CN117209516A - Boron-amine complex monomer with strong charge separation, boron-amine conjugated polymer, and preparation method and application thereof - Google Patents
Boron-amine complex monomer with strong charge separation, boron-amine conjugated polymer, and preparation method and application thereof Download PDFInfo
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- CN117209516A CN117209516A CN202210622248.6A CN202210622248A CN117209516A CN 117209516 A CN117209516 A CN 117209516A CN 202210622248 A CN202210622248 A CN 202210622248A CN 117209516 A CN117209516 A CN 117209516A
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- 239000000178 monomer Substances 0.000 title claims abstract description 50
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 44
- 238000000926 separation method Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- KKRPPVXJVZKJON-UHFFFAOYSA-N trimethyl-(5-trimethylstannylthiophen-2-yl)stannane Chemical compound C[Sn](C)(C)C1=CC=C([Sn](C)(C)C)S1 KKRPPVXJVZKJON-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 10
- GRINSTOOFGVAJF-UHFFFAOYSA-N BrC1=CC=C(S1)[Sn](C)(C)C Chemical compound BrC1=CC=C(S1)[Sn](C)(C)C GRINSTOOFGVAJF-UHFFFAOYSA-N 0.000 claims abstract description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- -1 pyridine compound Chemical class 0.000 claims description 5
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical group [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 4
- BSDGZUDFPKIYQG-UHFFFAOYSA-N 4-bromopyridine Chemical compound BrC1=CC=NC=C1 BSDGZUDFPKIYQG-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 3
- ZMQLKBAJUGKDDO-UHFFFAOYSA-N 4-(3,5-dipyridin-4-ylphenyl)pyridine Chemical compound C1=NC=CC(C=2C=C(C=C(C=2)C=2C=CN=CC=2)C=2C=CN=CC=2)=C1 ZMQLKBAJUGKDDO-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- LYRCQNDYYRPFMF-UHFFFAOYSA-N trimethyltin Chemical compound C[Sn](C)C LYRCQNDYYRPFMF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- GSPPDMIMNFYKRI-UHFFFAOYSA-N boron tin Chemical group [B].[Sn] GSPPDMIMNFYKRI-UHFFFAOYSA-N 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000003775 Density Functional Theory Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000371 solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013317 conjugated microporous polymer Substances 0.000 description 2
- 239000013311 covalent triazine framework Substances 0.000 description 2
- 239000013310 covalent-organic framework Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
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- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- IBXMKLPFLZYRQZ-UHFFFAOYSA-N 1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1C=CC(=O)C=CC1=CC=CC=C1 IBXMKLPFLZYRQZ-UHFFFAOYSA-N 0.000 description 1
- MPZMVUQGXAOJIK-UHFFFAOYSA-N 4-bromopyridine;hydron;chloride Chemical compound Cl.BrC1=CC=NC=C1 MPZMVUQGXAOJIK-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical group [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
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Abstract
The invention discloses a boron-amine complex monomer with strong charge separation, a boron-amine conjugated polymer, and a preparation method and application thereof. Aiming at the problem that most of the existing organic catalyst structural units are not completely separated in charge, the invention designs a boron-amine complex monomer with strong charge separation, and utilizes a boron-tin exchange reaction as a polymerization means to prepare a boron-amine conjugated polymer catalyst with strong charge separation. The boron-amine complex monomer of the invention adopts BBr 3 The invention relates to a preparation method of a boron-amine conjugated polymer which is prepared from raw materials of (5-bromothiophene-2-yl) trimethylstannane and pyridine compoundsThe complex monomer and 2, 5-bis (trimethylstannyl) thiophene are used as raw materials, and the catalyst is prepared by boron-tin exchange polymerization. The boron-amine conjugated polymer prepared by the invention has high catalytic activity and efficiency, and the preparation method is simple, and has good application prospect in the field of photocatalytic hydrogen production.
Description
Technical Field
The invention relates to a boron-amine complex monomer with strong charge separation, a boron-amine conjugated polymer and a preparation method and application thereof, belonging to the technical field of photocatalytic water production and hydrogen production.
Background
At present, due to the serious energy shortage and environmental pollution caused by the large-scale use of fossil fuels, people are strongly seeking clean and renewable energy sources. The development of clean and efficient hydrogen energy is a sustainable and promising road, scientists are inspired by natural photosynthesis, and the strategy of using a semiconductor photocatalyst to decompose water into hydrogen and oxygen under visible light driving can directly convert solar energy into chemical energy.
Fujishima and Honda since 1972 [1] TiO is used 2 After being used as a photocatalyst for photocatalytic water production, various inorganic semiconductor photocatalysts have been developed, and most of the photocatalysts are based on d 0 、d 10 Oxides, sulfides, nitrides, and the like of metals [2] . However, inorganic photocatalysts have inherent disadvantages [3-4] Such as: the energy band gap is larger>3.0 eV), poor solar light utilization (most of which can only absorb ultraviolet light), low solar energy conversion efficiency, and difficulty in fine adjustment. In the photocatalyst library developed so far, an organic conjugated polymer [5] As an emerging photocatalyst, the photocatalyst has the unique advantages of sufficient light absorption efficiency, excellent stability, adjustable electronic characteristics, economic applicability and the like. The search for organic conjugated polymers with photocatalytic activity can be traced back to 1985 [6] However, the photocatalytic efficiency is disappointing, especially in the visible region. In recent decades, organic conjugated polymers have made significant progress in visible light driven water splitting, and various organic photocatalysts have been developed including mainly graphite carbon nitride polymers [7-8] (g-C 3 N 4 ) Linear conjugated polymer [9-10] (CPs), conjugated microporous polymers [11-13] (CMPs), covalent organic frameworks [14-15] (COFs), covalent triazine frameworks [16-17] (CTFs) and Polymer Point [18] Etc.
Most of the current common catalyst structural units are not completely separated in charge and are all planar molecules. Generally, when light irradiates a catalyst molecule, photons are absorbed by the catalyst to generate electrons and holes, and as the electrons and holes migrate to the surface, water generates hydrogen and oxygen at the electrons and holes, respectively. However, if the separation of LUMO from HOMO during the photogeneration of electrons and holes is not complete, the electron and hole are easily annihilated by recombination, which causes a major energy loss, and electron-hole recombination annihilation is faster than free electron and hole formation and migration, which is extremely disadvantageous for achieving high photocatalytic activity and efficiency. In order to realize the high-efficiency separation capability of photo-generated electrons and holes, the main strategy of the current design of the catalyst by scientific researchers is to introduce acceptor functional groups with strong electron attraction into the structure so as to achieve the purpose of pulling electrons out of a conjugated framework to realize charge separation. Based on this, we designed a class of boron-amine complex monomers with strong charge separation, and there is no report on this class of compounds. In the previous research, a series of novel triaryl boron conjugated polymer porous materials are prepared by utilizing boron-tin exchange reaction as a polymerization means, and based on the same polymerization means, the boron-amine conjugated polymer catalyst with strong charge separation is prepared by utilizing boron-amine complex monomers, so that the catalyst is favorable for realizing high photocatalytic activity and high efficiency, and has important significance in the field of photocatalytic hydrogen production.
Reference is made to:
1.Fujishima,K.H.,Electrochemical Photolysis of Water at a Semiconductor Electrode.Nature 1972,238,37-38.
2.Xing,J.；Fang,W.Q.；Zhao,H.J.；Yang,H.G.,Inorganic photocatalysts for overall water splitting.Chem Asian J 2012,7,642-657.
3.Kazuhiko Maeda,M.H.,Daling Lu,Ryu Abe,and Kazunari Domen,Efficient Nonsacrificial Water Splitting through Two-Step Photoexcitation by Visible Light using a Modified Oxynitride as a Hydrogen Evolution Photocatalyst.J.Am.Chem.Soc.2010,132,5858-5868.
4.Kudo,A.；Miseki,Y.,Heterogeneous photocatalyst materials for water splitting.Chem.Soc.Rev.2009,38,253-278.
5.Dai,C.；Liu,B.,Conjugated polymers for visible-light-driven photocatalysis.Energy&Environmental Science 2020,13,24-52.
6.Shozo Yanagida,A.K.,Kunihiko Mizumoto,Chyongjin Pac,and Katsumi Yoshino,Poly(pphenylene1-catalysed Photoreduction of Water to Hydrogen.J.Chem.Soc.,Chem.Commun.1985,474-475.
7.Wang,X.；Maeda,K.；Thomas,A.；Takanabe,K.；Xin,G.；Carlsson,J.M.；Domen,K.；Antonietti,M.,A metal-free polymeric photocatalyst for hydrogen production from water under visible light.Nat.Mater.2009,8,76-80
8.Yu,Y.；Yan,W.；Wang,X.；Li,P.；Gao,W.；Zou,H.；Wu,S.；Ding,K.Surface Engineering for Extremely Enhanced Charge Separation and Photocatalytic Hydrogen Evolution on g-C3N4.Adv.Mater.2018,30,1705060.
9.Sprick,R.S.；Bonillo,B.；Clowes,R.；Guiglion,P.；Brownbill,N.J.；Slater,B.J.；Blanc,F.；Zwijnenburg,M.A.；Adams,D.J.；Cooper,A.I.Visible-Light-Driven Hydrogen Evolution using Planarized Conjugated Polymer Photocatalysts.Angew.Chem.,Int.Ed.2016,128,1824-1828.
10.Maruyama,T.；Yamamoto,M.Effective Photocatalytic System Based on Chelatingπ-Conjugated Poly(2,2′-bipyridine-5,5′-diyl)and Platinum for Photoevolution of H 2 from Aqueous Media and Spectroscopic Analysis of the Catalyst.J.Phys.Chem.B 1997,101,3806-3810.
11.Li,L.；Cai,Z.；Wu,Q.；Lo,W.-Y.；Zhang,N.；Chen,L.；Yu,L.Rational Design of Porous Conjugated Polymers and Roles of Residual Palladium for Photocatalytic Hydrogen Production.J.Am.Chem.Soc.2016,138,7681-7686.
12.Yang,C.；Ma,B.；Zhang,L.；Lin,S.；Ghasimi,S.；Landfester,K.；Zhang,K.；Wang,X.Molecular Engineering of Conjugated Polybenzothiadiazoles for Enhanced Hydrogen Production by Photosynthesis.Angew.Chem.,Int.Ed.2016,55,9202-9206.
13.Xu,Y.；Mao,N.；Feng,S.；Zhang,C.；Wang,F.；Chen,Y.；Zeng,J.；Jiang,J.-X.Perylene-Containing Conjugated Microporous Polymers for Photocatalytic Hydrogen Evolution.Macromol.Chem.Phys.2017,218,1700049.
14.Patra,B.C.；Khilari,S.；Manna,R.N.；Mondal,S.；Pradhan,D.；Pradhan,A.；Bhaumik,A.A Metal-Free Covalent Organic Polymer for Electrocatalytic Hydrogen Evolution.ACS Catal.2017,7,6120-6127.
15.Pachfule,P.；Acharjya,A.；Roeser,J.；Langenhahn,T.；Schwarze,M.；Schomacker,R.；Thomas,A.；Schmidt,J.Diacetylene Functionalized Covalent Organic Framework(COF)for Photocatalytic Hydrogen Generation.J.Am.Chem.Soc.2018,140,1423-1427.
16.Schwinghammer,K.；Hug,S.；Mesch,M.B.；Senker,J.；Lotsch,B.V.Phenyl-Triazine Oligomers for Light-Driven Hydrogen Evolution.Energy Environ.Sci.2015,8,3345-3353.
17.Wang,K.；Yang,L.-M.；Wang,X.；Guo,L.；Cheng,G.；Zhang,C.；Jin,S.；Tan,B.；Cooper,A.I.Covalent Triazine Frameworks via a Low-Temperature Polycondensation Approach.Angew.Chem.,Int.Ed.2017,56,14149-14153.
18.Wang,L.；Fernandez-Teran,R.；Zhang,L.；Fernandes,D.L.A.；Tian,L.；Chen,H.；Tian,H.Organic Polymer Dots as Photocatalysts for Visible Light-Driven Hydrogen Generation.Angew.Chem.,Int.Ed.2016,55,12306-12310.
disclosure of Invention
The invention solves the technical problems that: at present, most of organic catalyst structural units are not completely separated in charge, so that the problems of being unfavorable for realizing improvement of photocatalytic activity and efficiency and the like are solved.
In order to solve the above technical problems, the present invention provides a boron-amine complex monomer having strong charge separation, which is any one of BN3, BN4, BN6, and BN9 shown below:
the invention also provides a preparation method of the boron-amine complex monomer with strong charge separation, which comprises the following steps:
step 1: BBr is used for 3 Dissolving (5-bromothiophene-2-yl) trimethylstannane in benzene solvent, and reacting under inert atmosphere condition to obtain an intermediate A;
step 2: reacting an intermediate A, a pyridine compound and a benzene organic solvent under an inert atmosphere, removing the solvent from the obtained mixture after the reaction is finished, and purifying to obtain a boron-amine complex monomer, wherein boron-amine complex monomer BN3 is prepared from the intermediate A and pyridine, boron-amine complex monomer BN4 is prepared from the intermediate A, 4-bromopyridine and triethylamine hydrochloride, boron-amine complex monomer BN6 is prepared from the intermediate A and 4,4' -bipyridine, and boron-amine complex monomer BN9 is prepared from the intermediate A and 1,3, 5-tri (4-pyridyl) benzene.
Wherein, the chemical structural formula of the 4,4' -bipyridine is as follows:
the chemical structural formula of the 1,3, 5-tris (4-pyridyl) benzene is as follows:
preferably, the benzene-based organic solvent in the step 1 and the step 2 is at least one of toluene, xylene and chlorobenzene.
Preferably, BBr in said step 1 3 And (5-bromothiophen-2-yl) trimethylstannane in a molar ratio of 1:3-3.5, wherein the reaction conditions are as follows: reacting for 2-4 days at 100-150 ℃.
Preferably, the reaction conditions in the step 2 are: reacting for 2-4 days at room temperature; the purification in the step 2 is performed by column chromatography.
The invention also provides a boron-amine conjugated polymer with strong charge separation, which is prepared by taking the boron-amine complex monomer and 2, 5-bis (trimethylstannyl) thiophene as raw materials through boron-tin exchange polymerization, and has a structural unit shown in the following formula I, formula II, formula III or formula IV:
the invention also provides a preparation method of the boron-amine conjugated polymer with strong charge separation, and the chemical reaction formula is shown as follows:
the method comprises the following steps:
heating and reacting a boron-amine complex monomer, 2, 5-bis (trimethylstannyl) thiophene, an organic palladium catalyst, an organic phosphorus ligand and a benzene organic solvent for a period of time under an inert atmosphere condition according to a certain feeding proportion to generate a precipitate, sequentially adding a halogenated hydrocarbon solvent under the inert condition after the reaction is finished to wash the precipitate, filtering to obtain a solid product, and vacuum drying the obtained solid product to obtain a corresponding conjugated polymer containing a boron-nitrogen structure;
wherein, the conjugated polymer containing the structural unit shown in the formula I is prepared by the reaction of boron-amine complex monomer BN3 and 2, 5-bis (trimethylstannyl) thiophene;
the conjugated polymer containing the structural unit shown in the formula II is prepared by reacting boron-amine complex monomer BN4 and 2, 5-bis (trimethylstannyl) thiophene;
the conjugated polymer containing the structural unit shown in the formula III is prepared by reacting boron-amine complex monomer BN6 and 2, 5-bis (trimethylstannyl) thiophene;
conjugated polymers containing structural units of formula IV are prepared by reacting boron-amine complex monomers BN9 with 2, 5-bis (trimethylstannyl) thiophene.
Preferably, the organic palladium catalyst is tris (dibenzylideneacetone) dipalladium, the organophosphorus ligand is tris (o-methylphenyl) phosphorus, the benzene organic solvent is at least one of toluene, xylene and chlorobenzene, and the chlorinated hydrocarbon solvent is dichloromethane and/or chloroform.
Preferably, the boron-amine complex monomer and the 2, 5-bis- (trimethylstannyl) thiophene are fed according to the molar ratio of bromine atoms in the boron-amine complex monomer to trimethyltin in the 2, 5-bis- (trimethylstannyl) thiophene of 1:1.
Preferably, the organopalladium catalyst is fed in an amount of 5 to 15% of the molar amount of the boron-amine complex monomer; the organophosphorus ligand is added according to 20-60% of the molar quantity of the boron-amine complex monomer.
Preferably, the temperature of the heating reaction is 80-100 ℃ and the time is 36-60 h.
Preferably, the halogenated hydrocarbon solvent is a water-scavenging oxygen-scavenging solvent.
The invention also provides application of the boron-amine conjugated polymer with strong charge separation in photocatalytic hydrogen production.
Compared with the prior art, the invention has the following beneficial effects:
1. aiming at the problem that most of the charge separation of the existing organic catalyst structural units is incomplete, the invention designs a boron-amine complex monomer with strong charge separation, and utilizes the boron-tin exchange reaction as a polymerization means to prepare a boron-amine conjugated polymer catalyst with strong charge separation, thereby overcoming the problems of incomplete charge separation, low photocatalytic activity and efficiency and the like of most of the existing organic catalyst structural units;
2. the boron-amine conjugated polymer has high catalytic activity and efficiency, and the preparation method is simple, and has good application prospect in the field of photocatalytic hydrogen production.
Drawings
FIG. 1 is an Infrared (IR) spectrum of polymer PBN-3 prepared in example 1;
FIG. 2 is an Infrared (IR) spectrum of polymer PBN-4 prepared in example 2;
FIG. 3 is an Infrared (IR) spectrum of polymer PBN-6 prepared in example 3;
FIG. 4 is a charge separation display of template molecules.
FIG. 5 is a graph showing the photocatalytic hydrolysis hydrogen production curve.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Example 1
Boron-amine complex monomer tri (5-bromothiophen-2-yl) boron-pyridine complex with strong charge separation, denoted as BN3, of formula (C 4 H 2 BrS) 3 B·C 5 H 5 N, its structure is:
the synthetic route and the steps are as follows:
in Schlenk tube, BBr is first prepared 3 (0.57 g,2.26 mmol) was added to the tube, followed by addition of 5mL of toluene, and the compound (5-bromothiophen-2-yl) trimethylstannane (2.43 g,7.46 mmol) was dissolved in toluene and slowly added dropwise, the total amount of solvent was made up to 20mL, the Schlenk tube was transferred to an oil bath, and the branch was stirred at 120℃with nitrogen for 3 days. After the completion of the reaction, the Schlenk tube was cooled and transferred to a glove box and dried under vacuum. After adding 0.94mL of pyridine, about 10mL of toluene was added and the reaction was continued in a glove box for three days at room temperature. After the reaction was completed, the solvent was removed by rotary evaporation, and the residue was purified by silica gel column chromatography using petroleum ether and methylene chloride (1:1). Finally, 0.97g of white solid was obtained. 1 H NMR(400MHz，CDCl 3 )：δ8.63-8.55(m，2H)，8.13(t，J＝7.6Hz，1H)，7.63(t，J＝7.0Hz，2H)，7.00(d，J＝3.6Hz，3H)，6.72(d，J＝3.6Hz，3H)； 13 C NMR(101MHz，CDCl 3 )：δ146.80，141.80，132.07，130.60，125.60，113.56； 11 B NMR(128MHz，CDCl 3 )：δ-1.43ppm。
Example 2
Boron-amine complex monomer tri (5-bromothiophen-2-yl) boron-4-bromopyridine complex with strong charge separation, denoted as BN4, and chemical formula (C) 4 H 2 BrS) 3 B·C 5 H 4 BrN has the structural formula:
the synthetic route and the steps are as follows:
the synthesis of compound BN4 is divided into two steps: the first step is the preparation of 4-bromopyridine, 4-bromopyridine hydrochloride (2.4 g,12.3 mmol), triethylamine (2.6 mL,18.7 mmol), and toluene (50 mL) were sequentially added to a 100mL flask, and the mixture was stirred at room temperature for 12h. The second step is the preparation of the compound BN4, BBr is first prepared in a Schlenk tube 3 (0.61 g,2.44 mmol) was added to the tube, followed by addition of 5mL of toluene, and after dissolving the compound (5-bromothiophen-2-yl) trimethylstannane (2.63 g,8.07 mmol) in toluene, the total amount of solvent was slowly added dropwise, the Schlenk tube was transferred to an oil bath and the branch was stirred with nitrogen at 120℃for 3 days. After the completion of the reaction, the Schlenk tube was cooled and transferred to a glove box and dried under vacuum. After adding a mixture of 4-bromopyridine and triethylamine hydrochloride, the mixture was reacted in a glove box at room temperature for three days after adding about 10mL of toluene. After the reaction was completed, the solvent was removed by rotary evaporation, and the residue was purified by silica gel column chromatography using petroleum ether and methylene chloride (1:1). Finally, 1.08g of white solid was obtained. 1 H NMR(400MHz，CDCl 3 )：δ8.39(d，J＝6.9Hz，2H)，7.76(d，J＝6.9Hz，2H)，7.01(d，J＝3.6Hz，3H)，6.73(d，J＝3.5Hz，3H)； 13 C NMR(101MHz，CDCl 3 )：δ147.17，139.92，132.25，130.69，129.29，113.86ppm； 11 B NMR(128MHz，CDCl 3 )：δ-1.12ppm。
Example 3
Boron-amine complex monomer tri (5-bromothiophen-2-yl) boron-4, 4' -bipyridine complex with strong charge separation, which is marked as BN6, and has a chemical formula (C) 4 H 2 BrS) 3 B·NC 5 H 4 -C 5 H 4 N·B(C 4 H 2 BrS) 3 The structural formula is as follows:
the synthetic route and the steps are as follows:
the synthesis of compound BN6 was carried out in the same way as BN3 (example 1), the following materials were added: BBr (BBr) 3 (0.47 g,1.86 mmol), (5-bromothiophen-2-yl) trimethylstannane (2.0 g,6.14 mmol), 4' -bipyridine (0.14 g,0.87 mmol), 20mL toluene. Finally, 0.85g of yellow solid was obtained. 1 H NMR(400MHz，CDCl 3 )：δ8.81(d，J＝6.9Hz，4H)，7.85(d，J＝6.3Hz，4H)，7.04(d，J＝3.6Hz，6H)，6.81(6H)； 13 C NMR(101MHz，D-Acetone)：δ147.65，146.44，132.11，130.77，125.05，112.74ppm； 11 B NMR(128MHz，D-Acetone)：δ-1.42ppm。
Example 4
A boron-amine conjugated polymer with strong charge separation, designated PBN-3, having a basic structural unit represented by formula I:
the synthetic route and the steps are as follows:
into a Schlenk tube was added successively boron-amine complex monomer BN3 (0.3 g,0.52 mmol), 2, 5-bis (trimethylstannyl) thiophene (0.32 g,0.78 mmol), tris (dibenzylideneacetone) dipalladium (Pd) 2 (dba) 3 0.034g,0.037 mmol) and tris (o-methylphenyl) phosphorus (P (o-tol) 3 After (0.056 g,0.18 mmol), 8mL toluene was added and stirred in an oil bath at 90℃for 48h. After the reaction was completed, the Schlenk tube was cooled and transferred to a glove box. The solid was repeatedly washed with water-deoxygenated dichloromethane in a glove box and filtered through a sand funnel. Finally, the solid was transferred into a small bottle and extracted under vacuum for 4 hours to obtain 190.0mg of brown solid, namely boron-amine conjugated polymer PBN-3. 11 B MAS SSNMR(400MHz)：δ (iso )-2.2ppm。IR:C-B stretching signal:1035cm -1 ；C＝C-stretching:1490cm -1 ；B-N stretching:1412cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The IR spectrum is shown in FIG. 1.
Example 5
A boron-amine conjugated polymer with strong charge separation, denoted PBN-4, having a basic structural unit represented by formula II:
the synthetic route and the steps are as follows:
the conjugated polymer PBN-4 was synthesized in the same manner as PBN-3 (example 4). Feeding: boron-amine Complex monomer BN4 (0.3 g,0.46 mmol), 2, 5-bis (trimethylstannyl) thiophene (0.38 g,0.92 mmol), tris (dibenzylideneacetone) dipalladium (0.03 g,0.033 mmol) and tris (o-methylphenyl) phosphorus (0.049 g,0.16 mmol) and 8mL toluene. Finally 223.0mg of orange-red solid is obtained, namely the boron-amine conjugated polymer PBN-4. 11 B MAS SSNMR(400MHz)δ (iso) -5.6ppm。IR:C-B stretching signal:1039cm -1 ；C＝C stretching:1495cm -1 ；B-N stretching:1416cm -1 The IR spectrum is shown in figure 2.
Example 6
A boron-amine conjugated polymer with strong charge separation, designated PBN-6, having a basic structural unit represented by formula III:
the synthetic route and the steps are as follows:
the synthesis of PBN-6 was carried out in the same manner as PBN-3 (example 4). Feeding: boron-amine Complex monomer BN6 (0.3 g,0.26 mmol), 2, 5-bis (trimethylstannyl) thiophene (0.32 g,0.78 mmol), dibenzylideneacetone dipalladium (0.024 g,0.026 mmol) and tris (o-methylphenyl) phosphorus (0.04 g,0.13 mmol) and 8mL toluene. Finally, 252.0mg of orange-red solid is obtained, namely the boron-amine conjugated polymer PBN-6. 11B MAS SSNMR (400 MHz): delta (iso) -1.7ppm. IR C-B stretching signal 1038cm -1 ；-C＝C-stretching:1493cm -1 ；B-N stretching:1415cm -1 The method comprises the steps of carrying out a first treatment on the surface of the The IR spectrum is shown in figure 3.
Application examples
Theoretical calculation and research charge separation:
we have used density functional theory (Density Functional Theor, DFT) in gaussian software to study the charge separation properties of template molecules. First we use DFT to optimize the molecular structure. After obtaining the optimized configuration, we calculated the front molecular orbital of the molecule using Time-dependent density functional theory (Time-Dependent Density Functional Theory, TD-DFT). As shown in fig. 4, the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) exhibited distinct charge separation characteristics.
Photocatalytic hydrolysis to produce hydrogen (exemplified by PBN-3 prepared in example 4):
5mg of PBN-3 powder was added to 100mL0.1M aqueous ascorbic acid. Ultrasonic treatment was carried out for 30 minutes to obtain a well-dispersed suspension. 3wt% Pt as promoter. The resulting suspension was transferred to a top-illuminated two-necked Pyrex reaction vessel connected to a closed gas system. The reaction mixture was evacuated several times to ensure complete removal of air prior to the reaction. Irradiation was performed using a 300W xenon lamp (PLS-SXE 300/300 UV) with a 400nm cutoff filter. The duration of photocatalytic hydrogen production was 7 hours. Hydrogen is released from the system, and is detected once per hour by an automatic online trace gas analysis system (Labsor-6A) with nitrogen as carrier gas, so as to obtain a hydrogen production curve shown in FIG. 5, and the hydrogen production rate is calculated to be 18 mu mol g -1 h -1 。
While the invention has been described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A boron-amine complex monomer having strong charge separation, characterized by being any one of BN3, BN4, BN6 and BN9 shown below:
2. the method for preparing a boron-amine complex monomer having strong charge separation according to claim 1, comprising the steps of:
step 1: BBr is used for 3 Dissolving (5-bromothiophene-2-yl) trimethylstannane in benzene solvent, and reacting under inert atmosphere to obtain the final productPreparing an intermediate A;
step 2: reacting an intermediate A, a pyridine compound and a benzene organic solvent under an inert atmosphere, removing the solvent from the obtained mixture after the reaction is finished, and purifying to obtain a boron-amine complex monomer, wherein boron-amine complex monomer BN3 is prepared from the intermediate A and pyridine, boron-amine complex monomer BN4 is prepared from the intermediate A, 4-bromopyridine and triethylamine hydrochloride, boron-amine complex monomer BN6 is prepared from the intermediate A and 4,4' -bipyridine, and boron-amine complex monomer BN9 is prepared from the intermediate A and 1,3, 5-tri (4-pyridyl) benzene.
3. The boron-amine conjugated polymer with strong charge separation is characterized in that the boron-amine conjugated polymer is prepared by taking the boron-amine complex monomer and 2, 5-bis (trimethylstannyl) thiophene as raw materials, and has the structural units shown in the following formula I, formula II, formula III or formula IV:
4. a method for preparing a boron-amine conjugated polymer having strong charge separation as defined in claim 3, wherein the chemical reaction formula is as follows:
the method comprises the following steps:
heating and reacting a boron-amine complex monomer, 2,5 bis (trimethylstannyl) thiophene, an organic palladium catalyst, an organic phosphorus ligand and a benzene organic solvent for a period of time under an inert atmosphere condition according to a certain feeding proportion to generate a precipitate, adding a halogenated hydrocarbon solvent in turn under the inert condition after the reaction is finished to wash the precipitate, filtering to obtain a solid product, and vacuum drying the obtained solid product to obtain the corresponding boron-amine conjugated polymer;
wherein, the conjugated polymer containing the structural unit shown in the formula I is prepared by the reaction of boron-amine complex monomer BN3 and 2, 5-bis (trimethylstannyl) thiophene;
the conjugated polymer containing the structural unit shown in the formula II is prepared by reacting boron-amine complex monomer BN4 and 2, 5-bis (trimethylstannyl) thiophene;
the conjugated polymer containing the structural unit shown in the formula III is prepared by reacting boron-amine complex monomer BN6 and 2, 5-bis (trimethylstannyl) thiophene;
conjugated polymers containing structural units of formula IV are prepared by reacting boron-amine complex monomers BN9 with 2, 5-bis (trimethylstannyl) thiophene.
5. The method for preparing a boron-amine conjugated polymer with strong charge separation according to claim 4, wherein the organic palladium catalyst is tris (dibenzylideneacetone) dipalladium, the organophosphorus ligand is tris (o-methylphenyl) phosphorus, the benzene-based organic solvent is at least one of toluene, xylene and chlorobenzene, and the chlorinated hydrocarbon solvent is dichloromethane and/or chloroform.
6. The method for preparing a boron-amine conjugated polymer with strong charge separation according to claim 4, wherein the boron-amine complex monomer and 2, 5-bis (trimethylstannyl) thiophene are fed in a molar ratio of bromine atoms in the boron-amine complex monomer to trimethyltin in the 2, 5-bis (trimethylstannyl) thiophene of 1:1.
7. The method for preparing a boron-amine conjugated polymer with strong charge separation according to claim 4, wherein the organopalladium catalyst is fed in an amount of 5 to 15% of the molar amount of the boron-amine complex monomer; the organophosphorus ligand is added according to 20-60% of the molar quantity of the boron-amine complex monomer.
8. The method for preparing a boron-amine conjugated polymer having strong charge separation according to claim 4, wherein the heating reaction is carried out at a temperature of 80 to 100 ℃ for 36 to 60 hours.
9. The method for preparing a boron-amine conjugated polymer having strong charge separation according to claim 4, wherein said halogenated hydrocarbon solvent is a water-removing oxygen-removing solvent.
10. Use of a boron-amine conjugated polymer with strong charge separation according to claim 3 for photocatalytic hydrogen production.
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