CN106179372B - A kind of C@Fe based on biomass porous carbon3O4The Preparation method and use of@Bi composite photo-catalyst - Google Patents
A kind of C@Fe based on biomass porous carbon3O4The Preparation method and use of@Bi composite photo-catalyst Download PDFInfo
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- CN106179372B CN106179372B CN201610622043.2A CN201610622043A CN106179372B CN 106179372 B CN106179372 B CN 106179372B CN 201610622043 A CN201610622043 A CN 201610622043A CN 106179372 B CN106179372 B CN 106179372B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000002028 Biomass Substances 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims description 24
- 239000004098 Tetracycline Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 235000019364 tetracycline Nutrition 0.000 claims description 16
- 150000003522 tetracyclines Chemical class 0.000 claims description 16
- 229960002180 tetracycline Drugs 0.000 claims description 15
- 229930101283 tetracycline Natural products 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910016874 Fe(NO3) Inorganic materials 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000008247 solid mixture Substances 0.000 claims description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 20
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 19
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical group O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- BDJYZEWQEALFKK-UHFFFAOYSA-N bismuth;hydrate Chemical compound O.[Bi] BDJYZEWQEALFKK-UHFFFAOYSA-N 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The present invention provides a kind of C@Fe based on biomass porous carbon3O4The Preparation method and use of@Bi composite photo-catalyst, includes the following steps: the preparation of step 1, porous carbon；The preparation of porous carbon after step 2, modification；Step 3, C@Fe3O4The preparation of@Bi composite photo-catalyst.C@Fe prepared by the present invention3O4The separation and recovery of@Bi composite photo-catalyst is more convenient, efficient；The C@Fe3O4@Bi composite photo-catalyst has preferable photocatalytic activity and stability, while using biomass corncob as carbon source, realizing waste and rationally utilizing, and saves resource.
Description
Technical field
The invention belongs to technical field of environmental material preparation, and in particular to a kind of C@Fe based on biomass porous carbon3O4@
The Preparation method and use of Bi composite photo-catalyst.
Background technique
Environmental pollution is social urgent problem to be solved now, wherein atmosphere pollution and water pollution and we live manner of breathing
It closes.Antibiotic is a kind of for treating the drug of various Non-viral infections, the inhibition for the various germs being usually used in medicine and is gone out
It kills, but due to the factor of antibiotic itself, causes to fully absorb in human or animal's body, so that a large amount of antibiotic is with generation
It thanks to object even ortho states to be discharged into environment, water body environment is polluted.Many experts and scholars are more by physics, chemistry and biology etc.
Kind method solves the above problems to remove, but these method efficiency are lower, and easily cause secondary pollution, therefore, it has been found that one
Novel processing technique-the photocatalysis of kind, photocatalysis technology is usually using solar energy as light source, and cost is relatively low, and passes through photocatalysis skill
Degradation of Antibiotics in environment can be the inorganic matters such as carbon dioxide, water by art, therefore it is a kind of ideal green environmental protection technique.
In numerous photochemical catalysts, titanium dioxide (TiO2) to have many advantages, such as that relative low price, chemical property are stablized nontoxic and wide
General use, but its greater band gap, light abstraction width relative narrowness, solar energy utilization ratio is not high, and photocatalytic activity is caused to drop
Low, bismuth series photocatalyst causes the extensive concern of people due to its photocatalytic activity with higher.
Bi is a kind of semi-metallic, has both metallicity and nonmetal character, and semimetal Bi has high anisotropy Fermi
The advantages that surface, lesser effective electron mass, low carrier density and longer free path, makes semimetal Bi become research
Hot spot (J. Zhao, Q.F.Han, J.W.Zhu, X.D.Wu, X.Wang, Synthesis of Bi nanowire networks
and their superior photocatalytic activity for Cr(VI)reduction,Nanoscale,6
(2014) 10062-10070), while semimetal Bi has lesser band-gap energy, can be used as a direct plasma photocatalysis
Agent (F.Dong, T.Xiong, Y.J.Sun, Z.W. Zhao, Y.Zhou, X.Feng, Z.B.Wu, A semimetal bismuth
element as a direct plasmonic photocatalyst, Chem.Commun,50(2014)10386-
10389), it is applied to photocatalysis technology.However semimetal Bi is weaker to the adsorption capacity of pollutant, in order to improve adsorptivity, this
Text introduces biomass carbon (corncob), is processed into porous carbon materials.Porous carbon materials specific surface is larger, unique more
Pore structure can not only be such that the efficiency of light energy utilization increases, but also can increase the absorption of pollutant.By biomass carbon (corncob) conduct
Carrier material and semimetal Bi are compound, pollutant can be adsorbed onto around semiconductor particle, increase local concentration and accelerate instead
Speed is answered, to further increase photocatalysis efficiency.In addition, it is contemplated that economic cost, we select magnetic material (Fe3O4) with
Semimetal Bi and the progress of the porous carbon materials as prepared by corncob are compound, and composite photo-catalyst prepared by the present invention has good
Good Magneto separate characteristic, greatly improves cost recovery and secondary use rate.
Summary of the invention
Herein using high-temperature calcination as preparation means, prepare a kind of based on biomass porous carbon C@Fe3O4@Bi complex light
The preparation method of catalyst can be good at the tetracycline in degradation environmental wastewater, has synthesis simply and degradation rate is high
Feature.
The technical scheme is that
A kind of C@Fe based on biomass porous carbon3O4The preparation method of@Bi composite photo-catalyst, includes the following steps:
Corncob: being washed with deionized three times first, dry after removing surface impurity by the preparation of step 1, porous carbon,
Corncob after drying is placed in tube furnace, in N2It is calcined under atmosphere, taking-up is cooled to room temperature to the end of reacting, obtains product
A；
Suitable KOH is weighed, appropriate amount of deionized water is added, obtains KOH solution, product A is added in KOH solution, is stirred
It mixes, is then filtered obtained material and is put into baking oven and dry, be denoted as product B；
Product B is placed in tube furnace, in N2It is calcined under atmosphere, taking-up is cooled to room temperature to the end of reacting, is spent
Ion water washing, resulting sample are porous carbon (C)；
The preparation of porous carbon after step 2, modification: the porous carbon that step 1 is obtained is immersed in HNO3In, under magnetic agitation
Water bath with thermostatic control reaction is carried out, solid mixture is filtered and washed after completion of the reaction, until cleaning solution is in neutrality, is put into true
It is dried in empty baking oven, gained sample is the porous carbon after modification；
Step 3, C@Fe3O4The preparation of@Bi composite photo-catalyst: the porous carbon after modification obtained in step 2 is added to
It in ethylene glycol, mixes, five nitric hydrate bismuths is then added, ultrasound mixes, then carries out magnetic agitation, be added nine after stirring
Nitric hydrate iron continues to stir, and stirring terminates, and obtains mixture D, is put into baking oven and dries；The mixture D of drying is set
In in tube furnace, in N2It is calcined under atmosphere, last gained sample is C@Fe3O4@Bi composite photo-catalyst.
In step 1, heating rate when calcining corncob is 4~6 DEG C/min, and calcination temperature is 400~500 DEG C, calcining
Time is 20~60min.
In step 1, the concentration of KOH solution is 1mol/L, and the mass ratio of the quality and the resulting substance A of step 1 of KOH is
1:2.5~1:3.5.
In step 1, heating rate when calcined product B is 4 DEG C~6 DEG C/min, and calcination temperature is 600~800 DEG C, calcining
Time is 50~120min.
In step 2, the HNO3Concentration be 63wt.%, water bath with thermostatic control reaction temperature is 80 DEG C when magnetic agitation, constant temperature
Water-bath time is 3h.
In step 3, the magnetic agitation time is 1h.
In step 3, when preparing mixture D, porous carbon, five nitric hydrate bismuths, nine nitric hydrates after used modification
The amount ratio of iron and ethylene glycol is 0.3g:1.44g~3.36g:0.8g:20mL.
In step 3, the heating rate of the calcining is 4 DEG C~6 DEG C/min, and calcination temperature is 300~600 DEG C, when calcining
Between be 1~3h.
In step 1~3, the drying temperature is 60 DEG C.
The C@Fe of the method preparation3O4@Bi composite photo-catalyst is used for photocatalytic degradation tetracycline.
The utility model has the advantages that
C@Fe prepared by the present invention3O4The separation and recovery of@Bi composite photo-catalyst is more convenient, efficient；The C@Fe3O4@
Bi composite photo-catalyst has preferable photocatalytic activity and stability, while using biomass corncob as carbon source, realizing
Waste rationally utilizes, and saves resource.
Detailed description of the invention
Fig. 1: for the C@Fe of embodiment 13O4The XRD diagram of@Bi composite photo-catalyst, wherein a is in embodiment 9 when five hydrations
The C@Fe that the additional amount of bismuth nitrate is prepared when being 1.44g3O4@Bi composite photo-catalyst；B is in embodiment 9 when five nitric hydrate bismuths
Additional amount C@Fe for preparing when being 1.92g3O4@Bi composite photo-catalyst；C is C@Fe prepared by embodiment 13O4@Bi is compound
Photochemical catalyst；E is the C@Fe prepared in embodiment 9 when the additional amount of five nitric hydrate bismuths is 2.88g3O4@Bi complex light
Catalyst；F is the C@Fe prepared in embodiment 9 when the additional amount of five nitric hydrate bismuths is 3.36g3O4@Bi composite photocatalyst
Agent, wherein gray circles represent Fe3O4The peak XRD；
Fig. 2: for the XPS spectrum figure of sample, wherein a is C@Fe prepared by embodiment 13O4@Bi composite photo-catalyst, b-d points
Not Wei Bi 4f, Fe 2p and C 1s high-resolution XPS spectrum figure；
Fig. 3: scheming for the SEM and TEM of different samples, and wherein a is the SEM figure of porous carbon prepared by embodiment 1；B and its insert
Figure is the TEM figure of porous carbon prepared by embodiment 1；C, e is C@Fe prepared by embodiment 13O4The SEM of@Bi composite photo-catalyst
Figure；D, f is C@Fe prepared by embodiment 13O4The TEM of@Bi composite photo-catalyst schemes；
Fig. 4: for the specific surface area figure of porous carbon prepared by embodiment 1, illustration is the hole of porous carbon prepared by embodiment 1
Diameter distribution map；
Fig. 5: scheming for the DRS of different synthetic samples, and wherein a is simple substance Bi photochemical catalyst prepared by embodiment 10, and b is to implement
C@Fe prepared by example 13O4@Bi composite photo-catalyst；
Fig. 6: for the absorption figure of different synthetic samples, wherein a is porous carbon prepared by embodiment 1；B be embodiment 9 in when
The C@Fe that the additional amount of five nitric hydrate bismuths is prepared when being 1.44g3O4@Bi composite photo-catalyst；C is in embodiment 9 when five hydrations
The C@Fe that the additional amount of bismuth nitrate is prepared when being 2.4g3O4@Bi composite photo-catalyst；D is in embodiment 9 when five nitric hydrate bismuths
Additional amount C@Fe for preparing when being 1.92g3O4@Bi composite photo-catalyst；E is the addition in embodiment 9 when five nitric hydrate bismuths
The C@Fe that amount is prepared when being 2.88g3O4@Bi composite photo-catalyst；F is in embodiment 9 when the additional amount of five nitric hydrate bismuths is
The C@Fe prepared when 3.36g3O4@Bi composite photo-catalyst；G is simple substance Bi photochemical catalyst prepared by embodiment 10；
Fig. 7: the investigation figure of the sample of different calcination temperatures light degradation tetracycline under visible light, wherein a is embodiment 12
In when calcination temperature is 400 DEG C the C@Fe for preparing3O4@Bi composite photo-catalyst；B is the C@Fe prepared in embodiment 13O4@Bi
Composite photo-catalyst；C is the C@Fe prepared in embodiment 12 when calcination temperature is 600 DEG C3O4@Bi composite photo-catalyst；
Fig. 8: the investigation figure of different samples light degradation tetracycline under visible light, wherein a is in embodiment 9 when five are hydrated nitre
The C@Fe that the additional amount of sour bismuth is prepared when being 3.36g3O4@Bi composite photo-catalyst；B is in embodiment 9 when five nitric hydrate bismuths
The C@Fe that additional amount is prepared when being 1.92g3O4@Bi composite photo-catalyst；C is C@Fe prepared by embodiment 13O4@Bi complex light
Catalyst；D is the C@Fe prepared in embodiment 9 when the additional amount of five nitric hydrate bismuths is 2.88g3O4@Bi composite photocatalyst
Agent；E is the C@Fe prepared in embodiment 9 when the additional amount of five nitric hydrate bismuths is 1.44g3O4@Bi composite photo-catalyst；F is
Bi photochemical catalyst prepared by embodiment 10；
Fig. 9: after different capturing agents are added, the C@Fe of the preparation of embodiment 13O4@Bi composite photo-catalyst photocatalytic degradation four
Ring sketch map, wherein TEOA is triethanolamine；BQ is 1,4-benzoquinone；TEA is the tert-butyl alcohol；
Figure 10: the C@Fe prepared for embodiment 13O45 times of@Bi composite photo-catalyst photocatalytic degradation tetracycline follow
Ring photocatalysis effect figure.
Specific embodiment
The invention will be further described combined with specific embodiments below:
Photocatalytic activity evaluation: carrying out in D1 type photochemical reactor (being purchased from Educational Instrument Factory of Yangzhou University), will
The tetracycline simulated wastewater of 100mL 20mg/L is added in reaction flask, adds magneton and 0.1g photochemical catalyst, opens visible light
Power supply and aerator carry out Dynamic Adsorption, and starting external thermostatic water-circulator bath control temperature of reaction system is 30 DEG C.It reaches and inhales
Illumination reaction is carried out after attached balance, primary every sampling in 10 minutes, centrifuge separation is surveyed the concentration of tetracycline in supernatant, passed through
C/C0To judge the degradation effect of tetracycline.Wherein, C0For the concentration of tetracycline after adsorption equilibrium, Fourth Ring when C is reaction time T
The concentration of element.
Embodiment 1:
(1) corncob: being washed with deionized three times first, dry after removing surface impurity by the preparation of porous carbon, will
Corncob after drying is placed in tube furnace, with the heating rate of 5 DEG C/min in N230 points are calcined under atmosphere at 450 DEG C
Clock is cooled to room temperature taking-up to the end of reacting.Suitable KOH is weighed, deionized water is added, KOH is configured to concentration is 1mol/L
Solution, the substance after charing is added in KOH solution, make KOH and charing after material mass ratio 1:3.5, stir 30
Minute, it is then filtered and is placed in oven and dried.Then the substance of drying is placed in tube furnace, with the liter of 5 DEG C/min
Warm rate is in N2It is calcined 90 minutes at 750 DEG C under atmosphere, taking-up is cooled to room temperature to the end of reacting, and more with deionized water
Secondary washing, resulting sample are porous carbon.
(2) modification of porous carbon: the HNO of suitable 63wt.% is measured3, above-mentioned porous carbon is then added, makes porous carbon-impregnated
Not in nitric acid, and heating water bath stirring is carried out at 80 DEG C, then mixture is filtered and washed, in solution is in
Property, it is put into vacuum drying oven and dries, gained sample is the porous carbon after modification.
(3)C@Fe3O4The preparation of@Bi composite photo-catalyst: the porous carbon after 0.3g is modified is added to 20ml ethylene glycol
In, it stirs evenly, five nitric hydrate bismuth of 2.4g is then added, ultrasound mixes, then carries out magnetic agitation, be added after stirring
0.8g Fe(NO3)39H2O continues to stir, and stirring terminates, and mixture is put into baking oven in 80 DEG C of baking ovens dry.Most
Dry mixture is placed in tube furnace afterwards, with the heating rate of 5 DEG C/min in N22 h are calcined under atmosphere at 500 DEG C,
Last gained sample is C@Fe3O4@Bi composite photo-catalyst.
(4) sample in 0.1g (2) is taken to carry out photocatalytic degradation test in photochemical reactor, experimental result is with ultraviolet point
Light luminometric analysis measures the C@Fe3O4@Bi composite photo-catalyst is obvious to the light degradation effect of tetracycline, shows the C@
Fe3O4@Bi composite photo-catalyst has stronger photocatalytic activity.
Embodiment 2:
It is carried out by the same step of 1 preparation process of embodiment, the difference is that the temperature setting of tube furnace is 400 in step (1)
DEG C and 500 DEG C prepare different charing carbon materials, and then synthesize C@Fe3O4@Bi composite photo-catalyst.
Embodiment 3:
It is carried out by the same step of 1 preparation process of embodiment, the difference is that the calcination time of tube furnace is set as in step (1)
20min and 60min prepares different charing carbon materials, and then synthesizes C@Fe3O4@Bi composite photo-catalyst.
Embodiment 4:
It is carried out by the same step of 1 preparation process of embodiment, the difference is that the heating rate of tube furnace is respectively in step (1)
4 DEG C/min, 6 DEG C/min to prepare different charing carbon materials, and then synthesize C@Fe3O4@Bi composite photo-catalyst.
Embodiment 5:
Carried out by the same step of 1 preparation process of embodiment, unlike substance in step (2) after KOH and charing matter
Amount synthesizes C Fe than being respectively 1:2.5 and 1:33O4@Bi composite photo-catalyst.
Embodiment 6:
It is carried out by the same step of 1 preparation process of embodiment, the difference is that the temperature setting of step (3) tube furnace is 600 DEG C
Different porous carbon samples is prepared with 800 DEG C, and then synthesizes C@Fe3O4@Bi composite photo-catalyst.
Embodiment 7:
It is carried out by the same step of 1 preparation process of embodiment, the difference is that the time of step (3) tube furnace is set as 50min
Different porous carbon samples is prepared with 120min, and then synthesizes C@Fe3O4@Bi composite photo-catalyst.
Embodiment 8:
It is carried out by the same step of 1 preparation process of embodiment, the difference is that the heating rate of step (3) tube furnace is respectively 4
DEG C/min, 6 DEG C/min, to prepare different porous carbon samples, and then synthesize C@Fe3O4@Bi composite photo-catalyst.
Embodiment 9:
It is carried out by the same step of 1 preparation process of embodiment, the difference is that the addition of five nitric hydrate bismuths measures in step (5)
1.44 g, 1.92g, 2.88g and 3.36g, to prepare different C@Fe3O4@Bi composite photo-catalyst investigates five nitric hydrate bismuths
Additional amount to C@Fe3O4The influence of@Bi composite photo-catalyst photocatalytic activity.
It is C@Fe that sample prepared by the application is demonstrated in Fig. 1 Fig. 2 really3O4@Bi composite photo-catalyst.It can be in Fig. 5
Find out, Bi photochemical catalyst is being that 350nm or so has stronger absorption close to UV light region and visible light region wavelength, is shown
Bi photochemical catalyst can simultaneously generate ultraviolet light and visible light and respond, and compound C@Fe later3O4@Bi composite photo-catalyst is can
Light-exposed region has stronger absorption.Under visible light illumination, the additional amount of different five nitric hydrate bismuths is to C@Fe3O4@Bi is multiple
The influence result of light combination catalyst degradation is as shown in figure 8, when the additional amount of five nitric hydrate bismuths is 2.4g, prepared sample
With preferable photocatalytic degradation tetracycline property.When five nitric hydrate bismuths additional amount be 1.44g, 1.92g, 2.88g and
When 3.36g, prepared sample all shows preferable activity.When the additional amount of five nitric hydrate bismuths is less than 2.4g, with
The increase of the additional amount of five nitric hydrate bismuths, C@Fe3O4The photocatalyst activity of@Bi composite photo-catalyst gradually increases, Dang Wushui
When closing the additional amount of bismuth nitrate greater than 2.4g, with the increase of the additional amount of five nitric hydrate bismuths, C@Fe3O4@Bi composite photocatalyst
The photocatalyst activity of agent is gradually reduced, it is contemplated that the photocatalytic activity of sample, the five nitric hydrate bismuths that the application chooses add
Enter when amount is 2.4g and prepares C@Fe3O4@Bi composite photo-catalyst.
Embodiment 10:
Carried out by the same step of 1 preparation process of embodiment, unlike be added without in step (5) porous carbon after modification and
Fe(NO3)39H2O investigates simple substance Bi photochemical catalyst photocatalytic activity, as a result as shown in figure 8, pure list to prepare Bi photochemical catalyst
Matter Bi photochemical catalyst photocatalytic activity is lower, and it is compound after C@Fe3O4The photocatalyst activity of@Bi composite photo-catalyst increases
Greatly, show that compound system is conducive to the promotion of photochemical catalyst catalytic degradation performance.
Embodiment 11:
It is carried out by the same step of 1 preparation process of embodiment, the difference is that the heating rate of step (5) tube furnace is respectively 4
DEG C/min, 6 DEG C/min, to prepare different C@Fe3O4@Bi composite photo-catalyst.
Embodiment 12:
It is carried out by the same step of 1 preparation process of embodiment, the difference is that the temperature of step (5) tube furnace is respectively set to
300 DEG C, 400 DEG C and 600 DEG C, to prepare different C@Fe3O4@Bi composite photo-catalyst, as a result as shown in fig. 7, calcination temperature is
The C@Fe prepared at 500 DEG C3O4The degradation activity highest of@Bi composite photo-catalyst, the C@prepared when calcination temperature is 600 DEG C
Fe3O4The Photocatalytic activity of@Bi composite photo-catalyst is less than the composite photo-catalyst prepared when calcination temperature is 400 DEG C, examines
Consider the activity of sample, the reasonable utilization of reactant and economic value, it is 500 DEG C of preparation C@that the application, which chooses calcination temperature,
Fe3O4@Bi composite photo-catalyst.
Embodiment 13:
C@Fe is investigated by (4) step in embodiment 13O45 circulation photocatalytic degradation tetracyclines of@Bi composite photo-catalyst are anti-
The photochemical stability of raw element waste water, the results are shown in Figure 10, as can be seen from Figure 10 after 5 circulations, C@Fe3O4@Bi is multiple
The photocatalytic activity of light combination catalyst does not significantly decrease, and illustrates C Fe prepared by the application3O4@Bi composite photo-catalyst
With good photochemical stability, recycling that can be multiple.
Fig. 1 is different C@Fe3O4The XRD diagram of@Bi composite photo-catalyst, it can be seen from the figure that prepared complex light is urged
2 θ=22.6 ° of diffraction maximum of agent, 27.2 °, 38.1 °, 39.7 ° and 48.8 ° respectively with Bi (JCPDS No. in standard card valut
(003), (012), (104), (110) 44-1246) are corresponding with (202) crystal face, and the circle of grey represents Fe in figure3O4Spread out
Peak is penetrated, illustrates successfully to have synthesized C@Fe by a calcination method3O4@Bi composite photo-catalyst.By can be seen that five in figure
The difference of the additional amount of nitric hydrate bismuth, to C@Fe3O4The diffraction maximum of@Bi composite photo-catalyst does not have an impact.It is not sent out in figure
Existing miscellaneous peak, shows C@Fe3O4The purity with higher of@Bi composite photo-catalyst.
Fig. 2 is the XPS spectrum figure of sample, and figure a is C@Fe3O4The XPS of@Bi composite photo-catalyst schemes, it can be concluded that closing from figure
At composite photo-catalyst in there are the elements such as C, O, Fe and Bi, show that composite photo-catalyst is successfully synthesized, scheme b, c and d
Middle is the high power XPS figure of Bi 4f, Fe 2p and C 1s respectively.It spins corresponding to Bi 4f at peak at 159.1eV and 164.4eV
Orbit splitting peak, i.e. Bi 4f7/2 and 5/2 correspond to Bi-O key, are mainly derived from some quilts on composite photo-catalyst surface
The substance of air oxidation, and there are two acromions of 157.1eV and 162.5eV in the low combination energy side of Bi 4f 7/2 and 5/2,
It corresponds mainly to metal Bi, schemes the peak Fe 2p in c and shows to contain Fe in the composite photo-catalyst synthesized3O4, scheme two of C1s in d
The combination at a peak can be respectively 284.5eV and 288.9eV, correspond to sp2-C and C=O key.
Fig. 3 is that the SEM and TEM of different samples scheme, as can be seen that being successfully prepared beautiful based on biomass from a, b figure
The porous carbon of meter Xin, the specific surface data (Fig. 4) in conjunction with different samples are available, the main about 2nm or so in the aperture of porous carbon.
Fig. 4 is the adsorption/desorption curve figure of porous carbon, and illustration is pore-size distribution, it can be seen from the figure that this isothermal is bent
Line is the combination of I type (typical micropore carbon atom) and IV type (characteristic of mesoporous material), this shows a large amount of micropore and mesoporous
Presence, this is consistent with TEM result, the application preparation porous carbon specific surface area reach 893.4m3g-1, table is compared after compound
Area falls to 58.92m3g-1, thus further illustrate C@Fe3O4@Bi composite photo-catalyst is successfully synthesized.
Fig. 6 is the absorption figure of different synthetic samples, it can be seen from the figure that porous carbon adsorptivity is preferable, pure simple substance Bi light
The adsorptivity of catalyst is poor, and adsorbance is smaller.When Bi photochemical catalyst and C@Fe3O4After compound, the absorption of composite photo-catalyst
Property is promoted, and with the increase of the amount of five nitric hydrate bismuths, the adsorbance of composite photo-catalyst is gradually reduced.
Fig. 9 is that C@Fe after different capturing agents is added3O4@Bi composite photo-catalyst photocatalytic degradation Fourth Ring sketch map, can from figure
To find out, compared with capturing agent is not added, after different capturing agents is added, the light degradation tetracycline performance of composite photo-catalyst has
Declined, shown in this application, hydroxyl radical free radical, during hole and superoxide radical are photocatalytic degradation tetracycline
Active specy.Triethanolamine capturing agent is added can inhibit the activity of composite photo-catalyst to the greatest extent later, show this Shen
For composite photo-catalyst that please be prepared during photocatalyst for degrading tetracycline, hole is main active specy.
Claims (9)
1. a kind of C@Fe based on biomass porous carbon3O4The preparation method of@Bi composite photo-catalyst, which is characterized in that including such as
Lower step:
The preparation of step 1, porous carbon: corncob is washed with deionized three times first, dries, will dry after removing surface impurity
Corncob after dry is placed in tube furnace, in N2It is calcined under atmosphere, taking-up is cooled to room temperature to the end of reacting, obtain product A；
KOH is weighed, deionized water is added, obtains KOH solution, product A is added in KOH solution, stirs, is then filtered
Obtained material is put into baking oven and dries, and is denoted as product B；
Product B is placed in tube furnace, in N2It is calcined under atmosphere, taking-up is cooled to room temperature to the end of reacting, uses deionized water
Washing, resulting sample is porous carbon；
The preparation of porous carbon after step 2, modification: the porous carbon that step 1 is obtained is immersed in HNO3In, it is carried out under magnetic agitation
Water bath with thermostatic control reaction, solid mixture after completion of the reaction filtered and washed, until cleaning solution is in neutrality, is put into vacuum baking
It is dried in case, gained sample is the porous carbon after modification；
Step 3, C@Fe3O4The preparation of@Bi composite photo-catalyst: the porous carbon after modification obtained in step 2 is added to second two
It in alcohol, mixes, five nitric hydrate bismuths is then added, ultrasound mixes, and then carries out magnetic agitation, and nine hydrations are added after stirring
Ferric nitrate continues to stir, and stirring terminates, and obtains mixture D, is put into baking oven and dries；When preparing mixture D, used
Modification after porous carbon, five nitric hydrate bismuths, Fe(NO3)39H2O and ethylene glycol amount ratio be 0.3 g:1.44 g ~
3.36 g:0.8 g:20mL；The mixture D of drying is placed in tube furnace, in N2It is calcined under atmosphere, last gained sample is
C@Fe3O4@Bi composite photo-catalyst.
2. a kind of C@Fe based on biomass porous carbon according to claim 13O4The preparation side of@Bi composite photo-catalyst
Method, which is characterized in that in step 1, heating rate when calcining corncob is 4 ~ 6 DEG C/min, and calcination temperature is 400 ~ 500 DEG C,
Calcination time is 20 ~ 60min.
3. a kind of C@Fe based on biomass porous carbon according to claim 13O4The preparation side of@Bi composite photo-catalyst
Method, which is characterized in that in step 1, the concentration of KOH solution is 1 mol/L, the quality of KOH and the matter of the resulting product A of step 1
Amount is than being 1:2.5 ~ 1:3.5.
4. a kind of C@Fe based on biomass porous carbon according to claim 13O4The preparation side of@Bi composite photo-catalyst
Method, which is characterized in that in step 1, heating rate when calcined product B is 4 DEG C ~ 6 DEG C/min, and calcination temperature is 600 ~ 800 DEG C,
Calcination time is 50 ~ 120 min.
5. a kind of C@Fe based on biomass porous carbon according to claim 13O4The preparation side of@Bi composite photo-catalyst
Method, which is characterized in that in step 2, the HNO3Concentration be 63 wt.%, water bath with thermostatic control reaction temperature is 80 when magnetic agitation
DEG C, the water bath with thermostatic control reaction time is 3h.
6. a kind of C@Fe based on biomass porous carbon according to claim 13O4The preparation side of@Bi composite photo-catalyst
Method, which is characterized in that in step 3, the magnetic agitation time is 1h.
7. a kind of C@Fe based on biomass porous carbon according to claim 13O4The preparation side of@Bi composite photo-catalyst
Method, which is characterized in that in step 3, the heating rate of the calcining is 4 DEG C ~ 6 DEG C/min, and calcination temperature is 300 ~ 600 DEG C, is forged
The burning time is 1 ~ 3h.
8. a kind of C@Fe based on biomass porous carbon according to claim 13O4The preparation side of@Bi composite photo-catalyst
Method, which is characterized in that in step 1 ~ 3, the drying temperature is 60 DEG C.
9. a kind of C@Fe based on biomass porous carbon according to claim 13O4The preparation side of@Bi composite photo-catalyst
Method, which is characterized in that the C@Fe of the method preparation3O4@Bi composite photo-catalyst is used for photocatalytic degradation tetracycline.
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| CN108479756A (en) * | 2018-03-05 | 2018-09-04 | 江苏大学 | A kind of Bi based on the carbon-based modification of phoenix tree leaf biomass2WO6The Preparation method and use of composite photo-catalyst |
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