CN106268891A - A kind of lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material, prepare and apply - Google Patents
A kind of lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material, prepare and apply Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 107
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 103
- 239000004065 semiconductor Substances 0.000 title claims abstract description 77
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 74
- 230000008878 coupling Effects 0.000 title claims abstract description 73
- 238000010168 coupling process Methods 0.000 title claims abstract description 73
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 73
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 28
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000003756 stirring Methods 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000007605 air drying Methods 0.000 claims abstract description 10
- 150000001621 bismuth Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 108
- 239000000243 solution Substances 0.000 claims description 75
- 239000011259 mixed solution Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 241000233948 Typha Species 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- -1 potassium halide Chemical class 0.000 claims description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims description 7
- 239000010865 sewage Substances 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 3
- 238000005255 carburizing Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 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 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 44
- 238000007146 photocatalysis Methods 0.000 abstract description 41
- 238000006731 degradation reaction Methods 0.000 abstract description 15
- 238000001035 drying Methods 0.000 abstract description 9
- 238000011068 loading method Methods 0.000 abstract description 8
- 240000001398 Typha domingensis Species 0.000 abstract 1
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 31
- 229910052794 bromium Inorganic materials 0.000 description 27
- 229910052801 chlorine Inorganic materials 0.000 description 26
- 229910052740 iodine Inorganic materials 0.000 description 26
- 239000002131 composite material Substances 0.000 description 19
- 238000002835 absorbance Methods 0.000 description 15
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 15
- 229940043267 rhodamine b Drugs 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 229910052724 xenon Inorganic materials 0.000 description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229960000935 dehydrated alcohol Drugs 0.000 description 7
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009432 framing Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- YWWMUOCIAHODNK-UHFFFAOYSA-N CC(C)(C)CCCCCCCCCCCCCCCCl.N Chemical compound CC(C)(C)CCCCCCCCCCCCCCCCl.N YWWMUOCIAHODNK-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical group [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
-
- B01J35/39—
-
- B01J35/50—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- 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
- 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 discloses a kind of lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material, prepares and apply.Step is as follows: the cattail after air-drying is placed in tube furnace, and carbonization a period of time under inert gas shielding, the black powder of collection is lotus-like porous carbon.Lotus-like for certain mass porous carbon added alcoholic solution and bismuth salt and stirs, being designated as solution 1；Halogenide is dissolved in the solution of identical alcohol simultaneously, is designated as solution 2；Solution 2 after stirring is rapidly joined in solution 1, and continuously stirred a period of time；Above-mentioned mixed liquid loading microwave reactor different capacity is carried out microwave reaction 1 190 minutes；It is centrifuged out the precipitate washing post-drying of reaction, obtains lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material.Finally, weigh catalysis material and add certain density organic pollution, put into photocatalysis instrument and carry out light degradation reaction, the performance of lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material can be recorded.
Description
Technical field
The present invention relates to a kind of lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material, prepare and apply, be one
Plant the ecological restoration material of organic pollution in visible light photocatalytic degradation water body environment, belong to material preparation and environment remediation
Field.
Background technology
For a long time, various commercial production need to use substantial amounts of chemical raw material, and then produces the water of a large amount of high concentration
Body pollution thing.These sewage often contain the most poisonous organic substance, the most treated or process halfway discharge,
Through water resource being caused serious pollution.Because these organic pollutions are difficult to be degraded, there are the strongest toxicity and carcinogenecity, therefore
It has become as the big problem of harm human survival.Therefore, the method removing Organic Pollutants In Water is found to have become as urgently
Problem in science to be solved and practical problem.
Photocatalysis oxidation reaction is using semi-conducting material as photocatalyst, it is possible to be degraded to by the oxidation operation of difficult degradation
Low toxicity or the little molecule of nontoxic aliphatic or direct mineralising are CO2And H2The inorganic matters such as O, are that the green of a kind of great potential is senior
Oxidation technology.Conductor photocatalysis material stable, cheap, high performance is the core of photocatalysis technology.TiO2There is oxidability
By force, it is catalyzed the advantages such as activity is high, stable, nontoxic, but, TiO2A kind of intrinsic wide bandgap semiconductor, its quantum efficiency low with
The difficult problem that solar energy utilization ratio is low governs TiO all the time2The large-scale industrial application of catalysis material.Therefore, research worker one
Directly it is actively working to new and effective, the exploitation of visible ray (accounting for sunlight gross energy 43%) responsible photocatalytic material.
Bismuth based semiconductor is as the important component part of catalysis material, and its most representational compound surely belongs to BiOX (X
=Cl, Br, I) class novel lamellar semi-conducting material.Bismuth-containing compound has inexpensively, the feature of environmental protection, is recently increasingly becoming light and urges
One focus of agent research and development.BiOX photocatalyst has good catalytic performance, and they are all deposited in visible region
Significantly absorbing.Its reason is, BiOX compound BiOX (X=Cl, Br, I) have along c-axis direction ion layer and
Bi2O2The layered crystal structure of the alternately arranged composition of layer, is the important layer structure quasiconductor of a class, this have open and
The layered crystal structure of indirect transition beneficially photo-generate electron-hole is to efficiently separating and electric charge transfer.Wherein, BiOBr and
The energy gap of BiOI narrower can directly by excited by visible light, but its photo-generate electron-hole to compound fast so that quantum efficiency
Low, and pure BiOX (X=Cl, Br, I) is not sufficiently stable (P.Wang, Angew.Chem.Int.Ed.2008,47,7931-7933；
X.Wang, Nature Mater.2009,8,76-80.), limit their actual application.
Although BiOX (X=Cl, Br, I) is considered a new generation high-performance environment-friendly, visible light-responded photocatalysis material
Material, but nevertheless suffer from the restriction of following three big key scientific problems: and (1) monomer BiOX (X=Cl, Br, I) quantum efficiency is low.
BiOX (X=Cl, Br, I) is although unique layer structure and indirect band gap transition pattern beneficially photo-generate electron-hole are to having
Effect separates and shifts with electric charge, but in monomer BiOX (X=Cl, Br, I), light induced electron and hole yet suffer from transition process
Bigger recombination probability, greatly reduces its photocatalysis efficiency so that it is contain hardly degraded organic substance or organic processing some
During the industrial wastewater that substrate concentration is higher, amount is bigger, it is difficult to meet and use requirement.(2) broad-band gap BiOX (X=Cl, Br) is to the sun
Energy utilization rate is low.Broad-band gap BiOCl is only to ultraviolet light response, and BiOBr is limited in scope to visible light-responded, although BiOI is to visible
Light has stronger absorption, but provides the iodine salt of I-, as NaI, KI are expensive, is unfavorable for the large-scale application of BiOI.Cause
How this, expand broad-band gap BiOX (X=Cl, Br) response range to visible ray, improves quantum yield, becomes BiOX (X=
Cl, Br, I) one of key issue needing solution badly in material.(3) BiOX (X=Cl, Br, I) nano-photocatalyst is immobilized: mesh
Before, synthesized different microstructure form BiOX (X=Cl, Br, I) are powder body material.Although powder body catalyst is at reactant liquor
Middle good dispersion is big with reactant liquor contact area, catalytic efficiency is high, but existence is easily reunited, is difficult to recycle and reuse and two
The problem of secondary pollution.Therefore, how BiOX (X=Cl, Br, I) nano structured unit introducing suitable carrier will realize catalysis
Agent is immobilized, has become as the another key issue in the research of BiOX (X=Cl, Br, I) catalysis material.
The limitation developed in view of current catalysis material, the relevant organic research of photocatalytic degradation is still in experiment
The room stage.Although oneself proves that most Organic substance can successfully be degraded, but is still restricted (1. by above-mentioned three big key issues
Quantum efficiency is low；2. broad-band gap is low to solar energy utilization ratio；3. the immobilized problem of nano-photocatalyst).Therefore technique is not yet
Can well carry out actual application.Therefore, preparation has simple, environmental friendliness, microfabricated tunable control and is suitable to large-scale production
While the preparation method of advantage, can effectively solve again above-mentioned three big critical problem in science, for photocatalyst material
Development with application most important.
Summary of the invention
Present invention aim to address tradition photocatalytic degradation material energy gap big, quantum efficiency is low, stability not
The problems such as good, visible light activity is weak, it is provided that a kind of based on lotus-like micro-nano hierarchy porous carbon materials and BiOX (X=Cl,
Br, I) preparation method of compound high efficiency photocatalysis degrading composite and use it for processing making of Organic Pollutants In Water
Use method.
The technical scheme is that to obtain the photocatalytic degradation composite that novel Cheap highly effective easily reclaims, need
Choose low cost, the carrier of easily preparation, and on this carrier loaded optic catalyst to reach organic contamination in efficient degradation water body
The purpose of thing, studies its use condition and recovery method, with obtain novel, low cost, the most easily reclaim, reusable
Organic wastewater photocatalytic degradation composite.Cattail base porous carbon materials not only remains the framing structure of cattail intrinsic,
And have the pore structure of the lotus-like porous carbon that is interconnected/oxyhalogen bismuth semiconductors coupling catalysis material-micro-nano classification, because of
This, it can be as the carrier of photocatalyst, and the doping body of supported on carriers nanometer BiOX (X=Cl, Br, I) is prepared as efficiency light
Catalytic degradation composite, for water body environment reparation.
A kind of lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material, uses microwave irradiation to be prepared tool
Body comprises the following steps:
(1) cattail after air-drying is placed in tube furnace, carbonization under inert gas shielding, the black powder collected after cooling
End is lotus-like porous carbon；
(2) lotus-like porous carbon is added in ethanol and ethylene glycol mixed solution stirring, is subsequently adding bismuth salt, is designated as molten
Liquid 1；The halogenide of identical mol ratio is dissolved in ethanol and ethylene glycol mixed solution simultaneously, is designated as solution 2；
(3) quickly stir under solution 1 and 2 room temperature；Solution 2 after stirring is rapidly joined in solution 1, and at room temperature continues
Continuous stirring；
(4) above-mentioned mixed liquid is loaded microwave reactor, use different capacity to carry out microwave reaction；
(5) treat that solution naturally cools to room temperature, after being centrifuged out precipitate, use distilled water and absolute ethanol washing, then very
Dry in empty drying baker, obtain lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material.
Further, the lotus-like porous carbon carburizing temperature obtained in step (1) is 550 DEG C-1200 DEG C, and carbonization time is
0.5-10 hour.
Further, in step (2), the volume ratio of ethanol and ethylene glycol mixed solution is 1:0.1～10.
Further, in step (2), halogenide is potassium halide or sodium halide.Potassium halide is KI, the one in KCl, KBr；Halogen
Change sodium is NaI, the one in NaCl, NaBr.
Further, in step (2), halogenide can also be surfactant-based cetyl trimethylammonium bromide or ten
Six alkyl trimethyl ammonium chlorides.
Further, in step (2), bismuth salt is Bi (NO3)3·5H2O or BiCl3。
Further, in step (4), the reaction power of microwave reactor is 100～1500W, and the response time of microwave reaction is
1～90min.
Lotus-like porous carbon of the present invention/oxyhalogen bismuth semiconductors coupling catalysis material is used for processing in sewage difficult fall
Solve organic pollution.Detailed process is:
(1) weigh the lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material of certain mass, pour into containing organic
In the photocatalysis apparatus of waste water, illumination a period of time, carry out light-catalyzed reaction；
(2) test by lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling photocatalysis material according to absorbance or additive method
Concentration after material degraded, until the content of organics in sewage is up to standard.
The described organic pollution in organic sewage is methyl orange, rhodamine B, phenol and polycyclic aromatic hydrocarbon, bisphenol-A etc..
The present invention utilizes the cattail of low cost to be prepared as lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material
Prepare novel high-performance visible light photocatalytic degradation composite process Organic Pollutants In Water.Compared with existing technology,
Have an advantage in that:
(1) present invention is the system of a kind of lotus-like porous carbon/BiOX (X=Cl, Br, I) semiconductors coupling catalysis material
Preparation Method, its raw material cattail material source enriches, is conveniently easy to get, with low cost, and preparation flow is simple, low-carbon environment-friendly, can
Realize large-scale production；
(2) present invention provides a kind of lotus-like porous carbon/BiOX (X=Cl, Br, I) semiconductors coupling catalysis material
Preparation method, this composite good stability, catalytic capability are strong；
(3) composite prepared by the present invention, it is used for processing persistent organic pollutants in sewage, and effect is notable.
Principle is explained:
BiOX (X=Cl, Br, I) is combined with porous carbon materials, is possible not only to improve the stability of photocatalyst, and
The absorption property that porous carbon materials is superpower can be utilized, reduce the reaction distance of organic pollution and BiOX (X=Cl, Br, I),
Thus increase the efficiency of photocatalytic degradation.The perfume (or spice) that applicant's direct carbonization is withered finds after littering, cattail base porous carbon materials,
Not only remain the framing structure of cattail intrinsic, and there is the pore structure of the lotus-like-micro-nano classification that is interconnected, greatly
Add the specific surface area of material.This porous carbon materials is combined into lotus-like porous carbon/BiOX with BiOX (X=Cl, Br, I)
(X=Cl, Br, I) micro-nano hierarchical composite material, may be used for photocatalytic degradation Organic Pollutants In Water.With BiOX (X=
Cl, Br, I) in recombination process, this pore passage structure being interconnected makes the BiOX (X=Cl, Br, I) can be well into duct
It is combined with porous carbon, so that this composite has good " cooperative effect ".In photocatalytic process, porous carbon is superpower
Organic pollution can firmly be adsorbed on surface and internal gutter by absorbability, considerably increase BiOX (X=Cl, Br, I) with
The contact area of organic pollution, also can greatly reduce the distance of reaction simultaneously.Therefore, this lotus-like porous carbon and BiOX
(X=Cl, Br, I) high efficiency photocatalysis performance combines, and its " Synergy " being had enhances its photocatalysis performance.
Specific surface area that lotus-like porous carbon is high and lotus-like macropore, to the active adsorption of reactant molecule and to light
Efficiently separating of raw electron-hole pair is the three big factors that improve of composite property.Composite two is alternate defines C-Bi
The combination of chemical bond, this chemical bond is formed such that the structure of lotus-like porous carbon is more complete, greatly improves compound
The photocatalysis performance of material.It is hopeful to promote the lotus-like porous carbon of cattail base and bismuth based compound composite thereof to protect at environment
Protect, Optical Electro-Chemistry conversion, the application in the field such as photocatalytic water.
Accompanying drawing explanation
Fig. 1 be lotus-like porous carbon obtained by embodiment 1/BiOI semiconductors coupling catalysis material (a) SEM figure and
(b) partial enlarged drawing.
Fig. 2 is the XRD figure spectrum of lotus-like porous carbon obtained by embodiment 1/BiOI semiconductors coupling catalysis material.
Fig. 3 is that lotus-like porous carbon/BiOI semiconductors coupling catalysis material (a) ultraviolet-visible obtained by embodiment 1 overflows
Reflection collection of illustrative plates and (b) band gap magnitude collection of illustrative plates of correspondence thereof.
Fig. 4 is the photocatalysis collection of illustrative plates of lotus-like porous carbon obtained by embodiment 1/BiOI semiconductors coupling catalysis material.
Fig. 5 is the degradation rate collection of illustrative plates of lotus-like porous carbon obtained by embodiment 1/BiOI semiconductors coupling catalysis material.
Fig. 6 be lotus-like porous carbon obtained by embodiment 2/BiOBr semiconductors coupling catalysis material SEM figure (a) and
Partial enlarged drawing (b).
Fig. 7 is the photocatalysis collection of illustrative plates of lotus-like porous carbon obtained by embodiment 2/BiOBr semiconductors coupling catalysis material.
Fig. 8 is the degradation rate collection of illustrative plates of lotus-like porous carbon obtained by embodiment 2/BiOBr semiconductors coupling catalysis material.
Fig. 9 is lotus-like porous carbon/BiOI obtained by embodiment 30.5Br0.5The SEM figure of semiconductors coupling catalysis material
(a) and partial enlarged drawing (b).
Figure 10 is lotus-like porous carbon/BiOI obtained by embodiment 30.5Br0.5The light of semiconductors coupling catalysis material is urged
Change collection of illustrative plates.
Figure 11 is lotus-like porous carbon/BiOI obtained by embodiment 30.5Br0.5The degraded of semiconductors coupling catalysis material
Rate collection of illustrative plates.
Figure 12 be lotus-like porous carbon obtained by embodiment 4/BiOCl semiconductors coupling catalysis material SEM figure (a) and
Partial enlarged drawing (b).
Figure 13 is the photocatalysis figure of lotus-like porous carbon obtained by embodiment 4/BiOCl semiconductors coupling catalysis material
Spectrum.
Figure 14 is the degradation rate figure of lotus-like porous carbon obtained by embodiment 4/BiOCl semiconductors coupling catalysis material
Spectrum.
Figure 15 is lotus-like porous carbon/BiOI obtained by embodiment 50.5Cl0.5The SEM figure of semiconductors coupling catalysis material
(a) and partial enlarged drawing (b).
Figure 16 is lotus-like porous carbon/BiOI obtained by embodiment 50.5Cl0.5The light of semiconductors coupling catalysis material is urged
Change collection of illustrative plates.
Figure 17 is lotus-like porous carbon/BiOI obtained by embodiment 50.5Cl0.5The degraded of semiconductors coupling catalysis material
Rate collection of illustrative plates.
Figure 18 is lotus-like porous carbon/BiOI obtained by embodiment 60.2Br0.8The SEM figure of semiconductors coupling catalysis material
(a) and partial enlarged drawing (b).
Figure 19 is lotus-like porous carbon/BiOI obtained by embodiment 60.2Br0.8The light of semiconductors coupling catalysis material is urged
Change collection of illustrative plates.
Figure 20 is lotus-like porous carbon/BiOI obtained by embodiment 60.2Br0.8The degraded of semiconductors coupling catalysis material
Rate collection of illustrative plates.
Figure 21 is lotus-like porous carbon/BiOBr obtained by embodiment 70.5Cl0.5The SEM of semiconductors coupling catalysis material
Figure.
Figure 22 is lotus-like porous carbon/BiOBr obtained by embodiment 70.5Cl0.5The light of semiconductors coupling catalysis material is urged
Change collection of illustrative plates.
Figure 23 is lotus-like porous carbon/BiOBr obtained by embodiment 70.5Cl0.5The degraded of semiconductors coupling catalysis material
Rate collection of illustrative plates.
Detailed description of the invention
Utilize cattail base porous carbon materials to remain the framing structure of cattail intrinsic, and there is the Rhizoma Nelumbinis that is interconnected
The feature of the pore structure of shape-micro-nano classification.Simple process preparation is used to have the hole knot that is interconnected with cattail for raw material
The 3D porous carbon materials of structure, this pore passage structure being interconnected make BiOX (X=Cl, Br, I) can well into duct with
Porous carbon is combined, so that this composite plays its " Synergy ", prepares reusable, efficient novel visible
Photocatalytic degradation composite.For degradable organic pollutant, reach the purpose of pollution control of water.
Embodiment 1
1. prepared by material:
(1) cattail after air-drying is placed in tube furnace, carbonization a period of time under inert gas shielding, collects after cooling
Black powder is lotus-like porous carbon.
(2) it is added to the lotus-like porous carbon of 36mg in 20ml ethanol and ethylene glycol mixed solution beaker stirs 30 points
Clock (wherein ethanol 8ml, ethylene glycol 12ml), is subsequently adding the Bi (NO of 3m mol (1.4553g)3)3·5H2O, is designated as solution 1；
The KI (0.4980g) of 3m mol is dissolved in (wherein ethanol 8ml, ethylene glycol in 20ml ethanol and ethylene glycol mixed solution simultaneously
12ml), solution 2 it is designated as；
(3) 30min is quickly stirred under solution 1 and 2 room temperature；Solution 2 after stirring is rapidly joined in solution 1, and in room
60min is quickly stirred under temperature；
(4) above-mentioned mixed liquid loading microwave reactor 500W is carried out microwave reaction 50 minutes；
(5) solution after microwave reaction naturally cools to room temperature, is centrifuged out precipitate and with distilled water and dehydrated alcohol
Respectively wash secondary, dry in the drying baker of 60 DEG C the most again, obtain lotus-like porous carbon/iodine oxygen bismuth semiconductors coupling photocatalysis material
Material.
2. materials application:
(1) weigh lotus-like porous carbon/BiOI semiconductors coupling catalysis material 10mg, pour in photocatalysis bottle；
(2) measure the rhodamine B solution 50ml of configured good 10mg/L, pour in above-mentioned photocatalysis bottle；
(3) mixed solution is loaded in photocatalysis instrument, quickly stir, secretly adsorb 60min so that it is reach adsorption equilibrium；
(4) by syringe draw solution 4ml, label lucifuge store；
(5) open 500W xenon lamp, and start timing, repeated process in (4) every 10 minutes, until sampling 120 minutes is
Only；
(6) sample of taking-up is centrifuged, takes supernatant with Dispette and instill in cuvette, and use ultraviolet-visible
Absorbance measured by spectrophotometer；
(7) the lotus-like porous carbon/BiOI semiconductors coupling catalysis material of preparation is calculated to organic dirt according to absorbance
The degradation rate of dye thing rhodamine B.
Fig. 1 is the SEM figure of sample obtained by embodiment 1, it can be seen that BiOI is grown in the form of sheet
The surface of lotus-like porous carbon.
Fig. 2 is the XRD figure spectrum of sample obtained by embodiment 1, and 2 θ angles have diffraction maximum to divide at 29.65 °, 45.38 °, 55.15 °
The main crystal face such as corresponding (102), (200), (212), not consistent with BiOI standard spectrogram (JCPDS No.10-0445), wherein
2 θ angles are maximum at 29.65 ° of corresponding diffraction peak intensities；And 2 θ angles 31.59 °, 66.23 °, 75.23 ° of corresponding diffraction maximums be C
Diffraction maximum.This shows really to have synthesized lotus-like porous carbon/BiOI semiconductors coupling catalysis material.
Fig. 3 (a) is the UV-Vis DRS spectrum of this composite, as seen from the figure this composite 400～
There is stronger absorption the visible region of 600nm.By UVDRS collection of illustrative plates according to formula (ahv)1/2=A (hv-Eg), with (ahv)1/2Right
Hv maps, and obtains figure (b).From (b) figure, the band gap of composite has the most significantly decline (pure BiOI than pure BiOI
Energy gap be 1.72～1.93).This shows that the composite prepared improves the absorption rate to visible ray, for improving
Visible light catalysis activity provides possibility.
Fig. 4 Fig. 5 is visible, and the lotus-like porous carbon/BiOI semiconductors coupling catalysis material of reaction preparation has good
Photocatalysis performance.Under 500W xenon lamp irradiates, 120 minutes these composites to the degradation rate of RhB up to more than 85%.
Embodiment 2
Prepared by material: the cattail after (1) air-dries is placed in tube furnace, carbonization a period of time under inert gas shielding, cold
The black powder collected the most afterwards is lotus-like porous carbon.
(2) it is added to the lotus-like porous carbon of 36mg in 20ml ethanol and ethylene glycol mixed solution beaker stirs 30 points
Clock (wherein ethanol 8ml, ethylene glycol 12ml), is subsequently adding the Bi (NO of 3m mol (1.4553g)3)3·5H2O, is designated as solution 1；
The KBr (0.3570g) of 3m mol is dissolved in (wherein ethanol 8ml, ethylene glycol in 20ml ethanol and ethylene glycol mixed solution simultaneously
12ml), solution 2 it is designated as；
(3) 30min is quickly stirred under solution 1 and 2 room temperature；Solution 2 after stirring is rapidly joined in solution 1, and in room
60min is quickly stirred under temperature；
(4) above-mentioned mixed liquid loading microwave reactor 600W is carried out microwave reaction 40 minutes；
(5) solution after microwave reaction naturally cools to room temperature, is centrifuged out precipitate and with distilled water and dehydrated alcohol
Respectively wash secondary, dry in the drying baker of 60 DEG C the most again, obtain lotus-like porous carbon/BiOBr semiconductors coupling photocatalysis material
Material
Materials application:
(1) weigh lotus-like porous carbon/BiOBr semiconductors coupling photocatalysis material 10mg, pour in photocatalysis bottle；
(2) measure the rhodamine B solution 50ml of configured good 10mg/L, pour in above-mentioned photocatalysis bottle；
(3) mixed solution is loaded in photocatalysis instrument, quickly stir, secretly adsorb 60min so that it is reach adsorption equilibrium；
(4) by syringe draw solution 4ml, label lucifuge store；
(5) open 500W xenon lamp, and start timing, repeated process in (4) every 10 minutes, until sampling 120 minutes is
Only；
(6) sample of taking-up is centrifuged, takes supernatant with Dispette and instill in cuvette, and use ultraviolet-visible
Absorbance measured by spectrophotometer；
(7) the lotus-like porous carbon/BiOBr semiconductors coupling catalysis material of preparation is calculated to organic dirt according to absorbance
The degradation rate of dye thing rhodamine B.
Embodiment 3
(1) cattail after air-drying is placed in tube furnace, carbonization a period of time under inert gas shielding, collects after cooling
Black powder is lotus-like porous carbon.
(2) it is added to the lotus-like porous carbon of 36mg in 20ml ethanol and ethylene glycol mixed solution beaker stirs 30 points
Clock (wherein ethanol 8ml, ethylene glycol 12ml), is subsequently adding the Bi (NO of 3m mol (1.4553g)3)3·5H2O, is designated as solution 1；
The KBr (0.1785g) of the KI (0.2490g) and 1.5m mol of 1.5m mol is dissolved in 20ml ethanol simultaneously and ethylene glycol mixing is molten
In liquid (wherein ethanol 8ml, ethylene glycol 12ml), it is designated as solution 2；
(3) 30min is quickly stirred under solution 1 and 2 room temperature；Solution 2 after stirring is rapidly joined in solution 1, and in room
60min is quickly stirred under temperature；
(4) above-mentioned mixed liquid loading microwave reactor 700W is carried out microwave reaction 35 minutes；
(5) solution after microwave reaction naturally cools to room temperature, is centrifuged out precipitate and with distilled water and dehydrated alcohol
Respectively wash secondary, dry in the drying baker of 60 DEG C the most again, obtain lotus-like porous carbon/BiOI0.5Br0.5Semiconductors coupling light is urged
Formed material
Materials application:
(1) lotus-like porous carbon/BiOI is weighed0.5Br0.5Semiconductors coupling catalysis material 10mg, pours photocatalysis bottle into
In；
(2) measure the rhodamine B solution 50ml of configured good 10mg/L, pour in above-mentioned photocatalysis bottle；
(3) mixed solution is loaded in photocatalysis instrument, quickly stir, secretly adsorb 60min so that it is reach adsorption equilibrium；
(4) by syringe draw solution 4ml, label lucifuge store；
(5) open 500W xenon lamp, and start timing, repeated process in (4) every 10 minutes, until sampling 120 minutes is
Only；
(6) sample of taking-up is centrifuged, takes supernatant with Dispette and instill in cuvette, and use ultraviolet-visible
Absorbance measured by spectrophotometer；
(7) the lotus-like porous carbon/BiOI of preparation is calculated according to absorbance0.5Br0.5Semiconductors coupling catalysis material pair
The degradation rate of organic pollution rhodamine B.
Embodiment 4
(1) cattail after air-drying is placed in tube furnace, carbonization a period of time under inert gas shielding, collects after cooling
Black powder is lotus-like porous carbon.
(2) the lotus-like porous carbon of 36mg is added to 20ml ethanol and ethylene glycol mixed solution stirs 30 minutes (wherein
Ethanol 8ml, ethylene glycol 12ml), it is subsequently adding the Bi (NO of 3m mol (1.4553g)3)3·5H2O, is designated as solution 1；Simultaneously by 3m
The KCl (0.225g) of mol is dissolved in 20ml ethanol and ethylene glycol mixed solution (wherein ethanol 8ml, ethylene glycol 12ml), is designated as molten
Liquid 2；
(3) 30min is quickly stirred under solution 1 and 2 room temperature；Solution 2 after stirring is rapidly joined in solution 1, and in room
60min is quickly stirred under temperature；
(4) above-mentioned mixed liquid loading microwave reactor 500W is carried out microwave reaction 50 minutes；
(5) solution after microwave reaction naturally cools to room temperature, is centrifuged out precipitate and with distilled water and dehydrated alcohol
Respectively wash secondary, dry in the drying baker of 60 DEG C the most again, obtain lotus-like porous carbon/BiOCl semiconductors coupling photocatalysis material
Material
Materials application:
(1) weigh lotus-like porous carbon/BiOCl semiconductors coupling catalysis material 10mg, pour in photocatalysis bottle；
(2) measure the rhodamine B solution 50ml of configured good 10mg/L, pour in above-mentioned photocatalysis bottle；
(3) mixed solution is loaded in photocatalysis instrument, quickly stir, secretly adsorb 60min so that it is reach adsorption equilibrium；
(4) by syringe draw solution 4ml, label lucifuge store；
(5) open 500W xenon lamp, and start timing, repeated process in (4) every 10 minutes, until sampling 120 minutes is
Only；
(6) sample of taking-up is centrifuged, takes supernatant with Dispette and instill in cuvette, and use ultraviolet-visible
Absorbance measured by spectrophotometer；
(7) the lotus-like porous carbon/BiOCl semiconductors coupling catalysis material of preparation is calculated to organic dirt according to absorbance
The degradation rate of dye thing rhodamine B.
Embodiment 5
(1) cattail after air-drying is placed in tube furnace, carbonization a period of time under inert gas shielding, collects after cooling
Black powder is lotus-like porous carbon.
(2) the lotus-like porous carbon of 36mg is added to 20ml ethanol and ethylene glycol mixed solution stirs 30 minutes (wherein
Ethanol 8ml, ethylene glycol 12ml), it is subsequently adding the Bi (NO of 3m mol (1.4553g)3)3·5H2O, is designated as solution 1；To simultaneously
The trimethyl cetyl chloride ammonium of 1.5m mol and the KI of 1.5m mol, be dissolved in 20ml ethanol and ethylene glycol mixed solution
(wherein ethanol 4ml, ethylene glycol 16ml), is designated as solution 2；
(3) 30min is quickly stirred under solution 1 and 2 room temperature；Solution 2 after stirring is rapidly joined in solution 1, and in room
60min is quickly stirred under temperature；
(4) above-mentioned mixed liquid loading microwave reactor 600W is carried out microwave reaction 40 minutes；
(5) solution after microwave reaction naturally cools to room temperature, is centrifuged out precipitate and with distilled water and dehydrated alcohol
Respectively wash secondary, dry in the drying baker of 60 DEG C the most again, obtain lotus-like porous carbon/BiOI0.5Cl0.5Semiconductors coupling light is urged
Formed material
Materials application:
(1) lotus-like porous carbon/BiOI is weighed0.5Cl0.5Semiconductors coupling catalysis material 10mg, pours photocatalysis bottle into
In；
(2) measure the rhodamine B solution 50ml of configured good 10mg/L, pour in above-mentioned photocatalysis bottle；
(3) mixed solution is loaded in photocatalysis instrument, quickly stir, secretly adsorb 60min so that it is reach adsorption equilibrium；
(4) by syringe draw solution 4ml, label lucifuge store；
(5) open 500W xenon lamp, and start timing, repeated process in (4) every 10 minutes, until sampling 120 minutes is
Only；
(6) sample of taking-up is centrifuged, takes supernatant with Dispette and instill in cuvette, and use ultraviolet-visible
Absorbance measured by spectrophotometer；
(7) the lotus-like porous carbon/BiOI of preparation is calculated according to absorbance0.5Cl0.5Semiconductors coupling catalysis material pair
The degradation rate of organic pollution rhodamine B.
Embodiment 6
(1) cattail after air-drying is placed in tube furnace, carbonization a period of time under inert gas shielding, collects after cooling
Black powder is lotus-like porous carbon.
(2) the lotus-like porous carbon of 36mg is added to 20ml ethanol and ethylene glycol mixed solution stirs 30 minutes (wherein
Ethanol 8ml, ethylene glycol 12ml), it is subsequently adding the Bi (NO of 3m mol (1.4553g)3)3·5H2O, is designated as solution 1；To simultaneously
The cetyl trimethylammonium bromide of the KI (0.225g) and 2.4m mol of 0.6m mol is dissolved in 20ml ethanol and ethylene glycol mixing
In solution (wherein ethanol 2ml, ethylene glycol 18ml), it is designated as solution 2；
(3) 30min is quickly stirred under solution 1 and 2 room temperature；Solution 2 after stirring is rapidly joined in solution 1, and in room
60min is quickly stirred under temperature；
(4) above-mentioned mixed liquid loading microwave reactor 700W is carried out microwave reaction 35 minutes；
(5) solution after microwave reaction naturally cools to room temperature, is centrifuged out precipitate and with distilled water and dehydrated alcohol
Respectively wash secondary, dry in the drying baker of 60 DEG C the most again, obtain lotus-like porous carbon/BiOI0.2Br0.8 semiconductors coupling light
Catalysis material
Materials application:
(1) lotus-like porous carbon/BiOI is weighed0.2Br0.8Semiconductors coupling catalysis material 10mg, pours photocatalysis bottle into
In；
(2) measure the rhodamine B solution 50ml of configured good 10mg/L, pour in above-mentioned photocatalysis bottle；
(3) mixed solution is loaded in photocatalysis instrument, quickly stir, secretly adsorb 60min so that it is reach adsorption equilibrium；
(4) by syringe draw solution 4ml, label lucifuge store；
(5) open 500W xenon lamp, and start timing, repeated process in (4) every 10 minutes, until sampling 120 minutes is
Only；
(6) sample of taking-up is centrifuged, takes supernatant with Dispette and instill in cuvette, and use ultraviolet-visible
Absorbance measured by spectrophotometer；
(7) the lotus-like porous carbon/BiOI of preparation is calculated according to absorbance0.2Br0.8Semiconductors coupling catalysis material pair
The degradation rate of organic pollution rhodamine B.
Embodiment 7
(1) cattail after air-drying is placed in tube furnace, carbonization a period of time under inert gas shielding, collects after cooling
Black powder is lotus-like porous carbon.
(2) it is added to the lotus-like porous carbon of 36mg in 20ml ethanol and ethylene glycol mixed solution stir 30 minutes (its
Middle ethanol 8ml, ethylene glycol 12ml), it is subsequently adding the Bi (NO of 3m mol (1.4553g)3)3·5H2O, is designated as solution 1；To simultaneously
The KCl (0.7456g) of 1m mol, the trimethyl cetyl chloride ammonium of 0.5m mol, the NaBr (0.1029g) of 1m mol and
The trimethyl cetyl ammonium bromide of 0.5m mol is dissolved in (wherein ethanol 5ml, second two in 20ml ethanol and ethylene glycol mixed solution
Alcohol 15ml), it is designated as solution 2；
(3) 30min is quickly stirred under solution 1 and 2 room temperature；Solution 2 after stirring is rapidly joined in solution 1, and in room
60min is quickly stirred under temperature；
(4) above-mentioned mixed liquid loading microwave reactor 1000W is carried out microwave reaction 25 minutes；
(5) solution after microwave reaction naturally cools to room temperature, is centrifuged out precipitate and with distilled water and dehydrated alcohol
Respectively wash secondary, dry in the drying baker of 60 DEG C the most again, obtain lotus-like porous carbon/BiOBr0.5Cl0.5Semiconductors coupling light
Catalysis material
Materials application:
(1) lotus-like porous carbon/BiOBr is weighed0.5Cl0.5Semiconductors coupling catalysis material 10mg, pours photocatalysis bottle into
In；
(2) measure the rhodamine B solution 50ml of configured good 10mg/L, pour in above-mentioned photocatalysis bottle；
(3) mixed solution is loaded in photocatalysis instrument, quickly stir, secretly adsorb 60min so that it is reach adsorption equilibrium；
(4) by syringe draw solution 4ml, label lucifuge store；
(5) open 500W xenon lamp, and start timing, repeated process in (4) every 10 minutes, until sampling 120 minutes is
Only；
(6) sample of taking-up is centrifuged, takes supernatant with Dispette and instill in cuvette, and use ultraviolet-visible
Absorbance measured by spectrophotometer；
(7) the lotus-like porous carbon/BiOBr0.5Cl0.5 semiconductors coupling catalysis material of preparation is calculated according to absorbance
Degradation rate to organic pollution rhodamine B.
Claims (10)
1. lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material, it is characterised in that use microwave irradiation to enter
Row preparation specifically includes following steps:
(1) cattail after air-drying is placed in tube furnace, carbonization under inert gas shielding, and the black powder collected after cooling is i.e.
For lotus-like porous carbon；
(2) lotus-like porous carbon is added in ethanol and ethylene glycol mixed solution stirring, is subsequently adding bismuth salt, is designated as solution 1；
The halogenide of identical mol ratio is dissolved in ethanol and ethylene glycol mixed solution simultaneously, is designated as solution 2；
(3) quickly stir under solution 1 and 2 room temperature；Solution 2 after stirring is rapidly joined in solution 1, and at room temperature continues to stir
Mix；
(4) above-mentioned mixed liquid is loaded microwave reactor, use different capacity to carry out microwave reaction；
(5) treat that solution naturally cools to room temperature, use distilled water and absolute ethanol washing after being centrifuged out precipitate, then do in vacuum
Dry in dry case, obtain lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material.
Lotus-like porous carbon the most according to claim 1/oxyhalogen bismuth semiconductors coupling catalysis material, it is characterised in that
The lotus-like porous carbon carburizing temperature obtained in step (1) is 550 DEG C-1200 DEG C, and carbonization time is 0.5-10 hour.
Lotus-like porous carbon the most according to claim 1/oxyhalogen bismuth semiconductors coupling catalysis material, it is characterised in that
In step (2), the volume ratio of ethanol and ethylene glycol mixed solution is 1:0.1～10.
Lotus-like porous carbon the most according to claim 1/oxyhalogen bismuth semiconductors coupling catalysis material, it is characterised in that
In step (2), halogenide is potassium halide or sodium halide.
Lotus-like porous carbon the most according to claim 4/oxyhalogen bismuth semiconductors coupling catalysis material, it is characterised in that
Potassium halide is KI, the one in KCl, KBr；Sodium halide is NaI, the one in NaCl, NaBr.
Lotus-like porous carbon the most according to claim 1/oxyhalogen bismuth semiconductors coupling catalysis material, it is characterised in that
In step (2), halogenide is to may also be surfactant-based cetyl trimethylammonium bromide or cetyl trimethyl chlorination
Ammonium.
Lotus-like porous carbon the most according to claim 1/oxyhalogen bismuth semiconductors coupling catalysis material, it is characterised in that
In step (2), bismuth salt is Bi (NO3)3·5H2O or BiCl3。
Lotus-like porous carbon the most according to claim 1/oxyhalogen bismuth semiconductors coupling catalysis material, it is characterised in that
In step (4), the reaction power of microwave reactor is 100～1500W, and the response time of microwave reaction is 1～90min.
9. the method that microwave irradiation prepares lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material, its feature
It is, comprises the following steps:
(1) cattail after air-drying is placed in tube furnace, and carbonization under inert gas shielding, carburizing temperature is 550 DEG C-1200
DEG C, carbonization time is 0.5-10 hour, and the black powder collected after cooling is lotus-like porous carbon；
(2) lotus-like porous carbon is added in ethanol and ethylene glycol mixed solution stirring, is subsequently adding bismuth salt, is designated as solution 1；
The halogenide of identical mol ratio is dissolved in ethanol and ethylene glycol mixed solution simultaneously, is designated as solution 2；Described ethanol and ethylene glycol mix
The volume ratio closing solution is 1:0.1～10；Described halogenide is potassium halide or sodium halide or surfactant cetyl front three
Base ammonium bromide or hexadecyltrimethylammonium chloride；Bismuth salt is Bi (NO3)3·5H2O or BiCl3；
(3) quickly stir under solution 1 and 2 room temperature；Solution 2 after stirring is rapidly joined in solution 1, and at room temperature continues to stir
Mix；
(4) above-mentioned mixed liquid is loaded microwave reactor, use different capacity to carry out microwave reaction, microwave reactor
Reaction power is 100～1500W, and the response time of microwave reaction is 1～90min；
(5) treat that solution naturally cools to room temperature, use distilled water and absolute ethanol washing after being centrifuged out precipitate, then do in vacuum
Dry in dry case, obtain lotus-like porous carbon/oxyhalogen bismuth semiconductors coupling catalysis material.
10. the lotus-like porous carbon described in claim 1/oxyhalogen bismuth semiconductors coupling catalysis material is used for processing in sewage difficulty
Degradable organic pollutant.
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| CN107349903A (en) * | 2017-08-29 | 2017-11-17 | 扬州大学 | A kind of preparation method and applications of porous carbon ecological restoration material |
| CN108607583A (en) * | 2018-06-11 | 2018-10-02 | 北京北林先进生态环保技术研究院有限公司 | A kind of carbon-based oxyhalogen bismuth composite catalyst of photocatalytic degradation volatile organic matter and its preparation method and application |
| CN110422905A (en) * | 2019-09-05 | 2019-11-08 | 太原师范学院 | A method of BiOCl catalytic eliminating bisphenol-A is loaded using coke |
| CN113289647A (en) * | 2021-05-12 | 2021-08-24 | 南京师范大学 | Biochar-doped BiOBrxCl1-xPhotocatalyst, preparation method and application |
| CN115382555A (en) * | 2022-09-26 | 2022-11-25 | 青岛理工大学 | Bi 2 O 3 Foam Ni and microwave radiation preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107349903A (en) * | 2017-08-29 | 2017-11-17 | 扬州大学 | A kind of preparation method and applications of porous carbon ecological restoration material |
| CN108607583A (en) * | 2018-06-11 | 2018-10-02 | 北京北林先进生态环保技术研究院有限公司 | A kind of carbon-based oxyhalogen bismuth composite catalyst of photocatalytic degradation volatile organic matter and its preparation method and application |
| CN110422905A (en) * | 2019-09-05 | 2019-11-08 | 太原师范学院 | A method of BiOCl catalytic eliminating bisphenol-A is loaded using coke |
| CN110422905B (en) * | 2019-09-05 | 2021-07-23 | 太原师范学院 | Method for removing bisphenol A by coke-loaded BiOCl catalysis |
| CN113289647A (en) * | 2021-05-12 | 2021-08-24 | 南京师范大学 | Biochar-doped BiOBrxCl1-xPhotocatalyst, preparation method and application |
| CN113289647B (en) * | 2021-05-12 | 2023-09-22 | 南京师范大学 | Biochar doped BiOBr x Cl 1-x Photocatalyst, preparation method and application |
| CN115382555A (en) * | 2022-09-26 | 2022-11-25 | 青岛理工大学 | Bi 2 O 3 Foam Ni and microwave radiation preparation method thereof |
| CN115382555B (en) * | 2022-09-26 | 2023-11-03 | 青岛理工大学 | Bi (Bi) 2 O 3 Foam Ni and microwave radiation preparation method thereof |
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