CN110237810A - A kind of preparation method of the bismuth oxychloride of synergistic sorption-photocatalytic degradation terramycin wastewater/graphene three-dimensional aeroge - Google Patents
A kind of preparation method of the bismuth oxychloride of synergistic sorption-photocatalytic degradation terramycin wastewater/graphene three-dimensional aeroge Download PDFInfo
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 31
- 229940073609 bismuth oxychloride Drugs 0.000 title claims abstract description 21
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 title claims abstract description 18
- 229940063650 terramycin Drugs 0.000 title claims abstract description 18
- 239000002351 wastewater Substances 0.000 title claims abstract description 16
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 229910001868 water Inorganic materials 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 235000019441 ethanol Nutrition 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 4
- 239000012498 ultrapure water Substances 0.000 claims abstract description 4
- 238000002604 ultrasonography Methods 0.000 claims abstract description 4
- 239000000017 hydrogel Substances 0.000 claims abstract description 3
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 239000000499 gel Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000004964 aerogel Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 230000010748 Photoabsorption Effects 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005186 environmental transport Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical group Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0262—Compounds of O, S, Se, Te
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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—
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- B01J35/39—
-
- B01J35/60—
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Abstract
The invention discloses a kind of synergistic sorption-photocatalytic degradation terramycin wastewater bismuth oxychloride/graphene three-dimensional aeroge preparation methods, 0.018-0.09g BiOCl photochemical catalyst is added in ultrapure water and ultrasonic disperse obtains dispersion liquid A, 0.09g graphene oxide is added in 30mL water and ultrasonic disperse 2 hours obtain dispersion liquid B, then dispersion liquid A is mixed with dispersion liquid B, continue ultrasound 1 hour, add 0.2mL ammonium hydroxide and 0.1mL hydrazine hydrate, it is transferred in reaction kettle and is reacted 4 hours in 180 DEG C after mixing evenly, cooled to room temperature, up to bismuth oxychloride graphene three dimensional hydrogel, it is impregnated 8 hours with water and ethyl alcohol respectively, it is placed in -20 DEG C of freezen protectives again 48 hours, most afterwards through vacuum freeze drying 48 hours up to synergistic sorption- The bismuth oxychloride of photocatalytic degradation terramycin wastewater/graphene three-dimensional aeroge.Bismuth oxychloride produced by the present invention/graphene three-dimensional aeroge had not only had excellent absorption property, but also can be in efficient degradation terramycin wastewater under simulated solar irradiation.
Description
Technical field
The invention belongs to the synthesis technical fields of new function material, and in particular to a kind of synergistic sorption-photocatalytic degradation
The bismuth oxychloride of terramycin wastewater/graphene three-dimensional aeroge preparation method.
Background technique
Terramycin is widely applied as a kind of Tetracyclines broad-spectrum antibiotic in medical treatment, herding and aquaculture field.It adjusts
Display is looked into, the year usage amount of Chinese terramycin is about 1360 tons, and has the situation increased year by year.But terramycin cannot be by human body
Or animal fully absorbs, except small part through hydroxylating, be cracked to form inactive product in addition to, it is most of with raw medicine or metabolin
Form is discharged into environment, is entered environmental transport and transfer conversion through water body and food chain, is become a kind of emerging environmental contaminants.Cause
This, takes proper technology to be particularly important its fully degraded.
Photocatalysis technology can make the CO that pollutant permineralization is nontoxic, harmless under light illumination2And H2O, have energy conservation,
Efficiently and thorough advantage is purified, can be applied to the processing of used water difficult to degradate.It is using photocatalysis technology processing waste water key
Exploitation efficiently, has the catalyst of visible light activity.
BiOCl is a kind of layer structure semiconductor of indirect band gap with high anisotropy, because of good visible light
Catalytic performance receives significant attention.But BiOCl the defects of there are forbidden bandwidth is larger and photo-generate electron-hole recombination rate is high,
It is not able to satisfy practical application request still.In order to improve its utilization rate to solar energy, photocatalytic activity is improved, convenient for actually answering
With having reported is enhanced using the methods of Morphological control, metal or nonmetal doping, building plasma, establishment two-dimensional hetero-junction
The visible light catalytic performance of BiOCl.The present invention uses simple hydrothermal synthesis method by the compound preparation three of BiOCl and graphene oxide
Aeroge is tieed up, the optical response range and photocatalytic activity of material prepared are significantly increased compared with BiOCl, and so far there are no, and correlation is reported
Road.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of density of material low, good mechanical property, large specific surface area, conduction
Function admirable, absorption and photo absorption property be strong, stable cycle performance and synergistic sorption easy to be recycled-photocatalytic degradation soil are mould
The bismuth oxychloride of plain waste water/graphene three-dimensional aeroge preparation method.
The present invention adopts the following technical scheme that a kind of synergistic sorption-photocatalytic degradation soil is mould to solve above-mentioned technical problem
The bismuth oxychloride of plain waste water/graphene three-dimensional aeroge preparation method, it is characterised in that specific steps are as follows:
Step S1: in ice-water bath, 1g graphite powder being added in the 23mL concentrated sulfuric acid, is stirred 10 minutes, is added 3g KMnO4,
Then reaction 1 hour, solution are stirred 1 hour in 30 DEG C in blackish green, 46mL deionized water is added later, and kept for 96 DEG C and stirred
It mixes 30 minutes, is eventually adding 10mL hydrogen peroxide and 140mL deionized water terminates reaction, take out, be cooled to room temperature, in 4000 rpm
It is centrifuged 10 minutes under revolving speed, then successively uses 5wt% hydrochloric acid solution and ethanol washing 3-4 times, every time sufficiently after washing, required
It is centrifuged 5 minutes under 4000rpm revolving speed and then discards waste liquid, finally in 60 DEG C of dry obtained graphene oxides；
Step S2: 4mmol KCl is dissolved in 50mL deionized water, and 2mmol Bi (NO is added under the conditions of magnetic agitation3)3·
5H2O is further continued for stirring 30 minutes, and solution is then transferred in ptfe autoclave to be placed in constant temperature in 180 DEG C of baking ovens anti-
It answers 12 hours, cooled to room temperature, centrifuge separation successively use water and ethanol washing to get BiOCl photocatalysis after the reaction was completed
Agent；
Step S3: 0.018-0.09g BiOCl photochemical catalyst being added in ultrapure water and ultrasonic disperse obtains dispersion liquid A, will
0.09g graphene oxide is added in 30mL water and ultrasonic disperse 2 hours obtain dispersion liquid B, then by dispersion liquid A and dispersion liquid
B mixing, continues ultrasound 1 hour, adds 0.2mL ammonium hydroxide and 0.1mL hydrazine hydrate, is transferred in reaction kettle after mixing evenly in 180
DEG C reaction 4 hours, it is small that cooled to room temperature to get bismuth oxychloride graphene three dimensional hydrogel, respectively impregnates 8 with water and ethyl alcohol
When, then it is placed in -20 DEG C of freezen protectives 48 hours, most afterwards through vacuum freeze drying 48 hours up to synergistic sorption-photocatalytic degradation
The bismuth oxychloride of terramycin wastewater/graphene three-dimensional aeroge.
Preferably, the mass ratio that feeds intake of BiOCl photochemical catalyst described in step S3 and graphene oxide is 2:5.
Bismuth oxychloride produced by the present invention/graphene three-dimensional aeroge had not only had excellent absorption property, but also can simulate
Efficient degradation terramycin wastewater under sunlight.The absorption spectrum ranges of the composite catalyst are wide, performance stablize, it is efficient, nontoxic, at
This cheap, organic pollutant for the difficult for biological degradation that can be used for degrading has good market application prospect.
Detailed description of the invention
Fig. 1 is different materials absorption terramycin performance curve；
Fig. 2 is different materials degradation terramycin performance curve；
Fig. 3 is the XRD spectrum of different materials；
Fig. 4 is the SEM figure that bismuth oxychloride/graphene three-dimensional aeroge is made in embodiment.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this
The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair
Bright range.
Embodiment
In ice-water bath, 1g graphite powder is added in the 23mL concentrated sulfuric acid, stirs 10 minutes, adds 3g KMnO4, instead
It answers 1 hour, then solution is stirred 1 hour in 30 DEG C in blackish green, 46mL deionized water is added later, and keep 96 DEG C of stirrings
It 30 minutes, is eventually adding 10mL hydrogen peroxide and 140mL deionized water terminates reaction, take out, be cooled to room temperature, turn in 4000 rpm
Speed lower centrifugation 10 minutes, then 5wt% hydrochloric acid solution and ethanol washing 3-4 times are successively used, every time sufficiently after washing, require
It is centrifuged 5 minutes under 4000rpm revolving speed and then discards waste liquid, finally in 60 DEG C of dry obtained graphene oxides；
4mmol KCl is dissolved in 50mL deionized water, 2mmol Bi (NO is added under the conditions of magnetic agitation3)3·5H2O, then
Continue stirring 30 minutes, solution is then transferred in ptfe autoclave to be placed in isothermal reaction 12 in 180 DEG C of baking ovens small
When, cooled to room temperature, centrifuge separation successively use water and ethanol washing to get BiOCl photochemical catalyst after the reaction was completed；
0,0.018g, 0.036g, 0.054g, 0.072g, 0.09g BiOCl photochemical catalyst are added in ultrapure water and are surpassed respectively
Sound disperses to obtain dispersion liquid A, and 0.09g graphene oxide is added in 30mL water and ultrasonic disperse 2 hours obtain dispersion liquid B,
Dispersion liquid A is mixed with dispersion liquid B then, continues ultrasound 1 hour, adds 0.2mL ammonium hydroxide and 0.1mL hydrazine hydrate, stirring is equal
It is transferred to after even in reaction kettle and is reacted 4 hours in 180 DEG C, cooled to room temperature is to get bismuth oxychloride/graphene three-dimensional water-setting
Glue successively uses deionized water and soaked in absolute ethyl alcohol 8 hours, then is placed in -20 DEG C of freezen protectives 48 hours, most afterwards through vacuum refrigeration
Dry 48 hours up to different weight percentage composition bismuth oxychloride/graphene three-dimensional aeroge (be denoted as 0,20% BGA respectively,
40% BGA, 60% BGA, 80% BGA, 100% BGA).Compare each catalyst (300W xenon lamp) degradation soil under simulated solar irradiation
Mycin waste water (20mg L−1) performance, the optimal bismuth oxychloride of effect/graphene aerogel illumination 3 hours removes terramycin
Except rate is 92.35%, purer BiOCl photochemical catalyst is high by 27.19%, in best degradation efficiency bismuth oxychloride/graphene aerogel
The weight additive amount of BiOCl is 40%.
Comparative example
4mmol KCl is dissolved in 50mL deionized water, 2mmol Bi (NO is added under the conditions of magnetic agitation3)3·5H2O, then
Continue stirring 30 minutes, solution is then transferred in ptfe autoclave to be placed in isothermal reaction 12 in 180 DEG C of baking ovens small
When, cooled to room temperature, centrifuge separation successively use water and ethanol washing to get BiOCl photochemical catalyst after the reaction was completed.?
(300W xenon lamp) degradation terramycin wastewater (20 mg L under simulated solar irradiation−1) 3 hours removal rates are 65.16%.
Embodiment above describes basic principles and main features of the invention and advantage, the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within
In the scope of protection of the invention.
Claims (2)
1. a kind of synergistic sorption-photocatalytic degradation terramycin wastewater bismuth oxychloride/graphene three-dimensional aeroge preparation method,
It is characterized in that specific steps are as follows:
Step S1: in ice-water bath, 1g graphite powder being added in the 23mL concentrated sulfuric acid, is stirred 10 minutes, is added 3g KMnO4,
Then reaction 1 hour, solution are stirred 1 hour in 30 DEG C in blackish green, 46mL deionized water is added later, and kept for 96 DEG C and stirred
It mixes 30 minutes, is eventually adding 10mL hydrogen peroxide and 140mL deionized water terminates reaction, take out, be cooled to room temperature, in 4000 rpm
It is centrifuged 10 minutes under revolving speed, then successively uses 5wt% hydrochloric acid solution and ethanol washing 3-4 times, every time sufficiently after washing, required
It is centrifuged 5 minutes under 4000rpm revolving speed and then discards waste liquid, finally in 60 DEG C of dry obtained graphene oxides；
Step S2: 4mmol KCl is dissolved in 50mL deionized water, and 2mmol Bi (NO is added under the conditions of magnetic agitation3)3·
5H2O is further continued for stirring 30 minutes, and solution is then transferred in ptfe autoclave to be placed in constant temperature in 180 DEG C of baking ovens anti-
It answers 12 hours, cooled to room temperature, centrifuge separation successively use water and ethanol washing to get BiOCl photocatalysis after the reaction was completed
Agent；
Step S3: 0.018-0.09g BiOCl photochemical catalyst being added in ultrapure water and ultrasonic disperse obtains dispersion liquid A, will
0.09g graphene oxide is added in 30 mL water and ultrasonic disperse 2 hours obtain dispersion liquid B, then by dispersion liquid A and dispersion
Liquid B mixing, continue ultrasound 1 hour, add 0.2 mL ammonium hydroxide and 0.1 mL hydrazine hydrate, be transferred in reaction kettle after mixing evenly in
180 DEG C are reacted 4 hours, and cooled to room temperature is impregnated with water and ethyl alcohol respectively to get bismuth oxychloride graphene three dimensional hydrogel
8 hours, then it is placed in -20 DEG C of freezen protectives 48 hours, most dropped afterwards through vacuum freeze drying 48 hours up to synergistic sorption-photocatalysis
Solve bismuth oxychloride/graphene three-dimensional aeroge of terramycin wastewater.
2. synergistic sorption according to claim 1-photocatalytic degradation terramycin wastewater bismuth oxychloride/graphene three-dimensional gas
The preparation method of gel, it is characterised in that: the mass ratio that feeds intake of BiOCl photochemical catalyst described in step S3 and graphene oxide is
2:5。
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