CN114685535B - Carboxyl substituted ruthenium complex and preparation method and application thereof - Google Patents
Carboxyl substituted ruthenium complex and preparation method and application thereof Download PDFInfo
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- CN114685535B CN114685535B CN202111054250.XA CN202111054250A CN114685535B CN 114685535 B CN114685535 B CN 114685535B CN 202111054250 A CN202111054250 A CN 202111054250A CN 114685535 B CN114685535 B CN 114685535B
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- 239000012327 Ruthenium complex Substances 0.000 title claims abstract description 34
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims abstract description 10
- VJPQAOIOTKBTBM-UHFFFAOYSA-N ethyl 2,6-bis(1,8-naphthyridin-2-yl)pyridine-4-carboxylate Chemical compound CCOC(C1=CC(C2=NC3=NC=CC=C3C=C2)=NC(C2=NC3=NC=CC=C3C=C2)=C1)=O VJPQAOIOTKBTBM-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 87
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000007864 aqueous solution Substances 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- -1 carboxyl-substituted ruthenium Chemical class 0.000 claims description 25
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 12
- 229940126214 compound 3 Drugs 0.000 claims description 12
- 229940095102 methyl benzoate Drugs 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 11
- 229940125782 compound 2 Drugs 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 229940107700 pyruvic acid Drugs 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- HVCNXQOWACZAFN-UHFFFAOYSA-N 4-ethylmorpholine Chemical compound CCN1CCOCC1 HVCNXQOWACZAFN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 229940125898 compound 5 Drugs 0.000 claims description 4
- NXMFJCRMSDRXLD-UHFFFAOYSA-N 2-aminopyridine-3-carbaldehyde Chemical compound NC1=NC=CC=C1C=O NXMFJCRMSDRXLD-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000012264 purified product Substances 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims 1
- 239000003504 photosensitizing agent Substances 0.000 abstract description 9
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 12
- 239000012065 filter cake Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000000746 purification Methods 0.000 description 11
- 239000012043 crude product Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229960005070 ascorbic acid Drugs 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 4
- 239000011668 ascorbic acid Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229960001701 chloroform Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- MCRPKBUFXAKDKI-UHFFFAOYSA-N ethyl pyridine-4-carboxylate Chemical compound CCOC(=O)C1=CC=NC=C1 MCRPKBUFXAKDKI-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 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
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000004424 polypyridyl Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- 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
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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Abstract
The invention belongs to the field of photosensitizers, and discloses a carboxyl substituted ruthenium complex and a preparation method and application thereof. The invention designs and synthesizes a novel carboxyl-substituted polydentate nitrogen-containing heterocyclic ligand and a ruthenium complex thereof, and compounds 2,6-di (1,8-naphthyridin-2-yl) isonicotinic acid ethyl ester and [ Ru III py(COOEt)(bny) 2 ]Cl 3 And then synthesizing [ Ru ] with the two compounds II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 Namely a carboxyl substituted ruthenium complex. The carboxyl substituted ruthenium complex has great potential in photocatalytic reactions related to energy sources, such as photocatalytic water reduction hydrogen production, photocatalytic carbon dioxide and the like.
Description
Technical Field
The invention belongs to the field of photosensitizers, and particularly relates to a carboxyl substituted ruthenium complex, and a preparation method and application thereof.
Background
With the rapid consumption of traditional energy resources by human society, energy shortage and environmental pollution become important factors restricting the sustainable development of human society, and the construction of a clean and environment-friendly renewable new energy system becomes an important strategy and focus of attention of each country. Among a plurality of green, environment-friendly and sustainable new energy development technical routes, the photocatalytic reaction is one of the most promising methods for solving the energy and environmental problems. The photocatalytic reaction is an oxidation-reduction reaction in which a photocatalytic system is excited by light energy and passes through an excited state of a compound or a material. According to different purposes, the photocatalysis can be applied to the fields of synthesis of solar fuel, conversion of carbon dioxide, degradation of pollutants and the like. When the photocatalysis is applied to practical production, a photosensitizer (also called as a light trapping agent) is one of important components of a photocatalysis system, and the light trapping capacity of the photosensitizer in the photocatalysis system directly determines the performance of a photocatalysis reaction.
The complex compound taking nitrogen-containing heterocycle as organic ligand and metallic ruthenium (Ru) element as center is widely applied to photocatalytic reaction research as photosensitizer. The photosensitizer can absorb visible light to form an excited state with higher oxidation or reduction activity, has very long excited state service life, and is beneficial to the implementation of a photocatalytic reaction. The common nitrogen heterocyclic ligand of the metal ruthenium complex is a polybipyridine compound, including 2,2 '-bipyridine, 2,2' -o-phenanthroline, terpyridine and the like. The polypyridyl compound as the ruthenium complex ligand has the advantages of having wide organic synthesis modification potential and being capable of adjusting the physicochemical property of the ruthenium complex photosensitizer through ligand modification. Designing and synthesizing novel organic ligands and corresponding ruthenium complexes thereof is an effective way for optimizing and applying photocatalytic reactions.
Disclosure of Invention
The invention aims to provide a carboxyl substituted ruthenium complex with a novel ligand structure.
Another object of the present invention is to provide a process for producing the above carboxyl-substituted ruthenium complex.
The invention further aims to provide the application of the carboxyl substituted ruthenium complex as a photosensitizer in photocatalytic hydrogen production.
The purpose of the invention is realized by the following scheme:
carboxyl substituted ruthenium complex, namely bis (2,6-bis (1,8-naphthyridin-2-yl) pyridine-4-carboxylic acid) ruthenium ([ Ru II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 ) The concrete structure is as follows:
[Ru II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2
a preparation method of the carboxyl-substituted ruthenium complex comprises the following steps:
(1) Adding methyl isonicotinate and pyruvic acid into a sulfuric acid aqueous solution, and then adding a catalyst and an oxidant to react to obtain a compound 1 (2,6-diacetyl methyl benzoate);
(2) Under the protection of inert gas, 2,6-diacetyl methyl benzoate, 2-amino-3-pyridine formaldehyde, ethanol and pyrrolidine are mixed and then react to obtain a compound 2, 6-bis (1,8-naphthyridin-2-yl) ethyl isonicotinate ];
(3) 2,6-bis (1,8-naphthyridin-2-yl) isonicotinic acid ethyl ester and RuCl 3 ·3H 2 O is reacted to obtain the compound 3[ Ru ]) III py(COOEt)(bny) 2 ]Cl 3 ；
(4) Mixing the compound 2, the compound 3, a pH regulator and a solvent for carrying out a first-step reaction, removing insoluble impurities from the obtained reaction liquid after the reaction is finished, and then adding NH into the reaction liquid 4 PF 6 The aqueous solution is subjected to the second-step reaction to obtain a compound of 4[ Ru ]) II (py(COOEt)(bny) 2 ) 2 ](PF 6 ) 2 ；
(5) Mixing the compound 4 with ethanol and sodium hydroxide aqueous solution for the first step reaction, purifying the obtained product, and then mixing the purified product with sulfuric acid aqueous solution and NH 4 PF 6 Mixing the aqueous solution to carry out the second reaction to obtain the compound 5[ Ru ]) II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 。
The concentration of the sulfuric acid aqueous solution in the step (1) is 0.1-2 mol/L;
the dosage of the methyl isonicotinate, the pyruvic acid and the sulfuric acid aqueous solution in the step (1) meets the following requirements: the molar ratio of the methyl isonicotinate to the pyruvic acid is 1.5-5.5; the volume ratio of the methyl isonicotinate to the sulfuric acid aqueous solution is 1; the volume ratio of the pyruvic acid to the sulfuric acid aqueous solution is 1.
In the step (1), the oxidant is at least one of ammonium persulfate, potassium persulfate and sodium persulfate, preferably ammonium persulfate.
The catalyst in the step (1) is silver nitrate solution, and the concentration of the silver nitrate solution is 0.1-1.5 mol/L;
the dosage of the catalyst and the oxidant in the step (1) meets the following requirements: the molar ratio of silver nitrate to oxidant in the catalyst is 1; the molar ratio of the methyl isonicotinate to the oxidant is 1:1-8.
The reaction in step (1) is stirred at room temperature for 6-18h, preferably 12h.
The method also comprises an extraction step and a purification step after the reaction in the step (1) is finished.
The extraction steps are as follows: extracting the reaction solution after the reaction is finished by dichloromethane, combining organic phases and then using saturated Na 2 CO 3 The solution was extracted with saturated brine and the organic phase was collected. Wherein the reaction solution, dichloromethane and saturated Na 2 CO 3 The volume ratio of the saturated saline solution is 1.1-0.5: 0.01 to 0.2:0.01 to 0.2.
The purification steps are as follows: and removing water from the collected organic phase after extraction by using anhydrous magnesium sulfate, filtering under reduced pressure, removing the solvent by rotary evaporation to obtain a yellow solid crude product, recrystallizing the crude product by using methanol, filtering, washing the recrystallized crude product by using methanol, and drying the washed recrystallized crude product to obtain the purified compound 1, 6-diacetyl methyl benzoate.
The molar ratio of 2,6-diacetylbenzoic acid methyl ester and 2-amino-3-pyridinecarbaldehyde in the step (2) is 1:1 to 5; the molar ratio of 2,6-diacetyl methyl benzoate to ethanol is 1; the molar ratio of 2,6-diacetyl methyl benzoate to pyrrolidine is 1:1-10.
The reaction in the step (2) is heated and refluxed for 20-48h, and is preferably heated and refluxed for 40h at 90 ℃.
The method further comprises a purification step after the reaction in the step (2), wherein the purification step comprises the following steps: cooling the reaction liquid after the reaction to room temperature, removing the solvent by rotary evaporation to obtain a light brown solid, adding trichloromethane and ethanol into the light brown solid, heating to dissolve the solid, then adding a large amount of diethyl ether to form a precipitate, filtering under reduced pressure, washing the precipitate by using a mixed solution of trichloromethane and diethyl ether, and drying the washed precipitate to obtain the purified compound 2, 6-bis (1,8-naphthyridin-2-yl) ethyl isonicotinate.
2,6-bis (1,8-naphthyridin-2-yl) isonicotinic acid ethyl ester and RuCl described in step (3) 3 ·3H 2 The molar ratio of O is 1.
The solvent for the reaction in the step (3) is at least one of ethanol, methanol, acetone and ethyl acetate, preferably ethanol; the reaction is heating reflux for 0.5-8h.
The method further comprises a purification step after the reaction in the step (3), wherein the purification step comprises the following steps: cooling the reaction solution after the reaction to room temperature to obtain a dark green turbid solution, filtering the dark green turbid solution under reduced pressure, washing the filter cake with ethanol until the filtrate is light green in color, and drying the obtained filter cake to obtain the purified compound 3[ Ru ], III py(COOEt)(bny) 2 ]Cl 3 。
in the step (4), the solvent is at least one of ethanol, methanol and ethyl acetate, preferably ethanol; the pH regulator is at least one of N-ethyl morpholine, triethylamine and ethylenediamine, preferably N-ethyl morpholine, and the pH of the solution is regulated to be 8-9; the volume ratio of the pH adjuster to the solvent is preferably 1.
The mol ratio of the compound 2 to the compound 3 in the step (4) is 0.5 to 2:1;
the first step reaction in the step (4) is carried out under the condition of stirring and microwave heating to 100-190 ℃ for 1-60min, preferably 160 ℃ for 10min.
NH described in step (4) 4 PF 6 The concentration of the aqueous solution is 0.1-5 mol/L, NH 4 PF 6 The molar ratio of the compound to the compound 3 is 1 to 5:1.
The step (4) of removing insoluble impurities from the reaction solution refers to filtering under reduced pressure by using diatomite as a filter aid to remove insoluble impurities;
the second step reaction condition in the step (4) is that the mixture is stirred for 1-15min at room temperature.
The step (4) further comprises a purification step after the second-step reaction is finished, and the specific purification step is as follows: the solution after the second step reaction is used for spinningRemoving most of the solvent by using a rotary evaporator, leaving a small amount of deep red turbid liquid, filtering the turbid liquid under reduced pressure, washing a filter cake by using ethanol and water in sequence, and drying the filter cake to obtain the purified compound 4[ Ru II (py(COOEt)(bny) 2 ) 2 ](PF 6 ) 2 。
The compound 4 and the ethanol and sodium hydroxide aqueous solution in the step (5) are used in the following amounts: 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, ethanol and water are used as solvents, and the molar ratio of the compound 4 to the sodium hydroxide is 1:5-80.
The first step of reaction in the step (5) is heating reflux for 2-24h.
The second step of reaction in the step (5) is carried out under the condition of stirring at room temperature for 2-45 min.
The purification after the first-step reaction in the step (5) is specifically performed as follows: and (3) cooling the reaction liquid obtained after the first-step reaction to room temperature, adjusting the pH of the reaction liquid to be less than 7, and removing the solvent by rotary evaporation.
The step (5) further comprises a purification step after the second-step reaction is finished, and the specific purification step is as follows: filtering the reaction liquid obtained after the second step reaction is finished under reduced pressure, and sequentially using NH 4 PF 6 The water solution and the water wash filter cake, and the compound [ 5 ], [ Ru ] is obtained after the filter cake is dried II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2
The carboxyl substituted ruthenium complex [ Ru II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 The synthetic route of (2) is shown in FIG. 1.
The carboxyl substituted ruthenium complex is applied to photocatalytic proton reduction hydrogen production reaction (HER).
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention designs and synthesizes a novel carboxyl-substituted polydentate nitrogen-containing heterocyclic ligand and a ruthenium complex thereof, and Pt is used as a cocatalyst, and the carboxyl-substituted ruthenium complex is used as a photosensitizer, so that the hydrogen production reaction by photocatalytic proton reduction becomes possible, and the novel carboxyl-substituted polydentate nitrogen-containing heterocyclic ligand has great potential in photocatalytic reactions related to energy sources, such as photocatalytic hydrogen production by water reduction, photocatalytic carbon dioxide and the like.
Drawings
FIG. 1 shows a carboxyl group-substituted ruthenium complex [ Ru ] according to the present invention II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 Synthetic route maps of (1).
FIG. 2 shows the preparation of the compound methyl 1, 6-diacetylbenzoate 1 H NMR spectrum.
FIG. 3 is a drawing of the ethyl ester of the compound 2, 6-bis (1,8-naphthyridin-2-yl) isonicotinic acid 1 H NMR spectrum.
FIG. 4 is the compound 2[ Ru 2 ] II (py(COOEt)(bny) 2 ) 2 ](PF 6 ) 2 1 H NMR spectrum.
FIG. 5 is the compound [ 5 ], [ Ru II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 1 H NMR spectrum.
Fig. 6 pH =5,1mg mL -1 [Ru II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 ，0.5mmol/L H 2 PtCl 4 0.5mol/L suspension of ascorbic acid in visible light (C)>420 nm) hydrogen production over time under catalysis.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The reagents used in the examples are commercially available without specific reference.
EXAMPLE 1 Compound [ Ru II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 Preparation of
(1) Preparation of compound 1, 6-diacetyl methyl benzoate
Adding methyl isonicotinate (4.824mL, 40mmol) and pyruvic acid (9.86mL, 140mmol) into a beaker containing 500mL of 0.4mol/L sulfuric acid solution, and then adding 0.54g of AgNO 3 (dissolved in 5mL of water) and (NH) 4 ) 2 S 2 O 8 (36.5g, 160mmol), adding a stirring bar, and stirring at room temperature for 12h; by CH 2 Cl 2 After the reaction was completed, the product in the reaction solution was extracted 3 times (40 mL. Times.3), and the organic phases were combined and saturated Na was added 2 CO 3 Washing the solution and saturated saline solution by 70mL respectively, and collecting an organic phase; adding a proper amount of anhydrous magnesium sulfate to remove water in the organic phase, filtering under reduced pressure, and removing the solvent by using a rotary evaporator to obtain a yellow solid crude product; adding methanol into the crude product to dissolve and transfer the crude product into a beaker, evaporating the methanol for recrystallization, filtering under reduced pressure when solid is separated out, washing with the methanol, and drying the product in vacuum to obtain white needle-shaped solid which is the compound 2,6-diacetyl methyl benzoate, wherein the yield is 18%.
(2) Preparation of compound 2 (2,6-bis (1,8-naphthyridin-2-yl) isonicotinic acid ethyl ester)
Adding 2,6-diacetyl methyl benzoate (1.32g, 6mmol), 2-amino-3-pyridinecarboxaldehyde (1.8g, 14.4mmol) and pyrrolidine (1.8 mL) into 40mL of ultra-dry ethanol, heating to 90 ℃ and refluxing for 40h; the solvent was removed from the solution by rotary evaporator to give a crude product as a light brown solid to which was added 30mL of CHCl 3 Slowly heating with 0.5mL of ethanol to obtain a clear brown solution, and adding a large amount of diethyl ether into the solution to generate a precipitate; the solid was collected by filtration under reduced pressure and washed with a solution containing CHCl 3 (2 mL) 20mL ether wash and dry the product in vacuo; the light brown solid is the compound 2Ethyl 6-bis (1,8-naphthyridin-2-yl) isonicotinate.
(3) Compound 3[ Ru ] III py(COOEt)(bny) 2 ]Cl 3 Preparation of
Taking 2,6-di (1,8-naphthyridin-2-yl) isonicotinic acid ethyl ester (0.300g, 0.736 mmol) and RuCl 3 ·3H 2 O (0.199g, 0.760mmol) was added to 60mL of ethanol, and after heating under reflux for 5 hours, it was cooled to room temperature, giving a dark green turbid solution. The turbid solution was filtered under reduced pressure and the filter cake was washed several times with ethanol until the filtered solution was a pale green liquid. The filter cake was collected and dried in vacuo to afford compound 3 as a dark green solid in 86.0% yield.
(4) Compound 4[ Ru ] II (py(COOEt)(bny) 2 ) 2 ](PF 6 ) 2 Preparation of
Adding a compound 3 (0.092g, 0.15mmol) and a compound 2,6-bis (1,8-naphthyridin-2-yl) isonicotinic acid ethyl ester (0.061g, 0.15mmol) into a thick-wall reactor special for a microwave reactor with the capacity of 30mL, adding 10mL of ethanol, 0.05mL of N-ethylmorpholine and a stirrer, carrying out water bath ultrasonic treatment on the mixture at room temperature for two minutes to fully mix the reactants, and then heating the mixture to 160 ℃ for reaction for 10min to obtain a dark purple solution. After the solution was cooled to room temperature, the solution was filtered under reduced pressure using celite as a filter aid to remove insoluble impurities. To the filtrate was added 2mL of 0.2M NH 4 PF 6 The aqueous solution was stirred at room temperature for 1-15min, and then most of the solvent was removed by rotary evaporator to leave about 10mL of a deep red turbid solution. The cloudy solution was filtered under reduced pressure and the filter cake was washed with 20mL of ethanol and 10mL of water in that order. The filter cake was collected and dried in vacuo to give a dark red powder, compound 4, in 67% yield.
Process for preparation of Compound 4 1 H NMR spectrum such asAs shown in fig. 4, the specific data are as follows: 1 H NMR(600MHz,DMSO-d 6 )δ9.78(s,2H),9.16(d,J＝8.7Hz,2H),8.55(d,J＝8.7Hz,2H),8.30(dd,J＝8.1,1.8Hz,2H),8.24(dd,J＝4.3,1.9Hz,2H),7.47(dd,J＝7.9,4.3Hz,2H),4.77(q,J＝7.1Hz,2H),1.69(t,J＝7.2Hz,3H)。
(5) Compound 5[ Ru ] II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 Preparation of
Compound 4 (0.571g, 0.474mmol) was mixed with 6mL of ethanol, and 6mL of 6M aqueous NaOH solution, and heated under reflux for 12h. After the reaction was cooled, the solution pH was adjusted with 2M HCl approximately equal to 0.5. The solvent was removed by rotary evaporation to give a crude product as a dark purple powder. The crude product was contacted with 10mL of 4M H 2 SO 4 Aqueous solution, 10mL, 0.8MNH 4 PF 6 The aqueous solutions were mixed and stirred at room temperature for 20min. Filtering the turbid solution under reduced pressure, sequentially using 20mL0.04M NH 4 PF 6 The aqueous solution and 10mL of water washed the filter cake. Collecting the filter cake and vacuum drying to obtain black purple powder which is the compound [ 5 ], [ Ru ] Ru II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 The yield was 89%.
Process for preparation of compound 5 1 The H NMR spectrum is shown in FIG. 5, and the specific data are as follows: 1 H NMR(600MHz,DMSO-d 6 )δ9.73(s,2H),9.07(d,J＝8.7Hz,2H),8.48(d,J＝8.7Hz,2H),8.24(d,J＝8.0Hz,2H),8.18–8.06(m,2H),7.40(dd,J＝7.7,4.2Hz,2H)。
example 2: photocatalytic experiment
We chose 1mol/L aqueous ascorbic acid buffer as a vehicle for the photocatalytic HER reaction test experiment. To ensure the reproducibility of the experiments, the ascorbic acid buffer solution was prepared just before each use.
The configuration method of the photocatalytic system is 60mg [ Ru ] II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 The solid was added to a thick-walled beaker with 30mL of deionized water. The sample was sonicated for 30min to give a black-purple suspension (2 mg mL) -1 ). Adding 30mL 1mol/L ascorbic acid buffer solution into the suspension, stirring and mixing uniformly, and dissolving with 1mol/L sodium hydroxide according to the purpose of catalytic test experimentAdjusting pH =5 to obtain pH =5,1mg mL -1 [Ru II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 0.5mol/L ascorbic acid suspension for visible light catalysis HER experiment test.
The visible light catalysis HER experiment method is that prepared 60mL suspension is added into a photocatalysis glass reactor with the capacity of 270mL, and then 424 mu L H is added 2 PtCl 4 The solution was deoxygenated by bubbling Ar for 30min while keeping out of the light. The photocatalytic reaction was performed under irradiation with a 300W xenon lamp (Perfect Light PLS-SXE 300) with a 420nm filter. The yield of hydrogen during the reaction was determined by gas chromatography. The first 20min after illumination began sampling, after which a gas sample was taken every 20min to measure hydrogen production.
pH＝5，1mg mL -1 [Ru II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 0.5mol/L suspension of ascorbic acid in visible light (C)>420 nm) hydrogen production versus time as shown in FIG. 6 per gram [ Ru ] II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 Can be catalytically reduced to obtain 54.9 mu mol of hydrogen in 1 hour, and the catalytic proton reduction rate can reach 54.9 mu mol g -1 h -1 。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (13)
1. A carboxyl-substituted ruthenium complex characterized by the structure:
2. a method for preparing a carboxyl-substituted ruthenium complex according to claim 1, comprising the steps of:
(1) Adding methyl isonicotinate and pyruvic acid into a sulfuric acid aqueous solution, and then adding a catalyst and an oxidant to react to obtain a compound 1, namely 2,6-diacetyl methyl benzoate;
(2) Under the protection of inert gas, 2,6-diacetyl methyl benzoate, 2-amino-3-pyridine formaldehyde, ethanol and pyrrolidine are mixed and then react to obtain a compound 2, namely 2,6-bis (1,8-naphthyridin-2-yl) isonicotinic acid ethyl ester;
(3) 2,6-bis (1,8-naphthyridin-2-yl) isonicotinic acid ethyl ester and RuCl 3 ·3H 2 O is reacted to obtain the compound 3, namely [ Ru III py(COOEt)(bny) 2 ]Cl 3 ；
(4) Mixing the compound 2, the compound 3, a pH regulator and a solvent for carrying out a first-step reaction, removing insoluble impurities from the obtained reaction liquid after the reaction is finished, and then adding NH into the reaction liquid 4 PF 6 The aqueous solution is subjected to the second step reaction to obtain compound 4[ 2 ], [ Ru ] II (py(COOEt)(bny) 2 ) 2 ](PF 6 ) 2 ；
(5) Mixing the compound 4 with ethanol and sodium hydroxide aqueous solution for the first step reaction, purifying the obtained product, and then mixing the purified product with sulfuric acid aqueous solution and NH 4 PF 6 Mixing the aqueous solution to carry out the second reaction to obtain the compound 5[ Ru ]) II (py(COOH)(bny) 2 ) 2 ](PF 6 ) 2 Namely, the carboxyl-substituted ruthenium complex;
the oxidant in the step (1) is at least one of ammonium persulfate, potassium persulfate and sodium persulfate;
the catalyst in the step (1) is silver nitrate solution, and the concentration of the silver nitrate solution is 0.1-1.5 mol/L;
the concentration of the sulfuric acid aqueous solution in the step (1) is 0.1-2 mol/L;
the dosage of the methyl isonicotinate, the pyruvic acid and the sulfuric acid aqueous solution in the step (1) meets the following requirements: the molar ratio of the methyl isonicotinate to the pyruvic acid is 1.5-5.5; the volume ratio of the methyl isonicotinate to the sulfuric acid aqueous solution is 1; the volume ratio of the pyruvic acid to the sulfuric acid aqueous solution is 1;
the dosage of the catalyst and the oxidant in the step (1) meets the following requirements: the molar ratio of silver nitrate to oxidant in the catalyst is 1; the molar ratio of the methyl isonicotinate to the oxidant is 1:1-8;
the molar ratio of 2,6-diacetylbenzoic acid methyl ester and 2-amino-3-pyridinecarbaldehyde in the step (2) is 1:1 to 5;
the molar ratio of 2,6-diacetyl methyl benzoate to ethanol in the step (2) is 1;
the molar ratio of 2,6-diacetyl methyl benzoate to pyrrolidine in the step (2) is 1:1-10;
2,6-bis (1,8-naphthyridin-2-yl) isonicotinic acid ethyl ester and RuCl described in step (3) 3 ·3H 2 The molar ratio of O is 1;
the solvent for the reaction in the step (3) is at least one of ethanol, methanol, acetone and ethyl acetate;
the pH regulator in the step (4) is at least one of N-ethylmorpholine, triethylamine and ethylenediamine; adjusting the pH of the solution to be 8-9;
the mol ratio of the compound 2 to the compound 3 in the step (4) is 0.5 to 2:1;
NH described in step (4) 4 PF 6 The concentration of the aqueous solution is 0.1-5 mol/L, NH 4 PF 6 The mol ratio of the compound to the compound 3 is 1 to 5:1;
the solvent in the step (4) is at least one of ethanol, methanol and ethyl acetate;
the compound 4 in the step (5) and the dosage of ethanol and sodium hydroxide aqueous solution meet the following requirements: 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, ethanol and water are used as solvents, and the molar ratio of the compound 4 to sodium hydroxide is 1:5-80;
the compound 4, the sulfuric acid aqueous solution and NH in the step (5) 4 PF 6 The dosage of the aqueous solution satisfies the following conditions: compound 4 and NH 4 PF 6 Has a molar ratio of 1:4-20 4 PF 6 The concentration of the aqueous solution is 0.1-5 mol/L; 10-40 mL of sulfuric acid water is added into every 1mmol of compound 4The concentration of the solution and the sulfuric acid aqueous solution is 0.5-6 mol/L.
3. The method for producing a carboxyl-substituted ruthenium complex according to claim 2, wherein:
the oxidant in the step (1) is ammonium persulfate.
4. The method for producing a carboxyl-substituted ruthenium complex according to claim 3, wherein:
the reaction in the step (1) is stirred for 6-18h at room temperature.
5. The method for producing a carboxyl-substituted ruthenium complex according to claim 3, wherein:
the reaction in the step (1) is stirred for 12 hours at room temperature.
6. The method for producing a carboxyl-substituted ruthenium complex according to claim 2, wherein:
the reaction in the step (2) is heating reflux for 20-48h.
7. The method for producing a carboxyl-substituted ruthenium complex according to claim 6, wherein:
the reaction in the step (2) is heating reflux at 90 ℃ for 40h.
8. The method for producing a carboxyl-substituted ruthenium complex according to claim 2, wherein:
the reaction in the step (3) is heating reflux for 0.5-8h.
9. The method for producing a carboxyl-substituted ruthenium complex according to claim 2, wherein:
the pH regulator in the step (4) is N-ethyl morpholine;
and (4) the solvent is ethanol.
10. The method for producing a carboxyl-substituted ruthenium complex according to claim 2, wherein:
the first step of reaction in the step (4) is carried out under the condition of stirring and microwave heating to 100-190 ℃ for 1-60min;
the second step reaction condition in the step (4) is that the mixture is stirred for 1-15min at room temperature.
11. The method for producing a carboxyl-substituted ruthenium complex according to claim 10, wherein:
the first step of reaction in the step (4) is carried out under the condition of stirring and microwave heating to 160 ℃ for 10min.
12. The method for producing a carboxyl-substituted ruthenium complex according to claim 2, wherein:
the first step of reaction in the step (5) is heating reflux for 2-24h;
the second reaction step in the step (5) is stirring at room temperature for 2-45 min.
13. The application of the carboxyl substituted ruthenium complex in the photocatalytic proton reduction hydrogen production reaction according to claim 1.
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