CN113600239A - Triptycene modified graphite-phase carbon nitride and preparation method and application thereof - Google Patents
Triptycene modified graphite-phase carbon nitride and preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 100
- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical compound C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims description 27
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- -1 triptycene modified graphite Chemical class 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
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- 238000012546 transfer Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 description 32
- 229910052739 hydrogen Inorganic materials 0.000 description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 31
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- 230000000052 comparative effect Effects 0.000 description 16
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- 239000000243 solution Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000001052 transient effect Effects 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
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- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 238000009776 industrial production Methods 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- 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
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Abstract
The invention belongs to the technical field of photocatalytic materials, and particularly relates to triptycene modified graphite-phase carbon nitride and a preparation method and application thereof. The invention provides triptycene modified graphite-phase carbon nitride, which comprises graphite-phase carbon nitride and chemically-doped triptycene. In the invention, after the triazine ring element and the triptycene in the graphite-phase carbon nitride are polymerized in a conjugated manner, the delocalization degree of pi electrons on the graphite-phase carbon nitride skeleton is increased, and the separation, migration and interface transfer efficiency of carriers in the graphite-phase carbon nitride phase are improved. And the carbon content in the triptycene modified graphite-phase carbon nitride is improved by doping triptycene, so that the photoresponse band gap width of the graphite-phase carbon nitride is reduced, the visible light absorption range of the graphite-phase carbon nitride is expanded, the absorption capacity of the triptycene modified graphite-phase carbon nitride to sunlight is improved, and the photocatalytic reaction efficiency of the triptycene modified graphite-phase carbon nitride is further improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to triptycene modified graphite-phase carbon nitride and a preparation method and application thereof.
Background
The energy crisis and environmental pollution are the serious challenges facing all countries in the world at present, the photocatalysis technology can simulate the photosynthesis of plants, and the photo-generated holes and electrons generated by irradiating the semiconductor with light are used for decomposing water to generate clean hydrogen energy, thereby showing attractive prospect on solving the problem of energy shortage. For decades, people develop a series of researches around a catalyst for hydrogen production by photolysis of water, and develop semiconductor photocatalytic materials such as metal oxides, sulfides, nitrides, phosphides and the like. However, most semiconductor photocatalytic materials have insufficient photocatalytic hydrogen production efficiency.
Wherein the graphite phase carbon nitride (g-C)3N4) The photocatalyst has the advantages of good thermal stability and chemical stability, band gap of about 2.7eV, proper energy band structure, low preparation cost, environmental friendliness and the like, and becomes the leading edge and hot spot of the photocatalytic research field in the global range. However, the most key problems of the material are that a photogenerated electron-hole pair is easy to recombine and the transmission of a photogenerated carrier is slow, and under the condition that Pt is used as an auxiliary agent and triethanolamine is used as a hole sacrificial agent, the quantum efficiency of photocatalytic hydrogen production is only 0.1% (lambda is 420-460 nm).
Disclosure of Invention
In view of the above, the invention provides triptycene modified graphite-phase carbon nitride and a preparation method and application thereof.
In order to solve the technical problem, the invention provides triptycene modified graphite-phase carbon nitride, which comprises graphite-phase carbon nitride and chemically-doped triptycene.
Preferably, the doping amount of the triptycene is 0.01-5 wt.%.
Preferably, the graphite-phase carbon nitride has a basic structural unit of a heptazine ring.
The invention also provides a preparation method of the triptycene modified graphite-phase carbon nitride, which comprises the following steps:
mixing polyamino triptycene and cyanamide to perform a polycondensation reaction to obtain triptycene modified graphite-phase carbon nitride; the polyaminotriptycene contains more than three amino groups.
Preferably, the temperature of the polycondensation reaction is 450-550 ℃, and the heat preservation time of the polycondensation reaction is 3.8-4.2 h.
Preferably, the polycondensation reaction is carried out under a protective atmosphere, the protective atmosphere comprises argon, and the flow rate of the argon is 4.8-5.2 mL/min.
Preferably, the mass ratio of the polyaminotriptycene to the cyanamide is 0.1-50: 1000.
Preferably, the polyaminotriptycene comprises 2,6, 14-triaminetripentaene, 2,7, 14-triaminetetraene, 1,7, 13-triaminetetraene, 2,7, 13-triaminetetraene or 2,3,6,7,14, 15-hexaaminotrtriptycene.
Preferably, the cyanamide comprises a cyanamide, a dicyandiamide, or a melamine.
The invention provides application of the triptycene modified graphite-phase carbon nitride in the technical scheme or the triptycene modified graphite-phase carbon nitride prepared by the preparation method in the technical scheme as a photocatalytic material.
The invention provides triptycene modified graphite-phase carbon nitride, which comprises graphite-phase carbon nitride and chemically-doped triptycene. From g to C3N4In view of the composition and structure of (1), g-C3N4Has a theoretical molar ratio of C/N of 0.75 and has a structure in which the C atom is sp2Hybrid form, N in sp2And sp3The hybridization forms jointly form a stable six-membered ring conjugated system, most delocalized pi electrons are enriched around nitrogen atoms (namely, the electron cloud density near the nitrogen atoms is higher) due to the electronegativity difference of carbon and nitrogen atoms, the pi electron conjugated system is insufficiently expanded and has low charge mobility, which causes g-C3N4The root cause of low quantum yield of the photocatalytic reaction. In the invention, after the triazine ring element and the triptycene in the graphite-phase carbon nitride are polymerized in a conjugated manner, the delocalization degree of pi electrons on the graphite-phase carbon nitride skeleton is increased, and the separation, migration and interface transfer efficiency of carriers in the graphite-phase carbon nitride phase are improved. Moreover, the carbon content in the triptycene modified graphite-phase carbon nitride is improved by doping triptycene, so that the photoresponse band gap width of the graphite-phase carbon nitride is reduced, the visible light absorption range of the graphite-phase carbon nitride is expanded, the absorption capacity of the triptycene modified graphite-phase carbon nitride to sunlight is improved, and the light of the triptycene modified graphite-phase carbon nitride is further improvedThe efficiency of the catalytic reaction.
The invention also provides a preparation method of the triptycene modified graphite-phase carbon nitride, which comprises the following steps: mixing polyamino triptycene and cyanamide to perform a polycondensation reaction to obtain triptycene modified graphite-phase carbon nitride; the polyaminotriptycene contains more than three amino groups. The triptycene modified graphite-phase carbon nitride prepared by the preparation method provided by the invention has excellent performance of photocatalytic water decomposition to produce hydrogen, and can be repeatedly used. The preparation method provided by the invention has the advantages of simple process, low cost, environmental friendliness and easiness in industrial production.
Drawings
FIG. 1 is an SEM image of samples prepared in example 2 and comparative example 1, wherein a is an SEM image of graphite phase carbon nitride prepared in comparative example 1, and b is an SEM image of triptycene modified graphite phase carbon nitride prepared in example 2;
FIG. 2 is an XRD spectrum of samples prepared in examples 1 to 3 and comparative example 1;
FIG. 3 is an infrared spectrum of samples prepared in examples 1 to 3 and comparative example 1;
FIG. 4 is a graph showing transient fluorescence spectra of samples prepared in example 2 and comparative example 1;
fig. 5 is a point diagram of hydrogen production rate of photocatalytic hydrolysis hydrogen production, where (a) is a point diagram of hydrogen production rate of photocatalytic hydrolysis hydrogen production using samples prepared in examples 1 to 3 and comparative example 1, and (b) is a point diagram of hydrogen production rate of photocatalytic hydrolysis hydrogen production using triptycene-modified graphite-phase carbon nitride cycle prepared in example 2.
Detailed Description
The invention provides triptycene modified graphite-phase carbon nitride, which comprises graphite-phase carbon nitride and chemically-doped triptycene.
In the invention, the doping amount of triptycene in the triptycene modified graphite-phase carbon nitride is preferably 0.01-5 wt.%, and more preferably 0.05-0.5 wt.%. In the present invention, the graphite-phase carbon nitride has a basic structural unit of a heptazine ring, and an amino group in the triptycene is conjugated with an amino group in the graphite-phase carbon nitride.
In the invention, after the oxazine ring element and the triptycene in the graphite-phase carbon nitride are polymerized in a conjugated manner, due to the increase of the content of conjugated carbon (the graphite-phase carbon nitride is the conjugation of-C-N-oxazine ring), electrons originally localized on the heptazine ring are delocalized through the pi conjugation of the triptycene, the rapid transfer of photo-generated electrons on the graphite-phase carbon nitride ring is accelerated, and the recombination probability of photo-generated electron-hole pairs is effectively inhibited. And the carbon content in the triptycene modified graphite-phase carbon nitride is improved by doping triptycene through polycondensation, so that the photoresponse band gap width of the graphite-phase carbon nitride is reduced, the visible light absorption range of the graphite-phase carbon nitride is expanded, the absorption capacity of the triptycene modified graphite-phase carbon nitride to sunlight is improved, and the photocatalytic reaction efficiency of the triptycene modified graphite-phase carbon nitride is further improved. In the invention, the plane extension of the graphite-phase carbon nitride with a two-dimensional structure is limited by the triptycene doped in the triptycene modified graphite-phase carbon nitride through polycondensation, so that a microporous polymer is favorably formed, the polymer has a large specific surface area, the adsorption of reactants is favorably realized, and the photocatalytic oxidation reduction reaction of the triptycene modified graphite-phase carbon nitride serving as a photocatalyst is promoted.
The invention also provides a preparation method of the triptycene modified graphite-phase carbon nitride, which comprises the following steps:
mixing polyamino triptycene and cyanamide to perform a polycondensation reaction to obtain triptycene modified graphite-phase carbon nitride; the polyaminotriptycene contains more than three amino groups.
In the present invention, the raw materials are all conventional commercially available products unless otherwise specified.
In the present invention, the polyaminotriptycene preferably has three amino groups or six amino groups, preferably including 2,6, 14-triaminetycene, 2,7, 14-triaminetycene, 1,7, 13-triaminetycene, 2,7, 13-triaminetycene or 2,3,6,7,14, 15-hexaaminotrtriptycene, more preferably 2,6, 14-triaminetycene.
In the present invention, the cyanamide preferably includes cyanamide, dicyandiamide or melamine, more preferably melamine. In the invention, the mass ratio of triptycene to cyanamide is preferably 0.1-50: 1000, more preferably 0.5-5: 1000. In the present invention, the polyaminotriptycene and cyanamide are independently preferably analytically pure.
The mixing is not particularly limited in the present invention as long as it can be mixed uniformly. In the embodiment of the invention, the mixing is in a ball milling mode, the rotation speed of the ball milling is 400r/min, and the time is 0.5-5 h; the ball milling device is a planetary ball mill.
In the present invention, the polycondensation reaction is preferably carried out under a protective atmosphere, preferably comprising argon, the purity of which is preferably greater than 99.999%; the flow rate of the argon gas is preferably 4.8-5.2 mL/min, and more preferably 5 mL/min. The invention can prevent reactants and products from being oxidized and decomposed under high temperature condition by carrying out polycondensation reaction under the protective atmosphere.
In the invention, the temperature of the polycondensation reaction is preferably 450-550 ℃, and more preferably 500-550 ℃; the heat preservation time of the polycondensation reaction is preferably 3.8-4.2 h, and more preferably 4 h. In the present invention, the rate of temperature rise to the polycondensation reaction temperature is preferably 1.8 to 2.2 ℃/min, more preferably 2 ℃/min. In the polycondensation reaction process, cyanamide can be polymerized by itself to form heptazine ring graphite phase carbon nitride, and amino in triptycene and amino in graphite phase carbon nitride are subjected to polycondensation deamination to form triptycene modified graphite phase carbon nitride.
Taking 2,6, 14-triaminotriptycene and melamine as reactants for example, the formula of the polycondensation reaction is shown in formula 1:
the apparatus for the polycondensation reaction in the present invention is not particularly limited, and an apparatus conventional in the art may be used. In an embodiment of the invention, the polycondensation reaction is carried out in a tube furnace. In the invention, the triptycene modified graphite-phase carbon nitride is light yellow powder.
In the present invention, the polycondensation reaction preferably further comprises: and cooling the polycondensation reaction product to room temperature. In the invention, the room temperature is preferably 20-30 ℃, and more preferably 23-25 ℃. The cooling mode is not particularly limited, and the cooling can be carried out to room temperature. In the embodiment of the invention, the temperature is reduced by adopting a natural cooling mode.
The invention also provides application of the triptycene modified graphite-phase carbon nitride in the technical scheme or the triptycene modified graphite-phase carbon nitride prepared by the preparation method in the technical scheme as a photocatalytic material. In the invention, the triptycene modified graphite-phase carbon nitride can be used as a photocatalytic material to carry out photocatalytic decomposition on water to produce hydrogen. In the present invention, the photocatalytic decomposition of hydrogen production preferably comprises the steps of:
mixing triptycene modified graphite-phase carbon nitride, triethanolamine, chloroplatinic acid and water to obtain a reaction solution;
and carrying out photocatalytic reaction on the reaction solution.
According to the invention, triptycene modified graphite-phase carbon nitride, triethanolamine, chloroplatinic acid and water are mixed to obtain a reaction solution. In the present invention, the water is preferably deionized water. In the invention, the mass ratio of the triptycene modified graphite-phase carbon nitride to water is preferably 0.08-0.12: 100, more preferably 0.1: 100.
in the present invention, the mixing preferably comprises the steps of:
dissolving triethanolamine in the first part of water to obtain a triethanolamine aqueous solution;
dissolving chloroplatinic acid in the second part of water to obtain a chloroplatinic acid aqueous solution;
and mixing the triptycene modified graphite-phase carbon nitride, the triethanolamine aqueous solution, the chloroplatinic acid aqueous solution and the residual water to obtain a reaction solution.
The invention dissolves triethanolamine in a first part of water to obtain a triethanolamine aqueous solution. In the invention, in the triethanolamine aqueous solution, the volume ratio of the triethanolamine to the first part of water is preferably 8-12: 100, and more preferably 10: 100. The present invention is not particularly limited as long as the dissolution can be completed.
In the invention, chloroplatinic acid is dissolved in the second part of water to obtain chloroplatinic acid aqueous solution. In the invention, the concentration of the chloroplatinic acid aqueous solution is preferably 0.8-1.2 mg/mL, and more preferably 1 mg/mL. The present invention is not particularly limited as long as the dissolution can be completed.
After obtaining the triethanolamine aqueous solution and the chloroplatinic acid aqueous solution, mixing the triptycene modified graphite-phase carbon nitride, the triethanolamine aqueous solution, the chloroplatinic acid aqueous solution and the residual water to obtain a reaction solution. In the present invention, the first portion of water, the second portion of water and the remaining water are all water. In the invention, the volume ratio of the triethanolamine aqueous solution to the chloroplatinic acid aqueous solution is preferably 9-11: 1, and more preferably 10: 1. In the invention, the mixing is preferably carried out under the condition of ultrasound, and the power of the ultrasound is preferably 50-150W, and more preferably 90-110W; the time of the ultrasonic treatment is preferably 4-6 min, and more preferably 5 min.
After the reaction solution is obtained, the invention carries out photocatalytic reaction on the reaction solution. Before the photocatalytic reaction is carried out, the method preferably further comprises the following steps: introducing high-purity nitrogen into the reaction solution, wherein the purity of the high-purity nitrogen is preferably more than 99.999%; the flow rate of the high-purity nitrogen is preferably 10-30 mL/min, and more preferably 20 mL/min; the time for introducing the high-purity nitrogen is preferably 0.8-1.2 h, and more preferably 1 h. The purpose of the present invention is to remove dissolved oxygen from the reaction solution by introducing high-purity nitrogen gas into the reaction solution.
In the invention, the temperature of the photocatalytic reaction is preferably 5-7 ℃, and more preferably 6 ℃. In the invention, the light source for the photocatalytic reaction is preferably a xenon lamp, and the xenon lamp is preferably a CEL-HXUV300 type produced by Beijing Zhongjin Source company; in the invention, when the xenon lamp is used as a light source, the light with the wavelength less than 420nm is preferably filtered by a high-pass filter. In the present invention, the photocatalytic reaction is preferably carried out under vacuum conditions, and the degree of vacuum of the vacuum conditions is preferably-0.08 to-0.12 MPa, more preferably-0.1 MPa. In the present invention, the photocatalytic reaction is preferably accompanied by stirring; the stirring is preferably magnetic stirring.
The device for photocatalytic reaction is not particularly limited, and a CEL-SPH2N type photocatalytic water splitting hydrogen production system produced by Beijing Zhongzhijin company is adopted in the embodiment of the invention to carry out photocatalytic hydrolysis hydrogen production.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
3g of melamine and 1.5mg of 2,6, 14-triaminotriptycene are placed in an agate pot of a planetary ball mill and ground for 1h at the rotating speed of 400 r/min; and transferring the mixed white powder into a tube furnace, heating to 550 ℃ in an argon atmosphere (with the purity of 99.999 percent and the flow rate of 5mL/min) at the heating rate of 2 ℃/min to perform polycondensation for 4h, and naturally cooling to 25 ℃ to obtain the faint yellow triptycene modified graphite-phase carbon nitride, namely TCN-0.5.
Example 2
3g of melamine and 3mg of 2,6, 14-triaminotriptycene are placed in an agate pot of a planetary ball mill and ground for 1h under the condition of the rotating speed of 400 r/min; and transferring the mixed white powder into a tube furnace, heating to 550 ℃ in an argon atmosphere (with the purity of 99.999 percent and the flow rate of 5mL/min) at the heating rate of 2 ℃/min to perform polycondensation reaction for 4h, and naturally cooling to 25 ℃ to obtain the faint yellow triptycene modified graphite-phase carbon nitride, namely TCN-1.
Example 3
3g of melamine and 15mg of 2,6, 14-triaminotriptycene are placed in an agate pot of a planetary ball mill and ground for 1h under the condition of the rotating speed of 400 r/min; and transferring the mixed white powder into a tube furnace, heating to 550 ℃ in an argon atmosphere (with the purity of 99.999 percent and the flow rate of 5mL/min) at the heating rate of 2 ℃/min to perform polycondensation reaction for 4h, and naturally cooling to 25 ℃ to obtain the faint yellow triptycene modified graphite-phase carbon nitride, namely TCN-5.
Comparative example 1
Graphite phase carbon nitride, abbreviated CN, was prepared as in example 1, except that triptycene was not added during the preparation.
The morphology of the samples prepared in example 2 and comparative example 1 was observed with a Scanning Electron Microscope (SEM) model S-3500N manufactured by Hitachi, Japan, with an instrument operating voltage of 20kV and a sample chamber vacuum of less than 2.6X 10-5Pa. An SEM image is obtained, as shown in fig. 1, where a is an SEM image of the graphite-phase carbon nitride prepared in comparative example 1, and b is an SEM image of the triptycene-modified graphite-phase carbon nitride prepared in example 2. As can be seen from fig. 1, TCN-1 is fine particles compared with CN having a layered bulk structure, which indicates that polycondensation-doped triptycene can significantly suppress the growth of the oxazine ring structural unit of graphite-phase carbon nitride, and that the granularity of the obtained triptycene-modified graphite-phase carbon nitride is reduced.
XRD measurements were carried out on the samples prepared in examples 1 to 3 and comparative example 1 using a Smartlab X-ray powder diffractometer manufactured by Rigaku corporation of Japan, with operating voltages and currents of 40mV and 30mA, respectively, and a scanning speed of 4 o/min. An XRD spectrum was obtained as shown in FIG. 2. As can be seen from fig. 2, the samples prepared in examples 1 to 3 and comparative example 1 each had two diffraction peaks at 13.0 ° and 27.3 °, wherein the weak peak at 13.0 ° corresponds to the diffraction of the (100) crystal plane within the graphite-phase carbon nitride layer, and the strong peak at 27.3 ° corresponds to the diffraction of the (002) crystal plane between the graphite-phase carbon nitride layers; the triptycene modification can not generate obvious influence on the main structure of the oxazine ring of the graphite-phase carbon nitride.
FT-IR testing was performed on the samples prepared in examples 1 to 3 and comparative example 1 using a Nicolet iS50 type infrared spectrometer manufactured by Thermo Fisher Scientific, USA, to obtain an infrared spectrum, as shown in FIG. 3. As can be seen from FIG. 3, 809cm-1The sum is 900-1650 cm-1The spectral peaks respectively belong to an out-of-plane bending vibration absorption peak of a triazine ring of graphite-phase carbon nitride and a stretching vibration characteristic absorption peak of-C ═ N-in the triazine ring; 689cm after doping triptycene-1And 770cm-1The peak of the spectrum corresponds to the out-of-plane vibration absorption peak of the benzene ring C-H of triptycene, 1681cm-1And is corresponding to the C-N stretching vibration absorption peak of the triptycene with the benzene ring connected with the amino.
The samples prepared in example 2 and comparative example 1 were tested for transient fluorescence lifetime using an FLS920 type fluorescence spectrometer (excitation wavelength 402.8nm, scanning step 1nm) manufactured by Edinburgh, UK, to obtain a transient fluorescence spectrum, as shown in FIG. 4. As can be seen from fig. 4, compared with CN, the transient fluorescence decay change of TCN-1 is slower, and the fluorescence lifetime is significantly prolonged, mainly because the pi conjugation of triptycene and graphite-phase carbon nitride increases the delocalization degree of electrons on the graphite-phase carbon nitride ring, accelerates the migration rate of photo-generated electrons, reduces the recombination probability of photo-generated carriers, and is beneficial to improving the catalytic activity of triptycene-modified graphite-phase carbon nitride.
Testing the performance of hydrogen production by photocatalytic hydrolysis:
respectively carrying out ultrasonic treatment on 0.1g of samples prepared in examples 1-3 and comparative example 1, 10mL of triethanolamine aqueous solution with the mass concentration of 10%, 1mL of chloroplatinic acid aqueous solution with the mass concentration of 1mg/mL and 89mL of deionized water for 5min under the condition that the power is 100W to obtain reaction solution;
the reaction solution is connected with a photocatalytic water splitting hydrogen production system (CEL-SPH 2N type photocatalytic water splitting hydrogen production system produced by Miao national treasury of Beijing), a circulating condensing device of the reaction system is opened to enable the temperature of the system to be stabilized at 6 ℃, nitrogen with the purity of 99.999 percent is introduced into the reaction solution for 1h at the flow rate of 20mL/min, a sealed reactor is used for vacuumizing the reaction system to enable the vacuum degree to reach-0.1 MPa, a CEL-HXUV300 type xenon lamp produced by Miao national treasury of Beijing is used as a light source, a high-pass filter is used for filtering light with the wavelength of less than 420nm, and photocatalytic water splitting hydrogen production reaction is carried out under magnetic stirring. The concentration of the prepared hydrogen gas was automatically sampled and analyzed every 1 hour by an on-line gas chromatograph model 2014c manufactured by shimadzu corporation, japan. The results are shown in Table 1.
TABLE 1 hydrogen production rate for photocatalytic decomposition of water to produce hydrogen using samples prepared in examples 1 to 3 and comparative example 1
A point line graph of the hydrogen production rate of hydrogen produced by photocatalytic hydrolysis using the samples prepared in examples 1 to 3 and comparative example 1 is plotted according to table 1, as shown in fig. 5 (a).
And (3) carrying out photocatalytic decomposition on the triptycene modified graphite-phase carbon nitride prepared in the embodiment 2 circularly according to the scheme to prepare hydrogen. The time for each reaction was 5 hours, and the cycle was performed 3 times, and the hydrogen production rate was measured at intervals of 1 hour, and the results are shown in Table 2.
TABLE 2 hydrogen production rate for photocatalytic decomposition of water to produce hydrogen using the sample prepared in example 2
A point line graph of the hydrogen production rate of hydrogen production by photocatalytic hydrolysis using the triptycene-modified graphite-phase carbon nitride prepared in example 2 cyclically is drawn according to table 2, and is shown in fig. 5 (b).
As can be seen from table 1 and fig. 5(a), the photocatalytic hydrogen production activity of the triptycene-modified graphite-phase carbon nitride provided by the invention is significantly improved compared with that of graphite-phase carbon nitride, wherein the activity of the TCN-1 sample prepared in example 2 is the best, and the hydrogen production rate reaches 0.81mmol · h-1·g-1Is pure g-C3N47.8 times of the total weight of the powder.
As can be seen from table 2 and fig. 5(b), the triptycene-modified graphite-phase carbon nitride provided by the invention has stable hydrogen production activity, and the triptycene-modified graphite-phase carbon nitride does not have obvious inactivation in a 15-hour cycle test.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A triptycene modified graphite phase carbon nitride comprises graphite phase carbon nitride and chemically doped triptycene.
2. The triptycene-modified graphite-phase carbon nitride according to claim 1, wherein the triptycene is doped in an amount of 0.01-5 wt.%.
3. The triptycene-modified graphite-phase carbon nitride of claim 1, wherein the graphite-phase carbon nitride has a basic structural unit of a heptazine ring.
4. The preparation method of the triptycene modified graphite-phase carbon nitride as claimed in any one of claims 1 to 3, comprising the following steps:
mixing polyamino triptycene and cyanamide to perform a polycondensation reaction to obtain triptycene modified graphite-phase carbon nitride; the polyaminotriptycene contains more than three amino groups.
5. The method according to claim 4, wherein the temperature of the polycondensation reaction is 450 to 550 ℃ and the holding time of the polycondensation reaction is 3.8 to 4.2 hours.
6. The method according to claim 4 or 5, wherein the polycondensation is carried out under a protective atmosphere comprising argon at a flow rate of 4.8 to 5.2 mL/min.
7. The preparation method according to claim 4, wherein the mass ratio of the polyaminotriptycene to the cyanamide is 0.1-50: 1000.
8. The method according to claim 4 or 7, wherein the polyaminotriptycene comprises 2,6, 14-triaminotriptycene, 2,7, 14-triaminotriptycene, 1,7, 13-triaminotriptycene, 2,7, 13-triaminotriptycene, or 2,3,6,7,14, 15-hexaaminotrtriptycene.
9. The method according to claim 4, wherein the cyanamide comprises a cyanamide, a dicyandiamide, or a melamine.
10. Use of the triptycene-modified graphite-phase carbon nitride according to any one of claims 1 to 3 or the triptycene-modified graphite-phase carbon nitride prepared by the preparation method according to any one of claims 4 to 9 as a photocatalytic material.
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