CN115181265A - Methylene modified covalent triazine framework material and preparation method and application thereof - Google Patents
Methylene modified covalent triazine framework material and preparation method and application thereof Download PDFInfo
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- CN115181265A CN115181265A CN202210913824.2A CN202210913824A CN115181265A CN 115181265 A CN115181265 A CN 115181265A CN 202210913824 A CN202210913824 A CN 202210913824A CN 115181265 A CN115181265 A CN 115181265A
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- methylene
- covalent triazine
- framework material
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- terephthalonitrile
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- 239000000463 material Substances 0.000 title claims abstract description 66
- 239000013311 covalent triazine framework Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 title claims 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000001699 photocatalysis Effects 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 39
- 238000004519 manufacturing process Methods 0.000 claims description 21
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 150000004687 hexahydrates Chemical class 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 abstract description 28
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract description 2
- 230000004298 light response Effects 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 230000000694 effects Effects 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000010453 quartz Substances 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
- FUQCKESKNZBNOG-UHFFFAOYSA-N 2-[4-(cyanomethyl)phenyl]acetonitrile Chemical compound N#CCC1=CC=C(CC#N)C=C1 FUQCKESKNZBNOG-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000006006 cyclotrimerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009210 therapy by ultrasound 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
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
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- 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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- 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
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Abstract
The invention discloses a methylene modified covalent triazine framework material, a preparation method and application thereof, and the structural formula is
Compared with the traditional catalyst, the catalyst does not contain metal elements in a molecular structure, does not have the harm of metal dissolution, has stable structure and long service life, can realize the reutilization of the catalyst, and is acid-resistant and alkali-resistant; the methylene modified covalent triazine framework material has visible light response, contains an electron donor (methylene group) and an electron acceptor (cyano group) in molecules/molecules, can induce and accelerate intermolecular/intramolecular charge transfer, and can prepare hydrogen by photocatalytic water decomposition under the condition of visible light.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by decomposing water under visible light, and particularly relates to a methylene modified covalent triazine framework material and a preparation method and application thereof.
Background
TiO was first reported by Fujishima and Honda in 1972 (Nature 1972, 238 2 Since the photoelectrode decomposes water to generate hydrogen and oxygen, photocatalytic research has received high attention from governments and academia of various countries in the world. Hundreds of photocatalytic materials have been developed, mainly including inorganic semiconductor heterogeneous photocatalysts and organic molecular homogeneous photocatalysts. Due to the adjustability of the light absorption band gap and the band position, and the diversity of the types, the organic polymer semiconductor has become one of the important members of the photocatalyst, and the structure and function of the organic polymer semiconductor have complementarity with the traditional inorganic semiconductor photocatalyst, and each of the organic polymer semiconductor has advantages, which is a new research hotspot in the field of photocatalysis (nat. Mater, 2009, 8.
The covalent triazine framework material has the characteristics of stable chemical structure, higher heat resistance, high specific surface, porous hierarchical structure and the like, and has wide application prospect in catalytic reaction. The triazine ring group is an aromatic ring structure formed by alternately connecting C-N bonds, and is an extremely stable electron-withdrawing group. The triazine ring group is coupled into a polymer framework structure as an organic unit, and the energy band structure of the conjugated polymer can be effectively regulated and controlled, so that the conjugated polymer has visible light absorption. The covalent triazine framework material has been successfully reported to be applied to the photocatalytic water splitting reaction, and has better photocatalytic performance. In the early stage, people mainly adopt a molten salt method, a super-strong acid catalysis method and a mike addition reaction to synthesize a series of novel covalent triazine skeleton photocatalysts (Energy environ.sci.2015, 8. The synthetic methods are essentially to realize the coupling of the polymers by trimerizing organic monomers containing cyano groups to generate triazine rings. However, these methods are prone to cause low polymerization degree, more defects and even carbonization of triazine ring during polymerization, resulting in low separation efficiency of photogenerated carriers and insufficient utilization rate of visible light absorption of the prepared covalent triazine framework material, thereby limiting the photocatalytic application of the covalent triazine framework material (angelw. Chem. Int.ed.2022, 61.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a methylene modified covalent triazine framework material.
The invention also aims to provide a preparation method of the methylene modified covalent triazine framework material.
The invention further aims to provide application of the methylene modified covalent triazine framework material.
The technical scheme of the invention is as follows:
a methylene modified covalent triazine skeleton material with a structural formula
The preparation method of the methylene modified covalent triazine framework material comprises the following steps:
(1) Uniformly mixing terephthalonitrile and terephthalonitrile to obtain mixed powder;
(2) Dropwise adding a trifluoromethanesulfonic acid solution into the mixed powder while stirring at-5-0 ℃ to obtain a mixed solution;
(3) Stirring the mixed solution for 100-120min at-5-0 ℃, and then standing at room temperature for reaction for 2-5d;
(4) Washing the material obtained in the step (3) with chloroform and ammonia water, and performing centrifugal separation to obtain a precipitate;
(5) And purifying the precipitate by using methanol and dichloromethane, and then drying, grinding and screening to obtain the methylene modified covalent triazine framework material.
In a preferred embodiment of the present invention, the molar ratio of terephthalonitrile to terephthalonitrile is 6-122: 1.
In a preferred embodiment of the invention, the molar ratio of terephthalonitrile to trifluoromethanesulfonic acid is from 0.03 to 0.16: 1.
The methylene modified covalent triazine framework material is applied as a catalyst for hydrogen production by photocatalytic water decomposition.
In a preferred embodiment of the invention, a Pt promoter is also included.
A method for producing hydrogen by photocatalytic decomposition is characterized in that: the method comprises the following steps: uniformly mixing and dispersing the methylene modified covalent triazine framework material, the Pt promoter, water and triethanolamine, and then carrying out hydrogen production reaction under the irradiation of visible light with the wavelength of 420nm, wherein the temperature of the hydrogen production reaction is 4-6 ℃.
In a preferred embodiment of the invention, the concentration of the methylene-modified covalent triazine backbone material is between 50 and 5000mg/L.
Further preferably, the Pt promoter is chloroplatinic acid hexahydrate.
Still further preferably, the amount of the Pt promoter is 0.1 to 10wt% of the methylene modified covalent triazine backbone material.
The invention has the beneficial effects that:
1. compared with the traditional catalyst, the catalyst does not contain metal elements in the molecular structure, does not have the harm of metal dissolution, has stable structure and long service life, can realize the reutilization of the catalyst, and is acid-resistant and alkali-resistant.
2. The methylene modified covalent triazine framework material has visible light response, contains an electron donor (methylene group) and an electron acceptor (cyano group) in molecules/molecules, can induce and accelerate intermolecular/intramolecular charge transfer, and can prepare hydrogen by photocatalytic water decomposition under the condition of visible light.
3. The invention introduces the donor-acceptor, improves the visible light absorption capacity of the catalyst, promotes the separation efficiency of photon-generated carriers, and improves the activity of the reaction of decomposing water into hydrogen by photocatalysis.
4. The invention selects the terephthalonitrile and the terephthalonitrile, and prepares the methylene modified covalent triazine framework material through the cyclotrimerization reaction of the triflic acid catalyzed cyano group at a lower temperature.
5. The invention takes platinum as a cocatalyst, has high activity in preparing hydrogen by photocatalytic water decomposition under visible light, and effectively avoids the problems of low photocatalytic efficiency, low visible light utilization rate and insufficient reaction activity sites in the traditional catalyst method.
Drawings
FIG. 1 is a scanning electron microscope image of a triazine skeleton material prepared in example 1 of the present invention.
FIG. 2 is a transmission electron microscope image of the triazine skeleton material prepared in example 1 of the present invention.
FIG. 3 is a scanning image of the element plane of a transmission electron microscope of the triazine skeleton material prepared in example 1 of the invention.
Fig. 4 is an X-ray powder diffraction pattern of the triazine skeleton material produced in the example of the present invention and the comparative example.
FIG. 5 is a Fourier infrared spectrum of triazine skeleton materials prepared in examples of the present invention and comparative examples.
Fig. 6 shows uv-vis diffuse reflection spectra of triazine skeleton materials prepared in the examples of the present invention and the comparative examples.
FIG. 7 shows X-ray photoelectron spectrum valence band spectra of triazine skeleton materials prepared in the examples of the present invention and the comparative examples.
Fig. 8 is a graph showing photocatalytic hydrogen production activity of triazine framework materials prepared in examples of the present invention and comparative examples.
Fig. 9 is a graph showing the stability of photocatalytic hydrogen production activity of the triazine framework material prepared in example 1 of the present invention.
Fig. 10 is a graph of the photocatalytic hydrogen production quantum efficiency of the triazine framework material prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description in conjunction with the accompanying drawings.
Example 1
(1) Uniformly mixing terephthalonitrile (0.064g, 0.41mmol) and terephthalonitrile (1.28g, 10mmol) in a quartz mortar (50 mL) at a mass ratio of 5% to obtain a mixed powder;
(2) A rotor was placed in a 100mL beaker, placed in a 0 ℃ ice water bath, and trifluoromethanesulfonic acid (10mL, 80mmol) was added;
(3) Starting a magnetic stirrer, and slowly adding the mixed powder into the material obtained in the step (2) to obtain a mixed solution;
(4) Stirring the mixed solution in ice water bath at 0 deg.C for 120min at 400-500 r/min;
(5) Placing the material obtained in the step (4) in a quartz tube for reaction at room temperature for 3 days;
(6) Repeatedly washing the material obtained in the step (5) with chloroform and ammonia water for many times, and performing centrifugal separation to obtain a precipitate;
(7) Purifying the precipitate with methanol and dichloromethane, and drying;
(8) Grinding and screening the material obtained in the step (7) to obtain the methylene modified covalent triazine framework material (CH) 2 -CTF 0.05 )。
Example 2
20mg of the methylene-modified covalent triazine backbone material (CH) prepared in example 1 was weighed out 2 -CTF 0.05 ) The photocatalyst was placed in a glass reactor, and a chloroplatinic acid hexahydrate solution containing 3wt% of Pt, 100mL of deionized water, 10mL of triethanolamine were added and ultrasonically dispersed for 15min. And (3) after the ultrasonic treatment is finished, connecting the reactor to a full glass system, vacuumizing the reactor and the glass system, and opening a circulating cooling water system to keep the temperature of the hydrogen production process at 6 ℃. And (4) turning on a xenon lamp (a filter lambda is more than 420 nm) preheated in advance, automatically injecting sample per hour of chromatogram, and collecting hydrogen. The hydrogen production rate was 20.14 mmol/g -1 Hour(s) -1 。
Comparative example 1
The present embodiment differs from embodiment 1 in that: in the step (1), only terephthalonitrile is adopted to obtain the original covalent triazine framework material (CTF) TPN ). The other steps and parameters were the same as in example 1.
Comparative example 2
The present embodiment is different from embodiment 1 in that: in the step (1), only terephthalonitrile is adopted to obtain the methylene covalent triazine framework material (CTF) p-PHDA ). The other steps and parameters were the same as in example 1.
Comparative example 3
The difference between this embodiment and embodiment 2 is: 20mg of the starting material from comparative example 1 were weighed outCovalent triazine backbone materials (CTF) TPN ) Placed in a glass reactor. The other steps and parameters were the same as in example 2, and the hydrogen production rate was 1.98 mmol/g -1 Hour(s) -1 。
Comparative example 4
The difference between this embodiment and embodiment 2 is: 20mg of the methylene covalent triazine backbone material (CTF) prepared in comparative example 2 was weighed p-PHDA ) Placed in a glass reactor. The other steps and parameters were the same as in example 2, and the hydrogen production rate was 0.06 mmol/g -1 Hour(s) -1 。
FIG. 1 shows CH obtained in example 1 of the present invention 2 -CTF 0.05 Scanning electron micrograph (c). From the figure, CH can be known 2 -CTF 0.05 The sample showed a lamellar stacked nanosheet structure.
FIG. 2 shows CH obtained in example 1 of the present invention 2 -CTF 0.05 Transmission electron micrograph (c). And stripping the synthesized material by adopting a liquid-phase ultrasonic stripping method to obtain the ultrathin two-dimensional nanosheet material. The morphology is a two-dimensional nanosheet, and the thickness is only about 2 nm.
FIG. 3 shows CH obtained in example 1 of the present invention 2 -CTF 0.05 A plane scan of the transmission mirror element. CH (CH) 2 -CTF 0.05 The nano-sheet mainly comprises two elements of carbon and nitrogen, and the elements are uniformly distributed.
FIG. 4 is an X-ray powder diffraction pattern of catalysts prepared in examples of the present invention and comparative examples. At CTF TPN And CH 2 -CTF 0.05 Two distinct peaks, 14.1 ° and 25.2 ° respectively, can be seen in the catalyst, the low angle peak being the in-plane reflection (100) of the ideal structure, based on the in-plane reflection principle of three hexagonal unit cells with triazine bridging the individual aromatic units. While 25.2 ° can be attributed to stacking of interlayers (001), ascribed to a stacked conjugated aromatic system in a covalent triazine backbone, similar to layered materials such as graphite. The results show that the crystal structure of the covalent triazine skeleton is still remained after the introduction of the methylene structure. And CTF p-PHDA There is only one broad peak indicating that the polymer of pure p-phenylenediacetonitrile is amorphous.
FIG. 5 is a Fourier infrared spectrum of triazine skeleton materials prepared in examples of the present invention and comparative examples. CTF TPN And CH 2 -CTF 0.05 At 1508cm -1 And 1357cm -1 There are infrared absorption peaks corresponding to the tensile vibration band of C = N and the tensile vibration band of C-N, respectively, which indicates that the triazine unit has been successfully formed. For 2168cm appearing in the map -1 The signal at (A) is a characteristic peak of the terminal cyano group. The characteristic peak of the covalent triazine skeleton does not disappear after methylene modification, which shows that the main body framework structure of the triazine ring is not obviously changed after the methylene modification, and the triazine ring shows better stability. In addition, CH 2 -CTF 0.05 At 3000-2800 cm -1 The infrared absorption peak of (a) was attributed to the methylene group, which was retained after polymerization, indicating that the methylene group was successfully incorporated into the covalent triazine backbone material.
Fig. 6 shows uv-vis diffuse reflection spectra of triazine skeleton materials prepared in examples of the present invention and comparative examples. In order to obtain the optical band gaps (E) of the three materials after stripping g ) And performing ultraviolet-visible diffuse reflection characterization on the material. And CTF TPN Compared with, CH 2 -CTF 0.05 The absorption band edge of (a) is red-shifted. After the methylene structure is introduced, the covalent triazine framework material has wider absorption in a visible light range, and the intrinsic band gap value of the covalent triazine framework material is reduced. Converting the ultraviolet-visible diffuse reflection spectrum data to obtain a corresponding Tauc curve, and obtaining CTFTP N 、CH 2 -CTF 0.05 、CTF p-PHDA The optical band gaps of (a) are: 3.06eV, 2.33eV, and 2.27eV.
FIG. 7 shows X-ray photoelectron valence band spectra of triazine skeleton materials prepared in the examples of the present invention and the comparative examples. CTF TPN And CH 2 -CTF 0.05 The valence bands of (a) are 1.63eV and 1.60eV, respectively. The valence band spectrum shows that the introduction of methylene groups makes the valence band energy level position of the covalent triazine backbone material more negative.
Fig. 8 is a graph showing photocatalytic hydrogen production activity of triazine framework materials prepared in examples of the present invention and comparative examples. CTF TPN After the hydrogen reaction of photolysis water, the amount of the generated hydrogen is only 1.98 mmoleg -1 h -1 . After CTF is modified by methylene, the performance of photocatalyst for producing hydrogen by photolysis of water is obviously improved. CH (CH) 2 -CTF 0.05 The hydrogen production rate is 20.14 mmoleg -1 h -1 Is a CTF TPN 10.2 times of the total weight of the powder. Under the same conditions, CTF p-PHDA The hydrogen-generating activity of (2) is very weak.
FIG. 9 is a graph showing the stability of photocatalytic hydrogen production activity of the triazine framework material prepared in example 1 of the present invention. In a 25h cycling experiment, CH 2 -CTF 0.05 The photocatalytic activity is not changed greatly from the first round to the fifth round, and higher photocatalytic activity is still maintained, so that the high photocatalytic activity has good activity stability.
Fig. 10 is a graph of the photocatalytic hydrogen production quantum efficiency of the triazine framework material prepared in example 1 of the present invention. CH (CH) 2 -CTF 0.05 The photocatalytic hydrogen production quantum efficiency is gradually reduced along with the increase of the wavelength of incident light, and is consistent with the light absorption characteristic. CH (CH) 2 -CTF 0.05 The hydrogen production quantum efficiency under the illumination of 420nm wavelength is 5.0%.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A methylene-modified covalent triazine backbone material, comprising: the structural formula is
2. A process for the preparation of a methylene-modified covalent triazine backbone material of claim 1, wherein: the method comprises the following steps:
(1) Uniformly mixing terephthalonitrile and terephthalonitrile to obtain mixed powder;
(2) Dropwise adding a trifluoromethanesulfonic acid solution into the mixed powder at-5-0 ℃ while stirring to obtain a mixed solution;
(3) Stirring the mixed solution for 100-120min at-5-0 ℃, and then standing at room temperature for reaction for 2-5d;
(4) Washing the material obtained in the step (3) with chloroform and ammonia water, and performing centrifugal separation to obtain a precipitate;
(5) And purifying the precipitate by using methanol and dichloromethane, drying, grinding and screening to obtain the methylene modified covalent triazine framework material.
3. The method of claim 2, wherein: the mol ratio of the terephthalonitrile to the terephthalonitrile is 6-122: 1.
4. The method of claim 2, wherein: the molar ratio of the terephthalonitrile to the trifluoromethanesulfonic acid is 0.03-0.16: 1.
5. Use of the methylene-modified covalent triazine framework material of claim 1 as a catalyst for photocatalytic decomposition of water to produce hydrogen.
6. The use of claim 5, wherein: a Pt promoter is also included.
7. A method for producing hydrogen by photocatalytic decomposition is characterized in that: the method comprises the following steps: uniformly mixing and dispersing the methylene modified covalent triazine framework material of claim 1, a Pt promoter, water and triethanolamine, and then performing hydrogen production reaction under the irradiation of visible light with the wavelength of more than 420nm, wherein the temperature of the hydrogen production reaction is 4-6 ℃.
8. The method of claim 7, wherein the method comprises the steps of: the concentration of the methylene modified covalent triazine framework material is 50-5000mg/L.
9. The method for decomposing water into hydrogen by photocatalysis according to claim 8, wherein: the Pt cocatalyst is chloroplatinic acid hexahydrate.
10. The method of claim 9 for photocatalytic decomposition of hydrogen produced by water, wherein: the amount of the Pt promoter is 0.1-10wt% of the methylene modified covalent triazine backbone material.
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