CN113578382A - Thiophene-group-containing polymer photocatalyst with high photocatalytic water splitting hydrogen production activity and preparation method thereof - Google Patents
Thiophene-group-containing polymer photocatalyst with high photocatalytic water splitting hydrogen production activity and preparation method thereof Download PDFInfo
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- CN113578382A CN113578382A CN202110861415.8A CN202110861415A CN113578382A CN 113578382 A CN113578382 A CN 113578382A CN 202110861415 A CN202110861415 A CN 202110861415A CN 113578382 A CN113578382 A CN 113578382A
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- thiophene
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- polymer photocatalyst
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- 229920000642 polymer Polymers 0.000 title claims abstract description 63
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000000694 effects Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 12
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 125000001544 thienyl group Chemical group 0.000 claims abstract description 11
- 229930192474 thiophene Natural products 0.000 claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- -1 thiophene-2, 5-diboronic acid dipinacol ester Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- KMNBVODPWIFUSS-UHFFFAOYSA-N 3,7-dibromodibenzothiophene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3SC2=C1 KMNBVODPWIFUSS-UHFFFAOYSA-N 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- SKFDVFMUXZWWOW-UHFFFAOYSA-N (5-boronothiophen-2-yl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)S1 SKFDVFMUXZWWOW-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- MYTMXVHNEWBFAL-UHFFFAOYSA-L dipotassium;carbonate;hydrate Chemical compound O.[K+].[K+].[O-]C([O-])=O MYTMXVHNEWBFAL-UHFFFAOYSA-L 0.000 claims 1
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 5
- 125000005581 pyrene group Chemical group 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 4
- 125000001725 pyrenyl group Chemical group 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 abstract 2
- 150000003577 thiophenes Chemical class 0.000 abstract 2
- 238000010276 construction Methods 0.000 abstract 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 229920000620 organic polymer Polymers 0.000 description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 9
- 239000011668 ascorbic acid Substances 0.000 description 9
- 229960005070 ascorbic acid Drugs 0.000 description 9
- 235000010323 ascorbic acid Nutrition 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 7
- ZKBKRTZIYOKNRG-UHFFFAOYSA-N 1,3,6,8-tetrabromopyrene Chemical compound C1=C2C(Br)=CC(Br)=C(C=C3)C2=C2C3=C(Br)C=C(Br)C2=C1 ZKBKRTZIYOKNRG-UHFFFAOYSA-N 0.000 description 6
- 239000000370 acceptor Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006254 arylation reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 description 1
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical class C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- MVLGANVFCMOJHR-UHFFFAOYSA-N 1,4-diethynylbenzene Chemical compound C#CC1=CC=C(C#C)C=C1 MVLGANVFCMOJHR-UHFFFAOYSA-N 0.000 description 1
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- OETBGSAJFWSUDM-UHFFFAOYSA-N thianthrene 5,5,10,10-tetraoxide Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3S(=O)(=O)C2=C1 OETBGSAJFWSUDM-UHFFFAOYSA-N 0.000 description 1
- UMHFSEWKWORSLP-UHFFFAOYSA-N thiophene 1,1-dioxide Chemical compound O=S1(=O)C=CC=C1 UMHFSEWKWORSLP-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 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 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- 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
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
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- 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
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- 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
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- C08G2261/40—Polymerisation processes
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- C08G2261/411—Suzuki reactions
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a polymer photocatalyst containing thienyl with high photocatalytic water splitting hydrogen production activity and a preparation method thereof, the photocatalyst is prepared by simple Suzuki coupling reaction of ternary copolymerization, and the construction unit comprises: pyrene, thiophene or thiophene derivatives and dibenzothiophene sulfone. The pyrenyl monomer and the dibenzothiophene sulfone monomer used for polymerization have the same polymerizable functional group, and can simultaneously generate Suzuki coupling reaction with thiophene or thiophene derivative monomers so as to ensure that pyrene units and dibenzothiophene sulfone units in a polymer structure are connected through thiophene or thiophene derivative units. The polymer photocatalyst has the characteristics of high photocatalytic hydrogen production activity, high apparent quantum efficiency, narrow optical band gap, continuously adjustable structure and composition, simple preparation process, high yield and stable performance, can release hydrogen under sunlight, and can be used in the field of photocatalytic hydrogen production.
Description
Technical Field
The invention belongs to the technical field of materials for producing hydrogen by photocatalytic water decomposition, and particularly relates to a thiophene-based polymer photocatalyst with high photocatalytic water decomposition hydrogen production activity and a preparation method thereof.
Background
The method for producing hydrogen by decomposing water by utilizing solar energy is a simple, economic and efficient technical means for converting solar energy into chemical energy, and is always highly concerned by global scientists. Over the last several decades, a great deal of scientific research has been carried out around improving the photocatalytic efficiency of semiconductor photocatalysts at home and abroad, and thousands of semiconductor photocatalysts have been developed for photocatalytic decomposition of water to produce hydrogen/oxygen.
The semiconductor photocatalyst is a key material for producing hydrogen by decomposing water through solar photocatalysis, and the improvement of the photocatalytic activity of the semiconductor photocatalyst is mainly realized by regulating and controlling the structure and the composition of a semiconductor. Among them, the organic polymer photocatalyst has a great development potential in the field of hydrogen production by photocatalytic water splitting due to the advantages of various synthesis methods, easy structure design, easy regulation of physicochemical properties and the like, and has been widely researched and paid attention in recent years. The D-A type polymer photocatalyst can effectively promote the separation efficiency of photo-generated charges due to the strong electron pulling effect of the receptor unit, and further improves the photocatalytic activity of the polymer photocatalyst. For example, 1, 4-phenyl diboronic acid and 4, 7-dibromo-2, 1, 3-benzothiadiazole can be used for preparing an organic polymer photocatalyst B-BT-1,4 with a D-A structure through a Suzuki coupling reaction, Triethanolamine (TEOA) is used as a sacrificial agent, and 2.32mmol h is obtained under the conditions of using a Pt cocatalyst and irradiating visible light-1g-1The photocatalytic hydrogen production rate of (angelw.chem.int.ed., 2016,55, 9202-. When a pyrene unit is used as an electron donor, diazosulfide is used as an electron acceptor, D-A type polymer L-PyBT is obtained through Suzuki coupling reaction, TEOA is used as a sacrificial agent, Pt is used as a cocatalyst, and 1.67mmol h is obtained under visible light-1g-1The photocatalytic hydrogen production rate (polymer. chem.,2018,9, 4468-4475). PySO polymers obtained by modification of the attachment site of dibenzothiophenesulfones to pyrene units when dibenzothiophenesulfones are used as electron acceptors and pyrenyl as electron donors (Small,2018,14, 18018)39) P16PySO (appl. Surf. Sci.,2019,495,143537) and PyDOBT-1(Macromolecules,2018,51,9502-9508), respectively, gave 4.74mmol h under visible light when Pt was not supported with TEOA as a sacrificial agent-1g-1、6.38mmol h-1g-1And 5.70mmol h-1g-1The photocatalytic hydrogen production activity. The polymer PyDF obtained by the Suzuki coupling reaction of fluorine substituted dibenzothiophene sulfone and pyrenyl under the condition of taking TEOA as a sacrificial agent and not loading Pt obtains 4.09mmol h under visible light-1g-1The photocatalytic hydrogen production rate (J.Mater.chem.A., 2020,8, 2404-2411). When thianthrene-5, 5,10, 10-tetraoxide as electron acceptor was coupled with pyrenyl as electron donor by Suzuki, the resulting polymer PySEO-1 gave 4.51mmol h under visible light when Pt was not supported with TEOA as sacrificial agent-1g-1Photocatalytic hydrogen production activity (ChemSusChem,2020,13, 369-375). When 9, 9-spirobifluorene was used as an electron donor, the S-CMP3 polymer obtained by Suzuki coupling reaction of 9, 9-spirobifluorene with dibenzothiophene sulfone gave 3.11mmol h when Triethylamine (TEA) was used as a sacrificial agent without loading Pt-1g-1Visible light catalytic hydrogen production activity (chem. mater.,2019,31, 305-313). Polymers P7(Angew. chem. int. Ed.,2016,55, 1792-containing 1796) and DBTD-CMP1(ACS Catal.,2018,8, 8590-containing 8596) obtained by Suzuki coupling reaction of phenyl and dibenzothiophene sulfone respectively obtain 3.68mmol h under visible light and respectively taking TEA and TEOA as sacrificial agents without loading Pt-1g-1And 2.46mmol h-1g-1The photocatalytic hydrogen production rate. When the benzotrithiophene is used as an electron donor, the polymer BTT-CPP obtained by the Suzuki coupling reaction of the benzotrithiophene and dibenzothiophene sulfone obtains 12.63mmol h under visible light when the Pt is not loaded by using Ascorbic Acid (AA) as a sacrificial agent-1g-1The photocatalytic hydrogen production rate (Macromolecules,2021,54, 2661-2666). When phenyl was used as the electron donor and thienyl and pyrazinyl as the electron acceptor, the polymers P13(J.Mater. chem.A., 2018,6, 11994-5703) and P28(chem.Mater.,2018,30,5733-5742) obtained by Suzuki coupling reaction respectively obtained 0.25mmol h when TEA was used as the sacrificial agent without loading Pt-1g-1And 0.96mmol h- 1g-1The hydrogen production rate is catalyzed by the visible light.
The organic polymers listed above have wide band gaps, are weak in absorbing visible light, and are difficult to fully utilize visible light in sunlight, so that the hydrogen production performance by photocatalytic water decomposition under visible light is low. B-FOBT-1,4-E obtained by Sonogashira coupling of 1, 4-diethynylbenzene as an electron donor and fluorine and methoxy substituted benzothiadiazole as an electron acceptor gave 13.3mmol h without loading Pt promoter under visible light with TEOA as a sacrificial agent-1g-1The photocatalytic hydrogen production rate (ACS Energy Lett.,2018,3, 2544-. 1,3,6, 8-tetrabromopyrene and 2, 5-dibromo-dithieno [3,2-b:2',3' -d]The polymer PyDTDO-3 obtained by the direct C-H arylation coupling reaction of the thiophenesulfone under visible light, without loading Pt and with AA as a sacrificial agent, obtains 16.32mmol H-1g-1The photocatalytic hydrogen production activity of (chem. Sci.,2021,12, 1796-. The polymer CP1(J.Mater.Chem.A,2019,7,24222-24230) obtained by the direct C-H arylation coupling reaction of 1,3,6, 8-tetrabromophyrene and 2, 2-dithiophene has the photocatalytic hydrogen production rate of 15.97mmol H under the condition of visible light and taking AA as a sacrificial agent-1g-1. When 1,3,6, 8-tetrabromopyrene is respectively reacted with 2, 5-bis (trimethylstannyl) thiophene and 2, 5-bis (trimethylstannyl) thieno [3,2-b ]]Thiophene and 2, 5-bis (trimethylstannyl) dithieno [3,2-b:2',3' -d]When thiophene is polymerized by Stille coupling reaction, polymers Py-T, Py-Tt and Py-Ttt (J.Mater.Chem.A,2021,9, 5787-containing 5795) are obtained, and 38.1mmol h is respectively obtained under the condition that AA is taken as a sacrificial agent and Pt is not loaded-1g-1、45.8mmol h-1g-1And 38.9mmol h-1g-1The hydrogen production rate is catalyzed by the visible light. The main reason for the improved performance of Py-Tt compared to CP1 may be due to the better coplanarity of Py-Tt, which facilitates the transport of photo-generated electrons. The photocatalytic performance of the polymer catalysts is improved mainly because the polymer catalysts have narrower band gaps and improve the absorption of visible light. Although Py-T, Py-Tt and Py-Ttt have lower band gaps, they do not have strong electron withdrawing units, resulting in photo-generated electrons and holes being unavailableThe efficiency is separated, which limits further improvement of the photocatalytic performance.
The organic polymer photocatalysts listed above are all obtained by polymerizing two functionalized monomers through a coupling reaction. Researches show that the optical property and the electrical property of the polymer can be regulated and controlled and the photocatalytic activity of the organic polymer can be regulated and controlled by a ternary or multiple copolymerization mode. For example, Cooper et al obtained a series of organic polymer photocatalysts CP-CMP1-15 by means of ternary polymerization, and the regulation of the optical band gap, specific surface area and photocatalytic performance of the organic polymer was realized by adjusting the charge ratio of the three units (J.Am.chem.Soc.2015,137, 3265-3270). By adjusting the charge ratio of the tetraphenylvinyl, the phenyl and the 9-fluorenone, the terpolymer F is obtained0.5CMP with Na2S/Na2SO4For the sacrificial agent not loaded with Pt, 0.66mmol h was obtained-1g-1The visible light hydrogen production activity (chem. eur. j.,2019,25, 3867-3874). When a benzene unit is introduced into the polymer skeleton as a bridge bond to connect a pyrene unit and a dibenzothiophene sulfone unit, by adjusting the charge ratio of a donor unit and an acceptor unit, the obtained D-pi-A polymer PyBS-3(adv. mater.,2021,2008498) obtains 14mmol h when the TEOA is used as a sacrificial agent and Pt is not loaded-1g-1The visible light of (2) decomposes water to generate hydrogen activity. When AA was used as sacrificial agent, 36mmol h were obtained-1g-1Compared with PyDOBT-1 and PyBS-3, the hydrogen production activity of decomposing water by visible light is greatly improved, mainly because the introduction of the benzene bridge bond reduces the distortion degree between molecules, which is beneficial to the transmission of electrons, but the energy band structure is still wider, so that the hydrogen production activity of catalyzing is lower under the irradiation of visible light.
Disclosure of Invention
The invention aims to provide a polymer photocatalyst containing thienyl which has high photocatalytic water splitting hydrogen production activity under the irradiation of visible light, and provides a preparation method with simple process steps and high yield for the polymer photocatalyst.
Aiming at the purposes, the structure of the polymer photocatalyst containing the thienyl adopted by the invention is shown as a formula A or a formula B:
the molar ratio of n to m in the formula A is 1: 3-10, and the molar ratio of x to y in the formula B is 1: 2-10.
The preparation method of the polymer photocatalyst containing the thienyl group comprises the following steps: under the protection of nitrogen, adding a potassium carbonate aqueous solution, 1,3,6, 8-tetrabromophyrene, thiophene-2, 5-diboronic acid dipinacol ester or 2, 5-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) thieno [3,2-B ] thiophene, 3, 7-dibromo dibenzothiophene sulfone and tetrakis (triphenylphosphine) palladium into an organic solvent, heating to reflux for 24-72 hours, cooling to room temperature after the reaction is finished, washing with dichloromethane, methanol and water, and drying in vacuum to obtain a thiophene-containing polymer photocatalyst (recorded as Py-TP-BTDO) shown in a formula A or a thiophene-containing polymer photocatalyst (recorded as Py-TTP-BTDO) shown in a formula B, wherein the reaction equation is as follows:
in the above preparation method, it is preferable that the molar ratio of 1,3,6, 8-tetrabromopyrene to 3, 7-dibromodibenzothiophene sulfone is 1:3 to 10, the molar ratio of 1,3,6, 8-tetrabromopyrene to 3, 7-dibromodibenzothiophene sulfone is 1:2 to 10, and the amount of thiophene-2, 5-diboronic acid dipivalol ester or 2, 5-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) thieno [3,2-b ] thiophene is the sum of twice the molar amount of 1,3,6, 8-tetrabromopyrene and the molar amount of 3, 7-dibromodibenzothiophene sulfone.
In the preparation method, the adding amount of the tetrakis (triphenylphosphine) palladium is preferably 0.8-2% of the molar amount of the total bromine functional groups in 1,3,6, 8-tetrabromophyrene and 3, 7-dibromodibenzothiophene sulfone, and the adding amount of the potassium carbonate is preferably 2-5 times of the molar amount of the total bromine functional groups in 1,3,6, 8-tetrabromophyrene and 3, 7-dibromodibenzothiophene sulfone.
In the above preparation method, the reaction mixture is further preferably heated to reflux reaction for 36 to 48 hours.
In the preparation method, the organic solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and tetrahydrofuran.
The invention has the following beneficial effects:
1. according to the invention, thiophene or thieno [3,2-b ] thiophene with a narrow band gap structure is introduced between a pyrene unit and a dibenzothiophene sulfone unit, so that the band gap of a polymer can be effectively reduced, the coplanarity of polymer molecular chains can be improved, the existence of dibenzothiophene sulfone with a strong electron unit is ensured, and the narrow-band-gap polymer photocatalyst with high activity of hydrogen production by catalytic decomposition of water by visible light is obtained.
2. The polymer photocatalyst is prepared by a ternary polymerization method, the obtained photocatalyst has good repeatability, large specific surface area, narrow band gap, high visible light activity and high photocatalytic hydrogen production stability, still has high photocatalytic hydrogen production activity under the irradiation of visible light, has good separation effect of photo-generated electrons and holes, is simple in preparation process, low in cost and small in toxicity, and is beneficial to environmental protection and large-scale application. Compared with most reported organic polymer photocatalysts, the photocatalyst prepared by the invention has more excellent photocatalytic performance when being used for catalyzing and decomposing water hydrogen, and is at the leading level at home and abroad.
Drawings
FIG. 1 is an infrared spectrum of the polymer photocatalyst prepared in examples 1 and 2.
FIG. 2 is a solid NMR carbon spectrum of the polymer photocatalyst prepared in examples 1 and 2.
FIG. 3 is a scanning electron micrograph of the polymer photocatalyst prepared in examples 1 and 2.
Figure 4 is an XRD pattern of the polymer photocatalyst prepared in examples 1 and 2.
FIG. 5 is a graph of the UV-VIS absorption spectra of the polymer photocatalysts prepared in examples 1 and 2.
FIG. 6 is a graph of the photocatalytic hydrogen production rate versus illumination time for polymer photocatalysts prepared in examples 1 and 2 under illumination with wavelengths greater than 300 nm.
FIG. 7 is a graph of the photocatalytic hydrogen production rate versus illumination time for polymer photocatalysts prepared in examples 1 and 2 under illumination with a wavelength greater than 420 nm.
FIG. 8 is a photo-catalytic hydrogen production test of the polymer photocatalyst prepared in example 1 under simulated sunlight (λ >300 nm).
FIG. 9 is a photo-catalytic hydrogen production test of the polymer photocatalyst prepared in example 2 under simulated sunlight (λ >300 nm).
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
Under the protection of nitrogen, 20mL of N, N-dimethylformamide and 2mL of 2mol/L potassium carbonate aqueous solution are added into a reaction bottle filled with 68.9m (0.13mmol) of 1,3,6, 8-tetrabromophyrene, 262.1mg (0.78mmol) of thiophene-2, 5-diboronic acid dipinacol ester, 194.5mg (0.52mmol) of 3, 7-dibromodibenzothiophene sulfone and 25.0mg (21.6 mu mol) of tetrakis (triphenylphosphine) palladium, the mixture is heated to 150 ℃ for reflux reaction for 48 hours, after the reaction is finished, the mixture is cooled to room temperature, the mixture is washed with dichloromethane, methanol and water for multiple times, and the mixture is dried under the vacuum condition of 100 ℃ for 24 hours to obtain orange yellow solid powder Py-TP-BTDO, wherein the molar ratio of N to m is 1: 4.
Example 2
Under the protection of nitrogen, 20mL of N, N-dimethylformamide and 2mL of potassium carbonate solution (2mol L-1) Adding into a reactor containing 68.9m (0.13mmol) of 1,3,6, 8-tetrabromopyrene, 305.8mg (0.78mmol) of 2, 5-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) thieno [3,2-b ]]Thiophene, 194.5mg (0.52mmol) of 3, 7-dibromodibenzothiophenesulfone and 25.0mg (21.6. mu. mol) of tetrakis (triphenylphosphine) palladium were heated to 150 ℃ in a reaction flask and reacted under reflux for 48 hours, after the reaction was completed, the reaction mixture was cooled to room temperature, washed with methylene chloride, methanol and water several times, and dried under vacuum at 100 ℃ for 24 hours to obtain Py-TTP-BTDO as a red powder, wherein the molar ratio of x: y was 1: 4.
The chemical structures of the products prepared in the examples 1 and 2 are characterized by infrared spectroscopy and solid nuclear magnetic carbon spectroscopy, and the results are shown in the figures 1-2. 1596cm in FIG. 1-1And 1591cm-1The peak of (A) is ascribed toVibration of aromatic skeleton, 1306cm-1And 1154cm-1The peak at (A) is the oscillation peak of the sulfone group. In FIG. 2, 110 to 150ppm are peak-appearing signal regions of carbon atoms on the aromatic ring, and 138ppm is a signal peak of a carbon atom bonded to a sulfur atom on the sulfone group. As can be seen from fig. 3, the product prepared in example 1 has a nanosheet stacking morphology, and the product prepared in example 2 has a nanoparticle morphology. The XRD results of fig. 4 show that the products of example 1 and example 2 are both amorphous structures.
In order to prove the beneficial effects of the invention, the inventor respectively carries out a photocatalytic water decomposition hydrogen production test by using the polymer photocatalyst prepared in the embodiment 1-2, and the specific method comprises the following steps:
the method comprises the steps of ultrasonically dispersing 10mg of polymer photocatalyst into 100mL of mixed liquid containing 1mol/L of AA and DMF in a volume ratio of 9:1, taking AA as a sacrificial agent and DMF as a dispersing agent, pouring the dispersed polymer catalyst into a reactor, connecting a photocatalytic system with a 300W xenon lamp as a light source and a 420nm optical filter for simulating visible light, carrying out photocatalytic decomposition water hydrogen production test on the polymer photocatalyst prepared in the embodiment 1-2 under visible light and ultraviolet-visible light respectively, and carrying out photocatalytic decomposition hydrogen production on-line analysis by adopting gas chromatography, wherein the results are shown in Table 1.
TABLE 1 optical band gap, sacrificial agent used and hydrogen production rate (. lamda. >420nm)
As can be seen from Table 1, the polymer photocatalyst of the invention has very high photocatalytic activity under visible light, and the hydrogen production rate under visible light can reach 80.65mmol h at most-1g-1Compared with an organic polymer PyDOBT-1 in a document (Macromolecules 2018,51,9502-9508), the photocatalytic hydrogen production rate under visible light is improved by 141-215 times; compared with an organic polymer PyBS-3 in a document (adv.Mater.,2021,2008498), the photocatalytic hydrogen production rate of the polymer under visible light is improved by 21-23 times.
To further prove the beneficial effects of the polymer photocatalyst of the present invention, the inventors have respectively conducted observation experiments of decomposing water to release hydrogen by photocatalysis using the polymer photocatalysts prepared in examples 1 and 2, and the specific methods are as follows:
uniformly coating 5mg of polymer photocatalyst on a glass plate adhered with a double-sided adhesive tape, wherein the double-sided adhesive tape is a common double-sided adhesive tape and is only used for fixing the polymer photocatalyst, slowly and obliquely placing the glass plate adhered with the polymer photocatalyst into a quartz container filled with AA, and vertically irradiating the quartz container by using a 300W xenon lamp to simulate sunlight. During the photocatalytic reaction, a large number of distinct bubbles (hydrogen gas) were visible to the naked eye (see fig. 8 and 9).
Claims (6)
1. A polymer photocatalyst containing thienyl which has high photocatalytic water splitting hydrogen production activity is characterized in that the structure of the polymer photocatalyst is shown as formula A or formula B:
the molar ratio of n to m in the formula A is 1: 3-10, and the molar ratio of x to y in the formula B is 1: 2-10.
2. A method for preparing a thienyl group containing polymer photocatalyst according to claim 1, wherein: under the protection of nitrogen, adding a potassium carbonate water solution, 1,3,6, 8-tetrabromophyrene, thiophene-2, 5-diboronic acid dipinacol ester or 2, 5-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) thieno [3,2-B ] thiophene, 3, 7-dibromo dibenzothiophene sulfone and tetrakis (triphenylphosphine) palladium into an organic solvent, heating to reflux for reaction for 24-72 hours, cooling to room temperature after the reaction is finished, washing with dichloromethane, methanol and water, and drying in vacuum to obtain the thiophene-containing polymer photocatalyst shown in formula A or formula B, wherein the reaction equation is as follows:
the molar ratio of n to m in the formula A is 1: 3-10, and the molar ratio of x to y in the formula B is 1: 2-10.
3. A method for preparing a thienyl group containing polymer photocatalyst according to claim 2, wherein: the molar ratio of the 1,3,6, 8-tetrabromophyrene to the 3, 7-dibromo dibenzothiophene sulfone is 1: 3-10, the molar ratio of the 1,3,6, 8-tetrabromophyrene to the 3, 7-dibromo dibenzothiophene sulfone is 1: 2-10, and the dosage of thiophene-2, 5-diboronic acid dipivalol ester or 2, 5-bis (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) thieno [3,2-b ] thiophene is the sum of twice of the molar quantity of the 1,3,6, 8-tetrabromophyrene and the molar quantity of the 3, 7-dibromo dibenzothiophene sulfone.
4. A method for preparing a thienyl group containing polymer photocatalyst according to claim 2, wherein: the addition amount of the tetrakis (triphenylphosphine) palladium is 0.8-2% of the molar amount of the total bromine functional groups in 1,3,6, 8-tetrabromophyrene and 3, 7-dibromo-dibenzothiophene sulfone, and the addition amount of the potassium carbonate is 2-5 times of the molar amount of the total bromine functional groups in 1,3,6, 8-tetrabromophyrene and 3, 7-dibromo-dibenzothiophene sulfone.
5. A method for preparing a thienyl group containing polymer photocatalyst according to claim 2, wherein: heating to reflux reaction for 36-48 hours.
6. A method for preparing a thienyl group containing polymer photocatalyst according to claim 2, wherein: the organic solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and tetrahydrofuran.
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