CN115078490A - For detecting CN – Preparation method of iridium (III) complex sensitized NiO photocathode - Google Patents
For detecting CN – Preparation method of iridium (III) complex sensitized NiO photocathode Download PDFInfo
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- CN115078490A CN115078490A CN202210629682.7A CN202210629682A CN115078490A CN 115078490 A CN115078490 A CN 115078490A CN 202210629682 A CN202210629682 A CN 202210629682A CN 115078490 A CN115078490 A CN 115078490A
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- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 title claims description 8
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000002120 nanofilm Substances 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- 238000007605 air drying Methods 0.000 claims 1
- 238000005485 electric heating Methods 0.000 claims 1
- 238000010791 quenching Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 abstract description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003504 photosensitizing agent Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000002835 absorbance Methods 0.000 abstract 3
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical compound O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 abstract 1
- 238000004873 anchoring Methods 0.000 abstract 1
- 208000017983 photosensitivity disease Diseases 0.000 abstract 1
- 231100000434 photosensitization Toxicity 0.000 abstract 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XCMRHOMYGPXALN-UHFFFAOYSA-N 4-(bromomethyl)-2-[4-(bromomethyl)pyridin-2-yl]pyridine Chemical compound BrCC1=CC=NC(C=2N=CC=C(CBr)C=2)=C1 XCMRHOMYGPXALN-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 1
- NYOYIBKBWJNURJ-UHFFFAOYSA-N 2-(4-ethoxycarbonylpyridin-2-yl)pyridine-4-carboxylic acid Chemical compound CCOC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 NYOYIBKBWJNURJ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 108010007101 Cytochromes a3 Proteins 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 208000003443 Unconsciousness Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- YETOELZRMMQMSA-UHFFFAOYSA-N [4-(hydroxymethyl)-2-pyridin-2-yl-3h-pyridin-4-yl]methanol Chemical compound C1=CC(CO)(CO)CC(C=2N=CC=CC=2)=N1 YETOELZRMMQMSA-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- -1 ammonium hexafluorophosphate Chemical compound 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004098 cellular respiration Effects 0.000 description 1
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 208000029039 cyanide poisoning Diseases 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- QELUYTUMUWHWMC-UHFFFAOYSA-N edaravone Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1 QELUYTUMUWHWMC-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 230000008673 vomiting Effects 0.000 description 1
- 229910006400 μ-Cl Inorganic materials 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses an iridium complex (III) ([ (dmpp) 2 Ir(PM‑ppy)]PF 6 ]PF 6 ) Photocathode preparation method of sensitized NiO for CN – Detection of (3). Firstly, an iridium complex (III) photosensitizer which takes methylene phosphonate as an anchoring group and has a recognition site is designed and synthesized, and then the photosensitizer is assembled on a NiO surface through chemical bond bonding to prepare [ (dmpp) 2 Ir(PM‑ppy)]PF 6 ]PF 6 ) Sensitized NiO photocathodes. In the absence of CN – In the presence of [ (dmpp) 2 Ir(PM‑ppy)]PF 6 ]PF 6 Strong absorbance at 510nm, large photocurrent due to photosensitization, and high light absorbance at CN – In the presence of the compound, the absorbance of the cyclometalated iridium complex at 510nm is reduced, so that the photocurrent is reduced, and further the CN is treated – The invention has wide linear range, good selectivity and high reproducibilityAnd the like.
Description
Technical Field
The invention belongs to the field of dye-sensitized photoelectrochemical analysis, and particularly relates to a method for detecting CN – The preparation method and the application of the cyclometalated iridium (III) complex sensitized NiO photocathode with the recognition function.
Background
Cyanide ions can interact with the active site of cytochrome a3 to inhibit cellular respiration in mammals, and cyanide poisoning can cause vomiting, loss of consciousness, and ultimately death. Since cyanide is now used in large quantities in industry, methods for environmental detection of cyanide are gaining attention. The detection methods developed at present comprise a voltage method, a potential method and an electrochemical method, but all have the defects of complicated instruments, complicated procedures, high detection limit or lack of on-site monitoring and the like, so that the development of a cyanide detection method with high sensitivity and high selectivity is very meaningful.
The photoelectrochemical analysis combines the advantages of photochemistry and electrochemistry, and compared with an expensive spectrum signal instrument, the photoelectrochemical analysis taking photocurrent as an output signal has the characteristics of low background signal and high sensitivity. Heretofore, n-type semiconductors have been considered to have a great weight in the field of photoelectric analysis in photoanode analysis, while photocathode analysis of p-type semiconductors has been considered to be more and more important for the anti-interference capability of reducing substances present in monitoring systems. The p-type photocathode semiconductor which is most widely applied at present is NiO, the band gap of which is about 3.5eV, and the nano-structure can be prepared by a simple method. However, NiO-based photocathodes have poor performance and therefore require photosensitizers to improve absorption in the visible region. The iridium complex has good stability and excited state oxidation, so that the iridium complex is more beneficial to injecting holes of a p-type semiconductor. Iridium (iii) has a major disadvantage as a photosensitizer in that it has poor absorption properties in the visible light range, and thus improvement of the absorption properties of visible light is a major concern. The invention develops an iridium complex sensitized NiO photocathode for CN – Identification of (1).
The invention content is as follows:
in view of the defects of the prior art, the invention provides an iridium (III) complex with a recognition function as a photosensitizer, constructs a dye-sensitized NiO photocathode and is used for CN in an aqueous system – The detection has the characteristics of high sensitivity, good selectivity, low cost and wide linear range.
Based on the above purpose, the technical scheme of the invention is as follows:
the invention aims to provide a preparation based on iridium (III)Compound ([ (dmpp) 2 Ir(PM-ppy)]PF 6 ) (wherein dmpp is main ligand and PM-ppy is auxiliary ligand) sensitized NiO photocathode preparation method for detecting CN – 。[(dmpp) 2 Ir(PM-ppy)]PF 6 The structural formula of (A) is:
the method comprises the following steps:
(1) preparing the NiO nano-film modified ITO electrode: and immersing the cleaned ITO electrode into a mixed solution containing 0.25M nickel nitrate hexahydrate and 0.25M hexamethylenetetramine, heating for 60 minutes at 90 ℃, naturally cooling, cleaning for three times by using ultrapure water, then placing the ITO electrode into a muffle furnace, keeping for 30 minutes at 300 ℃, and naturally cooling to obtain the NiO/ITO electrode.
(2)[(dmpp) 2 Ir(PM-ppy)]PF 6 assembling/NiO/ITO electrode: fixing the NiO/ITO electrode prepared in the step (1) with sealing glue with the area of (0.5cm multiplied by 0.5cm), and soaking in [ (dmpp) 2 Ir(PM-ppy)]PF 6 (0.5mM) in DMF for 12 hours, and then [ (dmpp) 2 Ir(PM-ppy)]PF 6 Assembled to the NiO surface. The electrode adopts CH 3 CN after washing, drying in air to obtain photocathode [ (dmpp) 2 Ir(PM-ppy)]PF 6 /NiO/ITO。
(3)CN – Detection of (2): subjecting the photocathode prepared in step (2) [ (dmpp) 2 Ir(PM-ppy)]PF 6 soaking/NiO/ITO in solution containing CN with different concentrations – In a buffer solution of PBS (0.1M, pH 7.4), for 10 minutes to [ (dmpp) 2 Ir(PM-ppy)]PF 6 the/NiO/ITO is used as a working electrode to record photocurrent. Adopts 510nm light excitation, sets 20s switch light source once, and the bias voltage is 0V, thereby realizing the CN of different concentrations – The signal response of (c).
The invention has the beneficial effects that:
(1) the invention discloses an iridium complex [ (dmpp) 2 Ir(PM-ppy)]PF 6 Preparation method of/NiO/ITO sensitized NiO photocathode used for CN – Detection of (3).
(2) Application of photocathode sensor prepared by adopting disclosed iridium complex sensitized NiO in CN (carbon nitride) - The detection has the advantages of high sensitivity and good specificity, the wide linear range is from 0.001 to 1 mu M, and the detection limit is 0.398 nM.
Description of the drawings:
FIG. 1[ (dmpp) 2 Ir(PM-ppy)]PF 6 Preparation and detection CN of/NiO/ITO photocathode – Schematic diagram of (1).
FIG. 2[ (dmpp) 2 Ir(PM-ppy)]PF 6 the/NiO/ITO light cathode pair has CN with different concentrations – Photocurrent response graph of (a).
FIG. 3[ (dmpp) 2 Ir(PM-ppy)]PF 6 CN/NiO/ITO light cathode pair – Linear dependence of concentration. I is 0 And I represents photocathode and CN respectively - Photocurrent intensity before and after reaction.
FIG. 4[ (dmpp) 2 Ir(PM-ppy)]PF 6 SO/NiO/ITO light cathode pair 4 2– 、Br – 、ClO 4 – 、Cl – 、AcO – 、I – Selectivity of interfering ions.
Detailed Description
The present invention will be further described with reference to examples, but the following description is only for the purpose of explaining the present invention and does not limit the contents thereof.
1. The dyes of the present invention [ (dmpp) 2 Ir(PM-ppy)]PF 6 The preparation method comprises the following steps:
(1) synthesis of dmpp
P-dimethylaminobenzaldehyde (1.49g,10mmol) and 1-phenyl-3-methyl-5-pyrazolone (1.72g,10mmol) are dissolved in 80mL of glacial acetic acid solution, then sodium acetate (1.36g,10mmol) is added into the mixed solution at one time, the mixed solution is heated to 120 ℃ and refluxed for 8 hours, and after the reaction is ended, the mixed solution is filtered while hot, and the filtrate is cooled to room temperature. Filtration was performed using a sand-core funnel in order to remove excess sodium acetate, and the filtrate was then rotary evaporated under reduced pressure to give the final red product (2.3g, 76% yield). 1H NMR(CDCl 3 ,500MHz)δ:8.62(d,J＝3.2,2H),8.52(d,J＝5.6,2H), 8.19(d,J＝4.7,1H),7.85(t,J＝7.9,1H),7.45(s,1H),7.18(dd,J＝7.4 1H),6.72(d,J＝5.8,2H), 3.13(s,6H),2.31(s,3H).
(2) Synthesis of PM-bpy
2,2 '-Bipyridinyl-4, 4' -dicarboxylic acid (1.05g,4.12mmol) was dissolved in ethanol (40mL), and 98% sulfuric acid (2mL) was added to the mixed solution. The mixture was heated under reflux at 85 ℃ for 24 hours under nitrogen atmosphere, during which time the reaction was observed several times using a silica gel thin layer chromatography plate and the reaction was confirmed to be complete. A light pink solution was obtained. The combined solution was stripped of solvent under vacuum to leave a pale pink oil, and then deionized water (20mL) was added to the solution and extracted with dichloromethane (3X 50 mL). The combined organic components were dried over anhydrous magnesium sulfate, the mixed solution was filtered, the filtrate was subjected to reduced pressure rotary evaporation, and the volume of the solvent was reduced to about 20mL under vacuum. Addition of methanol (20mL) resulted in formation of a pale pink precipitate, which was filtered using a Buchner funnel and the filtrate was dried under vacuum to give the final product as a white solid (964mg, 76% yield).
The compound 2, 2-bipyridyl-4,4-Dimethanol (300mg,1.38mmol) was dissolved in dichloromethane (50mL), placed in an ice-water mixture at 0 ℃ and 1.3mL of PBr was added dropwise 3 In the above-mentioned mixed solution. Stirring was carried out overnight at room temperature. And observing the reaction condition by using a silica gel thin-layer chromatography plate for many times during the period, and determining that the reaction is finished. Cooling the mixture solution to 0 deg.C, and adding saturated sodium carbonate aqueous solution dropwise, wherein the temperature is kept below 5 deg.C during the dropwise addition process. The organic phase was separated after the solution was made alkaline, and the aqueous phase was extracted with dichloromethane (3X 30 mL). The organic phases were combined and the combined untreated organic phases were dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the product as a white powder of 4,4 '-bis (bromomethyl) -2,2' -bipyridine (370mg, 67% yield).
4,4 '-bis (bromomethyl) -2,2' -bipyridine (370mg,1.1mmol) was dissolved in 10mL of chloroform, 10mL of triethyl phosphite was added, and the mixture was refluxed for 5 hours at 80 ℃ under nitrogen protection, during which time the reaction was observed by using a silica gel thin layer chromatography plate several times to confirm completion of the reaction. The solvent was removed under reduced pressure and the crude product was isolated by silica gel column chromatography (polarity dichloromethane: methanol 20:1) to give the final product PM-bpy. 1 H NMR(CDCl 3 ,500MHz)δ:8.60(d,J＝5.0Hz,2H),8.33(s,2H),7.42– 7.28(m,J＝8.1,2H),4.07(dq,J＝8.1,7.1Hz,8H),3.23(d,J＝22.2Hz,4H),1.27(t,J＝7.1Hz, 12H)。
(3) Synthesis [ (dmpp) 2 Ir(PM-ppy)]PF 6
Dmpp (335mg,1.1mmol) and IrCl 3 ·3H 2 O (158mg,0.5mmol) was dissolved in a 2-ethoxyethanol/water solution (3:1,30 mL). And heating and refluxing the mixed solution at 120 ℃ for 24 hours under the protection of nitrogen, and determining that the reaction is finished. The reaction solution was then filtered using a sand-core funnel and the precipitate was finally collected to give the final product as a black precipitate (251mg, 55% yield).
Will [ (dmpp) 2 Ir(μ-Cl)] 2 (150mg,0.89mmol) and PM-bpy (90mg,0.197mmol) were dissolved in 30mL of dichloromethane, and then silver trifluoromethanesulfonate (46mg,0.178mmol) was added to the mixed solution. At room temperatureThen, the reaction was observed with a silica gel thin layer chromatography plate for a plurality of times during the stirring, and after the completion of the reaction was confirmed after 13 hours of the reaction, the dark red mixed solution was cooled to room temperature, and a 10-fold excess of ammonium hexafluorophosphate was added to the mixed solution. The suspension was stirred overnight and then filtered to remove insoluble inorganic salts. The filtered solution was rotary evaporated to dryness under reduced pressure. Finally, the resulting product was isolated by silica gel column chromatography using methylene chloride to give a brown solid (382mg, yield 61%).
2、[(dmpp) 2 Ir(PM-ppy)]PF 6 Preparation of/NiO/ITO photocathode
The prepared NiO/ITO electrode was fixed to an area of 0.5 cm. times.0.5 cm, and then immersed in a solution containing [ (dmpp) 2 Ir(PM-ppy)]PF 6 (1mM) in a centrifuge tube, and soaking at room temperature for 12 hours to obtain [ (PM-ppy) 2 Ir(daf-Rh)]PF 6 Assembled to the NiO surface. Electrodes with DMF and CH in sequence 3 CN after washing, drying in air to give [ (dmpp) 2 Ir(PM-ppy)]PF 6 /NiO/ITO。
3、[(dmpp) 2 Ir(PM-ppy)]PF 6 /NiO/ITO light cathode pair Hg 2+ Detection of (2)
[(dmpp) 2 Ir(PM-ppy)]PF 6 Target CN of/NiO/ITO light cathode pair – Will [ (dmpp) 2 Ir(PM-ppy)]PF 6 the/NiO/ITO photocathode is prepared by adding CN with different concentrations – The corresponding photocurrent response was recorded in PBS (0.1M, pH 7.4). With CN – Concentration increase, photocurrent gradual increase, photocurrent intensity increase and CN – The concentration showed a good linear relationship in the range of 0.001-1. mu.M, with a limit of detection (LOD) of 0.398 nM.
Claims (2)
1. For detecting CN – Iridium (III) complex ([ (dmpp) 2 Ir(PM-ppy)]PF 6 ) Method for preparing sensitized NiO photocathode, wherein iridium (III) complex [ (dmpp) 2 Ir(PM-ppy)]PF 6 The structural formula of (A) is:
the method comprises the following steps:
(1) preparing the NiO nano-film modified ITO electrode: and sequentially putting the ITO electrodes with fixed areas into absolute ethyl alcohol, acetone, absolute ethyl alcohol and ultrapure water, cleaning and drying. Then the electrode is immersed in a solution containing Ni (NO) 3 ) 2 ·6H 2 And heating the mixed solution of O and hexamethylenetetramine in an electric heating constant-temperature air drying oven, and naturally cooling to room temperature. Washing with ultrapure water, and naturally drying. And finally, placing the ITO electrode in a muffle furnace for quenching to obtain a NiO modified electrode (NiO/ITO).
(2)[(dmpp) 2 Ir(PM-ppy)]PF 6 assembling/NiO/ITO electrode: soaking the NiO/ITO electrode prepared in the step (1) in an iridium (III) complex [ (dmpp) 2 Ir(PM-ppy)]PF 6 In the solution for 12 hours, the electrode adopts CH 3 CN is washed and naturally dried to obtain the iridium (III) complex sensitized NiO photocathode ([ (dmpp) 2 Ir(PM-ppy)]PF 6 /NiO/ITO)。
(3CN – Detection of (2): subjecting the photocathode prepared in step (2) [ (dmpp) 2 Ir(PM-ppy)]PF 6 soaking/NiO/ITO in CN with different concentrations – In a buffer solution of PBS (0.1M, pH 7.4), for 10 minutes to [ (dmpp) 2 Ir(PM-ppy)]PF 6 the/NiO/ITO is used as a working electrode to record photocurrent. Adopts 510nm light excitation, sets 20s switch light source once, and the bias voltage is 0V, thereby realizing the CN of different concentrations – The signal response of (c).
2. [ (dmpp) prepared by the method of claim 1 2 Ir(PM-ppy)]PF 6 the/NiO/ITO electrode is in CN – Application in detection.
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