CN108404940B - A kind of preparation method and application of perite nanometer piece - Google Patents
A kind of preparation method and application of perite nanometer piece Download PDFInfo
- Publication number
- CN108404940B CN108404940B CN201810105601.7A CN201810105601A CN108404940B CN 108404940 B CN108404940 B CN 108404940B CN 201810105601 A CN201810105601 A CN 201810105601A CN 108404940 B CN108404940 B CN 108404940B
- Authority
- CN
- China
- Prior art keywords
- nanometer piece
- bismuth
- preparation
- perite nanometer
- light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 9
- 150000001621 bismuth Chemical class 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- 239000011780 sodium chloride Substances 0.000 claims description 13
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 22
- 238000006731 degradation reaction Methods 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 19
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000000356 contaminant Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000003256 environmental substance Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 abstract 1
- AHUBLGVDRKDHAT-UHFFFAOYSA-N [Bi]=O.[Cl] Chemical compound [Bi]=O.[Cl] AHUBLGVDRKDHAT-UHFFFAOYSA-N 0.000 description 32
- 239000003054 catalyst Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 27
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 23
- 229960000623 carbamazepine Drugs 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 14
- 229960005404 sulfamethoxazole Drugs 0.000 description 13
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 238000005286 illumination Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- 238000002336 sorption--desorption measurement Methods 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 230000001678 irradiating effect Effects 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XWNOTOKFKBDMAP-UHFFFAOYSA-N [Bi].[N+](=O)(O)[O-] Chemical compound [Bi].[N+](=O)(O)[O-] XWNOTOKFKBDMAP-UHFFFAOYSA-N 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 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 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 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
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical compound [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- NWEKXBVHVALDOL-UHFFFAOYSA-N butylazanium;hydroxide Chemical compound [OH-].CCCC[NH3+] NWEKXBVHVALDOL-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229960001193 diclofenac sodium Drugs 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 239000002355 dual-layer Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- JGMJQSFLQWGYMQ-UHFFFAOYSA-M sodium;2,6-dichloro-n-phenylaniline;acetate Chemical compound [Na+].CC([O-])=O.ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 JGMJQSFLQWGYMQ-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- B01J27/06—Halogens; Compounds thereof
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of preparation methods of perite nanometer piece, belong to environmental chemical engineering photocatalysis water-treatment technology field, tetrabutylammonium hydroxide is dissolved in deionized water by this method, chloride is added, bismuth salt is added again, the precipitating that stirring obtains after standing is cleaned with deionized water and ethyl alcohol, and perite nanometer piece is made after dry；The present invention synthesizes catalysis material with innocuous agents by simple method, meets environmentally protective requirement, which has the ability of stronger degradation of contaminant under visible light or/and full light；There is higher application value in fields such as pollution control, new energy preparation and selective catalytic oxidations.
Description
Technical field
The present invention relates to a kind of preparation method and applications of visible-light response type perite nanometer piece, belong to environmental chemical engineering light
It is catalyzed water-treatment technology field.
Background technique
With the development of dye industry, produces waste water and have become one of currently the most important pollution source of water body；Dyestuff is dirty
Water has the characteristics that color depth, complicated component, COD value are higher and difficult to degrade, brings serious harm to ecological environment.Place at present
The method of reason waste water from dyestuff mainly has: absorption method, membrane separation process, photocatalytic oxidation, electrochemical oxidation process, ultrasonic degradation skill
Art etc..Photocatalytic oxidation has the characteristics that energy-efficient, contaminant degradation is thorough.TiO2It is the photocatalysis being most widely used
Agent, but its wider band gap (~3.2 eV) makes its that only light to wavelength less than 387 nm generates response, and to accounting for solar energy
45~50% wavelength is that the visible light of 400~750 nm does not respond to but.The crystal structure of chlorine oxygen bismuth is PbFCl type, symmetrically
Property: D4h, space group: P4/nmm belongs to tetragonal crystal system.Chlorine oxygen bismuth has layer structure, the chlorine oxygen bismuth atom layer of dual layer arrangement
Between by Cl atom pass through non-bonding force (Van der Waals force) combine.Chlorine oxygen bismuth valence band is mainly O2pAnd Cl3pIt occupies, conduction band is mainly
Bi6pThe contribution of track.The layer structure of chlorine oxygen bismuth high anisotropy is convenient for the separation of photo-generate electron-hole, ensure that bismuth nitrate
Well stable photocatalytic activity；However broad-band gap (~3.4 eV) equally limits utilization of the chlorine oxygen bismuth to visible light.Therefore,
How to make the band-gap energy of chlorine oxygen bismuth reduces, and becomes focus concerned by people using solar energy so as to more sufficiently effective.Currently,
Has the correlative study of some enhancing chlorine oxygen bismuth visible light response activities by wide coverage.Xiong etc. reports auxiliary in mannitol
The lower two-dimentional perite nanometer piece that square is prepared for using hydro-thermal method is helped, the band gap of the catalyst is obviously reduced (~2.92
EV)；The catalyst shows good photocatalytic activity to rhodamine B under visible light, and catalyst amount is 0.5 gL-1
When, 10-5 mol·L-1Rhodamine B solution is degradable in 8 minutes (RSC Advances, 2011,1:1542-1553).
The band gap of chlorine oxygen bismuth is reduced to 2.65 eV from 3.5 eV by the irradiation of ultraviolet light by Ye et al..This is because the photograph of ultraviolet light
Penetrating makes to form Lacking oxygen in chlorine oxygen bismuth catalyst body phase.Under visible light illumination, degrading activity of the catalyst to rhodamine B
Than the catalyst before ultraviolet light activity improve nearly 20 times (Phys. Chem. Chem. Phys., 2012,14:
82-85).Chen et al. is prepared for chlorine oxygen bismuth (~2.87 using bismuth trichloride and nitric acid as raw material under l- lysine corrective action
EV) photochemical catalyst.Narrow band gap may be (110) crystal face of the pattern and high exposure due to nano flower-like.In the nm light source of λ >=435
After irradiating 50 min, 10 mgL-1RhB decolourizes completely, and degradation rate constant is up to 0.1186 min-1(Catalysis
Communications, 2012,23:54 ~ 57)；Report relevant to the application is had no at present.
Summary of the invention
It is needed for the removing of chlorine oxygen bismuth photochemical catalyst difficulty and the degradation of the organic pollutant of the prior art efficient visible
The problem of photochemical catalyst, the present invention provides a kind of preparation methods of perite nanometer piece, utilize the big of tetrabutylammonium hydroxide
Ion stripping performance makes chlorine oxygen is bismuth laminated to peel away, and the absorption spectrum of chlorine oxygen bismuth photochemical catalyst is widened visible light
Area passes through stirring, precipitating, separation, washing and drying steps system using bismuth salt, chloride and tetrabutylammonium hydroxide as raw material
It is standby to obtain visible-light response type two dimension perite nanometer piece photochemical catalyst.
This method is easy to operate, and raw material is easy to get, is easily achieved and securely and reliably, does not need that strong acid is added；The present invention is four
Chlorine oxygen bismuth through precipitation method preparation under butyl ammonium hydroxide effect is relatively not added under tetrabutylammonium hydroxide effect through precipitating legal system
Standby chlorine oxygen bismuth has stronger visible light catalytic effect to degradation carbamazepine at visible light (> 420nm), while in full light
Under can also degrade sulfamethoxazole and C14H10Cl2NNaO2, preferable degradation effect has all been shown to a variety of Organic substance in water.
Perite nanometer piece of the present invention the preparation method is as follows:
(1) tetrabutylammonium hydroxide is dissolved in deionized water, chloride is added after dissolution, mixed, wherein tetrabutylammonium hydrogen
The molar ratio of amine-oxides and chloride is 1:(0.2 ~ 6)；
(2) bismuth salt is added into the mixed solution of step (1), after being stirred 3 ~ 8h, stands 1 ~ 3h at room temperature, wherein chlorine
The molar ratio of compound and bismuth salt is 1:(1 ~ 1.5)；
(3) step (2) mixture is filtered, precipitating cleaned with deionized water after again with washes of absolute alcohol 1 ~ 2 time, 40 ~
50 DEG C are drying to obtain perite nanometer piece.
The chloride is NaCl, KCl or HCl.
The bismuth salt is bismuth nitrate.
The present invention is another object is that applying perite nanometer piece made from above-mentioned preparation method in degradation Organic substance in water
In.
The Organic substance in water is carbamazepine, sulfamethoxazole or C14H10Cl2NNaO2.
Perite nanometer piece of the present invention in the pending water containing organic matter in use, add perite nanometer piece, In
Room temperature is protected from light lower adsorption treatment to perite nanometer piece and reaches adsorption desorption balance, then declines in visible light or/and full striation part
The organic matter of desorption.
Advantages of the present invention and technical effect are as follows:
1, chlorine oxygen bismuth of the present invention through precipitation method preparation under tetrabutylammonium hydroxide effect is relatively not added with tetrabutyl hydrogen-oxygen
Change the lower chlorine oxygen bismuth prepared of ammonium effect, has stronger visible light catalytic effect to carbamazepine at visible light (> 420nm), together
Can also degrade sulfamethoxazole and C14H10Cl2NNaO2 under Shi Quan light (200nm ~ 780nm), all show a variety of Organic substance in water
There is preferable degradation effect out；
2, catalysis material is synthesized using simple synthetic method and innocuous agents, prepares two-dimentional perite nanometer piece, it is full
The environmentally protective requirement of foot；
3, preparation process under normal temperature and pressure conditions, does not require control pH, does not need that strong acid is added, easy to operate and safe,
Suitable for industrialized production and marketing application, have in fields such as pollution control, new energy preparation and selective catalytic oxidations
Higher application value.
Detailed description of the invention
Fig. 1 be the embodiment of the present invention 1 prepare control group chlorine oxygen bismuth photochemical catalyst BiOCl-0 and embodiment 2 prepare can
The X-ray diffracting spectrum (XRD) of light-exposed response type chlorine oxygen bismuth photochemical catalyst BiOCl-1；
Fig. 2 be the embodiment of the present invention 1 prepare control group chlorine oxygen bismuth photochemical catalyst BiOCl-0 and embodiment 2 prepare can
The photoelectric current I-T of light-exposed response type chlorine oxygen bismuth photochemical catalyst BiOCl-1 schemes；
Fig. 3 is scanning electron microscope (SEM) shape appearance figure；Wherein figure a is that control group prepared by the embodiment of the present invention 1 does not add four fourths
The chlorine oxygen bismuth photochemical catalyst BiOCl-0 of base ammonium hydroxide；Figure b is that chlorine source prepared by embodiment 2 is sodium chloride addition tetrabutylammonium hydrogen
The perite nanometer piece BiOCl-1 of amine-oxides；Figure c is the perite nanometer that chlorine source is potassium chloride addition tetrabutylammonium hydroxide
Piece.
Specific embodiment
Below by attached drawing and embodiment, invention is further described in detail, but the scope of the present invention does not limit to
In the content.
Embodiment 1
The present embodiment does not add tetrabutylammonium hydroxide；In deionized water by sodium chloride dissolution, bismuth nitrate is then added,
After being stirred to react 6h, 1h is stood at room temperature, obtains suspension, and wherein the molar ratio of sodium chloride and bismuth nitrate is 1:1；By suspension
It is filtered, filter cake is washed 2 times with dehydrated alcohol again after being cleaned with deionized water, is then dried at 40 DEG C to get chlorine oxygen bismuth
Nanometer sheet；
Perite nanometer piece is used for oxidation processes carbamazepine, degradation step are as follows:
Step (1): accurately weighing the carbamazepine of 7 mg, be dissolved in distilled water, and is settled to 1000 mL, is made 7
mg·L-1Carbamazepine solution；
Step (2): accurately pipetting carbamazepine solution that 50 mL steps (1) obtain with pipette into reactor, and adds
Enter 0.04 g chlorine oxygen bismuth photochemical catalyst, temperature of reaction system is controlled at 20~20.5 DEG C, be protected from light it is lower first adsorb 1 h, reach
Adsorption/desorption balance；
Step (3): step (2) acquired solution is subjected to photocatalytic degradation reaction under light illumination；Through Quan Guang (200nm ~
It samples after irradiating 30min or visible light (> 420nm) irradiation 180min under 780nm), and is measured with UV-VIS spectrophotometry
The absorbance of carbamazepine simultaneously calculates its conversion ratio, the results are shown in Table 1, Fig. 1,2,3a；Catalyst is under full light as can be seen from Table 1
30min is that 59.9 % have Partial digestion to the degradation rate of carbamazepine, under visible light drop of the 180min to carbamazepine
Solution rate is 15.0% almost without removal；From Fig. 1,2 known to crystal face change and photoelectric current compared with the application perite nanometer piece
It is weak；Control group product structure in the form of sheets is known from Fig. 3 a.
Embodiment 2
In deionized water by tetrabutylammonium hydroxide dissolution；Then sodium chloride is added to dissolve again, is eventually adding nitric acid
Bismuth after being stirred 6h, stands 1h at room temperature, obtains suspension, and wherein tetrabutylammonium hydroxide and the molar ratio of sodium chloride are
The molar ratio of 1:0.5, sodium chloride and bismuth nitrate is 1:1；Suspension is filtered, filter cake uses nothing after being cleaned with deionized water again
Water-ethanol washs 2 times, then dries at 40 DEG C to get visible-light response type perite nanometer piece.
Perite nanometer piece is used for oxidation processes carbamazepine；Degradation step are as follows:
Step (1): accurately weighing the carbamazepine of 7 mg, be dissolved in distilled water, and is settled to 1000 mL, is made 7
mg·L-1Carbamazepine solution；
Step (2): accurately pipetting carbamazepine solution that 50 mL steps (1) obtain with pipette into reactor, and adds
Enter 0.04 g chlorine oxygen bismuth photochemical catalyst, temperature of reaction system is controlled at 20~20.5 DEG C, be protected from light it is lower first adsorb 1 h, reach
Adsorption/desorption balance；
Step (3): step (2) acquired solution is subjected to photocatalytic degradation reaction under light illumination.Quan Guang (200nm ~ 780nm)
It is sampled after lower irradiation 30min or visible light (> 420nm) irradiation 180min, and western with UV-VIS spectrophotometry measurement Karma
Flat absorbance simultaneously calculates its conversion ratio, the results are shown in Table 1, Fig. 1,2,3b；From table 1, Fig. 1, in 2 it can be seen that the present embodiment catalysis
Agent is in 30min(94.8 %), 180min(44.3%) degradation rate of carbamazepine is above and does not add tetrabutylammonium hydroxide
The preparation process of ammonium, diffraction maximum sharply illustrate better crystallinity degree, and crystal face changes and photoelectric current is significantly stronger；This is known from Fig. 3 b
The chlorine oxygen bismuth of application structure in the form of sheets.
Embodiment 3
In deionized water by tetrabutylammonium hydroxide dissolution；Then potassium chloride is added to dissolve again, is eventually adding nitric acid
Bismuth after being stirred 3h, stands 3h at room temperature and obtains suspension, wherein tetrabutylammonium hydroxide and the molar ratio of potassium chloride are 1:
2, the molar ratio of potassium chloride and bismuth nitrate is 1:1.2；Suspension is filtered, filter cake cleaned with deionized water after again with anhydrous
It ethanol washing 1 time, then dries at 45 DEG C to get visible-light response type perite nanometer piece.
Perite nanometer piece is used for oxidation processes carbamazepine, degradation step are as follows:
Step (1): accurately weighing the carbamazepine of 7 mg, be dissolved in distilled water, and is settled to 1000 mL, is made 7
mg·L-1Carbamazepine solution；
Step (2): accurately pipetting carbamazepine solution that 50 mL steps (1) obtain with pipette into reactor, and adds
Enter 0.04 g chlorine oxygen bismuth photochemical catalyst, temperature of reaction system is controlled at 20~20.5 DEG C, be protected from light it is lower first adsorb 1 h, reach it
It is balanced to adsorption/desorption；
Step (3): step (2) acquired solution is subjected to photocatalytic degradation reaction under light illumination；Through Quan Guang (200nm ~
It samples after irradiating 30min or visible light (> 420nm) irradiation 180min under 780nm), and is measured with UV-VIS spectrophotometry
The absorbance of carbamazepine simultaneously calculates its conversion ratio, the results are shown in Table 1, Fig. 3 c；The present embodiment catalyst exists as can be seen from Table 1
30min(89.6%), 180min(40.5%) degradation rate of carbamazepine is above and does not add tetrabutylammonium hydroxide
Preparation process, the chlorine oxygen bismuth of the present embodiment structure in the form of sheets known to Fig. 3 c.
Embodiment 4
Compound concentration 0.067mol L-1Hydrochloric acid solution, will tetrabutylammonium hydroxide be added hydrochloric acid solution in dissolve, finally
Bismuth nitrate is added, after being stirred 8h, stands 1h at room temperature and obtains suspension, wherein mole of tetrabutylammonium hydroxide and hydrochloric acid
Than for 1:3, the molar ratio of hydrochloric acid and bismuth nitrate is 1:1.5；Suspension is filtered, suspension is filtered, filter cake is used
It is washed 2 times with dehydrated alcohol again after deionized water cleaning, then dries at 50 DEG C and urged to get visible-light response type chlorine oxygen bismuth light
Agent.
Photochemical catalyst is used for oxidation processes carbamazepine, degradation step are as follows:
Step (1): accurately weighing the carbamazepine of 7 mg, be dissolved in distilled water, and is settled to 1000 mL, is made 7
mg·L-1Carbamazepine solution；
Step (2): accurately pipetting carbamazepine solution that 50 mL steps (1) obtain with pipette into reactor, and adds
Enter 0.04 g chlorine oxygen bismuth photochemical catalyst, temperature of reaction system is controlled at 20~20.5 DEG C, be protected from light it is lower first adsorb 1 h, reach
Adsorption/desorption balance；
Step (3): step (2) acquired solution is subjected to photocatalytic degradation reaction under light illumination；Through Quan Guang (200nm ~
It samples after irradiating 30min or visible light (> 420nm) irradiation 180min under 780nm), and is measured with ultraviolet-visible spectrophotometry
The absorbance of carbamazepine simultaneously calculates its conversion ratio, the results are shown in Table 1；The present embodiment catalyst is as can be seen from the table
30min(92.7%), 180min(30.8%) system for not adding tetrabutylammonium hydroxide is above to the degradation rate of carbamazepine
Standby technique.
Embodiment 5
The present embodiment does not add tetrabutylammonium hydroxide, in deionized water by sodium chloride dissolution, bismuth nitrate is then added,
After being stirred to react 5h, 2h is stood at room temperature, obtains suspension, and wherein the molar ratio of sodium chloride and bismuth nitrate is 1:1；By suspension
It is filtered, filter cake is washed 2 times with dehydrated alcohol again after being cleaned with deionized water, is then dried at 40 DEG C to get chlorine oxygen bismuth
Nanometer sheet；
Perite nanometer piece is used for oxidation processes sulfamethoxazole；Degradation step are as follows:
Step (1): accurately weighing the sulfamethoxazole of 7 mg, be dissolved in distilled water, and is settled to 1000 mL, system
Obtain 7 mgL-1Sulfamethoxazole solution；
Step (2): accurately pipetting sulfamethoxazole solution that 50 mL steps (1) obtain with pipette into reactor, and
Be added 0.04 g chlorine oxygen bismuth photochemical catalyst, temperature of reaction system is controlled at 20~20.5 DEG C, be protected from light it is lower first adsorb 1 h, reach it
It is balanced to adsorption/desorption；
Step (3): step (2) acquired solution is subjected to photocatalytic degradation reaction under light illumination；Through Quan Guang (200nm ~
It is sampled after irradiating 30min under 780nm), and with the absorbance of UV-VIS spectrophotometry measurement sulfamethoxazole and calculates it
Conversion ratio the results are shown in Table 1, and the present embodiment catalyst is in degradation rate of the 30min to sulfamethoxazole as can be seen from the table
59.4%。
Embodiment 6
In deionized water by tetrabutylammonium hydroxide dissolution；Then sodium chloride is added to dissolve again, is eventually adding nitric acid
Bismuth after being stirred 6h, stands 1h at room temperature, obtains suspension, and wherein tetrabutylammonium hydroxide and the molar ratio of sodium chloride are
The molar ratio of 1:0.5, sodium chloride and bismuth nitrate is 1:1；Suspension is filtered, filter cake uses nothing after being cleaned with deionized water again
Water-ethanol washs 2 times, then dries at 40 DEG C to get perite nanometer piece.
Perite nanometer piece is used for oxidation processes sulfamethoxazole, degradation step are as follows:
Step (1): accurately weighing the sulfamethoxazole of 7 mg, be dissolved in distilled water, and is settled to 1000 mL, system
Obtain 7 mgL-1Sulfamethoxazole solution；
Step (2): accurately pipetting sulfamethoxazole solution that 50 mL steps (1) obtain with pipette into reactor, and
Be added 0.04 g chlorine oxygen bismuth photochemical catalyst, temperature of reaction system is controlled at 20~20.5 DEG C, be protected from light it is lower first adsorb 1 h, reach it
It is balanced to adsorption/desorption；
Step (3): step (2) acquired solution is subjected to photocatalytic degradation reaction under light illumination.Through Quan Guang (200nm ~
It is sampled after irradiating 30min under 780nm), and with the absorbance of UV-VIS spectrophotometry measurement sulfamethoxazole and calculates it
Conversion ratio the results are shown in Table 1, and the present embodiment catalyst is in 30min(68.0% as can be seen from the table) to the drop of sulfamethoxazole
Solution rate is higher than the preparation process (59.4%) that embodiment 5 does not add tetrabutylammonium hydroxide.
Embodiment 7
The preparation process of the present embodiment perite nanometer piece is with embodiment 6, while tetrabutylammonium hydroxide is not added in setting
Control, method is the same as embodiment 5；
Perite nanometer piece is used for oxidation processes C14H10Cl2NNaO2, degradation step are as follows:
Step (1): accurately weighing the C14H10Cl2NNaO2 of 7 mg, be dissolved in distilled water, and is settled to 1000 mL, system
Obtain 7 mgL-1Diclofenac sodium solution；
Step (2): accurately pipetting Diclofenac sodium solution that 50 mL steps (1) obtain with pipette into reactor, and
Be added 0.04 g chlorine oxygen bismuth photochemical catalyst, temperature of reaction system is controlled at 20~20.5 DEG C, be protected from light it is lower first adsorb 1 h, make it
Reach adsorption/desorption balance；
Step (3): step (2) acquired solution is subjected to photocatalytic degradation reaction under light illumination.Through Quan Guang (200nm ~
It is sampled after irradiating 30min under 780nm), and with the absorbance of UV-VIS spectrophotometry measurement C14H10Cl2NNaO2 and calculates it
Conversion ratio the results are shown in Table 1, and the present embodiment catalyst is in 30min(88.3% as can be seen from the table) to the drop of C14H10Cl2NNaO2
Solution rate is higher than the preparation process (78.5%) for not adding tetrabutylammonium hydroxide.
Table 1: the degradation of the 180min under 30min and visible light under full light of perite nanometer piece made from distinct methods
As a result
。
Claims (3)
1. a kind of preparation method of perite nanometer piece, which comprises the following steps:
(1) tetrabutylammonium hydroxide is dissolved in deionized water, chloride is added after dissolution, mixed, wherein tetrabutylammonium hydroxide
The molar ratio of ammonium and chloride is 1:(0.2 ~ 6)；
(2) bismuth salt is added into the mixed solution of step (1), after being stirred 3 ~ 8h, stands 1 ~ 3h at room temperature, wherein chloride
Molar ratio with bismuth salt is 1:(1 ~ 1.5)；
(3) step (2) mixture is filtered, precipitating is used washes of absolute alcohol 1 ~ 2 time, 40 ~ 50 DEG C again after being cleaned with deionized water
It is drying to obtain perite nanometer piece.
2. the preparation method of perite nanometer piece according to claim 1, it is characterised in that: chloride is NaCl or KCl.
3. the preparation method of perite nanometer piece according to claim 1, it is characterised in that: bismuth salt is bismuth nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810105601.7A CN108404940B (en) | 2018-02-02 | 2018-02-02 | A kind of preparation method and application of perite nanometer piece |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810105601.7A CN108404940B (en) | 2018-02-02 | 2018-02-02 | A kind of preparation method and application of perite nanometer piece |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108404940A CN108404940A (en) | 2018-08-17 |
| CN108404940B true CN108404940B (en) | 2019-11-08 |
Family
ID=63127494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810105601.7A Active CN108404940B (en) | 2018-02-02 | 2018-02-02 | A kind of preparation method and application of perite nanometer piece |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108404940B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109092342A (en) * | 2018-08-31 | 2018-12-28 | 中国环境科学研究院 | Protonate g-C3N4/ BiOBr heterojunction photocatalyst and preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103313940A (en) * | 2010-11-16 | 2013-09-18 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | Bismuth oxyhalide compounds useful as photocatalysts |
| CN104588049A (en) * | 2015-01-07 | 2015-05-06 | 南京信息工程大学 | Solid acid catalyst as well as preparation method and application of solid acid catalyst |
| CN106975498A (en) * | 2017-05-08 | 2017-07-25 | 昆明理工大学 | A kind of near infrared light catalyst BiOCl or BiOBr preparation method and applications |
-
2018
- 2018-02-02 CN CN201810105601.7A patent/CN108404940B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103313940A (en) * | 2010-11-16 | 2013-09-18 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | Bismuth oxyhalide compounds useful as photocatalysts |
| CN104588049A (en) * | 2015-01-07 | 2015-05-06 | 南京信息工程大学 | Solid acid catalyst as well as preparation method and application of solid acid catalyst |
| CN106975498A (en) * | 2017-05-08 | 2017-07-25 | 昆明理工大学 | A kind of near infrared light catalyst BiOCl or BiOBr preparation method and applications |
Non-Patent Citations (1)
| Title |
|---|
| 多级结构BiOCl的可控制备及对药物废水的有效降解;赵晓霞等;《高等学校化学学报》;20150531;第36卷(第5期);956-958 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108404940A (en) | 2018-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fan et al. | Rapid synthesis of Ag/AgCl@ ZIF-8 as a highly efficient photocatalyst for degradation of acetaminophen under visible light | |
| Feng et al. | Applications of anodized TiO2 nanotube arrays on the removal of aqueous contaminants of emerging concern: a review | |
| Lin et al. | Immobilized TiO2-reduced graphene oxide nanocomposites on optical fibers as high performance photocatalysts for degradation of pharmaceuticals | |
| Vieira et al. | CeO2/TiO2 nanostructures enhance adsorption and photocatalytic degradation of organic compounds in aqueous suspension | |
| Yao et al. | One-pot synthesis of ternary Ag2CO3/Ag/AgCl photocatalyst in natural geothermal water with enhanced photocatalytic activity under visible light irradiation | |
| Wang et al. | Hollow spherical WO3/TiO2 heterojunction for enhancing photocatalytic performance in visible-light | |
| Li et al. | Photodegradation of an azo dye using immobilized nanoparticles of TiO2 supported by natural porous mineral | |
| Gholami et al. | Sonophotocatalytic degradation of sulfadiazine by integration of microfibrillated carboxymethyl cellulose with Zn-Cu-Mg mixed metal hydroxide/g-C3N4 composite | |
| Meng et al. | Sonocatalytic degradation of Rhodamine B in the presence of C60 and CdS coupled TiO2 particles | |
| CN103252244B (en) | Preparation method and application method of visible-light response type bismuth oxychloride photocatalyst | |
| CN110918126A (en) | Preparation method of flower-shaped molybdenum disulfide combined UiO-66 photocatalyst | |
| Ahmed et al. | Surfactant-free synthesis of m-BiVO4 nanoribbons and enhanced visible-light photocatalytic properties | |
| Elias et al. | An experimental and theoretical study of the effect of Ce doping in ZnO/CNT composite thin film with enhanced visible light photo-catalysis | |
| Vadivel et al. | Facile synthesis of broom stick like FeOCl/g-C3N5 nanocomposite as novel Z-scheme photocatalysts for rapid degradation of pollutants | |
| CN104801292A (en) | Preparation method for zinc oxide hollow nanosphere/graphene composite material | |
| CN110180565A (en) | A kind of photochemical catalyst Bi5O7The synthetic method and its application of Br | |
| Mera et al. | Improvement of the BiOI photocatalytic activity optimizing the solvothermal synthesis | |
| Tang et al. | Degradation mechanism and pathway of tetracycline in milk by heterojunction N-TiO2-Bi2WO6 film under visible light | |
| Zhao et al. | Bi4O5Br2 nanoflower and CdWO4 nanorod heterojunctions for photocatalytic synthesis of ammonia | |
| Anku et al. | MWCNTs attached neodymium doped-ZnO photocatalysts for efficient removal of dyes from wastewater | |
| Salehian et al. | Photocatalytic TiO2@ MIL-88A (Fe)/polyacrylonitrile mixed matrix membranes: Characterization, anti-fouling properties, and performance on the removal of natural organic matter | |
| Li et al. | P123-assisted preparation of Ag/Ag2O with significantly enhanced photocatalytic performance | |
| Chen et al. | Efficient degradation of ciprofloxacin by Cu2O/g-C3N4 heterostructures with different morphologies driven under the visible light | |
| Zou et al. | Oxalic acid modified hexagonal ZnIn2S4 combined with bismuth oxychloride to fabricate a hierarchical dual Z-scheme heterojunction: Accelerating charge transfer to improve photocatalytic activity | |
| Yang et al. | Photocatalytic reduction of Cr (VI) on a 3.0% Au/Sr0. 70Ce0. 20WO4 photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |