CN111686806B - Preparation method and application of poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst - Google Patents
Preparation method and application of poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst Download PDFInfo
- Publication number
- CN111686806B CN111686806B CN202010475493.XA CN202010475493A CN111686806B CN 111686806 B CN111686806 B CN 111686806B CN 202010475493 A CN202010475493 A CN 202010475493A CN 111686806 B CN111686806 B CN 111686806B
- Authority
- CN
- China
- Prior art keywords
- ethanol
- thienyl
- graphite
- poly
- carbon nitride
- 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.)
- Active
Links
- YYPNNBPPDFTQFX-UHFFFAOYSA-N 2-thiophen-3-ylethanol Chemical compound OCCC=1C=CSC=1 YYPNNBPPDFTQFX-UHFFFAOYSA-N 0.000 title claims abstract description 171
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 239000002131 composite material Substances 0.000 title claims abstract description 92
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 65
- 239000001257 hydrogen Substances 0.000 claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 238000003421 catalytic decomposition reaction Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 54
- 239000010439 graphite Substances 0.000 claims description 54
- 229910002804 graphite Inorganic materials 0.000 claims description 54
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 29
- 239000007800 oxidant agent Substances 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 abstract description 16
- 238000012360 testing method Methods 0.000 abstract description 16
- 229920000642 polymer Polymers 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000003993 interaction Effects 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 16
- 238000001514 detection method Methods 0.000 description 13
- 230000031700 light absorption Effects 0.000 description 11
- 238000000862 absorption spectrum Methods 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 238000000103 photoluminescence spectrum Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum 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
-
- B01J35/39—
-
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- 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
Abstract
A preparation method and application of a poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst. The invention belongs to the technical field of photocatalysis. The invention aims to solve the technical problem that the visible light catalytic hydrogen production performance of the existing polymer semiconductor is not ideal due to weak interaction between heterojunction interfaces. The invention firstly adopts a method of calcining urea at high temperature to synthesize graphite-phase carbon nitride, then adopts a chemical oxidation method to synthesize poly [2- (3-thienyl) ethanol ], and then adopts a wet chemical method to prepare the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light catalyst. Tests prove that the composite visible-light-driven photocatalyst prepared by the invention has high visible-light-driven hydrogen production performance and good circulation stability, and the visible-light-driven hydrogen production rate is up to 2475.1 mu mol/g/h, which is about 13 times that of graphite-phase carbon nitride; after 3 visible light hydrogen production tests with a period of 15 hours, the hydrogen production amount is not obviously changed. The composite visible light catalyst can be used for hydrogen production by visible light catalytic decomposition of water in the field of environmental energy.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a preparation method and application of a poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst.
Background
Along with the rapid development of the world and the increase of environmental pollution and energy crisis, people are urgently required to develop new technology for providing clean and cheap renewable energy. The energy density of hydrogen is the highest in addition to nuclear energy, and hydrogen is considered as the renewable clean energy with the most development potential, along with the advantages of environmental friendliness and no secondary pollution. The hydrogen element is abundant in the environment and widely exists in water, hydrocarbon (such as methane) and some polymers. A significant challenge to using hydrogen as a renewable clean energy source is how to efficiently extract hydrogen from these compounds or polymers. The photocatalytic technology using a semiconductor catalyst as a core can utilize solar light to catalyze and decompose water to generate hydrogen, which is considered to be an efficient and environment-friendly strategy. Since visible radiation accounts for about 46% of the total solar radiation spectrum, the development of visible light semiconductor catalysts is of more scientific significance and practical value.
In recent years, the carbon nitride of graphite phase has attracted extensive attention of the scientific community because the main constituent elements C and N are abundant on earth, do not contain metal elements, are simple to prepare, absorb visible light, have high chemical stability, and more importantly have a proper energy band structure for hydrogen production. However, the visible light catalytic hydrogen production performance of graphite phase carbon nitride is still not ideal enough, mainly because the recombination of photo-generated electrons and holes is serious, so that the available photo-generated electrons are few. Meanwhile, the band gap of graphite phase carbon nitride is 2.7eV, and the available visible light range (lambda is less than 460nm) is narrow. Therefore, improving the separation of photo-generated electrons and holes of the graphite phase carbon nitride and expanding the visible light absorption range of the graphite phase carbon nitride become important means for improving the hydrogen production performance of the visible light catalysis.
Researchers have attempted to modify graphite-phase carbon nitride by various methods, such as nanostructure design, metal deposition, and heterojunction construction. The heterojunction construction can effectively promote the transfer and separation of photogenerated charges, remarkably improve the separation of photogenerated electrons and holes, and further improve the hydrogen production performance of visible light catalysis. Compared with an inorganic semiconductor/graphite phase carbon nitride heterojunction material, the polymer semiconductor/graphite phase carbon nitride heterojunction material has the advantages of environmental friendliness, easiness in regulating and controlling energy band matching positions, good interface compatibility and the like. However, compared with inorganic semiconductors which generally have exciton binding energy of 0.01eV order, the exciton binding energy of photogenerated carriers in polymer semiconductors is very large, so that the recombination of photogenerated electrons and holes is serious, and the photocatalytic hydrogen production performance is influenced. Therefore, the construction of the polymer semiconductor heterojunction is particularly important, and particularly, the separation of photogenerated electrons and holes at the interface is considered to be the key for improving the hydrogen production performance of the polymer semiconductor heterojunction photocatalyst. The heterojunction interface connection degree can directly influence the separation of the photogenerated electrons and holes at the polymer semiconductor heterojunction interface and the hydrogen production performance of the polymer semiconductor heterojunction photocatalyst. It can be concluded from this that increasing the heterojunction interfacial interactions becomes the key to the preparation of polymer semiconductor/graphite phase carbon nitride composite visible light photocatalysts.
Disclosure of Invention
The invention provides a preparation method and application of a poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst, aiming at solving the technical problem that the hydrogen production performance of visible-light catalysis is not ideal due to weak interaction between heterojunction interfaces of the existing polymer semiconductor.
The preparation method of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst comprises the following steps:
firstly, preparing graphite phase carbon nitride: calcining urea at high temperature to obtain graphite-phase carbon nitride with hydroxyl on the surface;
preparation of poly [2- (3-thienyl) ethanol ]: adding a 2- (3-thienyl) ethanol monomer into acetonitrile, and stirring until the 2- (3-thienyl) ethanol monomer is completely dissolved to obtain a monomer solution; dissolving anhydrous ferric trichloride in acetonitrile to obtain an oxidant solution; dropwise adding the oxidant solution obtained in the step (i) into the monomer solution obtained in the step (i), continuously stirring at room temperature for polymerization reaction for 3-12 h, washing with anhydrous methanol after suction filtration, and drying to obtain poly [2- (3-thienyl) ethanol ];
thirdly, preparing the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light catalyst: and (2) dispersing the graphite-phase carbon nitride with hydroxyl on the surface obtained in the step one and the poly [2- (3-thienyl) ethanol ] obtained in the step two in a solvent, and obtaining the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst by a wet chemical method under the ultrasonic condition.
Further limiting, the method for obtaining graphite-phase carbon nitride with hydroxyl groups on the surface by calcining urea at high temperature in the step one is concretely as follows: adding urea into a quartz crucible, then putting the quartz crucible into a muffle furnace for calcining, grinding the obtained light yellow blocky solid, washing the light yellow blocky solid by using a nitric acid solution, then washing the light yellow blocky solid to be neutral by using distilled water, carrying out suction filtration, and drying to obtain the graphite-phase carbon nitride with hydroxyl on the surface.
Further limiting, the calcination process in the first step is: heating from room temperature to 500-600 ℃ at a heating rate of 0.2-2 ℃/min, then preserving heat for 2-4 h at the temperature, and then cooling to room temperature.
Further limiting, the calcination process in the first step is: the mixture was heated from room temperature to 550 ℃ at a ramp rate of 0.5 ℃/min, then incubated at that temperature for 3 hours, and subsequently cooled to room temperature.
Further limiting, the concentration of the nitric acid solution in the step one is 0.2 mol/L-1.0 mol/L.
Further limiting, the concentration of the nitric acid solution in the first step is 0.5 mol/L.
Further limiting, the drying parameters in the step one are as follows: the temperature is 50-70 ℃.
Further limiting, the drying parameters in the step one are as follows: the temperature was 60 ℃.
Further limiting, in the second step, the concentration of the 2- (3-thienyl) ethanol in the monomer solution is 0.10-0.20 mol/L.
Further limiting, the concentration of the 2- (3-thienyl) ethanol in the monomer solution in the second step is 0.18 mol/L.
Further limiting, the concentration of the anhydrous ferric trichloride in the oxidant solution in the second step is 1.20-2.40 mol/L.
Further limiting, in the second step, the concentration of the anhydrous ferric trichloride in the oxidant solution is 2.16 mol/L.
Further limiting, the molar ratio of anhydrous ferric trichloride in the oxidant solution to 2- (3-thienyl) ethanol in the monomer solution in the second step is (3-12): 1.
Further limiting, the molar ratio of anhydrous ferric trichloride in the oxidant solution in the second step to 2- (3-thienyl) ethanol in the monomer solution is 6: 1.
Further limiting, the polymerization reaction time in the second step is 3-12 h.
Further limiting, the polymerization reaction time in the second step is 6 h.
Further limiting, the drying parameters in the second step are as follows: the temperature is 50-70 ℃.
Further limiting, the drying parameters in the second step and the third step are as follows: the temperature was 60 ℃.
Further limiting, in the third step, the ratio of the mass of the poly [2- (3-thienyl) ethanol ] to the total mass of the poly [2- (3-thienyl) ethanol ] and the graphite-phase carbon nitride is (1-15): 100.
further limiting, in the third step, the ratio of the mass of the poly [2- (3-thienyl) ethanol ] to the total mass of the poly [2- (3-thienyl) ethanol ] and the graphite-phase carbon nitride is (3-10): 100.
further defined, the ratio of the mass of the poly [2- (3-thienyl) ethanol ] to the total mass of the poly [2- (3-thienyl) ethanol ] and the graphite-phase carbon nitride in step three is 5: 100.
further defined, the ratio of the mass of the poly [2- (3-thienyl) ethanol ] to the volume of the solvent in the third step is (1-30) mg: 80 mL.
Further defined, the ratio of the mass of the poly [2- (3-thienyl) ethanol ] to the volume of the solvent in the third step is (6-20) mg: 80 mL.
Further defined, the ratio of the mass of the poly [2- (3-thienyl) ethanol ] to the volume of the solvent in step three is 10 mg: 80 mL.
Further limiting, the steps of preparing the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible-light-induced photocatalyst by the wet chemical method in the third step are as follows: after ultrasonic treatment for 0.25-2 h, evaporating to dryness in a water bath at 50-80 ℃.
Further limiting, the steps of preparing the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible-light-induced photocatalyst by the wet chemical method in the third step are as follows: after 0.5h of sonication, the mixture was evaporated to dryness in a water bath at 60 ℃.
Further limiting, in the third step, the solvent is absolute ethyl alcohol, water or N, N-dimethylformamide.
The poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst is applied to the field of hydrogen production by decomposing water under the catalysis of visible light.
Compared with the prior art, the invention has the remarkable effects that:
the poly [2- (3-thienyl) ethanol ] prepared by the invention has high charge mobility and chemical stability as a polythiophene derivative. The band gap of the poly [2- (3-thienyl) ethanol ] is 2.09eV, and the energy level position can be well matched with the energy level position of the graphite phase carbon nitride to construct a heterojunction. And the hydroxyl at the beta position enables the poly [2- (3-thienyl) ethanol ] to be easily dispersed in some solvents, thereby being beneficial to realizing more effective compounding with the graphite phase carbon nitride by a wet chemical method. More importantly, the beta-position hydroxyl of the poly [2- (3-thienyl) ethanol ] can form hydrogen bonds with the surface hydroxyl of the graphite-phase carbon nitride, so that the heterojunction interface connection constructed by the beta-position hydroxyl and the graphite-phase carbon nitride is tighter, the transfer of photo-generated charges between interfaces is promoted, and the photo-generated charge separation is improved. In addition, the poly [2- (3-thienyl) ethanol ] with narrow band gap can expand the visible light absorption range of the visible light photocatalyst compounded with graphite-phase carbon nitride. Therefore, the hydrogen production performance of the visible light catalysis of the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light catalyst can be improved by constructing a tight heterojunction by the poly [2- (3-thienyl) ethanol and the graphite phase carbon nitride.
The poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst prepared by the invention is an efficient visible-light-responsive photocatalytic hydrogen production material. A series of tests such as a scanning electron microscope, a nuclear magnetic resonance hydrogen spectrum, an infrared spectrum, an X-ray photoelectron spectrum, an X-ray powder diffraction, a steady-state surface photovoltage, a photoluminescence spectrum, a visible light photocurrent, an ultraviolet-visible spectrum and the like prove that the poly [2- (3-thienyl) ethanol ] is successfully prepared, a poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride heterojunction is successfully constructed, interface connection is enhanced through hydrogen bonds between the poly [2- (3-thienyl) ethanol ] and the graphite-phase carbon nitride, photo-generated charge separation is improved, and the visible light absorption range is expanded. The visible light hydrogen production test proves that the composite visible light catalyst has high visible light catalytic hydrogen production performance and good circulation stability. The hydrogen production rate of visible light is as high as 2475.1 mu mol/g/h, which is about 13 times of that of graphite phase carbon nitride. After 3 visible light hydrogen production tests with a period of 15 hours, the hydrogen production amount of the hydrogen production test has no obvious change.
The composite visible-light-driven photocatalyst prepared by the invention is a polymer heterojunction visible-light-driven catalyst which is novel in structure, simple to prepare, high in visible-light-driven hydrogen production performance and good in circulation stability, and can be used for hydrogen production by decomposing water under the catalysis of visible light in the field of environmental energy.
Drawings
FIG. 1 is a scanning electron micrograph of graphite-phase carbon nitride obtained in one of the first to third steps of the embodiment;
FIG. 2 is a scanning electron micrograph of poly [2- (3-thienyl) ethanol ] obtained in one or more steps II of the embodiment;
FIG. 3 is an SEM image of a poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst obtained in accordance with embodiment II;
FIG. 4 is a NMR spectrum of 2- (3-thienyl) ethanol monomer used in one embodiment, the first step, the second step, the third step;
FIG. 5 is a NMR spectrum of poly [2- (3-thienyl) ethanol ] obtained in one or more steps II;
FIG. 6 is an infrared spectrum of poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst, graphite-phase carbon nitride, and poly [2- (3-thienyl) ethanol ] obtained in accordance with embodiments one to three;
FIG. 7 is an enlarged view of FIG. 6 at area a;
FIG. 8 is an X-ray photoelectron spectrum of S2p of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light catalyst and poly [2- (3-thienyl) ethanol ] obtained in the second embodiment;
FIG. 9 is an X-ray powder diffraction pattern of poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light catalyst, graphite-phase carbon nitride, and poly [2- (3-thienyl) ethanol ] obtained in accordance with embodiments one to three;
FIG. 10 is a steady state surface photo-voltage spectrum of the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light catalyst and graphite phase carbon nitride obtained in accordance with embodiments one to three;
FIG. 11 is a graph showing photoluminescence spectra of a poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst and graphite-phase carbon nitride obtained in accordance with embodiments one to three;
FIG. 12 is a graph showing the photocurrent of visible light measured by the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light catalyst and graphite-phase carbon nitride according to embodiments one to three;
FIG. 13 is a graph showing UV/VIS absorption spectra of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light photocatalyst, graphite-phase carbon nitride, and poly [2- (3-thienyl) ethanol ] obtained in accordance with the first to third embodiments;
FIG. 14 is a graph showing an ultraviolet-visible light absorption spectrum and a band gap of graphite-phase carbon nitride obtained in accordance with embodiments one to three;
FIG. 15 is a graph showing an ultraviolet-visible absorption spectrum and a band gap of poly [2- (3-thienyl) ethanol ] obtained in accordance with embodiments one to three;
FIG. 16 is a graph of the visible light hydrogen production performance of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst and graphite-phase carbon nitride obtained in the first to third embodiments;
fig. 17 is a visible light hydrogen production cycle test chart of the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light photocatalyst obtained in the second embodiment.
Detailed Description
The first embodiment is as follows: in this embodiment, the preparation method of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst is performed according to the following steps:
firstly, preparing graphite phase carbon nitride: adding 35g of urea into a quartz crucible, and then putting the quartz crucible into a muffle furnace for calcination, wherein the calcination process comprises the following steps: heating to 550 ℃ from room temperature at a heating rate of 0.5 ℃/min, then preserving heat for 3 hours at the temperature, then cooling to room temperature, grinding the obtained light yellow blocky solid, washing 1g of the ground light yellow blocky solid with 100mL of nitric acid solution with the concentration of 0.5mol/L, then washing the solid with distilled water to be neutral, performing suction filtration, and drying at 60 ℃ to obtain graphite-phase carbon nitride with hydroxyl on the surface, which is marked as CN;
preparation of poly [2- (3-thienyl) ethanol ]: adding 200 mu L of 2- (3-thienyl) ethanol monomer into 10mL of acetonitrile, and stirring until the 2- (3-thienyl) ethanol monomer is completely dissolved to obtain a monomer solution with the concentration of 0.18 mol/L; dissolving 1.7518g of anhydrous ferric chloride in 5mL of acetonitrile to obtain an oxidant solution with the concentration of 2.16 mol/L; thirdly, dropwise adding the oxidant solution obtained in the second step into the monomer solution obtained in the first step according to the molar ratio of anhydrous ferric trichloride to 2- (3-thienyl) ethanol of 6:1, continuously stirring and polymerizing at room temperature for 6 hours, washing with anhydrous methanol after suction filtration, and drying at 60 ℃ to obtain poly [2- (3-thienyl) ethanol ], which is marked as PTETOH;
thirdly, preparing the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light catalyst: and (2) dispersing 194mg of the graphite-phase carbon nitride obtained in the first step and 6mg of the poly [2- (3-thienyl) ethanol ] obtained in the second step in 80mL of absolute ethanol, performing ultrasonic treatment for 30min, evaporating to dryness in a water bath at 60 ℃, and preparing the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst by a wet chemical method, wherein the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst is marked as 3 PTETOH/CN.
The second embodiment is as follows: in this embodiment, the preparation method of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst is performed according to the following steps:
firstly, preparing graphite phase carbon nitride: adding 35g of urea into a quartz crucible, and then putting the quartz crucible into a muffle furnace for calcination, wherein the calcination process comprises the following steps: heating the mixture from room temperature to 550 ℃ at the heating rate of 0.5 ℃/min, then preserving heat for 3h at the temperature, then cooling to room temperature, grinding the obtained light yellow blocky solid, washing 1g of the light yellow blocky solid with 100mL of nitric acid solution with the concentration of 0.5mol/L, washing the washed solid with distilled water to be neutral, performing suction filtration, and drying at the temperature of 60 ℃ to obtain graphite-phase carbon nitride with hydroxyl on the surface, which is marked as CN;
preparation of poly [2- (3-thienyl) ethanol ]: adding 200 mu L of 2- (3-thienyl) ethanol monomer into 10mL of acetonitrile, and stirring until the 2- (3-thienyl) ethanol monomer is completely dissolved to obtain a monomer solution with the concentration of 0.18 mol/L; 1.7518g of anhydrous ferric chloride is dissolved in 5mL of acetonitrile to obtain an oxidant solution with the concentration of 2.16 mol/L; thirdly, dropwise adding the oxidant solution obtained in the second step into the monomer solution obtained in the first step according to the molar ratio of anhydrous ferric trichloride to 2- (3-thienyl) ethanol of 6:1, continuously stirring and polymerizing at room temperature for 6 hours, washing with anhydrous methanol after suction filtration, and drying at 60 ℃ to obtain poly [2- (3-thienyl) ethanol ], which is marked as PTETOH;
thirdly, preparing the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light catalyst: and (2) dispersing 190mg of the graphite-phase carbon nitride obtained in the first step and 10mg of the poly [2- (3-thienyl) ethanol ] obtained in the second step in 80mL of absolute ethanol, performing ultrasonic treatment for 30min, evaporating to dryness in a water bath at 60 ℃, and preparing the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light catalyst by a wet chemical method, wherein the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light catalyst is marked as 5 PTETOH/CN.
The third concrete implementation mode: in this embodiment, the preparation method of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst is performed according to the following steps:
firstly, preparing graphite phase carbon nitride: adding 35g of urea into a quartz crucible, and then putting the quartz crucible into a muffle furnace for calcination, wherein the calcination process comprises the following steps: heating to 550 ℃ from room temperature at a heating rate of 0.5 ℃/min, then preserving heat for 3 hours at the temperature, then cooling to room temperature, grinding the obtained light yellow blocky solid, washing 1g of the ground light yellow blocky solid with 100mL of nitric acid solution with the concentration of 0.5mol/L, then washing the solid with distilled water to be neutral, performing suction filtration, and drying at 60 ℃ to obtain graphite-phase carbon nitride with hydroxyl on the surface, which is marked as CN;
and II, preparing poly [2- (3-thienyl) ethanol ]: adding 200 mu L of 2- (3-thienyl) ethanol monomer into 10mL of acetonitrile, and stirring until the 2- (3-thienyl) ethanol monomer is completely dissolved to obtain a monomer solution with the concentration of 0.18 mol/L; dissolving 1.7518g of anhydrous ferric chloride in 5mL of acetonitrile to obtain an oxidant solution with the concentration of 2.16 mol/L; thirdly, dropwise adding the oxidant solution obtained in the second step into the monomer solution obtained in the first step according to the molar ratio of anhydrous ferric trichloride to 2- (3-thienyl) ethanol of 6:1, continuously stirring and polymerizing at room temperature for 6 hours, washing with anhydrous methanol after suction filtration, and drying at 60 ℃ to obtain poly [2- (3-thienyl) ethanol ], which is marked as PTETOH;
thirdly, preparing the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light catalyst: and (2) dispersing 180mg of graphite-phase carbon nitride obtained in the first step and 20mg of poly [2- (3-thienyl) ethanol ] obtained in the second step into 80mL of absolute ethanol, performing ultrasonic treatment for 30min, evaporating in a water bath at 60 ℃, and preparing the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst by a wet chemical method, wherein the visible-light-induced photocatalyst is marked as 10 PTEOH/CN.
Detection test
Scanning electron microscope detection is carried out on the graphite phase carbon nitride with hydroxyl groups on the surface, which is obtained in the first step, the second step, and the third step, so as to obtain a scanning electron microscope image of the graphite phase carbon nitride as shown in figure 1. It can be seen from fig. 1 that the prepared graphite-phase carbon nitride is nanosheet-shaped.
And (II) carrying out scanning electron microscope detection on the poly [2- (3-thienyl) ethanol ] obtained in the first step to the second step to obtain a scanning electron microscope image of the poly [2- (3-thienyl) ethanol ] shown in the figure 2. As can be seen from FIG. 2, the prepared poly [2- (3-thienyl) ethanol ] is nanoparticles of about 50 nm.
And (III) performing scanning electron microscope detection on the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst obtained in the second embodiment to obtain an SEM image of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst shown in figure 3. It can be seen from fig. 3 that the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light photocatalyst prepared according to the second embodiment has poly [2- (3-thienyl) ethanol ] nanoparticles uniformly dispersed on the graphite-phase carbon nitride nanosheets.
And (IV) performing nuclear magnetic resonance hydrogen spectrum detection on the 2- (3-thienyl) ethanol monomer used in the first step to the second step to obtain a nuclear magnetic resonance hydrogen spectrum of the 2- (3-thienyl) ethanol monomer shown in the figure 4. 1H NMR (400MHz, DMSO-d6, δ, ppm) 7.39(dd, J ═ 4.9,3.0,1H),7.16(dd, J ═ 2.7,0.8,1H),7.02(dd, J ═ 4.9,1.1,1H),4.70(t, J ═ 5.2,1H),3.67(td, J ═ 7.0,5.2,2H),2.79(t, J ═ 7.1,2H), the peaks in fig. 4 corresponding to 7.39ppm, 7.16ppm, 7.02ppm correspond to the three hydrogen elements on the thiophene ring, the peaks in 4.70ppm correspond to the hydrogen elements on the hydroxyl groups in the ethanol group, and the peaks in 3.67ppm and 2.79ppm correspond to the hydrogen elements on the two methylene groups in the ethanol group, respectively.
(V) Poly [2- (3-thienyl) ethanol obtained in one embodiment to three embodiments]Performing NMR hydrogen spectrum detection to obtain poly [2- (3-thienyl) ethanol shown in FIG. 5]Nuclear magnetic resonance hydrogen spectrum of (a). 1H NMR (400MHz, DMSO-d6, delta, ppm) 7.10(b, CH),4.16(b, CH) 2 OH),2.87(b,CH 2 ) 1.92(b, OH) the broad peak around 7.10ppm in FIG. 5 corresponds to the hydrogen element on the thiophene ring, the peaks of 4.16ppm and 2.87ppm correspond to the hydrogen elements on the two methylene groups in the ethanol group, respectively, the peak of 1.92ppm corresponds to the hydrogen element on the hydroxyl group in the ethanol group, and in combination with FIG. 1, it can be confirmed that the respective peaks are broadened, and that poly [2- (3-thienyl) ethanol is successfully produced]。
(VI) Poly [2- (3-thienyl) ethanol obtained in accordance with embodiments one to three]Graphite phase carbon nitride composite visible light catalyst, graphite phase carbon nitride with hydroxyl on surface and poly [2- (3-thienyl) ethanol]Performing infrared spectrum detection to obtain poly [2- (3-thienyl) ethanol shown in figure 6]Graphite phase carbon nitride composite visible light catalyst, graphite phase carbon nitride and poly [2- (3-thienyl) ethanol]And an enlarged view of the region a in fig. 6 as shown in fig. 7. As can be seen from FIGS. 6 to 7, the composite visible-light-driven photocatalyst showed a characteristic peak (3179 cm) of graphite-phase carbon nitride -1 The left and right parts are the stretching vibration peak of hydroxyl-OH at 1238-1650cm -1 Is at the stretching vibration peak of C-N heterocycle at 808cm -1 Bending vibration of heptazine ring at left and right) and poly [2- (3-thienyl) ethanol]Characteristic peak of (2) (2950 cm) -1 And 2878cm -1 At the left and right position-CH 2 And the peak of the asymmetric stretching vibration of 1046cm -1 At the left and right position-O-CH 2 Asymmetric stretching vibration peak of-C), proving that graphite phase carbon nitride and poly [2- (3-thienyl) ethanol]The composition was successful. With poly [2- (3-thienyl) ethanol]The mass percentage of the composite visible light catalyst is increased, and the composite visible light catalyst is 3179cm -1 The peak strength of the hydroxyl groups at the left and right sides became weak, indicating that poly [2- (3-thienyl) ethanol]There is an interaction with the hydroxyl groups of the graphite phase carbon nitride.
And (seventhly) carrying out X-ray photoelectron spectroscopy detection on the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light catalyst and the poly [2- (3-thienyl) ethanol ] obtained in the second embodiment to obtain an X-ray photoelectron spectroscopy of S2p of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light catalyst and the poly [2- (3-thienyl) ethanol ] shown in the figure 8. As can be seen from fig. 8, the peak position of S2p of the composite visible-light-driven photocatalyst was not changed compared to poly [2- (3-thienyl) ethanol ], and it can be confirmed from fig. 6 to 7 that: s of the poly [2- (3-thienyl) ethanol ] does not interact with hydroxyl of the graphite phase carbon nitride, but the hydroxyl of the poly [2- (3-thienyl) ethanol ] interacts with the hydroxyl of the graphite phase carbon nitride to form a hydrogen bond, so that the interaction between the poly [2- (3-thienyl) ethanol ] and the graphite phase carbon nitride interface can be enhanced, and the photo-generated charge transfer and separation are facilitated.
(VIII) X-ray powder diffraction detection is performed on the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst, the graphite-phase carbon nitride with hydroxyl groups on the surface and the poly [2- (3-thienyl) ethanol ] obtained in the first to third embodiments, so as to obtain an X-ray powder diffraction pattern of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst, the graphite-phase carbon nitride and the poly [2- (3-thienyl) ethanol ] shown in FIG. 9. As can be seen from FIG. 9, the prepared composite visible-light-driven photocatalyst has a diffraction peak similar to that of graphite-phase carbon nitride, indicating that the composite poly [2- (3-thienyl) ethanol ] does not significantly change the lattice structure of graphite-phase carbon nitride.
And (nine) performing steady-state surface photovoltage detection on the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst and the graphite-phase carbon nitride with hydroxyl groups on the surface, which are obtained in the first to third embodiments, to obtain a steady-state surface photovoltage spectrogram of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst and the graphite-phase carbon nitride shown in the figure 10. As can be seen from FIG. 10, the photovoltage signal for the graphite phase carbon nitride is low, indicating poor separation of the photo-generated charge; the photovoltage signal is obviously increased after the poly [2- (3-thienyl) ethanol ] is compounded, but the photovoltage signal of 10PTETOH/CN is obviously reduced, probably because excessive poly [2- (3-thienyl) ethanol ] is easily agglomerated on graphite phase carbon nitride and is not beneficial to the effective transfer and separation of photogenerated charges. Notably, 5 ptethoh/CN showed the highest photovoltage signal, indicating that 5 ptethoh/CN exhibited the highest photogenerated charge separation.
And (ten) carrying out photoluminescence spectrum detection on the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst and the graphite-phase carbon nitride with hydroxyl groups on the surfaces obtained in the first to third embodiments to obtain a photoluminescence spectrum (PL) diagram of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst and the graphite-phase carbon nitride shown in the figure 11. As can be seen in fig. 11, the PL signal of the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible photocatalyst is significantly reduced compared to graphite phase carbon nitride, showing enhanced photogenerated charge separation, especially with 5 ptethoh/CN having the highest photogenerated charge separation.
And eleventh, performing a visible light photocurrent test on the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst and the graphite-phase carbon nitride with hydroxyl groups on the surface, which are obtained in the first to third embodiments, to obtain a visible light photocurrent test chart of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst and the graphite-phase carbon nitride shown in fig. 12. As can be seen from fig. 12, the intensity of the visible light photocurrent of the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light photocatalyst was increased compared to that of graphite phase carbon nitride, and particularly, the intensity of the visible light photocurrent of 5 ptethoh/CN was the highest, which is consistent with the steady state surface photovoltage and photoluminescence test results. In addition, under the illumination of visible light of 700s, the photocurrent intensity of the prepared composite visible-light-driven photocatalyst still keeps good stability. The results prove that the compounding of a certain amount of poly [2- (3-thienyl) ethanol ] and graphite-phase carbon nitride is beneficial to photo-generated charge separation, and 5PTETOH/CN has the highest photo-generated charge separation, which indicates that the PTETOH/CN has the highest visible light catalytic hydrogen production activity.
And (twelfth) performing ultraviolet and visible light absorption spectrum detection on the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light photocatalyst, the graphite-phase carbon nitride with hydroxyl groups on the surface, and the poly [2- (3-thienyl) ethanol ] obtained in the first to third embodiments to obtain an ultraviolet and visible light absorption spectrum diagram of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light photocatalyst, the graphite-phase carbon nitride, and the poly [2- (3-thienyl) ethanol ] shown in fig. 13. As can be seen from FIG. 13, the absorption peak of poly [2- (3-thienyl) ethanol ] is in the long wavelength region as compared with the graphite-phase carbon nitride; with the increase of the mass percentage of the composite poly [2- (3-thienyl) ethanol ], the absorption peak of the graphite phase carbon nitride at about 460nm has a small red shift, and the absorption in a long wave region is obviously enhanced, which proves the successful composite of the poly [2- (3-thienyl) ethanol ] and the graphite phase carbon nitride, and thereby the visible light absorption range is also expanded.
(thirteen) ultraviolet and visible light absorption spectrum detection was performed on the graphite-phase carbon nitride having hydroxyl groups on the surface obtained in the first to third embodiments, and an ultraviolet and visible light absorption spectrum and a band gap pattern of the graphite-phase carbon nitride as shown in fig. 14 were obtained. As can be seen from fig. 14, the band gap of the graphite phase carbon nitride was 2.70 eV.
And (fourteen) detecting the ultraviolet and visible light absorption spectrum of the poly [2- (3-thienyl) ethanol ] obtained in the first to third embodiments to obtain the ultraviolet and visible light absorption spectrum diagram and the band gap diagram of the poly [2- (3-thienyl) ethanol ] shown in fig. 15. As is clear from FIG. 15, the band gap of poly [2- (3-thienyl) ethanol ] was 2.09 eV.
And (fifteen) performing a visible light catalytic decomposition water hydrogen production performance test on the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light catalyst and the graphite phase carbon nitride with hydroxyl on the surface, which are obtained in the first to third embodiments, under the test conditions that: 300W xenon lamp (light source), filter (lambda >420nm), 100mg photocatalyst, 90mL water, 10mL triethanolamine, 0.75mL chloroplatinic acid (0.004 g/mL).
And (4) conclusion: the visible light hydrogen production performance diagram of the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light catalyst and graphite phase carbon nitride shown in fig. 16 is obtained. As can be seen from FIG. 16, the graphite-phase carbon nitride has a low visible-light hydrogen production performance, and the hydrogen production rate is 185.2. mu. mol/g/h. As predicted in the foregoing, the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light catalyst has significantly improved hydrogen production performance due to enhanced photo-generated charge separation, and particularly 5PTETOH/CN has the highest visible light hydrogen production performance, and the hydrogen production rate can reach 2475.1 mu mol/g/h, which is about 13 times of the graphite phase carbon nitride hydrogen production rate.
Sixthly, performing visible light hydrogen production cycle test on the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light photocatalyst 5PTETOH/CN obtained in the second specific embodiment to obtain a visible light hydrogen production cycle test chart of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light photocatalyst 5PTETOH/CN shown in FIG. 17. As can be seen from FIG. 17, after 3 cycles of the 5PTETOH/CN and 15 hours of visible light hydrogen production tests, the hydrogen production amount of visible light has no obvious change, and the 5PTETOH/CN can be proved to have good circulation stability in the visible light catalytic hydrogen production process.
In conclusion, the invention provides a polymer semiconductor composite visible-light-induced photocatalyst and a preparation method thereof, the polymer semiconductor composite visible-light-induced photocatalyst prepared by the invention is a poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst, and the polymer semiconductor composite visible-light-induced photocatalyst is novel in structure and simple to prepare; according to the data of the embodiment, in the test of hydrogen production performance by decomposing water under visible light catalysis, the hydrogen production rate of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light catalyst prepared by the method is obviously higher than that of graphite-phase carbon nitride, and the composite visible light catalyst has high visible light catalysis hydrogen production performance and good cycle stability.
Claims (8)
1. A preparation method of a poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst is characterized by comprising the following steps:
firstly, preparing graphite phase carbon nitride: calcining urea at high temperature to obtain graphite-phase carbon nitride with hydroxyl on the surface;
preparation of poly [2- (3-thienyl) ethanol ]: adding a 2- (3-thienyl) ethanol monomer into acetonitrile, and stirring until the 2- (3-thienyl) ethanol monomer is completely dissolved to obtain a monomer solution; dissolving anhydrous ferric trichloride in acetonitrile to obtain an oxidant solution; dropwise adding the oxidant solution obtained in the step (i) into the monomer solution obtained in the step (i), continuously stirring at room temperature for polymerization reaction for 3-12 h, washing with anhydrous methanol after suction filtration, and drying to obtain poly [2- (3-thienyl) ethanol ];
thirdly, preparing the poly [2- (3-thienyl) ethanol ]/graphite phase carbon nitride composite visible light catalyst: dispersing the graphite-phase carbon nitride with hydroxyl on the surface obtained in the step one and the poly [2- (3-thienyl) ethanol ] obtained in the step two in a solvent, and obtaining a poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible light catalyst by a wet chemical method under the ultrasonic condition, wherein the ratio of the mass of the poly [2- (3-thienyl) ethanol ] to the total mass of the poly [2- (3-thienyl) ethanol ] and the graphite-phase carbon nitride is (1-15): 100, respectively; the ratio of the mass of the poly [2- (3-thienyl) ethanol ] to the volume of the solvent is (1-30) mg: 80mL, wherein the solvent is absolute ethyl alcohol, water or N, N-dimethylformamide.
2. The method for preparing the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst according to claim 1, wherein the method for obtaining graphite-phase carbon nitride with hydroxyl groups on the surface by calcining urea at high temperature in the first step is as follows: adding urea into a quartz crucible, then putting the quartz crucible into a muffle furnace for calcining, grinding the obtained light yellow blocky solid, washing the light yellow blocky solid by using a nitric acid solution, then washing the light yellow blocky solid to be neutral by using distilled water, carrying out suction filtration, and drying to obtain the graphite-phase carbon nitride with hydroxyl on the surface.
3. The preparation method of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst according to claim 1, wherein the calcination process in the first step is as follows: heating from room temperature to 500-600 ℃ at a heating rate of 0.2-2 ℃/min, then preserving heat for 2-4 h at the temperature, and then cooling to room temperature.
4. The method for preparing the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst according to claim 2, wherein the concentration of the nitric acid solution in the first step is 0.2mol/L to 1.0 mol/L.
5. The preparation method of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst according to claim 1, wherein the concentration of the 2- (3-thienyl) ethanol in the monomer solution in the second step is 0.10mol/L to 0.20 mol/L; and in the second step, the concentration of the anhydrous ferric trichloride in the oxidant solution is 1.20-2.40 mol/L.
6. The preparation method of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst according to claim 1, wherein the molar ratio of anhydrous ferric trichloride in the oxidant solution to 2- (3-thienyl) ethanol in the monomer solution in the step two (c) is (3-12): 1.
7. The method for preparing the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst according to claim 1, wherein the step of preparing the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-induced photocatalyst by the wet chemical method in the third step is as follows: after ultrasonic treatment for 0.25-2 h, evaporating to dryness in a water bath at 50-80 ℃.
8. The application of the composite visible-light-driven photocatalyst prepared by the preparation method of the poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst as claimed in any one of claims 1 to 7 is characterized in that the composite visible-light-driven photocatalyst is applied to the field of hydrogen production by visible-light catalytic decomposition of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010475493.XA CN111686806B (en) | 2020-05-29 | 2020-05-29 | Preparation method and application of poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010475493.XA CN111686806B (en) | 2020-05-29 | 2020-05-29 | Preparation method and application of poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111686806A CN111686806A (en) | 2020-09-22 |
| CN111686806B true CN111686806B (en) | 2022-09-30 |
Family
ID=72478798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010475493.XA Active CN111686806B (en) | 2020-05-29 | 2020-05-29 | Preparation method and application of poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111686806B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE754820R (en) * | 1969-08-13 | 1971-02-15 | Schering Ag | NEW PYRIMIDINE DERIVATIVES, THEIR METHODS OF PREPARATION AND THEIR |
| AU2009275838A1 (en) * | 2008-08-01 | 2010-02-04 | Abbott Healthcare Products B.V. | Synthesis of 3,4-diaryl-4,5-dihydro-(1H)-pyrazole-1- carboxamidine derivatives |
| CN102921458A (en) * | 2012-11-02 | 2013-02-13 | 武汉科技大学 | Polythiophene nanometer photocatalyst and preparation and regeneration method thereof |
| EP2792639A1 (en) * | 2011-12-12 | 2014-10-22 | Panasonic Corporation | Carbon-based material, electrode catalyst, oxygen reduction electrode catalyst, gas diffusion electrode, aqueous solution electrolytic device, and production method for carbon-based material |
| CN104231623A (en) * | 2014-09-11 | 2014-12-24 | 黑龙江大学 | Method for preparing oxidized graphene/polyaniline composite electrode materials with different morphologies by doping with metal ions |
| CN105289726A (en) * | 2015-10-28 | 2016-02-03 | 江苏大学 | Magnetic P<3>HT/TNT heterojunction photocatalyst with specific orientation ability and preparation method thereof |
| CN108620133A (en) * | 2018-05-03 | 2018-10-09 | 同济大学 | A kind of preparation method and applications of the visible light-responded catalysis production hydrogen material of two-dimensional transversal polymer hetero-junctions |
| CN108751177A (en) * | 2018-06-21 | 2018-11-06 | 合肥艾飞新材料有限公司 | A kind of preparation method of polythiophene intercalated graphite alkene |
| CN110775958A (en) * | 2019-11-06 | 2020-02-11 | 渤海大学 | Carbon nano tube derived from thienyl nickel complex and synthetic method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109107612A (en) * | 2018-09-19 | 2019-01-01 | 平顶山学院 | A kind of poly- 3,4- ethylenedioxy thiophene/biomass carbon/SnO2-xThe preparation method of nanocomposite |
-
2020
- 2020-05-29 CN CN202010475493.XA patent/CN111686806B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE754820R (en) * | 1969-08-13 | 1971-02-15 | Schering Ag | NEW PYRIMIDINE DERIVATIVES, THEIR METHODS OF PREPARATION AND THEIR |
| AU2009275838A1 (en) * | 2008-08-01 | 2010-02-04 | Abbott Healthcare Products B.V. | Synthesis of 3,4-diaryl-4,5-dihydro-(1H)-pyrazole-1- carboxamidine derivatives |
| EP2792639A1 (en) * | 2011-12-12 | 2014-10-22 | Panasonic Corporation | Carbon-based material, electrode catalyst, oxygen reduction electrode catalyst, gas diffusion electrode, aqueous solution electrolytic device, and production method for carbon-based material |
| CN102921458A (en) * | 2012-11-02 | 2013-02-13 | 武汉科技大学 | Polythiophene nanometer photocatalyst and preparation and regeneration method thereof |
| CN104231623A (en) * | 2014-09-11 | 2014-12-24 | 黑龙江大学 | Method for preparing oxidized graphene/polyaniline composite electrode materials with different morphologies by doping with metal ions |
| CN105289726A (en) * | 2015-10-28 | 2016-02-03 | 江苏大学 | Magnetic P<3>HT/TNT heterojunction photocatalyst with specific orientation ability and preparation method thereof |
| CN108620133A (en) * | 2018-05-03 | 2018-10-09 | 同济大学 | A kind of preparation method and applications of the visible light-responded catalysis production hydrogen material of two-dimensional transversal polymer hetero-junctions |
| CN108751177A (en) * | 2018-06-21 | 2018-11-06 | 合肥艾飞新材料有限公司 | A kind of preparation method of polythiophene intercalated graphite alkene |
| CN110775958A (en) * | 2019-11-06 | 2020-02-11 | 渤海大学 | Carbon nano tube derived from thienyl nickel complex and synthetic method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Controlled Synthesis of Nitro-Terminated Poly[2-(3-thienyl)-ethanol]/g‑C3N4 Nanosheet Heterojunctions for Efficient Visible-Light Photocatalytic Hydrogen Evolution;Qi Zhao et.al;《ACS Sustainable Chem. Eng.》;20210517;全文 * |
| In situ FTIR spectroelectrochemistry of poly[2-(3-thienyl)ethyl acetate] and its hydrolyzed derivatives;Andrea Kellenberger et.al;《Electrochimica Acta》;20080518;全文 * |
| Molecular doping of carbon nitride photocatalysts with tunable bandgap and enhanced activity;Jinshui Zhang et.al;《Journal of Catalysis》;20130212;全文 * |
| 氮化碳/碳复合光催化剂及其光解水产氢性能;曹煜祺等;《江苏理工学院学报》;20200415;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111686806A (en) | 2020-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shen et al. | Accelerating photocatalytic hydrogen evolution and pollutant degradation by coupling organic co-catalysts with TiO2 | |
| CN103143338B (en) | Porous titanium dioxide/graphene composite material and preparation method thereof | |
| CN104128184B (en) | A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof | |
| CN103752334B (en) | Graphite phase carbon nitride nanosheet visible-light-induced photocatalyst synthesized by promotion of ionic liquid | |
| CN108794756A (en) | A kind of preparation method and applications of the covalent organic frame material of nickel ion modification | |
| CN104277219B (en) | Photocatalytic material polyimide, as well as preparation method and applications thereof | |
| CN110586183B (en) | Method for preparing TiO by using supercritical carbon dioxide2Method for preparing/COF catalytic material | |
| CN107899618B (en) | Macrocyclic compound photosensitive dye and titanium dioxide-based hybrid material, preparation method thereof and application thereof in photocatalysis | |
| CN103071535A (en) | Preparation method and application of zinc oxide visible-light-induced photocatalyst sensitized by squarylium cyanine | |
| CN112500546B (en) | Preparation method of spherical porous structure two-dimensional covalent organic framework material | |
| CN111151285A (en) | Nitrogen-doped porous carbon loaded ZnS nano composite material and preparation method and application thereof | |
| CN113942983A (en) | Preparation method of novel carbon nitride-based material combining copolymerization and thermal induction | |
| CN113751047A (en) | Covalent organic framework-carbon nitride nanosheet hybrid photocatalytic hydrogen evolution material and preparation method and application thereof | |
| CN106914266B (en) | g-C for fast degrading pollutant3N4Composite photocatalyst and preparation method thereof | |
| CN115007182A (en) | Preparation method of potassium-oxygen co-doped graphite-phase carbon nitride photocatalyst | |
| CN113000061B (en) | Preparation method of banded graphite carbon nitride nanosheets | |
| CN111686806B (en) | Preparation method and application of poly [2- (3-thienyl) ethanol ]/graphite-phase carbon nitride composite visible-light-driven photocatalyst | |
| CN113058601A (en) | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting | |
| CN106964388A (en) | A kind of preparation method of the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping | |
| CN108404948B (en) | One kind (BiO)2CO3-BiO2-xComposite photocatalyst and preparation method and application thereof | |
| CN115181265B (en) | Methylene modified covalent triazine framework material and preparation method and application thereof | |
| CN111644185A (en) | Bi stripping by cell crusher3O4Method for Cl and in photocatalytic reduction of CO2Application of aspects | |
| CN110639587A (en) | Preparation method and application of carbon-bridged modified carbon nitride photocatalytic material | |
| CN116120505A (en) | Halogen-containing pyrenyl covalent organic framework polymer photocatalyst, and preparation method and application thereof | |
| CN114308126A (en) | K4Nb6O17micro-flower/Co-TCPP MOF hydrogen evolution catalyst and preparation method and application thereof |
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 |