CN106732705A - A kind of Fe3O4@C@(BiO)2CO3The Preparation method and use of composite photo-catalyst - Google Patents
A kind of Fe3O4@C@(BiO)2CO3The Preparation method and use of composite photo-catalyst Download PDFInfo
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims abstract description 65
- NAOLWIGVYRIGTP-UHFFFAOYSA-N 1,3,5-trihydroxyanthracene-9,10-dione Chemical compound C1=CC(O)=C2C(=O)C3=CC(O)=CC(O)=C3C(=O)C2=C1 NAOLWIGVYRIGTP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000002028 Biomass Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000004098 Tetracycline Substances 0.000 claims description 13
- 235000019364 tetracycline Nutrition 0.000 claims description 13
- 150000003522 tetracyclines Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229960002180 tetracycline Drugs 0.000 claims description 12
- 229930101283 tetracycline Natural products 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 240000008042 Zea mays Species 0.000 claims description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 4
- 235000005822 corn Nutrition 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 14
- 238000007792 addition Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 2
- 229940036358 bismuth subcarbonate Drugs 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010977 jade Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241001198704 Aurivillius Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- 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
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of Fe3O4@C@(BiO)2CO3The Preparation method and use of composite photo-catalyst, step is as follows：Step 1, Fe3O4Preparation；The preparation of step 2, the saccharic acid liquid of biomass corncob；Step 3, Fe3O4The preparation of@C；Step 4, Fe3O4@C@(BiO)2CO3Preparation.Fe prepared by method of the present invention3O4@C@(BiO)2CO3The separation and recovery of composite photo-catalyst is more convenient, efficient；The Fe3O4@C@(BiO)2CO3Composite photo-catalyst has preferable photocatalytic activity and stability, while using biomass corncob as carbon source, realize waste and rationally utilize, save resources.
Description
Technical field
The invention belongs to technical field of environmental material preparation, and in particular to a kind of Fe based on biomass corncob3O4@C@
(BiO)2CO3The Preparation method and use of composite photo-catalyst.
Background technology
Tetracycline is that a class is usually used in the suppression of various germs and the antibiotic killed on adjacent bed, due to Tetracyclines antibiosis
The a large amount of of element make its generally existing in the environment, so as to result in the drug resistance of bacterium, on the other hand, the residual of tetracycline
Considerable influence can be produced to environment, it may be present in soil, surface water, underground water etc., human body is produced compared with major injury, therefore,
Effective removal tetracycline is particularly important.In recent years, many experts and scholars are solved the above problems using many methods, but this
A little methods are less efficient, and secondary pollution is easily caused again, and people have found a kind of new technology-photocatalysis technology by studying, and it is one
The green technology of kind of rationality, can be the inorganic matter such as carbon dioxide, water of environmental sound by organic matter degradation.
(BiO)2CO3(bismuth subcarbonate) is the new bismuth series photocatalyst of a class, with Aurivillius type oxide knots
One of representative of bismuth based compound semiconductor of structure, possesses a kind of typical " sill é n " structure, i.e. Bi-O atomic layers and (CO3
)2-Atomic layer is orthogonal staggeredly symbiosis (J.D.Grice, A solution to the crystal structures of
Bismuth and Beyerite,Can.Mineral.40(2002)693–698.).The band gap of bismuth subcarbonate is larger, only has
Ultraviolet catalytic activity, it is impossible to which by excited by visible light, therefore researchers are one after another by a series of technological means to (BiO)2CO3Photochemical catalyst carries out modification and improves its photocatalytic activity.With solvent structure there is visible light catalytic to live herein
The flower-shaped Fe of 3D of property3O4@C@(BiO)2CO3Composite photo-catalyst, the 3D hierarchies of composite photo-catalyst can not only lure light into
Produce multiple SSR effects, thus increase photon effective light path and absorbed possibility (J.Lee,
W.Choi.Photocatalytic reactivity of surface platinized TiO2:substrate
specificity and the effect of Pt oxidation state.J.Phys.Chem.B,2005,109(15):
7399-7406.), while 3D flower-like structures increase contact of the composite photo-catalyst with pollutant, catalyst is improve to pollution
The absorption of thing, so as to improve photocatalytic activity.At the same time, the carbon source for being used in this experiment is biomass corncob, is reached useless
The purpose that thing is rationally utilized.In addition, it is contemplated that financial cost, we select magnetic material (Fe3O4) and (BiO)2CO3With by jade
Meter Xin is that carbon material prepared by carbon source is combined, and the composite photo-catalyst prepared by the present invention has good Magneto separate special
Property, greatly improve cost recovery and secondary utilization rate.
The content of the invention
The present invention prepares a kind of Fe based on biomass corncob with hydro-thermal method as preparation means3O4@C@(BiO)2CO3
The preparation method of composite photo-catalyst, can be good at the tetracycline in degraded environmental wastewater, simple fast with degraded with synthesis
The characteristics of rate is high.
The technical scheme is that：
A kind of Fe3O4@C@(BiO)2CO3The preparation method of composite photo-catalyst, step is as follows：
Step 1, Fe3O4Preparation：FeCl3·6H2O is added in ethylene glycol, stirring to FeCl3·6H2O all dissolves,
Anhydrous sodium acetate is added, continues to stir to solution to become to clarify, solution is then transferred to autoclave and is put into baking oven
Row solvent thermal reaction；After baking oven naturally cools to room temperature, by reactor take out and by the solid sample in reactor spend from
, then be put into sample in baking oven and dry by sub- water and absolute ethanol washing, obtains Fe3O4, it is standby；
The preparation of step 2, the saccharic acid liquid of biomass corncob：Corn cob granule is scattered in H2SO4In, protect in a water bath
Hold magnetic agitation to be reacted, then filtered the mixed liquor of acquisition, obtain saccharic acid liquid, then with NaOH solution to saccharic acid
Liquid carries out neutralization reaction, untill treating that solution is changed into neutrality, obtains the saccharic acid liquid of biomass corncob；
Step 3, Fe3O4The preparation of@C：Fe is added in the saccharic acid liquid of the biomass corncob obtained to step 23O4And carry out
Ultrasound, then pours into autoclave mixed solution, and autoclave is put into baking oven carries out solvent thermal reaction, treats
After baking oven naturally cools to room temperature, reactor is taken out and by the sample deionized water and absolute ethanol washing in reactor,
Sample is then put into drying for standby in baking oven, Fe is designated as3O4@C；
Step 4, Fe3O4@C@(BiO)2CO3Preparation：Weigh Bi (NO3)3·5H2O, is dissolved in ethanol, stirring to solution
Become clarification, the Fe for adding step 3 to obtain3O4@C, continue to stir, and stirring adds urea (CH after terminating4N2) and cetyl O
Trimethylammonium bromide (CTAB), continues to stir, and then pours into autoclave mixed liquor, and autoclave is put into baking
Solvent thermal reaction is carried out in case, question response is finished after naturally cooling to room temperature, reactor is taken out and by the solid sample in kettle
With deionized water and absolute ethanol washing, sample is then put into drying for standby in baking oven, obtains Fe3O4@C@(BiO)2CO3。
In step 1, the FeCl3·6H2O, ethylene glycol, the amount ratio of anhydrous sodium acetate are 1.35g:40mL:3.6g；It is molten
The temperature of agent thermal response is 200 DEG C, and the reaction time is 6h.
In step 2, the H for being used2SO4Concentration be 55~75wt%, bath temperature be 45~65 DEG C, during magnetic agitation
Between be 5~20min；The concentration of NaOH solution is 10~27.5mol/L.
In step 3, the Fe3O4It is 0.01~0.05g with the amount ratio of corncob saccharic acid liquid:32mL；Solvent thermal reaction
Temperature is 180 DEG C, reacts 4h.
In step 4, the Bi (NO3)3·5H2O, urea, CTAB, Fe3O4The amount ratio of@C and ethanol be 1.46g~
4.0g:0.5g:0.5g:0.014g~0.143g:70mL.
In step 1, step 3, step 4, the drying temperature of sample is 60 DEG C.
Fe prepared by described method3O4@C@(BiO)2CO3Composite photo-catalyst be used for photocatalytic degradation tetracycline.
Beneficial effect：
Fe prepared by method of the present invention3O4@C@(BiO)2CO3The separation and recovery of composite photo-catalyst is more convenient,
Efficiently；The Fe3O4@C@(BiO)2CO3Composite photo-catalyst has preferable photocatalytic activity and stability, while with biomass
Corncob realizes waste and rationally utilizes as carbon source, save resources.
Brief description of the drawings
Fig. 1 is the Fe of embodiment 13O4@C@(BiO)2CO3The XRD of composite photo-catalyst, wherein a are prepared for embodiment 1
Fe3O4@C@(BiO)2CO3Composite photo-catalyst；B is (BiO) prepared by embodiment 122CO3Photochemical catalyst；
Fig. 2 is the XPS spectrum figure of sample, and wherein a is Fe prepared by embodiment 13O4@C@(BiO)2CO3Composite photo-catalyst,
B-d is followed successively by Bi 4f, the high-resolution XPS spectrum figure of C 1s and O 1s；
Fig. 3 is SEM and the TEM figure of different samples, and wherein a is pure (BiO) prepared by embodiment 122CO3Photochemical catalyst
SEM schemes；B is Fe prepared by embodiment 13O4@C@(BiO)2CO3The SEM figures of composite photo-catalyst；C is the pure of the preparation of embodiment 12
(BiO)2CO3The TEM figures of photochemical catalyst；Fe prepared by d and its illustration embodiment 13O4@C@(BiO)2CO3Composite photo-catalyst
TEM schemes；
Fig. 4 is the DRS figures of different synthetic samples, pure (BiO) that wherein prepared by a embodiments 122CO3Photochemical catalyst, b is real
Apply the Fe of the preparation of example 13O4@C@(BiO)2CO3Composite photo-catalyst；
Fig. 5 is the investigation figure of different samples light degradation tetracycline under visible light, and wherein a is prepared by embodiment 12
(BiO)2CO3Catalyst；B be embodiment 9 in work as Fe3O4The Fe that@C additions are prepared when being 0.014g3O4@C@(BiO)2CO3It is compound
Photochemical catalyst；C be embodiment 9 in work as Fe3O4The Fe that@C additions are prepared when being 0.021g3O4@C@(BiO)2CO3Composite photocatalyst
Agent；D is Fe prepared by embodiment 13O4@C@(BiO)2CO3Composite photo-catalyst；E be embodiment 9 in work as Fe3O4@C additions are
The Fe prepared during 0.068g3O4@C@(BiO)2CO3Composite photo-catalyst；F be embodiment 9 in work as Fe3O4@C additions are 0.068g
When the Fe for preparing3O4@C@(BiO)2CO3Composite photo-catalyst；
Fig. 6 is Fe prepared by embodiment 13O4@C@(BiO)2CO3The 4 of composite photo-catalyst photocatalytic degradation tetracycline
Secondary circulation photocatalysis effect figure.
Specific embodiment
With reference to specific embodiment, the invention will be further described：
Photocatalytic activity evaluation：Carried out in D1 type photochemical reactions instrument (being purchased from Educational Instrument Factory of Yangzhou University), will
The tetracycline simulated wastewater of 100mL20mg/L is added in reaction bulb, adds magneton and 0.02g photochemical catalysts, opens visible ray
Power supply and aerator carry out Dynamic Adsorption, and start external thermostatic water-circulator bath to control temperature of reaction system is 30 DEG C.Reach and inhale
Illumination reaction is carried out after attached balance, every sampling in 10 minutes once, the concentration of tetracycline in supernatant is surveyed in centrifugation, is passed through
C/C0To judge the degradation effect of tetracycline.Wherein, C0It is the concentration of tetracycline after adsorption equilibrium, Fourth Ring when C is reaction time T
The concentration of element
Embodiment 1：
(1)Fe3O4Preparation：1.35g FeCl3·6H2O is added in 40mL ethylene glycol, stirring to FeCl3·6H2O is complete
Portion dissolves, and adds 3.6g anhydrous sodium acetates, and continuing to stir to solution becomes clarification, and solution then is transferred into autoclave simultaneously
Being put into baking oven carries out solvent thermal reaction.It is 200 DEG C to set oven temperature, reacts 6h.After baking oven naturally cools to room temperature, will
Reactor is taken out and the sample deionized water and absolute ethanol washing in reactor is multiple, and then sample is put into baking oven
Drying for standby, is designated as Fe3O4。
(2) preparation of the saccharic acid liquid of biomass corncob：5g corn cob granules are weighed, with 68wt%H2SO4Mixing, 55
Reacted in DEG C water-bath, the reaction time is 10min, is then filtered the mixed liquor of acquisition, obtains saccharic acid liquid, then used
Concentration carries out neutralization reaction for the NaOH of 27.5mol/L to above-mentioned saccharic acid liquid, and untill treating that solution is changed into neutrality, this solution is designated as jade
Rice core saccharic acid liquid.
(3)Fe3O4The preparation of@C：Above-mentioned 32mL corncobs saccharic acid liquid is measured, 0.02g Fe are added3O4And ultrasound 20min,
Then mixed liquor is poured into autoclave, and autoclave is put into baking oven, regulation oven temperature is 180 DEG C, instead
4h is answered, after baking oven naturally cools to room temperature, reactor is taken out and by the sample deionized water and anhydrous second in reactor
Alcohol washing is multiple, and sample then is put into drying for standby in baking oven, is designated as Fe3O4@C。
(4)Fe3O4@C@(BiO)2CO3Preparation：Weigh 2.45g Bi (NO3)3·5H2O, is dissolved in 70mL ethanol solutions,
Stirring to solution becomes clarification, weighs 0.032g Fe3O4@C, continue to stir, and stirring adds 0.5g urea after terminating
(CH4N2O) and 0.5g CTAB, continue to stir, then pour into autoclave mixed liquor, and autoclave is put into baking
In case, regulation oven temperature is 180 DEG C, and the reaction time is 12h, after baking oven naturally cools to room temperature, reactor is taken out simultaneously
By the sample deionized water and absolute ethanol washing in kettle repeatedly, sample is then put into drying for standby in baking oven, is designated as
Fe3O4@C@(BiO)2CO3。
Embodiment 2：
Carried out by the same step of preparation technology of embodiment 1, unlike in step (2) corn cob granule consumption for 3g and
8g prepares the saccharic acid liquid of various concentrations, and then synthesizes Fe3O4@C@(BiO)2CO3Composite photo-catalyst.
Embodiment 3：
Carried out by the same step of preparation technology of embodiment 1, the difference is that H in step (2)2SO4Concentration for 55wt%,
60wt% and 75wt% prepare the saccharic acid liquid of various concentrations, and then synthesize Fe3O4@C@(BiO)2CO3Composite photo-catalyst.
Embodiment 4：
Carried out by the same step of preparation technology of embodiment 1, the difference is that bath temperature is 45 DEG C and 65 DEG C in step (2)
The saccharic acid liquid of various concentrations is prepared, and then synthesizes Fe3O4@C@(BiO)2CO3Composite photo-catalyst.
Embodiment 5：
Carried out by the same step of preparation technology of embodiment 1, unlike in step (2) the magnetic agitation time be 5min,
15min and 20min, and then synthesize Fe3O4@C@(BiO)2CO3Composite photo-catalyst.
Embodiment 6：
Carried out by the same step of preparation technology of embodiment 1, unlike in step (2) concentration of NaOH be 10mol/L,
15mol/L and 20mol/L prepare the saccharic acid liquid of various concentrations, and then synthesize Fe3O4@C@(BiO)2CO3Composite photo-catalyst.
Embodiment 7：
Carried out by the same step of preparation technology of embodiment 1, the difference is that Fe in step (3)3O4Consumption is 0.01g, 0.03g
And 0.05g, and then synthesize Fe3O4@C@(BiO)2CO3Composite photo-catalyst.
Embodiment 8：
Carried out by the same step of preparation technology of embodiment 1, the difference is that Bi (NO in step (3)3)3·5H2O consumptions are
1.46g, 1.94g and 4.0g, and then synthesize Fe3O4@C@(BiO)2CO3Composite photo-catalyst.
Embodiment 9：
Carried out by the same step of preparation technology of embodiment 1, the difference is that Fe in step (3)3O4@C consumptions be 0.014g,
0.021g, 0.068g and 0.143g, and then synthesize Fe3O4@C@(BiO)2CO3Composite photo-catalyst.
Embodiment 10：
Carried out by the same step of preparation technology of embodiment 1, the difference is that oven temperature is 160 DEG C and 200 in step (4)
DEG C, and then synthesize Fe3O4@C@(BiO)2CO3Composite photo-catalyst.
Embodiment 11：
Carried out by the same step of preparation technology of embodiment 1, unlike in step (4) reaction time be 8h and 16h, and then
Synthesis Fe3O4@C@(BiO)2CO3Composite photo-catalyst.
Embodiment 12：
Carried out by the same step of preparation technology of embodiment 1, the difference is that being added without Fe in step (4)3O4@C are pure to prepare
(BiO)2CO3Photochemical catalyst, investigates (BiO)2CO3Photochemical catalyst photocatalytic activity, as a result as shown in figure 5, pure (BiO)2CO3Light is urged
Agent photocatalytic activity is relatively low, and the Fe after being combined3O4@C@(BiO)2CO3The photocatalyst activity of composite photo-catalyst increases
Greatly, show that compound system is conducive to the lifting of photochemical catalyst catalytic degradation performance, with the Fe for adding3O4The increase of@C amounts, is combined
The photocatalysis performance of photochemical catalyst has been lifted, as addition Fe3O4@C are measured during more than 2.5%, the photocatalytic of composite photo-catalyst
Can begin to decline.
Embodiment 13：
Fe is investigated by (4) step in embodiment 13O4@C@(BiO)2CO34 circulation photocatalytic degradations four of composite photo-catalyst
Ring element antibiotic waste water photochemical stability, as a result as shown in fig. 6, as can be seen from Figure 64 times circulation after, Fe3O4@C@
(BiO)2CO3The photocatalytic activity of composite photo-catalyst does not significantly decrease, and illustrates the Fe prepared by the application3O4@C@
(BiO)2CO3Composite photo-catalyst has good photochemical stability, recycling that can be multiple.
The sample that Fig. 1 demonstrates prepared by the application is (BiO) really2CO3And Fe3O4@C@(BiO)2CO3Composite photocatalyst
Agent.
Fig. 2 is the XPS spectrum figure of sample, and figure a is Fe3O4@C@(BiO)2CO3The XPS figures of composite photo-catalyst, can from figure
To have the elements such as C, O and Bi in the composite photo-catalyst for drawing synthesis, show that composite photo-catalyst is successfully synthesized, figure b,
It is respectively the high power XPS figures of Bi 4f, C 1s and O 1s in c and d.Peak at 159.1eV and 164.2eV corresponds to Bi 4f certainly
Rotation orbit splitting peak, i.e. Bi 4f7/2 and 5/2, corresponding to Bi-O keys, it is mainly derived from some of composite photo-catalyst surface
The material of oxidation by air, C 1s peaks in figure c, is the DIC of catalyst surface positioned at the peak of 284.6eV, and is located at
The peak of 288.8eV is attributed to (BiO)2CO3In CO3 2-.Figure d is the spectrum of O 1s, is (BiO) positioned at the peak of 530.4eV2CO3
In CO3 2-Characteristic peak, peak 529.9eV be Bi-O characteristic peaks, positioned at 534.4eV peaks for catalyst surface inorganic matter carbon
Peak.
Fig. 3 is SEM and the TEM figure of different samples, as can be seen that pure (BiO) from a, c figure2CO3Photochemical catalyst is presented nothing
Regular sheet, Fe is can be seen that from b, d and its illustration3O4@C@(BiO)2CO3Composite photo-catalyst shows more regular 3D
It is flower-shaped.
As can be seen that (BiO) in Fig. 42CO3Photochemical catalyst is being 370nm near UV light region and visible region wavelength
Left and right has stronger absorption, Fe after being combined3O4@C@(BiO)2CO3Composite photo-catalyst has stronger in visible region
Absorb.
Claims (7)
1. a kind of Fe3O4@C@(BiO)2CO3The preparation method of composite photo-catalyst, it is characterised in that step is as follows：
Step 1, Fe3O4Preparation：FeCl3·6H2O is added in ethylene glycol, stirring to FeCl3·6H2O all dissolves, and adds
Anhydrous sodium acetate, continue stir to solution become clarify, then by solution be transferred to autoclave and be put into baking oven carry out it is molten
Agent thermal response；After baking oven naturally cools to room temperature, reactor is taken out and by the solid sample deionized water in reactor
And absolute ethanol washing, then sample is put into baking oven and is dried, obtain Fe3O4, it is standby；
The preparation of step 2, the saccharic acid liquid of biomass corncob：Corn cob granule is scattered in H2SO4In, magnetic is kept in a water bath
Power stirring is reacted, and is then filtered the mixed liquor of acquisition, obtains saccharic acid liquid, and saccharic acid liquid is entered with NaOH solution then
Row neutralization reaction, untill treating that solution is changed into neutrality, obtains the saccharic acid liquid of biomass corncob；
Step 3, Fe3O4The preparation of@C：Fe is added in the saccharic acid liquid of the biomass corncob obtained to step 23O4And carry out ultrasound,
Then mixed solution is poured into autoclave, and autoclave is put into baking oven is carried out solvent thermal reaction, treat baking oven
After naturally cooling to room temperature, reactor is taken out and by the sample deionized water and absolute ethanol washing in reactor, then
Sample is put into drying for standby in baking oven, Fe is designated as3O4@C；
Step 4, Fe3O4@C@(BiO)2CO3Preparation：Weigh Bi (NO3)3·5H2O, is dissolved in ethanol, and stirring to solution becomes clear
Clearly, the Fe for adding step 3 to obtain3O4@C, continue to stir, and stirring adds urea and CTAB after terminating, and continue to stir, and then will
Mixed liquor is poured into autoclave, and autoclave is put into baking oven carries out solvent thermal reaction, and question response finishes nature
After being cooled to room temperature, reactor is taken out and by the solid sample deionized water and absolute ethanol washing in kettle, then by sample
Product are put into drying for standby in baking oven, obtain Fe3O4@C@(BiO)2CO3。
2. a kind of Fe according to claim 13O4@C@(BiO)2CO3The preparation method of composite photo-catalyst, its feature exists
In, in step 1, the FeCl3·6H2O, ethylene glycol, the amount ratio of anhydrous sodium acetate are 1.35g:40mL:3.6g；Solvent heat is anti-
The temperature answered is 200 DEG C, and the reaction time is 6h.
3. a kind of Fe according to claim 13O4@C@(BiO)2CO3The preparation method of composite photo-catalyst, its feature exists
In, in step 2, the H for being used2SO4Concentration be 55~75wt%, bath temperature be 45~65 DEG C, the magnetic agitation time be 5
~20min；The concentration of NaOH solution is 10~27.5mol/L.
4. a kind of Fe according to claim 13O4@C@(BiO)2CO3The preparation method of composite photo-catalyst, its feature exists
In, in step 3, the Fe3O4It is 0.01~0.05g with the amount ratio of corncob saccharic acid liquid:32mL；The temperature of solvent thermal reaction
It is 180 DEG C, reacts 4h.
5. a kind of Fe according to claim 13O4@C@(BiO)2CO3The preparation method of composite photo-catalyst, its feature exists
In, in step 4, the Bi (NO3)3·5H2O, urea, CTAB, Fe3O4The amount ratio of@C and ethanol is 1.46g~4.0g:
0.5g:0.5g:0.014g~0.143g:70mL.
6. a kind of Fe according to claim 13O4@C@(BiO)2CO3The preparation method of composite photo-catalyst, its feature exists
In in step 1, step 3, step 4, the drying temperature of sample is 60 DEG C.
7. the Fe that prepared by the method described in claim 1~6 any one3O4@C@(BiO)2CO3Composite photo-catalyst is urged for light
Change the purposes of degraded tetracycline.
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| CN112108150A (en) * | 2020-09-13 | 2020-12-22 | 通化师范学院 | Based on magnetic Fe3O4Modified corncob biomass carbon dot composite Bi2WO6Preparation method and application of photocatalyst |
| CN112480930A (en) * | 2020-12-10 | 2021-03-12 | 广东省科学院资源综合利用研究所 | Preparation method of magnetic soil heavy metal restoration agent, heavy metal restoration agent and application |
| CN112774706A (en) * | 2021-01-31 | 2021-05-11 | 湖南科技大学 | Bismuth oxycarbonate/sepiolite composite photocatalyst and preparation method thereof |
| CN112808287A (en) * | 2021-01-31 | 2021-05-18 | 湖南科技大学 | Magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst and preparation method thereof |
| CN115176816A (en) * | 2022-08-30 | 2022-10-14 | 河北科技师范学院 | Fe 3 O 4 @CuO x Composite material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112108150A (en) * | 2020-09-13 | 2020-12-22 | 通化师范学院 | Based on magnetic Fe3O4Modified corncob biomass carbon dot composite Bi2WO6Preparation method and application of photocatalyst |
| CN112480930A (en) * | 2020-12-10 | 2021-03-12 | 广东省科学院资源综合利用研究所 | Preparation method of magnetic soil heavy metal restoration agent, heavy metal restoration agent and application |
| CN112774706A (en) * | 2021-01-31 | 2021-05-11 | 湖南科技大学 | Bismuth oxycarbonate/sepiolite composite photocatalyst and preparation method thereof |
| CN112808287A (en) * | 2021-01-31 | 2021-05-18 | 湖南科技大学 | Magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst and preparation method thereof |
| CN112808287B (en) * | 2021-01-31 | 2023-10-20 | 湖南科技大学 | Magnetic core-shell bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof |
| CN112774706B (en) * | 2021-01-31 | 2023-10-24 | 湖南科技大学 | Bismuth oxide carbonate/sepiolite composite photocatalyst and preparation method thereof |
| CN115176816A (en) * | 2022-08-30 | 2022-10-14 | 河北科技师范学院 | Fe 3 O 4 @CuO x Composite material and preparation method and application thereof |
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