CN108607541A - A kind of Bi adulterated for carbon source based on L-cysteine2WO6The Preparation method and use of photochemical catalyst - Google Patents
A kind of Bi adulterated for carbon source based on L-cysteine2WO6The Preparation method and use of photochemical catalyst Download PDFInfo
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- CN108607541A CN108607541A CN201810401106.0A CN201810401106A CN108607541A CN 108607541 A CN108607541 A CN 108607541A CN 201810401106 A CN201810401106 A CN 201810401106A CN 108607541 A CN108607541 A CN 108607541A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004098 Tetracycline Substances 0.000 claims abstract description 21
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 20
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 20
- 229960002180 tetracycline Drugs 0.000 claims abstract description 18
- 229930101283 tetracycline Natural products 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 35
- 239000004201 L-cysteine Substances 0.000 claims description 18
- 235000013878 L-cysteine Nutrition 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 238000013019 agitation Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000005447 environmental material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 235000018417 cysteine Nutrition 0.000 abstract 2
- 150000001945 cysteines Chemical class 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 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 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 230000003115 biocidal effect Effects 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000005375 photometry Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229940072172 tetracycline antibiotic Drugs 0.000 description 2
- 229940040944 tetracyclines Drugs 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 239000013307 optical fiber Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- 239000002689 soil Substances 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to technical field of environmental material preparation, disclose a kind of based on the Bi that L cysteines are carbon source doping2WO6The preparation method and application of photochemical catalyst, preparation process include：Acetic acid solution containing bismuth nitrate and L cysteines and contain Na2WO6Aqueous solution mixing, then add PVP, pass through the Bi of one-step hydrothermal synthesis of carbon source doping2WO6Photochemical catalyst.Bi2WO6It is a kind of novel organic visible light catalyst, is used for photocatalytic degradation tetracycline.Equally, carbon material has excellent electronic transmission performance.The introducing of carbon-based nonmetallic materials and Bi2WO6Synergistic effect, improve photocatalysis effect so that C BW photochemical catalysts prepared by the present invention have good stability and catalytic activity.
Description
Technical field
The invention belongs to technical field of environmental material preparation, and in particular to it is a kind of based on L-cysteine be carbon source doping
Bi2WO6The Preparation method and use of photochemical catalyst.
Background technology
With the development and development of antibiotic in pharmaceuticals industry, the tetracycline antibiotics as broad-spectrum antibiotic are extensive
It applies in the disease treatment of human and animal and Agricultural Activities, it is well known that antibiotic is treatment infectious diseases
Common drug, it in nineteen forty-one be applied to clinic, it may be said that antibiotic is the greatest medical discovery of twentieth century, it makes one
The average life span of class at least extends 10 years.Tetracycline is that one kind is usually used in the clinically inhibition of various germs and the antibiosis killed
Element, since a large amount of uses of tetracycline antibiotics make its generally existing in the environment, so as to cause the drug resistance of bacterium, separately
On the one hand, the residual of tetracycline can produce bigger effect environment, soil, surface water, underground water etc. be may be present in, to human body
It generates compared with major injury, therefore, the effective tetracycline that removes is particularly important.In recent years, many experts and scholars utilize many sides
Method solves the above problems, but these methods are less efficient, and easily causes secondary pollution, and people have found a kind of new skill by studying
Art-photocatalysis technology, it is a kind of green technology of rationality, can by organic matter degradation be environmental sound carbon dioxide,
The inorganic matters such as water.
Photocatalysis technology is a kind of emerging energy-efficient Modern sewage treatment technology, is equal to 1972 from Fujishima
TiO is delivered2After the research paper of monocrystalline water electrolysis hydrogen production, light-catalyzed reaction causes chemistry, physics, material, environmental protection etc.
Over the past decade, the environmental science worker of various countries is using semiconductor as the photocatalysis skill of catalyst by the attention of many scholars in field
Art processing method has carried out numerous studies to the feasibility for the treatment of of dyeing wastewater.From the point of view of result of study and present situation, this method pair
Homogencous dyes and the effect of actual dying processing have been recognized.This is mainly due to photocatalytic oxidations to have very strong oxygen
Change ability finally decomposes organic pollution complete oxidation.Photocatalytic method have simple in structure, operating condition be easy to control, oxygen
The advantages that change ability is strong, non-secondary pollution.
According to band theory, semiconductor energy gap is by being full of electronics and the lower valence band of energy (VB) and the higher sky of energy
Conduction band (CB) constitute, the region between conduction band and valence band is then referred to as forbidden band, and the size of energy gap is to influence semiconductor
An important factor for material light catalysis property.Since the energy band of semiconductor is discontinuous, when it is by wide equal to or more than forbidden band
The relatively low Electron absorption energy of energy, which is excited, when spending the energy excitation of (Eg), in valence band transits to conduction band, forms electronegative electricity
Son.Meanwhile positively charged hole is left in valence band, generate electron-hole pair.Photo-generate electron-hole and half under certain condition
The H of conductive surface2O, O2The effects that generate highly active OH, O2 -Free radical.These living radicals by with pollution
The interaction of object molecule can be broken down into the even permineralization of harmless, nontoxic micromolecular compound.
Tungstate material is in scintillation material, optical fiber, photoluminescence material, microwave applications, humidity sensor, magnetic device
Part, catalyst and corrosion inhibiter etc. have a good application prospect, and become the hot spot studied in recent years.From Kudo in 1999 etc.
Bismuth tungstate (Bi is reported for the first time2WO6) wavelength more than 420nm visible optical radiation under have photocatalytic activity after, Bi2WO6Cause
Its relatively narrow energy gap (about 2.7eV) can have higher catalytic activity to make by excited by visible light and under visible light
More and more concerns are caused for a kind of novel catalysis material, as recent study is found under visible light-responded
Bi2WO6Can effectively be degraded the harmful substances such as chloroform and acetaldehyde, and can effective degradation of dye waste water.Therefore, Bi2WO6Light is urged
The research for changing material will be that photocatalysis removal and degradable organic pollutant open up a new way, in the depollution of environment and new energy
There is very important practical value in terms of the exploitation of source.
Bi2WO6It has great application prospect in terms of the ability for absorbing visible light, accounts for 50% or more of sun total amount.
However, pure Bi2WO6There are two disadvantages, one is that absorbing incident light rate is low, the other is non-porous structure and relatively low low surface
Product.In order to overcome first disadvantage, researcher to start to modify Bi2WO6To improve its photocatalysis absorption efficiency and electronics inhibited to carry
Body it is compound.Modification mode is mainly with metal ion-modified, and the semiconductors couplings such as nonmetal particle is modified are modified as representing, at this
In a little method of modifying, it is not recommended that metal ion-modified, because the deposition of one side noble metal is expensive, metal may be toxic
, and catalyst may inactivate；On the other hand, the load thermally labile of metal, this will be as the center of electron-hole recombinations.
It is nonmetallic ion-doped to have caused extensive concern because nonmetallic ion can enter semiconductor and substitute oxygen with
Metal ion forms stable chemical bond.F, C, N are adulterated, the nonmetallic ions such as S can adjust Bi2WO6Band structure, to
Improve photocatalysis performance.Traditional coprecipitation is very simple, but may cause product purity difference and uncontrollable form and
Size.In recent years, due to having many advantages, such as low reaction temperatures and easily controlled form, Bi2WO6Hydrothermal synthesis have become it is excellent
The method of choosing.By including reaction condition, the control means including precursor and template can obtain variously-shaped and size
Bismuth tungstate, good form can improve light absorption and catalytic activity.In these forms, there are the three of reflection and scattering effect
Dimension (3D) layered structure can increase the absorption of light.
Invention content
This paper presents a kind of new hydro-thermal methods to prepare a kind of C-BWO photochemical catalysts, and Bi may be implemented2WO6Carbon adulterate and
The dual purpose of pattern control.It is templated synthesis carbon with PVP K-30 (PVP) using L-cysteine as carbon source
The three-dimensional layered structure Bi of doping2WO6(C-BWO), the antibiotic that can be degraded well in water body, has that raw material is cheap, performance
The features such as stablizing.
The technical scheme is that：
A kind of Bi adulterated for carbon source based on L-cysteine2WO6The preparation method of photochemical catalyst, steps are as follows：
(1) by a certain amount of Bi (NO3)3·5H2O is dissolved in acetic acid, and magnetic agitation is completely dissolved to it；It will be a certain amount of
L-cysteine be dissolved in above-mentioned solution, and magnetic agitation, referred to as solution A；
(2) by a certain amount of Na2WO6·2H2O is dissolved into a certain amount of deionized water, and magnetic agitation, referred to as solution
B；
(3) solution B is added drop-wise in solution A, and a certain amount of polyvinylpyrrolidone (PVP), above-mentioned mixing is added
Liquid is transferred in stainless steel cauldron, and reaction kettle heats under certain condition carries out hydro-thermal reaction, after reaction, natural cooling
It to after room temperature, with deionized water and ethyl alcohol washed product, centrifuges, vacuum drying obtains product, is marked as C-BWO.
In step (1), Bi (NO3)3·5H2A concentration of 0.033g/mL of O acetic acid solutions；Bi (the NO3)3·5H2O
Usage ratio with L-cysteine is 0.5~5：0.066-0.198.
In step (2), Na2WO4·2H2A concentration of 0.005g/mL of O solution.
In step (1) and step (2), the time of the magnetic agitation reaction is 20min.
In step (3), the volume ratio of solution A and solution B is 15~150：20~200；The amount of PVP is 0.01g.
In step (3), the hydrothermal temperature is 180 DEG C, and the hydro-thermal reaction time 25h, described is vacuum drying
Temperature is 60~90 DEG C.The photochemical catalyst that the method prepares C-BWO is used for photocatalytic degradation tetracycline, 90 minutes degradation rates
Up to 80%.
Beneficial effects of the present invention are：
C-BWO photochemical catalysts prepared by method of the present invention have preferable photocatalytic activity and stability.
Description of the drawings
Fig. 1 is the XRD diagram of sample prepared by embodiment 1；Respectively C, Bi2WO6, C-BW-1%, C-BW-3%, C-BW-
The XRD curves of 5%, C-BW-7%；
Fig. 2 is the XRD enlarged drawings of sample prepared by embodiment 1；Respectively Bi2WO6, C-BW-1%, C-BW-3%, C-BW-
The XRD curves of 5%, C-BW-7%；
Fig. 3 is the UV-vis DRS figures of sample prepared by embodiment 1；Respectively Bi2WO6With the UV-vis of C-BW-5%
DRS curves；
Fig. 4 is the degradation effect of the C-BW-5% photochemical catalyst photocatalytic degradation tetracyclines of sample prepared by embodiment 1
Fruit is changed with time figure.
Specific implementation mode
With reference to specific embodiment, the invention will be further described：
Photocatalytic activity evaluation：It is carried out in D1 types photochemical reactor (being purchased from Educational Instrument Factory of Yangzhou University), it will
The tetracycline simulated wastewater of 100mL20mg/L is added in reaction bulb, adds magneton and 0.05g photochemical catalysts, opens visible light
Power supply and aerator carry out Dynamic Adsorption, and it is 30 DEG C to start external thermostatic water-circulator bath control temperature of reaction system.It reaches and inhales
Illumination reaction is carried out after attached balance, it is primary every 15min samplings, it centrifuges, surveys the concentration of tetracycline in supernatant, pass through C/
C0To judge the degradation effect of tetracycline.Wherein, C0For the concentration of tetracycline after adsorption equilibrium, tetracycline when C is reaction time T
Concentration.
The step of the present invention is as follows：
A kind of Bi adulterated for carbon source based on L-cysteine2WO6The preparation method of photochemical catalyst, steps are as follows：
The preparation of step 1, carbon doping bismuth tungstate：By a certain amount of Bi (NO3)3·5H2O is dissolved in acetic acid, magnetic agitation
It is completely dissolved to it, referred to as solution A.A certain amount of L-cysteine is dissolved in solution A, and magnetic agitation.It will be a certain amount of
Na2WO6·2H2O is dissolved into a certain amount of deionized water, and magnetic agitation, referred to as solution B.Solution B is added drop-wise to solution A
In, and a certain amount of polyvinylpyrrolidone (PVP) is added, above-mentioned mixed liquor is transferred in 100mL stainless steel cauldrons, instead
Kettle is answered to heat under certain condition, it is heavy by centrifuging with deionized water and ethyl alcohol washed product after naturally cooling to room temperature
Starch puts the precipitate in drying for standby in vacuum drying oven, is marked as C-BWO.
Embodiment 1：
In step 1, used Bi (NO3)3·5H2The dosage of O is 1.0g, and the dosage of used acetic acid is 30mL；Institute
The amount of the L-cysteine of addition is 0.066g, used Na2WO4·2H2The dosage of O is 0.3g, and the dosage of deionized water is
50mL；The amount of PVP is 0.01g, and the heating temperature is 180 DEG C, heating time 25h, be stirred to react under the constant temperature when
Between be drying temperature described in 2h. be 60 DEG C, time 1h.Product is prepared.
It takes the C-BW in 0.05g steps 1 to be added to 100mL and contains 20mg L-1In the reactor of tetracycline, at 30 DEG C
It is protected from light stirring and reaches adsorption equilibrium；It opens xenon lamp and is aerated, sampling is primary at regular intervals, takes 5mL every time, is taken after centrifugation clear
Clear liquid, it is the absorbance value at 357nm to be used in combination ultraviolet spectrometry photometry to measure in wavelength.
Embodiment 2：
In step 1, used Bi (NO3)3·5H2The dosage of O is 0.5g, and the dosage of used acetic acid is 15mL；Institute
The amount of the L-cysteine of addition is 0.132g, used Na2WO4·2H2The dosage of O is 0.1g；The dosage of deionized water is
20mL；The amount of PVP is 0.01g, and the heating temperature is 180 DEG C, heating time 25h；Be stirred to react under the constant temperature when
Between be drying temperature described in 3h. be 80 DEG C, time 3h.Product is prepared.
It takes the C-BW in 0.05g steps 1 to be added to 100mL and contains 20mg L-1In the reactor of tetracycline, at 30 DEG C
It is protected from light stirring and reaches adsorption equilibrium；It opens xenon lamp and is aerated, sampling is primary at regular intervals, takes 5mL every time, is taken after centrifugation clear
Clear liquid, it is the absorbance value at 357nm to be used in combination ultraviolet spectrometry photometry to measure in wavelength.
Embodiment 3：
In step 1, used Bi (NO3)3·5H2The dosage of O is 5g, and the dosage of used acetic acid is 150mL；Institute
The amount of the L-cysteine of addition is 0.198g；Used Na2WO4·2H2The dosage of O is 1g；The dosage of deionized water is
200mL；The amount of PVP is 0.01g, and the heating temperature is 180 DEG C, heating time 25h.Be stirred to react under the constant temperature when
Between be drying temperature described in 5h. be 90 DEG C, time 5h.Product is prepared.
It takes the C-BW in 0.05g steps 1 to be added to 100mL and contains 20mg L-1In the reactor of tetracycline, at 30 DEG C
It is protected from light stirring and reaches adsorption equilibrium；It opens xenon lamp and is aerated, sampling is primary at regular intervals, takes 5mL every time, is taken after centrifugation clear
Clear liquid, it is the absorbance value at 357nm to be used in combination ultraviolet spectrometry photometry to measure in wavelength.
Photocatalytic activity evaluation：It is carried out in DW-01 type photochemical reactors, it is seen that light light irradiation, by 100mL 20mg
L-1Tetracycline simulated wastewater is added in reactor and measures its initial value, photochemical catalyst is then added, magnetic agitation simultaneously opens exposure
Device of air is passed through air and maintains the catalyst in suspension or afloat, samples after dark adsorption equilibrium, is spaced in During Illumination
15min sampling analyses take supernatant liquor to measure absorbance at spectrophotometer λ max=357nm, and pass through after centrifugation
Formula：DC=[(C0-Ci)/C0] × 100% calculates degradation rate, wherein C0The absorbance of tetracycline, C when to reach adsorption equilibriumi
For timing sampling measure be tetracycline absorbance.
Fig. 1 show C, Bi2WO6And the X-ray diffractogram of the photochemical catalyst of C-BW different proportions, as can be seen from the figure
Pure Bi2WO62 θ=28.3 ° of characteristic diffraction peak, 32.9 °, 47.3 °, 56.2 °, 58.8 °, 68.7 °, 76.3 ° and 78.5 ° and standard
Card is corresponding.Illustrate that we successfully prepare Bi2WO6Catalysis material；And in the photochemical catalyst after carbon adulterates,
Bi2WO6Feature peak intensity die down, illustrate that the doping of carbon produces strong influence, further shadow for the lattice of bismuth tungstate
Ring its photocatalysis effect.
Fig. 2 show Bi2WO6And the enlarged drawing at the X-ray diffraction main body peak of the photochemical catalyst of C-BW different proportions, from figure
In it can be seen that apparent offset has occurred in the peak positions C-BW of different proportion, the introducing of carbon changes the lattice of bismuth tungstate, this
Adequately demonstrate the bismuth tungstate photocatalyst for successfully preparing carbon doping.
It is Bi as shown in Figure 32WO6And UV-vis DRS the spectrograms of C-BW photochemical catalysts, it can be seen from the figure that Bi2WO6
Optical absorption edge with C-BW photochemical catalysts is in 450nm or so, still, notable to the absorption of visible light with the introducing C-BW of C
Enhancing.So by analysis the introducing of C play the role of to the light absorption of catalysis material it is vital.
The absorbance for being illustrated in figure 4 C-BW-5% degradation tetracyclines changes over time curve graph, as can be seen from the figure
As light application time extends, the characteristic peak of tetracycline gradually weakens, and the characteristic peak of tetracycline disappears substantially after illumination 90 minutes,
This has absolutely proved that the C-BW-5% that we prepare has higher photocatalytic activity.
Claims (7)
1. a kind of based on the Bi that L-cysteine is carbon source doping2WO6The preparation method of photochemical catalyst, which is characterized in that including such as
Lower step：
(1) by a certain amount of Bi (NO3)3·5H2O is dissolved in acetic acid, and magnetic agitation is completely dissolved to it；By a certain amount of L-
Cysteine is dissolved in above-mentioned solution, and magnetic agitation, referred to as solution A；
(2) by a certain amount of Na2WO6·2H2O is dissolved into a certain amount of deionized water, and magnetic agitation, referred to as solution B；
(3) solution B is added drop-wise in solution A, and a certain amount of polyvinylpyrrolidone (PVP) is added, above-mentioned mixed liquor turns
It moves on in stainless steel cauldron, reaction kettle heats progress hydro-thermal reaction and naturally cools to room after reaction under certain condition
Wen Hou is centrifuged with deionized water and ethyl alcohol washed product, and vacuum drying obtains product, is marked as C-BWO.
2. as described in claim 1 a kind of based on the Bi that L-cysteine is carbon source doping2WO6The preparation method of photochemical catalyst,
It is characterized in that, in step (1), Bi (NO3)3·5H2A concentration of 0.033g/mL of O acetic acid solutions；Bi (the NO3)3·
5H2The usage ratio of O and L-cysteine is 0.5~5：0.066-0.198.
3. as described in claim 1 a kind of based on the Bi that L-cysteine is carbon source doping2WO6The preparation method of photochemical catalyst,
It is characterized in that, in step (2), Na2WO4·2H2A concentration of 0.005g/mL of O solution.
4. as described in claim 1 a kind of based on the Bi that L-cysteine is carbon source doping2WO6The preparation method of photochemical catalyst,
It is characterized in that, in step (1) and step (2), the time of the magnetic agitation reaction is 20min.
5. as described in claim 1 a kind of based on the Bi that L-cysteine is carbon source doping2WO6The preparation method of photochemical catalyst,
It is characterized in that, in step (3), the volume ratio of solution A and solution B is 15~150：20~200；The amount of PVP is 0.01g.
6. as described in claim 1 a kind of based on the Bi that L-cysteine is carbon source doping2WO6The preparation method of photochemical catalyst,
It is characterized in that, in step (3), the hydrothermal temperature is 180 DEG C, the hydro-thermal reaction time 25h, the vacuum drying
Temperature be 60~90 DEG C.
7. the Bi that will be adulterated for carbon source based on L-cysteine made from preparation method described in claim 1~6 any one2WO6
Photochemical catalyst is used for the purposes of photocatalytic degradation tetracycline.
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| CN106964339A (en) * | 2017-04-14 | 2017-07-21 | 武汉理工大学 | Ultra-thin Bismuth tungstate nano-sheet catalysis material of carbon doping and preparation method thereof |
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| CN107349927A (en) * | 2017-08-30 | 2017-11-17 | 陕西科技大学 | A kind of laurustinus tufted bismuth tungstate/charcoal composite photocatalyst material and its preparation method and application |
| CN107486198A (en) * | 2017-08-02 | 2017-12-19 | 江苏大学 | A kind of Bi based on the modification of peach blossom biomass carbon2WO6The Preparation method and use of composite photo-catalyst |
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| CN106964339A (en) * | 2017-04-14 | 2017-07-21 | 武汉理工大学 | Ultra-thin Bismuth tungstate nano-sheet catalysis material of carbon doping and preparation method thereof |
| CN107096523A (en) * | 2017-05-17 | 2017-08-29 | 重庆大学 | A kind of knitting wool ball composite photo-catalyst carbon doping pucherite@multi-walled carbon nanotubes and preparation method thereof |
| CN107486198A (en) * | 2017-08-02 | 2017-12-19 | 江苏大学 | A kind of Bi based on the modification of peach blossom biomass carbon2WO6The Preparation method and use of composite photo-catalyst |
| CN107349927A (en) * | 2017-08-30 | 2017-11-17 | 陕西科技大学 | A kind of laurustinus tufted bismuth tungstate/charcoal composite photocatalyst material and its preparation method and application |
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