CN107684928B - Contain graphite-phase C3N4The organic porous material of structure, its preparation and application - Google Patents
Contain graphite-phase C3N4The organic porous material of structure, its preparation and application Download PDFInfo
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- CN107684928B CN107684928B CN201710848156.9A CN201710848156A CN107684928B CN 107684928 B CN107684928 B CN 107684928B CN 201710848156 A CN201710848156 A CN 201710848156A CN 107684928 B CN107684928 B CN 107684928B
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- 239000011148 porous material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 239000002262 Schiff base Substances 0.000 claims abstract description 13
- 238000010276 construction Methods 0.000 claims abstract description 12
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 abstract description 24
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 23
- 229960001553 phloroglucinol Drugs 0.000 abstract description 20
- 239000001257 hydrogen Substances 0.000 abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 150000003254 radicals Chemical class 0.000 description 19
- -1 Aldehyde radical Chemical class 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 13
- 229940043267 rhodamine b Drugs 0.000 description 13
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 12
- 229940012189 methyl orange Drugs 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 6
- 238000006303 photolysis reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003419 tautomerization reaction Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- WQOWBWVMZPPPGX-UHFFFAOYSA-N 2,6-diaminoanthracene-9,10-dione Chemical compound NC1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 WQOWBWVMZPPPGX-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 5
- 230000015843 photosynthesis, light reaction Effects 0.000 description 5
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009411 base construction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000004867 thiadiazoles Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B01J35/39—
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/617—
-
- B01J35/618—
-
- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- 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
The invention belongs to new material preparation and photocatalysis technology fields, and in particular to one kind contains graphite-phase C3N4The organic porous material of structure, preparation method and its photocatalysis field application.By with 1,3,5- tri- aldehyde radical phloroglucin (Tp) for aldehyde radical construction unit, one kind being prepared for amino construction unit generation schiff base reaction with six ring (melem) of-three-three nitrogen of triamido and contains graphite-phase C3N4Structure has high-specific surface area and the regulatable organic porous material of band structure, compared to graphite-phase C3N4, specific surface area improves a lot；And band structure can reach controllable by the adjusting of monomer；The material has very wide visible absorption range, has apparent Photocatalytic activity to organic pollutants, simultaneously can be used for that water hydrogen manufacturing is catalytically decomposed under visible light；This method mild condition, resulting materials performance are stablized, and large-scale production and application are suitble to.
Description
Technical field
The invention belongs to new material preparation and photocatalysis technology fields, and in particular to one kind contains graphite-phase C3N4Structure
Organic porous material preparation and its photocatalysis field application.
Background technique
It how to be that people make great efforts to solve the problems, such as always by the chemical energy that is converted into of solar energy highly effective abundant.Since discovery
Titanium dioxide water decomposition can be generated hydrogen in the case where absorbing ultraviolet light and oxygen, photochemical catalyst just cause people's
Extensive concern.At present for inorganic material, there is d0Or d10The oxide of the transition metal of electronic structure, nitride and vulcanization
Object research is the most extensive.But since titanium dioxide can only absorb ultraviolet light, and transition metal is expensive, therefore for sunlight
In visible light but can not efficiently utilize always.
Confirm within 2009 that carbonitride can be used to photolysis water hydrogen, subsequent graphite-phase as the catalyst of visible light for the first time
Carbonitride C3N4As the most representational organic polymer for being used as photochemical catalyst and it is widely studied.Graphite-phase
C3N4It is the two-dimensional layer material connected using three nitrogen, six ring as skeleton, can be absorbed by its powerful conjugated system visible
Light, and played the role of by transmitting of the electronics in system light-catalysed.But graphite-phase C3N4Specific surface area it is low, and energy band knot
Structure is fixed, and has certain limitation to the absorption of visible region, these factors directly affect graphite-phase C3N4Utilization to visible light
Efficiency.
Summary of the invention
For the above defects or improvement requirements of the existing technology, the present invention provides one kind to contain graphite-phase C3N4Knot
Organic porous material, preparation method and the application of structure, its object is to by being with 1,3,5- tri- aldehyde radical phloroglucin (Tp)
Aldehyde radical construction unit can also contain binary or polynary with six ring (melem) of-three-three nitrogen of triamido for amino construction unit simultaneously
Aromatic rings, heterocycle or the condensed ring of amino, generation schiff base reaction are prepared one kind and contain graphite-phase C3N4Having for structure has height
Specific surface area and the controllable organic porous material of band structure, thus solve the graphite-phase C of the prior art3N4Specific surface area it is low and
The single technical problem of band structure.
To achieve the above object, according to one aspect of the present invention, it provides one kind and contains graphite-phase C3N4Structure it is organic
Porous material has the general structure as shown in formula (one):
Wherein, R1To R6It is each independently the group containing aromatic rings, heterocycle or condensed ring.
Preferably, the R1To R6Formula (two) is each independently one of to formula (six) group:
Preferably, the specific surface area of the organic porous material is 50~1500m2/ g, the range of forbidden bandwidth is 1.25
~2.80eV.
Other side according to the invention provides the preparation method of organic porous material described in one kind, with 1,3,
Tri- aldehyde radical phloroglucin (Tp) of 5- is aldehyde radical construction unit, with six ring (melem) of-three-three nitrogen of triamido for amino construction unit,
Organic solvent is added, separating-purifying obtains after schiff base reaction occurs.
Preferably, the ratio of the aldehyde radical and amino is 2:0.8~2.2.
Preferably, the reaction temperature of the reaction is 80~150 DEG C；Reaction time is 12~48h.
Preferably, the amino construction unit further includes one or more binary or polynary amino-compound.
Preferably, the binary or polynary amino-compound are aromatic rings, heterocycle or the annelation of binary or polynary amino
Close object.
Preferably, the binary or polynary amino aromatic compound are three (4- aminophenyl) amine.
Preferably, the binary or polynary amino-heterocyclic compounds are 4,7- bis- (4- aminophenyls) -2,1,3- benzo thiophene
Diazole or 2,4,6- tri- (4- aminophenyl) -1,3,5- triazine.
Preferably, the binary or polynary amino fused ring compound are 2,6- diamino-anthraquinone.
Preferably, the organic solvent is dioxane, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene and N, N- diformazan
Base formamide (DMF) is one or more.
Preferably, the organic solvent is DMSO.
Preferably, the separating-purifying step include: obtained by methanol or tetrahydrofuran Soxhlet extraction after reaction it is described
Organic porous material.
Other side according to the invention provides the application of organic porous material described in one kind, is used for visible light
Catalytic field.
Preferably, the organic porous material is applied to photolysis water hydrogen or applied to organic dirt in photocatalytic degradation water
Contaminate object.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) the present invention provides one kind to contain graphite-phase C3N4The organic porous material of structure, compared to graphite-phase C3N4,
Specific surface area improves a lot；And band structure (forbidden bandwidth) can be achieved the purpose that by the adjustment of monomer it is controllable, can
Be prepared band structure it is low containing graphite-phase C3N4Structure organic porous material increases the absorption in visible region.
(2) the present invention provides one kind to contain graphite-phase C3N4The preparation method of the organic porous material of structure, with 1,3,5-
Three aldehyde radical phloroglucins (Tp) and six ring of-three-three nitrogen of triamido can also add one or more binary or more as monomer
Schiff base reaction occurs after first amino-compound mixing, is obtained after methanol purification containing graphite-phase C3N4Structure it is organic more
Porous materials.This method reaction condition is mild, simple process, at low cost, is suitble to large-scale production.
(3) present invention contains graphite-phase C for what is be prepared3N4The organic porous material of structure is applied to photocatalysis and leads
Domain, can the organic pollutants such as fast degradation rhodamine B, and photocatalytic water hydrogen generation efficiency with higher, before having good application
Scape.
Detailed description of the invention
Fig. 1 is the Fourier transform infrared spectrum of the preparation-obtained organic porous material of embodiment 1；
Fig. 2 is the C of the preparation-obtained organic porous material of embodiment 1 and graphite-phase3N4Ultraviolet-ray visible absorbing light
Spectrogram；
Fig. 3 is the preparation-obtained organic porous material of embodiment 1 N at 77K2Absorption and desorption curve；
Fig. 4 is the graph of pore diameter distribution of the preparation-obtained organic porous material of embodiment 1；
Fig. 5, which is 1 gained organic porous material of embodiment, to be carried out the time during photolysis water hydrogen as photochemical catalyst and produces hydrogen
The relational graph of amount；
Fig. 6 be 1 gained organic porous material of embodiment as photochemical catalyst come rhodamine B when rhodamine B in water of degrading
The ultraviolet variation responded with the light degradation time；
Fig. 7 be 1 gained organic porous material of embodiment degrade as photochemical catalyst rhodamine B in water when residual concentration
It changes with time；
Fig. 8 be 1 gained organic porous material of embodiment as photochemical catalyst come in water of degrading when methyl orange methyl orange purple
The outer variation responded with the light degradation time；
Fig. 9 be 1 gained organic porous material of embodiment degrade as photochemical catalyst methyl orange in water when residual concentration
It changes with time；
Figure 10 is the Fourier transform infrared spectrum for the organic porous material that embodiment 2 is prepared；
Figure 11 is the Fourier transform infrared spectrum for the organic porous material that embodiment 3 is prepared；
Figure 12 is the Fourier transform infrared spectrum for the organic porous material that embodiment 4 is prepared；
Figure 13 is the Fourier transform infrared spectrum for the organic porous material that embodiment 5 is prepared；
Figure 14 is the Fourier transform infrared spectrum for the organic porous material that embodiment 6 is prepared.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides one kind to contain graphite-phase C3N4The organic porous material of structure has as shown in formula (one)
General structure:
Wherein, R1To R6It is each independently the group containing aromatic rings, heterocycle or condensed ring.Such as R1To R6It can be respective
Formula (two) independently is one of to formula (six) group:
Wherein, formula (two) is 2,4,6- tri- (4- phenyl) -1,3,5-triazines bases, and formula (three) is three (4- phenyl) amidos, formula
It (four) is 2,6- anthraquinonyl, formula (five) is bis- (the 4- phenyl) -2 of 4,7-, and 1,3- diazosulfide base, formula (six) is three nitrogen, six ring
Base.The specific surface area of the organic porous material is 50~1500m2/ g, the range of forbidden bandwidth is in 1.25~2.80eV.
The preparation method of above-mentioned organic porous material is the following steps are included: with tri- aldehyde radical phloroglucin (Tp) of 1,3,5- for aldehyde
Organic solvent is added with six ring (melem) of-three-three nitrogen of triamido for amino construction unit in base construction unit, and schiff bases occurs
It purifies to obtain by methanol or tetrahydrofuran Soxhlet after reaction.The molar ratio of aldehyde radical and amino is 2:0.8~2.2；Aldehyde radical with
The ratio of amino is too high or too low to lead to that complete hole cannot be formed, and reaction temperature is 80~150 DEG C；Reaction time be 12~
48h。
Wherein amino construction unit can also include one or more binary or polynary amino-compound.The binary is polynary
Amino-compound is aromatic rings, heterocycle or the fused ring compound of binary or polynary amino.The binary or polynary amino fragrance
Compound is preferably three (4- aminophenyl) amine, and the binary or polynary amino-heterocyclic compounds are preferably bis- (the 4- amino of 4,7-
Phenyl) -2,1,3- diazosulfide or 2,4,6- tri- (4- aminophenyl) -1,3,5-triazines, the binary or polynary amino are thick
Cycle compound be preferably 2,6- diamino-anthraquinone organic solvent be dioxane, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene,
One of n,N-Dimethylformamide (DMF) is a variety of, preferably DMSO.
Present invention selection contains C3N4The tri- aldehyde radical phloroglucin of melem and 1,3,5- of nuclear structure constructs list for core
Member, by adding different amino structure units, by the screening and optimization of reaction time, reaction temperature and reaction dissolvent, most
It obtains containing graphite-phase C with such eventually3N4The organic porous material of structure.In the method, can by adjusting monomer type and
Quantity controls the specific surface area and band structure of material, purposive can prepare the material.The present invention provides a kind of contain
There is graphite-phase C3N4The preparation method of the organic porous material of structure, reaction condition is mild, simple process, at low cost, is suitble to big rule
Mould production.
The present invention is prepared containing graphite-phase C3N4The organic porous material of structure, compared to graphite-phase C3N4, specific surface area
It improves a lot；And band structure can be achieved the purpose that controllable by the adjustment of monomer, and it is low band structure can be prepared
Contain graphite-phase C3N4Structure organic porous material increases the absorption in visible region.It can be applied to visible light catalyst,
Such as applied to photolysis water hydrogen or applied to the organic pollutant in degradation water.The present invention contains graphite-phase for what is prepared
C3N4The organic porous material of structure is applied to photocatalysis field, can the organic pollutants such as fast degradation rhodamine B, methyl orange,
And have higher photocatalytic water hydrogen generation efficiency, it has a good application prospect.
The following are embodiments:
Embodiment 1
By six ring (melem) (0.0436g, 0.2mmol) of-three-three nitrogen of triamido, 1,3,5- tri- aldehyde radical phloroglucin
(0.084g, 0.4mmol) and 2,4,6- tri- (4- aminophenyl) -1,3,5-triazines (0.0709g, 0.2mmol) are added to 5mL
In the solvent of DMSO.In 150 DEG C of reaction 12h.6h is first reacted at 80 DEG C, is then warming up to 120 DEG C of reaction 12h.Reaction is completed
Afterwards, it filters, and is washed with methanol and remove remaining oligomer etc..Solid is collected, after vacuum drying, obtains black powder 0.173g,
Yield is 98%.
Attached drawing 1 is the Fourier transform infrared spectrum of the preparation-obtained organic porous material of embodiment 1, the material structure
Formula such as (one) is shown, wherein R1To R6Respectively stand alone as 2,4,6- tri- shown in three nitrogen, six ring group or formula (two) shown in formula (six)
(4- phenyl)-cyanuro 1,3,5.It, which is constructed in primitive melem, is located at 3344cm-1And 3097cm-1The amino characteristic peak at place
It disappears, 2,4,6- tri- (4- aminophenyl) -1,3,5-triazines are located at 3462cm-1、3322cm-1And 3211cm-1The amino at place is special
Sign peak also disappears；It is located at 2894cm in tri- aldehyde radical phloroglucin of 1,3,5--1The C-H bond characteristic peak at place disappears and is located at
1645cm-1The carbonyl characteristic peak at place disappears, and illustrates amino, 2,4,6- tri- (4- aminophenyl) -1,3,5-triazines in melem
In tri- aldehyde radical phloroglucin of amino and 1,3,5- in aldehyde radical schiff base reaction has occurred.Meanwhile solvent hot exists
1280cm-1There is carbonnitrogen bond characteristic peak and in 1578cm in place-1There is carbon-carbon double bond characteristic peak in place, illustrates that enol-has occurred in product
Keto-acid tautomerism contains graphite-phase C3N4The organic porous material of structure is successfully prepared.
Attached drawing 2 is the C of the preparation-obtained organic porous material of embodiment 1 and graphite-phase3N4Ultraviolet-ray visible absorbing
Spectrogram.The C of graphite-phase3N4Forbidden bandwidth be 2.58eV, compared to the C of graphite-phase3N4, which can absorb light area
Range increases, and band structure is reduced to 1.43eV, has higher absorption efficiency to visible light.
Attached drawing 3 is the preparation-obtained organic porous material of embodiment 1 N at 77K2Absorption and desorption curve, attached drawing 4
It is the graph of pore diameter distribution of the preparation-obtained polymer of embodiment 1.The result shows that the polymer specific surface area is 552m2/ g belongs to
Microporous polymer.And graphite-phase C3N4Specific surface area be only 46m2/g.The result shows that the Porous-Organic material of preparation method synthesis
Expect specific surface area with higher.
Attached drawing 5 be 1 gained organic porous material of embodiment as photochemical catalyst come during photolysis water hydrogen the time with
The relational graph of hydrogen output.Polymer volume is 50mg, and the triethanolamine of water 90ml, 10ml are sacrifice agent, by restoring chlorine platinum
The mode of acid loads the co-catalyst of 3wt%Pt, and photocatalytic water test is carried out at visible wavelength (λ >=420nm).In terms of result
The polymer has good photodissociation aquatic products hydrogen activity out.
Attached drawing 6 be 1 gained organic porous material of embodiment as photochemical catalyst come rhodamine B when rhodamine B in water of degrading
Ultraviolet response with the light degradation time variation, Fig. 6 medium wavelength range 500 to 600 nanometers of corresponding ultraviolet response curves from
Top-down light degradation time legend shown in arrow is corresponding in turn under above；Fig. 7 is 1 gained organic porous material of embodiment
Degrade as photochemical catalyst rhodamine B in water when residual concentration change with time.Find out from Fig. 6 and Fig. 7, with illumination
The ultraviolet absorption value of the increase of time, rhodamine B reduces, and rhodamine B concentration is reducing in water, has degraded in 25min rhodamine B
Entirely.The aqueous solution 80ml of the rhodamine B of polymer volume 4mg, 10ppm, first dark treatment 1h, then visible wavelength (λ >=
It is tested under 420nm).Find out that the polymer has good activity to degradation organic pollutants rhodamine B from result.
Fig. 8 be 1 gained organic porous material of embodiment as photochemical catalyst come in water of degrading when methyl orange methyl orange purple
Outer response with the light degradation time variation, Fig. 8 medium wavelength range 400 to 500 nanometers of corresponding ultraviolet response curves from upper and
Under be corresponding in turn to top-down light degradation time legend shown in arrow；Fig. 9 is 1 gained organic porous material conduct of embodiment
Photochemical catalyst changes with time come the residual concentration in water of degrading when methyl orange.Find out from Fig. 8 and Fig. 9, with light application time
Increase, the ultraviolet absorption value of methyl orange reduces, and methyl orange concentration is reducing in water, in 63min methyl orange degradation 93% and becomes
In balance.The aqueous solution 80ml of the methyl orange of polymer volume 4mg, 10ppm, first dark treatment 1h, then in visible wavelength
It is tested under (λ >=420nm).Find out that the polymer has good activity to degradation methyl orange from result.
Embodiment 2
By six ring (melem) of 1,3,5- tri- aldehyde radical phloroglucin (0.042g, 0.2mmol) and-three-three nitrogen of triamido
(0.0436g, 0.2mmol) is added in the solvent of 5mL dimethylformamide.In 80 DEG C of reaction 12h, after the reaction was completed, take out
Filter, and washed with methanol and remove remaining oligomer etc..Solid is collected, after vacuum drying, obtains black powder 0.060g, yield is
40%.
Attached drawing 10 is the Fourier transform infrared spectrum for the organic porous material that embodiment 2 is prepared.The material structure
Formula such as (one) is shown, wherein R1To R6It is three nitrogen, six ring group shown in formula (six).As seen from the figure, it constructs in primitive melem
Be located at 3344cm-1And 3097cm-1The amino characteristic peak at place disappears；It is located at 2894cm in tri- aldehyde radical phloroglucin of 1,3,5--1
The C-H bond characteristic peak at place disappears and positioned at 1645cm-1The carbonyl characteristic peak at place disappears, and illustrates the amino in melem and 1,
Schiff base reaction has occurred in aldehyde radical in tri- aldehyde radical phloroglucin of 3,5-.Meanwhile solvent hot is in 1211cm-1There is carbon nitrogen in place
Key characteristic peak and in 1615cm-1There is carbon-carbon double bond characteristic peak in place, illustrates that enol-keto formula tautomerism has occurred in product, contains
Graphite-phase C3N4The organic porous material of structure is successfully prepared.By the ratio table for the organic porous polymer that embodiment 2 is prepared
Area is 56m2/ g, forbidden bandwidth 1.92eV.
Embodiment 3
By six ring (melem) (0.0436g, 0.2mmol) of-three-three nitrogen of triamido, 1,3,5- tri- aldehyde radical phloroglucin
(0.084g, 0.4mmol) and 2,6- diamino-anthraquinone (0.0715g, 0.3mmol) are added in the solvent of 5mL dioxane.?
100 DEG C of reaction 36h.After the reaction was completed, it filters, and is washed with methanol and remove remaining oligomer etc..Collect solid, vacuum drying
Afterwards, brown ceramic powder 0.170g, yield 95% are obtained.
Attached drawing 11 is the Fourier transform infrared spectrum for the organic porous material that embodiment 3 is prepared.The material structure
Formula such as (one) is shown, wherein R1To R6It is each independently three nitrogen six shown in 2,6- anthraquinonyl shown in formula (four) or formula (six)
Ring group.As seen from Figure 11, it constructs in primitive melem and is located at 3344cm-1And 3097cm-1The amino characteristic peak at place disappears,
2,6- diamino-anthraquinone is located at 3423cm-1、3333cm-1And 3210cm-1The amino characteristic peak at place also disappears；Tri- aldehyde of 1,3,5-
It is located at 2894cm in base phloroglucin-1The C-H bond characteristic peak at place disappears and positioned at 1645cm-1The carbonyl characteristic peak at place disappears
It loses, illustrates the amino in melem, the amino in 2,6- diamino-anthraquinone and 1, the aldehyde radical hair in 3,5- tri- aldehyde radical phloroglucins
Schiff base reaction is given birth to.Meanwhile solvent hot is in 1255cm-1There is carbonnitrogen bond characteristic peak and in 1571cm in place-1There is carbon in place
Carbon double bond characteristic peak illustrates that enol-keto formula tautomerism has occurred in product, contains graphite-phase C3N4The organic porous material of structure
It successfully prepares.The specific surface area for the organic porous polymer being prepared by embodiment 3 is 189m2/ g, forbidden bandwidth are
2.17eV。
Embodiment 4
By six ring (melem) (0.0436g, 0.2mmol) of-three-three nitrogen of triamido, 1,3,5- tri- aldehyde radical phloroglucin
(0.084g, 0.4mmol) and three (4- aminophenyl) amine (0.058g, 0.2mmol) are added in the solvent of 5mLDMSO.In N2
Protection under, 120 DEG C reaction for 24 hours.After the reaction was completed, it filters, and removes remaining oligomer with the purification of tetrahydrofuran Soxhlet
Deng.Solid is collected, after vacuum drying, obtains brown-black powder 0.151g, yield 89%.
Attached drawing 12 is the Fourier transform infrared spectrum for the organic porous material that embodiment 4 is prepared.The material structure
Formula such as (one) is shown, wherein R1To R6It is each independently three shown in formula (three) three shown in (4- phenyl) amido or formula (six)
Six ring group of nitrogen.It, which is constructed in primitive melem, is located at 3344cm-1And 3097cm-1The amino characteristic peak at place disappears, three (4- amino
Phenyl) amine be located at 3409cm-1、3336cm-1And 3211cm-1The amino characteristic peak at place also disappears；Tri- aldehyde radical isophthalic three of 1,3,5-
It is located at 2894cm in phenol-1The C-H bond characteristic peak at place disappears and positioned at 1645cm-1The carbonyl characteristic peak at place disappears, explanation
Amino in melem, aldehyde radical in the tri- aldehyde radical phloroglucin of amino and 1,3,5- in three (4- aminophenyl) amine have occurred
Schiff base reaction.Meanwhile product is in 1280cm-1There is carbonnitrogen bond characteristic peak and in 1610cm in place-1There is carbon-carbon double bond feature in place
Peak illustrates that enol-keto formula tautomerism has occurred in product, contains graphite-phase C3N4The organic porous material of structure is successfully prepared.
The specific surface area for the organic porous polymer being prepared by embodiment 4 is 760m2/ g, forbidden bandwidth 1.45eV.
Embodiment 5
By six ring (melem) of 1,3,5- tri- aldehyde radical phloroglucin (0.042g, 0.2mmol) and-three-three nitrogen of triamido
(0.0436g, 0.2mmol) is added in the solvent of 5mL DMSO.In 80 DEG C of reaction 48h, after the reaction was completed, filter, and with four
The washing of hydrogen furans removes remaining oligomer etc..Solid is collected, after vacuum drying, obtains black powder 0.127g, yield 85%.
Attached drawing 13 is the Fourier transform infrared spectrum for the organic porous material that embodiment 5 is prepared.The material structure
Formula such as (one) is shown, wherein R1To R6It is three nitrogen, six ring group shown in formula (six).Find out from result, constructs in primitive melem
Be located at 3344cm-1And 3097cm-1The amino characteristic peak at place disappears；It is located at 2894cm in tri- aldehyde radical phloroglucin of 1,3,5--1
The C-H bond characteristic peak at place disappears and positioned at 1645cm-1The carbonyl characteristic peak at place disappears, and illustrates the amino in melem and 1,
Schiff base reaction has occurred in aldehyde radical in tri- aldehyde radical phloroglucin of 3,5-.Meanwhile solvent hot is in 1211cm-1There is carbon nitrogen in place
Key characteristic peak and in 1615cm-1There is carbon-carbon double bond characteristic peak in place, illustrates that enol-keto formula tautomerism has occurred in product, contains
Graphite-phase C3N4The organic porous material of structure is successfully prepared.By the ratio table for the organic porous polymer that embodiment 5 is prepared
Area is 970m2/ g, forbidden bandwidth 2.27eV.
Embodiment 6
By six ring (melem) (0.0436g, 0.2mmol) of-three-three nitrogen of triamido, 1,3,5- tri- aldehyde radical phloroglucin
(0.084g, 0.4mmol) and 4, bis- (the 4- aminophenyls) -2 of 7-, 1,3- diazosulfide (0.095g, 0.3mmol) are added to
In the solvent of 5mL DMSO.6h is first reacted at 80 DEG C, is then warming up to 120 DEG C of reaction 12h.After the reaction was completed, it filters, is used in combination
The purification of methanol Soxhlet removes remaining oligomer etc..Solid is collected, after vacuum drying, obtains brown-red powder 0.189g, yield is
94%.
Attached drawing 14 is the Fourier transform infrared spectrum for the organic porous material that embodiment 6 is prepared.The material structure
Formula such as (one) is shown, wherein R1To R6It is each independently bis- (4- the phenyl) -2,1,3- diazosulfides of 4,7- shown in formula (five)
Three nitrogen, six ring group shown in base or formula (six).Find out from result, constructs in primitive melem and be located at 3344cm-1And 3097cm-1The amino characteristic peak at place disappears, 4,7- bis- (4- aminophenyls) -2, and 1,3- diazosulfide is located at 3366cm-1Amino it is special
Sign peak also disappears；It is located at 2894cm in tri- aldehyde radical phloroglucin of 1,3,5--1The C-H bond characteristic peak at place disappears and is located at
1645c m-1The carbonyl characteristic peak at place disappears, and illustrates bis- (the 4- aminophenyls) -2 of amino, 4, the 7- in melem, 1,3- benzo
Schiff base reaction has occurred in the aldehyde radical in tri- aldehyde radical phloroglucin of amino and 1,3,5- in thiadiazoles.Meanwhile solvent hot
In 1294cm-1There is carbonnitrogen bond characteristic peak and in 1589cm in place-1There is carbon-carbon double bond characteristic peak in place, illustrates that alkene has occurred in product
Alcohol -one formula tautomerism contains graphite-phase C3N4The organic porous material of structure is successfully prepared.It is prepared by embodiment 6
The specific surface area of organic porous polymer is 1207m2/ g, forbidden bandwidth 2.12eV.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. one kind contains graphite-phase C3N4The organic porous material of structure, which is characterized in that it includes the structures as shown in formula (one)
General formula:
Wherein, R1To R6It is each independently the group containing aromatic rings, heterocycle or condensed ring.
2. organic porous material as described in claim 1, which is characterized in that the R1To R6It is each independently formula (two) extremely
One of formula (six) group:
3. organic porous material as described in claim 1, which is characterized in that the specific surface area of the organic porous material is 50
~1500m2/ g, the range of forbidden bandwidth is in 1.25~2.80eV.
4. the preparation method of organic porous material as described in claim 1, which is characterized in that with 1,3,5- tri- aldehyde radical isophthalic three
Phenol is aldehyde radical construction unit, and using six ring of-three-three nitrogen of triamido as amino construction unit, organic solvent is added, it is anti-that schiff bases occurs
Separating-purifying obtains after answering.
5. preparation method as claimed in claim 4, which is characterized in that the ratio of the aldehyde radical and amino is 2:0.8~2.2.
6. preparation method as claimed in claim 4, which is characterized in that the reaction temperature of the schiff base reaction is 80~150
℃；Reaction time is 12~48h.
7. preparation method as claimed in claim 4, which is characterized in that the amino construction unit further includes one or more two
First or polynary amino-compound.
8. preparation method as claimed in claim 7, which is characterized in that the binary or polynary amino-compound are binary or more
Aromatic rings, heterocycle or the fused ring compound of first amino.
9. preparation method as claimed in claim 4, which is characterized in that the organic solvent be dioxane, dimethyl sulfoxide,
Toluene, dimethylbenzene and N,N-dimethylformamide are one or more.
10. the application of the organic porous material as described in claims 1 to 3 any one, which is characterized in that be applied to visible light
Catalytic field.
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