CN112213289A - Quick-response and completely reversible optical hydrogen peroxide sensor and preparation method thereof - Google Patents
Quick-response and completely reversible optical hydrogen peroxide sensor and preparation method thereof Download PDFInfo
- Publication number
- CN112213289A CN112213289A CN201910617737.0A CN201910617737A CN112213289A CN 112213289 A CN112213289 A CN 112213289A CN 201910617737 A CN201910617737 A CN 201910617737A CN 112213289 A CN112213289 A CN 112213289A
- Authority
- CN
- China
- Prior art keywords
- hydrogen peroxide
- response
- oxygen
- catalyst
- preparation
- 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.)
- Pending
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 197
- 230000004044 response Effects 0.000 title claims abstract description 58
- 230000003287 optical effect Effects 0.000 title claims abstract description 40
- 230000002441 reversible effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000001301 oxygen Substances 0.000 claims abstract description 63
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 63
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003421 catalytic decomposition reaction Methods 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 15
- 239000011540 sensing material Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 230000003321 amplification Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 238000002795 fluorescence method Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000003199 nucleic acid amplification method Methods 0.000 claims description 5
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011943 nanocatalyst Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 102000003992 Peroxidases Human genes 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004964 aerogel Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000007606 doctor blade method Methods 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000013384 organic framework Substances 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 108040007629 peroxidase activity proteins Proteins 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 230000007480 spreading Effects 0.000 claims 1
- 238000003892 spreading Methods 0.000 claims 1
- 238000012544 monitoring process Methods 0.000 abstract description 5
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 abstract description 3
- 238000012271 agricultural production Methods 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 238000001514 detection method Methods 0.000 description 11
- 229920002799 BoPET Polymers 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000017 hydrogel Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 108010001336 Horseradish Peroxidase Proteins 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- JDUBRUYGFPDQNN-UHFFFAOYSA-N [Pt+2].FC1=C(C(=C(C(=C1C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=C(C(=C(C(=C5F)F)F)F)F)N4)C4=C(C(=C(C(=C4F)F)F)F)F)N3)C3=C(C(=C(C(=C3F)F)F)F)F)=N2)F)F)F)F Chemical compound [Pt+2].FC1=C(C(=C(C(=C1C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)C5=C(C(=C(C(=C5F)F)F)F)F)N4)C4=C(C(=C(C(=C4F)F)F)F)F)N3)C3=C(C(=C(C(=C3F)F)F)F)F)=N2)F)F)F)F JDUBRUYGFPDQNN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- WQRWUSWJYHBQNF-UHFFFAOYSA-N 4-phenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=CC=CN=C21 WQRWUSWJYHBQNF-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- 229960004830 cetylpyridinium Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GQNZGCARKRHPOH-RQIKCTSVSA-N miocamycin Chemical compound C1[C@](OC(C)=O)(C)[C@@H](OC(=O)CC)[C@H](C)O[C@H]1O[C@H]1[C@H](N(C)C)[C@@H](O)[C@H](O[C@@H]2[C@H]([C@H](OC(=O)CC)CC(=O)O[C@H](C)C/C=C/C=C/[C@H](OC(C)=O)[C@H](C)C[C@@H]2CC=O)OC)O[C@@H]1C GQNZGCARKRHPOH-RQIKCTSVSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002324 mouth wash Substances 0.000 description 1
- 229940051866 mouthwash Drugs 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Molecular Biology (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pathology (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Materials Engineering (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention belongs to the technical field of measurement and analysis, relates to a hydrogen peroxide sensor and a preparation method thereof, and particularly relates to a preparation method of a quick-response and completely reversible optical hydrogen peroxide sensor. Firstly, laying a coating sensitive to oxygen on a substrate, then preparing a catalyst capable of catalytically decomposing hydrogen peroxide into water and oxygen by a nanotechnology, enriching the catalyst at high concentration, and then laying the catalyst in a sensing film with oxygen permeability to prepare a hydrogen peroxide catalytic decomposition coating; and finally, the real-time on-line monitoring of the hydrogen peroxide is indirectly realized by detecting the content of the oxygen generated by the catalytic decomposition of the hydrogen peroxide, and the optical hydrogen peroxide sensor with quick response and complete reversibility is prepared. The sensor prepared by the invention has the characteristics of high sensitivity, good stability, high accuracy, quick response, complete reversibility and the like, and can be used for monitoring hydrogen peroxide in industrial and agricultural production in real time.
Description
Technical Field
The invention belongs to the technical field of measurement and analysis, relates to a hydrogen peroxide sensor and a preparation method thereof, and particularly relates to a preparation method of a quick-response and completely reversible optical hydrogen peroxide sensor.
Background
The prior art discloses that hydrogen peroxide is an important active oxygen substance and has been widely applied to the fields of paper making, textile industry, chemical manufacturing, environmental protection, electronic industry and the like; the data also discloses that hydrogen peroxide can be added into daily necessities such as mouthwash, wound antibacterial agents, cleaning agents, mildew removing agents and the like in a proper amount, and has the functions of cleaning, deodorizing, bleaching and the like; however, studies have shown that excessive hydrogen peroxide is very harmful, and may cause environmental pollution and damage to the ecosystem, as well as human diseases such as cancer and senile dementia. According to statistics, the quantity of hydrogen peroxide generated worldwide is millions of tons, so that the hydrogen peroxide sensor has very important significance in detecting hydrogen peroxide in the environment, and particularly has urgent practical requirements and wide application prospects in real-time rapid and reversible detection. Compared with an electrochemical method, a colorimetric method and the like, the optical hydrogen peroxide sensor has the obvious advantages of anti-interference of an electroactive substance, easiness in miniaturization, capability of remote monitoring and the like. With the aid of a suitable catalyst, hydrogen peroxide can be decomposed into water and oxygen, which, after generation, is automatically separated from the hydrogen peroxide solution without side reactions taking place, so that the concentration of hydrogen peroxide can be determined indirectly by measuring the oxygen production. In 1989, Posch and Wolfbeis (Mikrochim. acta 1989, 1, 41-50.) designed and prepared a novel photochemical hydrogen peroxide multilayer sensing film, and proposed a concept for hydrogen peroxide detection based on the oxygen fluorescence quenching principle, but the response time of the sensor is as long as 5min, and the reversibility and stability are not ideal, so that the sensor is difficult to be applied industrially. Since then, researchers in the industry began to explore how to improve the overall performance of such hydrogen peroxide optical sensors (Sens. actual B-chem.2003, 90, 324; Analyst 2007, 132, 566; 571.), but the response speed was long (about 5min) and reversibility was generally poor. Therefore, response speed and reversibility are important bottleneck problems that restrict the wide application of the optical hydrogen peroxide sensor.
Based on the current state of the art, the inventors of the present application propose to provide a new hydrogen peroxide sensor and a method of manufacturing, in particular a fast response and fully reversible optical hydrogen peroxide sensor.
The invention content is as follows:
the invention aims to provide a novel hydrogen peroxide sensor and a preparation method thereof, in particular to a preparation method of a quick-response and fully reversible optical hydrogen peroxide sensor, aiming at the problems of slow response speed, poor reversibility and the like of the existing optical hydrogen peroxide sensor based on the current situation of the prior art. The optical hydrogen peroxide sensor prepared by the invention has the characteristics of high sensitivity, good stability, high accuracy, quick response, complete reversibility and the like, and can realize quick, complete reversibility and real-time monitoring of hydrogen peroxide.
The fast response and fully reversible optical hydrogen peroxide sensor of the present invention is prepared by the following preparation method, which comprises the steps of:
(1) preparation of oxygen sensitive coating: dissolving a certain amount of oxygen sensing material and a certain amount of luminous complex with oxygen response in an organic solvent to form a uniform solution, and then laying an oxygen sensing film with the thickness of one micron to one millimeter on a certain substrate by means of spraying, spin coating or doctor blade coating.
(2) Preparation of hydrogen peroxide catalytic decomposition coating: firstly, synthesizing a porous material with a large specific surface area by using a nanotechnology, then directly modifying a catalyst with the capability of catalytically decomposing hydrogen peroxide into water and oxygen in the porous material by using an in-situ reduction method, and then wrapping and coating the porous material loaded with the catalyst on the oxygen sensing film prepared in the step (1) through the oxygen sensing material to form a hydrogen peroxide catalytic decomposition coating with the thickness of one micron to one millimeter.
(3) And after the solvent is evaporated and the sensing film is dried, obtaining the optical hydrogen peroxide sensing film with completely reversible response and high response speed, measuring the fluorescence intensity and the fluorescence life change by a photoelectric conversion and phase-locked amplification circuit or a time-resolved fluorescence method, substituting the fluorescence intensity and the fluorescence life change into a Stern-Volmer equation to calculate the concentration of the hydrogen peroxide, and obtaining the optical hydrogen peroxide sensor with rapid response and completely reversible.
In the preparation method of the invention, the raw materials,
in the step (1), the oxygen sensing material is an organic polymer, an organic-inorganic hybrid material (0r mosil) or a Sol-gel (Sol-gel) material, and the oxygen sensing material can have good adhesive force on substrates such as glass, organic films and the like;
the oxygen-responsive phosphorescent luminescent complex is a complex of metals such as aluminum, copper, ruthenium, platinum, palladium, iridium, osmium, europium and the like, which can reversibly quench luminescence thereof, and comprises a metalloporphyrin complex;
the organic solvent can simultaneously dissolve the oxygen sensing material and the organic solvent of the luminescent complex, and includes but is not limited to ethanol, toluene, dichloromethane, acetone and the like or a mixture of a plurality of solvents;
the oxygen sensing membrane is characterized by a thickness that may range from one micron to one millimeter.
In the step (2), the porous material has large specific surface area, the diameter size of the material is between 50nm and 600 mu m, and the size of the pores is between 5nm and 500 nm;
the porous material includes, but is not limited to, silica, organic-inorganic hybrid materials, organic framework Materials (MOF), aerogel materials, etc.;
the hydrogen peroxide catalyst can catalytically decompose hydrogen peroxide into water and oxygen, and the material of the hydrogen peroxide catalyst comprises but is not limited to platinum nanoparticles, gold and silver nanoparticles, platinum-palladium alloy nanoparticles, ruthenium dioxide particles, manganese dioxide particles, peroxidase and the like;
the porous material loaded with the catalyst is a nano catalyst which directly grows in the porous material by adopting an in-situ reduction method for an inorganic catalyst, wherein the catalyst is an inorganic catalyst and is selected from platinum nano particles, gold/silver nano particles, platinum/palladium or platinum-palladium alloy nano particles, ruthenium dioxide particles and/or manganese dioxide particles;
in the invention, the porous material for loading the catalyst has the characteristics of good mechanical stability, difficult loss of the catalyst and the like;
in the present invention, the hydrogen peroxide decomposition coating may have a thickness of from one micron to one millimeter;
in the invention, the hydrogen peroxide sensing film is mainly characterized by at least comprising three parts, namely a supporting substrate, an oxygen sensitive coating and a hydrogen peroxide catalytic decomposition coating.
In the step (3), the hydrogen peroxide sensor is mainly characterized in that the response of the sensor is completely reversible, signals of the sensor in hydrogen peroxide solutions with different concentrations conform to a Stern-Vomer equation, and the response speed of the sensor is high through the high-concentration enrichment catalyst, and the response time is less than 5 minutes;
the measurement method of the fluorescence intensity and the fluorescence lifetime is to measure by a photoelectric conversion, a phase-locked amplification circuit or a time-resolved fluorescence method;
the hydrogen peroxide sensing film has completely reversible response, and the response speed is high and is less than 5 minutes; the stability is good, and the product can be continuously used for more than seven days; the selectivity is good and is not influenced by chloride ions and the like; the response ranged from 0.1 micromoles per liter to 500 millimoles per liter.
The main measurement principle of the optical hydrogen peroxide sensor prepared by the invention is that hydrogen peroxide is rapidly decomposed into water and oxygen by utilizing the hydrogen peroxide catalytic decomposition coating, oxygen molecules are diffused to the oxygen sensitive coating, so that the luminous coordination compound in the oxygen sensitive coating is quenched, the fluorescence intensity or the fluorescence life is reduced, the fluorescence intensity and the fluorescence life change are measured by a photoelectric conversion and phase-locked amplification circuit or a time-resolved fluorescence method, and the indirect detection of the hydrogen peroxide is realized. The method has the characteristics of high sensitivity, good stability, high accuracy, quick response, complete reversibility and the like, can realize quick and complete reversibility of the hydrogen peroxide in real time, can meet urgent practical requirements, and has wide application prospects.
The invention provides a method for preparing a quick-response and completely reversible optical hydrogen peroxide sensor, which can be used for preparing the optical hydrogen peroxide sensor with the characteristics of high sensitivity, good stability, high accuracy, quick response, complete reversibility and the like, and the prepared optical hydrogen peroxide sensor can realize the quick and complete reversibility of hydrogen peroxide and is used for monitoring the hydrogen peroxide in industrial and agricultural production in real time.
Description of the drawings:
FIG. 1 is a schematic diagram of the preparation of a nanosensor of example 1 of the invention.
FIG. 2 is a transmission electron micrograph of a material prepared in example 1 of the present invention; wherein, a transmission electron microscope picture of the prepared porous material; b transmission electron microscopy of the prepared catalyst-loaded porous material.
FIG. 3 is a graph of the sustained response of the optical hydrogen peroxide sensor prepared in example 1 of the present invention to different concentrations of hydrogen peroxide, wherein a. the timescan curve of fluorescence intensity; b. the corresponding Stern-Volmer curve.
FIG. 4 is a graph showing the persistent reversibility of hydrogen peroxide by the optical hydrogen peroxide sensor prepared in example 1 of the present invention.
Detailed Description
The invention is further explained by the specific embodiment in the following with the attached drawings.
Example 1
2.0mg/mL of tetrahydrofuran dye of phosphorescence oxygen probe tetrakis (pentafluorophenyl) porphyrin platinum (II) (PtTFPP) and an oxygen sensing material 5% D4 Hydrogel matrix are mixed uniformly according to the volume ratio of 1: 4 to obtain a red oxygen sensing membrane solution. Coating the oxygen sensing film solution on a high-temperature resistant polyester film (PET film) by a scraper, wherein the thickness of the oxygen sensing film solution is 125 mu m, and the thickness of the oxygen sensing film solution is 3 mu m after the oxygen sensing film solution is dried at room temperature;
dissolving 12mmol of tetraethyl orthosilicate (TEOS) in a mixed solution of cyclohexane (30mL) and 1-pentanol (1.5mL), adding a deionized water solution in which 1.0g of cetylpyridinium hydrate and 0.6g of urea are dissolved, uniformly stirring to obtain a white suspension, reacting for 30 minutes in an oil bath at 25 ℃, and then carrying out hydrothermal reaction for 4 hours at 120 ℃. Naturally cooling to room temperature, centrifugally separating and washing the prepared product, drying in air at room temperature for 24h, and burning at 550 ℃ for 6h to obtain fibrous SiO2And (3) mesoporous microspheres KCC-1. As can be seen from a transmission electron microscope figure 2a, the size of the prepared mesoporous material KCC-1 is 500-600nm, a large number of fibrous mesopores with the aperture of 8-10nm exist, and the mesoporous material has a large specific surface area;
0.4g of the obtained fibrous SiO2Placing the microspheres in a vacuum drying oven, vacuum drying at 120 deg.C for 16h, and naturally cooling to 60 deg.C under vacuum. 2.4mL of hot methanol solution in which 1.9mmol of 3-glycidyloxypropyltrimethoxysilane was dissolved was added to the reaction, and the mixture was stirred in an oil bath at 60 ℃ for 1.5 hours. 2.4mL of hot methanol solution of 0.45mmol of PEI was added to the above reaction mixture and stirred in an oil bath at 60 ℃ for 5 h. The obtained product is centrifugally separated, washed and dried for 12 hours in vacuum at 80 ℃ to obtain white solid KCC-1-PEI. 200mg of the prepared KCC-1-PEI was dispersed in 20mL of deionized water. After ultrasonic dispersion, the mixture was stirred vigorously in an oil bath at 25 ℃ for 10 min. 4mL of deionized water in which 0.257mmol of potassium (II) chloroplatinate was dissolved was then added dropwise, and the reaction mixture was sonicated in an oil bath at 25 ℃ for 30min and stirred in an oil bath at 25 ℃ for 2 h. 2mL of 1M aqueous sodium borohydride solution was added dropwise and stirred in an oil bath at 25 ℃ for 2 h. The obtained product is centrifugally separated, washed and dried for 16 hours at 80 ℃ to obtain the grey solid KCC-1-PEI/PtNPs. As shown in a transmission electron microscope 2b, the prepared Pt nanoparticles are uniformly loaded on the surface of KCC-1-PEI, and are also loaded in a large number of fibrous mesopores, so that the Pt nanoparticles are prevented from being agglomerated, the decomposition and catalysis capability on hydrogen peroxide is greatly improved, and the loss of the Pt nanoparticles in the detection process is effectively prevented;
10mg of KCC-1-PEI/PtNPs powder was dispersed in 500. mu.L of 5% D4 Hydrogel matrix to give a gray film solution. Dispersing 50 μ L of the film solution on a PET film with a thickness of 125 μm, and drying at room temperature to obtain a film with a thickness of 3 μm;
the prepared optical sensor was used for continuous detection of hydrogen peroxide by means of a flow cell device under excitation light of 395 nm. As is evident from FIG. 3a, it has very good sustained response performance to different concentrations of hydrogen peroxide, and as can be seen from FIG. 3b, it responds to the Stern-Volmer equation, with response range of 0.001-10mM, and response time (t)95) Less than 1min, far lower than the response time of about 5min reported at present; as is evident from the continuous detection FIG. 4, the completely reversible detection can be realized, and the long-time continuous detection still has excellent stability, and the result proves that the optical sensor prepared by the invention can be used for the rapid and completely reversible detection of hydrogen peroxide successfully realized and can be used for the online continuous real-time detection.
Example 2
2.0mg/mL of tetrahydrofuran dye of phosphorescence oxygen probe tetrakis (pentafluorophenyl) porphyrin platinum (II) (PtTFPP) and an oxygen sensing material 5% D4 Hydrogel matrix are mixed uniformly according to the volume ratio of 1: 4 to obtain a red oxygen sensing membrane solution. Coating the oxygen sensing film solution on a high-temperature resistant polyester film (PET film) by a scraper, wherein the thickness of the oxygen sensing film solution is 125 mu m, and the thickness of the oxygen sensing film solution is 3 mu m after the oxygen sensing film solution is dried at room temperature;
preparing mesoporous Si02 nano KCC-1 with large specific surface area, and modifying PEI on the surface. 200mg of the prepared KCC-1-PEI was dispersed in 25mL of an aqueous glutaraldehyde solution (1%), stirred at room temperature for 20 minutes, separated by centrifugation, and then centrifugally washed 3 times with 0.01M phosphoric acid buffer solution having a pH of 7.4. Dispersing the obtained nanoparticles in 15mL of 0.5mg mL-1Stirring a 0.01M phosphoric acid buffer solution with pH 7.4 of horseradish peroxidase (HRP) at room temperature overnight, and finally centrifuging and washing to obtain KCC-1-PEI-HRP nanoparticles;
10mg of KCC-1-PEI-HRP nanoparticles were dispersed in 500. mu.L of 5% D4 Hydrogel matrix to obtain a membrane solution. Dispersing 50 μ L of the film solution on a PET film with a thickness of 125 μm, and drying at room temperature to obtain a film with a thickness of 3 μm;
the results show that the prepared optical sensor can be used for continuous detection of hydrogen peroxide by means of a flow cell device under excitation light of 395 nm.
Example 3
2.0mg/mL of phosphorescent oxygen probe tris (4, 7-phenyl-1, 10-phenanthroline) ruthenium (II) bis (ester) (Ru (dpp))3(ClO4)2) The tetrahydrofuran solution and the oxygen sensing material 5% D4 Hydrogel matrix are mixed evenly according to the volume ratio of 1: 4 to obtain the oxygen sensing membrane solution. Coating the oxygen sensing film solution on a PET film by a scraper, wherein the thickness of the PET film is 1.0mm, and the thickness of the PET film is 24 mu m after the PET film is dried at room temperature;
3.0g hexadecyl trimethyl ammonium bromide was added to a 100mL round bottom flask, 60mL deionized water and 0.5mL aqueous triethanolamine (triethanolamine/water (w/w) ═ 1/3) were sequentially added, the mixture was stirred and dissolved at 1000rpm in an oil bath at 60 ℃ for 30 minutes, 16mL cyclohexane was added, the mixture was stirred and stabilized for 5 minutes, 4mL TEOS was rapidly added, and the mixture was stirred and reacted for 6 hours. After the reaction is finished, pouring the solution into ethanol with the same volume, centrifugally separating at the rotating speed of 15000rpm, drying in the air at room temperature for 24 hours, and burning at 550 ℃ for 6 hours to obtain the dendritic Si02 mesoporous microspheres with large specific surface area;
prepared dendritic SiO2Mesoporous microPEI is modified on the surface of the ball, and then 200mg of prepared SiO is added2PEI was dispersed in 20mL of deionized water. After ultrasonic dispersion, the mixture was stirred vigorously in an oil bath at 25 ℃ for 10 min. 4mL of deionized water in which 0.257mmol of potassium (II) chloroplatinate was dissolved was then added dropwise, and the reaction mixture was sonicated in an oil bath at 25 ℃ for 30min and stirred in an oil bath at 25 ℃ for 2 h. 2mL of 1M aqueous sodium borohydride solution was added dropwise and stirred in an oil bath at 25 ℃ for 2 h. Centrifugally separating the obtained product, washing, and drying at 80 ℃ for 16h to obtain gray solid powder, wherein the Pt nano particles are uniformly loaded on the dendritic SiO2The surface of the mesoporous microsphere;
10mg of the powder was dispersed in 500. mu.L of 5% D4 Hydrogel matrix to give a grey film solution. Dispersing the film solution on a PET film with the thickness of 1.0mm, and drying at room temperature to obtain a film with the thickness of 24 μm; the results show that the prepared optical sensor can be used for continuous detection of hydrogen peroxide by means of a flow cell device under excitation light of 395 nm.
Claims (13)
1. An optical hydrogen peroxide sensor with fast response and complete reversibility, characterized by being prepared by the following preparation method, comprising the steps of:
(1) preparing an oxygen sensitive coating:
dissolving an oxygen sensing material and a luminescent complex with oxygen response in an organic solvent to form a uniform solution, and spreading an oxygen sensing film on a substrate by spraying, spin coating or doctor blade coating;
(2) preparing a hydrogen peroxide catalytic decomposition coating:
synthesizing a porous material with a large specific surface area by adopting a nanotechnology, then directly modifying a catalyst with the capability of catalytically decomposing hydrogen peroxide into water and oxygen in the synthesized porous material by using an in-situ reduction method, and wrapping and coating the porous material loaded with the catalyst on the oxygen sensing film prepared in the step (1) through an oxygen sensing material to form a hydrogen peroxide catalytic decomposition coating;
(3) and after the solvent is evaporated and the sensing film is dried, obtaining the optical hydrogen peroxide sensing film with completely reversible response and high response speed, measuring the fluorescence intensity and the fluorescence life change by a photoelectric conversion and phase-locked amplification circuit or a time-resolved fluorescence method, and substituting the measured fluorescence intensity and the fluorescence life change into a Stern-Volmer equation to calculate the concentration of the hydrogen peroxide, thereby obtaining the optical hydrogen peroxide sensor with fast response and completely reversible response.
2. The fast response and fully reversible optical hydrogen peroxide sensor according to claim 1, wherein in step (1) of the preparation method, the oxygen sensing material is an organic polymer, an organic-inorganic hybrid material (Ormosil) or a Sol-gel (Sol-gel) material, and the oxygen sensing material has good adhesion on a glass or organic film substrate.
3. The fast-response and fully reversible optical hydrogen peroxide sensor according to claim 1, wherein in step (1) of the preparation method, the luminescent complex having an oxygen response is a phosphorescent luminescent complex having an oxygen response or/and a complex of aluminum, copper, ruthenium, platinum, palladium, iridium, osmium or europium metal and metalloporphyrin complex thereof which reversibly quenches luminescence when oxygen is absorbed.
4. The fast response and fully reversible optical hydrogen peroxide sensor according to claim 1 wherein in step (1) of the preparation process, the organic solvent is an organic solvent capable of dissolving both the oxygen sensing material and the luminescent complex, and is selected from ethanol, toluene, dichloromethane or acetone or a mixture of the solvents.
5. The fast response and fully reversible optical hydrogen peroxide sensor according to claim 1 wherein in step (1) of the fabrication process, the oxygen sensing film is fabricated to have a thickness of one micron to one millimeter.
6. The fast response and fully reversible optical hydrogen peroxide sensor according to claim 1, wherein in step (2) of the preparation method, the porous material has a large specific surface area, a diameter of the material is between 50nm and 500 μm, and a pore size is between 5nm and 500 nm; the material of the porous material is selected from silicon dioxide, organic-inorganic hybrid material, organic framework Material (MOF) or aerogel material.
7. The fast response and fully reversible optical hydrogen peroxide sensor according to claim 1 wherein, in step (2), the hydrogen peroxide catalyst catalyzes the decomposition of hydrogen peroxide into water and oxygen, and the material is selected from the group consisting of platinum nanoparticles, gold and silver nanoparticles, platinum-palladium alloy nanoparticles, ruthenium dioxide particles, manganese dioxide particles, and peroxidase.
8. The fast response and fully reversible optical hydrogen peroxide sensor according to claim 1, wherein in step (2) of the preparation method, the porous material loaded with the catalyst is a nano-catalyst, and the nano-catalyst is an inorganic catalyst directly grown in the porous material by in-situ reduction, wherein the catalyst is an inorganic catalyst selected from platinum nanoparticles, gold/silver nanoparticles, platinum/palladium or platinum-palladium alloy nanoparticles, ruthenium dioxide particles and/or manganese dioxide particles.
9. The fast response and fully reversible optical hydrogen peroxide sensor according to claim 1 wherein in step (2) of the preparation process, a hydrogen peroxide decomposition coating is prepared having a thickness of from one micron to one millimeter.
10. The fast response and fully reversible optical hydrogen peroxide sensor according to claim 1 or 9 wherein in step (2) of the preparation process, a hydrogen peroxide sensing membrane is prepared comprising a support substrate, an oxygen sensitive coating and a hydrogen peroxide catalytic decomposition coating.
11. The fast response and fully reversible optical hydrogen peroxide sensor according to claim 1, wherein in step (3) of the manufacturing process, the hydrogen peroxide sensor rapidly decomposes hydrogen peroxide into water and oxygen using the hydrogen peroxide catalytic decomposition coating, and then indirectly detects hydrogen peroxide by detecting the generated oxygen using the oxygen sensitive coating; the sensor response is completely reversible, signals of the sensor in hydrogen peroxide solutions with different concentrations conform to a Stern-Vomer equation, the sensor response speed is high through the high-concentration enrichment catalyst, and the response time is shorter than 5 minutes.
12. The fast response and fully reversible optical hydrogen peroxide sensor according to claim 1 wherein in step (3) of the preparation method, the fluorescence intensity and fluorescence lifetime are measured by photoelectric conversion, phase-locked amplification circuit or time-resolved fluorescence method.
13. The fast response and fully reversible optical hydrogen peroxide sensor according to claim 1, wherein in step (3) of the preparation method, the hydrogen peroxide sensing film is prepared to have a fully reversible response with a response speed of less than 5 minutes; the stability is good, and the product can be continuously used for more than seven days; the selectivity is good and is not influenced by chloride ions; the response ranged from 0.1 micromoles per liter to 500 millimoles per liter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910617737.0A CN112213289A (en) | 2019-07-09 | 2019-07-09 | Quick-response and completely reversible optical hydrogen peroxide sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910617737.0A CN112213289A (en) | 2019-07-09 | 2019-07-09 | Quick-response and completely reversible optical hydrogen peroxide sensor and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112213289A true CN112213289A (en) | 2021-01-12 |
Family
ID=74048146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910617737.0A Pending CN112213289A (en) | 2019-07-09 | 2019-07-09 | Quick-response and completely reversible optical hydrogen peroxide sensor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112213289A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114894867A (en) * | 2022-03-25 | 2022-08-12 | 江南大学 | Hydrogen peroxide electrochemical detection method based on Au-Ag @ manganese dioxide nano material |
| CN117569014A (en) * | 2023-11-16 | 2024-02-20 | 齐鲁工业大学(山东省科学院) | H (H) 2 O 2 Preparation method of gas film sensing material and antibacterial property research thereof |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61219703A (en) * | 1985-03-24 | 1986-09-30 | Nakajima Doukoushiyo:Kk | Oxygen generating apparatus |
| WO2009097357A1 (en) * | 2008-01-29 | 2009-08-06 | Medtronic Minimed, Inc. | Analyte sensors having nanostructured electrodes and methods for making and using them |
| JP2010127830A (en) * | 2008-11-28 | 2010-06-10 | Nippon Sheet Glass Co Ltd | Method and apparatus for quantifying hydrogen peroxide |
| CN101915790A (en) * | 2010-07-09 | 2010-12-15 | 上海师范大学 | Method for preparing phytic acid micelle modified hydrogen peroxide sensor |
| CN102147389A (en) * | 2011-03-17 | 2011-08-10 | 南京师范大学 | Method for testing hydrogen peroxide in cell based on horseradish peroxidase-attapulgite nanometer composite material |
| CN102439164A (en) * | 2009-05-15 | 2012-05-02 | 霍夫曼-拉罗奇有限公司 | Enzyme stabilization in electrochemical sensors |
| CN102735732A (en) * | 2012-07-19 | 2012-10-17 | 西南大学 | Preparation and application of nano-cuprous oxide based enzyme-free hydrogen peroxide sensor electrode |
| WO2013090818A1 (en) * | 2011-12-16 | 2013-06-20 | The Regents Of The University Of California | Multiscale platform for coordinating cellular activity using synthetic biology |
| CA2900460A1 (en) * | 2012-09-07 | 2014-03-13 | Clean Chemistry, Llc | Systems and methods for generation of reactive oxygen species and applications thereof |
| WO2014043204A1 (en) * | 2012-09-14 | 2014-03-20 | Senseonics, Incorporated | Integrated catalytic protection of oxidation sensitive materials |
| CN105181770A (en) * | 2015-09-09 | 2015-12-23 | 上海大学 | Preparation method of manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode for electrochemical detection of hydrogen peroxide and application of preparation method |
| CN105949495A (en) * | 2016-04-22 | 2016-09-21 | 哈尔滨工业大学 | Preparation method of polyporous photochemical oxygen-sensing film |
| CN105949473A (en) * | 2016-05-16 | 2016-09-21 | 南昌大学 | Preparation method of rare-earth coordination polymer fluorescence probe and application of rare-earth coordination polymer fluorescence probe in H2O2 and glucose detection |
| CN106770545A (en) * | 2016-11-30 | 2017-05-31 | 哈尔滨理工大学 | A kind of electrochemical sensor working electrode based on the Pt of heteropoly acid containing vanadium Pd/PB |
| CN107153052A (en) * | 2016-03-03 | 2017-09-12 | 朱泽策 | Raolical polymerizable and detection application that enzyme triggers |
| CN107179344A (en) * | 2016-03-10 | 2017-09-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Hydrogen peroxide sensor, its preparation method and application |
| CN108872344A (en) * | 2018-09-05 | 2018-11-23 | 赛特世纪（苏州）生物科技有限公司 | A kind of oxygen-enriched nano biologic enzyme electrode, sensor device and its preparation method and application |
| CN109135690A (en) * | 2018-09-07 | 2019-01-04 | 中石化石油工程技术服务有限公司 | Lubricant for drilling fluids composition containing lubrication capsule grain and preparation method thereof and water-base drilling fluid and its application |
-
2019
- 2019-07-09 CN CN201910617737.0A patent/CN112213289A/en active Pending
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61219703A (en) * | 1985-03-24 | 1986-09-30 | Nakajima Doukoushiyo:Kk | Oxygen generating apparatus |
| WO2009097357A1 (en) * | 2008-01-29 | 2009-08-06 | Medtronic Minimed, Inc. | Analyte sensors having nanostructured electrodes and methods for making and using them |
| JP2010127830A (en) * | 2008-11-28 | 2010-06-10 | Nippon Sheet Glass Co Ltd | Method and apparatus for quantifying hydrogen peroxide |
| CN102439164A (en) * | 2009-05-15 | 2012-05-02 | 霍夫曼-拉罗奇有限公司 | Enzyme stabilization in electrochemical sensors |
| CN101915790A (en) * | 2010-07-09 | 2010-12-15 | 上海师范大学 | Method for preparing phytic acid micelle modified hydrogen peroxide sensor |
| CN102147389A (en) * | 2011-03-17 | 2011-08-10 | 南京师范大学 | Method for testing hydrogen peroxide in cell based on horseradish peroxidase-attapulgite nanometer composite material |
| WO2013090818A1 (en) * | 2011-12-16 | 2013-06-20 | The Regents Of The University Of California | Multiscale platform for coordinating cellular activity using synthetic biology |
| CN102735732A (en) * | 2012-07-19 | 2012-10-17 | 西南大学 | Preparation and application of nano-cuprous oxide based enzyme-free hydrogen peroxide sensor electrode |
| CA2900460A1 (en) * | 2012-09-07 | 2014-03-13 | Clean Chemistry, Llc | Systems and methods for generation of reactive oxygen species and applications thereof |
| WO2014043204A1 (en) * | 2012-09-14 | 2014-03-20 | Senseonics, Incorporated | Integrated catalytic protection of oxidation sensitive materials |
| CN105181770A (en) * | 2015-09-09 | 2015-12-23 | 上海大学 | Preparation method of manganese dioxide/graphene/titanium dioxide-modified glassy carbon electrode for electrochemical detection of hydrogen peroxide and application of preparation method |
| CN107153052A (en) * | 2016-03-03 | 2017-09-12 | 朱泽策 | Raolical polymerizable and detection application that enzyme triggers |
| CN107179344A (en) * | 2016-03-10 | 2017-09-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Hydrogen peroxide sensor, its preparation method and application |
| CN105949495A (en) * | 2016-04-22 | 2016-09-21 | 哈尔滨工业大学 | Preparation method of polyporous photochemical oxygen-sensing film |
| CN105949473A (en) * | 2016-05-16 | 2016-09-21 | 南昌大学 | Preparation method of rare-earth coordination polymer fluorescence probe and application of rare-earth coordination polymer fluorescence probe in H2O2 and glucose detection |
| CN106770545A (en) * | 2016-11-30 | 2017-05-31 | 哈尔滨理工大学 | A kind of electrochemical sensor working electrode based on the Pt of heteropoly acid containing vanadium Pd/PB |
| CN108872344A (en) * | 2018-09-05 | 2018-11-23 | 赛特世纪（苏州）生物科技有限公司 | A kind of oxygen-enriched nano biologic enzyme electrode, sensor device and its preparation method and application |
| CN109135690A (en) * | 2018-09-07 | 2019-01-04 | 中石化石油工程技术服务有限公司 | Lubricant for drilling fluids composition containing lubrication capsule grain and preparation method thereof and water-base drilling fluid and its application |
Non-Patent Citations (4)
| Title |
|---|
| LONGJIANG DING等: ""Fully-reversible optical sensor for hydrogen peroxide with fast response"", 《ANALYTICAL CHEMISTRY》, vol. 90, no. 12, pages 7544 - 7551 * |
| 张春福等: "《半导体光伏器件》", vol. 1, 西安：西安电子科技大学出版社, pages: 339 - 343 * |
| 李章良;黄建辉;肖尚忠;郭海灵;: "活性炭负载Fe~(3+)催化H_2O_2氧化邻苯二甲酸二甲酯", 环境工程学报, no. 03, pages 31 - 37 * |
| 王海;欧阳科;谢珊;王倩影;陈哲;: "多壁碳纳米管的制备与可见光催化性能", 环境科学与技术, no. 07, pages 114 - 117 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114894867A (en) * | 2022-03-25 | 2022-08-12 | 江南大学 | Hydrogen peroxide electrochemical detection method based on Au-Ag @ manganese dioxide nano material |
| CN117569014A (en) * | 2023-11-16 | 2024-02-20 | 齐鲁工业大学(山东省科学院) | H (H) 2 O 2 Preparation method of gas film sensing material and antibacterial property research thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | MOF-derived Co3O4@ Co-Fe oxide double-shelled nanocages as multi-functional specific peroxidase-like nanozyme catalysts for chemo/biosensing and dye degradation | |
| Xu et al. | Conjugated conducting polymers PANI decorated Bi12O17Cl2 photocatalyst with extended light response range and enhanced photoactivity | |
| Duan et al. | Cu-doped carbon dots as catalysts for the chemiluminescence detection of glucose | |
| Tan et al. | A covalent triazine framework as an oxidase mimetic in the luminol chemiluminescence system: Application to the determination of the antioxidant rutin | |
| Ensafi et al. | Pd@ CeO2-SnO2 nanocomposite, a highly selective and sensitive hydrogen peroxide electrochemical sensor | |
| CN106483120A (en) | Chemical stain nano-particle, its manufacture method and the hydrogen sensor including it | |
| CN107531489A (en) | The complex of new iron compound and graphene oxide | |
| CN112213289A (en) | Quick-response and completely reversible optical hydrogen peroxide sensor and preparation method thereof | |
| Jiang et al. | Spontaneous deposition of uniformly distributed ruthenium nanoparticles on graphitic carbon nitride for quantifying electrochemically accumulated H2O2 | |
| Al-saida et al. | Enhanced dual catalytic activities of silver-polyaniline/titanium dioxide magnetic nanocomposite | |
| Zhang et al. | Oxygen-sensing materials based on ruthenium (II) complex covalently assembled mesoporous MSU-3 silica | |
| Yin et al. | Doping carbon nitride quantum dots into melamine‐silver matrix: an efficient photocatalyst with tunable morphology and photocatalysis for H2O2 evolution under visible light | |
| Liu et al. | Decorating Ag 3 PO 4 nanodots on mesoporous silica-functionalized NaYF 4: Yb, Tm@ NaLuF 4 for efficient sunlight-driven photocatalysis: synergy of broad spectrum absorption and pollutant adsorption-enrichment | |
| Yang et al. | Superior triethylamine sensing platform based on MOF activated by carbon dots for photoelectric dual-mode in biphasic system | |
| CN113059175A (en) | Preparation method of Au @ Ag @ AgCl nanoparticles and application of Au @ Ag @ AgCl nanoparticles in ammonia colorimetric detection | |
| Ding et al. | Fully reversible optical sensor for hydrogen peroxide with fast response | |
| CN111139065A (en) | Bio-based luminescent nano material and preparation method and application thereof | |
| Liu et al. | Ratiometric fluorescence determination of hydrogen peroxide using carbon dot-embedded Ag@ EuWO 4 (OH) nanocomposites | |
| Xie et al. | Detection and elimination of tetracycline: constructing multi-mode carbon dots for ultra-sensitive visual assay and CDs/TiO2 for photocatalytic degradation | |
| CN113083239B (en) | TEMPO pretreated nano-cellulose-cuprous oxide/silver micro-nano structure composite material and preparation method and application thereof | |
| Chavalala et al. | Pd nanocatalysts adsorbed onto silica nanoparticle coated indium tin oxide: a reusable nanozyme for glucose detection | |
| CN107748143B (en) | Hydrogen peroxide colorimetric sensing method based on fluorescent polymer mimic enzyme | |
| Liu et al. | Sunlight-driven selective oxidation of glycerol on formate oxidase mimicking AuPt/TiO2 | |
| Zhang et al. | Direct and specific detection of methyl-paraoxon using a highly sensitive fluorescence strategy combined with phosphatase-like nanozyme and molecularly imprinted polymer | |
| Xu et al. | An optical humidity sensor based on Ag nanodendrites |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220511 Address after: 202156 room 107, zone A-1, No. 2, Lane 921, Xinshen Road, Xinhe Town, Chongming District, Shanghai (Shanghai Fusheng Economic Development Zone) Applicant after: Shanghai fuoxygen Technology Co.,Ltd. Address before: Room 1907, 16 / F, building a, vitality Business Plaza, 185 jumao street, Yuanhe street, Xiangcheng District, Suzhou City, Jiangsu Province Applicant before: Suzhou reoxygenation Environmental Protection Technology Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221202 Address after: Room 1010, No. 781, Cailun Road, China (Shanghai) Pilot Free Trade Zone, Pudong New Area, Shanghai, March 2012 Applicant after: Shanghai shuopu Technology Co.,Ltd. Address before: 202156 room 107, zone A-1, No. 2, Lane 921, Xinshen Road, Xinhe Town, Chongming District, Shanghai (Shanghai Fusheng Economic Development Zone) Applicant before: Shanghai fuoxygen Technology Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210112 |