CN114414332A - Preparation method of antioxidant based on AI-CQDs and AI-CNSs - Google Patents
Preparation method of antioxidant based on AI-CQDs and AI-CNSs Download PDFInfo
- Publication number
- CN114414332A CN114414332A CN202210010937.1A CN202210010937A CN114414332A CN 114414332 A CN114414332 A CN 114414332A CN 202210010937 A CN202210010937 A CN 202210010937A CN 114414332 A CN114414332 A CN 114414332A
- Authority
- CN
- China
- Prior art keywords
- solution
- aluminum
- cqds
- cnss
- doped carbon
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 69
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002135 nanosheet Substances 0.000 claims abstract description 52
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 238000002848 electrochemical method Methods 0.000 claims abstract description 17
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims abstract description 13
- 238000012360 testing method Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 28
- 238000000502 dialysis Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 230000002292 Radical scavenging effect Effects 0.000 claims description 15
- 238000002189 fluorescence spectrum Methods 0.000 claims description 10
- 239000004695 Polyether sulfone Substances 0.000 claims description 9
- 238000002474 experimental method Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229920006393 polyether sulfone Polymers 0.000 claims description 9
- 239000012086 standard solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003825 pressing Methods 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- 239000012085 test solution Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000013100 final test Methods 0.000 claims description 2
- 239000008055 phosphate buffer solution Substances 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 20
- 150000003254 radicals Chemical class 0.000 description 12
- 239000008151 electrolyte solution Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- -1 hydroxyl radicals Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002096 quantum dot Substances 0.000 description 5
- 239000003642 reactive oxygen metabolite Substances 0.000 description 5
- 230000002000 scavenging effect Effects 0.000 description 5
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000004299 exfoliation Methods 0.000 description 4
- 230000007760 free radical scavenging Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910018516 Al—O Inorganic materials 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910003077 Ti−O Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 230000005778 DNA damage Effects 0.000 description 1
- 231100000277 DNA damage Toxicity 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910009819 Ti3C2 Inorganic materials 0.000 description 1
- 229910009817 Ti3SiC2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000036542 oxidative stress Effects 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006697 redox regulation Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- 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"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Biochemistry (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Carbon And Carbon Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a preparation method of an antioxidant based on Al-CQDs and Al-CNSs, belonging to the field of antioxidant application. The invention uses Ti3AlC2The MAX phase is a carbon source, and Al-doped carbon quantum dots and Al-doped carbon nano-sheets (Al-CQDs and Al-CNSs) are respectively prepared in the electrolyte by using an electrochemical method and regulating and controlling the electrolytic voltage. The prepared Al-CQDs and Al-CNSs are subjected to oxidation resistance tests so as to detect the oxidation resistance. The preparation method is simple, short in preparation period, low in cost, environment-friendly and certain in commercial feasibility; the prepared Al-CQDs and Al-CNSs have excellent oxidation resistance.
Description
Technical Field
The invention relates to the field of antioxidant application, in particular to preparation of an antioxidant based on aluminum-doped quantum dots (Al-CQDs) and aluminum-doped carbon nano-sheets (Al-CNSs), and belongs to the technical field of carbon materials.
Background
The high-efficiency antioxidant can control the concentration of ROS and eliminate excessive free radicals. Free radicals are molecules, atoms, ions or groups with one or more unpaired electrons on the outer orbital. Reactive Oxygen Species (ROS) are highly reactive radicals derived from oxygen molecules and some molecules, including singlet oxygen (C:)1O2) Hydrogen peroxide (H)2O2) Superoxide radical (O)2·-) Hydroxyl radical (. OH), and Nitric Oxide (NO), etc. An appropriate amount of ROS can repair or eliminate damaged cells and prevent the cells from dying due to oxidative stress. However, excessive ROS accumulation is irreversible and may cause a series of problems such as cell damage and apoptosis, aging, cancer, and DNA damage.
Carbon Quantum Dots (CQDs) are a novel zero-dimensional Carbon-based material with a particle size of less than 10nm consisting of dispersed spheroidal Carbon particles. Due to its excellent physicochemical properties, such as excellent fluorescence characteristics, low toxicity, biocompatibility, and good water solubility, carbon quantum dots are widely studied and applied in the fields of fluorescence sensing, biological imaging and sensing, drug delivery, and adsorption water purification. Carbon Nano Sheets (CNSs) are novel two-dimensional nano Carbon materials, have high specific surface area, excellent conductivity, biocompatibility and nontoxicity, and are expected to be applied to the fields of biomedicine, sensing, energy storage and the like. Since carbon quantum dots and carbon nanosheets have excellent hydrogen donating ability, electron transfer ability, fluorescent properties, and low toxicity, CQDs and CNSs are being investigated as antioxidants to scavenge free radicals.
The metal atom doping can endow CQDs and CNSs with unique electronegativity and has excellent oxidation resistance and redox regulation capability. According to the mechanism of action of antioxidants, the more easily an antioxidant loses electrons, the stronger the ability to scavenge free radicals, and the higher the antioxidant activity. The electrochemical method mainly uses a large amount of carbon-based materials as a carbon source and a working electrode to prepare the carbon quantum dots and the carbon nanosheets. The electrochemical method has the advantages of low material cost, mild conditions, simple post-treatment and unique advantages in surface structure analysis and luminescent mechanism research.
MAX is layered ternary transition metal carbide or nitride, wherein M is transition group metal element, A is a main group element mainly distributed in III and IV main groups, and X is C or N element, such as: al, Ga, Si, etc., and several tens of MAX compounds have been found, and Ti is a common compound3AlC2、Ti3SiC2And Ti2AlC, and the like. Therefore, the present invention uses Ti3AlC2The MAX phase is a carbon source, and electrolytic voltage is regulated and controlled by an electrochemical method, so that Al-doped carbon quantum dots and Al-doped carbon nano sheets (Al-CQDs and Al-CNSs) are respectively prepared. Hydroxyl radical scavenging experiments prove that the two materials both have good oxidation resistance and have great possibility and research value in the aspect of radical scavenging.
Disclosure of Invention
Technical problem to be solved
The metal atom doping can improve the semiconductor performance of the carbon quantum dots and the carbon nano sheets. Therefore, the present invention is to provide a method for producing Ti using the same raw material3AlC2The MAX phase is a carbon source, and the preparation method of two materials, namely aluminum-doped carbon quantum dots (Al-CQDs) and aluminum-doped carbon nano-sheets (Al-CNSs) is realized by regulating and controlling electrolytic voltage. The method is a simple, convenient, short-period and environment-friendly simple electrochemical method for preparing the aluminum-doped carbon quantum dots and the aluminum-doped carbon nanosheets. With Ti3AlC2The MAX phase is a carbon source, an electrochemical workstation is used, electrolytic voltage is regulated, and aluminum-doped carbon quantum dots (Al-CQDs) and aluminum-doped carbon nano sheets (Al-CNSs) are prepared in high-concentration alkali liquor, so that the oxidation resistance of the carbon quantum dots and the carbon nano sheets is improved, and the application of the MAX phase in the oxidation resistance field is expanded.
Another objective of the present invention is to provide a new design scheme of anti-oxidation material, i.e. a simple electrochemical method is adopted to use Ti3AlC2The MAX phase is a carbon source, Al-CQDs and Al-CNSs are prepared by regulating and controlling electrolytic voltage, and the oxidation resistance of the Al-CQDs and the Al-CNSs is evaluated. The prepared metal atom doped carbon nano material, namely the antioxidant is Al-CQDs and Al-CNSs.
(II) technical scheme
The purpose of the invention is realized by the following technical scheme:
a preparation method of an antioxidant based on Al-CQDs and Al-CNSs is characterized in that an electrochemical workstation is used, different electrolytic voltages are applied by an electrochemical method, and Ti is added at a certain scanning rate3AlC2Respectively electrolyzing the solution into aluminum-doped carbon quantum dots Al-CQDs and aluminum-doped carbon nano-sheets Al-CNSs in an electrolyte solution.
Further, the preparation method of the aluminum-doped carbon quantum dots, namely the Al-CQDs, is a two-electrode system potentiostatic method, and comprises the following steps:
(1) with Ti3AlC2Pressing the sheet as a carbon source, namely a working electrode, inserting the working electrode and a counter electrode into electrolyte by an electrochemical method, applying voltage by using an electrochemical workstation, controlling the scanning rate, and carrying out an electrolytic reaction for a certain time to obtain a product solution;
(2) and collecting the product solution, and filtering and dialyzing impurities by using a filter and a dialysis bag to obtain the aluminum-doped carbon quantum dot solution, wherein the solution has oxidation resistance.
Further, the preparation method of the aluminum-doped carbon nanosheets, namely the Al-CNSs, is a potentiostatic method of a two-electrode system, and comprises the following steps:
(1) with Ti3AlC2Pressing the sheet as a carbon source, namely a working electrode, inserting the working electrode and a counter electrode into electrolyte by an electrochemical method, applying voltage by using an electrochemical workstation, controlling the scanning rate, and carrying out an electrolytic reaction for a certain time to obtain a product solution;
(2) collecting the product solution, and filtering and separating out impurities by using a filter and a dialysis bag to obtain an aluminum-doped carbon nanosheet solution; the solution has oxidation resistance.
The application of the aluminum-doped carbon quantum dots and the carbon nano sheets prepared by the method is characterized in that the aluminum-doped carbon quantum dots and the carbon nano sheets prepared by the electrochemical method are used as antioxidants to remove hydroxyl radicals; the fluorescence emission spectra of the aluminum-doped carbon quantum dots and the carbon nanosheet solution are respectively tested through an antioxidant activity experiment, and the aluminum-doped carbon quantum dots and the carbon nanosheet solution are proved to have good oxidation resistance.
Further, in the preparation method of the aluminum-doped quantum dot, the electrolyte in the step (1) is 0.1M NaOH standard solution serving as the electrolyte, a potentiostatic method is adopted, the specific scanning rate is 0.08-0.12V/s, and the electrolytic voltage is 3-8V respectively; the adopted filter is a 220nm water system polyether sulfone needle filter, the dialysis bag is a dialysis bag with molecular interception amount of 8000-14000Da, and the continuous dialysis is carried out for 2-4 days by using deionized water.
Further, in the preparation method of the aluminum-doped carbon nanosheet, the electrolyte in the step (1) is 0.1M NaOH standard solution serving as the electrolyte, a potentiostatic method is adopted, the specific scanning rate is 0.08-0.12V/s, and the electrolytic voltage is 9.5-10.5V respectively; the adopted filter is a 220nm water system polyether sulfone needle filter, the dialysis bag is a dialysis bag with molecular interception amount of 8000-14000Da, and the continuous dialysis is carried out for 2-4 days by using deionized water.
Further, the hydroxyl radical scavenging experiments of the antioxidants based on Al-CQDs and Al-CNSs are as follows: 2mL of a solution containing 25mM PBS, 0.5mM terephthalic acid, 50. mu.g/mL TiO was used2And 50. mu.g/mL of Al-CQDs or Al-CNSs; after the solution is irradiated by 8W and 365nm ultraviolet rays for 1 hour, fluorescence emission spectra of the two solutions are tested.
The method for testing the antioxidant activity (hydroxyl radical scavenging) of the two antioxidants prepared by the method comprises the following specific testing steps:
(1) preparing a buffer solution: PBS phosphate buffer solution is used for protecting the reagent, and the concentration of PBS is 25 mM;
(2) preparing a hydroxyl radical solution: 0.5mM terephthalic acid and 50. mu.g/mL TiO were used2To generate hydroxyl radicals;
(3) preparing a test solution system: a2 mL solution system was prepared containing 25mM PBS, 0.5mM terephthalic acid, 50. mu.g/mL TiO2And 50. mu.g/mL of Al-CQDs or 50. mu.g/mL of Al-CNSs;
(4) and (3) illumination treatment: after 1h of UV illumination (8W, 365nm), the fluorescence emission spectra of the test solutions (final test results minus the fluorescence generated by Al-CQDs or Al-CNSs themselves.)
Step (1) in the preparation method of the aluminum-doped carbon quantum dot and Ti in step (1) in the preparation method of the aluminum-doped carbon nanosheet3AlC2The preform, i.e. the working electrode, is preferably of high-purity Ti with a diameter of about 1.5cm and a thickness of about 2mm3AlC2And (6) tabletting.
The counter electrode in the step (1) in the preparation method of the aluminum-doped carbon quantum dot and the counter electrode in the step (1) in the preparation method of the aluminum-doped carbon nano sheet are a platinum wire and a platinum sheet, and preferably a platinum wire counter electrode.
The electrochemical workstation used in the electrochemical method in the step (1) in the preparation method of the aluminum-doped carbon quantum dot and the step (1) in the preparation method of the aluminum-doped carbon nano sheet is preferably CHI 660D electrochemical workstation.
The electrochemical method in the step (1) in the preparation method of the aluminum-doped carbon quantum dot and the electrochemical method in the step (1) in the preparation method of the aluminum-doped carbon nanosheet are preferably constant-voltage scanning methods.
The electrolyte in the step (1) in the preparation method of the aluminum-doped carbon quantum dot and the electrolyte in the step (1) in the preparation method of the aluminum-doped carbon nano-sheet are NaOH or KOH, and preferably 0.1M NaOH standard solution is used as the electrolyte.
The scanning rate in the step (1) in the preparation method of the aluminum-doped carbon quantum dot and the scanning rate in the step (1) in the preparation method of the aluminum-doped carbon nano sheet are 0.08-0.12V/s, and preferably 0.1V/s.
The electrolytic voltage in the step (1) in the preparation method of the aluminum-doped carbon quantum dot is 3V-8V, and preferably 7.5V.
The electrolytic voltage in the step (1) in the preparation method of the aluminum-doped carbon nanosheet is 9.5V-10.5V, and preferably 10V.
The electrolysis time in the step (1) in the preparation method of the aluminum-doped carbon quantum dot and the step (1) in the preparation method of the aluminum-doped carbon nano sheet is 5.5-6.5 h, and preferably 6 h.
In the step (2) of the preparation method of the aluminum-doped carbon quantum dot and the step (2) of the preparation method of the aluminum-doped carbon nano-sheet, a filter, preferably a 220nm water-based polyether sulfone needle head type filter, is used for filtering impurities to remove residual partial impurities.
In the step (2) of the preparation method of the aluminum-doped carbon quantum dot and the step (2) of the preparation method of the aluminum-doped carbon nano-sheet, impurities are precipitated and a dialysis bag is used, and the dialysis bag with the molecular cutoff of 8000-14000Da is preferably selected.
The treatment time for precipitating impurities in the step (2) in the preparation method of the aluminum-doped carbon quantum dots and the treatment time for precipitating impurities in the step (2) in the preparation method of the aluminum-doped carbon nano-sheets are preferably 2 to 4 days, and preferably 3 days of dialysis time.
(III) the technical key points of the invention
1. The invention uses layered ternary transition metal carbide or nitride Ti3AlC2And selecting doped aluminum as a carbon source to prepare the carbon quantum dots and the carbon nanosheets. Compared with the conventional commonly used carbon quantum dots and carbon nano sheets, the doping of Al has the characteristics of increasing the binding capacity, charge transfer capacity and surface reaction activation sites of the carbon quantum dots and the carbon nano sheets with free radicals, so that the possibility of improving the antioxidant activity of the quantum dots is realized, and a good effect on the free radical removal is realized.
2. The doped aluminum is better in effect of preparing the carbon quantum dots and the carbon nano sheets than the undoped carbon quantum dots and the carbon nano sheets. Low cost, simple process and short preparation period.
3. In order to ensure the purity of the aqueous solution of Al-CQDs and Al-CNSs and meet the scavenging effect of free radicals, dialysis is required after electrolytic scanning. The cut-off molecular weight of the dialysis bag and the dialysis time are necessary quality guarantees.
(IV) advantageous effects
(1) The preparation method is simple, short in preparation period, low in cost, environment-friendly and certain in commercial feasibility;
(2) the Al-CQDs and Al-CNSs prepared by the electrochemical method have excellent oxidation resistance.
Drawings
FIG. 1 is a TEM image of electrochemically stripped CQDs (a) and CNSs (b);
FIG. 2 is an XRD pattern of CQDs (7.5V) and CNSs (10V);
FIG. 3 is an infrared image of CQDs (7.5V) and CNSs (10V);
FIG. 4 is an XPS survey of CQDs (7.5V) and CNSs (10V);
FIG. 5 is an Al 2p chromatogram of CQDs (7.5V);
FIG. 6 is an Al 2p spectrogram of CNSs (10V);
FIG. 7 is a PL map of CQDs (7.5V) and CNSs (10V);
FIG. 8 is a CV diagram of GCE, GQDs and Al-CQDs.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and drawings, but the present invention is not limited thereto.
Example 1
(1) Using high purity Ti3AlC2The pellet (purchased from Keyene ceramics powder company, diameter about 1.5cm, thickness about 2mm) was used as a working electrode, and was washed with absolute ethanol and deionized water for use.
(2) A platinum wire is used as a counter electrode, and after the platinum wire is carefully polished, the platinum wire is washed by absolute ethyl alcohol and deionized water for standby.
(3) Preparing an electrolyte solution: NaOH standard solution with the concentration of 0.1M is prepared to be used as electrolyte.
(4) The above-mentioned working electrode (Ti)3AlC2Tabletting) and a counter electrode platinum wire are respectively fixed by an electrode clamp, inserted into NaOH electrolyte solution, and subjected to a CHI 660D electrochemical workstation with the technical parameters of a potentiostatic method, the applied electrolysis voltage is 3V, and the reaction time is 6 h.
(5) After the reaction was completed, the solution was taken out and subjected to impurity filtration using a 220nm aqueous polyethersulfone needle filter.
(6) The filtered solution was placed in a dialysis bag with a cut-off of 8000-14000Da and dialyzed against deionized water for 3 days to remove the remaining impurities. The aluminum-doped carbon quantum dots with oxidation resistance can be obtained, the concentration is 50 mug/mL, and the aluminum-doped carbon quantum dots are stored for later use.
(7) Preparing a solution for a hydroxyl free radical scavenging experiment: a2 mL solution system was prepared containing 25mM PBS, 0.5mM terephthalic acid, 50. mu.g/mL TiO2And 50. mu.g/mL of Al-CQDs.
(8) Hydroxyl radical scavenging test: after the solution was irradiated with ultraviolet light (8W, 365nm) for 1 hour, the fluorescence emission spectrum of the solution was measured using a fluorescence photometer to evaluate the antioxidant activity of Al-CQDs, i.e., the scavenging ability of hydroxyl radicals (the final result of the measurement minus the fluorescence generated by Al-CQDs itself.)
Example 2
(1) Using high purity Ti3AlC2The pellet (purchased from Keyene ceramics powder company, diameter about 1.5cm, thickness about 2mm) was used as a working electrode, and was washed with absolute ethanol and deionized water for use.
(2) A platinum wire is used as a counter electrode, and after the platinum wire is carefully polished, the platinum wire is washed by absolute ethyl alcohol and deionized water for standby.
(3) Preparing an electrolyte solution: NaOH standard solution with the concentration of 0.1M is prepared to be used as electrolyte.
(4) The above-mentioned working electrode (Ti)3AlC2Tabletting) and a counter electrode platinum wire are respectively fixed by an electrode clamp, inserted into NaOH electrolyte solution, and subjected to a CHI 660D electrochemical workstation with the technical parameters of a potentiostatic method, specifically an applied electrolytic voltage of 6V and a reaction time of 6 h.
(5) After the reaction was completed, the solution was taken out and subjected to impurity filtration using a 220nm aqueous polyethersulfone needle filter.
(6) The filtered solution was placed in a dialysis bag with a cut-off of 8000-14000Da and dialyzed against deionized water for 3 days to remove the remaining impurities. The aluminum-doped carbon quantum dots with oxidation resistance can be obtained, the concentration is 50 mug/mL, and the aluminum-doped carbon quantum dots are stored for later use.
(7) Preparing a solution for a hydroxyl free radical scavenging experiment: a2 mL solution system was prepared containing 25mM PBS, 0.5mM terephthalic acid, 50. mu.g/mL TiO2And 50. mu.g/mL of Al-CQDs.
(8) Hydroxyl radical scavenging test: after the solution was irradiated with ultraviolet light (8W, 365nm) for 1 hour, the fluorescence emission spectrum of the solution was measured using a fluorescence photometer to evaluate the antioxidant activity of Al-CQDs, i.e., the scavenging ability of hydroxyl radicals (the final result of the measurement minus the fluorescence generated by Al-CQDs itself.)
Example 3
(1) Using high purity Ti3AlC2The pellet (purchased from Keyene ceramics powder company, diameter about 1.5cm, thickness about 2mm) was used as a working electrode, and was washed with absolute ethanol and deionized water for use.
(2) A platinum wire is used as a counter electrode, and after the platinum wire is carefully polished, the platinum wire is washed by absolute ethyl alcohol and deionized water for standby.
(3) Preparing an electrolyte solution: NaOH standard solution with the concentration of 0.1M is prepared to be used as electrolyte.
(4) The above-mentioned working electrode (Ti)3AlC2Tabletting) and a counter electrode platinum wire are respectively fixed by an electrode clamp, inserted into NaOH electrolyte solution, and subjected to a CHI 660D electrochemical workstation with the technical parameters of a potentiostatic method, specifically an applied electrolytic voltage of 7.5V and a reaction time of 6 h.
(5) After the reaction was completed, the solution was taken out and subjected to impurity filtration using a 220nm aqueous polyethersulfone needle filter.
(6) The filtered solution was placed in a dialysis bag with a cut-off of 8000-14000Da and dialyzed against deionized water for 3 days to remove the remaining impurities. The aluminum-doped carbon quantum dots with oxidation resistance can be obtained, the concentration is 50 mug/mL, and the aluminum-doped carbon quantum dots are stored for later use.
(7) Preparing a solution for a hydroxyl free radical scavenging experiment: a2 mL solution system was prepared containing 25mM PBS, 0.5mM terephthalic acid, 50. mu.g/mL TiO2And 50. mu.g/mL of Al-CQDs.
(8) Hydroxyl radical scavenging test: after the solution was irradiated with ultraviolet light (8W, 365nm) for 1 hour, the fluorescence emission spectrum of the solution was measured using a fluorescence photometer to evaluate the antioxidant activity of Al-CQDs, i.e., the scavenging ability of hydroxyl radicals (the final result of the measurement minus the fluorescence generated by Al-CQDs itself.)
(9) The morphology of the carbon quantum dots is shown in fig. 1 (a). The carbon quantum dots obtained by exfoliation were visible at an electrolytic voltage of 7.5V, were small in size, and did not significantly aggregate.
(10) Product structure and composition characterization: XRD: as shown in FIG. 2, the prepared carbon quantum dots did not show typical Ti3C2Characteristic peak of (A), original Ti was not observed either3AlC2Characteristic peaks of the phases, typical of amorphous signals, confirm the product in amorphous state; FT-IR: as shown in figure 3, the prepared carbon quantum dots are 3200-3500 cm-1Is a stretching vibration of-OH at 1667cm-1Stretching vibration with the position of C ═ O at 1260-1410 cm-1The position is due to the in-plane curvature of-OH, indicating that a large number of oxygen-containing groups are present on the surface of the carbon quantum dots prepared by electrochemical exfoliation. In the range of 500 to 725cm-1The characteristic peak with no obvious position, considered to be caused by the stretching vibration of Al-O/Ti-O, shows that the Ti is electrochemically stripped3AlC2The resulting carbon quantum dots form a certain amount of metal residues, which are aluminum-doped carbon quantum dots (Al-CQDs). ③ XPS: as shown in FIG. 4, the carbon quantum dots prepared at 7.5V are composed of three elements of carbon, oxygen and aluminum. On the Al partial peak of 7.5V (FIG. 5), a significant Al oxide bonding was seen.
(11) Hydroxyl radical scavenging ability of aluminum-doped carbon quantum dots: under ultraviolet irradiation, TiO2The solution will generate OH radicals, and the added terephthalic acid (TPA) can capture the OH radicals to form 2-hydroxyterephthalic acid with fluorescent substance (emission peak position is 430nm under 315nm excitation). As shown in FIG. 7, it was confirmed that the prepared Al-CQDs have a good hydroxyl radical scavenging ability by the strength change at a specific position of PL spectrum of Al-CQDs (7.5V).
(12) The excellent hydroxyl radical scavenging capacity of Al-CQDs can be demonstrated by studying the electron transfer capacity of the Al-CQDs. As shown in FIG. 8, CV graphs of GCE, GQDs and Al-CQDs are shown. According to the redox curve measured by cyclic voltammetry, the peak value of the exposed GCE electrode current is lower than that of the exposed GCE electrode current coated with the graphene quantum dots and Al-CQDs, so that the quantum dots prepared by the method have excellent charge transmission capability, which indicates the excellent semiconductor performance of the quantum dots.
Example 4
(1) Using high purity Ti3AlC2The pellet (purchased from Keyene ceramics powder company, diameter about 1.5cm, thickness about 2mm) was used as a working electrode, and was washed with absolute ethanol and deionized water for use.
(2) A platinum wire is used as a counter electrode, and after the platinum wire is carefully polished, the platinum wire is washed by absolute ethyl alcohol and deionized water for standby.
(3) Preparing an electrolyte solution: NaOH standard solution with the concentration of 0.1M is prepared to be used as electrolyte.
(4) The above-mentioned working electrode (Ti)3AlC2Tabletting) and a counter electrode platinum wire are respectively fixed by an electrode clamp, inserted into NaOH electrolyte solution, and subjected to a CHI 660D electrochemical workstation with the technical parameters of a potentiostatic method, the specific applied electrolytic voltage is 10V, and the reaction time is 6 h.
(5) After the reaction was completed, the solution was taken out and subjected to impurity filtration using a 220nm aqueous polyethersulfone needle filter.
(6) The filtered solution was placed in a dialysis bag with a cut-off of 8000-14000Da and dialyzed against deionized water for 3 days to remove the remaining impurities. The aluminum-doped carbon nanosheet with oxidation resistance can be obtained and stored for later use.
(7) Preparing a solution for a hydroxyl free radical scavenging experiment: a2 mL solution system was prepared containing 25mM PBS, 0.5mM terephthalic acid, 50. mu.g/mL TiO2And 50. mu.g/mL of Al-CNSs.
(8) Hydroxyl radical scavenging test: after the solution is subjected to ultraviolet irradiation (8W, 365nm) for 1h, a fluorescence emission spectrum of the solution is tested by using a fluorescence photometer to evaluate the antioxidant activity of the Al-CNSs, namely the scavenging capacity of hydroxyl radicals (the final result of the test subtracts the fluorescence generated by the Al-CNSs per se.)
(9) The morphology of the carbon nanosheets is characterized as shown in fig. 1 (b). At an electrolytic voltage of 10V, the carbon nanosheets obtained by exfoliation were clearly seen.
(10) Product structure and composition characterization: XRD: as shown in FIG. 2, preparedThe typical Ti of the carbon nano-sheet does not appear3C2Characteristic peak of (A), original Ti was not observed either3AlC2Characteristic peaks of the phases, typical of amorphous signals, confirm the product in amorphous state; FT-IR: as shown in figure 3, the prepared carbon nano sheet is 3200-3500 cm-1Is a stretching vibration of-OH at 1667cm-1Stretching vibration with the position of C ═ O at 1260-1410 cm-1The position is due to the in-plane curvature of-OH, indicating that a large number of oxygen-containing groups are present on the surface of the carbon nanosheets prepared by electrochemical exfoliation. In the range of 500 to 725cm-1The characteristic peak with no obvious position, considered to be caused by the stretching vibration of Al-O/Ti-O, shows that the Ti is electrochemically stripped3AlC2The obtained carbon nano-sheets form a certain amount of metal residues and are aluminum-doped carbon nano-sheets (Al-CNSs). ③ XPS: as shown in fig. 4, the carbon nanosheet prepared at 7.5V is composed of three elements, carbon, oxygen, and aluminum. On the Al peak at 10V (fig. 6), a significant Al oxide bonding can be seen.
(11) Hydroxyl radical scavenging ability of aluminum-doped carbon nanosheets: under ultraviolet irradiation, TiO2The solution will generate OH radicals, and the added terephthalic acid (TPA) can capture the OH radicals to form 2-hydroxyterephthalic acid with fluorescent substance (emission peak position is 430nm under 315nm excitation). As shown in FIG. 7, it was confirmed that the prepared Al-CNSs had good hydroxyl radical scavenging ability by the intensity change at a specific position of the PL pattern of Al-CNSs (7.5V).
The experimental result shows that the Al-CQSs and the Al-CNSs both show obvious antioxidant activity.
The present invention includes, but is not limited to, the above embodiments, and any equivalent substitutions or partial modifications made under the principle of the spirit of the present invention are considered to be within the scope of the present invention.
Claims (8)
1. A preparation method of an antioxidant based on Al-CQDs and Al-CNSs is characterized in that an electrochemical workstation is used, different electrolytic voltages are applied by an electrochemical method, and Ti is added at a certain scanning rate3AlC2In the electricityAnd respectively electrolyzing the solution into aluminum-doped carbon quantum dots Al-CQDs and aluminum-doped carbon nano sheets Al-CNSs.
2. The method of claim 1, wherein the aluminum-doped carbon quantum dots (Al-CQDs) are prepared by a two-electrode system potentiostatic method comprising the steps of:
(1) with Ti3AlC2Pressing the sheet as a carbon source, namely a working electrode, inserting the working electrode and a counter electrode into electrolyte by an electrochemical method, applying voltage by using an electrochemical workstation, controlling the scanning rate, and carrying out an electrolytic reaction for a certain time to obtain a product solution;
(2) and collecting the product solution, and filtering and dialyzing impurities by using a filter and a dialysis bag to obtain the aluminum-doped carbon quantum dot solution, wherein the solution has oxidation resistance.
3. The preparation method according to claim 1, wherein the preparation method of the aluminum-doped carbon nanosheets (Al-CNSs) is a two-electrode system potentiostatic method comprising the steps of:
(1) with Ti3AlC2Pressing the sheet as a carbon source, namely a working electrode, inserting the working electrode and a counter electrode into electrolyte by an electrochemical method, applying voltage by using an electrochemical workstation, controlling the scanning rate, and carrying out an electrolytic reaction for a certain time to obtain a product solution;
(2) collecting the product solution, and filtering and separating out impurities by using a filter and a dialysis bag to obtain an aluminum-doped carbon nanosheet solution; the solution has oxidation resistance.
4. The application of the aluminum-doped carbon quantum dots and the carbon nano sheets prepared by the method according to claim 1, wherein the prepared aluminum-doped carbon quantum dots and the carbon nano sheets are used as an antioxidant for removing hydroxyl radicals; the fluorescence emission spectra of the aluminum-doped carbon quantum dots and the carbon nanosheet solution are respectively tested through an antioxidant activity experiment, and the aluminum-doped carbon quantum dots and the carbon nanosheet solution are proved to have good oxidation resistance.
5. The preparation method according to claim 2, wherein the electrolyte in the step (1) is 0.1M NaOH standard solution as an electrolyte, a potentiostatic method is adopted, the specific scanning rate is 0.08-0.12V/s, and the electrolytic voltage is 3-8V respectively; the adopted filter is a 220nm water system polyether sulfone needle filter, the dialysis bag is a dialysis bag with molecular interception amount of 8000-14000Da, and the continuous dialysis is carried out for 2-4 days by using deionized water.
6. The preparation method according to claim 3, wherein the electrolyte in the step (1) is 0.1M NaOH standard solution as an electrolyte, a potentiostatic method is adopted, the specific scanning rate is 0.08-0.12V/s, and the electrolytic voltage is 9.5-10.5V respectively; the adopted filter is a 220nm water system polyether sulfone needle filter, the dialysis bag is a dialysis bag with molecular interception amount of 8000-14000Da, and the continuous dialysis is carried out for 2-4 days by using deionized water.
7. The use of aluminum-doped carbon quantum dots and carbon nanoplatelets according to claim 4 wherein the hydroxyl radical scavenging experiments for the Al-CQDs and Al-CNSs based antioxidants are: 2mL of a solution containing 25mM PBS, 0.5mM terephthalic acid, 50. mu.g/mL TiO was used2And 50. mu.g/mL of Al-CQDs or Al-CNSs; after the solution is irradiated by 8W and 365nm ultraviolet rays for 1 hour, fluorescence emission spectra of the two solutions are tested.
8. The application of the aluminum-doped carbon quantum dots and carbon nanosheets as claimed in claim 7, wherein the two prepared antioxidants have antioxidant activity, namely a method for testing hydroxyl radical scavenging activity, comprising the following specific testing steps:
(1) preparing a buffer solution: PBS phosphate buffer solution is used for protecting the reagent, and the concentration of PBS is 25 mM;
(2) preparing a hydroxyl radical solution: 0.5mM of terephthalic acid and 50. mu.g/mL ofTiO2To generate hydroxyl radicals;
(3) preparing a test solution system: a2 mL solution system was prepared containing 25mM PBS, 0.5mM terephthalic acid, 50. mu.g/mL TiO2And 50. mu.g/mL of Al-CQDs or 50. mu.g/mL of Al-CNSs;
(4) and (3) illumination treatment: after the solution is irradiated by ultraviolet light of 8W and 365nm for 1h, the fluorescence emission spectrum of the solution is tested, and the fluorescence generated by Al-CQDs or Al-CNSs is subtracted from the final test result.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210010937.1A CN114414332B (en) | 2022-01-05 | 2022-01-05 | Preparation method of antioxidant based on Al-CQDs and Al-CNSs |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210010937.1A CN114414332B (en) | 2022-01-05 | 2022-01-05 | Preparation method of antioxidant based on Al-CQDs and Al-CNSs |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114414332A true CN114414332A (en) | 2022-04-29 |
| CN114414332B CN114414332B (en) | 2024-04-16 |
Family
ID=81271696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210010937.1A Active CN114414332B (en) | 2022-01-05 | 2022-01-05 | Preparation method of antioxidant based on Al-CQDs and Al-CNSs |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114414332B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285973A (en) * | 2023-02-27 | 2023-06-23 | 大连海事大学 | Purple light carbon dot and preparation method and application thereof |
| CN116836701A (en) * | 2023-07-04 | 2023-10-03 | 广东药科大学 | Aluminum-doped carbon dot, preparation method, application and Hg removal method 2+ Is a method of (2) |
Citations (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003060465A2 (en) * | 2001-12-19 | 2003-07-24 | Millennium Pharmaceuticals, Inc. | Compositions, kits, and methods for identification, assessment, prevention, and therapy of rheumatoid arthritis |
| US20060062902A1 (en) * | 2004-09-18 | 2006-03-23 | Nanosolar, Inc. | Coated nanoparticles and quantum dots for solution-based fabrication of photovoltaic cells |
| WO2006112777A2 (en) * | 2005-04-18 | 2006-10-26 | Optovent Ab | Uses of rhcc in drug delivery, real filtering, chemical catalysis and production of nanoparticles |
| CN101165947A (en) * | 2007-09-17 | 2008-04-23 | 广东工业大学 | Carbon nanometer composite nickel-hydrogen power battery cathode sheet preparation method and its uses |
| CN101428781A (en) * | 2008-12-08 | 2009-05-13 | 广州丰江电池新技术有限公司 | Conglobation type nanostructured lithium iron phosphate anode material and method for producing the same |
| JP2010280759A (en) * | 2009-06-02 | 2010-12-16 | Kuraray Co Ltd | High polymer molecule transducer |
| WO2012024499A1 (en) * | 2010-08-18 | 2012-02-23 | Massachusetts Institute Of Technology | Stationary, fluid redox electrode |
| CN102533163A (en) * | 2011-12-28 | 2012-07-04 | 广州鹿山新材料股份有限公司 | Preparing method of high reflectance rate ethylene-vinyl-acetate copolymer composition |
| US20130247363A1 (en) * | 2012-03-21 | 2013-09-26 | Jennifer A. Nelson | Methods of making metal-doped nickel oxide active materials |
| WO2014028603A1 (en) * | 2012-08-17 | 2014-02-20 | First Solar, Inc. | Method and apparatus providing multi-step deposition of thin film layer |
| WO2014181329A1 (en) * | 2013-05-06 | 2014-11-13 | Bar-Ilan University | Doped metal oxide nanoparticles of and uses thereof |
| WO2015117194A1 (en) * | 2014-02-10 | 2015-08-13 | Newcastle Innovation Limited | Doped electrode and uses thereof |
| CN104941643A (en) * | 2015-06-16 | 2015-09-30 | 北京科技大学 | Preparation method of Ag-GQDs(Graphene Quantum Dots)/ZnO ternary photocatalyst |
| CN104941651A (en) * | 2015-07-13 | 2015-09-30 | 北京科技大学 | Coppery zinc oxide/graphene quantum dot catalyst and preparing method |
| CN106880757A (en) * | 2017-03-07 | 2017-06-23 | 庞会心 | A kind of compound Cordyceps sinensis preparation and its manufacture method for strengthening immunity of organisms |
| CN107863505A (en) * | 2017-10-20 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | A kind of boron nitride nano-tube/silicon/carbon nano tube compound material and preparation, application |
| CA3055122A1 (en) * | 2017-03-07 | 2018-09-13 | OP2 Drugs | Desmethylanethole trithione derivatives for the treatment of diseases linked to mitochondrial reactive oxygen species (ros) production |
| CN109085226A (en) * | 2018-10-23 | 2018-12-25 | 青岛大学 | Competitive type electrochemistry aptamer sensor based on MXene is used for the detection of Mucin1 |
| CN109111596A (en) * | 2018-06-29 | 2019-01-01 | 华南农业大学 | Carbon dots composite nanoparticle, carbon dots/fluoride composite material, preparation method and application |
| GB201907503D0 (en) * | 2019-05-28 | 2019-07-10 | Anb Sensors Ltd | Electrochemical ph sensor |
| CN110003896A (en) * | 2019-03-11 | 2019-07-12 | 江苏大学 | A kind of anti-oxidant cerium dopping carbon quantum dot and the preparation method and application thereof |
| CN110327980A (en) * | 2019-06-18 | 2019-10-15 | 中国石油大学(华东) | A kind of application of metal-doped carbon quantum dot |
| CN110607175A (en) * | 2019-09-26 | 2019-12-24 | 安徽师范大学 | Copper-doped carbon quantum dot, preparation method thereof and application of copper-doped carbon quantum dot as probe in hydrogen peroxide detection |
| CN111354952A (en) * | 2020-03-11 | 2020-06-30 | 沈阳建筑大学 | Graphite felt composite electrode and preparation method thereof |
| CA3124767A1 (en) * | 2018-12-28 | 2020-07-02 | Gnt Pharma Co., Ltd. | 5-benzylaminosalicylic acid compounds for treating neurodegenerative disorders |
| US20210145762A1 (en) * | 2019-11-15 | 2021-05-20 | Redox Balance Llc | Methods of treating oxidative stress to modulate redox balance, preventing oxidative stress induced cell damage and death |
-
2022
- 2022-01-05 CN CN202210010937.1A patent/CN114414332B/en active Active
Patent Citations (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003060465A2 (en) * | 2001-12-19 | 2003-07-24 | Millennium Pharmaceuticals, Inc. | Compositions, kits, and methods for identification, assessment, prevention, and therapy of rheumatoid arthritis |
| US20060062902A1 (en) * | 2004-09-18 | 2006-03-23 | Nanosolar, Inc. | Coated nanoparticles and quantum dots for solution-based fabrication of photovoltaic cells |
| WO2006112777A2 (en) * | 2005-04-18 | 2006-10-26 | Optovent Ab | Uses of rhcc in drug delivery, real filtering, chemical catalysis and production of nanoparticles |
| CN101165947A (en) * | 2007-09-17 | 2008-04-23 | 广东工业大学 | Carbon nanometer composite nickel-hydrogen power battery cathode sheet preparation method and its uses |
| CN101428781A (en) * | 2008-12-08 | 2009-05-13 | 广州丰江电池新技术有限公司 | Conglobation type nanostructured lithium iron phosphate anode material and method for producing the same |
| JP2010280759A (en) * | 2009-06-02 | 2010-12-16 | Kuraray Co Ltd | High polymer molecule transducer |
| WO2012024499A1 (en) * | 2010-08-18 | 2012-02-23 | Massachusetts Institute Of Technology | Stationary, fluid redox electrode |
| CN102533163A (en) * | 2011-12-28 | 2012-07-04 | 广州鹿山新材料股份有限公司 | Preparing method of high reflectance rate ethylene-vinyl-acetate copolymer composition |
| US20130247363A1 (en) * | 2012-03-21 | 2013-09-26 | Jennifer A. Nelson | Methods of making metal-doped nickel oxide active materials |
| WO2014028603A1 (en) * | 2012-08-17 | 2014-02-20 | First Solar, Inc. | Method and apparatus providing multi-step deposition of thin film layer |
| WO2014181329A1 (en) * | 2013-05-06 | 2014-11-13 | Bar-Ilan University | Doped metal oxide nanoparticles of and uses thereof |
| WO2015117194A1 (en) * | 2014-02-10 | 2015-08-13 | Newcastle Innovation Limited | Doped electrode and uses thereof |
| CN104941643A (en) * | 2015-06-16 | 2015-09-30 | 北京科技大学 | Preparation method of Ag-GQDs(Graphene Quantum Dots)/ZnO ternary photocatalyst |
| CN104941651A (en) * | 2015-07-13 | 2015-09-30 | 北京科技大学 | Coppery zinc oxide/graphene quantum dot catalyst and preparing method |
| CN106880757A (en) * | 2017-03-07 | 2017-06-23 | 庞会心 | A kind of compound Cordyceps sinensis preparation and its manufacture method for strengthening immunity of organisms |
| CA3055122A1 (en) * | 2017-03-07 | 2018-09-13 | OP2 Drugs | Desmethylanethole trithione derivatives for the treatment of diseases linked to mitochondrial reactive oxygen species (ros) production |
| CN107863505A (en) * | 2017-10-20 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | A kind of boron nitride nano-tube/silicon/carbon nano tube compound material and preparation, application |
| CN109111596A (en) * | 2018-06-29 | 2019-01-01 | 华南农业大学 | Carbon dots composite nanoparticle, carbon dots/fluoride composite material, preparation method and application |
| CN109085226A (en) * | 2018-10-23 | 2018-12-25 | 青岛大学 | Competitive type electrochemistry aptamer sensor based on MXene is used for the detection of Mucin1 |
| CA3124767A1 (en) * | 2018-12-28 | 2020-07-02 | Gnt Pharma Co., Ltd. | 5-benzylaminosalicylic acid compounds for treating neurodegenerative disorders |
| CN110003896A (en) * | 2019-03-11 | 2019-07-12 | 江苏大学 | A kind of anti-oxidant cerium dopping carbon quantum dot and the preparation method and application thereof |
| GB201907503D0 (en) * | 2019-05-28 | 2019-07-10 | Anb Sensors Ltd | Electrochemical ph sensor |
| CN110327980A (en) * | 2019-06-18 | 2019-10-15 | 中国石油大学(华东) | A kind of application of metal-doped carbon quantum dot |
| CN110607175A (en) * | 2019-09-26 | 2019-12-24 | 安徽师范大学 | Copper-doped carbon quantum dot, preparation method thereof and application of copper-doped carbon quantum dot as probe in hydrogen peroxide detection |
| US20210145762A1 (en) * | 2019-11-15 | 2021-05-20 | Redox Balance Llc | Methods of treating oxidative stress to modulate redox balance, preventing oxidative stress induced cell damage and death |
| CN111354952A (en) * | 2020-03-11 | 2020-06-30 | 沈阳建筑大学 | Graphite felt composite electrode and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| YAN LI等: "Aluminum-doped carbon quantum dots and carbon nanosheets from electrochemical peeled-off MAX phase and their antioxidant ability", INORGANIC CHEMISTRY COMMUNICATIONS, vol. 153, 27 May 2023 (2023-05-27), XP087338500, DOI: 10.1016/j.inoche.2023.110894 * |
| 周丹;刘博;陈思远;姜标;邢菲菲;赵虹;: "磷掺杂碳材料的制备、表征及应用进展", 工业催化, no. 06, 15 June 2020 (2020-06-15) * |
| 段体岗;马力;张海兵;许立坤;侯健;邢少华;辛永磊;: "TiO_2光生阴极保护纳米薄膜研究进展", 表面技术, no. 03, 20 March 2018 (2018-03-20) * |
| 蒋莉敏;魏作君;刘迎新;: "双金属催化剂用于肉桂醛选择性加氢合成肉桂醇的研究进展", 合成化学, no. 02, 6 November 2017 (2017-11-06) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285973A (en) * | 2023-02-27 | 2023-06-23 | 大连海事大学 | Purple light carbon dot and preparation method and application thereof |
| CN116285973B (en) * | 2023-02-27 | 2024-02-20 | 大连海事大学 | Purple light carbon dot and preparation method and application thereof |
| CN116836701A (en) * | 2023-07-04 | 2023-10-03 | 广东药科大学 | Aluminum-doped carbon dot, preparation method, application and Hg removal method 2+ Is a method of (2) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114414332B (en) | 2024-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114414332A (en) | Preparation method of antioxidant based on AI-CQDs and AI-CNSs | |
| Maruthamani et al. | Fine cutting edge shaped Bi2O3rods/reduced graphene oxide (RGO) composite for supercapacitor and visible-light photocatalytic applications | |
| Teng et al. | Enhanced photoelectrochemical performance of MoS2 nanobelts-loaded TiO2 nanotube arrays by photo-assisted electrodeposition | |
| Shen et al. | Electrostatically derived self-assembly of NH 2-mediated zirconium MOFs with graphene for photocatalytic reduction of Cr (vi) | |
| CN107245727A (en) | A kind of preparation method of porous phosphatization cobalt nanowire catalyst | |
| Suneetha et al. | Synthesis, structural and electrochemical characterization of Zn doped iron oxide/grapheneoxide/chitosan nanocomposite for supercapacitor application | |
| CN108037171B (en) | Preparation method and application of nitrogen-doped graphene quantum dots with high dispersion in water phase | |
| CN104555999B (en) | porous graphene and graphene quantum dot and preparation method thereof | |
| Wang et al. | Binary CuO/Co3O4 nanofibers for ultrafast and amplified electrochemical sensing of fructose | |
| Nduni et al. | Synthesis and characterization of aluminium oxide nanoparticles from waste aluminium foil and potential application in aluminium-ion cell | |
| Matsumoto et al. | Electrolytic graphene oxide and its electrochemical properties | |
| Jia et al. | Hierarchical Ni–Fe layered double hydroxide/MnO 2 sphere architecture as an efficient noble metal-free electrocatalyst for ethanol electro-oxidation in alkaline solution | |
| Cong et al. | Fabrication of electrochemically-modified BiVO4-MoS2-Co3O4composite film for bisphenol A degradation | |
| CN111719165B (en) | Method for preparing Bi nanosheet by electrochemical stripping method | |
| Zhu et al. | Electrochemical photocatalytic degradation of eriochrome black T dye using synthesized TiO2@ CNTs nanofibers | |
| KR20200094003A (en) | Preparation method of catalyst for hydrogen evolution reaction, catalyst prepared thereby, and electrolyte for hydrogen evolution reaction | |
| CN111215636B (en) | Preparation method of Ag nano particles | |
| JP2009106924A (en) | Catalyst material for producing oxygen gas from water, production method of oxygen gas using the catalyst material, catalyst material for synthesizing acetic acid or organic material from carbon dioxide, synthesis method of acetic acid or organic material using the catalyst material, electric-energy generation method, hydrogen-gas sensor, waste-liquid recycling method, and production method of r-type manganese dioxide | |
| Gong et al. | Electrochemical and photocatalytic properties of Ru-doped TiO2 nanostructures for degradation of methyl orange dye | |
| Phetcharee et al. | Enhancing specific capacitance and cycling stability of zinc oxide-based supercapacitors using gamma-irradiated, amine-passivated carbon dots | |
| Natarajan et al. | Ultrasonication-assisted synthesis of nickel tungstate decorated on polydimethoxyaniline nanocomposite catalyst for potential direct methanol fuel cell application | |
| Maddu et al. | Synthesis of graphene/polyaniline nanocomposite for supercapacitor electrodes | |
| CN113061907B (en) | Co-based catalyst and application thereof | |
| Inguanta et al. | Ruthenium oxide nanotubes via template electrosynthesis | |
| CN108795421B (en) | Preparation method and application of chlorine-doped graphene quantum dots |
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 |