method.
Ionic liquid-carbon nanobelts prepared by the present invention excite under the ultraviolet light irradiation of 365nm generates blue-fluorescence, is added
Fluorescence can be quenched after sulphion, other anion such as CH3COO-、HCO3 -、H2PO4 -、S2O8 2-、SCN-、HPO4 2-、Cl-、
NO3 -、NO2 -、Br-And S2O3 2-Its fluorescence cannot all be quenched, it was demonstrated that ionic liquid-carbon nanobelts prepared by the present invention are to sulphion
With good Selective recognition ability.
To control ionic liquid-carbon nanobelts aqueous solution fluorescence in the zone of reasonableness of analysis detection, ionic liquid-carbon is received
Rice band mother liquor need to be diluted through water, be diluted to ionic liquid-carbon nanobelts aqueous solution when carrying out sulphion Concentration Testing, be no more than
Fluorescence Spectrometer range.
The fluorescence intensity that ionic liquid-carbon nanobelts prepared by the present invention emit in acid or alkali environment is inconsistent, in acidity
Under the conditions of fluorescence intensity be higher than fluorescence intensity under alkaline condition, this is because higher pH can weaken carbon nanobelts
With BMIM+Between effect, and BMIM+Pyridine nitrogen can pass through N doping improve carbon nanobelts fluorescence intensity.Detect sulphur from
The period of the day from 11 p.m. to 1 a.m, the ionic liquid-carbon nanobelts aqueous solution pH are 2~11.Under conditions of the pH of solution is 4, ionic liquid-carbon
The intensity of the fluorescent quenching of nanobelt will be much higher than under other pH value conditions, preferably, the ionic liquid-carbon nanometer
PH with aqueous solution is 4.
When ionic liquid prepared by the present invention-carbon nanobelts detection sulphion, fluorescent quenching reaches balance after 1min.Make
To be preferred, the reaction time is 1~2min, i.e., sulphion and ionic liquid-carbon nanobelts action time are 1~2min.
When ionic liquid-carbon nanobelts prepared by the present invention detect sulphion under optimum condition, with sulphion concentration
Raising, ionic liquid-carbon nanobelts fluorescence is gradually quenched, and detection range reaches 0.1~300 μM, and detection limit is down to 85nM.
Preferably, ionic liquid-carbon nanobelts mother liquor after water dilutes and adjusts pH to 4, obtains ionic liquid-carbon nanometer
Band aqueous solution, solution is placed in Fluorescence Spectrometer, under the conditions of excitation wavelength 340nm, reads fluorescence at launch wavelength 425nm
A series of concentration are added in the sulphur of the known concentration of 0.1~300 μm of ol/L to ionic liquid-carbon nanobelts aqueous solution in intensity value
Acquired solution is placed in Fluorescence Spectrometer by deionized water solution after reacting 1min, under the conditions of excitation wavelength 340nm, reads hair
Fluorescence intensity level at the long 425nm of ejected wave reduces percentage as ordinate using fluorescence intensity, using sulphion concentration as abscissa, draws
Then the sulphion aqueous solution of unknown concentration is added in the ionic liquid-carbon nanobelts aqueous solution by working curve processed,
Under the conditions of excitation wavelength 340nm, the fluorescence intensity level at launch wavelength 425nm is read, fluorescence intensity is reduced into percentage and is substituted into
Sulfite ion concentration in institute's sample is calculated according to working curve in working curve.
Compared with prior art, the present invention have it is following the utility model has the advantages that
(1) ionic liquid-carbon nanobelts prepared by the present invention have good fluorescence property, have good crystallinity,
Structural homogeneity is good；
(2) sulphion alternative is quenched ionic liquid-carbon nanobelts fluorescence signal in the present invention, and CH3COO-、
HCO3 -、H2PO4 -、S2O8 2-、SCN-、HPO4 2-、Cl-、NO3 -、NO2 -、Br-、S2O3 2-Equal anion cannot be quenched ionic liquid-carbon and receive
The fluorescence signal of rice band；
(3) ionic liquid-carbon nanobelts prepared by the present invention can realize quick, the Sensitive Detection to trace sulphion.
Detailed description of the invention:
Figure 1A is that the present invention prepares ionic liquid-carbon nanobelts transmission electron microscope photo；
Figure 1B is that the present invention prepares ionic liquid-carbon nanobelts high resolution TEM figure；
Fig. 2 is that the present invention prepares the full spectrogram of ionic liquid-carbon nanobelts x-ray photoelectron spectroscopy；
Fig. 3 is that the present invention prepares ionic liquid-carbon nanobelts excitation spectrum (EX 425nm) and 330~380nm excitation
The excitation wavelength of the emission spectrum obtained under wavelength, the adjacent transmission curve of spectrum is separated by 10nm；
Fig. 4 A is the fluorescence curve that the present invention prepares that various concentration sulphion is added in ionic liquid-carbon nanobelts aqueous solution；
Fig. 4 B is the examination criteria song that the present invention prepares that various concentration sulphion is added in ionic liquid-carbon nanobelts aqueous solution
Line；
Fig. 5 is that the present invention prepares ionic liquid-carbon nanobelts aqueous assay sulphion kinetic curve；
Fig. 6 is the fluorescence intensity figure detected before and after sulphion in different pH value ionic liquid-carbon nanobelts aqueous solutions；
Fig. 7 is the fluorescence intensity that the present invention prepares ionic liquid-carbon nanobelts aqueous solution and different anions effect front and back
Ratio figure.
Specific embodiment:
The invention will be further described with attached drawing combined with specific embodiments below.
Embodiment 1
The synthesis of ionic liquid-carbon nanobelts electrochemical process:
By DC power supply, respectively using two graphite rods as positive and negative electrode, with ionic liquid ([BMIM] PF6) and water (V:V
=4:6) two-phase system be electrolyte solution, apply potential electrolysis graphite rod, the decomposition voltage of application is 8V, and electrolysis time is
4h, solution gradually become yellow by colourless, eventually become reddish brown.Then the appropriate distilled water of reaction product is diluted, it will
Solution is centrifuged 10min in the centrifuge that revolving speed is 12000rpm after dilution, and the filter membrane for being then 0.22 μm with aperture is to collection
Rufous supernatant be filtered by vacuum, just obtained ionic liquid-carbon nanobelts mother liquor.Gained ionic liquid-carbon nanometer
Band mother liquor is yellow solution under natural light irradiation, emits blue-fluorescence under 365nm ultraviolet light.
Gained ionic liquid-carbon nanobelts transmission electron microscope photo is as shown in Figure 1A, and Figure 1A scale is 20nm, gained ion
Liquid-carbon nanobelts high resolution TEM figure is as shown in Figure 1B, and Figure 1B scale is 5nm.It can be seen from the figure that ion
Liquid-carbon nanobelts are in banded structure, and length is about 40nm, and width is about 5nm.It can see clearly carbon lattice from Figure 1B
Line, it was demonstrated that ionic liquid-carbon nanobelts of preparation have good crystallinity.
The full spectrogram of gained ionic liquid-carbon nanobelts x-ray photoelectron spectroscopy as shown in Fig. 2, from the figure, it can be seen that
Ionic liquid-carbon nanobelts are made of five kinds of elements of C, N, O, F and P, this result demonstrates ionic liquid ([BMIM] PF6) at
It has been combined to function on fluorescence carbon nanobelts.Fig. 3 is ionic liquid-carbon nanobelts excitation spectrum (EX 425nm) and 330
The emission spectrum obtained under~380nm excitation wavelength (excitation wavelength of the adjacent transmission curve of spectrum is separated by 10nm).It can from figure
To find out, slight red shift is had occurred with the increase of excitation wavelength in ionic liquid-carbon nanobelts fluorescence emission peak of synthesis,
Show that it is the fluorescent emission that there is excitation wavelength to rely on, excitation spectrum and emission spectrum almost symmetry.
Embodiment 2
The fluorescence detection of sulphion:
Ionic liquid-carbon nanobelts mother liquor prepared by embodiment 1 is made into finely dispersed aqueous solution, the pH of aqueous solution is
4, it is placed in 6 centrifuge tubes.It is separately added into 100 μ L concentration thereto in the sulphion water of the known concentration of 0.1~300 μm of ol/L
Solution after reacting 1min, is measured the fluorescence intensity level before and after sulphion is added using Fluorescence Spectrometer, is reduced with fluorescence intensity
Percentage is ordinate, and sulphion concentration is abscissa, draws working curve, the working curve equation of piecewise fitting is respectively y
=0.0595x+0.0243 (0.1~1 μM), y=0.0022x+0.0885 (1~300 μM).Then by 100 μ L of unknown concentration
Sulphion sample solution is added in ionic liquid-carbon nanobelts aqueous solution, and the degree for measuring fluorescence intensity reduction is 43%, root
It is 155 μM that the sulfite ion concentration in institute's sample, which is calculated, according to second segment working curve.
The fluorescence curve that various concentration sulphion is added in ionic liquid-carbon nanobelts aqueous solution is as shown in Figure 4 A, detection
Working curve is as shown in Figure 4 B.As can be seen that the sulphion concentration with addition increases from Fig. 4 A, ionic liquid-carbon nanometer
The fluorescence of band is gradually quenched.And in figure 4b as can be seen that sulphion concentration is in 0.1~1 μm of ol/L and 1~300 μm of ol/L
In range, ionic liquid-carbon nanobelts fluorescence intensity reduces percentage and sulphion concentration has linear relationship, linearly related
Coefficient is respectively 0.998 and 0.996, calculates S under three times signal-to-noise ratio2-Detection be limited to 85nM.
Embodiment 3
The fluorescence detection of sulphion:
Ionic liquid-carbon nanobelts mother liquor prepared by embodiment 1 is made into finely dispersed aqueous solution, the pH of aqueous solution is
4, it is placed in 6 centrifuge tubes.Be added thereto 100 μ L concentration be 100 μm of ol/L sulphion aqueous solution, respectively react 20s,
After 40s, 60s, 80s, 100s, 120s, the fluorescence intensity level before and after sulphion is added is measured using Fluorescence Spectrometer, it is strong with fluorescence
For degree than being ordinate, the reaction time is abscissa, draws working curve, as shown in Figure 5.
It can see from ionic liquid-carbon nanobelts detection sulphion kinetic curve, after sulphion is added, ion
Liquid-carbon nanobelts fluorescent quenching just basically reaches balance in 60s, illustrate ionic liquid-carbon nanobelts can be used for sulphur from
The rapid fluorescence detection of son.
Embodiment 4
The fluorescence detection of sulphion:
Ionic liquid-carbon nanobelts mother liquor prepared by embodiment 1 is made into finely dispersed aqueous solution, is placed in 10 centrifugations
Guan Zhong, the pH of aqueous solution are respectively 2~11, and the sulphion aqueous solution that 100 μ L concentration are 100 μm of ol/L, reaction are added thereto
After 1min, the fluorescence intensity level before and after sulphion is added, using fluorescence intensity as ordinate, solution are measured using Fluorescence Spectrometer
PH is abscissa, draws fluorescence intensity figure, as shown in Figure 6.From the figure, it can be seen that fluorescence is quenched under conditions of pH value of solution is 4
The intensity gone out will be much higher than under other pH value conditions.
Embodiment 5
The fluorescence detection of sulphion:
Ionic liquid-carbon nanobelts mother liquor prepared by embodiment 1 is made into finely dispersed aqueous solution, the pH of aqueous solution is
4, it is placed in 13 centrifuge tubes.It is separately added into 100 μ L deionized waters thereto and 100 μ L concentration are containing for 100 μm of ol/L
CH3COO-、HCO3 -、H2PO4 -、S2O8 2-、SCN-、HPO4 2-、Cl-、NO3 -、S2-、NO2 -、Br-、S2O3 2-Aqueous solution, react 1min
Afterwards, the fluorescence intensity level before and after anion-containing aqueous solution is added using Fluorescence Spectrometer measurement, is vertical sit with fluorescence intensity ratio
Mark, anion species are abscissa, draw fluorescence intensity ratio figure, as shown in Figure 7.
From figure 7 it can be seen that only sulphion can significantly be quenched ionic liquid-carbon nanobelts fluorescence, and CH3COO-、
HCO3 -、H2PO4 -、S2O8 2-、SCN-、HPO4 2-、Cl-、NO3 -、NO2 -、Br-、S2O3 2-Equal anion are to ionic liquid-carbon nanobelts
Fluorescence is substantially without quenching effect, not interfering ion liquid-detection of the carbon nanobelts to sulphion.Therefore, ionic liquid-carbon is received
The selective enumeration method to sulphion can be achieved in rice band.
Claims (5)
1. a kind of utilize ionic liquid-carbon nanobelts fluorescence detection sulphion method characterized by comprising ionic liquid-
Carbon nanobelts mother liquor obtains ionic liquid-carbon nanobelts aqueous solution, measures its fluorescence intensity level after water dilutes and adjusts pH, to
It is wherein separately added into a series of sulphion aqueous solution of known concentrations, after reacted, measures its fluorescence intensity level, again with fluorescence
The percentage of strength reduction be ordinate, sulphion concentration be abscissa, draw working curve, then by the sulphur of unknown concentration from
Sub- aqueous solution is added in the ionic liquid-carbon nanobelts aqueous solution, is measured fluorescence intensity level, is calculated according to working curve
Sulfite ion concentration out, the ionic liquid-carbon nanobelts mother liquor are electricity with graphite rod the preparation method comprises the following steps: by DC power supply
Pole, ionic liquid [BMIM] PF6Two-phase system with water is electrolyte solution, applies 7 ~ 8 V potential electrolysis graphite rods, and electrolysis is anti-
After answering, product obtains ionic liquid-carbon nanobelts mother liquor after separating-purifying；Ionic liquid [BMIM] PF6And water
Volume ratio be 2/3 ~ 1/4.
2. described according to claim 1 utilize ionic liquid-carbon nanobelts fluorescence detection sulphion method, which is characterized in that
The time of the cell reaction is 3 ~ 4 h.
3. described according to claim 1 utilize ionic liquid-carbon nanobelts fluorescence detection sulphion method, which is characterized in that
The product process for separation and purification are as follows: reaction product is centrifuged 10 ~ 20 min in the centrifuge that revolving speed is 12000 rpm, then
The rufous supernatant of collection is filtered by vacuum with the filter membrane that aperture is 0.22 μm, gained filtrate is ionic liquid-carbon
Nanobelt mother liquor.
4. utilizing ionic liquid-carbon nanobelts fluorescence detection sulphion method according to claim 1, which is characterized in that
The ionic liquid-carbon nanobelts aqueous solution pH is 2 ~ 11.
5. utilizing ionic liquid-carbon nanobelts fluorescence detection sulphion method according to claim 1, which is characterized in that
Ionic liquid-carbon nanobelts mother liquor obtains ionic liquid-carbon nanobelts aqueous solution, solution is set after water dilutes and adjusts pH to 4
In Fluorescence Spectrometer, under the conditions of 340 nm of excitation wavelength, fluorescence intensity level at 425 nm of launch wavelength is read, to ionic liquid
A series of sulphion aqueous solution of known concentration of concentration in 0.1 ~ 300 μm of ol/L, reaction is added in body-carbon nanobelts aqueous solution
After 1min, acquired solution is placed in Fluorescence Spectrometer, under the conditions of 340 nm of excitation wavelength, is read at 425 nm of launch wavelength
Fluorescence intensity level reduces percentage as ordinate using fluorescence intensity, using sulphion concentration as abscissa, draws working curve, so
The sulphion aqueous solution of unknown concentration is added in the ionic liquid-carbon nanobelts aqueous solution afterwards, in excitation wavelength 340
Under the conditions of nm, the fluorescence intensity level at 425 nm of launch wavelength is read, fluorescence intensity is reduced into percentage and substitutes into working curve, root
Sulfite ion concentration in institute's sample is calculated according to working curve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610644258.4A CN106353286B (en) | 2016-08-04 | 2016-08-04 | A kind of preparation method and applications of ionic liquid-carbon nanobelts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610644258.4A CN106353286B (en) | 2016-08-04 | 2016-08-04 | A kind of preparation method and applications of ionic liquid-carbon nanobelts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106353286A CN106353286A (en) | 2017-01-25 |
| CN106353286B true CN106353286B (en) | 2019-03-29 |
Family
ID=57843731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610644258.4A Active CN106353286B (en) | 2016-08-04 | 2016-08-04 | A kind of preparation method and applications of ionic liquid-carbon nanobelts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106353286B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107367492A (en) * | 2017-05-18 | 2017-11-21 | 苏州纳光材料科技有限公司 | The method of its detection fewrricyanic acid radical ion of the preparation method and application of ionic liquid carbon point |
| CN110217776A (en) * | 2019-06-26 | 2019-09-10 | 南京工业大学 | Preparation method of multicolor carbon fluorescent powder with nanobelt and quantum dot hybrid structure |
| CN110441526A (en) * | 2019-07-10 | 2019-11-12 | 浙江理工大学 | A method of wool textile historical relic sample is identified based on protein biochip technology |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214954A (en) * | 2008-01-22 | 2008-07-09 | 东北师范大学 | Method for preparing conductive single-layer graphite sheet modified by ionic liquid cation group |
| US20120149117A1 (en) * | 2010-12-13 | 2012-06-14 | Schlumberger Technology Corporation | Hydrogen sulfide (h2s) detection using functionalized nanoparticles |
| CN102507694A (en) * | 2011-11-14 | 2012-06-20 | 西北师范大学 | Method for preparing H2O2 biosensor of MWNTs-IL/Cyt c/GCE |
| CN103924257A (en) * | 2013-01-15 | 2014-07-16 | 海洋王照明科技股份有限公司 | Graphene nanoribbons and preparation method thereof |
-
2016
- 2016-08-04 CN CN201610644258.4A patent/CN106353286B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214954A (en) * | 2008-01-22 | 2008-07-09 | 东北师范大学 | Method for preparing conductive single-layer graphite sheet modified by ionic liquid cation group |
| US20120149117A1 (en) * | 2010-12-13 | 2012-06-14 | Schlumberger Technology Corporation | Hydrogen sulfide (h2s) detection using functionalized nanoparticles |
| CN102507694A (en) * | 2011-11-14 | 2012-06-20 | 西北师范大学 | Method for preparing H2O2 biosensor of MWNTs-IL/Cyt c/GCE |
| CN103924257A (en) * | 2013-01-15 | 2014-07-16 | 海洋王照明科技股份有限公司 | Graphene nanoribbons and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| One-Pot Synthesis of Fluorescent Carbon Nanoribbons，Nanoparticles，and Graphene by the Exfoliation of Graphite in Ionic Liquids;Jiong Lu 等;《ACS NANO》;20090805;第3卷(第8期);第2368页左栏倒数第1段-第2369页左栏第1段，第2374页左栏"EXPERIMENTAL SECTION"部分 * |
| 碳纳米管和离子液体在生命分析领域中的应用;刘何萍等;《生命的化学》;20091231;第29卷(第4期);595-599 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106353286A (en) | 2017-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lim et al. | Graphene and carbon quantum dots electrochemistry | |
| Roushani et al. | Novel electrochemical sensor based on graphene quantum dots/riboflavin nanocomposite for the detection of persulfate | |
| Bagherzadeh et al. | Electrochemical detection of dopamine based on pre-concentration by graphene nanosheets | |
| Liu et al. | Facile one-pot preparation of Pd–Au/PEDOT/graphene nanocomposites and their high electrochemical sensing performance for caffeic acid detection | |
| CN106353286B (en) | A kind of preparation method and applications of ionic liquid-carbon nanobelts | |
| Ju et al. | Graphene quantum dots as fluorescence probes for sensing metal ions: synthesis and applications | |
| Shereema et al. | One step green synthesis of carbon quantum dots and its application towards the bioelectroanalytical and biolabeling studies | |
| Zhou et al. | Strong electrochemiluminescent interactions between carbon nitride nanosheet–reduced graphene oxide nanohybrids and folic acid, and ultrasensitive sensing for folic acid | |
| Tian et al. | A sensitive electrochemiluminescence glucose biosensor based on graphene quantum dot prepared from graphene oxide sheets and hydrogen peroxide | |
| Nasretdinova et al. | Electrochemical mediated synthesis of silver nanoparticles in solution | |
| CN107236541A (en) | The preparation method of nitrogen-doped graphene quantum dot and the detection method of ascorbic acid | |
| Wang et al. | Bionanosensor based on N-doped graphene quantum dots coupled with CoOOH nanosheets and their application for in vivo analysis of ascorbic acid | |
| CN111215636A (en) | Preparation method of Ag nano particles | |
| Singh et al. | Decoration of GO with Fe spinel-Naf/DMAP: an electrochemical probe for sensing H 2 O 2 reduction | |
| CN114414332B (en) | Preparation method of antioxidant based on Al-CQDs and Al-CNSs | |
| CN112408362B (en) | Carbon quantum dot and preparation method and application thereof | |
| Luo et al. | Direct and sensitive detection of sulfide ions based on one-step synthesis of ionic liquid functionalized fluorescent carbon nanoribbons | |
| CN109298038B (en) | MnCo2O4Preparation method and application of polyaniline modified glassy carbon electrode | |
| Baslak et al. | Electrolyte performance of green synthesized carbon quantum dots from fermented tea for high-speed capacitors | |
| Bao et al. | Electrochemical engineering of carbon nanodots | |
| Tao et al. | Synthesis and properties of BiDy composite electrode materials in electrochemical sensors | |
| CN107367492A (en) | The method of its detection fewrricyanic acid radical ion of the preparation method and application of ionic liquid carbon point | |
| Teradal et al. | Electrosensing of an alpha-adrenergic agonist psychoactive methyldopa using a sodium bentonite–graphene oxide nanocomposite | |
| CN113791129A (en) | Copper ion electrochemiluminescence detection electrode, detector, preparation method and application thereof | |
| CN111420678B (en) | Based on H 2 O 2 Method for preparing nano sulfur materials with different shapes by regulation and control |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201109 Address after: No.25 Chunhui Road, Zhangguo Town, Xinghua City, Taizhou City, Jiangsu Province Patentee after: Xinghua Lingyi science and Technology Consulting Service Co.,Ltd. Address before: Hangzhou City, Zhejiang province 310018 Xiasha Higher Education Park No. 2 Street No. 5 Patentee before: ZHEJIANG SCI-TECH University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211101 Address after: 750000 group 3, Hongxi village, Hongguang Town, Helan County, Yinchuan City, Ningxia Hui Autonomous Region Patentee after: Hao Cong Address before: No.25 Chunhui Road, Zhangguo Town, Xinghua City, Taizhou City, Jiangsu Province Patentee before: Xinghua Lingyi science and Technology Consulting Service Co.,Ltd. |
|
| CI03 | Correction of invention patent | ||
| CI03 | Correction of invention patent |
Correction item: Patentee|Address Correct: Xinghua Lingyi science and Technology Consulting Service Co., Ltd|No.25 Chunhui Road, Zhangguo Town, Xinghua City, Taizhou City, Jiangsu Province False: Hao Cong|750000 group 3, Hongxi village, Hongguang Town, Helan County, Yinchuan City, Ningxia Hui Autonomous Region Number: 46-02 Volume: 37 |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211119 Address after: 750000 group 3, Hongxi village, Hongguang Town, Helan County, Yinchuan City, Ningxia Hui Autonomous Region Patentee after: He Cong Address before: No.25 Chunhui Road, Zhangguo Town, Xinghua City, Taizhou City, Jiangsu Province Patentee before: Xinghua Lingyi science and Technology Consulting Service Co.,Ltd. |