CN106268960B - A kind of polyacrylonitrile fibre-hemin bionic catalysts and preparation method thereof - Google Patents
A kind of polyacrylonitrile fibre-hemin bionic catalysts and preparation method thereof Download PDFInfo
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- CN106268960B CN106268960B CN201610855881.4A CN201610855881A CN106268960B CN 106268960 B CN106268960 B CN 106268960B CN 201610855881 A CN201610855881 A CN 201610855881A CN 106268960 B CN106268960 B CN 106268960B
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- hemin
- bionic
- polyacrylonitrile fibre
- fibre
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 229940025294 hemin Drugs 0.000 title claims abstract description 51
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 46
- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- BTIJJDXEELBZFS-QDUVMHSLSA-K hemin Chemical compound CC1=C(CCC(O)=O)C(C=C2C(CCC(O)=O)=C(C)\C(N2[Fe](Cl)N23)=C\4)=N\C1=C/C2=C(C)C(C=C)=C3\C=C/1C(C)=C(C=C)C/4=N\1 BTIJJDXEELBZFS-QDUVMHSLSA-K 0.000 claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 23
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- -1 iron ion Chemical class 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 9
- 108010001336 Horseradish Peroxidase Proteins 0.000 abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 238000004088 simulation Methods 0.000 abstract description 3
- 229910001139 Telluric iron Inorganic materials 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000012876 carrier material Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- NTYJJOPFIAHURM-UHFFFAOYSA-N Histamine Chemical compound NCCC1=CN=CN1 NTYJJOPFIAHURM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QOSTVEDABRQTSU-UHFFFAOYSA-N 1,4-bis(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NC)=CC=C2NC QOSTVEDABRQTSU-UHFFFAOYSA-N 0.000 description 1
- 235000011330 Armoracia rusticana Nutrition 0.000 description 1
- 240000003291 Armoracia rusticana Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- GLNHIAPTFHWQKY-UHFFFAOYSA-L disodium 4-amino-3-[[4-[[4-[(2,4-diaminophenyl)diazenyl]phenyl]sulfonylamino]phenyl]diazenyl]-5-oxido-6-phenyldiazenyl-7-sulfonaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Nc1ccc(N=Nc2ccc(cc2)S(=O)(=O)Nc2ccc(cc2)N=Nc2c(N)c3c(O)c(N=Nc4ccccc4)c(cc3cc2S([O-])(=O)=O)S([O-])(=O)=O)c(N)c1 GLNHIAPTFHWQKY-UHFFFAOYSA-L 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229960001340 histamine Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- GCFAQSYBSUQUPL-UHFFFAOYSA-I pentasodium 5-[[4-chloro-6-[3-(2-sulfonatooxyethylsulfonyl)anilino]-1,3,5-triazin-2-yl]amino]-3-[(1,5-disulfonatonaphthalen-2-yl)diazenyl]-4-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].Oc1c(N=Nc2ccc3c(cccc3c2S([O-])(=O)=O)S([O-])(=O)=O)c(cc2cc(cc(Nc3nc(Cl)nc(Nc4cccc(c4)S(=O)(=O)CCOS([O-])(=O)=O)n3)c12)S([O-])(=O)=O)S([O-])(=O)=O GCFAQSYBSUQUPL-UHFFFAOYSA-I 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 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 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003403 water pollutant Substances 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
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/35—Heterocyclic compounds
- D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a kind of polyacrylonitrile fibre hemin bionic catalysts and preparation method thereof, and in threadiness, the polyacrylonitrile fibre being modified by 2 aminooimidazoles is formed the bionic catalyst after being reacted with a kind of native iron porphyrin compound hemin.Preparation method is：Reaction is modified to polyacrylonitrile fibre under the conditions of 95 DEG C of pH=9.5 and temperature using 2 aminooimidazoles first, it is set to obtain the active group containing imidazole ring structure, then the DMF solution of gained modified acrylic fibre and hemin are subjected to complexation reaction, obtain the polyacrylonitrile fibre hemin bionic catalysts of simulation horseradish peroxidase structure.Bionic catalyst of the present invention is suitable for the oxidative degradation of the organic pollutants such as dyestuff, and compared with the hemin of processing, the introducing of polyacrylonitrile fibre carrier not only clearly enhances its catalytic activity, but also greatly improves its pH applicability and stability in use.
Description
Technical field
It is specially a kind of for the organic pollutions such as Wastewater Dyes oxidation drop the invention belongs to bionic catalysis technical field
Polyacrylonitrile fibre-hemin the bionic catalysts in solution field and preparation method thereof.
Background technology
In recent years, bionic catalysis technology receives significant attention in the water such as dyestuff in the processing of persistent organic pollutants.
Wherein, metalloporphyrin has the metal ion of variable valence and is conjugated big pi-electron structure, to have redox characteristic, quilt
It is considered a kind of potential efficient bionic catalyst.However when handling organic pollutants, catalysis of metalloporphyrin agent is easily sent out
Be born from poly- and activity caused to be substantially reduced, but also there are pH narrow application ranges, stability difference and difficult separation and recyclings etc. no
Foot.Metalloporphyrin is carried on solid material surface and prepares catalyst, is a kind of important channel for overcoming its disadvantages mentioned above.
TiO2The materials such as film, graphene and activated carbon fiber can be used for carried metal porphyrin and prepare catalyst, Ta Menke
Effective activation H2O2Oxidative degradation organic pollution, but there are still preparation process complicated, high energy consumption or catalytic activity are undesirable etc. asks
Topic, these deficiencies limit its further application.
Invention content
Can be used for the efficient bionic catalysis that the organic pollutions such as dyestuff are handled in water the purpose of the present invention is to provide a kind of
Agent, the catalyst have the characteristics that simple preparation method, at low cost, high catalytic efficiency and stability in use are strong.
The technical solution adopted in the present invention is changed to polyacrylonitrile fibre side group cyano using 2- aminooimidazoles
Property, prepare the fiber carrier material containing imidazole ring structure.Then again by a kind of native iron porphyrin compound hemin (chlorination blood
Red pigment) it is combined by axial coordination and the imidazole ring on modified fibre, prepare simulation horseradish peroxidase structure
Polyacrylonitrile load iron porphyrin catalyst, the specific steps are:
1) by weight 1：(0.83-4.165) takes polyacrylonitrile fibre and 2- aminooimidazoles, and polyacrylonitrile fibre is added
Into 2- aminooimidazole aqueous solutions, pH value is adjusted to 9.5 with sodium hydroxide, reacts 2-6h under 95 DEG C and stirring condition, then
It takes out and with obtaining modified acrylic fibre after distilled water repeatedly cleaning, drying.
2) by weight 1：(0.1-0.5) takes modified acrylic fibre and hemin, and modified acrylic fibre is placed in
In the DMF solution of hemin, is taken out after reaction 1-2.5h under 40-60 DEG C and stirring condition, DMF and distilled water is used in combination to wash repeatedly
It is dried after washing, obtains polyacrylonitrile fibre-hemin bionic catalysts.
A concentration of 16.6-83.3g/L of the 2- aminooimidazoles aqueous solution.
A concentration of 1.0-5.0g/L of the DMF solution of the hemin.
For polyacrylonitrile fibre by the modified-reaction of side group cyano, can introduce can occur coordination with metal ion
Active group, to prepare catalyst as carrier material loaded metal ion.Compared with other carrier materials, polyacrylonitrile is fine
Dimension has cheap, physical and chemical performance excellent and the application mode unique advantages such as flexibly, becomes the preparation of carried metal porphyrin
The potential material of bionic catalyst.
With the catalase that horseradish peroxidase (Horseradish peroxidase, HRP) is representative, there is pole
High catalysis H2O2The efficiency for generating hydroxyl radical free radical is decomposed, gained strong oxidizing property free radical attack organic pollution and can make
Degradation reaction occurs in it.In horseradish peroxidase molecule, Fe3+High ferro is formed with four N atom complexs of plane porphyrin
Ferroheme is axially below N atoms in histamine H is170 residues in imidazole ring with iron coordination, and axial top then can be with
H2O2It is combined.In activation H2O2When reaction, the imidazole ring being connected with iron center can promote iron and oxygen by pushing away electronic action
Between electron transmission, to increase substantially the catalytic efficiency of reaction system.Pass through the mould to horseradish peroxidase structure
It is quasi-, ferriporphyrin is carried on the solid material containing imidazole ring structure, the catalyst of preparation is expected to obtain close to hydrogen peroxide
The catalytic activity of enzyme.
Compared with prior art, the beneficial effects of the present invention are：Use the modified polyacrylonitrile containing imidazole ring structure
Fiber loads the catalysis that ferriporphyrin prepares simulation horseradish peroxidase structure as carrier material, by axial coordination
Agent.Polyacrylonitrile fibre material not only has excellent flexibility, structural stability and mechanical performance as carrier, but also to dye
The organic pollutants such as material show stronger adsorptivity, greatly enhance practicability of the ferriporphyrin as catalysis material.
The catalyst characteristics are the preparation method using simple impregnation, do not need expensive equipment, and technological process is simple,
Low energy consumption during material preparation.The activation of catalyst H2O2Catalytic degradation water pollutant it is efficient because fiber carry
Imidazole ring can promote the electron transmission between activated centre iron and oxygen by axial coordination on body, with similar horseradish peroxide
The mode for changing hydrogen enzyme promotes the catalytic activity of ferriporphyrin.The catalyst also has the pH scope of applications wide and recycling performance
The features such as excellent.
Description of the drawings
Fig. 1 is the bionic catalyst of one to three gained of embodiment of bionic catalyst of the present invention with untreated hemin's
Catalytic activity compares (test condition：Rhdamine B：0.02mmol/L, H2O2：5.0mmol/L, catalyst：5.0g/L, pH=
6.0, temperature：50℃).
Fig. 2 is the bionic catalyst of one gained of embodiment of bionic catalyst of the present invention and untreated hemin in difference
(test condition is compared to the catalytic activity of dyestuff degradation under pH value condition：Rhdamine B：0.02mmol/L, H2O2：
5.0mmol/L, catalyst：5.0g/L, temperature：50 DEG C, the reaction time：60min).
Fig. 3 is the bionic catalyst of one gained of embodiment of bionic catalyst of the present invention and untreated hemin to difference
The dyestuff degradation catalytic activity of structure compares (test condition：Dye strength：0.02mmol/L, H2O2：5.0mmol/L, catalyst：
5.0g/L, pH=6.0, temperature：50 DEG C, the reaction time：60min).
Fig. 4 is reuse of the bionic catalyst of two gained of embodiment of bionic catalyst of the present invention in dyestuff degradation
Performance (test condition：Rhdamine B：0.02mmol/L, H2O2：5.0mmol/L, catalyst：5.0g/L, pH=6.0, temperature
Degree：50℃).
Specific implementation mode
Below in conjunction with embodiment and the attached drawing content that the present invention is furture elucidated, but these embodiments are not intended to limit this hair
Bright protection domain.
The present invention provides a kind of polyacrylonitrile fibre-hemin bionic catalysts (abbreviation bionic catalyst), the bionic catalysis
Agent is made of the modified acrylic fibre containing imidazole ring structure active group with hemin, wherein iron ion contains in threadiness
Amount is 1.5-18.9mg/g.
The present invention also provides a kind of polyacrylonitrile fibre-hemin bionic catalyst preparation methods, the specific steps are:
1) by weight 1：(0.83-4.165) takes polyacrylonitrile fibre and 2- aminooimidazoles, and polyacrylonitrile fibre is added
Into 2- aminooimidazole aqueous solutions, pH value is adjusted to 9.5 with sodium hydroxide, reacts 2-6h under 95 DEG C and stirring condition, then
It takes out and with obtaining modified acrylic fibre after distilled water repeatedly cleaning, drying.
2) by weight 1：(0.1-0.5) takes modified acrylic fibre and hemin, and modified acrylic fibre is placed in
In the DMF solution of hemin, is taken out after reaction 1-2.5h under 40-60 DEG C and stirring condition, DMF and distilled water is used in combination to wash repeatedly
It is dried after washing, obtains polyacrylonitrile fibre-hemin bionic catalysts.
A concentration of 16.6-83.3g/L of the 2- aminooimidazoles aqueous solution.
A concentration of 1.0-5.0g/L of the DMF solution of the hemin.
Embodiment one
1) the 1.0g polyacrylonitrile fibres of accurate weighing are put into the 2- aminooimidazole aqueous solutions of a concentration of 83.3g/L of 50ml
In, pH value is adjusted to 9.5 with sodium hydroxide, is reacted 4h under 95 DEG C and stirring condition, is then taken out and repeatedly clear with distilled water
Modified acrylic fibre is obtained after washing drying.
2) in the DMF solution for weighing the hemin that 1.0g modified acrylic fibres are placed in a concentration of 4.0g/L of 100ml,
It is taken out after reaction 2.5h under 60 DEG C and stirring condition, is dried after being used in combination DMF and distilled water to wash repeatedly, obtain the first polypropylene
Nitrile fiber-hemin bionic catalysts.
The nitrogen content that modified acrylic fibre before loading hemin is measured using elemental analyser is 34.5%, is commented with this
Its imidazole ring group content of valence.The measurement of catalyst iron ion content：Precise 0.1g catalyst, is dissolved in V (HNO3):V
(H2O2)=7:In 3 solution, using the iron concentration in Solution by Atomic Absorption Spectrophotometry, and calculate on catalyst according to this
Iron ion content is 15.6mg/g.
Embodiment two
2- aminooimidazole concentration in one step 1 of embodiment is adjusted to 66.7g/L, hemin concentration is adjusted in step 2
2.0g/L, remaining is as in the first embodiment, obtain second of polyacrylonitrile fibre-hemin bionic catalyst.After measured and calculate,
Nitrogen content is 30.1% in fiber carrier material, and catalyst iron ion content is 10.2mg/g.
Embodiment three, four
Hemin concentration in one step 2 of embodiment is adjusted separately as 1.5g/L and 3.0g/L, remaining as in the first embodiment,
To the third and the 4th kind of polyacrylonitrile fibre-hemin bionic catalyst.Its fiber carrier material nitrogen content is 34.5%,
Iron ion content is respectively 9.9mg/g and 12.3mg/g.
Embodiment five, six
Hemin concentration in two step 2 of embodiment is adjusted separately as 3.0g/L and 5.0g/L, remaining is obtained with embodiment two
To the 5th kind and the 6th kind of polyacrylonitrile fibre-hemin bionic catalyst.Its fiber carrier material nitrogen content is 30.1%,
Iron ion content is respectively 11.5mg/g and 15.3mg/g..
Embodiment seven, eight, nine
2- aminooimidazole concentration in one step 1 of embodiment is adjusted to 33.2g/L, hemin concentration is set separately in step 2
For 1.0g/L, 3.0g/L and 5.0g/L, remaining obtains the 7th kind, the 8th kind and the 9th kind polyacrylonitrile fibre-with embodiment 1
Hemin bionic catalysts.It after measured and calculates, nitrogen content is 26.5% in fiber carrier material, and catalyst iron ion contains
Amount is respectively 2.8mg/g, 6.7mg/g and 8.5mg/g.
Polyacrylonitrile fibre-hemin the bionic catalysts for choosing one to three gained of embodiment carry out catalytic activity investigation, profit
Wastewater Dyes degradation rate is measured with it.The specific method that bionic catalyst activity of the present invention is investigated is：First will
Bionic catalyst is placed in the aqueous solution of dyestuff, it is made to handle 60min under certain temperature and pH value condition, and dyestuff is imitative at this time
Absorption on raw catalyst reaches balance, then adds H2O2Start oxidative degradation, it is calculated according to the variation of dye strength
Degradation rate, and with the catalytic activity of the dyestuff degradation rate numerical Evaluation bionic catalyst.Fig. 1 is shown, when only hemin is deposited merely
When, react 60min after dyestuff degradation rate be 34.6%, this is because hemin can pass through between its Fe ionic valence condition turn
Become (Fe3+/Fe2+), it is catalyzed H2O2It decomposes and generates the extremely strong hydroxyl radical free radical of oxidisability, the latter makes dye by oxidation
Degradation reaction occurs for material.And in the presence of three gained bionic catalyst of embodiment one of the present invention, embodiment two or embodiment, instead
Dyestuff degradation rate illustrates close to 100% compared with unsupported hemin after answering 60min, and bionical obtained by three kinds of embodiments is urged
Agent catalytic activity is all greatly improved.This is because imidazole ring can lead in polyacrylonitrile fibre in catalyst of the present invention
Axial coordination is crossed to be combined with Fe ions in hemin, and by push away electronic action promote in catalyst system and catalyzing iron and oxygen it
Between electron transmission, to improve activation of catalyst H2O2Efficiency, make to generate more hydroxyl radical free radicals in system, finally lead
Cause more dye molecules that oxidative degradation occurs.
Fig. 2 shows that the catalytic activity of unsupported hemin is substantially reduced with the raising of pH value, especially in alkalinity (pH=
9.0) after reacting 60min under the conditions of, dyestuff degradation rate only has less than 10%.However the bionic catalyst of the gained of embodiment one is urged
Change activity is influenced not notable by pH value, and degradation reaction has occurred in the dyestuff that 90% is still had more than when pH value is increased to 9.0.This
Illustrate that the catalytic activity of hemin is not only greatly improved in polyacrylonitrile fibre-hemin bionic catalysts, but also greatly changes
It has been apt to its pH scope of application, it is made to all have very high catalytic activity within the scope of wider pH.
From figure 3, it can be seen that the oxidative degradation that bionic catalyst of the present invention can be suitable for a variety of different structure dyestuffs is anti-
Ying Zhong.In the oxidative degradation of ACID BLACK 234, cationic yellow 19, REACTIVE Red 195 and directly blue 14 4 kinds of dyestuffs, implement
The bionic catalyst of one gained of example all shows the catalytic activity far above hemin, and dyestuff degradation rate is close after reacting 60min
100%.This is because catalyst of the present invention can be by being catalyzed H2O2Decompose the hydroxyl radical free radical for generating strong oxidizing property, Hou Zheji
All organic matters can be aoxidized, it is logical that this so that catalyst of the present invention has in the oxidative degradation of different structure dyestuff
The property used.In addition, catalyst of the present invention also has good repeat performance.Fig. 4 shows two institute of CATALYST EXAMPLE of the present invention
In continuous 5 Oxidative Degradation Process to dye, rhodamine B, catalytic activity does not occur to reduce existing the bionic catalyst obtained
As illustrating that it can be applied multiple times in the oxidative degradation processing of waste water from dyestuff, there is good practicability, industrial applications tool
There is apparent economic benefit.
Claims (3)
1. a kind of polyacrylonitrile fibre-hemin bionic catalysts, which is characterized in that the bionic catalyst is in threadiness, by containing
The modified acrylic fibre of imidazole ring structure active group is constituted with hemin, and wherein iron ion content is 1.5-18.9mg/g,
Its preparation process is:
1) by weight 1：(0.83-4.165) takes polyacrylonitrile fibre and 2- aminooimidazoles, and polyacrylonitrile fibre is added to 2-
In aminooimidazole aqueous solution, pH value is adjusted to 9.5 with sodium hydroxide, 2-6h is reacted under 95 DEG C and stirring condition, then takes out
It is used in combination distilled water to obtain modified acrylic fibre after cleaning, drying repeatedly；
2) by weight 1：(0.1-0.5) takes modified acrylic fibre and hemin, and modified acrylic fibre is placed in
In the DMF solution of hemin, is taken out after reaction 1-2.5h under 40-60 DEG C and stirring condition, DMF and distilled water is used in combination to wash repeatedly
It is dried after washing, obtains polyacrylonitrile fibre-hemin bionic catalysts.
2. polyacrylonitrile fibre-hemin bionic catalysts according to claim 1, which is characterized in that the 2- amino miaow
A concentration of 16.6-83.3g/L of azoles aqueous solution.
3. polyacrylonitrile fibre-hemin bionic catalysts according to claim 1, which is characterized in that the hemin's
A concentration of 1.0-5.0g/L of DMF solution.
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