CN108579817A - A kind of preparation method of high catalytic activity material for heterogeneous class Fenton's reaction - Google Patents
A kind of preparation method of high catalytic activity material for heterogeneous class Fenton's reaction Download PDFInfo
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- CN108579817A CN108579817A CN201810227786.9A CN201810227786A CN108579817A CN 108579817 A CN108579817 A CN 108579817A CN 201810227786 A CN201810227786 A CN 201810227786A CN 108579817 A CN108579817 A CN 108579817A
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- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 229920002678 cellulose Polymers 0.000 claims abstract description 118
- 239000001913 cellulose Substances 0.000 claims abstract description 118
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 97
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 87
- 239000000017 hydrogel Substances 0.000 claims abstract description 76
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000007864 aqueous solution Substances 0.000 claims abstract description 44
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 39
- 239000002131 composite material Substances 0.000 claims abstract description 36
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 56
- 239000010439 graphite Substances 0.000 claims description 56
- 239000007788 liquid Substances 0.000 claims description 52
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- 238000004090 dissolution Methods 0.000 claims description 38
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 24
- 150000001336 alkenes Chemical class 0.000 claims description 21
- 229920000742 Cotton Polymers 0.000 claims description 12
- 230000001112 coagulating effect Effects 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002386 leaching Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 229920000875 Dissolving pulp Polymers 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000004043 dyeing Methods 0.000 abstract 1
- 238000010345 tape casting Methods 0.000 abstract 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RLLPVAHGXHCWKJ-IEBWSBKVSA-N (3-phenoxyphenyl)methyl (1s,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-IEBWSBKVSA-N 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940056319 ferrosoferric oxide Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000010457 zeolite 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
- B01J13/0065—Preparation of gels containing an organic phase
-
- B01J35/23—
-
- 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
-
- 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
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a kind of preparation methods of the high catalytic activity material for heterogeneous class Fenton's reaction.The preparation method is will to contain the combination solution dissolving cellulose of NaOH and urea, adds graphene oxide and prepares cellulose oxidation graphene solution；By cellulose oxidation graphene solution tape casting, cellulose/graphene oxide hydrogel is obtained, which is immersed into FeCl in succession3/FeCl2In mixed aqueous solution and in NaOH aqueous solutions, it is allowed to in-situ preparation Fe3O4Nano particle obtains cellulose/graphene oxide/Fe after washing3O4Hydrogel composite material.Graphene oxide in this composite hydrogel and Fe3O4Nano-particle forms synergistic effect, is used for heterogeneous class Fenton's reaction as high catalytic activity material, has the ability of removal persistent organic pollutants, embody in the wastewater treatments such as dyeing waste water, oily waste water, phenol wastewater and be widely applied very much.Present invention process process is simple, easy to operate, environmentally safe.
Description
Technical field
The present invention relates to the high catalytic activity design of material of heterogeneous class Fenton's reaction and synthesis field, more particularly to fiber
Element/graphite oxide is dilute/Fe3O4The method of the preparation of hydrogel composite material, degradation efficient for organic pollution and various useless
Water process.
Background technology
The waste water from dyestuff pollution that weaving, plastics and paper industry cause is the environmental problem of global concern.Current environmental protection
Regulation is increasingly stringent, and the processing of waste water from dyestuff is mandatory and height control.Fenton oxidation (Fenton reactions) technology has
Efficiently, inexpensively, it is less toxic and selectivity it is small the features such as, currently as a kind of high-level oxidation technology (Advanced Oxidation
Process, AOP) it is applied to the fields such as dye wastewater treatment, cause the very big concern of domestic and international scientist.AOP processes refer to
It is the hydroxyl radical free radical decomposing organic pollutant for generating high activity.However, Fenton oxidation technology still has certain limitation, such as
The utilization rate of H2O2 is not high, cannot abundant mineralising organic matter；The accumulation of the hydroxide sludge of iron and catalyst are non-renewable etc. asks
Topic.
Therefore, heterogeneous class fenton catalyst develops into an ideal selection.Heterogeneous class fenton catalyst is logical
Often by the ferropexy of various valence states on catalyst or carrier, such as clay, aluminium oxide, silicone zeolite and carbon material.Heterogeneous class
Fenton's reaction typically occurs on solid-liquid interface, and iron is remained essentially in as mineral or adion in solid phase.Wherein, carbon
Material fixes iron as catalyst carrier and has many applications for heterogeneous class Fenton's reaction, and including activated carbon, carbon is received
Mitron, mesoporous carbon and carbon aerogels etc..The graphene oxide (GO) that the present invention uses itself contains a large amount of oxygen-containing functional group, by
In its unique lamellar structure, it is easier to combine ferrous material than other carbon materials, is greatly improved class Fenton's reaction efficiency.
Invention content
The object of the present invention is to provide a kind of preparation method of the high catalytic activity material for heterogeneous class Fenton's reaction,
This method is realized for the first time fixes ferroso-ferric oxide in surface of graphene oxide and cellulose, makes graphene oxide and Fe3O4Nanometer
Particle forms synergistic effect in class Fenton's reaction, greatly improves its catalytic activity.The material preparation process process is simple and environmentally-friendly,
It is not related to poisonous and harmful substance, is easy to industrialize.
The purpose of the present invention is achieved through the following technical solutions：
(1) prepared by cellulose dissolution liquid：It will be pre-chilled containing the mixed aqueous solution of 6~8wt%NaOH and 10~14wt% urea
To -12~-13 DEG C, cellulose is added, is uniformly mixing to obtain cellulose dissolution liquid.
(2) prepared by cellulose/graphene oxide hydrogel：It is proportionally added into oxygen in the cellulose dissolution liquid of step (1)
Graphite alkene dispersion liquid (1~5wt%) is simultaneously cast after stirring evenly, solidifying through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Gu forming, obtains cellulose/graphene oxide hydrogel.
(3) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel prepared by step (2) immerses
FeCl containing 1~20wt%3And FeCl2Mixed aqueous solution in a period of time, then immerse again containing 1~5wt%NaOH aqueous solutions
Middle a period of time, in-situ preparation Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel is multiple
Condensation material.
To further realize the purpose of the present invention, it is preferable that cellulosic material can in the cellulose dissolution liquid in step (1)
For cotton linter pulp, content is 2~8wt%.
Preferably, FeCl in step (3)3And FeCl2Mixed aqueous solution in FeCl3And FeCl2Molar ratio be 2：1.
Preferably, hydrogel immerses FeCl in step (3)3And FeCl2Mixed aqueous solution in for a period of time be 5-
180min, it is 2-60min for a period of time to immerse in NaOH aqueous solutions.
Preferably, the ratio of graphene oxide and cellulose is 1:19~3:7, Fe3O4Content be 0.1~2wt%.
Compared with prior art, the present invention having the following advantages that：
Graphene oxide and graphene disperse to be more uniformly distributed in the matrix of cellulose in the present invention, obtained graphene-
Cellulose composite material electric conductivity and mechanical property are more excellent.Entire process conditions are mild, not high to equipment requirement, favorably
In industrialized production, waste liquid is easy recycling.The present invention is with sodium hydroxide, urea, water, cellulose, graphene etc.
Raw material, it is cheap, it is simple to operate, it is environmentally safe.
Description of the drawings
Fig. 1 is Fe3O4Catalysis Principles figure of the nano-particle in class Fenton's reaction.
Fig. 2 is Catalysis Principles figure of the graphene oxide in class Fenton's reaction.
Specific implementation mode
In order to more deeply understand the present invention, with reference to embodiment, the present invention is further illustrated, needs to illustrate
, the scope of protection of present invention be not limited to embodiment statement range.
Embodiment 1
The preparation method of a kind of high catalytic activity material for heterogeneous class Fenton's reaction, it is characterised in that including as follows
Step and process conditions：
(1) prepared by cellulose dissolution liquid：The mixed aqueous solution of 240 grams of urea containing 7wt%NaOH and 14wt% is pre-chilled to-
12 DEG C, cotton linter pulp (η=10 × 10 viscosity average molecular weigh M are taken immediately4) 9.5 grams of inputs wherein, stirred at 0 DEG C,
It can be prepared by cellulose dissolution liquid.
(2) prepared by cellulose/graphene oxide hydrogel：Graphite oxide is added in the cellulose dissolution liquid of step (1)
50 grams of alkene dispersion liquid (1wt%) is simultaneously cast after stirring evenly, and is frozen into through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Shape obtains cellulose/graphene oxide hydrogel.
(3) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel prepared by step (2) immerses
FeCl containing 1wt%3And FeCl2Mixed aqueous solution in 180min, then immerse again containing in 1~5wt%NaOH aqueous solutions
60min, in-situ preparation Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite wood
Material.
Above-mentioned steps prepare cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material, by weight, graphite oxide
The ratio of alkene and cellulose is 1：19, Fe3O4Content be 0.1wt%.
Embodiment 2
The preparation method of a kind of high catalytic activity material for heterogeneous class Fenton's reaction, it is characterised in that including as follows
Step and process conditions：
(1) prepared by cellulose dissolution liquid：The mixed aqueous solution of 200 grams of urea containing 8wt%NaOH and 10wt% is pre-chilled to-
13 DEG C, cotton linter pulp (η=10 × 10 viscosity average molecular weigh M are taken immediately4) 7 grams of inputs wherein, stirred at 0 DEG C, i.e.,
Cellulose dissolution liquid can be made.
(2) prepared by cellulose/graphene oxide hydrogel：Graphite oxide is added in the cellulose dissolution liquid of step (1)
60 grams of alkene dispersion liquid (5wt%) is simultaneously cast after stirring evenly, and is frozen into through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Shape obtains cellulose/graphene oxide hydrogel.
(4) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel prepared by step (2) immerses
FeCl containing 5wt%3And FeCl2Mixed aqueous solution in 5min, then immerse 2min in aqueous solution containing 5wt%NaOH again, it is in situ
Generate Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material.
Above-mentioned steps prepare cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material, by weight, graphite oxide
The ratio of alkene and cellulose is 3：7, Fe3O4Content be 2wt%.
Embodiment 3
The preparation method of a kind of high catalytic activity material for heterogeneous class Fenton's reaction, it is characterised in that including as follows
Step and process conditions：
(1) prepared by cellulose dissolution liquid：The mixed aqueous solution of 200 grams of urea containing 7wt%NaOH and 12wt% is pre-chilled to-
12 DEG C, cotton linter pulp (η=10 × 10 viscosity average molecular weigh M are taken immediately4) 9.5 grams of inputs wherein, stirred at 0 DEG C,
It can be prepared by cellulose dissolution liquid.
(2) prepared by cellulose/graphene oxide hydrogel：Graphite oxide is added in the cellulose dissolution liquid of step (1)
40 grams of alkene dispersion liquid (3wt%) is simultaneously cast after stirring evenly, and is frozen into through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Shape obtains cellulose/graphene oxide hydrogel.
(5) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel prepared by step (2) immerses
FeCl containing 1wt%3And FeCl2Mixed aqueous solution in 80min, then immerse 50min in aqueous solution containing 1wt%NaOH again, it is former
Position generates Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material.
Above-mentioned steps prepare cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material, by weight, graphite oxide
The ratio of alkene and cellulose is 1：19, Fe3O4Content be 0.1wt%.
Embodiment 4
The preparation method of a kind of high catalytic activity material for heterogeneous class Fenton's reaction, it is characterised in that including as follows
Step and process conditions：
(1) prepared by cellulose dissolution liquid：The mixed aqueous solution of 200 grams of urea containing 7wt%NaOH and 12wt% is pre-chilled to-
13 DEG C, cotton linter pulp (η=10 × 10 viscosity average molecular weigh M are taken immediately4) 7 grams of inputs wherein, stirred at 0 DEG C, i.e.,
Cellulose dissolution liquid can be made.
(2) prepared by cellulose/graphene oxide hydrogel：Graphite oxide is added in the cellulose dissolution liquid of step (1)
70 grams of alkene dispersion liquid (5wt%) is simultaneously cast after stirring evenly, and is frozen into through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Shape obtains cellulose/graphene oxide hydrogel.
(6) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel prepared by step (2) immerses
FeCl containing 4wt%3And FeCl2Mixed aqueous solution in 10min, then immerse 5min in aqueous solution containing 1wt%NaOH again, it is former
Position generates Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material.
Above-mentioned steps prepare cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material, by weight, graphite oxide
The ratio of alkene and cellulose is 4：7, Fe3O4Content be 1wt%.
Embodiment 5
The preparation method of a kind of high catalytic activity material for heterogeneous class Fenton's reaction, it is characterised in that including as follows
Step and process conditions：
(1) prepared by cellulose dissolution liquid：The mixed aqueous solution of 220 grams of urea containing 7wt%NaOH and 14wt% is pre-chilled to-
12 DEG C, cotton linter pulp (η=10 × 10 viscosity average molecular weigh M are taken immediately4) 8 grams of inputs wherein, stirred at 0 DEG C, i.e.,
Cellulose dissolution liquid can be made.
(2) prepared by cellulose/graphene oxide hydrogel：Graphite oxide is added in the cellulose dissolution liquid of step (1)
40 grams of alkene dispersion liquid (4wt%) is simultaneously cast after stirring evenly, and is frozen into through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Shape obtains cellulose/graphene oxide hydrogel.
(7) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel prepared by step (2) immerses
FeCl containing 2wt%3And FeCl2Mixed aqueous solution in 150min, then immerse 5min in aqueous solution containing 1wt%NaOH again, it is former
Position generates Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material.
Above-mentioned steps prepare cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material, by weight, graphite oxide
The ratio of alkene and cellulose is 2：7, Fe3O4Content be 1wt%.
Embodiment 6
The preparation method of a kind of high catalytic activity material for heterogeneous class Fenton's reaction, it is characterised in that including as follows
Step and process conditions：
(1) prepared by cellulose dissolution liquid：The mixed aqueous solution of 210 grams of urea containing 7wt%NaOH and 10wt% is pre-chilled to-
13 DEG C, cotton linter pulp (η=10 × 10 viscosity average molecular weigh M are taken immediately4) 9 grams of inputs wherein, stirred at 0 DEG C, i.e.,
Cellulose dissolution liquid can be made.
(2) prepared by cellulose/graphene oxide hydrogel：Graphite oxide is added in the cellulose dissolution liquid of step (1)
70 grams of alkene dispersion liquid (1wt%) is simultaneously cast after stirring evenly, and is frozen into through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Shape obtains cellulose/graphene oxide hydrogel.
(8) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel prepared by step (2) immerses
FeCl containing 4wt%3And FeCl2Mixed aqueous solution in 30min, then immerse 15min in aqueous solution containing 1wt%NaOH again, it is former
Position generates Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material.
Above-mentioned steps prepare cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material, by weight, graphite oxide
The ratio of alkene and cellulose is 3：7, Fe3O4Content be 1wt%.
Embodiment 7
The preparation method of a kind of high catalytic activity material for heterogeneous class Fenton's reaction, it is characterised in that including as follows
Step and process conditions：
(1) prepared by cellulose dissolution liquid：The mixed aqueous solution of 250 grams of urea containing 7wt%NaOH and 10wt% is pre-chilled to-
12 DEG C, cotton linter pulp (η=10 × 10 viscosity average molecular weigh M are taken immediately4) 10 grams of inputs wherein, stirred at 0 DEG C, i.e.,
Cellulose dissolution liquid can be made.
(2) prepared by cellulose/graphene oxide hydrogel：Graphite oxide is added in the cellulose dissolution liquid of step (1)
40 grams of alkene dispersion liquid (1wt%) is simultaneously cast after stirring evenly, and is frozen into through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Shape obtains cellulose/graphene oxide hydrogel.
(9) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel prepared by step (2) immerses
FeCl containing 15wt%3And FeCl2Mixed aqueous solution in 130min, then immerse 30min in aqueous solution containing 1wt%NaOH again,
In-situ preparation Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material.
Above-mentioned steps prepare cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material, by weight, graphite oxide
The ratio of alkene and cellulose is 1：10, Fe3O4Content be 2wt%.
Embodiment 8
The preparation method of a kind of high catalytic activity material for heterogeneous class Fenton's reaction, it is characterised in that including as follows
Step and process conditions：
(1) prepared by cellulose dissolution liquid：The mixed aqueous solution of 200 grams of urea containing 7wt%NaOH and 12wt% is pre-chilled to-
13 DEG C, cotton linter pulp (η=10 × 10 viscosity average molecular weigh M are taken immediately4) 7 grams of inputs wherein, stirred at 0 DEG C, i.e.,
Cellulose dissolution liquid can be made.
(2) prepared by cellulose/graphene oxide hydrogel：Graphite oxide is added in the cellulose dissolution liquid of step (1)
100 grams of alkene dispersion liquid (5wt%) is simultaneously cast after stirring evenly, and is frozen into through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Shape obtains cellulose/graphene oxide hydrogel.
(10) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel leaching prepared by step (2)
Enter the FeCl containing 1wt%3And FeCl2Mixed aqueous solution in 20min, then immerse 4min in aqueous solution containing 1wt%NaOH again,
In-situ preparation Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite material.
Above-mentioned steps prepare cellulose/graphite oxide it is dilute/Fe3O4 hydrogel composite materials, by weight graphite oxide
The ratio of alkene and cellulose is 3：7, Fe3O4 content is 0.5wt%.
Embodiment 9
The preparation method of a kind of high catalytic activity material for heterogeneous class Fenton's reaction, it is characterised in that including as follows
Step and process conditions：
(1) prepared by cellulose dissolution liquid：The mixed aqueous solution of 250 grams of urea containing 8wt%NaOH and 10wt% is pre-chilled to-
12 DEG C, cotton linter pulp (η=10 × 10 viscosity average molecular weigh M are taken immediately4) 8.5 grams of inputs wherein, stirred at 0 DEG C,
It can be prepared by cellulose dissolution liquid.
(2) prepared by cellulose/graphene oxide hydrogel：Graphite oxide is added in the cellulose dissolution liquid of step (1)
50 grams of alkene dispersion liquid (1wt%) is simultaneously cast after stirring evenly, and is frozen into through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Shape obtains cellulose/graphene oxide hydrogel.
(11) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel leaching prepared by step (2)
Enter the FeCl containing 2wt%3And FeCl2Mixed aqueous solution in 160min, then immerse again in aqueous solution containing 2wt%NaOH
50min, in-situ preparation Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite wood
Material.
Above-mentioned steps prepare cellulose/graphite oxide it is dilute/Fe3O4 hydrogel composite materials, by weight graphite oxide
The ratio of alkene and cellulose is 3：7, Fe3O4 content is 0.5wt%.
Embodiment 10
The preparation method of a kind of high catalytic activity material for heterogeneous class Fenton's reaction, it is characterised in that including as follows
Step and process conditions：
(1) prepared by cellulose dissolution liquid：The mixed aqueous solution of 200 grams of urea containing 8wt%NaOH and 14wt% is pre-chilled to-
13 DEG C, cotton linter pulp (η=10 × 10 viscosity average molecular weigh M are taken immediately4) 8.5 grams of inputs wherein, stirred at 0 DEG C,
It can be prepared by cellulose dissolution liquid.
(2) prepared by cellulose/graphene oxide hydrogel：Graphite oxide is added in the cellulose dissolution liquid of step (1)
60 grams of alkene dispersion liquid (4wt%) is simultaneously cast after stirring evenly, and is frozen into through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Shape obtains cellulose/graphene oxide hydrogel.
(12) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel leaching prepared by step (2)
Enter the FeCl containing 2wt%3And FeCl2Mixed aqueous solution in 150min, then immerse again in aqueous solution containing 3wt%NaOH
60min, in-situ preparation Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel composite wood
Material.
Above-mentioned steps prepare cellulose/graphite oxide it is dilute/Fe3O4 hydrogel composite materials, by weight graphite oxide
The ratio of alkene and cellulose is 1：10, Fe3O4 content is 1.5wt%.
Claims (5)
1. a kind of preparation method of high catalytic activity material for heterogeneous class Fenton's reaction, it is characterised in that including walking as follows
Rapid and process conditions：
(1) prepared by cellulose dissolution liquid：Mixed aqueous solution containing 6~8wt%NaOH and 10~14wt% urea is pre-chilled to -12
~-13 DEG C, cellulose is added, is uniformly mixing to obtain cellulose dissolution liquid.
(2) prepared by cellulose/graphene oxide hydrogel：It is proportionally added into oxidation stone in the cellulose dissolution liquid of step (1)
Black alkene dispersion liquid (1~5wt%) is simultaneously cast after stirring evenly, and is frozen into through the coagulating bath containing sulfuric acid or sulfuric acid/sodium sulphate
Shape obtains cellulose/graphene oxide hydrogel.
(3) cellulose/graphite oxide it is dilute/Fe3O4It is prepared by hydrogel composite material：Hydrogel prepared by step (2), which immerses, contains 1
The FeCl of~20wt%3And FeCl2Mixed aqueous solution in a period of time, then immerse again containing in 1~5wt%NaOH aqueous solutions
For a period of time, in-situ preparation Fe3O4Nano particle, by washing i.e. obtain cellulose/graphite oxide it is dilute/Fe3O4Hydrogel is compound
Material.
2. a kind of preparation method of high catalytic activity material for heterogeneous class Fenton's reaction according to claim 1,
It is characterized in that, cellulosic material can be cotton linter pulp in cellulose dissolution liquid in step (1), content is 2~8wt%.
3. a kind of preparation method of high catalytic activity material for heterogeneous class Fenton's reaction according to claim 1,
It is characterized in that, the molar ratio of FeCl3 and FeCl2 is 2 in the mixed aqueous solution of FeCl3 and FeCl2 in step (3)：1.
4. a kind of preparation method of high catalytic activity material for heterogeneous class Fenton's reaction according to claim 1,
It is characterized in that, hydrogel immerses FeCl in step (3)3And FeCl2Mixed aqueous solution in for a period of time be 5-180min, leaching
Enter in NaOH aqueous solutions is 2-60min for a period of time.
5. a kind of preparation method of high catalytic activity material for heterogeneous class Fenton's reaction according to claim 1,
It is characterized in that, the ratio of graphene oxide and cellulose is 1:19~3:7, Fe3O4Content be 0.1~2wt%.
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| CN110563960A (en) * | 2019-09-16 | 2019-12-13 | 中国科学院生态环境研究中心 | Nitrogen-doped iron-based graphene gel, and preparation method and application thereof |
| CN110918129A (en) * | 2019-11-25 | 2020-03-27 | 华南理工大学 | Cellulose/graphene oxide/ferroferric oxide composite hydrogel catalytic carrier applied to sewage treatment field and preparation method thereof |
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| CN102443180A (en) * | 2011-09-15 | 2012-05-09 | 复旦大学 | Method for preparing cellulose composite aerogel |
| CN104356421A (en) * | 2014-11-11 | 2015-02-18 | 亳州师范高等专科学校 | Cellulose-based composite material with three-dimensional porous structure and preparation method of cellulose-based composite material |
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| CN102443180A (en) * | 2011-09-15 | 2012-05-09 | 复旦大学 | Method for preparing cellulose composite aerogel |
| CN104356421A (en) * | 2014-11-11 | 2015-02-18 | 亳州师范高等专科学校 | Cellulose-based composite material with three-dimensional porous structure and preparation method of cellulose-based composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110563960A (en) * | 2019-09-16 | 2019-12-13 | 中国科学院生态环境研究中心 | Nitrogen-doped iron-based graphene gel, and preparation method and application thereof |
| CN110563960B (en) * | 2019-09-16 | 2021-04-02 | 中国科学院生态环境研究中心 | Nitrogen-doped iron-based graphene gel, and preparation method and application thereof |
| CN110918129A (en) * | 2019-11-25 | 2020-03-27 | 华南理工大学 | Cellulose/graphene oxide/ferroferric oxide composite hydrogel catalytic carrier applied to sewage treatment field and preparation method thereof |
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