CN112898542B - 一种d-a型共轭聚合物及其制备方法和应用 - Google Patents
一种d-a型共轭聚合物及其制备方法和应用 Download PDFInfo
- Publication number
- CN112898542B CN112898542B CN202110147183.XA CN202110147183A CN112898542B CN 112898542 B CN112898542 B CN 112898542B CN 202110147183 A CN202110147183 A CN 202110147183A CN 112898542 B CN112898542 B CN 112898542B
- Authority
- CN
- China
- Prior art keywords
- conjugated polymer
- polymer
- type conjugated
- hydrogen production
- photocatalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000547 conjugated polymer Polymers 0.000 title claims description 44
- 238000002360 preparation method Methods 0.000 title description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000011941 photocatalyst Substances 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000006880 cross-coupling reaction Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 238000000944 Soxhlet extraction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013317 conjugated microporous polymer Substances 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- UBHPRZXDFVCNHZ-UHFFFAOYSA-N 2-(3,5-dithiophen-2-ylphenyl)thiophene Chemical compound C1=CSC(C=2C=C(C=C(C=2)C=2SC=CC=2)C=2SC=CC=2)=C1 UBHPRZXDFVCNHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WAMNMWZTMRFWCM-UHFFFAOYSA-N 2-[3,5-bis(5-bromothiophen-2-yl)phenyl]-5-bromothiophene Chemical compound S1C(Br)=CC=C1C1=CC(C=2SC(Br)=CC=2)=CC(C=2SC(Br)=CC=2)=C1 WAMNMWZTMRFWCM-UHFFFAOYSA-N 0.000 description 1
- LUDZJVZEBHTEBB-UHFFFAOYSA-N 3,7-dibromodibenzothiophene 5,5-dioxide Chemical compound C1=C(Br)C=C2S(=O)(=O)C3=CC(Br)=CC=C3C2=C1 LUDZJVZEBHTEBB-UHFFFAOYSA-N 0.000 description 1
- -1 4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl Chemical group 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 150000003457 sulfones Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/13—Morphological aspects
- C08G2261/132—Morphological aspects branched or hyperbranched
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/411—Suzuki reactions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种D‑A型共轭聚合物及其制备方法和应用，所述聚合物由二苯并噻吩砜作为电子供体，与不同电子受体单元通过交叉偶联策略构筑得到，所述聚合物具有高化学稳定性和热稳定性，在可见光区展现了强的吸收，可以高效利用太阳光，可在不添加任何助催化剂的情况下，仍具有优良的光催化水分解制氢性能。
Description
技术领域
本发明涉及共轭聚合物材料技术领域，更具体地，涉及一种D-A型共轭聚合物及其制备方法和应用。
背景技术
全球经济迅猛发展，人类消耗能源的速度不断加快，但石油、煤矿等不可再生的矿产资源储量逐年减少，在不久的将来能源问题必将严重影响社会的发展和进步，同时矿石燃料的过度使用也带来了极端天气频发、生物灭绝速度加快等严重的环境问题。因此，研发一种绿色可持续能源具有十分重要的战略意义。利用太阳光照射在催化剂上引起光子的跃迁，在一定的条件下分解水产生氢气，可实现太阳能到化学能的转变，且氢气也是一种清洁无污染的二次能源，有着广阔的应用前景。与生物制氢、矿物资源的重整等传统制氢手段相比，光催化分解水制氢更加符合绿色环保的要求，被誉为最为理想的产氢技术。
目前用于制氢的光催化剂主要是含金属的无机半导体，但其存在可见光活性低，金属资源有限等缺点。从可持续发展来看，纯有机半导体光催化剂在光催化分解水制氢领域中占据重要地位。D-A型共轭聚合物作为一种新型的有机半导体光催化剂，由于其原料来源丰富、合成方法简单以及结构易于调控等独特的优势，引起了研究者们极大的关注。如Zijian W等人在氮气气氛下合成出了一种含二苯并噻吩二氧化物的CMP(共轭微孔聚合物)光催化剂(Zijian W,Xiye Y,Tongjia Y, et al.Dibenzothiophene Dioxide-BasedConjugated Microporous Polymers for Visible-Light-Driven Hydrogen Production[J].Acs Catalysis,2018)。然而，Zijian W 等人开发的聚合物光催化剂在没有Pt作为助催化剂条件下，析氢速率仅为 2460μmol h-1g-1，无法与含金属的无机半导体媲美。
发明内容
本发明的首要目的是克服现有技术所述聚合物用于光催化产氢时析氢速率低的问题，提供一种D-A型共轭聚合物，所述聚合物用于光催化分解水制氢时析氢速率高，化学稳定性和热稳定性好，且在可见光区展现了强的吸收。
本发明的进一步目的是提供所述D-A型共轭聚合物的制备方法。
本发明的另一目的是提供一种包含所述D-A型共轭聚合物的光催化剂及其应用。
本发明的上述目的通过以下技术方案实现：
一种D-A型共轭聚合物，所述聚合物化学结构式如下：
其中，聚合度n＝50～250，
单元设计为以下结构式中的任意一种；
本发明所述D-A型共轭聚合物具有多孔性，增加了将其用作光催化剂时催化反应的活性位点，同时砜基官能团的存在提高了聚合物的亲水性，增大了催化剂与水分子的接触面积，促进界面发生反应，提高光催化产氢性能。通过调整聚合物的组成结构，改变了聚合物的光谱响应范围和光学带隙，提高了聚合物对太阳光的有效利用率，进而提高了所述聚合物用于光催化产氢的反应速率。
优选地，所述D-A型共轭聚合物的聚合度为180～250。
上述D-A型共轭聚合物的制备方法，包括以下步骤：
在惰性气氛下，向二苯并噻吩砜与
单元的混合物中加入钯催化剂、无机碱和有机溶剂，加热反应，所得即为D-A型共轭聚合物。
优选地，所述有机溶剂选自氯苯、甲苯和N,N-二甲基甲酰胺中的一种或多种。
优选地，所述加热反应温度为100～160℃，反应时间为12～60h。
优选地，二苯并噻吩砜与
单元的摩尔比为(0.5～1.5)：1。
优选地，二苯并噻吩砜与钯催化剂的摩尔比为1：(0.01～0.015)。
在本发明中，所述钯催化剂为Pd(pph3)4或Pd(dppf)Cl2。。
优选地，二苯并噻吩砜与无机碱的摩尔比为1：(5～10)。
在本发明中，所述无机碱为碳酸钾或磷酸钾。
本发明还保护上述D-A型共轭聚合物组成的光催化剂。
本发明还保护上述光催化剂在光催化分解水制氢中的应用。
与现有技术相比，本发明的有益效果是：
本发明以二苯并噻吩砜作为电子供体，与不同电子受体单元通过交叉偶联策略构筑得到D-A型共轭聚合物，所述聚合物具有高化学稳定性和热稳定性，在可见光区展现了强的吸收，可高效利用太阳光，可在不添加任何助催化剂的情况下，实现高效光催化分解水制氢。
附图说明
图1为实施例1～3所述聚合物P1、P2和P3的紫外-可见吸收光谱图。
图2为实施例1～3所述聚合物P1、P2和P3的热失重分析图。
图3为实施例1～3所述光催化剂P1、P2和P3的光催化水分解产氢效率图。
具体实施方式
为了更清楚、完整的描述本发明的技术方案，以下通过具体实施例进一步详细说明本发明，应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明，可以在本发明权利限定的范围内进行各种改变。
实施例1
本实施例所述D-A型共轭聚合物的合成路线如下：
本实施例所述D-A型共轭聚合物的制备方法如下：
(1)单体M1的合成：
称量二苯并噻吩砜(10mmol，2.1625g)加入25mL圆底烧瓶中，加入70mL 浓硫酸，搅拌均匀后，在0℃下，分批次加入NBS(21mmol，3.7380g)；避光条件下反应24h后，将反应液倒入冰水中并搅拌，固体用水和甲醇洗至PH＝7，通过CH3Cl重结晶得3,7-二溴二苯并[b，d]噻吩5,5-二氧化物(白色固体)；
称量3,7-二溴二苯并[b，d]噻吩5,5-二氧化物(10mmol，3.7405g)，联硼酸频那醇酯(30mmol，7.620g)，醋酸钾(60mmol，5.880g)和Pd(dppf)Cl2(0.5mmol， 0.3658g)加入250mL双颈烧瓶，抽换气三次以除去氧气；加入无水DMF(60mL)，再次将反应液抽换气，然后加热到90℃，反应12h。用饱和NaCl溶液洗涤并用二氯甲烷萃取，粗产物通过硅胶色谱柱纯化，并用四氢呋喃/甲醇重结晶，得到白色晶体3,7-双(4,4,5,5-四甲基-1,3,2-二氧杂硼硼烷-2-基)二苯并[b，d]噻吩5,5- 二氧化物(M1)；
(2)共轭聚合物P1的合成：
将单体M1(0.5mmol，0.2341g)和单体M2(0.25mmol，0.100g)加入48ml 玻璃耐压瓶中；然后在充满氮气的手套箱中加入Pd(pph3)4(0.025mmol，29mg)， K2CO3(2mol/L，6mL)以及DMF(12mL)，拧紧四氟塞；在160℃条件下，反应48h。反应液冷却至室温后滴入甲醇溶液中，过滤得粗产物，分别用甲醇、正己烷、二氯甲烷、四氢呋喃进行索氏抽提。剩余固体用甲醇冲洗，真空干燥24h，得到142.0mg黄绿色共轭聚合物P1。经测试，聚合物P1的聚合度为207。
本实施例所述光催化剂由共轭聚合物P1组成。
实施例2
本实施例所述D-A型共轭聚合物的合成路线如下：
本实施例所述D-A型共轭聚合物的制备方法如下：
(1)共轭聚合物P2的合成；
将单体M1(0.5mmol，0.2341g)和单体M3(0.25mmol，0.1139g)加入48ml 玻璃耐压瓶中；然后在充满氮气的手套箱中加入Pd(pph3)4(0.025mmol，29mg)， K2CO3(2mol/L，6mL)以及DMF(12mL)，拧紧四氟塞；在160℃条件下，反应48h。反应液冷却至室温后滴入甲醇溶液中，过滤得粗产物，分别用甲醇、正己烷、二氯甲烷、四氢呋喃进行索氏抽提。剩余固体用甲醇冲洗，真空干燥24h，得到152.7mg黄棕色共轭聚合物P2。经测试，聚合物P2的聚合度为203。
本实施例所述光催化剂由共轭聚合物P2组成。
实施例3
本实施例所述D-A型共轭聚合物的合成路线如下：
本实施例所述D-A型共轭聚合物的制备方法如下：
(1)单体M5的合成：
称量1,3,5-三溴苯(10mmol，3.1480g)，噻吩-2-基硼酸(35mmol，4.4786g) 和Pd(pph3)4(0.5mmol，0.5778g)加入250mL双颈烧瓶，抽换气三次除去反应瓶中的氧气。加入磷酸钾(2mmol·L-1，10mL)和无水THF(100mL)。在85℃下反应20h。用饱和NaCl溶液洗涤并用二氯甲烷萃取，粗产物通过硅胶色谱柱纯化，并用四氢呋喃/甲醇重结晶，得白色固体1,3,5-三(噻吩-2-基)苯；
称量1,3,5-三(噻吩-2-基)苯(1mmol，0.3245g)加入圆底烧瓶，加入THF (20mL)；在0℃下，分批次加入NBS(4mmol，0.712g)，避光条件下反应一晚。用硫代硫酸钠淬灭反应后用饱和NaCl溶液洗涤并用二氯甲烷萃取，粗产物通过硅胶色谱柱纯化，并用四氢呋喃/甲醇重结晶，得微黄固体1,3,5-三(5-溴噻吩-2- 基)苯；
(2)共轭聚合物P3的合成：
将单体M5(0.8mmol，0.4489g)和单体M1(1.2mmol，0.5618g)加入75ml 玻璃耐压瓶中；然后在充满氮气的手套箱中加入Pd(pph3)4(0.014mmol，16mg)， K2CO3(2mol/L，5mL)以及DMF(20mL)，拧紧四氟塞；在120℃条件下，反应48h。反应液冷却至室温后滴入甲醇溶液中，过滤得粗产物，分别用甲醇、正己烷、二氯甲烷、四氢呋喃进行索氏抽提。剩余固体用甲醇冲洗，真空干燥24h，得到574mg黄色共轭聚合物P3。经测试，聚合物P3的聚合度为195。
本实施例所述光催化剂由共轭聚合物P3组成。
对比例1
本对比例所述D-A型共轭聚合物的合成路线如下：
本对比例所述D-A型共轭聚合物的制备方法如下：
(1)单体M4的合成：
称量3,7-二溴二苯并[b，d]噻吩(1mmol，0.3425g)，联硼酸频那醇酯(2.5mmol，0.635g)，醋酸钾(4mmol，0.392g)和Pd(dppf)Cl2(0.05mmol，0.0366g)加入 50mL两颈烧瓶，将反应物抽换气三次以除去氧气。加入干燥后的1,4-二氧六环 (15mL)，再次将反应液抽换气，然后加热到80℃，反应12h。用饱和NaCl溶液洗涤并用二氯甲烷萃取，粗产物通过硅胶色谱柱纯化，并用四氢呋喃/甲醇重结晶，得到白色晶体3,7-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)二苯并[b， d]噻吩(M4)。
(2)共轭聚合物P4的合成：
将单体M5(0.8mmol，0.4489g)和单体M4(1.2mmol，0.5234g)加入75ml 玻璃耐压瓶中；然后在充满氮气的手套箱中加入Pd(pph3)4(0.014mmol，16mg)， K2CO3(2mol/L，5mL)以及DMF(20mL)，拧紧四氟塞；在120℃条件下，反应48h。反应液冷却至室温后滴入甲醇溶液中，过滤得粗产物，分别用甲醇、正己烷、二氯甲烷、四氢呋喃进行索氏抽提。剩余固体用甲醇冲洗，真空干燥24h，得到558mg黄绿色共轭聚合物P4。经测试，聚合物P4的聚合度为196。
本对比例所述光催化剂由共轭聚合物P4组成。
对比例2
本对比例所述D-A型共轭聚合物的合成路线如下：
本对比例所述D-A型共轭聚合物的制备方法如下：
在烧瓶中加入3,3”，5,5”-四(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-1,1'：4'，1”-三联苯(734mg，1mmol)，3,7-二溴二苯并[b，d]噻吩5,5-二氧化物(748 mg，2.0mmol)，四三苯基膦钯(25mg，21.6μmol)，DMF(20mL)和K2CO3溶液(2.0M，3mL)加热搅拌，获得共轭聚合物。
本对比例所述光催化剂由上述共轭聚合物组成。
测试表征
分别将5mg实施例1～3及对比例1～2所述光催化剂加入到50mL去离子水中，牺牲剂选用抗坏血酸，超声30min分散均匀，用氙灯模拟太阳光光照，光功率为318mW/cm2，进行光催化产氢测试。反应过程中利用循环冷却水使反应溶液的温度保持在5℃。产生的氢气在带有热导检测器的在线GC7900气相色谱仪上进行检测，测试结果见表1。
表1实施例1～3及对比例1～2所述光催化剂析氢速率(μmol·g-1·h-1)
| 实施例1 | 实施例2 | 实施例3 | 对比例1 | 对比例2 | |
| 析氢速率 | 3120 | 5820 | 44100 | 189 | 116 |
图1为实施例1～3所述聚合物P1、P2和P3的紫外-可见吸收光谱图。从图 1中可知，本发明所述D-A型共轭聚合物在可见光范围内具有良好的吸收。
图2为实施例1～3所述聚合物P1、P2和P3的热失重分析图。从图2中可以看出，本发明所述D-A型共轭聚合物的热稳定性良好。
图3为实施例1～3所述光催化剂P1、P2和P3的光催化水分解产氢速率图。从图3可知，本发明所述光催化剂具有较高的产氢速率，其中P3具有最高的产氢速率。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。
Claims (3)
1.一种D-A型共轭聚合物，其特征在于，所述聚合物化学结构式如下：
2.一种光催化剂，其特征在于，包含权利要求1所述D-A型共轭聚合物。
3.权利要求2所述光催化剂在光催化分解水制氢中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110147183.XA CN112898542B (zh) | 2021-02-03 | 2021-02-03 | 一种d-a型共轭聚合物及其制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110147183.XA CN112898542B (zh) | 2021-02-03 | 2021-02-03 | 一种d-a型共轭聚合物及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112898542A CN112898542A (zh) | 2021-06-04 |
| CN112898542B true CN112898542B (zh) | 2022-06-24 |
Family
ID=76121750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110147183.XA Expired - Fee Related CN112898542B (zh) | 2021-02-03 | 2021-02-03 | 一种d-a型共轭聚合物及其制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112898542B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578382B (zh) * | 2021-07-29 | 2023-07-25 | 陕西师范大学 | 高光催化分解水制氢活性的含噻吩基聚合物光催化剂及其制备方法 |
| CN113501940B (zh) * | 2021-08-26 | 2023-01-20 | 广东工业大学 | 一种d-a型共轭聚合物及其制备方法和应用 |
| CN114405544B (zh) * | 2021-12-29 | 2023-11-21 | 盐城工学院 | 一种共轭聚合物负载金属铂纳米颗粒及其制备方法与在光催化析氢上的应用 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936969A (zh) * | 2013-01-23 | 2014-07-23 | 海洋王照明科技股份有限公司 | 含噻吩并噻吩-二苯并噻吩苯并二噻吩的共轭聚合物及其制备方法与应用 |
-
2021
- 2021-02-03 CN CN202110147183.XA patent/CN112898542B/zh not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936969A (zh) * | 2013-01-23 | 2014-07-23 | 海洋王照明科技股份有限公司 | 含噻吩并噻吩-二苯并噻吩苯并二噻吩的共轭聚合物及其制备方法与应用 |
Non-Patent Citations (2)
| Title |
|---|
| 《Conjugated donor-acceptor polymer photocatalysts with electron-output "tentacles" for efficient hydrogen evolution》;Zhi-An Lan et al.;《Applied Catalysis B: Environmental》;20190108;第245卷;第596-603页 * |
| 《Photocatalytic Hydrogen Evolution from Water Using Fluorene and Dibenzothiophene Sulfone-Conjugated Microporous and Linear Polymers》;Reiner Sebastian Sprick et al.;《Chemistry of Materials》;20181217;第31卷;第305-313页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112898542A (zh) | 2021-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112898542B (zh) | 一种d-a型共轭聚合物及其制备方法和应用 | |
| Cheng et al. | The effect of molecular structure and fluorination on the properties of pyrene-benzothiadiazole-based conjugated polymers for visible-light-driven hydrogen evolution | |
| CN113578382B (zh) | 高光催化分解水制氢活性的含噻吩基聚合物光催化剂及其制备方法 | |
| CN103071513A (zh) | 一种产氢光催化剂MoS2/ZnIn2S4及其制备方法 | |
| CN103025650B (zh) | 从作为氢载体的甲硅烷基化衍生物中制氢的氧化膦催化法 | |
| CN107899618B (zh) | 一种基于大环化合物光敏染料与二氧化钛的杂化材料及其制备方法和在光催化中的应用 | |
| CN109880087B (zh) | 一种具有三苯胺结构的共价三嗪有机框架材料及其制备方法和应用 | |
| CN110560170A (zh) | 一种新型Pd@MOF材料及其制备方法和其在联苯制备中的应用 | |
| CN113501940B (zh) | 一种d-a型共轭聚合物及其制备方法和应用 | |
| Luo et al. | Photocatalytic conversion of arylboronic acids to phenols by a new 2D donor–acceptor covalent organic framework | |
| CN111978516B (zh) | 一种供体-受体型离子多孔聚合物的制备及其催化应用 | |
| CN113248691B (zh) | 一种联噻吩线性有机共轭聚合物及其制备方法和应用 | |
| CN115286757B (zh) | 基于多氮烯烃连接的共价有机框架材料及其制备方法和应用 | |
| CN114736356B (zh) | 用于光催化分解水制氢的二苯并稠二萘基聚合物光催化剂及其制备方法 | |
| CN116120505A (zh) | 一类含卤素芘基共价有机框架聚合物光催化剂及其制备方法和应用 | |
| Zhu et al. | Visible-light-driven g-C3N4-doped Co catalyzed oxidation of benzylic hydroxylation of alkyl aromatic hydrocarbons | |
| Wang et al. | Fabrication of sulphonated hollow porous nanospheres and their remarkably improved catalytic performance for biodiesel synthesis | |
| CN108160097B (zh) | 一种用于乙炔氢氯化反应的无金属催化剂及其使用方法 | |
| CN112547027B (zh) | 一种掺杂高岭土的共轭微孔聚合物复合材料的制备方法 | |
| Zhang et al. | Benzotrithiophene-based sp2 carbon-conjugated microporous polymers for green light-triggered oxidation of amines to imines | |
| CN101982449B (zh) | 利用微波反应制备茚-c60双加成物的方法 | |
| CN106905195B (zh) | 一种苯乙烯焦油回收再利用制备磺酸盐的方法 | |
| CN114573796B (zh) | 三（4-乙炔苯基）胺类共轭微孔聚合物、制备方法及应用 | |
| CN109731611A (zh) | 一种基于光敏性金属-有机配位分子环与氮化碳的复合材料及其制备方法和应用 | |
| CN103601740B (zh) | 一种2,1,3-苯并噻二唑并二噻吩衍生溴代物及其合成方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220624 |