CN115449081B - Bimetallic porphyrin supermolecular film, preparation method and application thereof in photocatalytic hydrolysis hydrogen production - Google Patents
Bimetallic porphyrin supermolecular film, preparation method and application thereof in photocatalytic hydrolysis hydrogen production Download PDFInfo
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- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 27
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000001257 hydrogen Substances 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 20
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 19
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 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 claims abstract description 23
- 239000013110 organic ligand Substances 0.000 claims abstract description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- ANWXWWSYNQLVED-UHFFFAOYSA-N 5,10,15,20-tetrakis(4-bromophenyl)-21,23-dihydroporphyrin Chemical compound Brc1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(Br)cc2)c2ccc([nH]2)c(-c2ccc(Br)cc2)c2ccc(n2)c(-c2ccc(Br)cc2)c2ccc1[nH]2 ANWXWWSYNQLVED-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 239000004695 Polyether sulfone Substances 0.000 abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 5
- 229920006393 polyether sulfone Polymers 0.000 abstract description 5
- 229920001184 polypeptide Polymers 0.000 abstract description 5
- 102000004196 processed proteins & peptides Human genes 0.000 abstract description 5
- 108090000765 processed proteins & peptides Proteins 0.000 abstract description 5
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 230000021615 conjugation Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 3
- 125000001174 sulfone group Chemical group 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- -1 Porphyrin compounds Chemical class 0.000 description 6
- 239000003504 photosensitizing agent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 150000003457 sulfones Chemical group 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011191 terminal modification Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229930003270 Vitamin B Natural products 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002436 one-dimensional nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing 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
- 239000004246 zinc acetate Substances 0.000 description 1
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- 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
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- 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
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Abstract
The invention discloses a bimetallic porphyrin supermolecular film, a preparation method and application thereof in photocatalytic hydrolysis hydrogen production, wherein the bimetallic porphyrin supermolecular film has a structure shown in an abstract attached drawing, wherein R is hydrogen atom, alkyl long chain, alkoxy long chain, polypeptide chain, polyether sulfone chain, polyaromatic hydrocarbon ring chain and other functional chain-shaped structures with tail end modified; m1 and M2 are transition metal ions. The supermolecular membrane material provided by the invention has a two-dimensional planar structure, is constructed by self-assembly of metalloporphyrin terpyridine organic ligand L1 and transition metal ions through coordination bond guidance, has a stable structure, and has the characteristics of larger conjugation and large electron density, and the ordered assembly and arrangement among molecules can effectively improve the photoelectric performance of the supermolecular membrane material. The metalloporphyrin supermolecular film has good photocatalysis performance, and the metalloporphyrin supermolecular film has excellent performance in a photocatalysis hydrolysis hydrogen production experiment.
Description
Technical Field
The invention relates to the field of photocatalytic hydrogen production, in particular to a bimetallic porphyrin supermolecular film, a preparation method and application thereof in photocatalytic hydrogen production by hydrolysis.
Background
Porphyrin compounds are widely used in living bodies in nature and play an important role in vital activities, and chlorophyll, heme, vitamin B and the like can be regarded as metalloporphyrin compounds, so that artificial synthesis of porphyrin compounds to simulate various properties of natural porphyrins has become one of the research hotspots in recent years. As porphyrin is a large conjugated system with 18 pi electrons, the mobility of electrons in the ring is very good, and porphyrin and compounds thereof have great prospects in various fields of photoelectric materials, molecular assembly, environmental protection, energy sources and the like. 2,2',6',2 "-terpyridine (tpy) is an effective ligand system and relatively few metalloporphyrin complexes based on tpy are reported. Therefore, the metalloporphyrin complex with the tpy group is designed and synthesized, the photophysical and chemical characteristics of the material are studied in detail, and the application field of the transition metalloporphyrin complex is widened.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a supermolecular material film and application thereof in hydrogen production by photocatalytic hydrolysis based on synthesis and self-assembly of metalloporphyrin terpyridine ligand.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the present invention provides a bimetallic porphyrin supermolecular film, which is a two-dimensional film structure, and has a structure of formula i, as follows:
wherein, R is hydrogen atom, alkyl long chain, alkoxy long chain, polypeptide chain, polyether sulfone chain, polyaromatic hydrocarbon ring chain and other functional chain structures with terminal modification; m1 and M2 are transition metal ions.
The R group is mainly a chain structure for modifying the supermolecule metal sphere, and is generally beneficial to improving the solubility and the conductivity of the supermolecule structure and the bonding performance indicated by metal oxide or graphene.
The R group is mainly a chain structure for modifying the supermolecule metal ball, which is generally beneficial to improving the solubility and the conductivity of the supermolecule structure and the bonding performance indicated by metal oxide or graphene, so that the material can be related to more fields. In theory, it is possible to select a hydrogen atom, an alkyl long chain, an alkoxy long chain, a polypeptide chain, a polyether sulfone chain, a polyaromatic hydrocarbon ring chain, a functional chain structure modified at the end thereof, and the like, and hydrogen atoms are preferable in the present invention.
Preferably, M1 is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ And at least two of various transition metal ion coordination.
Preferably, the M2 is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ And at least one of a plurality of transition metal ion ligands.
In a second aspect, the invention provides a method for preparing a bimetallic porphyrin supermolecular film, comprising the following steps:
(1) Dissolving metalloporphyrin terpyridine organic ligand shown in formula II in DMF and water mixed solution;
(2) Adding a metal salt solution, then heating and reacting, wherein the reaction solution is clear and transparent from violet, and a large amount of solids float, thus obtaining the bimetallic porphyrin supermolecular film.
Wherein, formula II has the following structure:
wherein, R is hydrogen atom, alkyl long chain, alkoxy long chain, polypeptide chain, polyether sulfone chain, polyaromatic hydrocarbon ring chain and other functional chain structures with terminal modification.
Preferably, in the step (1), the volume ratio of DMF to water in the DMF and water mixed solution is 8:1-10:1.
Preferably, in the step (1), the volume ratio of DMF to water in the DMF and water mixed solution is 8:1.
The DMF and water mixed solvent adopted by the invention plays an important role in the generation of the supermolecular film, and the DMF and water mixed solvent can well dissolve metalloporphyrin terpyridine organic ligands, and the metal organic supermolecular film assembled into the film has poor dissolution in the DMF and water mixed solution.
Preferably, in step (2), the metal salt is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ And at least one of metal salts which are readily soluble in water.
Preferably, in step (2), the anions of the metal salt comprise nitrate, sulfate or chloride ions, etc.
Preferably, in the step (2), the heating reaction is performed at a temperature of 120 ℃ and a temperature of 150 ℃ for 24 to 48 hours.
Preferably, the preparation method of the metalloporphyrin terpyridine organic ligand comprises the following steps:
(1) 5, 10, 15, 20-tetra (4-bromophenyl) porphyrin and M1 2+ Carrying out coordination reaction to obtain an intermediate 1;
(2) And (3) carrying out reflux reaction on the intermediate 1 and 4-phenylboronic acid terpyridine in a toluene/water/methanol mixed solution containing a tetrakis (triphenylphosphine) palladium catalyst to obtain the metalloporphyrin terpyridine organic ligand.
Preferably, M1 in step (1) is at least one of the Cr, mn, fe, co, ni, zn, cu, cd, ru transition metals.
Preferably, the time of the reflux reaction in step (2) is 96 hours.
In a third aspect, the invention provides an application of a bimetallic porphyrin supermolecular film in hydrogen production by photocatalytic hydrolysis.
The beneficial effects of the invention are as follows:
1. the supermolecular material provided by the invention has a two-dimensional planar structure, is constructed by self-assembly of metalloporphyrin terpyridine organic ligand L1 and transition metal ions through coordination bond guidance, has a stable structure, and the formed two-dimensional planar structure has the characteristics of larger conjugation and large electron density, and can effectively improve the photoelectric performance of the supermolecular material through ordered assembly and arrangement among molecules. The metalloporphyrin supermolecular film has good photocatalysis performance, and the metalloporphyrin supermolecular film has excellent performance in a photocatalysis hydrolysis hydrogen production experiment.
2. The invention provides a supermolecular material, which is used for preparing hydrogen by photocatalytic hydrolysis, conducting high molecular polymer and reducing CO by photocatalysis 2 The dye sensitized solar cell and the like.
3. The preparation method of the supermolecular material provided by the invention is simple, the reaction condition is mild, and the large-scale industrial production is facilitated.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a transmission electron microscope image of a two-dimensional supramolecular film M1 prepared in example 1 of the present invention;
FIG. 2 is an atomic force microscope image of a two-dimensional supramolecular film M1 prepared in example 1 of the present invention;
FIG. 3 is an elemental mapping of a two-dimensional supramolecular film M1 prepared in example 1 of the present invention;
FIG. 4 is a one-dimensional nuclear magnetic resonance hydrogen spectrum of the metal organic ligand L1 prepared in example 1 of the present invention;
FIG. 5 shows a two-dimensional supramolecular film M1, a metal-organic ligand L1 and a photosensitizer Ru (bpy) prepared according to example 1 of the present invention 3 Cl 2 The photocatalytic hydrolysis hydrogen production activity map of (2).
FIG. 6 is a flow chart of a two-dimensional supramolecular film M1 prepared in example 1 of the present invention;
FIG. 7 is a molecular structure diagram of a bimetallic porphyrin supermolecular film prepared in example 1 of the present invention.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention is further described below with reference to the drawings and examples.
Example 1
Referring to fig. 1-7, the preparation method of the bimetallic porphyrin supermolecule film provided in the embodiment includes the following steps:
1. preparation of metalloporphyrin terpyridine organic ligand (L1) of formula ii:
(1) Preparation of 5, 10, 15, 20-tetrakis (4-bromophenyl) zinc porphyrin 5, 10, 15, 20-tetrakis (4-bromophenyl) porphyrin (0.5 g,0.54 mmol) and zinc acetate (2.2 g,10 mmol) were added to a mixed solution of chloroform (20 ml) and DMF (10 ml), the mixture was heated to 80℃under reflux for 4 hours, the mixed solution was cooled to room temperature and concentrated under reduced pressure to give a purple solid which was repeatedly washed with deionized water to give 5, 10, 15, 20-tetrakis (4-bromophenyl) zinc porphyrin.
(2) 5, 10, 15, 20-tetrakis (4-bromophenyl) zinc porphyrin (200 mg,0.2 mmol), 4-phenylboronic acid terpyridine (436 mg,1.2 mmol), and sodium carbonate (270 mg,2.55 mmol) were added to methanol: water: toluene (12:3:5, v:v:v) =100 ml, to the mixture was added tetrakis (triphenylphosphine) palladium (58 mg,0.0826 mmol), the mixture was heated to reflux at 85 c under N2 for 4 days, cooled to room temperature, the mixture was extracted with dichloromethane, the combined organic phases concentrated under reduced pressure, the solid was refluxed with dichloromethane, and the metalloporphyrin terpyridine organic ligand (L1) was obtained as a purple solid by suction filtration.
2. Preparation of supramolecular film (M1) consisting of the unit structure represented by formula i:
the flow is shown in fig. 6, and comprises the following steps:
weighing metalloporphyrin terpyridine organic ligand (formula II) (20 mg, 0.010mmol) and adding into thick-wall pressure-resistant pipe, adding into 8ml DMF solution, and collecting Co (NO) 3 ) 2 ·6H 2 O (6.2 mg,0.02 mmol) is dissolved in 1ml water, added into a thick-wall pressure-resistant pipe, screwed up to a bottle mouth for reaction at 120 ℃ for 48 hours, the solution turns into clear and transparent from violet, a large amount of solid is separated out, purple solid is obtained through centrifugation, DMF and water are used for repeated washing, redundant ligand and metal salt are removed, vacuum drying is carried out at 80 ℃ to obtain 20mg of purple solid, namely the supermolecular material, and the yield is 76%.
Example 2
The preparation method of the bimetallic porphyrin supermolecular film provided by the embodiment comprises the following steps:
(1) Dissolving a metalloporphyrin terpyridine organic ligand shown in a formula II (same as in example 1) in a mixed solution of DMF and water;
(2) Adding metal salt solution, heating to react, and obtaining the bimetallic porphyrin supermolecular film I (same as in example 1) from violet to clear and transparent, and floating a large amount of solids.
Wherein, R is hydrogen atom, alkyl long chain, alkoxy long chain, polypeptide chain, polyether sulfone chain, polyaromatic hydrocarbon ring chain and other functional chain structures with terminal modification.
In the step (1), the volume ratio of DMF to water in the DMF and water mixed solution is 8:1-10:1.
In the step (1), the volume ratio of DMF to water in the DMF and water mixed solution is 8:1.
In the step (2), the metal salt is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ And at least one of metal salts which are readily soluble in water.
In step (2), the anions of the metal salt include nitrate ions, sulfate ions, chloride ions, or the like.
In the step (2), the temperature of the heating reaction is 120 ℃ and 150 ℃ and the time is 24-48 hours.
In the step (1), the preparation method of the metalloporphyrin terpyridine organic ligand (L1) shown in the formula II comprises the following steps:
(1) 5, 10, 15, 20-tetra (4-bromophenyl) porphyrin and M1 2+ Carrying out coordination reaction to obtain an intermediate 1;
(2) And (3) carrying out reflux reaction on the intermediate 1 and 4-phenylboronic acid terpyridine in a toluene/water/methanol mixed solution containing a tetrakis (triphenylphosphine) palladium catalyst to obtain the metalloporphyrin terpyridine organic ligand.
In the step (1), M1 is at least one of Cr, mn, fe, co, ni, zn, cu, cd, ru transition metals.
The time for the reflux reaction in step (2) was 96 hours.
Application and detection example
The bimetallic porphyrin supermolecular film prepared in example 1 is detected as follows:
(1) The morphology of the supermolecular film M1 is characterized by a transmission electron microscope, and the result is shown in figure 1;
(2) The morphology of the supermolecular film M1 is characterized by an atomic force microscope, and the result is shown in figure 2;
(3) The element of the supramolecular film M1 was analyzed by EDS spectroscopy and the results are shown in fig. 3.
(4) The one-dimensional nuclear magnetic resonance spectrum of the metal organic ligand L1 was detected, and the result is shown in FIG. 4.
Application example
Application detection of hydrogen production by photocatalytic hydrolysis of the bimetallic porphyrin supermolecular film M1 prepared in example 1:
the catalytic process adopts a 300W xenon lamp to simulate a solar light source, a lens adopts a UVIRCUT400 ultraviolet cut-off filter, the emergent spectrum is 420-780 nm, and the distance between the light source and the irradiation liquid level is about 15cm. Taking a 100ml beaker, adding 60ml acetonitrile, 30ml water and 10g triethanolamine into the beaker, stirring the mixture uniformly, and adding photosensitizer Ru (bpy)) 3 Cl 2 (50 mg) was stirred uniformly, and finally, after adding the supramolecular film M1 (10 mg) and stirring for five minutes, a sealing device was installed to prevent air leakage, and vacuum was applied until the liquid surface did not bubble or the number of bubbles was small, and a sample was taken every half an hour until the gas type and the mass in the gas chromatograph test beaker were tested for a total of 4 hours. Metalloporphyrin terpyridine organic ligands L1 and Ru (bpy) are subjected to the same conditions 3 Cl 2 A photocatalytic hydrolysis hydrogen production test was performed in which Ru (bpy) 3 Cl 2 Ru (bpy) in the photocatalytic hydrolysis hydrogen production test 3 Cl 2 Not the photosensitizer but as a photocatalyst, 10mg Ru (bpy) was added during this test 3 Cl 2 The other solvent conditions were unchanged. The test results were calculated from n=v/Vm and are unified in μmol/g.
Under the same conditions, as shown in FIG. 5, the activity of hydrogen is 2700 mu mol/g by photocatalytic hydrolysis of a photosensitizer and a two-dimensional supermolecular film M1 4, 1700 mu mol/g by photocatalytic hydrolysis of hydrogen is produced by photocatalytic hydrolysis of a photosensitizer and a metalloporphyrin terpyridine organic ligand L1 4, and Ru (bpy) is used as a photosensitizer 3 Cl 2 The photocatalytic hydrolysis for 4 hours as a photocatalyst produces hydrogen with an activity of 337 mu mol/g.
The supermolecular membrane material provided by the embodiment of the invention has a two-dimensional planar structure, is constructed by self-assembly of metalloporphyrin terpyridine organic ligand L1 and transition metal ions guided by coordination bonds, has a stable structure, and has the characteristics of larger conjugation and large electron density, and the ordered assembly and arrangement among molecules can effectively improve the photoelectric performance of the supermolecular membrane material. The metalloporphyrin supermolecular film has good photocatalysis performance, and the metalloporphyrin supermolecular film has excellent performance in a photocatalysis hydrolysis hydrogen production experiment.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The bimetallic porphyrin supermolecular membrane is characterized by a two-dimensional membrane structure, and has the structure shown in the following formula I:
wherein R is a hydrogen atom; m1 and M2 are transition metal ions;
the M1 is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ At least two of (a) and (b);
the M2 is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ At least one of them.
2. A method for preparing the bimetallic porphyrin supermolecular film according to claim 1, comprising the following steps:
(1) Dissolving metalloporphyrin terpyridine organic ligand shown in formula II in DMF and water mixed solution;
(2) Adding a metal salt solution, then heating and reacting, wherein the reaction solution is clear and transparent from violet, and a large amount of solids float, so that the bimetallic porphyrin supermolecular film is obtained;
wherein, formula II has the following structure:
wherein R is a hydrogen atom.
3. The method for preparing a bimetallic porphyrin supermolecular film according to claim 2, wherein in the step (1), the volume ratio of DMF to water in the mixed solution of DMF and water is 8:1-10:1.
4. The method for producing a bimetallic porphyrin supermolecular film according to claim 2, wherein in step (2), the metal salt is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Zn 2+ 、Cu 2+ 、Cd 2+ 、Ru 2+ At least one of the metal salts readily soluble in water; the anions of the metal salts include nitrate, sulfate or chloride.
5. The method for producing a bimetallic porphyrin supermolecular film according to claim 2, wherein in the step (2), the heating reaction is carried out at 120-150 ℃ for 24-48 hours.
6. The method for preparing a bimetallic porphyrin supermolecular film according to claim 2, wherein the method for preparing metalloporphyrin terpyridine organic ligand comprises the following steps:
(1) 5, 10, 15, 20-tetra (4-bromophenyl) porphyrin and M1 2+ Carrying out coordination reaction to obtain an intermediate 1;
(2) And (3) carrying out reflux reaction on the intermediate 1 and 4-phenylboronic acid terpyridine in a toluene/water/methanol mixed solution containing a tetrakis (triphenylphosphine) palladium catalyst to obtain the metalloporphyrin terpyridine organic ligand.
7. The method for preparing a bimetallic porphyrin supermolecular film according to claim 6, wherein M1 in the step (1) is at least one of Cr, mn, fe, co, ni, zn, cu, cd, ru transition metals; the time for the reflux reaction in step (2) was 96 hours.
8. Use of the bimetallic porphyrin supermolecular film of claim 1 in the production of hydrogen by photocatalytic hydrolysis.
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| JP2008095050A (en) * | 2006-10-16 | 2008-04-24 | Hidetoshi Tsuchida | Albumin-metal porphyrin complex and photosensitizer |
| CN111875642A (en) * | 2020-08-11 | 2020-11-03 | 中南大学 | Poly-terpyridyl metal organic ligand compound, five-membered flower ring-shaped supramolecule assembled by same and preparation method of five-membered flower ring-shaped supramolecule |
| CN111995761A (en) * | 2020-08-18 | 2020-11-27 | 中南大学 | Tripyridyl transition metal organic polymer, preparation method thereof and application thereof in carbon dioxide photocatalytic reduction |
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| JP2008095050A (en) * | 2006-10-16 | 2008-04-24 | Hidetoshi Tsuchida | Albumin-metal porphyrin complex and photosensitizer |
| CN111875642A (en) * | 2020-08-11 | 2020-11-03 | 中南大学 | Poly-terpyridyl metal organic ligand compound, five-membered flower ring-shaped supramolecule assembled by same and preparation method of five-membered flower ring-shaped supramolecule |
| CN111995761A (en) * | 2020-08-18 | 2020-11-27 | 中南大学 | Tripyridyl transition metal organic polymer, preparation method thereof and application thereof in carbon dioxide photocatalytic reduction |
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