CN105728053A - Metal phthalocyanine/carbon-based photocatalyst and preparation method thereof - Google Patents
Metal phthalocyanine/carbon-based photocatalyst and preparation method thereof Download PDFInfo
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- CN105728053A CN105728053A CN201610058969.3A CN201610058969A CN105728053A CN 105728053 A CN105728053 A CN 105728053A CN 201610058969 A CN201610058969 A CN 201610058969A CN 105728053 A CN105728053 A CN 105728053A
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- titanium carbide
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 18
- 239000002184 metal Substances 0.000 title claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 22
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- -1 bromobenzene epoxide Chemical class 0.000 claims description 17
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 230000005540 biological transmission Effects 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical class OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000004298 light response Effects 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 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 15
- 229940043267 rhodamine b Drugs 0.000 description 15
- 229910009819 Ti3C2 Inorganic materials 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002118 epoxides Chemical class 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 5
- 229920006391 phthalonitrile polymer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000000640 hydroxylating effect Effects 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000006416 CBr Chemical group BrC* 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- IYZPEGVSBUNMBE-UHFFFAOYSA-N 2-[[5-[1-[3-[[carboxylatomethyl(carboxymethyl)azaniumyl]methyl]-4-hydroxy-5-methylphenyl]-3-oxo-2-benzofuran-1-yl]-2-hydroxy-3-methylphenyl]methyl-(carboxymethyl)azaniumyl]acetate Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3C(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 IYZPEGVSBUNMBE-UHFFFAOYSA-N 0.000 description 1
- XTWFKMOELYYKGC-UHFFFAOYSA-N 3-phenoxybenzene-1,2-dicarbonitrile Chemical compound N#CC1=CC=CC(OC=2C=CC=CC=2)=C1C#N XTWFKMOELYYKGC-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ORTRRYJFZBWTOH-UHFFFAOYSA-N [N+](=O)([O-])C=1C=C(C(C#N)=CC1)C#N.[N+](=O)([O-])C=1C=C(C(C#N)=CC1)C#N Chemical compound [N+](=O)([O-])C=1C=C(C(C#N)=CC1)C#N.[N+](=O)([O-])C=1C=C(C(C#N)=CC1)C#N ORTRRYJFZBWTOH-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000002023 wood Substances 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
Classifications
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
-
- 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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a metal phthalocyanine/carbon-based photocatalyst and a preparation method thereof. The synthesis of the catalyst adopts 4-nitrophthalonitrile as a raw material, and a visible light response type phthalocyanine/titanium carbide composite material is synthesized through reactions including nucleophilic substitution, a DBU liquid-phase catalysis method and the like. The material is a visible light photocatalyst which takes a phthalocyanine substance as an electron donor, takes titanium carbide as a novel donor-acceptor of the electron donor, and is organically and inorganically doped; and the titanium carbide has excellent thermal stability and good conductivity, so that the service life of electrons in a transferring process is effectively prolonged, the catalytic performance of the material is improved, and the photocatalyst has a relatively high application value in the field of catalysis.
Description
Technical field
The present invention relates to a kind of photocatalyst and preparation method thereof.
Background technology
Along with the progress of society, people gradually recognize the importance of water resource.In order to solve office instantly
The difficulty that portion's regional water is poor, finding environmentally friendly sewage degradable material the most progressively becomes and grinds now
The popular domain studied carefully.
In degraded system catalyst serve vital effect, especially metal phthalocyanine due to its highlight
Electron transfer properties frequently as electron donor material active occur in the field such as quasiconductor, photocatalyst.
The electric conductivity that titanium carbide is good substantially increases the life-span of electronics, the beneficially high efficiency of transmission of electronics in transmission way.
The metal phthalocyanine of reacted synthesis/carbon back photocatalyst combines both characteristics, be a class novel to-receptor has
The visible light catalyst of machine inorganic doping, has higher using value in this field.But, in photocatalysis
Material Field, owing to preparing the cost of material of photocatalyst costly, is difficult to obtain, and the light synthesized is urged
Agent stability is the highest, and all factors cause the actual utility ratio of photocatalyst the highest.
Summary of the invention
It is an object of the invention to provide a kind of photocatalysis efficiency height, stable performance and metal phthalein with low cost
Cyanines/carbon back composite visible light catalytic material and preparation method thereof.
The metal phthalocyanine of the present invention/carbon back composite visible light catalyst uses 4-nitrophthalonitrile to be raw material,
Visible-light response type phthalocyanine/carbon back composite wood is synthesized out by nucleophilic displacement of fluorine, DBU liquid catalytic etc.
Material.DBU is the organic catalyst that a kind of alkalescence is stronger, under the catalytic action of DBU, is heated to reflux adjacent benzene two
Nitriles substance can synthesize metal phthalocyanine with the primary alconol solution of slaine, and the metal phthalocyanine of end group bromination can be with table
The hydroxylated titanium carbide in face combines, and is formed using phthalocyanine material as electron donor, and titanium carbide is electron acceptor
Novel give-receptor organic-inorganic doping visible light catalyst, this composite catalyst is the powder of black, tool
Having preferable dispersibility, the electric conductivity that titanium carbide is good is effectively increased the life-span of electronics in transmission way.
1, the metal phthalocyanine of the present invention/carbon back photocatalyst is composite visible light catalyst, has a below general formula I:
This photocatalyst is by end position Br ion and titanium carbide OH-1Ions binding, produces the transmission of an electronics
Passage, the electric conductivity that titanium carbide is good substantially increases the life-span of electronics in transmission way.
2, the preparation method of above-mentioned metal phthalocyanine/carbon back photocatalyst is as follows:
(1) taking 2～6g 4-nitrophthalonitriles, 2～6g p bromophenols are dissolved in 20～100mL and are dried
In DMF (DMF), under argon shield, it is to slowly warm up to 80 DEG C of reactions, at temperature-rise period
In, weigh catalyst potassium carbonate powder 6～20g, in the 3h pass into solution in three times of interval, detected by a plate
Reaction process, is considered as reaction when raw material point disappears and terminates；Product is carried out sucking filtration, removes unreacted carbon
Filtrate being poured in 200ml distilled water after acid potassium, adding dilute hydrochloric acid regulation solution ph is to be stirred by magnetic force after 1
After mixing 1h, sucking filtration takes filter cake afterwards, then rinses with distilled water.Method finally by recrystallization improves product
Purity, is placed in 80 DEG C of vacuum drying ovens vacuum drying 24h by crystal.
(2) 1～3g 4-is weighed to bromobenzene epoxide phthalonitrile, 0.2～0.6g FeCl2Join three mouthfuls of round bottoms
In flask, first reaction unit is evacuated to 0.098MPa, then measures the n-amyl alcohol that 15ml is dried and join
In three neck round bottom flask, under argon shield, it is to slowly warm up to 135 DEG C.Temperature-rise period measures 1.5～5ml 1,8-
Diazabicylo 11 carbon-7-alkene (DBU) adds in flask.Reaction process is detected, to limp by TLC
Raw material point disappearance stopped reaction.After reaction terminates, be warming up to 160 DEG C to remove the n-amyl alcohol in flask, treat cold
But to room temperature, add 200～500ml methanol, after standing 48h, separate out out product.Sucking filtration takes filter cake again, and
Product is placed in 75 DEG C of dry 12h of vacuum in vacuum drying oven.
(3) weigh 300mg respectively bromobenzene epoxide FePC, 20mg titanium carbide, 300mg potassium carbonate are depended on
Secondary addition there-necked flask, measures the DMF that 10ml is dried, and is to slowly warm up to 80 DEG C under conditions of magnetic agitation,
Reaction 24h.After reaction terminates, take out flask and be cooled to room temperature, carry out sucking filtration.Filter cake is rinsed with dilute hydrochloric acid,
Remove the catalyst potassium carbonate of residual.Rinse with DMF again, remove unreacted to bromobenzene epoxide FePC.
Take filter cake to prepare bromobenzene epoxide FePC/titanium carbide composite after vacuum drying oven vacuum drying 24h.
The advantage of the compound synthesized by the present invention is:
1, in the present invention, the raw material used by compound of synthesis is easy to get, low price, and reaction yield is high, and institute
The compound of synthesis has goodish heat stability and chemical stability.
2, metal phthalocyanine has prominent electron transfer properties, and titanium carbide has the good electric conductivity can bigger raising
In the life-span of electronics in transmission way, the beneficially high efficiency of transmission of electronics, metal phthalocyanine/C-base composte material is urged at light
The application aspect of formed material has huge potentiality.
Accompanying drawing explanation
Fig. 1 is 4-nitrophthalonitrile and product 1 (4-is to bromobenzene epoxide phthalonitrile) in the embodiment of the present invention 1
Infared spectrum figure.
Fig. 2 is product 2 in the embodiment of the present invention 1 (β-to bromobenzene epoxide FePC) infared spectrum figure.
Fig. 3 is β in the embodiment of the present invention 1-to bromobenzene epoxide FePC and hydroxylating titanium carbide PBP-FePc ultraviolet
Visible absorbance figure spectrogram.
Fig. 4 is the red of end product in the embodiment of the present invention 1 (to bromobenzene epoxide FePC/titanium carbide composite)
Outer light figure spectrogram.
Fig. 5 is the thermogravimetric curve comparison diagram of OH-Ti3C2, PBP-FePc and PBP-FePc/OH-Ti3C2
Fig. 6 is RhB aqueous solution ultraviolet-ray visible absorbing figure spectrogram under different catalysis time
Fig. 7 is PBP-FePc/OH-Ti3C2 catalyst absorption-degradation curve figure to RhB dyestuff
Fig. 8 is PBP-FePc Yu PBP-FePc/OH-Ti3C2 catalytic performance comparison diagram
Detailed description of the invention
Embodiment is given below so that the present invention to be specifically described, it is necessary to it is pointed out here that be following enforcement
Example is served only for being further detailed the present invention, it is impossible to be interpreted as limiting the scope of the invention,
The person skilled in the art of this area the present invention is made according to the content of the invention described above some nonessential change
Enter and adjustment still falls within protection scope of the present invention.
Embodiment 1
(1) taking 2g 4-nitrophthalonitrile, 2g p bromophenol is dissolved in the N that 20mL is dried, N-dimethyl methyl
In amide (DMF), weigh 6g potassium carbonate powder and add in three times as catalyst, interval 3h, argon guarantor
Protect down and be to slowly warm up to 80 DEG C of reactions, some plate detection reaction process；Product is carried out sucking filtration, removes unreacted
Potassium carbonate, filtrate pours in 200ml distilled water, and adding dilute hydrochloric acid to pH is 1, after stirring 1 hour, takes out
Leaching filter cake, then rinse with distilled water.Last recrystallization improves product purity.Crystal is placed in vacuum drying
Case is vacuum dried 24 hours.By 4-nitrophthalonitrile and product 1 (4-is to bromobenzene epoxide phthalonitrile)
By its spectrogram of infrared spectroscopic determination.
As it is shown in figure 1, A, B are respectively 4-nitrophthalonitrile (4-Nitrophthalonitrile) and product 1
Infrared spectrum, A Yu B compares it can be seen that 3100cm in the general figure of A-1Place is phenyl ring skeleton=C-H
Bending vibration peak, 2240cm-1The sharp peak at place is the characteristic peak of-CN, 1538cm-1And 1348cm-1
The stronger sharp peak of peak shape at place is antisymmetric stretching vibration peak and the symmetrical stretching vibration peak of Ar-NO2 respectively,
869cm-1Place is the symmetrical stretching vibration peak of C-N.In the general figure of B, the characteristic absorption peak of-CN is 2230cm-1,
The absworption peak of Ar-NO2 disappears, 1480cm-1、1245cm-1Locating sharp-pointed absworption peak is ehter bond on phenyl ring
(Ar-O-R) asymmetrical stretching vibration peak, 520cm-1The characteristic absorption peak that absworption peak is C-Br key at place.
Therefore, analyzed by infared spectrum, can tentatively judge that p bromophenol has been coupled to 4-nitro O-phthalic
On the nitro of nitrile, obtain target product 1 for 4-to bromobenzene epoxide phthalonitrile (4-P-bromine phenoxy
phthalonitrile)。
(2) 1g 4-is weighed to bromobenzene epoxide phthalonitrile, 0.1591g FeCl2Join three mouthfuls of 100ml
In round-bottomed flask, reaction unit is evacuated to 0.098MPa, then measures the n-amyl alcohol that 15ml is dried and join
In three neck round bottom flask, under nitrogen protection, it is to slowly warm up to 135 DEG C.Temperature-rise period measures 1.5ml DBU
Add in flask.TLC detects reaction process, to walking board raw material point disappearance stopped reaction.After reaction terminates,
It is warming up to 160 DEG C and removes n-amyl alcohol, be cooled to room temperature, add proper amount of methanol, stand 2d and separate out out product.
Sucking filtration take 75 DEG C of filter cake vacuum be dried within 12 hours, obtain product 2.Equally product 2 is passed through infrared spectrometry
Measure its spectrogram.
It is illustrated in figure 2 the infrared spectrogram of product 2, it can be seen that 2911cm-1For on phenyl ring
C-H vibration absorption peak, 2230cm-1-CN the peak gone out disappears, it was demonstrated that intermediate product reaction is complete, 1500cm-1
For the eigen vibration absworption peak of phthalocyanine ring, 1200cm-1And 1000cm-1The strong absworption peak that place occurs is aryl oxide
Asymmetric and symmetrical stretching vibration, it was demonstrated that the existence of aryl oxide structure, 819cm-1The spike at place be ferrous iron from
The characteristic peak of the coordinate bond of son and phthalocyanine ring, 495cm-1Place is the characteristic absorption peak of C-Br key.By infrared
Atlas analysis, can tentatively judge to have prepared β-to bromobenzene epoxide FePC (PBP-FePc) this compound.
It is the purple of β-bromobenzene epoxide FePC (PBP-FePc) is dissolved in dichloromethane solution as shown in Figure 3
Outer visible absorbance collection of illustrative plates, it can be seen that the ultraviolet-visible absorption spectroscopy of PBP-FePc substantially has two stronger suctions
Take-up, the roomy absworption peak type B band of 360nm vicinity, the characteristic absorption band Q of 700nm vicinity phthalocyanine
Band.
(3) 300mg is weighed respectively to bromobenzene epoxide FePC, 20mg titanium carbide, 300mg potassium carbonate
It is sequentially added into there-necked flask, measures the DMF that 10ml is dried, magnetic agitation, be to slowly warm up to 80 DEG C, instead
Answer 24 hours.After having reacted, take out flask and be cooled to room temperature, carry out sucking filtration, rinse filter cake with dilute hydrochloric acid,
Remove catalyst potassium carbonate.Rinsing with DMF, removing may be unreacted to bromobenzene epoxide FePC again.Take
Filter cake is vacuum dried 24 hours in vacuum drying oven, obtains end product.And end product is passed through infrared light
Spectrometry obtains its spectrogram.
β-to bromobenzene epoxide FePC (PBP-FePc) and hydroxylating titanium carbide (OH-Ti3C2) compound after make
End product infared spectrum as shown in Figure 4, at 3500cm-1The neighbouring wider absworption peak occurred is carbon
Change [45] that chemical bond stretching vibration complicated in titanium causes, 2900cm-1Place is-C-H stretching vibration on phenyl ring
Absworption peak, 1650cm-1Place is phenyl ring skeleton asymmetrical stretching vibration absworption peak, 1460cm-1Place is Ti-C
Vibration absorption peak, 1227cm-1Asymmetrical stretching vibration absworption peak for-C-O-C-, it was demonstrated that aryl oxide structure
Existence.From infared spectrum, we tentatively judge PBP-FePc and hydroxylating titanium carbide successful connection.Comprehensively
More than can be determined that prepared is to bromobenzene epoxide FePC/titanium carbide composite.
Embodiment 2
By surface hydroxylation titanium carbide, bromobenzene epoxide FePC and composite are carried out thermogravimetric analysis, analyze
Result as it is shown in figure 5, it can be seen that titanium carbide material thermally-stabilised well, in heating process
Almost without the loss of quality, good heat stability is titanium carbide as one of advantage of carrier of catalyst.
Experiment synthesis bromobenzene epoxide FePC is drastically decomposed about 200 DEG C beginnings, tend to about 400 DEG C
Steadily, until reaching about 58% close to 700 DEG C of total weight losses.Compare the material that load titanium carbide is later,
Between 400 DEG C and 700 DEG C, FePC/titanium carbide material has the most thermally-stabilised advantage.Load
The metal phthalocyanine visible light catalyst of titanium carbide has possessed higher heat stability.
Embodiment 3
Study β-to bromobenzene epoxide FePC and FePC/titanium carbide composite visible light catalyst respectively in simulation
Catalytic test to rhodamine B (RhB) under radiation of visible light, by degraded RhB evaluate sample can
See photocatalysis performance.Experiment is using the xenon source of 300W as visible light source, by two kinds of catalyst samples
Adding 3mg 10mL concentration under two parts of similarity conditions respectively is 10-5In the aqueous solution of mol/L rhodamine B.
Experiment starts magnetic agitation, the most separately sampled ultraviolet-visible light analysis of spectrum under dark condition
Instrument measures the absorption intensity of rhodamine B, until spectrum is unchanged.Open light source, under conditions of illumination,
It is spaced identical time sampling and measuring.
Fig. 6 is PBP-FePc/OH-Ti in catalysis system3C2Visible light catalyst catalytic degradation rhodamine B
Ultraviolet-ray visible absorbing collection of illustrative plates time history plot.By figure this it appears that along with catalysis time
Increasing, rhodamine B characteristic absorption peak intensity at 550nm is gradually lowered, and peak shape broadens, and color development is described
Group phenylamino, carbonyl bond are destroyed.
It can be seen from figure 7 that catalyst is by the dyestuff in adsorption absorption waste water under dark condition,
60min absorbing dye wastewater flow rate reaches saturated, and the concentration of rhodamine B no longer changes, and adsorbance is
10%.Illumination starts, and the concentration of rhodamine B reduces rapidly, after illumination 6h, and rhodamine B fall in waste water
Solve 80%.PBP-FePc/OH-Ti under illumination condition3C2Catalyst absorb after photon by ground state transition to
Excited state, produces light induced electron and hole, and valence-band electrons transits on conduction band, produces sky in valence band simultaneously
Cave, valence band hole can direct oxidation rhodamine B degradation.Unstable excited state is to stable ground state transition
Cheng Zhong, can discharge certain energy, can produce list after being captured by triplet oxygen by the way of energy shifts
Line state oxygen, singlet oxygen has the ability of oxidation Decomposition rhodamine B.After PBP-FePc loads on titanium carbide,
The specific surface area of composite catalyst increases, and the dissolubility oxygen molecule amount being adsorbed onto surface increases, the dissolving of absorption
Property oxygen molecule can be reduced by the light induced electron on conduction band, generate superoxide radical, beneficially dye molecule Luo Dan
The decomposition of bright B.PBP-FePc/OH-Ti3C2Be electronics to-acceptor systems, in this system, it is possible to have
Effect extends electronics at PBP-FePc/OH-Ti3C2The transmission life-span on composite, thus play raising material and urge
Change the effect of performance.Rhodamine B is by after illumination simultaneously, and also can be stimulated generation light induced electron, these light
Electronics can be injected on the conduction band of catalyst, thus promotes the carrying out of photocatalytic degradation.
By PBP-FePc and PBP-FePc/OH-Ti3C2Carry out visible light catalytic Experimental Comparison result such as Fig. 8
Shown in.
As shown in Figure 8, it is seen that photocatalysis effect PBP-FePc/OH-Ti3C2It is better than PBP-FePc, i.e.
PBP-FePc/OH-Ti3C2The excellent catalytic effect of composite visible light catalyst.Reason is that PBP-FePc loads to
After on titanium carbide, specific surface area increases, and the dissolubility oxygen molecule being adsorbed onto surface increases, and it is molten that these adsorb
Solution property oxygen molecule can be reduced by the light induced electron on conduction band, generates superoxide radical, beneficially dye molecule sieve
The decomposition of red bright B.PBP-FePc/OH-Ti3C2Composite visible light catalyst is Electron donor-acceptor system,
In this system, it is possible to extend the electronics transmission life-span on molecule, thus play raising material catalytic
The effect of energy.
Claims (4)
1. metal phthalocyanine/carbon back photocatalyst, described catalyst molecule chemical structural formula is:
Wherein M is metal.
The preparation method of metal phthalocyanine the most according to claim 1/carbon back photocatalyst, its feature is as follows:
(1) taking 2～6g 4-nitrophthalonitriles, 2～6g p bromophenols are dissolved in 20～100mL and are dried
In DMF (DMF), under argon shield, it is to slowly warm up to 80 DEG C of reactions, at temperature-rise period
In, weigh catalyst potassium carbonate powder 6～20g, in the 3h pass into solution in three times of interval, detected by a plate
Reaction process, is considered as reaction when raw material point disappears and terminates；Product is carried out sucking filtration, removes unreacted carbon
Filtrate being poured in 200ml distilled water after acid potassium, adding dilute hydrochloric acid regulation solution ph is to be stirred by magnetic force after 1
After mixing 1h, sucking filtration takes filter cake afterwards, then rinses with distilled water.Method finally by recrystallization improves product
Purity, is placed in crystal in 80 DEG C of vacuum drying ovens vacuum drying 24h and obtains product；
(2) product and the 0.2～0.6g FeCl of 1～3g step (1) are weighed2Join in three neck round bottom flask,
First reaction unit is evacuated to 0.098MPa, then measures the n-amyl alcohol that 15ml is dried and join three mouthfuls of round bottoms
In flask, under argon shield, it is to slowly warm up to 135 DEG C, temperature-rise period measures 1.5～5ml 1,8-diaza two
Ring 11 carbon-7-alkene (DBU) adds in flask.Detect reaction process by TLC, disappear to walking board raw material point
Lose stopped reaction.After reaction terminates, be warming up to 160 DEG C to remove the n-amyl alcohol in flask, be cooled to room temperature
Rear addition 200～500ml methanol, separates out out product after standing 48h, then sucking filtration takes filter cake, and put by product
In vacuum drying oven, 75 DEG C of dry 12h of vacuum obtain product；
(3) weigh the product of 300mg step (2) respectively, 20mg titanium carbide, 300mg potassium carbonate depend on
Secondary addition there-necked flask, measures the DMF that 10ml is dried, and is to slowly warm up to 80 DEG C under conditions of magnetic agitation,
Reaction 24h, after reaction terminates, takes out flask and is cooled to room temperature, carry out sucking filtration.Filter cake is rinsed with dilute hydrochloric acid,
Remove the catalyst potassium carbonate of residual, then rinse with DMF, remove unreacted to bromobenzene epoxide FePC,
Take filter cake to prepare bromobenzene epoxide FePC/titanium carbide composite after vacuum drying oven vacuum drying 24h.
Metal phthalocyanine the most according to claim 1/carbon back photocatalyst, it is characterised in that by end position
Br ion and titanium carbide OH-1Ions binding, produces the transmission channel of an electronics.
4. the metal phthalocyanine of claim 1/carbon back photocatalyst, it is characterised in that: this photocatalyst is as dirt
The application of water degraded catalysis.
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| CN101590428A (en) * | 2008-05-30 | 2009-12-02 | 南开大学 | The preparation method of the immobilized sulfonic acid iron-phthalocyanine of mesopore material HMS photochemical catalyst |
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