CN113578382B - Thienyl-containing polymer photocatalyst with high photocatalytic water splitting hydrogen production activity and preparation method thereof - Google Patents
Thienyl-containing polymer photocatalyst with high photocatalytic water splitting hydrogen production activity and preparation method thereof Download PDFInfo
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- CN113578382B CN113578382B CN202110861415.8A CN202110861415A CN113578382B CN 113578382 B CN113578382 B CN 113578382B CN 202110861415 A CN202110861415 A CN 202110861415A CN 113578382 B CN113578382 B CN 113578382B
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- thiophene
- containing polymer
- sulfone
- hydrogen production
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- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 53
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 44
- 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 21
- 125000001544 thienyl group Chemical group 0.000 title claims abstract description 17
- 239000001257 hydrogen Substances 0.000 title abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 41
- 238000004519 manufacturing process Methods 0.000 title abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 12
- -1 3, 7-dibromodibenzothiophene sulfone Chemical class 0.000 claims description 18
- 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 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 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 10
- 238000000034 method Methods 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 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 6
- 150000002148 esters Chemical class 0.000 claims description 5
- 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 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 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
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 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
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 10
- 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
- 230000003287 optical effect Effects 0.000 abstract description 5
- 125000005581 pyrene group Chemical group 0.000 abstract description 5
- 229930192474 thiophene Natural products 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 abstract 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 abstract 2
- 150000003577 thiophenes Chemical class 0.000 abstract 2
- 238000010276 construction Methods 0.000 abstract 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene sulfoxide Natural products C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-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 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 229920000620 organic polymer Polymers 0.000 description 10
- 239000011668 ascorbic acid Substances 0.000 description 9
- 229960005070 ascorbic acid Drugs 0.000 description 9
- 235000010323 ascorbic acid Nutrition 0.000 description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 125000001725 pyrenyl group Chemical group 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006254 arylation reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 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
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-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
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- AVRWEULSKHQETA-UHFFFAOYSA-N Thiophene-2 Chemical compound S1C=2CCCCCC=2C(C(=O)OC)=C1NC(=O)C1=C(F)C(F)=C(F)C(F)=C1F AVRWEULSKHQETA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction 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
- 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
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000012704 multi-component copolymerization Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 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
- 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
- HDZULVYGCRXVNQ-UHFFFAOYSA-N trimethyl-(5-trimethylstannylthieno[3,2-b]thiophen-2-yl)stannane Chemical compound S1C([Sn](C)(C)C)=CC2=C1C=C([Sn](C)(C)C)S2 HDZULVYGCRXVNQ-UHFFFAOYSA-N 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- 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
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- 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
- C08G2261/122—Copolymers statistical
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- 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
- C08G2261/31—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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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a thienyl-containing polymer photocatalyst with high photocatalytic water splitting hydrogen production activity and a preparation method thereof, wherein the photocatalyst is prepared by adopting a simple ternary polymerization Suzuki coupling reaction, and a construction unit comprises: pyrene, thiophene or thiophene derivatives and dibenzothiophene sulfone. The pyrene monomer and the dibenzothiophene sulfonyl monomer used for polymerization have the same polymerizable functional group, and can simultaneously perform Suzuki coupling reaction with thiophene or thiophene derivative monomers, so that the pyrene unit and the dibenzothiophene sulfone unit in the polymer structure are connected through the thiophene or thiophene derivative unit. The polymer photocatalyst has the characteristics of high photocatalytic hydrogen production activity, high apparent quantum efficiency, narrow optical band gap, continuous and 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 photocatalytic water splitting hydrogen production materials, and particularly relates to a thienyl-containing polymer photocatalyst with high photocatalytic water splitting hydrogen production activity and a preparation method thereof.
Background
The use of solar energy to decompose aquatic hydrogen is a simple, economical and efficient means of converting solar energy into chemical energy, and has been highly focused by global scientists. In recent 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 decomposing water into hydrogen by utilizing solar energy photocatalysis, and the improvement of the photocatalytic activity of the semiconductor photocatalyst is realized mainly by regulating and controlling the structure and the composition of a semiconductor. The organic polymer photocatalyst has great development potential in the field of photocatalytic water splitting hydrogen production due to the advantages of various synthesis methods, easy design of structures, easy regulation and control of physicochemical properties and the like, and has been widely researched and paid attention in recent years. Wherein D-AThe polymer photocatalyst can effectively promote the separation efficiency of photo-generated charges due to the strong electron pulling effect of the receptor units, so that the photo-catalytic activity of the polymer photocatalyst is improved. For example, 1, 4-Benzenedicarboxylic acid and 4, 7-dibromo-2, 1, 3-benzothiadiazole can be prepared into an organic polymer photocatalyst B-BT-1,4 with D-A structure by Suzuki coupling reaction, triethanolamine (TEOA) is used as a sacrificial agent, and 2.32mmol h is obtained under the conditions of using Pt promoter and visible light irradiation -1 g -1 Is a photocatalytic hydrogen production rate (Angew.chem.int.ed., 2016,55,9202-9206). When a pyrene unit is used as an electron donor, benzothiadiazole is used as an electron acceptor, D-A polymer L-PyBT obtained through Suzuki coupling reaction is obtained, TEOA is used as a sacrificial agent, pt is used as a cocatalyst, and 1.67mmol h is obtained under visible light -1 g -1 Is a photocatalytic hydrogen production rate (Polym. Chem.,2018,9,4468-4475). When dibenzothiophene sulfone is used as an electron acceptor and pyrenyl is used as an electron donor, polymers PySO (Small, 2018,14,1801839) obtained by changing the connection site of dibenzothiophene sulfone and pyrene units, P16PySO (appl. Surf. Sci.,2019,495,143537) and PyDOBT-1 (Macromolecules, 2018,51,9502-9508), respectively, obtained under visible light with TEOA as a sacrificial agent without Pt loading -1 g -1 、6.38mmol h -1 g -1 And 5.70mmol h -1 g -1 Is a photocatalytic hydrogen-generating activity. Polymer PyDF obtained by Suzuki coupling reaction of fluorine-substituted dibenzothiophene sulfone and pyrenyl is obtained under the visible light after 4.09mmol h when TEOA is taken as a sacrificial agent and Pt is not loaded -1 g -1 Is described (J.Mater. Chem. A., 2020,8,2404-2411). When thianthrene-5, 10-tetraoxide is used as an electron acceptor and pyrenyl of an electron donor is subjected to Suzuki coupling reaction, the obtained polymer PySEO-1 is used as a sacrificial agent to obtain 4.51mmol h under visible light when Pt is not loaded -1 g -1 Is a photocatalytic hydrogen-generating activity (ChemSusChem 2020,13,369-375). When 9, 9-spirobifluorene is used as an electron donor, a polymer S-CMP3 obtained by Suzuki coupling reaction of 9, 9-spirobifluorene and dibenzothiophene sulfone obtains 3.11mmol h when Triethylamine (TEA) is used as a sacrificial agent and Pt is not loaded -1 g -1 Visible light catalysis of (2)Hydrogen production activity (chem. Mater.,2019,31,305-313). Polymers P7 (Angew.chem.Int.ed., 2016,55,1792-1796) and DBTD-CMP1 (ACS catalyst, 2018,8,8590-8596) obtained by Suzuki coupling reaction of phenyl and dibenzothiophene sulfone, under visible light, TEA and TEOA are used as sacrificial agents respectively, and when Pt is not loaded, 3.68mmol h is obtained respectively -1 g -1 And 2.46mmol h -1 g -1 Is a photocatalytic hydrogen production rate. When using benzotrithiophene as electron donor, the polymer BTT-CPP obtained by Suzuki coupling reaction of the benzotrithiophene and dibenzothiophene sulfone, 12.63mmol h was obtained under visible light when Pt was not supported by using Ascorbic Acid (AA) as a sacrificial agent -1 g -1 Is a photocatalytic hydrogen production rate (Macromolecules, 2021,54,2661-2666). When phenyl was used as electron donor and thienyl and pyrazinyl were used as electron acceptor, polymers P13 (J. Mater. Chem. A,2018,6,11994-12003) and P28 (chem. Mater.,2018,30,5733-5742) obtained by Suzuki coupling reaction obtained 0.25mmol h, respectively, when TEA was used as sacrificial agent without Pt loading -1 g -1 And 0.96mmol h - 1 g -1 Is a visible light catalytic hydrogen production rate.
The organic polymers listed above have wide band gaps and weak absorption to visible light, and are difficult to fully utilize visible light in sunlight, so that the hydrogen production performance by photocatalytic water splitting under the visible light is low. B-FOBT-1,4-E obtained by Sonogashira coupling of 1, 4-diacetylene benzene as electron donor and fluorine and methoxy-substituted benzothiadiazole as electron acceptor, under visible light with TEOA as sacrificial agent, 13.3mmol h was obtained without Pt promoter -1 g -1 Is a photocatalytic hydrogen production rate (ACS Energy lett.,2018,3,2544-2549). 1,3,6, 8-tetrabromopyrene and 2, 5-dibromodithioeno [3,2-b:2',3' -d]Polymer PyDTDO-3 obtained by direct C-H arylation coupling reaction of thiophene sulfone, under visible light, without loading Pt and taking AA as sacrificial agent, 16.32mmol H is obtained -1 g -1 Is a photocatalytic hydrogen-generating activity (chem. Sci.,2021,12,1796-1802). Polymer CP1 (J.Mater. Chem. A,2019,7,24222-24230) obtained by direct C-H arylation coupling reaction of 1,3,6, 8-tetrabromopyrene and 2, 2-Dithiofuran under visible light conditionsWhen AA is used as a sacrificial agent, the photocatalytic hydrogen production rate is 15.97mmol h -1 g -1 . When 1,3,6, 8-tetrabromopyrene is respectively combined 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 was polymerized by Stille coupling reaction, polymers Py-T, py-Tt and Py-Ttt (J. Mater. Chem. A,2021,9,5787-5795) were obtained, respectively, 38.1mmol h with AA as sacrificial agent without Pt loading -1 g -1 、45.8mmol h -1 g -1 And 38.9mmol h -1 g -1 Is a visible light catalytic hydrogen production rate. The main reason for the improved Py-Tt performance compared to CP1 may be that Py-Tt has better coplanarity, facilitating the transport of photogenerated electrons. The photocatalytic performance of the above polymer catalysts is improved, mainly because they have a narrower band gap, which improves the absorption of visible light. Although Py-T, py-Tt, py-Ttt have a lower band gap, they do not have a strong electron withdrawing unit, resulting in inefficient separation of photogenerated electrons and holes, which also limits further improvement of their photocatalytic performance.
The organic polymer photocatalysts listed above are all polymerized from two functionalized monomers by coupling reactions. Research shows that the optical property, the electrical property and the photocatalytic activity of the organic polymer can be regulated and controlled by a ternary or multicomponent copolymerization mode. For example, cooper et al have adopted a series of organic polymer photocatalysts CP-CMP1-15 by way of ternary polymerization, have realized the regulation and control of organic polymer optical band gap, specific surface area and photocatalytic performance by adjusting the feed ratio of three units (J.Am. Chem. Soc.2015,137, 3265-3270). By adjusting the feed ratio of tetrastyryl, phenyl and 9-fluorenone, the resulting terpolymer F 0.5 CMP under Na 2 S/Na 2 SO 4 0.66mmol h was obtained without Pt loading for the sacrificial agent -1 g -1 Is a visible light hydrogen-generating activity (chem. Eur. J.,2019,25,3867-3874). When benzene units are introduced into the polymer skeleton as bridging bonds to connect pyrene units and dibenzothiophene sulfone units, by adjusting the feed ratio of the donor units to the acceptor units,the resulting D-pi-A polymer PyBS-3 (adv. Mater.,2021,2008498) gave 14mmol h when Pt was not supported on TEOA as sacrificial agent -1 g -1 Is used for decomposing water to obtain hydrogen activity. When AA was used as sacrificial agent, 36mmol h was obtained -1 g -1 Compared with PyDOBT-1 and PyBS-3, the visible light decomposition water hydrogen production activity of the catalyst is greatly improved, and the hydrogen production activity is mainly improved because the introduction of benzene bridging reduces the distortion degree between molecules, is beneficial to the transmission of electrons, but the energy band structure is still wider, so that the catalyst shows lower catalytic hydrogen production activity under the irradiation of visible light.
Disclosure of Invention
The invention aims to provide a thienyl-containing polymer photocatalyst with high photocatalytic water splitting activity under visible light irradiation, and provides a preparation method with simple process steps and high yield for the polymer photocatalyst.
In order to achieve the above object, the structure of the thienyl group containing polymer photocatalyst adopted by the invention is shown as formula A or formula B:
the molar ratio of n to m in the formula A=1:3-10, and the molar ratio of x to y in the formula B=1:2-10.
The preparation method of the thienyl-containing polymer photocatalyst comprises the following steps: under the protection of nitrogen, adding aqueous solution of potassium carbonate, 1,3,6, 8-tetrabromopyrene, thiophene-2, 5-diboronic acid dippinacol ester or 2, 5-bis (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) thieno [3,2-B ] thiophene, 3, 7-dibromodibenzothiophene 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 thienyl-containing polymer photocatalyst (shown as Py-TP-BTDO) shown as formula A or a thienyl-containing polymer photocatalyst (shown as Py-TTP-BTDO) shown as formula B, wherein the reaction 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 10,1,3,6,8-tetrabromopyrene to 3, 7-dibromodibenzothiophene sulfone is 1:2 to 10, and the amount of the thiophene-2, 5-diboronic acid dippinacol ester or 2, 5-bis (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) thieno [3,2-b ] thiophene is the sum of the twice of the molar amount of 1,3,6, 8-tetrabromopyrene and the molar amount of 3, 7-dibromodibenzothiophene sulfone.
In the preparation method, the addition amount of the tetra (triphenylphosphine) palladium is preferably 0.8-2% of the total mole amount of the bromine functional groups in the 1,3,6, 8-tetrabromopyrene and the 3, 7-dibromodibenzothiophene sulfone, and the addition amount of the potassium carbonate is preferably 2-5 times of the total mole amount of the bromine functional groups in the 1,3,6, 8-tetrabromopyrene and the 3, 7-dibromodibenzothiophene sulfone.
In the above preparation method, it is further preferable to heat the mixture to reflux for 36 to 48 hours.
In the preparation method, the organic solvent is any one of N, N-dimethylformamide, N-dimethylacetamide and tetrahydrofuran.
The beneficial effects of the invention are as follows:
1. according to the invention, thiophene or thieno [3,2-b ] thiophene with a narrow bandgap structure is introduced between a pyrene unit and a dibenzothiophene sulfone unit, so that the bandgap of a polymer can be effectively reduced, the coplanarity of a polymer molecular chain can be improved, the existence of the dibenzothiophene sulfone with a strong pulling electronic unit is ensured, and a narrow bandgap polymer photocatalyst with high hydrogen production activity by catalyzing and decomposing water with visible light is obtained.
2. The polymer photocatalyst is prepared by a ternary polymerization method, and the obtained photocatalyst has the advantages of good repeatability, large specific surface area, narrow band gap, high visible light activity, high photocatalytic hydrogen production stability, high photocatalytic hydrogen production activity under the irradiation of visible light, good separation effect of photo-generated electrons and holes, simple preparation process, low cost and little toxicity, and is beneficial to environmental protection and large-scale application. Compared with most of reported organic polymer photocatalysts, the photocatalyst prepared by the invention has more excellent photocatalytic performance when being used for catalyzing and decomposing water to produce hydrogen, and is at a 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 state nuclear magnetic resonance 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 showing the ultraviolet-visible absorption spectra of the polymer photocatalysts prepared in examples 1 and 2.
FIG. 6 is a graph of photocatalytic hydrogen production rate versus time for light at wavelengths greater than 300nm for the polymer photocatalysts prepared in examples 1 and 2.
FIG. 7 is a graph of photocatalytic hydrogen production rate versus time for light at wavelengths greater than 420nm for the polymer photocatalysts prepared in examples 1 and 2.
FIG. 8 is a photograph of a test for photocatalytic hydrogen production of the polymer photocatalyst prepared in example 1 under simulated sunlight (lambda >300 nm).
FIG. 9 is a photograph of a test for photocatalytic hydrogen production of the polymer photocatalyst prepared in example 2 under simulated sunlight (lambda >300 nm).
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
20mL of N, N-dimethylformamide, 2mL of 2mol/L of an aqueous potassium carbonate solution were added under nitrogen atmosphere to a reaction vessel containing 68.9m (0.13 mmol) of 1,3,6, 8-tetrabromopyrene, 262.1mg (0.78 mmol) of thiophene-2, 5-diboron diphenoyl ester, 194.5mg (0.52 mmol) of 3, 7-dibromodibenzothiophene sulfone and 25.0mg (21.6. Mu. Mol) of tetrakis (triphenylphosphine) palladium, heated to 150℃and reacted under reflux for 48 hours, cooled to room temperature after completion of the reaction, washed with methylene chloride, methanol and water a plurality of times, and dried under vacuum at 100℃for 24 hours to obtain orange-yellow solid powder Py-TP-BTDO in which the molar ratio of n to m was 1:4.
Example 2
20mL of N, N-dimethylformamide and 2mL of potassium carbonate solution (2 mol L- 1 ) Added to a mixture containing 68.9m (0.13 mmol) of 1,3,6, 8-tetrabromopyrene, 305.8mg (0.78 mmol) of 2, 5-bis (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) thieno [3,2-b]Thiophene, 194.5mg (0.52 mmol) of 3, 7-dibromodibenzothiophene sulfone and 25.0mg (21.6 mu mol) of tetrakis (triphenylphosphine) palladium are heated to 150 ℃ for reflux reaction for 48 hours, cooled to room temperature after the reaction is finished, washed with dichloromethane, methanol and water for multiple times, and dried under vacuum condition at 100 ℃ for 24 hours to obtain red powder Py-TTP-BTDO, wherein the molar ratio of x to y is 1:4.
The chemical structures of the products prepared in example 1 and example 2 were characterized by using infrared spectra and solid nuclear magnetic carbon spectra, and the results are shown in fig. 1-2. In FIG. 1, 1596cm -1 And 1591cm -1 The peak at this point was attributed to vibration of the aromatic skeleton, 1306cm -1 And 1154cm -1 The peak at the position is a vibration peak of the sulfonyl group. In FIG. 2, 110 to 150ppm are peak-emitting signal regions of carbon atoms on an aromatic ring, and 138ppm are signal peaks of carbon atoms connected to sulfur atoms on a sulfone group. As can be seen from fig. 3, the product prepared in example 1 shows a nano-sheet stacking morphology, and the product prepared in example 2 shows a nano-particle morphology. The XRD results of fig. 4 indicate 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 adopts the polymer photocatalysts prepared in the examples 1-2 to respectively carry out photocatalytic decomposition water hydrogen production test, and the specific method is as follows:
10mg of the polymer photocatalyst is ultrasonically dispersed in 100mL of mixed solution containing 1mol/L AA and DMF with the volume ratio of 9:1, AA is used as a sacrificial agent, DMF is used as a dispersing agent, after the polymer catalyst is dispersed, the mixed solution is poured into a reactor and is connected into a photocatalytic system, a 300W xenon lamp is used as a light source, a 420nm optical filter is used for simulating visible light, the polymer photocatalysts prepared in examples 1-2 are subjected to photocatalytic decomposition of water to produce hydrogen under visible light and ultraviolet-visible light respectively, and gas chromatography is adopted for carrying out online analysis of photocatalytic decomposition of water to produce hydrogen, so that the results are shown in Table 1.
TABLE 1 optical band gap, sacrificial agent used and hydrogen production rate (lambda >420 nm)
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 the highest -1 g -1 Compared with the organic polymer PyDOBT-1 in the literature (Macromolecules 2018,51,9502-9508), the photocatalytic hydrogen production rate under visible light is improved by 141-215 times; compared with the organic polymer PyBS-3 in the literature (Adv. Mater.,2021,2008498), the photocatalytic hydrogen production rate of the polymer under visible light is improved by 21-23 times.
In order to further demonstrate the beneficial effects of the polymer photocatalysts of the present invention, the inventors conducted observation experiments for releasing hydrogen by photocatalytic decomposition of water using the polymer photocatalysts prepared in example 1 and example 2, respectively, and the specific methods are as follows:
5mg of the polymer photocatalyst is uniformly coated on a glass plate adhered with double faced adhesive tape, the double faced adhesive tape is common double faced adhesive tape and is only used for fixing the polymer photocatalyst, then the glass plate adhered with the polymer photocatalyst is slowly and obliquely placed into a quartz container filled with AA, and a 300W xenon lamp is used for simulating the vertical irradiation of sunlight on the quartz container. During the photocatalytic reaction, a large number of distinct bubbles (hydrogen gas) are produced by the naked eye (see fig. 8 and 9).
Claims (6)
1. A thienyl-containing polymer photocatalyst with high photocatalytic water splitting activity is characterized in that the structure of the polymer photocatalyst is shown as a formula A or a formula B:
the molar ratio of n to m in the formula A=1:3-10, and the molar ratio of x to y in the formula B=1:2-10.
2. A method for preparing the thienyl group containing polymer photocatalyst of claim 1, wherein: under the protection of nitrogen, adding a potassium carbonate aqueous solution, 1,3,6, 8-tetrabromopyrene, thiophene-2, 5-diboronic acid dippinacol ester or 2, 5-bis (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) thieno [3,2-B ] thiophene, 3, 7-dibromodibenzothiophene 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 thienyl-containing polymer photocatalyst shown in a formula A or a formula B, wherein the reaction equation is as follows:
the molar ratio of n to m in the formula A=1:3-10, and the molar ratio of x to y in the formula B=1:2-10.
3. The method for preparing the thienyl group containing polymer photocatalyst according to claim 2, wherein: the molar ratio of the 1,3,6, 8-tetrabromopyrene to the 3, 7-dibromodibenzothiophene sulfone is 1:3-10,1,3,6,8-tetrabromopyrene to the 3, 7-dibromodibenzothiophene sulfone is 1:2-10, and the dosage of thiophene-2, 5-diboronic acid dippinacol ester or 2, 5-bis (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) thieno [3,2-b ] thiophene is the sum of twice the molar quantity of the 1,3,6, 8-tetrabromopyrene and the molar quantity of the 3, 7-dibromodibenzothiophene sulfone.
4. The method for preparing the thienyl group containing polymer photocatalyst according to claim 2, wherein: the addition amount of the tetra (triphenylphosphine) palladium is 0.8-2% of the total mole amount of the bromine functional groups in the 1,3,6, 8-tetrabromopyrene and the 3, 7-dibromodibenzothiophene sulfone, and the addition amount of the potassium carbonate is 2-5 times of the total mole amount of the bromine functional groups in the 1,3,6, 8-tetrabromopyrene and the 3, 7-dibromodibenzothiophene sulfone.
5. The method for preparing the thienyl group containing polymer photocatalyst according to claim 2, wherein: heating to reflux reaction for 36-48 hr.
6. The method for preparing the 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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