CN115078490B - Be used for detecting CN–Preparation method of iridium (III) complex sensitized NiO photocathode - Google Patents
Be used for detecting CN–Preparation method of iridium (III) complex sensitized NiO photocathode Download PDFInfo
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- CN115078490B CN115078490B CN202210629682.7A CN202210629682A CN115078490B CN 115078490 B CN115078490 B CN 115078490B CN 202210629682 A CN202210629682 A CN 202210629682A CN 115078490 B CN115078490 B CN 115078490B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 title claims description 10
- 238000001514 detection method Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 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
- 238000010438 heat treatment Methods 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
- 238000005406 washing Methods 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- 150000001768 cations Chemical class 0.000 claims 1
- 238000011010 flushing procedure Methods 0.000 claims 1
- 238000007689 inspection Methods 0.000 claims 1
- 238000010791 quenching Methods 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 abstract description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003504 photosensitizing agent Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 238000002835 absorbance Methods 0.000 abstract 2
- TTZMPOZCBFTTPR-UHFFFAOYSA-N O=P1OCO1 Chemical compound O=P1OCO1 TTZMPOZCBFTTPR-UHFFFAOYSA-N 0.000 abstract 1
- 238000004873 anchoring Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000001914 filtration Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006870 function Effects 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
- 239000000047 product Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 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
- 108010007101 Cytochromes a3 Proteins 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 208000003443 Unconsciousness Diseases 0.000 description 1
- 206010047700 Vomiting Diseases 0.000 description 1
- RRXGRDMHWYLJSY-UHFFFAOYSA-N [2-[4-(hydroxymethyl)pyridin-2-yl]pyridin-4-yl]methanol Chemical compound OCC1=CC=NC(C=2N=CC=C(CO)C=2)=C1 RRXGRDMHWYLJSY-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 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
- 230000004098 cellular respiration Effects 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 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
- 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
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012265 solid product 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
Classifications
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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 & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Biochemistry (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Hybrid Cells (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a preparation method of a photocathode of NiO sensitized by iridium complex (III) ([ (dmpp) 2Ir(PM-ppy)]PF6]PF6) for detecting CN –. Firstly, designing and synthesizing an iridium complex (III) photosensitizer which takes methylene phosphonate as an anchoring group and has a recognition site, and then assembling the iridium complex (III) photosensitizer on the surface of NiO through chemical bonding to prepare the [ (dmpp) 2Ir(PM-ppy)]PF6]PF6) sensitized NiO photocathode. When CN – is not present, [ (dmpp) 2Ir(PM-ppy)]PF6]PF6 has strong absorbance at 510nm, the photosensitive effect makes the photocurrent larger, and when CN – is present, the absorbance of the cyclometalated iridium complex at 510nm is reduced, so that the photocurrent is reduced, and further, the high-sensitivity detection of CN – is realized.
Description
Technical Field
The invention belongs to the field of photoelectrochemical analysis of dye sensitization, and particularly relates to a preparation method and application of a cyclometallated iridium (III) complex sensitized NiO photocathode with an identification function for detecting CN –.
Background
Cyanide ions can interact with the active site of cytochrome a3, inhibit cellular respiration in mammals, and cyanide poisoning can cause vomiting, loss of consciousness, and ultimately death. Because cyanide is now used in large quantities in industry, environmental methods for detecting cyanide are receiving attention. The detection methods developed at present are a voltage method, a potential method and an electrochemical method, but all have the defects of complex instruments, complex procedures, high detection limit, 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 significant.
Photoelectrochemical analysis combines the advantages of photochemistry and electrochemistry, and has the characteristics of low background signal and high sensitivity compared with an expensive spectrum signal instrument by taking photocurrent as an output signal. Hitherto, n-type semiconductors have been put to a great deal of weight in the field of photoanode analysis in the field of photoelectric analysis, while p-type semiconductor photocathode analysis has been increasingly emphasized because of a certain ability to resist interference with reducing substances present in a monitoring system. The p-type photocathode semiconductor most widely used 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. Iridium complex has good stability and oxidation in excited state, so that the iridium complex is more beneficial to the injection of holes of p-type semiconductor. Iridium (iii) has a major disadvantage of poor absorption in the visible range as a photosensitizer, and thus improvement of the absorption of visible light is a major concern. The invention develops an iridium complex sensitized NiO photocathode for identifying CN –.
The invention comprises the following steps:
In view of the defects of the prior art, the invention provides an iridium (III) complex with an identification function as a photosensitizer, and a dye-sensitized NiO photocathode is constructed and used for detecting CN – in a water system, and the invention has the characteristics of high sensitivity, good selectivity, low cost and wide linear range.
Based on the above object, the technical scheme of the invention is as follows:
The invention aims to provide a method based on iridium (III) coordination substance ([ (dmpp) 2Ir(PM-ppy)]PF6) (wherein dmpp is the primary ligand, PM-ppy is an auxiliary ligand) sensitized NiO photocathode, the structural formula for detecting CN –.[(dmpp)2Ir(PM-ppy)]PF6 is:
the method comprises the following steps:
(1) Preparation of an ITO electrode modified by a NiO nano film: immersing the cleaned ITO electrode into a mixed solution containing 0.25M nickel nitrate hexahydrate and 0.25M hexamethylenetetramine, heating at 90 ℃ for 60 minutes, naturally cooling, cleaning with ultrapure water for three times, then placing into a muffle furnace, keeping at 300 ℃ for 30 minutes, and naturally cooling to obtain the NiO/ITO electrode.
(2) [ (Dmpp) assembly of 2Ir(PM-ppy)]PF6/NiO/ITO electrode: the NiO/ITO electrode prepared in the step (1) was fixed with a sealer to an area of (0.5 cm. Times.0.5 cm), immersed in a solution of [ (dmpp) 2Ir(PM-ppy)]PF6 (0.5 mM) in DMF for 12 hours at room temperature, and [ (dmpp) 2Ir(PM-ppy)]PF6 was assembled on the NiO surface. After the electrode was washed with CH 3 CN, it was dried in air to give photocathode [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO.
(3) Detection of CN –: the photocathode prepared in the step (2) of [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO ] was immersed in a buffer solution of PBS (0.1 m, ph=7.4) containing CN – at different concentrations for 10 minutes, and photocurrent was recorded with [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO ] as a working electrode. The excitation of 510nm light is adopted, a 20s switch light source is arranged once, the bias voltage is 0V, and the signal response to CN – with different concentrations is realized.
The invention has the beneficial effects that:
(1) The invention discloses a preparation method of an iridium complex [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO sensitized NiO photocathode, which is used for detecting CN –.
(2) The photocathode sensor prepared by sensitizing NiO with the disclosed iridium complex has the advantages of high sensitivity and good specificity when used for detecting CN -, and the wide linear range is from 0.001 to 1 mu M, and the detection limit is 0.398nM.
Description of the drawings:
FIG. 1[ (dmpp) 2Ir(PM-ppy)]PF6/preparation of NiO/ITO photocathode and schematic diagram of detection CN –.
FIG. 2[ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO photo-cathode photo-current response to different concentrations of CN –.
FIG. 3 is a graph of linear relationship between [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO photocathode versus CN – concentration. I 0, I represents the photocurrent intensity before and after the photocathode reacts with CN -, respectively.
FIG. 4 is a graph of the selectivity of [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO photocathode to SO 4 2–、Br–、ClO4 –、Cl–、AcO–、I– interfering ions.
Detailed Description
The present invention will be further described with reference to examples, but it should be understood that the following description is only for the purpose of illustrating the invention and is not to be construed as limiting the invention.
1. The preparation method of the dye [ (dmpp) 2Ir(PM-ppy)]PF6 in the invention comprises the following steps:
(1) dmpp Synthesis
P-dimethylaminobenzaldehyde (1.49 g,10 mmol) and 1-phenyl-3-methyl-5-pyrazolone (1.72 g,10 mmol) were dissolved in 80mL of glacial acetic acid solution, then sodium acetate (1.36 g,10 mmol) was added to the above mixed solution in one portion, the mixed solution was heated to 120℃and refluxed for 8 hours, and after completion of the reaction, the hot solution was filtered, and the filtrate was cooled to room temperature. Filtration was carried out using a sand funnel in order to remove excess sodium acetate, and the filtrate was then subjected to rotary evaporation under reduced pressure to give the final red product (2.3 g, yield 76％).1H NMR(CDCl3,500MHz)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 '-Bipyridyl-4, 4' -dicarboxylic acid (1.05 g,4.12 mmol) was dissolved in ethanol (40 mL), and 98% sulfuric acid (2 mL) 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 using a silica gel thin layer chromatography plate multiple times to confirm completion of the reaction. A pale pink solution was obtained. The solvent was removed from the mixture under vacuum to leave a pale pink oil, which was then added to deionized water (20 mL) 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 rotary evaporation under reduced pressure, and the solvent volume was reduced to about 20mL under vacuum. Addition of methanol (20 mL) resulted in the formation of a pale pink precipitate, filtration using a buchner funnel, and drying of the filtrate under vacuum gave the final product as a white solid (964 mg, 76% yield).
Ethyl 2,2 '-bipyridyl-4, 4' -dicarboxylate (750 mg,2.4 mmol) was dissolved in ethanol (50 mL), followed by the addition of sodium borohydride (2 g,53 mmol). The mixture was heated to reflux at 65 ℃ for 3 hours under nitrogen atmosphere. The reaction condition is observed by using the silica gel thin layer chromatography plate for multiple times during the reaction period, and the completion of the reaction is determined. After about 1 hour of reaction, gel formation on the surface of the reaction mixture was observed. The gel formed was dissolved by adding a further 30mL of ethanol solution. After cooling the mixed solution to room temperature, saturated ammonium chloride (80 mL) was added to the mixture, and stirring was continued for 15 minutes. Ethanol was removed under vacuum and the resulting white precipitate was dissolved in a minimum amount of water (150 mL) and the solution was extracted with ethyl acetate (4 x 50 mL), the organic phases combined and dried over anhydrous magnesium sulfate. Filtration was performed using a buchner funnel. The solvent was removed from the filtrate under vacuum to form the final pale pink solid product (306 mg, 50% yield).
Compound 2, 2-bipyridine-4, 4-dimethanol (300 mg,1.38 mmol) was dissolved in dichloromethane (50 mL), then placed in an ice-water mixture at 0deg.C, and 1.3mL of PBr 3 was added dropwise to the above mixed solution. Stirring was carried out at room temperature overnight. The reaction condition is observed by using the silica gel thin layer chromatography plate for multiple times during the reaction period, and the completion of the reaction is determined. After the mixture solution was cooled to 0 ℃, a saturated aqueous sodium carbonate solution was added dropwise, and the temperature was kept below 5 ℃ all the time during the addition. After the solution had been made alkaline, the organic phase was separated and the aqueous phase was extracted with dichloromethane (3X 30 mL). The organic phases were combined and the combined untreated organic phases were then dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give the product as a white powder 4,4 '-bis (bromomethyl) -2,2' -bipyridine (370 mg, 67% yield).
4,4 '-Bis (bromomethyl) -2,2' -bipyridine (370 mg,1.1 mmol) was dissolved in 10mL chloroform, 10mL triethyl phosphite was added thereto and refluxed under nitrogen at 80℃for 5 hours, during which the reaction was observed with 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 separated by column chromatography on silica gel (polarity dichloromethane: methanol=20:1) to give the final product PM-bpy.1H NMR(CDCl3,500MHz)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) 2Ir(PM-ppy)]PF6
Dmpp (335 mg,1.1 mmol) and IrCl 3·3H2 O (158 mg,0.5 mmol) were dissolved in a solution of 2-ethoxyethanol/water (3:1, 30 mL). The mixture was heated to reflux at 120℃for 24 hours under nitrogen atmosphere to confirm completion of the reaction. The reaction solution was then filtered using a sand core funnel, and the precipitate was collected to give a final product as a black precipitate (251 mg, yield 55%).
[ (Dmpp) 2Ir(μ-Cl)]2 (150 mg,0.89 mmol) and PM-bpy (90 mg, 0.197mmol) were dissolved in 30mL of methylene chloride, and then silver trifluoromethane sulfonate (46 mg,0.178 mmol) was added to the mixed solution. Stirring was carried out at room temperature, during which time the reaction was observed using a silica gel thin layer chromatography plate several times, after 13 hours of reaction, the completion of the reaction was confirmed, and then the dark red mixed solution was cooled to room temperature, and 10-fold excess ammonium hexafluorophosphate was added to the above mixed solution. The suspension was stirred overnight and then filtered to remove insoluble inorganic salts. The filtered solution was spin-evaporated to dryness under reduced pressure. Finally, the mixture was separated by silica gel column chromatography using methylene chloride to obtain a brown solid (382 mg, yield 61%).
2. Preparation of [ (dmpp) 2Ir(PM-ppy)]PF6/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 centrifuge tube containing [ (dmpp) 2Ir(PM-ppy)]PF6 (1 mM) at room temperature for 12 hours, and [ (PM-ppy) 2Ir(daf-Rh)]PF6 was assembled on the NiO surface. After washing the electrode with DMF and CH 3 CN in this order, it was dried in air to give [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO.
3. [ (Dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO photo-cathode detection of Hg 2+
The [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO photocathode was used to record the corresponding photocurrent response by recording in PBS (0.1 m, ph=7.4) containing different concentrations of CN –, [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO photocathode sensing performance to target CN –. With increasing concentration of CN –, the photocurrent is gradually increased, the increase of the photocurrent intensity and the concentration of CN – show good linear relation in the range of 0.001-1 mu M, and the detection Limit (LOD) is 0.398nM.
Claims (2)
1. A method for preparing an iridium (III) complex [ (dmpp) 2Ir(PM-ppy)]PF6 sensitized NiO photocathode) for detecting CN –, wherein the cation [ (dmpp) 2 Ir (PM-ppy) ] of the iridium (III) complex has the structural formula:
The method comprises the following steps:
(1) Preparation of an ITO electrode modified by a NiO nano film: sequentially placing the ITO electrode with fixed area into absolute ethyl alcohol, acetone, absolute ethyl alcohol and ultrapure water in sequence, cleaning and drying; immersing the electrode into a mixed solution containing Ni (NO 3)2·6H2 O and hexamethylenetetramine), heating in an electrothermal constant-temperature blast drying oven, naturally cooling to room temperature, flushing with ultrapure water, naturally drying, and finally quenching the ITO electrode in a muffle furnace to obtain NiO modified electrode NiO/ITO;
(2) [ (dmpp) assembly of 2Ir(PM-ppy)]PF6/NiO/ITO electrode: soaking the NiO/ITO electrode prepared in the step (1) in an iridium (III) complex [ (dmpp) 2Ir(PM-ppy)]PF6 solution for 12 hours, washing the electrode by CH 3 CN, and naturally drying to obtain an iridium (III) complex sensitized NiO photocathode [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO;
(3) Detection of CN –: immersing the photocathode [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO) prepared in the step (2) in PBS buffer solution containing CN – with different concentrations for 10 minutes, and recording photocurrent by taking [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO as a working electrode; the excitation of 510nm light is adopted, a 20s switch light source is arranged once, the bias voltage is 0V, and the signal response to CN – with different concentrations is realized.
2. The use of [ (dmpp) 2Ir(PM-ppy)]PF6/NiO/ITO photocathode prepared according to the method of claim 1 in CN – inspection.
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