CN109225278A - A kind of preparation method of biomass auxiliary synthesis BiOX photocatalyst - Google Patents
A kind of preparation method of biomass auxiliary synthesis BiOX photocatalyst Download PDFInfo
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- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002028 Biomass Substances 0.000 title claims abstract description 16
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 16
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 19
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 17
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- -1 potassium halide Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 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 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 18
- 238000006731 degradation reaction Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 11
- 239000004098 Tetracycline Substances 0.000 abstract description 9
- 229960002180 tetracycline Drugs 0.000 abstract description 9
- 229930101283 tetracycline Natural products 0.000 abstract description 9
- 235000019364 tetracycline Nutrition 0.000 abstract description 9
- 150000003522 tetracyclines Chemical class 0.000 abstract description 9
- 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 abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 6
- 150000001621 bismuth Chemical class 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 28
- 239000013078 crystal Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 229940073609 bismuth oxychloride Drugs 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 4
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 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 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229940105329 carboxymethylcellulose Drugs 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
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- 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
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- 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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Abstract
The present invention relates to a kind of preparation method of bismuth series photocatalyst more particularly to a kind of preparation methods of biomass auxiliary synthesis BiOX photocatalyst.It is that sodium carboxymethylcellulose is added during synthesizing BiOX, generates BiOX-CMC, wherein X indicates halogen.The present invention can form the BiOX photocatalyst of 3D structure, to obtain better degradation effect.And the sodium carboxymethylcellulose that the present invention selects is biomass derivatives, effect harmless to the human body has good environment friendly.Preparation method simple process of the present invention, easily controllable, low in cost, compared with conventional hydrothermal method, specific surface area obtains biggish raising, therefore has preferable performance in degradation rhodamine and tetracycline.
Description
Technical field
The present invention relates to a kind of preparation method of bismuth series photocatalyst more particularly to a kind of biomass auxiliary synthesis zirconyl oxyhalides
The preparation method of bismuth photochemical catalyst.
Background technique
Photocatalysis technology is a kind of clean light-use substance transformation technology, its application field includes photocatalytic water system
Hydrogen, the organic pollutant in degradation water body, volatile organic matter (VOCs) and simulating plant photosynthesis in degradation air
Process etc..Realize that the technology of light-catalyzed reaction obtains more and more extensive concern by semiconductor material.
It is reported that bismuth series photocatalyst has good catalytic performance, they have apparent absorption in visible light region,
This shows that these substances can be with responding to visible light, the ability with visible light catalytic oxidation processing organic pollutant.BiOX's
Conduction band and valence band location determine by the 2p track of the d electron orbit of Bi element and oxygen atom respectively, X atom to take part in track miscellaneous
Change, forms new continuous valence band.Therefore have preferable visible light-responded.
Typically, the BiOX of two kinds of leading crystal faces is most widely studied, i.e. exposure { 001 } and exposure
{ 010 } two kinds of crystal face, because { 001 } crystal face contains more terminal active O atoms in research, and its photo-generated carrier is in internal electric field
There is shorter body mutually to show higher photocatalysis performance to the transmission range on surface under effect.But also some studies pointed out that exposures
{ 010 } BiOX of the 2D structure of crystal face often has superthin structure, the only thickness of a few to tens of nanometers, or the flower of composition 3D
Shape BiOX, therefore there is higher specific surface area, to keep the photocatalytic degradation with adsorption light-catalyzed reaction premise anti-
Better degradation effect should be obtained.
The 3D-BiOCl haveing excellent performance now is obtained in the art and usually uses solvent-thermal method, and the solvent of selection includes
PVP, DMF, EG, PEG etc., these solvents are petrochemical industry product, and some even has certain toxicity.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of system of biomass auxiliary synthesis BiOX photocatalyst
Preparation Method, can form the BiOX photocatalyst of 3D structure, to obtain better degradation effect.And the carboxylic that the present invention selects
Sodium carboxymethylcellulose pyce is biomass derivatives, effect harmless to the human body, has good environment friendly.
The present invention is implemented as follows:
A kind of preparation method of biomass auxiliary synthesis BiOX photocatalyst, during synthesizing BiOX,
Sodium carboxymethylcellulose is added, generates BiOX-CMC, wherein X indicates halogen.
Preferably, the X=Cl or Br.
Preferably, the solvent that synthesis process uses is sodium carboxymethyl cellulose solution.
The method specifically includes following steps:
Bismuth nitrate is dissolved in sodium carboxymethyl cellulose solution, solution A is obtained, potassium halide is separately dissolved in carboxymethyl cellulose
In plain sodium water solution, solution B is obtained, then solution B is added dropwise in solution A, is stirred evenly, moves into polytetrafluoroethylene (PTFE) high pressure
In reaction kettle, after 120 DEG C of -160 DEG C of reaction 12-24h, product is the washed, photocatalysis filtering, be dried to obtain BiOX (CMC)
Agent.
The present invention is, using hydro-thermal method, to be aided with biomass solution (carboxymethyl cellulose using bismuth nitrate and potassium halide as raw material
Sodium solution) system synthesize there is preferable visible light-responded BiOX (CMC) catalysis material, can be used for light under visible light
Organic dyestuff and antibiotic in catalytic degradation waste water.
Derivative of the sodium carboxymethylcellulose that the present invention uses as plant fiber, the difunctionality with hydroxyl and carboxyl
Unity structure can generate complexing with metallic element.In the synthesis process of BiOX, the carboxymethylcellulose sodium solution of addition,
With metal bismuth element complex reaction can occur for its carboxyl, to play the purpose of its reaction speed, at the same time, hydroxyl
Structure can also have an impact reaction process, and the pattern of the product finally made and leading crystal face change.
The present invention has the advantage that
(1) preparation method simple process of the present invention, easily controllable, low in cost；Utilize sodium carboxymethylcellulose
Difunctional, its pattern and crystal form are had an impact in the synthesis process of BiOX, and improve photocatalysis performance in turn.
(2) compared with conventional solvent-thermal method, the sodium carboxymethylcellulose that the present invention selects is biomass derivatives, to people
Body nonhazardous effect has good environment friendly, and product is the BiOX that { 010 } dominates crystal face, both obtains and compares table
The biggish 3D-BiOCl of area is avoided in reaction process because of highly basic, the use bring corrosivity of organic solvent and toxicity etc.
Problem.
(3) bismuth oxychloride in the present invention using sodium carboxymethylcellulose as auxiliary synthesis has exposure { 010 } crystal face
3D flower-like structure, compared with conventional hydrothermal method, specific surface area obtains biggish raising, therefore in degradation rhodamine and four
There is preferable performance in ring element.
Detailed description of the invention
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is BiOCl, BiOCl- (CMC), XRD spectra (2 θ=5- of BiOBr, BiOBr- (CMC) photochemical catalyst sample
90°)。
Fig. 2 is BiOCl, BiOCl- (CMC), SEM the and HRTEM spectrogram of BiOBr, BiOBr- (CMC), wherein (a) (b)
BiOCl、(c)(d)BiOCl-(CMC)、(e)(f)BiOBr、(g)(h)BiOBr-(CMC)。
Fig. 3 is BiOCl, BiOCl- (CMC), the N of BiOBr, BiOBr- (CMC)2The adsorption isotherm of adsorption-desorption.
Fig. 4 is BiOCl, BiOCl- (CMC), the UV-vis DRS spectrum (UV-DIS) of BiOBr, BiOBr- (CMC)
Figure.
Fig. 5 is BiOCl, BiOCl- (CMC), (the α h ν) of BiOBr, BiOBr- (CMC)1/2Vs.h ν spectrogram.
When Fig. 6 is that the rhodamine B for being 20mg/l to 200ml concentration carries out photocatalysis, the BiOCl- under different sample times
(CMC) the ultraviolet-visible absorption spectra figure of sample.
When Fig. 7 is that the rhodamine B for being 20mg/l to 200ml concentration carries out photocatalysis, the BiOCl sample under different sample times
The ultraviolet-visible absorption spectra figure of product.
Fig. 8 be the different samples curve that light degradation tetracycline changes over time under visible light, abscissa be Time (when
Between), unit is min (minute), ordinate C/C0, C0To react the initial concentration for starting preceding tetracycline, C is under sample time
The concentration of tetracycline.
Fig. 9 is the efficiency for the photocatalytic degradation tetracycline that different samples change over time under visible light.
Specific embodiment
Embodiment 1: preparation BiOX (CMC) photochemical catalyst, the X=Cl or Br.
Sodium carboxymethylcellulose is dissolved in and configures the solution that solubility is 0.5% in deionized water.By the Bi of 5mmol
(NO3)5·3H2O is dissolved in 0.5% carboxymethylcellulose sodium solution of 20ml, obtains solution A；The another KX for measuring 5mmol is molten
Solution obtains solution B in 20ml0.5% carboxymethylcellulose sodium solution；Solution B is added dropwise in solution A, magnetic agitation
30min is moved it into the polytetrafluoroethylene (PTFE) autoclave of 100ml, after 120 DEG C of reactions for 24 hours, by product through distilled water and second
The photochemical catalyst of BiOX (CMC) is obtained in 80 DEG C of dry 12h after alcohol washing filtering.
Embodiment 2: preparation BiOX photochemical catalyst, the X=Cl or Br.
By the Bi (NO of 5mmol3)5It is dissolved in the deionized water of 20ml, obtains solution A；The another KX dissolution for measuring 5mmol
In 20ml deionized water, solution B is obtained；Solution B is added dropwise in solution A, magnetic agitation 30min moves it into 100ml
Polytetrafluoroethylene (PTFE) autoclave in, 120 DEG C reaction for 24 hours after, by product through distilled water and ethanol washing filtering after in 80 DEG C
Dry 12h obtains the photochemical catalyst of BiOX.
As shown in Figure 1, the position of BiOCl diffraction maximum can fit like a glove with standard card (JCPDS NO.06-0249), not
There is any impurity phase, can determine that the sample of preparation is pure bismuth oxychloride.The position of BiOBr diffraction maximum and standard card
(JCPDS No.09-0393) fits like a glove, and does not occur any impurity phase, can determine that the sample of preparation is pure bismuth oxybromide.
Wherein belong to (001) of { 001 } crystal face group, (002), the diffraction maximum of (003), the diffracted intensity of the BiOCl synthesized in water
Higher than BiOCl- (CMC).This phenomenon shows that different solvents helps to synthesize the bismuth oxychloride of different crystal face directions, closes in water
At BiOCl have stronger directionality on [001] direction.The diffracted intensity of (001) and (110) is compared, BiOCl and
For the intensity of BiOCl- (CMC) than being respectively 1.84and 0.17, this shows BiOCl- (CMC) size in [110] crystal plane direction
It is bigger.Similar phenomenon also appears in the XRD diffraction spectrogram of BiOBr and BiOBr- (CMC).These are research shows that in hydro-thermal method
The BiOX of synthesis tends to just grow up along C axis [001], and the dominant growth direction of BiOX (CMC) is [010] direction,
It is set to expose the crystal face of { 001 } and { 010 } respectively.
As shown in Fig. 2, the nanometer sheet that the BiOX (X=Cl, Br) of hydro-thermal method synthesis is a large amount of 2D, BiOCl is that size is about
The square nanometer sheet of 2um, and BiOBr is 1-3 μm of diameter of round nanometer sheet.BiOCl and BiOBr sample in HETEM figure
(110) interplanar distance is respectively 0.275nm and 0.278nm, and therefore, the exposure crystal face of BiOCl and BiOBr are { 001 } crystal face.
The 3D graded structure being combined by 2D nanometer sheet is then presented in the sample topography of BiOX (X=Cl, Br)-CMC, and the 2D formed receives
Rice chip size is smaller than the sample that conventional hydrothermal method synthesizes, BiOCl- (CMC) and BiOBr- (CMC) sample in HETEM figure
(002) interplanar distance is respectively 0.369nm and 0.398nm, and therefore, the exposure crystal face of BiOCl- (CMC) and BiOBr- (CMC) are
{ 010 } crystal face.This conclusion is consistent with XRD's.
As shown in figure 3, the adsorption isotherm in figure is II type thermoisopleth, hysteretic loop belongs to H3 type.H3 type hysteresis loop
May be due to the aggregation of plate-like particles cause slit-shaped hole rise caused by and scanning electron microscope the result is that being consistent
's.In addition, BiOX (X=Cl, Br)-(CMC) sample N2Adsorbance is higher than BiOX (X=Cl, Br), the data of specific surface area
It is listed in table 1, is 21.853m respectively2·g-1,2.911m2·g-1,17.793m2·g-1and 3.546m2·g-1.Obviously, BiOX
The specific surface area of (X=Cl, Br)-CMC is greater than BiOX (X=Cl, Br), shows that BiOX (X=Cl, Br)-CMC can be provided more
Reaction site, and facilitate from 2D to 3D sample self-assembled structures the increase of pore volume.
1 BET of table tests specific surface area and hole body volume data
As shown in figure 4, the absorption peak edge of BiOCl is in 370nm, and BiOCl- (CMC) 200-800nm it is ultraviolet-can
There is continuous absorption in light-exposed range, and is higher than BiOCl in the visible region absorption intensity of 400-800nm.This may be with
The 3D graded structure of BiOCl- (CMC) is related, and this 3D structure increases incident light in the refraction of sample, improves light quantum
Utilization efficiency.The spectral absorption situation of BiOBr sample is similar with BiOCl, and the absorption peak edge of BiOBr is better than in 440nm
BiOCl and BiOCl (CMC).As shown in figure 5, BiOCl, BiOCl- (CMC) theoretical according to Kubelka-Munk, BiOBr,
The forbidden bandwidth of BiOBr- (CMC) is respectively 3.4eV, 3.3eV, 2.8eV, 2.7eV.Therefore, carboxymethylcellulose sodium solution is made
It uses the forbidden bandwidth for making sample to reduce for solvent, increases sample to can be by the absorption of light.
Photocatalytic activity test method: using PLS-SXE300 type xenon source, weighs 50mg photochemical catalyst and 200ml is added
20mg/L rhodamine liquor (or tetracycline) in, dark reaction 30min opens light source after reaching adsorption equilibrium.Pass through purple
Outer visible spectrophotometer measures rhodamine liquor (or tetracycline) concentration, calculates its degradation efficiency.
Biomass auxiliary synthesis bismuth oxychloride photocatalyst prepared by the present invention is shone in the xenon source for adding 420nm optical filter
It penetrates down, can degrade in 15min to the rhodamine B of the 20mg/L in waste water, such as Fig. 6, better than the bismuth oxychloride pair of conventional synthesis
The degradation (Fig. 7) of rhodamine B.
Also there is preferable degradation effect to such as tetracycline of the antibiotic in water body.As shown in figure 8, in the effect of visible light
Under, BiOBr- (CMC) shows best degradation effect, and in 60 minutes, degradation efficiency has reached 97%, is better than
The 82%, 38% and 60% of BiOBr, BiOCl, BiOCl- (CMC).As shown in figure 9, BiOBr- (CMC), BiOBr, BiOCl-
(CMC), the degradation constant of BiOCl sample is respectively 0.05096min-1,0.03014min-1,0.01335min-1and
0.00464min-1.Therefore, the degradation efficiency of BiOBr- (CMC) is about 3 times of BiOCl.This shows that sodium carboxymethylcellulose is joined
With the synthesis of oxyhalide be conducive to the degradation of pollutant.
To sum up, the invention has the following advantages:
1, the 3D graded structure of BiOX (X=Cl, Br) has been synthesized by sodium carboxymethylcellulose biomass auxiliary for the first time
Photochemical catalyst.
2, the 3D graded structure accelerates the separation of photo-generated carrier, reduces the recombination probability of photo-generate electron-hole,
Sample is improved to the absorption efficiency and specific surface area of visible light, is significantly better than the photocatalysis effect of semiconductor monomer.
3, realize and 97% reached to the degradation rate of tetracycline in water body have preferable in 60 shorter minutes
Practical value.
4, the preparation method simple possible of the composite photo-catalyst, cheap.
Although specific embodiments of the present invention have been described above, those familiar with the art should be managed
Solution, we are merely exemplary described specific embodiment, rather than for the restriction to the scope of the present invention, it is familiar with this
The technical staff in field should be covered of the invention according to modification and variation equivalent made by spirit of the invention
In scope of the claimed protection.
Claims (4)
1. a kind of preparation method of biomass auxiliary synthesis BiOX photocatalyst, it is characterised in that: in synthesis BiOX
During, sodium carboxymethylcellulose is added, generates BiOX-CMC, wherein X indicates halogen.
2. the preparation method of biomass auxiliary synthesis BiOX photocatalyst according to claim 1, it is characterised in that:
The X=Cl or Br.
3. the preparation method of biomass auxiliary synthesis BiOX photocatalyst according to claim 1, it is characterised in that:
The solvent that synthesis process uses is sodium carboxymethyl cellulose solution.
4. the preparation method of biomass auxiliary synthesis BiOX photocatalyst according to claim 1, it is characterised in that:
Bismuth nitrate is dissolved in sodium carboxymethyl cellulose solution, solution A is obtained, it is water-soluble that potassium halide is separately dissolved in sodium carboxymethylcellulose
In liquid, solution B is obtained, then solution B is added dropwise in solution A, is stirred evenly, moves into polytetrafluoroethylene (PTFE) autoclave
In, after 120 DEG C of -160 DEG C of reaction 12-24h, photochemical catalyst that is product is washed, filtering, be dried to obtain BiOX-CMC.
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| CN113231094A (en) * | 2021-05-08 | 2021-08-10 | 山西铭睿恒信环保工程有限公司 | Monoatomic catalytic material for removing refractory organic pollutants and preparation method thereof |
| CN114377699A (en) * | 2021-12-16 | 2022-04-22 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Preparation method of ultrathin-structure bismuth oxyhalide material |
| CN114377699B (en) * | 2021-12-16 | 2023-10-24 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Preparation method of bismuth oxyhalide material with ultrathin structure |
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