CN112094236B - Indazole zinc dicarboxylate complex with photocatalytic degradation function and preparation method and application thereof - Google Patents
Indazole zinc dicarboxylate complex with photocatalytic degradation function and preparation method and application thereof Download PDFInfo
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- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 33
- ZMKBKYHAWOMBFY-UHFFFAOYSA-N 1h-indazole;zinc Chemical compound [Zn].C1=CC=C2C=NNC2=C1 ZMKBKYHAWOMBFY-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- TZDAOUURVYQRQT-UHFFFAOYSA-N 1H-indazole-3,4-dicarboxylic acid zinc Chemical compound C1=CC(=C2C(=C1)NN=C2C(=O)O)C(=O)O.[Zn] TZDAOUURVYQRQT-UHFFFAOYSA-N 0.000 claims abstract description 34
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- OURCZCQCVGCRTL-UHFFFAOYSA-N 1h-indazole-3,4-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=NNC2=C1 OURCZCQCVGCRTL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 16
- 239000013067 intermediate product Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- 230000000593 degrading effect Effects 0.000 claims abstract description 8
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 230000015556 catabolic process Effects 0.000 claims description 21
- 238000006731 degradation reaction Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- 239000013110 organic ligand Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- -1 bis-indazole zinc Chemical compound 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- YLKPTYMNELPKOL-UHFFFAOYSA-N ethyl 1h-indazole-3-carboxylate Chemical compound C1=CC=C2C(C(=O)OCC)=NNC2=C1 YLKPTYMNELPKOL-UHFFFAOYSA-N 0.000 claims 1
- MYRXNCLHJHXJJN-UHFFFAOYSA-N C(=O)OCC.N1N=CC2=CC=CC=C12 Chemical compound C(=O)OCC.N1N=CC2=CC=CC=C12 MYRXNCLHJHXJJN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000012086 standard solution Substances 0.000 description 11
- 238000002835 absorbance Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- KBSSQWOPCBSAFN-UHFFFAOYSA-N ethyl indazole-2-carboxylate Chemical compound C1=CC=CC2=NN(C(=O)OCC)C=C21 KBSSQWOPCBSAFN-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 3
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- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PYOUGUKLRFUIMC-UHFFFAOYSA-N C1=CC(C(O)=O)=C2C(C(=O)OC)=NNC2=C1 Chemical compound C1=CC(C(O)=O)=C2C(C(=O)OC)=NNC2=C1 PYOUGUKLRFUIMC-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCUARRIEZVDMPT-UHFFFAOYSA-N Indole-2-carboxylic acid Chemical class C1=CC=C2NC(C(=O)O)=CC2=C1 HCUARRIEZVDMPT-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
- C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention discloses an indazole zinc dicarboxylate complex with a photocatalytic degradation function, and a preparation method and application thereof. Indazole dicarboxylic acid preparation: (1) mixing indazole-2-ethyl formate, acetonitrile, a base and ethyl chloroacetate, and heating to react; (2) filtering after reaction, and concentrating the filtrate to obtain an intermediate product; (3) hydrolyzing and heating the intermediate product for reaction, concentrating after the reaction, adjusting the pH value, and separating out white solid; (4) washing and drying the solid to obtain indazole dicarboxylic acid; indazole zinc dicarboxylate complex preparation: (1) indazole dicarboxylic acid and a zinc source are dissolved to obtain a mixed solution; (2) heating the mixed solution for reaction; (3) and cooling after reaction, precipitating crystals, washing and drying to obtain the indazole dicarboxylic acid zinc complex. The method for preparing the indazole zinc dicarboxylate complex is simple, high in yield and low in cost; the rhodamine B degrading agent is used for degrading rhodamine B, has a good degrading effect and can be recycled. The structural formula of the indazole dicarboxylic acid zinc complex is shown as the formula (A):
Description
Technical Field
The invention relates to the field of synthesis of transition metal complexes, in particular to an indazole zinc dicarboxylate complex with a photocatalytic degradation function, and a preparation method and application thereof.
Background
Indole carboxylic acids containing two nitrogen atoms and two carboxyl groups are somewhat similar to pyrazoles and are relatively easy to form metal complexes with special skeletons with transition metal or rare earth metal ions (CN 104877673A; CN 104140434A). In addition, the nitrogen atom on the indazole and the oxygen atom corresponding to the carboxyl can just form a five-membered ring or six-membered ring stable structure after being coordinated with the metal, and in addition, the carboxyl which does not participate in coordination can also induce and activate carbonyl compounds through hydrogen bond action due to containing a plurality of oxygen atoms (or carboxyl), so that the electrophilic performance of the carbonyl compounds is enhanced. The cheap transition metal zinc has good coordination performance (oxophilic and oxophilic), is a Lewis acid with strong activation capability, and can well activate functional groups such as carbonyl, cyano and the like, thereby enhancing the electrophilic performance of the functional groups and playing a role in catalysis. In addition, indazole is connected with carboxyl, has a good fluorescence effect after being coordinated with zinc due to a special conjugated structure, can absorb visible light and form a single electron, and can promote oxygen to form singlet oxygen and a corresponding free radical, so that various organic pollutants can be degraded.
Rhodamine B, also known as rose bengal, was used as a food additive, but later experiments demonstrated that rhodamine B is carcinogenic, day 27/10 in 2017, the latest carcinogen list provided by the world health organization international agency for research on cancer showed that rhodamine B is on the list as a class 3 carcinogen. At present, the rhodamine B is not allowed to be used for food dyeing, however, the rhodamine B is commonly used as an excellent dyeing agent in industrial dyes, the dyes enter water bodies to pollute the water sources, and therefore, the degradation of organic dyes in the water bodies is beneficial to improving the water body environment and eliminating the environmental pollution.
Disclosure of Invention
The invention aims to provide an indazole dicarboxylic acid zinc complex with a photocatalytic degradation function, which is used for catalytically degrading rhodamine B in a water body, and can be recycled; another object of the present invention is to provide a simple and high-yield method for preparing a zinc indazole dicarboxylate complex.
The invention is realized by the following technical scheme:
an indazole dicarboxylic acid zinc complex with a photocatalytic degradation function is characterized in that the structural formula of the indazole dicarboxylic acid zinc complex is shown as a formula (A):
The preparation method of the indazole zinc dicarboxylate complex with the photocatalytic degradation function comprises the following steps:
firstly, preparing organic ligand indazole dicarboxylic acid:
(1) indazole-2-ethyl formate, acetonitrile, alkali and ethyl chloroacetate are added into a beaker and uniformly stirred, and then heating reaction is carried out;
(2) filtering after reaction, and concentrating the obtained filtrate to obtain a light yellow intermediate product;
(3) hydrolyzing the intermediate product to obtain yellow liquid, heating the obtained liquid for reaction, concentrating after the reaction, adjusting the pH value to be acidic, and separating out to obtain white solid;
(4) the obtained white solid is washed and dried to obtain indazole dicarboxylic acid;
preparation of indazole dicarboxylic acid zinc complex:
(1) adding the indazole dicarboxylic acid and a zinc source into a solvent, and ultrasonically dissolving to obtain a mixed solution;
(2) placing the mixed solution in a reaction kettle for heating reaction;
(3) and cooling after reaction, precipitating crystals, washing and drying the crystals to obtain the indazole dicarboxylic acid zinc complex with the photocatalytic degradation function.
Further, preparation of mono-organic ligand indazole dicarboxylic acid: the molar volume ratio of the indazole-2-ethyl formate to the acetonitrile in the step (1) is 0.1-1 mol/L; the mass ratio between the indazole-2-carboxylic acid ethyl ester, the base and the chloroacetic acid ethyl ester is 1: (1-2): (1.5-3); the alkali is any one of potassium carbonate, sodium carbonate and sodium hydroxide; the heating temperature is 70-90 ℃, and the reaction is carried out for 4-8 hours.
Further, preparation of mono-organic ligand indazole dicarboxylic acid: dissolving the intermediate product in ethanol, adding an aqueous solution of sodium hydroxide for hydrolysis to obtain yellow liquid, reacting the obtained liquid in an oil bath at 40-70 ℃ for 3-6 hours, decompressing and concentrating to remove ethanol after reaction, adjusting the pH value of a water phase to 2-4 by hydrochloric acid, standing at room temperature for 4-8 hours, and separating out white solid; the volume ratio of the ethanol to the sodium hydroxide aqueous solution to the acetonitrile is 1: 1-1.5; the concentration of the sodium hydroxide aqueous solution is 3-5 mol/L.
Further, preparation of mono-organic ligand indazole dicarboxylic acid: and (4) washing the obtained white solid with ice water and absolute ethyl alcohol in sequence, and then drying the white solid in a vacuum drying oven at the temperature of 50-60 ℃ for 1-3 hours to obtain the indazole dicarboxylic acid.
Further, preparation of a bis (indazole) zinc dicarboxylate complex: the solvent in the step (1) is any one of distilled water, dioxane and N, N-dimethylformamide; the zinc source is Zn (NO)3)2·6H2O; the molar volume ratio of the indazole dicarboxylic acid to the solvent is 0.01-1 mol/L; the mass ratio of indazole dicarboxylic acid to zinc source is 2: 1.
Further, preparation of a bis (indazole) zinc dicarboxylate complex: in the step (2), the heating temperature is 80-120 ℃, and the reaction is carried out for 12-48 hours.
Further, preparation of a bis (indazole) zinc dicarboxylate complex: and (3) cooling to room temperature after the reaction in the step (3) is finished, precipitating colorless crystals, and washing the crystals for 3-5 times by using distilled water to obtain the indazole dicarboxylic acid zinc complex with the photocatalytic degradation function.
The application of the indazole dicarboxylic acid zinc complex with the photocatalytic degradation function is characterized in that the indazole dicarboxylic acid zinc complex is used for catalytically degrading rhodamine B in a water body.
Further, the process of catalyzing and degrading rhodamine B is as follows: adding the rhodamine B solution into a photoreaction device, then adding an indazole dicarboxylic acid zinc complex, turning on a xenon lamp to perform visible light irradiation on the rhodamine B solution, and stirring to complete the degradation of the rhodamine B; the concentration of the rhodamine B solution is 5-20 mg/L; the mass-to-volume ratio of the indazole dicarboxylic acid zinc complex to the rhodamine B solution is 0.5-1 mg/mL.
The invention has the beneficial effects that:
(1) the invention synthesizes a brand new indazole dicarboxylic acid zinc complex, the synthesis method is simpler, the yield is higher, the used metal is common cheap metal zinc, and the cost is lower; provides a certain basis for metal complexes containing nitrogen and carboxylic acid at the same time; the indazole dicarboxylic acid zinc complex can efficiently catalyze the degradation of rhodamine B under the condition of visible light, is beneficial to the treatment of environmental pollutants, can be repeatedly used, and improves the utilization value;
(2) the indazole zinc dicarboxylate complex prepared by the invention belongs to a heterogeneous catalyst, can recycle the catalyst in a degraded solution, can be recycled after being washed and dried, can be used for a photocatalytic degradation experiment again, and has good application value and development potential.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a crystal structure diagram of an indazole zinc dicarboxylate complex prepared according to example 1 of the present invention;
FIG. 2 is a standard curve of concentration and absorbance of a rhodamine B standard solution;
FIG. 3 is a degradation rate effect diagram of a degradation cycle test of rhodamine B.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the indazole zinc dicarboxylate complex with the photocatalytic degradation function comprises the following steps:
firstly, preparing organic ligand indazole dicarboxylic acid:
(1) 19.2g (100mmol) of indazole-2-carboxylic acid ethyl ester, 250mL of acetonitrile, 27.6g (200mmol) of potassium carbonate and 21.4mL (150mmol) of ethyl chloroacetate were added to a 1000mL beaker and mechanically stirred well at room temperature, then heated to 80 ℃ in an oil bath for 6 hours;
(2) after the reaction is finished, filtering to remove potassium carbonate, and then concentrating the obtained filtrate under reduced pressure to obtain a light yellow intermediate product which is indazole dicarboxylic acid methyl ester;
(3) placing the obtained intermediate product in a 1000mL flask, adding 200mL of ethanol and 200mL of sodium hydroxide aqueous solution (5mol/L) for hydrolysis to obtain clear yellow liquid, reacting the obtained yellow liquid for 4 hours at 60 ℃ in an oil bath, observing the completion of the reaction by a thin layer chromatography tracking point plate, decompressing and concentrating to remove the ethanol, adjusting the pH value of an aqueous phase to 4 by hydrochloric acid, and standing for 6 hours at room temperature to separate out a large amount of white solid;
(4) washing the obtained white solid with ice water and absolute ethyl alcohol in sequence, and then drying the white solid in a vacuum drying oven at 50 ℃ for 3 hours to obtain 20.7g of white solid indazole dicarboxylic acid; this is the organic ligand compound, the yield is 94%;
identification data for this organic ligand:
infrared IR (KBr) v 3519, 3401, 1697, 1595, 1494cm-1.
Hydrogen nuclear magnetic resonance spectroscopy:1h NMR (DMSO,400 MHz). delta.8.12-8.08 (m,1H),7.63-7.57(m,1H),7.45-7.37(m,1H),7.28-7.22(m,1H),5.03(s,2H). melting point: 283 ℃ and 285 ℃.
Preparation of bis-indazole zinc dicarboxylate complexes:
(1) 220mg (1mmol) of indazole dicarboxylic acid and 148mg (0.5mmol) of Zn (NO)3)2·6H2Adding O into 10mL of distilled water and dissolving by ultrasonic to obtain a mixed solution;
(2) placing the mixed solution in a reaction kettle, heating to 100 ℃ and reacting for 20 hours;
(3) after the reaction, the reaction mixture was cooled to room temperature to precipitate colorless crystals, which were washed with distilled water 5 times and then dried to obtain 237mg of an indazole zinc dicarboxylate complex (C) having a photocatalytic degradation function20H18N4O10Zn), the yield was 88%, and the crystal structure thereof is shown in FIG. 1.
The above reaction process is as follows:
example 2
The preparation method of the indazole zinc dicarboxylate complex with the photocatalytic degradation function comprises the following steps:
firstly, preparing organic ligand indazole dicarboxylic acid:
(1) 19.2g (100mmol) of indazole-2-carboxylic acid ethyl ester, 500mL of acetonitrile, 15.9g (150mmol) of sodium carbonate and 42.8mL (300mmol) of ethyl chloroacetate were added to a 1000mL beaker and mechanically stirred well at room temperature, then heated to 70 ℃ in an oil bath for 4 hours;
(2) after the reaction is finished, filtering to remove sodium carbonate, and then concentrating the obtained filtrate under reduced pressure to obtain a light yellow intermediate product;
(3) placing the obtained intermediate product in a 1000mL flask, adding 500mL of ethanol and 500mL of sodium hydroxide aqueous solution (3mol/L) for hydrolysis to obtain clear yellow liquid, reacting the obtained yellow liquid for 6 hours at 70 ℃ in an oil bath, carrying out reduced pressure concentration to remove the ethanol after the reaction is finished by checking a thin layer chromatography tracking point plate, adjusting the pH value of a water phase to be 2 by using hydrochloric acid, and standing for 8 hours at room temperature to separate out a large amount of white solid;
(4) washing the obtained white solid with ice water and absolute ethyl alcohol in sequence, and then drying the white solid in a vacuum drying oven at 60 ℃ for 2 hours to obtain 19.4g of white solid indazole dicarboxylic acid; this is the organic ligand compound, the yield is 88%;
preparation of bis-indazole zinc dicarboxylate complexes:
(1) 264mg (1.2mmol) of indazole dicarboxylic acid and 177.6mg (0.6mmol) of Zn (NO) were weighed out3)2·6H2Adding O into 2mL of N, N-dimethylformamide and carrying out ultrasonic dissolution to obtain a mixed solution;
(2) placing the mixed solution in a reaction kettle, heating to 80 ℃ and reacting for 48 hours;
(3) after the reaction, the reaction mixture was cooled to room temperature to precipitate colorless crystals, the crystals were washed with distilled water 3 times and then dried to obtain 275mg of the indazole dicarboxylic acid zinc complex having a photocatalytic degradation function, with a yield of 85%.
Example 3
The preparation method of the indazole zinc dicarboxylate complex with the photocatalytic degradation function comprises the following steps:
firstly, preparing organic ligand indazole dicarboxylic acid:
(1) 19.2g (100mmol) of indazole-2-carboxylic acid ethyl ester, 100mL of acetonitrile, 4.0g (100mmol) of sodium hydroxide and 28.5mL (200mmol) of ethyl chloroacetate were added to a 1000mL beaker and mechanically stirred well at room temperature, then heated to 90 ℃ in an oil bath for 8 hours;
(2) after the reaction is finished, filtering to remove sodium hydroxide, and then concentrating the obtained filtrate under reduced pressure to obtain a light yellow intermediate product;
(3) placing the obtained intermediate product in a 1000mL flask, adding 125mL of ethanol and 125mL of sodium hydroxide aqueous solution (4mol/L) for hydrolysis to obtain clear yellow liquid, reacting the obtained yellow liquid for 3 hours at 40 ℃ in an oil bath, observing the reaction completion by a thin layer chromatography tracking point plate, decompressing and concentrating to remove the ethanol, adjusting the pH value of a water phase to 3 by hydrochloric acid, and standing for 5 hours at room temperature to separate out a large amount of white solid;
(4) washing the obtained white solid with ice water and absolute ethyl alcohol in sequence, and then drying the white solid in a vacuum drying oven at the temperature of 55 ℃ for 1 hour to obtain 20.0g of white solid indazole dicarboxylic acid; this is the organic ligand compound, with a yield of 91%;
preparation of bis-indazole zinc dicarboxylate complexes:
(1) 330mg (1.5mmol) of indazole dicarboxylic acid and 222mg (0.75mmol) of Zn (NO)3)2·6H2Adding O into 30mL of dioxane, and dissolving by ultrasonic to obtain a mixed solution;
(2) placing the mixed solution in a reaction kettle, heating to 120 ℃ and reacting for 12 hours;
(3) after the reaction, the reaction mixture was cooled to room temperature to precipitate colorless crystals, and the crystals were washed with distilled water 5 times and then dried to obtain 305mg of a zinc indazole dicarboxylate complex having a photocatalytic degradation function, with a yield of 86%.
Application example 1
(1) Preparing a rhodamine B solution with the concentration of 50mg/L, and then diluting the solution step by step to obtain the rhodamine B standard solution with the concentration of 1mg/L, 2mg/L, 4mg/L, 6mg/L, 8mg/L and 10 mg/L. Then measuring the rhodamine B standard solution with the corresponding concentration at the wavelength lambda by using an ultraviolet spectrophotometermaxAnd (3) drawing a standard curve by taking the concentration of the rhodamine B standard solution as an abscissa and the absorbance as an ordinate, and obtaining a standard curve equation after linear fitting, wherein the absorbance at 550nm is as follows: 0.18217X-0.08839, R20.99478, its linear relationship is good as shown in fig. 2;
(2) 50mL of the rhodamine B standard solution (10mg/L) prepared above was put into a photoreaction apparatus, 30mg of the indazole zinc dicarboxylate complex prepared in example 1 was added,turning on a xenon lamp to irradiate the rhodamine B solution with visible light and stirring the solution: after 10 minutes of reaction, 1mL of the reaction solution was subjected to ultraviolet absorption spectroscopy at a wavelength of lambdamaxThe absorbance at 550nm was 0.98A, and then compared to the standard curve equation (i.e., fig. 2), it was found that the concentration of the rhodamine B standard solution after 10 minutes of catalytic degradation of the indazole zinc dicarboxylate complex prepared in example 1 was 6.1mg/L (i.e., the equilibrium concentration after degradation), and then according to the degradation rate formula:
calculating the degradation rate (R%) of rhodamine B, wherein: c0(mg/L) and Ce(mg/L) is respectively the initial concentration of the rhodamine B standard solution and the equilibrium concentration after degradation, and the degradation rate after 10 minutes of illumination is calculated to be 39 percent; ② after 20 minutes of reaction, 1mL of reaction solution is taken to carry out ultraviolet absorption spectrum test at the wavelength of lambdamaxThe absorbance at 550nm is 0.85A, then the concentration of the rhodamine B standard solution after 20 minutes of catalytic degradation is 5.2mg/L by contrasting a standard curve equation, and then the degradation rate after 20 minutes of illumination is calculated to be 48 percent according to the degradation rate formula; thirdly, repeating the steps, and calculating the degradation rate of 55 percent within 30 minutes; fourthly, the degradation rate of the indazole dicarboxylic acid zinc complex to rhodamine B is 73 percent after 40 minutes; the calculated result shows that the degradation rate of the indazole dicarboxylic acid zinc complex to rhodamine B is 83% after 50 minutes; sixthly, calculating that the rhodamine B standard solution becomes colorless after 60 minutes of illumination, and calculating that the degradation rate of the indazole zinc dicarboxylate complex on rhodamine B is 94%. While the rhodamine B of the control experiment without the indazole zinc dicarboxylate complex is still red.
The indazole zinc dicarboxylate complex prepared by the invention can be recycled after being used for photocatalytic degradation of rhodamine B:
the method specifically comprises the following steps: filtering the completely degraded rhodamine B standard solution, collecting the indazole dicarboxylic acid zinc complex, washing the indazole dicarboxylic acid zinc complex, drying the indazole dicarboxylic acid zinc complex, reusing the indazole dicarboxylic acid zinc complex for photocatalytic degradation of rhodamine B, and performing a cycle experiment, wherein the result shows that when the indazole dicarboxylic acid zinc complex is used for the second time, the degradation effect is still 93%, the result of repeating the cycle for five times is shown in figure 3, and the degradation rate is still more than 90% when the rhodamine B standard solution is circulated for five times. The indazole zinc dicarboxylate complex prepared by the method has high photocatalytic degradation efficiency, can be repeatedly used, and has good application value and development potential.
Table 1 shows the crystal parameters of the indazole zinc dicarboxylate complex prepared in example 1
The above-mentioned preferred embodiments of the present invention are provided for illustration only and not for the purpose of limiting the invention. Obvious variations or modifications of the present invention are within the scope of the present invention.
Claims (10)
1. An indazole dicarboxylic acid zinc complex with a photocatalytic degradation function is characterized in that the structural formula of the indazole dicarboxylic acid zinc complex is shown as a formula (A):
2. The method for preparing indazole zinc dicarboxylate complex having photocatalytic degradation function according to claim 1, wherein the method comprises the steps of:
firstly, preparing organic ligand indazole dicarboxylic acid:
(1) indazole-3-ethyl formate, acetonitrile, alkali and ethyl chloroacetate are added into a beaker and uniformly stirred, and then heating reaction is carried out;
(2) filtering after reaction, and concentrating the obtained filtrate to obtain a light yellow intermediate product;
(3) hydrolyzing the intermediate product to obtain yellow liquid, heating the obtained liquid for reaction, concentrating after the reaction, adjusting the pH value to be acidic, and separating out to obtain white solid;
(4) washing and drying the obtained white solid to obtain 1-acetic acid-indazole-3-carboxylic acid;
preparation of bis-indazole zinc dicarboxylate complexes:
(1) adding the obtained 1-acetic acid-indazole-3-carboxylic acid and a zinc source into a solvent, and performing ultrasonic dissolution to obtain a mixed solution;
(2) placing the mixed solution in a reaction kettle for heating reaction;
(3) and cooling after reaction, precipitating crystals, washing and drying the crystals to obtain the indazole dicarboxylic acid zinc complex with the photocatalytic degradation function.
3. The method for preparing the indazole zinc dicarboxylate complex having a photocatalytic degradation function according to claim 2, wherein the preparation of the organic ligand indazole dicarboxylic acid comprises the following steps: the molar volume ratio of the indazole-3-ethyl formate to the acetonitrile in the step (1) is 0.1-1 mol/L; the mass ratio of the indazole-3-carboxylic acid ethyl ester, the base and the chloroacetic acid ethyl ester is 1: (1-2): (1.5-3); the alkali is any one of potassium carbonate, sodium carbonate and sodium hydroxide; the heating temperature is 70-90 ℃, and the reaction is carried out for 4-8 hours.
4. The method for preparing the indazole zinc dicarboxylate complex having a photocatalytic degradation function according to claim 2, wherein the preparation of the organic ligand indazole dicarboxylic acid comprises the following steps: dissolving the intermediate product in ethanol, adding an aqueous solution of sodium hydroxide for hydrolysis to obtain yellow liquid, reacting the obtained liquid in an oil bath at 40-70 ℃ for 3-6 hours, decompressing and concentrating to remove ethanol after reaction, adjusting the pH value of a water phase to 2-4 by hydrochloric acid, standing at room temperature for 4-8 hours, and separating out white solid; the volume ratio of the ethanol to the sodium hydroxide aqueous solution to the acetonitrile is 1: 1: (1-1.5); the concentration of the sodium hydroxide aqueous solution is 3-5 mol/L.
5. The method for preparing the indazole zinc dicarboxylate complex having a photocatalytic degradation function according to claim 2, wherein the preparation of the organic ligand indazole dicarboxylic acid comprises the following steps: and (4) washing the obtained white solid with ice water and absolute ethyl alcohol in sequence, and then drying the white solid in a vacuum drying oven at the temperature of 50-60 ℃ for 1-3 hours to obtain the 1-acetic acid-indazole-3-carboxylic acid.
6. The method for preparing an indazole zinc dicarboxylate complex having a photocatalytic degradation function according to claim 2, wherein the preparation of the bis-indazole zinc dicarboxylate complex comprises: the solvent in the step (1) is any one of distilled water, dioxane and N, N-dimethylformamide; the zinc source is Zn (NO)3)2·6H2O; the molar volume ratio of the 1-acetic acid-indazole-3-carboxylic acid to the solvent is 0.01-1 mol/L; the mass ratio of the 1-acetic acid-indazole-3-carboxylic acid to the zinc source is 2: 1.
7. the method for preparing an indazole zinc dicarboxylate complex having a photocatalytic degradation function according to claim 2, wherein the preparation of the bis-indazole zinc dicarboxylate complex comprises: in the step (2), the heating temperature is 80-120 ℃, and the reaction is carried out for 12-48 hours.
8. The method for preparing an indazole zinc dicarboxylate complex having a photocatalytic degradation function according to claim 2, wherein the preparation of the bis-indazole zinc dicarboxylate complex comprises: and (3) cooling to room temperature after the reaction in the step (3) is finished, precipitating colorless crystals, washing the crystals for 3-5 times by using distilled water, and drying to obtain the indazole dicarboxylic acid zinc complex with the photocatalytic degradation function.
9. The application of indazole dicarboxylic acid zinc complex with photocatalytic degradation function is characterized in that the indazole dicarboxylic acid zinc complex according to claim 1 or prepared by the preparation method according to any one of claims 2 to 8 is used for catalytically degrading rhodamine B in water.
10. The application of the indazole dicarboxylic acid zinc complex with photocatalytic degradation function according to claim 9, wherein the process for catalytically degrading rhodamine B is as follows: adding the rhodamine B solution into a photoreaction device, then adding an indazole dicarboxylic acid zinc complex, turning on a xenon lamp to perform visible light irradiation on the rhodamine B solution, and stirring to complete the degradation of the rhodamine B; the concentration of the rhodamine B solution is 5-20 mg/L; the mass-to-volume ratio of the indazole dicarboxylic acid zinc complex to the rhodamine B solution is 0.5-1 mg/mL.
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