CN117191898A - Electrode material, preparation method and manganese ion sensor - Google Patents
Electrode material, preparation method and manganese ion sensor Download PDFInfo
- Publication number
- CN117191898A CN117191898A CN202311178213.9A CN202311178213A CN117191898A CN 117191898 A CN117191898 A CN 117191898A CN 202311178213 A CN202311178213 A CN 202311178213A CN 117191898 A CN117191898 A CN 117191898A
- Authority
- CN
- China
- Prior art keywords
- tio
- electrode material
- solution
- steps
- dmtp
- 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.)
- Withdrawn
Links
- 229910001437 manganese ion Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000007772 electrode material Substances 0.000 title claims abstract description 32
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 16
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 239000012265 solid product Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000005119 centrifugation Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims abstract description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 31
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 11
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 17
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 12
- 239000000725 suspension Substances 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 8
- 239000007853 buffer solution Substances 0.000 description 8
- 239000013310 covalent-organic framework Substances 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005498 polishing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 5
- 239000000872 buffer Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 238000005457 optimization Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 231100000956 nontoxicity Toxicity 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 206010064594 Oral mucosa erosion Diseases 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 description 1
- 206010000087 Abdominal pain upper Diseases 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 102000004452 Arginase Human genes 0.000 description 1
- 108700024123 Arginases Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 206010028813 Nausea Diseases 0.000 description 1
- 208000001738 Nervous System Trauma Diseases 0.000 description 1
- 208000027089 Parkinsonian disease Diseases 0.000 description 1
- 206010034010 Parkinsonism Diseases 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 108091000041 Phosphoenolpyruvate Carboxylase Proteins 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 102000004338 Transferrin Human genes 0.000 description 1
- 108090000901 Transferrin Proteins 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- -1 aldehyde amine Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 210000005095 gastrointestinal system Anatomy 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 102000005396 glutamine synthetase Human genes 0.000 description 1
- 108020002326 glutamine synthetase Proteins 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000002200 mouth mucosa Anatomy 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000008693 nausea Effects 0.000 description 1
- 208000028412 nervous system injury Diseases 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 210000000496 pancreas Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 210000002381 plasma Anatomy 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000012581 transferrin Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Abstract
The application discloses an electrode material, a preparation method and a manganese ion sensor, wherein the preparation method of the electrode material comprises the following preparation steps of S1: dropwise adding the 3-aminopropyl triethyl oxygen silicon solution into TiO 2 In the solution, obtaining a first solid product TiO after centrifugation and impurity removal 2 ‑NH 2 The method comprises the steps of carrying out a first treatment on the surface of the S2: providing TiO 2 ‑NH 2 Mixing the solution and DMTP solution, reacting under acidic condition, centrifuging, and removing impurities to obtain a second solid product TiO 2 ‑NH 2 @ DMTP; s3: providing TiO 2 ‑NH 2 Mixing the two solutions, reacting under acidic condition, centrifuging, removing impurities, and drying to obtain electrode material TiO 2 ‑NH 2 @COF DPTB . The electrode material of the application can be made into an electrochemical detector for detecting the concentration of manganese ions, and has the advantages of convenience, rapidness, low detection limit, high sensitivity and long-term useStability advantage.
Description
Technical Field
The application relates to the field of electrochemical sensors, in particular to an electrode material, a preparation method and a manganese ion sensor.
Background
Manganese element is one of trace elements necessary for normal human body, manganese exists in various foods, such as tea, beans, sesame, walnut, etc., and 2-5 mg of manganese element is required to be ingested by adults every day, and manganese is mainly stored in organs such as bones, livers, pancreas, kidneys, etc. in human body. Manganese is usually combined with albumin, transferrin and the like in blood plasma, participates in the transportation of energy and substances of a human body, provides energy for various tissues and organs of the human body, is simultaneously a component or an activator of various enzymes such as arginase, glutamine synthetase, phosphoenolpyruvate carboxylase and the like, is used for maintaining normal immune function in the human body, regulating blood sugar, cell energy, free radicals and the like, and is beneficial to the growth and development of the human body.
Manganese element is a trace element required by a human body, and after the intake quantity exceeds the standard, the human body health of an individual is affected, gastrointestinal system discomfort, nausea and stomach pain are firstly caused clinically, along with the development of illness, pathological changes can be caused at the oral mucosa part, oral mucosa erosion is caused, nervous system injury can be caused when the oral mucosa erosion is not treated timely, and parkinsonism is caused clinically.
The content of manganese element in food is regulated according to GB2760-2014 national food safety Standard food additive use Standard: the limit of manganese in the pigment food is 50mg/kg; the limit of manganese in the beverage food is 10mg/kg; the limit of manganese in the dietary supplement was 30mg/kg. In addition, the ineligible items of wine sampling inspection comprise excessive heavy metal manganese, and the content of manganese in wine is required to be not more than 2mg/L in the sanitary standard.
The current methods for detecting manganese ions include atomic absorption spectrometry, capillary electrophoresis, inductively coupled plasma atomic emission spectrometry, ion chromatography ultraviolet visible spectrometry, X-ray fluorescence spectrometry and the like. However, the method has the defects of complex pretreatment, complex operation, expensive instrument, low detection sensitivity, high technical operation requirement and the like.
Disclosure of Invention
The application aims to provide a manganese ion sensor which can conveniently and sensitively detect the concentration of manganese ions.
In order to achieve the above purpose, the application adopts the following technical scheme: there is provided a method for preparing an electrode material, comprising the following steps of S1: dropwise adding the 3-aminopropyl triethyl oxygen silicon solution into TiO 2 In the solution, obtaining a first solid product TiO after centrifugation and impurity removal 2 -NH 2 The method comprises the steps of carrying out a first treatment on the surface of the S2: providing TiO 2 -NH 2 Mixing the solution and DMTP solution, reacting under acidic condition, centrifuging, and removing impurities to obtain a second solid product TiO 2 -NH 2 @ DMTP; s3: providing the TiO 2 -NH 2 Mixing the two solutions, reacting under acidic condition, centrifuging, removing impurities, and drying to obtain the electrode material TiO 2 -NH 2 @COF DPTB 。
Preferably, the steps S2 and S3 are repeated several times to form the multi-shell coated electrode material TiO 2 -NH 2 @COF DPTB 。
As another preferable aspect, in the S2 and S3 steps, acetic acid is added to the mixed solution to form an acidic condition, wherein the molar mass of the acetic acid is 12M, and the addition amount of the acetic acid is 0.1 to 0.5mL.
As another preferable, absolute ethanol is used as a solvent in the S1 step, and 1, 4-dioxane is used as a solvent in the S2 and S3 steps.
There is provided an electrode material produced by any one of the above-described production methods.
There is provided a manganese ion sensor comprising a glassy carbon electrode made of the electrode material described above.
Compared with the prior art, the application has the beneficial effects that:
(1) The electrode material prepared by the application has the advantages of high electron mobility, no toxicity, good biocompatibility, low cost, good photochemical stability, larger specific surface area and good three-dimensional structure;
(2) The electrode material prepared by the application can be prepared into a manganese ion detector, is convenient and quick, has low detection limit, high sensitivity, repeatability and long-term stability, and is not interfered by other heavy metal ions.
Drawings
FIG. 1 is a schematic diagram of the synthesis of an electrode material of the present application;
FIG. 2 is a graph of concentration optimization of the electrode material of the present application applied to a manganese ion sensor;
FIG. 3 is a graph showing pH optimization of the electrode material of the present application applied to a manganese ion sensor;
FIG. 4 is a graph of optimization of enrichment potential of the electrode material of the present application applied to a manganese ion sensor;
FIG. 5 is a graph of the optimization of enrichment time of the electrode material of the present application applied to a manganese ion sensor;
FIG. 6 is a graph of sensitizer concentration optimization for a manganese ion sensor using the electrode material of the present application.
Detailed Description
The present application will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
The terms "comprises" and "comprising," along with any variations thereof, in the description and claims, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Covalent organic framework materials (COFs) are crystalline organic porous polymers and are long-range ordered frameworks connected through covalent bonds, and the covalent organic framework materials have the advantages of large specific surface area, low density, high porosity, good thermal stability, uniform pore diameter and the like, are widely applied to the fields of gas storage and separation, catalysis, photoelectricity and the like, and show great application prospects. However, the poor conductivity and biocompatibility of COFs limit their applications in the electrochemical field, the sensor field, and COFs are often modified to improve their performance.
As shown in fig. 1, the present application provides a method for preparing an electrode material, comprising the steps of:
s1: tiO is mixed with 2 And 3-aminopropyl triethyloxysilane (APS) are respectively dissolved in the solvent, and the APS solution is dripped into the TiO 2 In the solution, the reaction is stirred vigorously, the solid product is collected by centrifugation and washed to remove impurities, and the solid product is TiO 2 -NH 2 ；
S2: tiO is mixed with 2 -NH 2 And DMTP are respectively dispersed in the solutions, and the two solutions are uniformly mixed and dispersed to obtain a first dispersion liquid; reacting the first dispersion liquid under an acidic condition, centrifugally collecting a solid product after the reaction is finished, and washing to remove impurities to obtain TiO 2 -NH 2 @DMTP；
S3: tiO is mixed with 2 -NH 2 Dispersing @ DMTP and TAPB in solution by ultrasonic respectively, mixing the two solutions, reacting under acidic condition, centrifuging after the reaction is finished, collecting solids, washing to remove impurities, and vacuum drying the products to obtain the electrode material TiO 2 -NH 2 @COF DPTB 。
Preferably, the steps S2 and S3 are repeated three times to obtain 3 layers of coated electrode material TiO 2 -NH 2 @COF DPTB . The multi-layer coated material is beneficial to obtaining better stability and improving the detection accuracy of the sensor.
Preferably, the acidic environment is formed by dropwise addition of acetic acid solution in steps S2 and S3, and more preferably, the molar mass of acetic acid in the acetic acid solution in steps S2 and S3 is 12M and the addition amount of acetic acid is 0.1 to 0.5mL.
Preferably, in step S1, the APS solution is added dropwise to the TiO 2 The drop velocity in the solution is not more than 1 drop/s, and the preferred drop velocity is 1 drop/s.
Preferably, in step S2, tiO is added 2 -NH 2 And DMTP were dispersed in 1, 4-dioxane solution, respectively.
The application synthesizes the COFs material by taking TAPB and DMTP as monomers, and further passes through aldehyde amine SchiffAlkali condensation reaction is performed on amino-functionalized TiO 2 Surface growth COF DPTB Synthesizing TiO 2 -NH 2 @COF DPTB An electrode material.
The application prepares the TiO by a simple method 2 -NH 2 @COF DPTB The electrode material solves the problem of poor solubility of the COFs material due to large volume; meanwhile, the prepared material has the advantages of high electron mobility, no toxicity, good biocompatibility, low cost and good photochemical stability.
The application provides a glassy carbon electrode of a manganese ion sensor, which uses the TiO 2 -NH 2 @COF DPTB The product is prepared.
The preparation method of the glassy carbon electrode comprises the following steps:
l1: tiO prepared by the steps 2 -NH 2 @COF DPTB Dispersing in ultrapure water, and carrying out ultrasonic treatment to uniformly disperse the ultrapure water to obtain suspension;
l2: grinding a Glassy Carbon Electrode (GCE) on a polishing pad using an alumina polishing powder, and washing with absolute ethanol and ultrapure water, respectively; tiO is mixed with 2 -NH 2 @COF DPTB Is dripped on the surface of the GCE after polishing, and TiO is obtained after drying 2 -NH 2 @COF DPTB /GCE。
Preferably, the alumina polishing powder used in step L1 has a particle size of 0.02 to 0.07. Mu.m.
Preferred TiO in step L1 2 -NH 2 @COF DPTB The concentration of the catalyst is 0.5-2 mg/mL, and the concentration of the TiO in the step L2 is 0.5-2 mg/mL 2 -NH 2 @COF DPTB The amount of the suspension to be added is 8 to 12. Mu.L.
The application also provides a manganese ion sensor which is manufactured by using the glassy carbon electrode.
Preferably, the preparation method of the manganese ion sensor comprises the following preparation steps:
k1: adding NH to an electrolytic cell 3 -NH 4 Cl buffer solution, and a three-electrode system consisting of a glassy carbon electrode, a saturated calomel motor and a platinum electrode are placed in an electrolytic cell solution, wherein the glassy carbon electrode is the main electrodeTiO of application 2 -NH 2 @COF DPTB /GCE；
K2: high sensitivity detection was performed using SWCSV, setting an amplitude of 25mV, a frequency of 25Hz, an increment of 5mV, and a rest time of 5s, and the generated signal was detected by an electrochemical workstation and displayed on a computer.
Preferably, 0.03 to 0.07M NH is added in the K1 step 3 -NH 4 Cl buffer, buffer ph=9.5. More preferably, 1mM of the anionic Surfactant Dodecyl Sulfate (SDS) is added as a sensitizer.
Preferably, 550s are electrochemically deposited at 0.5V prior to each SWCSV test; after each test, the residue was removed by washing under-0.2V stirring for 120 s.
The electrode material is synthesized in a layer-by-layer wrapping mode and is modified on the surface of the glassy carbon electrode to prepare the electrochemical sensor. In the presence of NH 3 -NH 4 In the buffer solution of Cl, the response peak current and peak area of the blank solution are recorded, then manganese ions are added, and the changed peak current and peak area are recorded. As the manganese ions react in the solution to form solids, the electrons generated are transferred to the electrode surface, during which the current increases. Therefore, with the relationship between the increased current and the concentration of manganese ions, detection of manganese ions can be achieved, and a manganese ion sensor can be manufactured.
The manganese ion sensor prepared by the application has a good detection effect on manganese ions in white spirit. By NH at 1.0. Mu.M 3 -NH 4 Detection of equivalent amounts of Mn in Cl buffer 2+ 、Cu 2+ 、Pb 2+ 、Cr 3+ 、Cd 2+ 、Ag + And Fe (Fe) 3+ Is characterized in that other heavy metal ions influence the Mn of the electrochemical sensor 2+ The response of the sensor varies within + -10.0%, and the interference degree is acceptable, so that the Mn ion sensor of the application is enough for Mn in white spirit 2+ Is required for measurement.
[ example 1 ]
Preparation method of electrode material
S1: 76mg of TiO 2 Dispersing in 150mL absolute ethanol, and performing ultrasonic treatment for 10 hours to obtain a white uniform mixture; 1g of 3-aminopropyl triethyloxysilane (APS) was dissolved in 50mL of absolute ethanol to give an APS solution, the APS solution was dropped into a white homogeneous mixture at a rate of 1 second and 1 drop, the mixed solution was vigorously stirred at 80℃for 6 hours, followed by centrifugation and washing the resulting solid product with ethanol several times to give a product as TiO 2 -NH 2 ；
S2: 50mg of TiO 2 -NH 2 And 17.4mg DMTP were respectively ultrasonically dispersed in 5.0mL of 1, 4-dioxane, sonicated for 10min, and the two solutions were mixed and uniformly dispersed by further sonication, 0.25mL of acetic acid solution having a molar mass of 12M was slowly added to the solution, and reacted in an oven at 80℃for 2h. DMTP is grafted to TiO by Schiff base reaction 2 -NH 2 Surface, formation of pre-grafted TiO 2 -NH 2 Washing the crude product 3 times by using 1, 4-dioxane, centrifuging for 10min, and collecting to obtain TiO 2 -NH 2 The @ DMTP product;
s3: the obtained TiO 2 -NH 2 Dispersing @ DMTP in 5.0mL of 1, 4-dioxane solution, ultrasonically dissolving 21mg of TAPB in 15mL of 1, 4-dioxane, then mixing the two solutions, slowly dripping 0.25mL of 12M acetic acid into the mixed solution after ultrasonic treatment for 10min, placing the mixed solution in a 70 ℃ oven for reaction for 2h, centrifuging for 10min after the reaction is finished, collecting a product, and washing 3 times by using the 1, 4-dioxane;
repeating the steps S2 and S3 for 3 times to obtain 3 layers of wrapped TiO 2 -NH 2 @COF DPTB And the product was dried under vacuum overnight.
Preparation method of glassy carbon electrode
L1: 1.0mg of TiO thus prepared 2 -NH 2 @COF DPTB Dispersing in 1.0mL of ultrapure water, and carrying out ultrasonic treatment for 1h to obtain a uniformly dispersed suspension;
l2: grinding Glass Carbon Electrode (GCE) with 0.05 μm alumina polishing powder on polishing pad for 2min, respectively ultrasonic cleaning with anhydrous ethanol and ultrapure water for 3 times, and ultrasonic cleaning with 10.0 μl TiO 2 -NH 2 @COF DPTB Suspension dropletsAdding the mixture on the surface of the polished GCE, and infrared drying to obtain TiO 2 -NH 2 @COF DPTB /GCE。
Application method of manganese ion sensor
K1: 10mL of 0.05M NH was added to the cell 3 -NH 4 Cl buffer, ph=9.5 of buffer, and 1mM of Sodium Dodecyl Sulfate (SDS) as a sensitizer was added.
TiO is mixed with 2 -NH 2 @COF DPTB A three-electrode system consisting of the GCE, the saturated calomel electrode and the platinum electrode is placed in an electrolytic cell solution, high-sensitivity detection is carried out by using SWCSV, the amplitude is set to 25mV, the frequency is set to 25Hz, the increment is 5mV, the standing time is 5s, and the generated signal is detected by an electrochemical workstation and displayed by a computer.
K2: electrochemical deposition at 0.5V for 550s before each SWCSV test; after each test, the residue was removed by washing under-0.2V stirring for 120 s.
TiO in the present embodiment 2 Products such as 1,3, 5-tris (4-aminophenyl) benzene (TAPB, 98%), 2, 5-dimethoxy trimethoxy-trioxymethylene (DMTP, 97%) are commercially available, wherein DMTP (97%) is available from Africa chemical Co., ltd (Shanghai, china), tiO 2 Nanoparticles (99.8%, diameter: 5-10 nm), TAPB (98%), ammonia (NH) 3 ·H 2 O: 25-28%), manganese chloride and n-butanol were purchased from Shanghai microphone Lin Shenghua Co., ltd (China), methanol, acetic acid, tetrahydrofuran and NH 4 Cl is provided by Tianjin Fuchen chemical reagent Co., ltd (China), and ultrapure water (18.25 MΩ.cm) is prepared by Jingjiang Heng Xin environmental protection equipment Co., ltd (Jiangsu China).
[ example 2 ]
Preparing a suspension with the concentration of 0.6mg/mL in the step L1; the remaining preparation steps were identical to those of example 1.
[ example 3 ]
Preparing a suspension with the concentration of 0.8mg/mL in the step L1; the remaining preparation steps were identical to those of example 1.
[ example 4 ]
Preparing a suspension with the concentration of 1.2mg/mL in the step L1; the remaining preparation steps were identical to those of example 1.
[ example 5 ]
Preparing a suspension with the concentration of 1.4mg/mL in the step L1; the remaining preparation steps were identical to those of example 1.
[ example 6 ]
Preparing a suspension with the concentration of 1.6mg/mL in the step L1; the remaining preparation steps were identical to those of example 1.
[ example 7 ]
Preparing a suspension with the concentration of 1.8mg/mL in the step L1; the remaining preparation steps were identical to those of example 1.
[ example 8 ]
In step K1, a buffer solution with ph=8.0 was added to the cell, and the rest of the preparation steps were identical to those in example 1.
[ example 9 ]
In step K1, a buffer solution with ph=8.5 was added to the cell, and the rest of the preparation steps were identical to those in example 1.
[ example 10 ]
In step K1, a buffer solution with ph=9.0 was added to the cell, and the rest of the preparation steps were identical to those in example 1.
[ example 11 ]
In step K1, a buffer solution with ph=10.0 was added to the cell, and the rest of the preparation steps were identical to those in example 1.
[ example 12 ]
In step K1, a buffer solution with ph=10.5 was added to the cell, and the rest of the preparation steps were identical to those in example 1.
[ example 13 ]
The enrichment potential was adjusted to 0.3V in the K2 step, and the remaining preparation steps were identical to those in example 1.
[ example 14 ]
The enrichment potential was adjusted to 0.4V in the K2 step, and the remaining preparation steps were identical to those in example 1.
[ example 15 ]
The enrichment potential was adjusted to 0.6V in the K2 step, and the remaining preparation steps were identical to those in example 1.
[ example 16 ]
The enrichment potential was adjusted to 0.7V in the K2 step, and the remaining preparation steps were identical to those in example 1.
[ example 17 ]
The deposition time in the K2 step was adjusted to 450s and the remaining preparation steps were identical to those in example 1.
Example 18
The deposition time in the K2 step was adjusted to 500s and the remaining preparation steps were identical to those in example 1.
[ example 19 ]
The deposition time in the K2 step was adjusted to 600s and the remaining preparation steps were identical to those in example 1.
[ example 20 ]
The deposition time in the K2 step was adjusted to 650s and the remaining preparation steps were identical to those in example 1.
[ example 21 ]
The concentration of the anionic surfactant sodium dodecyl sulfate in the K1 step was adjusted to 0.6mM, and the remaining preparation steps were the same as in example 1.
[ example 22 ]
The concentration of the anionic surfactant sodium dodecyl sulfate in the K1 step was adjusted to 0.8mM, and the remaining preparation steps were the same as in example 1.
Example 23
The concentration of the anionic surfactant sodium dodecyl sulfate in the K1 step was adjusted to 1.2mM, and the remaining preparation steps were the same as in example 1.
[ example 24 ]
The concentration of the anionic surfactant sodium dodecyl sulfate in the K1 step was adjusted to 1.4mM, and the remaining preparation steps were the same as in example 1.
Comparative example 1
And (2) adjusting the raw materials in the step S2 to be: 41.57mg TiO 2 And 17.4mg DMTP were ultrasonically dispersed in 5.0mL of 1, 4-dioxane, respectively; the remaining steps are identical to the preparation steps of example 1.
Comparative example 2
And (2) adjusting the raw materials in the step S2 to be: 128.94mg Fe 3 O 4 -NH 2 And 17.4mg DMTP were ultrasonically dispersed in 5.0mL of 1, 4-dioxane, respectively; the remaining steps are identical to the preparation steps of example 1.
[ Performance analysis ]
1. Electrochemical sensor performance detection
Electrochemical performance tests were performed on the electrochemical sensors prepared in each example.
FIG. 2 is a graph showing peak current and peak area signals of the electrochemical sensors prepared in examples 1 to 7, wherein suspensions of different concentrations of 0.6, 0.8, 1.0, 1.2, 1.4, 1.6 and 1.8mg/mL were set in examples 1 to 7, and finally, the performance of the electrochemical sensors was affected to some extent. From the detection results of FIG. 2, it was found that the optimum peak current response and peak area could be obtained when the concentration of the suspension in the L1 step was 1.0 mg/mL.
Fig. 3 is a graph showing peak current and peak area signals of the electrochemical sensors prepared in examples 8 to 12, and examples 1 and 8 to 12 were provided with buffer solutions having pH values of 8.0, 8.5, 9.0, 9.5, 10.0, and 10.5, and it is apparent from analysis of fig. 3 that the peak current and peak area signals are large when the pH values are 8.0 and 8.5, but the resulting voltammograms are deformed, so that the pH value was selected to be 9 as the optimum pH value.
FIG. 4 is a graph showing peak currents and peak area signals of the electrochemical sensors prepared in examples 13 to 16, wherein the enrichment potentials of examples 1 and 13 to 16 were set to 0.3, 0.4, 0.5, 0.6 and 0.7V, respectively. Analysis of FIG. 4 shows that the peak current and peak area are maximum at 0.5V, i.e., 0.5V is the optimal enrichment potential.
FIG. 5 is a graph showing peak current and peak area signals of the electrochemical sensors prepared in examples 17 to 20, and enrichment times of 450, 500, 550, 600, and 650s were set in examples 1 and 17 to 20, respectively. Analysis of FIG. 5 shows that peak current and peak area are maximum at an enrichment time of 550s, i.e., 550s is the optimal enrichment time.
FIG. 6 is a graph showing peak currents and peak area signals of the electrochemical sensors produced in examples 21 to 24, wherein the concentrations of sodium dodecyl sulfate were set to 0.6, 0.8, 1.0, 1.2 and 1.4mM in examples 1 and 21 to 24, respectively. As can be seen from the analysis of FIG. 6, the peak current and peak area corresponding to 1mM sodium dodecyl sulfate were maximized, i.e., 1mM sodium dodecyl sulfate was the optimal sensitizer concentration.
2. Testing of manganese ion content in white spirit
The electrochemical sensor prepared by the application is used for measuring manganese ion standard samples with different concentrations, and a manganese ion standard curve is drawn. The content of manganese ions in three white spirits purchased in a local supermarket is detected, 4 mu M of manganese standard solution is added by adopting a standard adding method, the content of manganese ions in the white spirits is calculated according to a manganese ion standard curve, the recovery rate and the Relative Standard Deviation (RSD) are calculated, and compared with the detection result of the electrochemical sensor of the application, and the result is recorded in the following table 1.
Table 1 comparison of the manganese ion test results of example 1 with comparative example 1 and comparative example 2
From the analysis of the detection results of Table 1, the detection sensitivity of the electrochemical sensor prepared in example 1 is superior to that of the electrochemical sensors prepared in comparative examples 1 and 2, i.e., the electrochemical sensor prepared in the present application provides a significant improvement in the detection effect of manganese ions, even in Cu 2+ 、Pb 2+ 、Cr 3+ 、Cd 2+ 、Ag + And Fe (Fe) 3+ Is detected in the interference of (a). The electrochemical sensor provided by the application also has a good manganese ion recovery rate.
The electrochemical sensor prepared by the application has the characteristics of high electron mobility, no toxicity, good biocompatibility, low cost, good photochemical stability and the like, has a larger specific surface area and a good three-dimensional structure, and can effectively increase the telephony surface area; in addition, TiO 2 -NH 2 @COF DPTB The material is an organic polymer that imparts a large amount of active ingredient to the compound.
TiO of the application 2 -NH 2 @COF DPTB The material has good manganese ion detection effect, can be used as a manganese ion detector, is convenient and quick to apply, has low detection limit, high sensitivity, repeatability and long-term stability, and has good recovery rate when detecting manganese ions in white spirit.
The foregoing has outlined the basic principles, features, and advantages of the present application. It will be understood by those skilled in the art that the present application is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present application, and various changes and modifications may be made therein without departing from the spirit and scope of the application, which is defined by the appended claims. The scope of the application is defined by the appended claims and equivalents thereof.
Claims (6)
1. A preparation method of an electrode material is characterized by comprising the following preparation steps,
s1: dropwise adding the 3-aminopropyl triethyl oxygen silicon solution into TiO 2 In the solution, obtaining a first solid product TiO after centrifugation and impurity removal 2 -NH 2 ；
S2: providing TiO 2 -NH 2 Mixing the solution and DMTP solution, reacting under acidic condition, centrifuging, and removing impurities to obtain a second solid product TiO 2 -NH 2 @DMTP；
S3: providing the TiO 2 -NH 2 Mixing the two solutions, reacting under acidic condition, centrifuging, removing impurities, and drying to obtain the electrode material TiO 2 -NH 2 @COF DPTB 。
2. The method according to claim 1, wherein the steps S2 and S3 are repeated a plurality of times in sequence to form the multi-shell coated electrode material TiO 2 -NH 2 @COF DPTB 。
3. The method according to claim 1, wherein in the steps S2 and S3, acetic acid is added to the mixed solution to form an acidic condition, the molar mass of the acetic acid is 12M, and the addition amount of the acetic acid is 0.1 to 0.5mL.
4. The method according to claim 1, wherein absolute ethanol is used as a solvent in the step S1, and 1, 4-dioxane is used as a solvent in the steps S2 and S3.
5. An electrode material, characterized by being produced by the production method according to any one of claims 1 to 4.
6. A manganese ion sensor comprising a glassy carbon electrode, wherein the glassy carbon electrode is made using the electrode material of claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311178213.9A CN117191898A (en) | 2023-09-13 | 2023-09-13 | Electrode material, preparation method and manganese ion sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311178213.9A CN117191898A (en) | 2023-09-13 | 2023-09-13 | Electrode material, preparation method and manganese ion sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117191898A true CN117191898A (en) | 2023-12-08 |
Family
ID=88992070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311178213.9A Withdrawn CN117191898A (en) | 2023-09-13 | 2023-09-13 | Electrode material, preparation method and manganese ion sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117191898A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19511138A1 (en) * | 1995-03-27 | 1996-10-02 | Eckehart Dipl Phys Schirmer | Method and device for measuring gases |
| CN104155357A (en) * | 2014-05-23 | 2014-11-19 | 济南大学 | Preparation method and application of three-dimensional cubic duct based mesoporous silica sensor |
| CN108362750A (en) * | 2018-03-07 | 2018-08-03 | 扬州大学 | A kind of preparation method for adulterating covalent organic framework composite electrode based on gold nanoparticle |
| CN108982641A (en) * | 2018-09-12 | 2018-12-11 | 江西农业大学 | A kind of preparation method of the electrochemical sensing of trace lead ion detection |
| CN111307895A (en) * | 2020-04-03 | 2020-06-19 | 山东农业大学 | Fast preparation COF @ NH2-method of CNT composite |
| CN114538530A (en) * | 2022-02-28 | 2022-05-27 | 上海健康医学院 | Basic cobalt carbonate nano material for electrochemical sensor and preparation method and application thereof |
-
2023
- 2023-09-13 CN CN202311178213.9A patent/CN117191898A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19511138A1 (en) * | 1995-03-27 | 1996-10-02 | Eckehart Dipl Phys Schirmer | Method and device for measuring gases |
| CN104155357A (en) * | 2014-05-23 | 2014-11-19 | 济南大学 | Preparation method and application of three-dimensional cubic duct based mesoporous silica sensor |
| CN108362750A (en) * | 2018-03-07 | 2018-08-03 | 扬州大学 | A kind of preparation method for adulterating covalent organic framework composite electrode based on gold nanoparticle |
| CN108982641A (en) * | 2018-09-12 | 2018-12-11 | 江西农业大学 | A kind of preparation method of the electrochemical sensing of trace lead ion detection |
| CN111307895A (en) * | 2020-04-03 | 2020-06-19 | 山东农业大学 | Fast preparation COF @ NH2-method of CNT composite |
| CN114538530A (en) * | 2022-02-28 | 2022-05-27 | 上海健康医学院 | Basic cobalt carbonate nano material for electrochemical sensor and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| LIANGYUN YU, ET AL.: ""Highly efficient determination of Mn2+ in Chinese liquor by using a novel electrochemical sensor based on TiO2-NH2@covalent organic framework nanocomposites"", ANALYTICAL METHODS, vol. 15, no. 21, 7 June 2023 (2023-06-07), pages 2622 - 2630 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Synthesis of Zr-coordinated amide porphyrin-based two-dimensional covalent organic framework at liquid-liquid interface for electrochemical sensing of tetracycline | |
| CN102426868B (en) | Water-soluble graphene-noble-metal nano-composite and preparation method and application thereof | |
| CN109307699B (en) | Preparation and application of electrochemical sensor based on halloysite nanotube and graphene | |
| CN111122677A (en) | Electrochemical aptamer sensor for quantitatively detecting ochratoxin A and application thereof | |
| CN109613083B (en) | High-sensitivity detection H of nano gold-protoporphyrin copper (II)2O2Construction of electrochemical sensor and application thereof | |
| CN107254180B (en) | AuNCs @521-MOF nanosheet composite and preparation method and application thereof | |
| CN108998013B (en) | Green fluorescent quantum dot, preparation method thereof and copper ion detection application | |
| CN111239213B (en) | Covalent organic framework material in-situ modified electrode and electrochemical biosensor | |
| CN114538409A (en) | Preparation method and application of nitrogen-doped carbon dot-reduced graphene oxide composite material | |
| CN110161103B (en) | Biological signal sensor for detecting 5-hydroxymethyl-2-furfural and preparation method and application thereof | |
| CN113004309B (en) | Metal copper phthalocyanine covalent-organic framework material, preparation method thereof, electrochemical sensor and application | |
| CN113504283B (en) | Preparation method and application of composite material modified electrode for detecting gallic acid | |
| Wei et al. | CoNi bimetallic metal–organic framework and gold nanoparticles-based aptamer electrochemical sensor for enrofloxacin detection | |
| CN110186966A (en) | A kind of preparation method and application for the composite material modified electrode detecting lactic acid concn | |
| CN109613082B (en) | High-sensitivity detection H of nano gold-protoporphyrin cobalt (II)2O2Construction and application of electrochemical sensor | |
| CN106053562B (en) | A kind of modified electrode and its preparation method and application detecting sodium nitrite | |
| Dai et al. | Highly efficient N-doped carbon quantum dots for detection of Hg2+ and Cd2+ ions in dendrobium huoshanense | |
| CN105891309A (en) | Method for detecting concentration of L-tryptophan in solution | |
| CN117191898A (en) | Electrode material, preparation method and manganese ion sensor | |
| CN114740190A (en) | For detecting aflatoxin B1Preparation method and application of electrochemical immunosensor | |
| CN110066399B (en) | Preparation and application of chitosan modified microporous polymer nano material | |
| CN112858407B (en) | Electrochemical sensor for detecting ciprofloxacin and detection method thereof | |
| Yang et al. | Novel dual-recognition electrochemical biosensor for the sensitive detection of AFM1 in milk | |
| CN111103336A (en) | Preparation method and application of electrochemical deposition modified glassy carbon electrode | |
| CN111693593A (en) | Silicon dioxide uniform pore membrane for H in blood2Electrochemical luminescence detection method of S |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20231208 |