CN115197127B - Ruthenium-containing complex, preparation method and application thereof - Google Patents
Ruthenium-containing complex, preparation method and application thereof Download PDFInfo
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- CN115197127B CN115197127B CN202210669612.4A CN202210669612A CN115197127B CN 115197127 B CN115197127 B CN 115197127B CN 202210669612 A CN202210669612 A CN 202210669612A CN 115197127 B CN115197127 B CN 115197127B
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- terpyridine
- ruthenium
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000012327 Ruthenium complex Substances 0.000 claims abstract description 14
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 11
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 177
- 238000006243 chemical reaction Methods 0.000 claims description 115
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 99
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 66
- 239000002904 solvent Substances 0.000 claims description 59
- 238000010992 reflux Methods 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 47
- -1 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine Chemical compound 0.000 claims description 43
- 239000012065 filter cake Substances 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 40
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 238000000746 purification Methods 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- NBEFMISJJNGCIZ-UHFFFAOYSA-N 3,5-dimethylbenzaldehyde Chemical compound CC1=CC(C)=CC(C=O)=C1 NBEFMISJJNGCIZ-UHFFFAOYSA-N 0.000 claims description 20
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 239000012295 chemical reaction liquid Substances 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000001914 filtration Methods 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical group CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 238000002390 rotary evaporation Methods 0.000 claims description 9
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000011085 pressure filtration Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 229940125782 compound 2 Drugs 0.000 claims description 4
- 229940126214 compound 3 Drugs 0.000 claims description 4
- 229940125898 compound 5 Drugs 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 abstract description 16
- 229940107698 malachite green Drugs 0.000 abstract description 16
- 239000002351 wastewater Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 10
- 239000003446 ligand Substances 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000007853 buffer solution Substances 0.000 description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 5
- 229910000397 disodium phosphate Inorganic materials 0.000 description 5
- 235000019800 disodium phosphate Nutrition 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 235000019799 monosodium phosphate Nutrition 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- UIFVCPMLQXKEEU-UHFFFAOYSA-N 2,3-dimethylbenzaldehyde Chemical compound CC1=CC=CC(C=O)=C1C UIFVCPMLQXKEEU-UHFFFAOYSA-N 0.000 description 2
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- UXDYTCZNECXIEG-UHFFFAOYSA-N [N].C(C)N1CCOCC1 Chemical compound [N].C(C)N1CCOCC1 UXDYTCZNECXIEG-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 2
- XRWSZZJLZRKHHD-WVWIJVSJSA-N asunaprevir Chemical compound O=C([C@@H]1C[C@H](CN1C(=O)[C@@H](NC(=O)OC(C)(C)C)C(C)(C)C)OC1=NC=C(C2=CC=C(Cl)C=C21)OC)N[C@]1(C(=O)NS(=O)(=O)C2CC2)C[C@H]1C=C XRWSZZJLZRKHHD-WVWIJVSJSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229940125961 compound 24 Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000006286 aqueous extract Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/55—Acids; Esters
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to the technical field of photosensitizers, and discloses a ruthenium-containing complex, a preparation method and application thereof, wherein the molecular formula of the ruthenium-containing complex is [ Ru ] II (tpy‑ph(COO ‑ ) 2 ) 2 ](PF 6 ) 2 . The ruthenium-containing complex prepared by the invention can be used as a photosensitizer, solves the problems that the waste water is treated by the traditional method to generate secondary waste and can not be poured, reduces the economic cost of waste water treatment, reduces the time consumed in treatment, and further improves the treatment effect of the waste materials in the waste water by degrading the dye in the waste water and cleaning the environment. The invention synthesizes a novel carboxyl substituted nitrogen-containing heterocyclic ligand and a ruthenium complex thereof, takes the ruthenium-containing complex as a photosensitizer, and performs preliminary study on the performance of the ruthenium-containing complex in photocatalytic degradation of malachite green to obtain the novel carboxyl substituted multidentate nitrogen-containing heterocyclic ligand and the ruthenium complex thereof with certain photocatalytic performance.
Description
Technical Field
The invention relates to the technical field of photosensitizers, in particular to a ruthenium-containing complex, a preparation method and application thereof.
Background
The rapid development of modern industrialization and human activities lead to pollution of air, water and land. Currently, water pollution is one of the major environmental problems in the case of limited water resources. Among these, dye pollution is a source of carcinogens and mutagens in environmental pollution. About 3000 tens of thousands of tons of textiles are produced annually worldwide, which require about 70 tens of thousands of different kinds of dyes, such as acid dyes, basic dyes, diazo dyes, azo dyes, etc., which, if improperly treated, can cause a high degree of damage to the ecosystem.
Ruthenium has excellent and easily-regulated photophysical and photochemical properties, is widely used as a photosensitizer in photocatalytic reaction research, and is a common metal ruthenium complex nitrogen heterocyclic ligand which is a polydipyridine compound and comprises 2,2 '-bipyridine, 2' -phenanthroline, bipyridine and the like. The polypyridine compound has the advantage of wide organic synthesis modification potential as the ligand of the ruthenium complex, and the physical and chemical properties of the ruthenium complex photosensitizer can be adjusted through ligand modification.
In recent years, many articles have reported methods for removing organic dyes from wastewater. Wherein, the technologies such as adsorption method, ion exchange method, membrane treatment method and the like are better applied; however, the treatment of wastewater by these methods produces secondary waste, which cannot be dumped, and is costly, time-consuming and inefficient; the dye in the photocatalytic degradation industrial wastewater can oxidize toxic pollutant dye into inorganic small molecules (CO 2 and H2O) to purify the wastewater; the reaction is thorough, and secondary pollution is not caused; photocatalysis is thus a potential alternative to degradation of dyes in wastewater and environmental cleaning.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides the ruthenium-containing complex, the preparation method and the application thereof, and the ruthenium-containing complex has the advantages of no pollution, convenient treatment, low cost, short time consumption, good effect and the like through synchronous improvement of components, proportions and preparation processes, so as to solve the problems that the waste water treated by the existing method generates secondary waste, cannot be poured, and has high cost, long time consumption and poor effect.
(II) technical scheme
In order to achieve the purposes that the waste water treated by the methods can generate secondary waste, cannot be poured, has high cost, long time consumption and poor effect, the invention provides the following technical scheme:
a ruthenium-containing complex is characterized in that the molecular formula of the ruthenium-containing complex is [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 The structural formula is as follows:
the invention provides a preparation method of a ruthenium-containing complex, which comprises the following steps: bis (4 '- (3, 5-dicarboxyphenyl) -2,2',6', 2' -terpyridine) ruthenium, comprising the steps of:
s1, mixing 3, 5-dimethylbenzaldehyde and 2-diacetylpyridine at a low temperature, adding strong base, and stirring for 8h under a solvent to obtain a compound 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine (compound 1);
s2, heating and refluxing 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine and 2-acetylpyridine in the presence of a solvent, strong alkali and ammonium hydroxide, and recrystallizing by using pyridine and water as the solvent to obtain a compound 4'- (3, 5-dimethylphenyl) -2,2':6',2' -terpyridine (compound 2);
s3, heating 4'- (3, 5-dimethylphenyl) -2,2',6', 2' -terpyridine in a reaction kettle for 2-24 hours in the presence of concentrated nitric acid and water to obtain 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid (compound 3);
s4, under the protection of inert gas, carrying out reflux reaction on 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid and ethanol for 8-80 hours in the presence of concentrated sulfuric acid to obtain 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid ethyl ester (compound 4);
s5, 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid ethyl ester and RuCl 3 ·3H 2 Heating and refluxing O in solvent for 0.5-10 hr to obtain Ru II (tpy-ph(COOEt) 2 Cl 3 (Compound 5);
s6, ru is formed II (tpy-ph(COOEt) 2 Cl 3 Mixing 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid, a pH regulator and a solvent for a first step reaction, removing insoluble impurities from the obtained reaction solution after the reaction, and adding NH into the reaction solution 4 PF 6 The aqueous solution is subjected to a second reaction step, and stirred at normal temperature for 1 to 40 minutes to obtain [ Ru ] II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 (Compound 6);
s7, mixing the compound 6 with ethanol and sodium hydroxide aqueous solution, heating and refluxing for 2-24 hours, cooling to room temperature, regulating the pH value of the reaction solution to be less than 7 to obtain a crude product, and mixing the crude product with sulfuric acid aqueous solution and HPF 6 Mixing the aqueous solutions, stirring for 2-45 min at room temperature, and purifying the obtained reaction solution to obtain [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 (Compound 7).
Preferably, in the step S1, the reaction is stirred for 7-12 hours at the temperature of 0-5 ℃, and the solvent is methanol and water with the volume ratio of 2: 0.5-2, 3, 5-dimethylbenzaldehyde and 2-diacetylpyridine in a molar ratio of 2-2.5: 1, the strong base is one of potassium hydroxide and sodium hydroxide, preferably sodium hydroxide, and the mole ratio of 3, 5-dimethylbenzaldehyde to the strong base is 1: 1.8-2, 3, 5-dimethylbenzaldehyde and methanol in a molar ratio of 1: 50-150,3,5-dimethylbenzaldehyde and water in a molar ratio of 1: 50-150, and after the reaction is finished, performing reduced pressure filtration by using a mixed solution of methanol and water, wherein the volume ratio of the methanol to the water is 1:0.5 to 10.
Preferably, in the step S2, the ammonium hydroxide concentration is set to 30%, the heating reflux temperature is 60 ℃, the reflux reaction time is 2-24 hours, the solvent is at least one of ethanol, methanol, acetonitrile and acetone, the strong base is one of sodium hydroxide and potassium hydroxide, and the volume ratio of pyridine to water is 2:0.5 to 5.
Preferably, in the step S3, the molar ratio of 4'- (3, 5-dimethylphenyl) -2,2':6',2' -terpyridine to concentrated nitric acid is 1:10-15, the concentration of the concentrated nitric acid is more than or equal to 33 weight percent, and the volume ratio of the concentrated nitric acid to water is 1:3-1, using a polytetrafluoroethylene reaction kettle to carry out reaction, wherein the heating temperature is 160 ℃, the reaction time is 2-24 hours, and after the reaction is finished, washing with pure water and decompressing and filtering.
Preferably, in the step S4, the molar ratio of 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid to ethanol is 1: 200-500, the concentration of the concentrated sulfuric acid is more than or equal to 33wt%, and the volume ratio of the concentrated sulfuric acid to the ethanol is 1: 30-60, and further comprises a purification step after the reflux reaction is finished, wherein the specific purification step is as follows: and (3) removing ethanol by rotary evaporation of the reaction liquid after the reflux, adding water into the reaction liquid, adjusting the pH to 6-10 by using sodium carbonate, extracting by using an organic solvent, collecting an organic phase, and drying a product obtained by rotary evaporation of the solvent.
Preferably, in step S5, 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid ethyl ester and RuCl 3 ·3H 2 The molar ratio of O is 1:0.5 to 5 percent, and the solvent for the reaction is ethanolAt least one of methanol, acetone and ethyl acetate, wherein the temperature of the heating reflux reaction is 90 ℃, the reaction time is 1-5 h, and the purification step is further included after the heating reflux reaction is finished, and the specific purification steps are as follows: and cooling the reaction liquid after the reaction is finished to room temperature to obtain a dark red suspension, decompressing and filtering the dark red suspension, washing a filter cake with ethanol until the filter cake has no color, and drying the obtained filter cake.
Preferably, in step S6, the solvent is at least one of ethanol, methanol, ethyl acetate and acetonitrile, the solvent for the reaction is ethanol, and the molar ratio of ethanol to 5- (2, 2':6',2 "-terpyridine) -4' -isophthalic acid is 1: 100-1000, wherein the pH regulator is at least one of N-ethylmorpholine, triethylamine and ethylenediamine, the pH regulator is N-ethylmorpholine, and the pH value of the solution is regulated to be 8-9; the volume ratio of the N-ethylmorpholine to the solvent is 1:50-500,5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid and Ru II (tpy-ph(COOEt) 2 Cl 3 The mol ratio of (2) is 1:0.8-2, and the conditions of the first reaction are as follows: heating and refluxing for 0.5-3 hours, NH 4 PF 6 The concentration of the aqueous solution is 0.1-5 mol/L, NH 4 PF 6 The molar ratio of the catalyst to 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid is 1: 2-5, using diatomite as a filter aid to remove insoluble impurities in the reaction liquid by decompression and filtration, and after the second step of reaction, further comprising a purification process, wherein the specific purification steps are as follows: and (3) removing most of the solvent from the solution after the reaction in the second step by using a rotary evaporator, remaining a small amount of red turbid liquid, carrying out reduced pressure filtration on the turbid liquid, washing a filter cake by using ethanol and water, and drying the filter cake.
Preferably, in the step S7, the concentration of the sodium hydroxide aqueous solution is 2-8 mol/L, and the volume ratio of the sodium hydroxide aqueous solution to the ethanol is 1:1, [ Ru ] II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 And sodium hydroxide in a molar ratio of 1: 2-100, the conditions of the first reaction are as follows: heating to 90deg.C, refluxing for 12 hr, and adjusting pH with 3M hydrochloric acid and water mixed solution to obtain [ Ru ] II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 And HPF 6 The molar ratio of (2) is 1:10 to50, purifying means that the obtained reaction liquid is decompressed and filtered, and then a filter cake is washed by water, and the filter cake is dried.
(III) beneficial effects
Compared with the prior art, the ruthenium-containing complex, the preparation method and the application thereof provided by the invention have the following beneficial effects:
1. the ruthenium-containing complex, the preparation method and the application thereof provided by the invention have the advantages of no pollution, convenient treatment, low cost, short time consumption, good effect and the like by synchronously improving the components, the proportion and the preparation process, so as to solve the problems that the waste water treated by the existing method can generate secondary waste, cannot be poured, and has high cost, long time consumption and poor effect.
2. According to the ruthenium-containing complex and the preparation method thereof, a novel carboxyl-substituted nitrogen-containing heterocyclic ligand and the ruthenium complex thereof are synthesized by designing, the ruthenium-containing complex is taken as a photosensitizer, and the photocatalytic degradation malachite green performance is subjected to preliminary research, so that the novel carboxyl-substituted multidentate nitrogen-containing heterocyclic ligand with certain photocatalytic performance and the ruthenium complex thereof are obtained.
3. According to the ruthenium-containing complex and the preparation method thereof, the novel ruthenium-containing complex is designed as the photosensitizer, so that the problem that secondary waste is generated and cannot be dumped in the traditional method for treating wastewater is solved, the economic cost of wastewater treatment is reduced, the time consumed in treatment is reduced, and the treatment effect on the waste in wastewater is further improved through degradation of dye in the wastewater and cleaning of the environment.
Drawings
FIG. 1 is a synthetic scheme of the ruthenium-containing compound prepared in example 1 of the present invention;
FIG. 2 is a 1H NMR spectrum of 5- (2, 2':6',2 "-terpyridine) -4' -ethyl isophthalate (compound 4) prepared in example 1 of the present invention;
FIG. 3 [ Ru ] obtained by the method of example 1 of the present invention II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 1H NMR spectrum of (Compound 6);
FIG. 4 shows the preparation of example 1 of the present invention[ Ru of (V) II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 1H NMR spectrum of (Compound 7);
FIG. 5 shows the variation of the characteristic ultraviolet absorption peak of the organic dye for carrying out the process of photocatalytic degradation of malachite green according to the present invention, initial concentration: 0.5mg/mL [ Ru II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 With 5ppm malachite green;
fig. 6 is a graph of percent residual concentration of malachite green in visible light (> 560) degradation versus time.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The molecular formula of the ruthenium-containing complex provided by the invention is [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 。
The preparation method of the ruthenium-containing complex comprises the following steps: bis (4 '- (3, 5-dicarboxyphenyl) -2,2',6', 2' -terpyridine) ruthenium.
Embodiment one:
the ruthenium-containing complex comprises the following raw materials in parts by weight: bis (4 '- (3, 5-dicarboxyphenyl) -2,2',6', 2' -terpyridine) ruthenium, the ruthenium-containing complex having the formula [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 The structural formula is as follows:
the invention provides a preparation method of a ruthenium-containing complex, which comprises the following steps:
s1, mixing 3, 5-dimethylbenzaldehyde and 2-diacetylpyridine at a low temperature, adding strong base, stirring for 8 hours in a solvent to obtain a compound 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine (compound 1), wherein in the step S1, the reaction is carried out for 7 hours at the temperature of 0 ℃, the solvent is methanol and water, and the volume ratio is 2: the molar ratio of 0.5 dimethylbenzaldehyde to 2-diacetylpyridine is 2, the strong base is sodium hydroxide, and the molar ratio of 3, 5-dimethylbenzaldehyde to strong base is 1:1.8 molar ratio of dimethylbenzaldehyde to methanol is 1:50,3,5-dimethylbenzaldehyde and water in a molar ratio of 1:50, after the reaction, the mixture of methanol and water was used for reduced pressure filtration, wherein the volume ratio of methanol to water was 1:0.5;
s2, heating and refluxing 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine and 2-acetylpyridine in the presence of a solvent, strong alkali and ammonium hydroxide, recrystallizing by using pyridine and water as the solvent to obtain a compound 4'- (3, 5-dimethylphenyl) -2,2':6',2' -terpyridine (compound 2), wherein in the step S2, the ammonium hydroxide concentration is set to be 30%, the heating and refluxing temperature is 60 ℃, the refluxing reaction time is 2h, the solvent is at least one of ethanol and methanol, the strong alkali is one of sodium hydroxide and potassium hydroxide, and the volume ratio of pyridine to water is 2:0.5;
s3, heating 4'- (3, 5-dimethylphenyl) -2,2',6', 2' -terpyridine in a reaction kettle for 2 hours in the presence of concentrated nitric acid and water to obtain 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid (compound 3), wherein in the step S3, the molar ratio of 4'- (3, 5-dimethylphenyl) -2,2':6',2' -terpyridine to concentrated nitric acid is 1:10, the concentration of the concentrated nitric acid is more than or equal to 33 weight percent, and the volume ratio of the concentrated nitric acid to the water is 1:3, using a polytetrafluoroethylene reaction kettle to perform reaction, wherein the heating temperature is 160 ℃, the reaction time is 2 hours, and after the reaction is finished, washing with pure water and decompressing and filtering;
s4, carrying out reflux reaction on 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid and ethanol for 8 hours under the protection of inert gas in the presence of concentrated sulfuric acid to obtain 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid ethyl ester (compound 4), wherein in the step S4, the molar ratio of 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid to ethanol is 1:200, the concentration of the concentrated sulfuric acid is more than or equal to 33 weight percent, and the volume ratio of the concentrated sulfuric acid to the ethanol is 1:30, after the reflux reaction is finished, a purification step is further included, and the specific purification step is as follows: removing ethanol by rotary evaporation of the reaction liquid after reflux, adding water into the reaction liquid, adjusting the pH to 6 by using sodium carbonate, extracting by using an organic solvent, collecting an organic phase, and drying a product obtained by rotary evaporation of the solvent;
s5, 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid ethyl ester and RuCl 3 ·3H 2 Heating and refluxing O in solvent for 0.5-10 hr to obtain Ru II (tpy-ph(COOEt) 2 Cl 3 (Compound 5), 5- (2, 2':6',2 "-terpyridine) -4' -isophthalic acid ethyl ester and RuCl in S5 3 ·3H 2 The molar ratio of O is 1:0.5, wherein the solvent for the reaction is at least one of ethanol and methanol, the temperature of the heating reflux reaction is 90 ℃, the reaction time is 1h, and the purification steps are further included after the heating reflux reaction is finished, and the specific purification steps are as follows: cooling the reaction liquid after the reaction to room temperature to obtain dark red suspension, decompressing and filtering the dark red suspension, washing a filter cake with ethanol until the filter cake has no color, and drying the obtained filter cake;
s6, ru is formed II (tpy-ph(COOEt) 2 Cl 3 Mixing 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid, a pH regulator and a solvent for a first step reaction, removing insoluble impurities from the obtained reaction solution after the reaction, and adding NH into the reaction solution 4 PF 6 The aqueous solution is subjected to a second reaction step, and stirred at normal temperature for 1min to obtain [ Ru ] II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 (Compound 6), the solvent is at least one of ethanol and methanol, the solvent for the reaction is ethanol, and the molar ratio of ethanol to 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid is 1:100, wherein the pH regulator is at least one of N-ethylmorpholine and triethylamine, the pH regulator is N-ethylmorpholine, and the pH value of the solution is regulated to be 8; the volume ratio of the N-ethylmorpholine to the solvent is 1:50,5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid and Ru II (tpy-ph(COOEt) 2 Cl 3 The molar ratio of (2) is 1:0.8, and the conditions of the first reaction are as follows: reflux heating for 0.5 h, NH 4 PF 6 The concentration of the aqueous solution is 0.1mol/L, NH 4 PF 6 The molar ratio of the catalyst to 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid is 1:2, using diatomite as a filter aid to remove insoluble impurities in the reaction liquid by decompression and filtration, and after the second step of reaction is finished, further comprising a purification process, wherein the specific purification steps are as follows: removing most of the solvent from the solution after the second step of reaction by using a rotary evaporator, remaining a small amount of red turbid liquid, performing reduced pressure filtration on the turbid liquid, washing a filter cake by using ethanol and water, and drying the filter cake;
s7, mixing the compound 6 with ethanol and sodium hydroxide aqueous solution, heating and refluxing for 2-24 hours, cooling to room temperature, regulating the pH value of the reaction solution to be less than 7 to obtain a crude product, and mixing the crude product with sulfuric acid aqueous solution and HPF 6 Mixing the aqueous solutions, stirring at room temperature for 2min, and purifying the obtained reaction solution to obtain [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 (Compound 7), in step S7, the concentration of the sodium hydroxide aqueous solution is 2mol/L, and the volume ratio of the sodium hydroxide aqueous solution to ethanol is 1:1, [ Ru ] II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 And sodium hydroxide in a molar ratio of 1:2, the conditions of the first reaction are as follows: heating to 90deg.C, refluxing for 12 hr, and adjusting pH with 3M hydrochloric acid and water mixed solution to obtain [ Ru ] II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 And HPF 6 The molar ratio of (2) is 1: the purification step 10 is to decompress and filter the obtained reaction liquid, wash the filter cake with water and dry the filter cake.
(1) Synthesis of Compound 1 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine
90mL of methanol was taken: 1.2g (33.6 mol) of sodium hydroxide, 2.5mL (18.7 mol) of 3, 5-dimethylbenzaldehyde, and a methanol solution of 20mL (2.2 g,18 mol) of 2-acetylpyridine were added to the mixture, stirred well, and the mixture was kept at 5℃for 8 hours. After the reaction was completed, the precipitate was washed with 50ml of a mixed solution of methanol and water (v/v=1:4) and suction-filtered under reduced pressure to give a pale yellow solid in 65% yield.
(2) Synthesis of Compound 24 ' - (3, 5-dimethylphenyl) -2,2':6',2 "-terpyridine
0.56g (10 mmol) of potassium hydroxide, 0.79g (3 mmol) of 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine, and 0.403mL (3 mmol) of 2-acetylpyridine were taken in a flask containing 40mL of ethanol and 25mL of ammonium hydroxide, and heated and stirred for 24 hours. After the reaction was completed, the precipitate was filtered off under reduced pressure, and recrystallized using a mixed solution of pyridine and water (v/v=2:1) as a solvent. Filtration gave 4' - (3, 5-dimethylphenyl) -2,2':6',2 "-terpyridine in 43% yield.
(3) Synthesis of Compound 3 5- (2, 2':6',2 "-terpyridine) -4' -isophthalic acid
A mixed solution of 0.218g (0.646 mmol) of 4' - (3, 5-dimethylphenyl) -2,2':6',2 "-terpyridine, water and nitric acid was taken in a polytetrafluoroethylene reaction vessel and stirred for 30min. Heated to 160℃and reacted for 24 hours. After the reaction is finished, cooling to room temperature, washing the filter cake for a plurality of times by using clear water, collecting the filter cake, and vacuum drying to obtain yellow solid, namely 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid.
(4) Synthesis of Compound 4 5- (2, 2':6',2 '-terpyridine) -4' -ethyl isophthalate
1.5g (4.45 mmol) of 5- (2, 2':6',2 "-terpyridine) -4' -isophthalic acid and 2mL of concentrated sulfuric acid were taken and added to 50mL of ethanol and refluxed for 3 days. After removing the solvent from the solution by rotary evaporator, 100mL of water was added to the residue, and the solution pH was adjusted to approximately 8 with saturated sodium carbonate solution. By CH 2 Cl 2 (50 mL. Times.3) the aqueous extracts were 3 times, the organic phases were combined, the combined organic phases were washed three times with water, the organic phases were collected and the solvent was removed by rotary evaporator and dried in vacuo to give ethyl 5- (2, 2':6',2 "-terpyridine) -4' -isophthalate in 93% yield.
The 1H NMR spectrum of compound 4 5- (2, 2':6',2 "-terpyridine) -4' -isophthalic acid ethyl ester is shown in FIG. 5, and the specific data are as follows: 1H NMR (600 MHz, chloro form-d) delta 8.79 (s, 2H), 8.77 (t, J=1.6 Hz, 1H), 8.75 (ddd, J=4.7, 1.8,0.9Hz, 2H), 8.72-8.68 (m, 4H), 7.91 (td, J=7.7, 1.8Hz, 2H), 7.39 (ddd, J=7.4, 4.8,1.2Hz, 2H), 5.30 (s, 0H), 4.48 (q, J=7.1 Hz, 4H), 1.46 (t, J=7.1 Hz, 6H).
(5) Compound 5Ru II (tpy-ph(COOEt) 2 Cl 3 Is synthesized by (a)
0.5g (1.15 mmol) of ethyl 5- (2, 2':6',2 '-terpyridine) -4' -isophthalate and RuCl were taken 3 ·3H 2 O (0.25 g,1.2 mmol) was added to 60mL of ethanol, and after refluxing with heat for 2 hours, the reaction product was cooled to room temperature to give a reddish brown cloudy solution. The cloudy solution was filtered under reduced pressure and the filter cake was washed several times until the filtered solution was a colorless liquid. Collecting the filter cake and vacuum drying to obtain brick red powder Ru II (tpy-ph(COOEt) 2 Cl 3 The yield was 79%.
(6) Compound 6 ([ Ru) II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 ) Is synthesized by (a)
Ru (Ru) II (tpy-ph(COOEt) 2 Cl 3 0.3g (0.455 mmol), 0.196g (0.45 mmol) of ethyl 5- (2, 2':6',2 "-terpyridine) -4' -isophthalate and 0.12 mL of nitrogen ethyl morpholine were charged into a pressure-resistant tube containing 20mL of ethanol, and heated under reflux for 3 hours to give a dark red solution. After the solution was cooled to room temperature, the reaction solution was filtered under reduced pressure using celite as a filter aid to remove insoluble impurities. About 3mL NH was added to the filtrate 4 PF 6 The aqueous solution was freed of most of the solvent using a rotary evaporator to give a dark red suspension. The suspension was filtered under reduced pressure and the filter cake was washed sequentially with 20mL ethanol and 10mL water, the filter cake was collected and dried in vacuo. Obtaining dark red powder which is compound 6 ([ Ru) II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 ) The yield was 97%.
Compound 6 ([ Ru) II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 ) The 1H NMR spectrum of (2) is shown in FIG. 6, and the specific data are as follows: 1H NMR (600 MHz, acetonitrile-d 3) δ9.10 (s, 4H), 9.01 (d, J=1.5 Hz, 4H), 8.85 (t, J=1.6 Hz, 2H), 8.72 (d, J=8.1 Hz, 4H), 7.99 (td, J=7.9, 1.5Hz, 4H), 7.47 (dd, J=5.8, 1.4Hz, 4H), 7.23 (ddd, J=7.1, 5.6,1.3Hz, 4H), 4.55(q,J＝7.1Hz,8H),1.51(t,J＝7.1Hz,12H)。
(7) Compound 7[ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 Is synthesized by (a)
Will ([ Ru) II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 ) (Compound 7) 0.386g (0.501 mmol) was mixed with 6mL of ethanol and 6mL of 3mol/L aqueous NaOH solution, and heated under reflux for 12h. After the reaction was cooled, the solution pH was adjusted to approximately 3 with hydrochloric acid. A dark red crude product is obtained, the crude product is mixed with 10mL of 4mol/L H SO4 aqueous solution and 10mL of 0.8mol/L NH 4 PF 6 The aqueous solutions were mixed and stirred at room temperature for 20min. The turbid liquid was filtered under reduced pressure, followed by 20mL of 0.04mol/L NH 4 PF 6 The filter cake was washed with aqueous solution and 10mL of water. Collecting the filter cake, and vacuum drying to obtain red powder [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 The yield was 91%.
Compound 7[ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 The 1H NMR spectrum of (2) is shown in FIG. 4, and specific data are 1H NMR (600 MHz, acetonitile-d 3) delta 9.08 (s, 4H), 8.99 (s, 4H), 8.81 (s, 2H), 8.69 (d, J=8.2 Hz, 4H), 7.95 (t, J=7.4 Hz, 4H), 7.43 (d, J=5.5 Hz, 4H), 7.21-7.17 (m, 4H).
In order to more clearly illustrate the invention, the invention also uses the products prepared by the above examples to perform photocatalysis experiments:
1. experiment preparation:
500mL of a 20.86mmol/L anhydrous Na2SO4,6.82mmol/L aqueous Na2HPO4 solution was prepared, stirred until completely dissolved and then the pH was adjusted to 8 using a 1mol/L NaOH solution to give a Na2HPO4/NaH2PO4 buffer solution.
2. The experimental process comprises the following steps:
the preparation method of the photocatalytic degradation mixed solution comprises the following steps: 1.2mg malachite green, 120mL Na, was added to a 250mL thick-wall beaker 2 HPO 4 /NaH 2 PO 4 And (5) buffering the solution, and uniformly stirring for standby. Another 50mL thick-wall beaker was taken and 21mg of [ Ru ] was added II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 21mL of buffer solution is subjected to ultrasonic vibration for 5min. 20mL of malachite green solution and 20mL of [ Ru ] were taken II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 The solution was mixed and stirred uniformly to obtain 0.5ppm [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 The 5ppm malachite green mixed solution is used for experiments of photocatalytic degradation of malachite green.
The experimental method for photocatalytic degradation of malachite green comprises the following steps: 40mL of the prepared mixed solution was added to the reaction vessel, and stirred under dark conditions for 30min. Immediately after 30min, 2mL of the mixed solution was taken with a disposable syringe, and filtered using a microporous filter membrane, and the collected filtrate was subjected to ultraviolet absorption test. The remaining solution was stirred under irradiation of a 300W xenon lamp to carry out photodegradation reaction. And 2mL of solution is taken every 15min after illumination, a microporous filter membrane is used for filtering, and the ultraviolet absorbance of the filtrate is tested.
Embodiment two:
the ruthenium-containing complex is characterized by comprising the following raw materials in parts by weight: bis (4 '- (3, 5-dicarboxyphenyl) -2,2',6', 2' -terpyridine) ruthenium, the ruthenium-containing complex having the formula [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 The structural formula is as follows:
the invention provides a preparation method of a ruthenium-containing complex, which comprises the following steps:
s1, mixing 3, 5-dimethylbenzaldehyde and 2-diacetylpyridine at a low temperature, adding strong base, stirring for 8 hours in a solvent to obtain a compound 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine (compound 1), wherein in the step S1, the reaction is carried out for 12 hours at a temperature of 5 ℃, the solvent is methanol and water, and the volume ratio is 2: the molar ratio of 2,3, 5-dimethylbenzaldehyde to 2-diacetylpyridine is 2.5:1, the strong base is one of potassium hydroxide and sodium hydroxide, preferably sodium hydroxide, and the mole ratio of 3, 5-dimethylbenzaldehyde to the strong base is 1: the molar ratio of 2,3, 5-dimethylbenzaldehyde to methanol is 1:150,3,5-dimethylbenzaldehyde and water in a molar ratio of 1:150, after the reaction, the mixture of methanol and water is used for decompression filtration, and the volume ratio of the methanol to the water is 1:10;
s2, heating and refluxing 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine and 2-acetylpyridine in the presence of a solvent, strong alkali and ammonium hydroxide, recrystallizing by using pyridine and water as the solvent to obtain a compound 4'- (3, 5-dimethylphenyl) -2,2':6',2' -terpyridine (compound 2), wherein in the step S2, the ammonium hydroxide concentration is set to be 30%, the heating and refluxing temperature is 60 ℃, the refluxing reaction time is 24 hours, the solvent is at least one of ethanol, methanol, acetonitrile and acetone, the strong alkali is one of sodium hydroxide and potassium hydroxide, and the volume ratio of pyridine to water is 2:5, a step of;
s3, heating 4'- (3, 5-dimethylphenyl) -2,2',6', 2' -terpyridine in the presence of concentrated nitric acid and water for 2-24 hours to obtain 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid (compound 3), wherein in the step S3, the molar ratio of 4'- (3, 5-dimethylphenyl) -2,2':6',2' -terpyridine to concentrated nitric acid is 1:15, the concentration of the concentrated nitric acid is more than or equal to 33 weight percent, and the volume ratio of the concentrated nitric acid to the water is 1:1, using a polytetrafluoroethylene reaction kettle to perform reaction, wherein the heating temperature is 160 ℃, the reaction time is 24 hours, and after the reaction is finished, washing with pure water and decompressing and filtering;
s4, carrying out reflux reaction on 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid and ethanol for 80 hours under the protection of inert gas in the presence of concentrated sulfuric acid to obtain 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid ethyl ester (compound 4), wherein in the step S4, the molar ratio of 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid to ethanol is 1:500, the concentration of the concentrated sulfuric acid is more than or equal to 33 weight percent, and the volume ratio of the concentrated sulfuric acid to the ethanol is 1:60, after the reflux reaction is finished, a purification step is further included, and the specific purification step is as follows: removing ethanol by rotary evaporation of the reaction liquid after reflux, adding water into the reaction liquid, adjusting the pH to 10 by using sodium carbonate, extracting by using an organic solvent, collecting an organic phase, and drying a product obtained by rotary evaporation of the solvent;
s5, 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid ethyl ester and RuCl 3 ·3H 2 Heating and refluxing O in solvent for 0.5-10 hr to obtain Ru II (tpy-ph(COOEt) 2 Cl 3 (Compound 5), 5- (2, 2':6',2 "-terpyridine) -4' -isophthalic acid ethyl ester and RuCl in S5 3 ·3H 2 The molar ratio of O is 1: and 5, at least one of ethanol, methanol, acetone and ethyl acetate is used as a solvent for the reaction, the temperature of the heating reflux reaction is 90 ℃, the reaction time is 5 hours, and the purification step is further included after the heating reflux reaction is finished, and the specific purification steps are as follows: cooling the reaction liquid after the reaction to room temperature to obtain dark red suspension, decompressing and filtering the dark red suspension, washing a filter cake with ethanol until the filter cake has no color, and drying the obtained filter cake;
s6, ru is formed II (tpy-ph(COOEt) 2 Cl 3 Mixing 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid, a pH regulator and a solvent for a first step reaction, removing insoluble impurities from the obtained reaction solution after the reaction, and adding NH into the reaction solution 4 PF 6 The aqueous solution is subjected to a second reaction step, and stirred at normal temperature for 40min to obtain ([ Ru) II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 ) (compound 6), the solvent is at least one of ethanol, methanol, ethyl acetate and acetonitrile, the solvent for reaction is ethanol, and the molar ratio of ethanol to 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid is 1: 100-1000, wherein the pH regulator is at least one of N-ethylmorpholine, triethylamine and ethylenediamine, the pH regulator is N-ethylmorpholine, and the pH value of the solution is regulated to be 9; the volume ratio of the N-ethylmorpholine to the solvent is 1:500,5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid and Ru II (tpy-ph(COOEt) 2 Cl 3 The molar ratio of (2) is 1:2, and the conditions of the first reaction are as follows: heating and refluxing for 3 hours, NH 4 PF 6 The concentration of the aqueous solution is 5mol/L, NH 4 PF 6 The molar ratio of the catalyst to 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid is 1:5 use of diatomaceous earth as a Filter aidThe solution is filtered under reduced pressure to remove insoluble impurities in the reaction solution, and the second step of reaction further comprises a purification process after the end of the second step of reaction, wherein the specific purification steps are as follows: removing most of the solvent from the solution after the second step of reaction by using a rotary evaporator, remaining a small amount of red turbid liquid, performing reduced pressure filtration on the turbid liquid, washing a filter cake by using ethanol and water, and drying the filter cake;
s7, mixing the compound 6 with ethanol and sodium hydroxide aqueous solution, heating and refluxing for 2-24 hours, cooling to room temperature, regulating the pH value of the reaction solution to be less than 7 to obtain a crude product, and mixing the crude product with sulfuric acid aqueous solution and HPF 6 Mixing the aqueous solutions, stirring at room temperature for 45min, and purifying the obtained reaction solution to obtain [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 (Compound 7), in step S7, the concentration of the sodium hydroxide aqueous solution is 2-8 mol/L, and the volume ratio of the sodium hydroxide aqueous solution to the ethanol is 1:1, [ Ru ] II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 And sodium hydroxide in a molar ratio of 1:100, the conditions of the first reaction are: heating to 90deg.C, refluxing for 12 hr, and adjusting pH with 3M hydrochloric acid and water mixed solution to obtain [ Ru ] II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 And HPF 6 The molar ratio of (2) is 1:50, purifying means that the obtained reaction liquid is decompressed and filtered, and then a filter cake is washed by water, and the filter cake is dried.
(1) Synthesis of Compound 1 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine
90mL of methanol was taken: 1.2g (33.6 mol) of sodium hydroxide, 2.5mL (18.7 mol) of 3, 5-dimethylbenzaldehyde, and a methanol solution of 20mL (2.2 g,18 mol) of 2-acetylpyridine were added to the mixture, stirred well, and the mixture was kept at 5℃for 8 hours. After the reaction was completed, the precipitate was washed with 50ml of a mixed solution of methanol and water (v/v=1:4) and suction-filtered under reduced pressure to give a pale yellow solid in 65% yield.
(2) Synthesis of Compound 24 ' - (3, 5-dimethylphenyl) -2,2':6',2 "-terpyridine
0.56g (10 mmol) of potassium hydroxide, 0.79g (3 mmol) of 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine, and 0.403mL (3 mmol) of 2-acetylpyridine were taken in a flask containing 40mL of ethanol and 25mL of ammonium hydroxide, and heated and stirred for 24 hours. After the reaction was completed, the precipitate was filtered off under reduced pressure, and recrystallized using a mixed solution of pyridine and water (v/v=2:1) as a solvent. Filtration gave 4' - (3, 5-dimethylphenyl) -2,2':6',2 "-terpyridine in 43% yield.
(3) Synthesis of Compound 3 5- (2, 2':6',2 "-terpyridine) -4' -isophthalic acid
A mixed solution of 0.218g (0.646 mmol) of 4' - (3, 5-dimethylphenyl) -2,2':6',2 "-terpyridine, water and nitric acid was taken in a polytetrafluoroethylene reaction vessel and stirred for 30min. Heated to 160℃and reacted for 24 hours. After the reaction is finished, cooling to room temperature, washing the filter cake for a plurality of times by using clear water, collecting the filter cake, and vacuum drying to obtain yellow solid, namely 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid.
(4) Synthesis of Compound 4 5- (2, 2':6',2 '-terpyridine) -4' -ethyl isophthalate
1.5g (4.45 mmol) of 5- (2, 2':6',2 "-terpyridine) -4' -isophthalic acid and 2mL of concentrated sulfuric acid were taken and added to 50mL of ethanol and refluxed for 3 days. After removing the solvent from the solution by rotary evaporator, 100mL of water was added to the residue, and the solution pH was adjusted to approximately 8 with saturated sodium carbonate solution. The aqueous solution was extracted 3 times with CH2Cl2 (50 mL. Times.3), the organic phases were combined, the combined organic phases were washed three times with water, the organic phases were collected and the solvent was removed by rotary evaporation, and dried in vacuo to give ethyl 5- (2, 2':6',2 "-terpyridine) -4' -isophthalate in 93% yield.
The 1H NMR spectrum of compound 4 5- (2, 2':6',2 "-terpyridine) -4' -isophthalic acid ethyl ester is shown in FIG. 5, and the specific data are as follows: 1H NMR (600 MHz, chloro form-d) delta 8.79 (s, 2H), 8.77 (t, J=1.6 Hz, 1H), 8.75 (ddd, J=4.7, 1.8,0.9Hz, 2H), 8.72-8.68 (m, 4H), 7.91 (td, J=7.7, 1.8Hz, 2H), 7.39 (ddd, J=7.4, 4.8,1.2Hz, 2H), 5.30 (s, 0H), 4.48 (q, J=7.1 Hz, 4H), 1.46 (t, J=7.1 Hz, 6H).
(5) Compound 5Ru II (tpy-ph(COOEt) 2 Cl 3 Is synthesized by (a)
Taking 5- (2, 2':6',2 '-terpyridine) -4'Ethyl isophthalate 0.5g (1.15 mmol) and RuCl 3 ·3H 2 O (0.25 g,1.2 mmol) was added to 60mL of ethanol, and after refluxing with heat for 2 hours, the reaction product was cooled to room temperature to give a reddish brown cloudy solution. The cloudy solution was filtered under reduced pressure and the filter cake was washed several times until the filtered solution was a colorless liquid. Collecting the filter cake and vacuum drying to obtain brick red powder Ru II (tpy-ph(COOEt) 2 Cl 3 The yield was 79%.
(6) Compound 6 ([ Ru) II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 ) Is synthesized by (a)
Ru (Ru) II (tpy-ph(COOEt) 2 Cl 3 0.3g (0.455 mmol), 0.196g (0.45 mmol) of ethyl 5- (2, 2':6',2 "-terpyridine) -4' -isophthalate and 0.12 mL of nitrogen ethyl morpholine were charged into a pressure-resistant tube containing 20mL of ethanol, and heated under reflux for 3 hours to give a dark red solution. After the solution was cooled to room temperature, the reaction solution was filtered under reduced pressure using celite as a filter aid to remove insoluble impurities. About 3mL NH was added to the filtrate 4 PF 6 The aqueous solution was freed of most of the solvent using a rotary evaporator to give a dark red suspension. The suspension was filtered under reduced pressure and the filter cake was washed sequentially with 20mL ethanol and 10mL water, the filter cake was collected and dried in vacuo. The dark red powder is obtained as (Ru) II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 ) The yield was 97%.
Compound 6 ([ Ru) II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 ) The 1H NMR spectrum of (2) is shown in FIG. 6, and the specific data are as follows: 1H NMR (600 MHz, acetonitrile-d 3) δ9.10 (s, 4H), 9.01 (d, J=1.5 Hz, 4H), 8.85 (t, J=1.6 Hz, 2H), 8.72 (d, J=8.1 Hz, 4H), 7.99 (td, J=7.9, 1.5Hz, 4H), 7.47 (dd, J=5.8, 1.4Hz, 4H), 7.23 (ddd, J=7.1, 5.6,1.3Hz, 4H), 4.55 (q, J=7.1 Hz, 8H), 1.51 (t, J=7.1 Hz, 12H).
(7) Compound 7[ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 Is synthesized by (a)
Will ([ Ru) II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 ) (Compound 6) 0.386g (0.501 mmol) was mixed with 6mL of ethanol and 6mL of 3mol/L aqueous NaOH solution, and heated under reflux for 12h. After the reaction was cooled, the solution pH was adjusted to approximately 3 with hydrochloric acid. A dark red crude product is obtained, the crude product is mixed with 10mL of 4mol/L H SO4 aqueous solution and 10mL of 0.8mol/L NH 4 PF 6 The aqueous solutions were mixed and stirred at room temperature for 20min. The turbid liquid was filtered under reduced pressure, followed by 20mL of 0.04mol/L NH 4 PF 6 The filter cake was washed with aqueous solution and 10mL of water. Collecting the filter cake, and vacuum drying to obtain red powder [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 The yield was 91%.
Compound 7[ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 Specific 1H NMR spectrum data of (1) HNMR (600 MHz, acetonitile-d 3) δ9.08 (s, 4H), 8.99 (s, 4H), 8.81 (s, 2H), 8.69 (d, J=8.2 Hz, 4H), 7.95 (t, J=7.4 Hz, 4H), 7.43 (d, J=5.5 Hz, 4H), 7.21-7.17 (m, 4H).
In order to more clearly illustrate the invention, the invention also uses the products prepared by the above examples to perform photocatalysis experiments:
1. experiment preparation:
500mL of a 20.86mmol/L anhydrous Na2SO4,6.82mmol/L aqueous Na2HPO4 solution was prepared, stirred to complete dissolution and then the pH was adjusted to 8 using a 1mol/LNaOH solution to give a Na2HPO4/NaH2PO4 buffer solution.
2. The experimental process comprises the following steps:
the preparation method of the photocatalytic degradation mixed solution comprises the following steps: 1.2mg of malachite green and 120mL of Na2HPO4/NaH2PO4 buffer solution were added to a 250mL thick-wall beaker and stirred well for use. Another 50mL thick-wall beaker was taken and 21mg of [ Ru ] was added II (tpy-ph(COO-) 2 ) 2 ](PF 6 ) 2 21mL of buffer solution is subjected to ultrasonic vibration for 5min. 20mL of malachite green solution and 20mL of [ Ru ] were taken II (tpy-ph(COO-) 2 ) 2 ](PF 6 ) 2 The solution was mixed and stirred uniformly to obtain 0.5ppm [ Ru ] II (tpy-ph(COO-) 2 ) 2 ](PF 6 ) 2 5ppm malachite green mixed solution for lightAnd (5) carrying out a catalytic degradation malachite green experiment.
The experimental method for photocatalytic degradation of malachite green comprises the following steps: 40mL of the prepared mixed solution was added to the reaction vessel, and stirred under dark conditions for 30min. Immediately after 30min, 2mL of the mixed solution was taken with a disposable syringe, and filtered using a microporous filter membrane, and the collected filtrate was subjected to ultraviolet absorption test. The remaining solution was stirred under irradiation of a 300W xenon lamp to carry out photodegradation reaction. And 2mL of solution is taken every 15min after illumination, a microporous filter membrane is used for filtering, and the ultraviolet absorbance of the filtrate is tested.
The ruthenium-containing complex prepared by the embodiment of the invention can be used as a photosensitizer, solves the problems that secondary waste is generated and cannot be poured when wastewater is treated by the traditional method, reduces the economic cost of wastewater treatment, reduces the time consumed during treatment, and further improves the treatment effect of the waste in the wastewater by degrading dye in the wastewater and cleaning the environment. The invention synthesizes a novel carboxyl substituted nitrogen-containing heterocyclic ligand and a ruthenium complex thereof, takes the ruthenium-containing complex as a photosensitizer, and performs preliminary study on the performance of the ruthenium-containing complex in photocatalytic degradation of malachite green to obtain the novel carboxyl substituted multidentate nitrogen-containing heterocyclic ligand and the ruthenium complex thereof with certain photocatalytic performance.
Other embodiments, which are specifically selected within the ranges of the components, the proportions and the processes described in the above embodiments of the present invention, can achieve the technical effects described in the present invention, and therefore, they are not listed one by one.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A ruthenium-containing complex is characterized in that the molecular formula of the ruthenium-containing complex is [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 The structural formula is as follows:
。
2. the method for preparing the ruthenium-containing complex according to claim 1, wherein the preparation raw material comprises bis (4 '- (3, 5-dicarboxylic acid phenyl) -2,2',6', 2' -terpyridine) ruthenium, and the method specifically comprises the following steps:
s1, mixing 3, 5-dimethylbenzaldehyde and 2-diacetylpyridine at a low temperature, adding strong base, and stirring for 8 hours under a solvent to obtain a compound 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine, namely a compound 1;
s2, heating and refluxing 3- (3 ',5' -dimethylphenyl) -cinnamoyl pyridine and 2-acetylpyridine in the presence of a solvent, strong alkali and ammonium hydroxide, and recrystallizing by using pyridine and water as the solvent to obtain a compound 4'- (3, 5-dimethylphenyl) -2,2':6',2' -terpyridine, namely a compound 2;
s3, heating 4'- (3, 5-dimethylphenyl) -2,2',6', 2' -terpyridine in a reaction kettle for 2-24 hours in the presence of concentrated nitric acid and water to obtain 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid, namely a compound 3;
s4, under the protection of inert gas, carrying out reflux reaction on 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid and ethanol for 8-80 hours in the presence of concentrated sulfuric acid to obtain 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid ethyl ester, namely a compound 4;
s5, 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid ethyl ester and RuCl 3 ·3H 2 The reaction of O in a solvent under reflux with heating for 0.5-10h gives RuII (tpy-ph (COOEt) 2 Cl 3 ) Namely compound 5;
s6, ru is formed II (tpy-ph(COOEt) 2 Cl 3 ) Mixing 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid, a pH regulator and a solvent for a first step reaction, removing insoluble impurities from the obtained reaction solution after the reaction, and adding NH into the reaction solution 4 PF 6 Aqueous solution ofThe second step of reaction, stirring for 1-40min at normal temperature to obtain (Ru) II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 ) I.e. compound 6;
s7, mixing the compound 6 with ethanol and sodium hydroxide aqueous solution, heating and refluxing for 2-24 hours, cooling to room temperature, regulating the pH value of the reaction solution to be less than 7 to obtain a crude product, and mixing the crude product with sulfuric acid aqueous solution and HPF 6 Mixing the aqueous solutions, stirring for 2-45 min at room temperature, and purifying the obtained reaction solution to obtain [ Ru ] II (tpy-ph(COO - ) 2 ) 2 ](PF 6 ) 2 I.e. compound 7.
3. The method for preparing ruthenium complex according to claim 2, wherein in the step S1, the reaction is performed at 0-5 ℃ for 8 hours with stirring, and the solvent is methanol and water with a volume ratio of 2: (0.5-2), the mole ratio of 3, 5-dimethylbenzaldehyde to 2-diacetylpyridine is (2-2.5): 1, the strong alkali is one of potassium hydroxide and sodium hydroxide, and the mol ratio of 3, 5-dimethylbenzaldehyde to the strong alkali is 1: (1.8-2), the mole ratio of 3, 5-dimethylbenzaldehyde to methanol is 1: (50-150), the mole ratio of 3, 5-dimethylbenzaldehyde to water is 1: (50-150), after the reaction, the mixed solution of methanol and water is used for decompression filtration, and the volume ratio of the methanol to the water is 1: (0.5-10).
4. The method for preparing ruthenium-containing complex according to claim 2, wherein in the step S2, the ammonium hydroxide concentration is set to 30%, the heating reflux temperature is 60 ℃, the reflux reaction time is 2-24 hours, the solvent is at least one of ethanol, methanol, acetonitrile and acetone, the strong base is one of sodium hydroxide and potassium hydroxide, and the volume ratio of pyridine to water is 2: (0.5-5).
5. The method for preparing a ruthenium complex according to claim 2, wherein in the step S3, the molar ratio of 4' - (3, 5-dimethylphenyl) -2,2':6',2 "-terpyridine to concentrated nitric acid is 1:10-15, the concentration of the concentrated nitric acid is more than or equal to 33 weight percent, and the volume ratio of the concentrated nitric acid to water is 1:3-1, using a polytetrafluoroethylene reaction kettle to carry out reaction, wherein the heating temperature is 160 ℃, the reaction time is 2-24 hours, and after the reaction is finished, washing with pure water and decompressing and filtering.
6. The method for preparing a ruthenium complex according to claim 2, wherein in the step S4, the molar ratio of 5- (2, 2':6',2 "-terpyridine) -4' -isophthalic acid to ethanol is 1: 200-500, the concentration of the concentrated sulfuric acid is more than or equal to 33wt%, and the volume ratio of the concentrated sulfuric acid to the ethanol is 1: (30-60), the method further comprises a purification step after the reflux reaction is finished, wherein the specific purification step is as follows: and (3) removing ethanol by rotary evaporation of the reaction liquid after the reflux, adding water into the reaction liquid, adjusting the pH to 6-10 by using sodium carbonate, extracting by using an organic solvent, collecting an organic phase, and drying a product obtained by rotary evaporation of the solvent.
7. The method for producing ruthenium complex according to claim 2, wherein in the step S5, ethyl 5- (2, 2':6',2 "-terpyridine) -4' -isophthalate and RuCl are used 3 ·3H 2 The molar ratio of O is 1: (0.5-5), wherein the solvent for the reaction is at least one of ethanol, methanol, acetone and ethyl acetate, the temperature of the heating reflux reaction is 90 ℃, the reaction time is 1-5 h, and the purification step is further included after the heating reflux reaction is finished, and the specific purification steps are as follows: and cooling the reaction solution after the reaction is finished to room temperature to obtain a dark red suspension, decompressing and filtering the dark red suspension, washing a filter cake with ethanol until the filter cake has no color, and drying the obtained filter cake.
8. The method for preparing ruthenium complex according to claim 2, wherein in the step S6, the solvent is ethanol, and the molar ratio of ethanol to 5- (2, 2':6',2 "-terpyridine) -4' -isophthalic acid is 1: 100-1000; the pH regulator is N-ethylmorpholine, and the pH value of the solution is regulated to be 8-9; the volume ratio of the N-ethylmorpholine to the solvent is 1:50-500,5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid and Ru II (tpy-ph(COOEt) 2 Cl 3 ) The molar ratio of (1) (0.8-2), the conditions of the first reaction are as follows: heating and refluxing for 0.5-3 hours, NH 4 The concentration of the PF6 aqueous solution is 0.1-5 mol/L, NH 4 PF 6 The molar ratio of the catalyst to 5- (2, 2':6',2 '-terpyridine) -4' -isophthalic acid is 1: (2-5), using diatomite as a filter aid to remove insoluble impurities in the reaction liquid by decompression filtration, and after the second step of reaction, further comprising a purification process, wherein the specific purification steps are as follows: and (3) removing most of the solvent from the solution after the reaction in the second step by using a rotary evaporator, remaining a small amount of red turbid liquid, carrying out reduced pressure filtration on the turbid liquid, washing a filter cake by using ethanol and water, and drying the filter cake.
9. The method according to claim 2, wherein in the step S7, the concentration of the aqueous sodium hydroxide solution is 2 to 8mol/L, and the volume ratio of the aqueous sodium hydroxide solution to ethanol is 1:1, [ Ru ] II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 And sodium hydroxide in a molar ratio of 1: (2-100), the conditions of the first reaction are as follows: heating to 90deg.C, refluxing for 12 hr, and adjusting pH with 3M hydrochloric acid and water mixed solution to obtain [ Ru ] II (tpy-ph(COOEt) 2 ) 2 ](PF 6 ) 2 And HPF 6 The molar ratio of (2) is 1: (10-50), purifying means that the obtained reaction liquid is filtered under reduced pressure, and then the filter cake is washed with water and dried.
10. Use of a ruthenium-containing complex according to claim 1 as a photosensitizer in the field of photocatalytic degradation.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102004099A (en) * | 2010-09-17 | 2011-04-06 | 大连理工大学 | Method for detecting malachite green through electrochemiluminescence |
| CN102617647A (en) * | 2012-02-28 | 2012-08-01 | 中山大学 | Terpyridyl ruthenium coordination compound, and preparation method and application thereof |
| CN102923696A (en) * | 2011-08-10 | 2013-02-13 | 中国科学院理化技术研究所 | Method for preparing graphene through photo-catalysis |
| CN104231001A (en) * | 2014-09-05 | 2014-12-24 | 昆明理工大学 | Symmetrical binuclear ruthenium complex and preparation method utilizing microwave |
| WO2015163440A1 (en) * | 2014-04-25 | 2015-10-29 | 高砂香料工業株式会社 | Ruthenium complex, method for producing same, and use of same |
| CN105669764A (en) * | 2016-01-04 | 2016-06-15 | 辽宁大学 | Ruthenium complex containing bisphenol hydroxyl azo naphthol structure and synthesis method and application thereof |
| CN110540656A (en) * | 2019-09-30 | 2019-12-06 | 河南工业大学 | Preparation method and application of photoinduced electron transfer supramolecular nanoparticles |
| CN114195827A (en) * | 2020-09-02 | 2022-03-18 | 广州大学 | Carboxyl substituted ruthenium complex and preparation method and application thereof |
-
2022
- 2022-06-14 CN CN202210669612.4A patent/CN115197127B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102004099A (en) * | 2010-09-17 | 2011-04-06 | 大连理工大学 | Method for detecting malachite green through electrochemiluminescence |
| CN102923696A (en) * | 2011-08-10 | 2013-02-13 | 中国科学院理化技术研究所 | Method for preparing graphene through photo-catalysis |
| CN102617647A (en) * | 2012-02-28 | 2012-08-01 | 中山大学 | Terpyridyl ruthenium coordination compound, and preparation method and application thereof |
| WO2015163440A1 (en) * | 2014-04-25 | 2015-10-29 | 高砂香料工業株式会社 | Ruthenium complex, method for producing same, and use of same |
| CN104231001A (en) * | 2014-09-05 | 2014-12-24 | 昆明理工大学 | Symmetrical binuclear ruthenium complex and preparation method utilizing microwave |
| CN105669764A (en) * | 2016-01-04 | 2016-06-15 | 辽宁大学 | Ruthenium complex containing bisphenol hydroxyl azo naphthol structure and synthesis method and application thereof |
| CN110540656A (en) * | 2019-09-30 | 2019-12-06 | 河南工业大学 | Preparation method and application of photoinduced electron transfer supramolecular nanoparticles |
| CN114195827A (en) * | 2020-09-02 | 2022-03-18 | 广州大学 | Carboxyl substituted ruthenium complex and preparation method and application thereof |
Non-Patent Citations (10)
| Title |
|---|
| Aromatic Amines as Co-sensitizers in Dye Sensitized Titania Solar Cells;Russell Gaudiana et al.;《JOURNAL OF MACROMOLECULAR SCIENCE》;第A40卷(第12期);第1295-1306页 * |
| Biljana Bozic-Weber et al..《Chem. Commun.》.2012,第48卷第5727-5729页. * |
| Catechol-Pendant Terpyridine Complexes: Electrodeposition Studies and Electrocatalysis of NADH Oxidation;Gregory D. Storrier et al.;《Inorg. Chem.》;第38卷;第559-565页 * |
| Development of a Ru complex-incorporated MOF photocatalyst for hydrogen production under visible-light irradiation;Takashi Toyao et al.;《Chem. Commun.》;第50卷;第6779-6781页 * |
| Modification of electron transfer properties in photoelectrochemical solar cells by substituting {Ru(terpy) 2 } 2þ dyes with thiophene;Egbert Figgemeier et al.;《Inorganic Chemistry Communications》;第7卷;第117-121页 * |
| New carboxy-functionalized terpyridines as precursors for zwitterionic ruthenium complexes for polymer-based solar cells;Virginie Duprez et al.;《Tetrahedron Letters》;第47卷;第3785-3789页 * |
| Rigid Linear and Star-Shaped ð-Conjugated 2,2′:6′,2′′-Terpyridine Ligands with Blue Emission;Si-Chun Yuan et al.;《Org. Lett.》;第8卷(第25期);第5701-5704页 * |
| Synthesis and Properties of Acridine and Acridinium Dye Functionalized Bis(terpyridine) Ruthenium(II) Complexes;Jens Eberhard et al.;《Eur. J. Org. Chem.》;第2682-2700页 * |
| 含钌(Ⅱ) 光敏配合物的合成及性能研究;张立攀 等;《化学研究与应用》;第29卷(第7期);第1025-1029页 * |
| 孔雀石绿-KIO4催化动力学光度法测定痕量钌;王洪福 等;《分析试验室》;第28卷(第8期);第90-93页 * |
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