CN115634702A - Bismuth oxycarbonate/biochar composite photocatalyst and preparation method and application thereof - Google Patents
Bismuth oxycarbonate/biochar composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 title claims abstract description 64
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002028 Biomass Substances 0.000 claims abstract description 12
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- 238000006731 degradation reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 7
- 230000015556 catabolic process Effects 0.000 claims abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
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- 239000011261 inert gas Substances 0.000 claims description 9
- 238000000197 pyrolysis Methods 0.000 claims description 9
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
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- 239000004098 Tetracycline Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000011425 bamboo Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229960002180 tetracycline Drugs 0.000 claims description 6
- 229930101283 tetracycline Natural products 0.000 claims description 6
- 235000019364 tetracycline Nutrition 0.000 claims description 6
- 150000003522 tetracyclines Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 2
- 244000105624 Arachis hypogaea Species 0.000 claims description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 2
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- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- PIMIKCFPAJSEQM-UHFFFAOYSA-N bismuth;trinitrate;hydrate Chemical compound O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PIMIKCFPAJSEQM-UHFFFAOYSA-N 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 235000020232 peanut Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 235000020238 sunflower seed Nutrition 0.000 claims description 2
- KAXSFJVZVAHLKM-UHFFFAOYSA-K trichlorobismuthane hydrate Chemical compound O.[Bi](Cl)(Cl)Cl KAXSFJVZVAHLKM-UHFFFAOYSA-K 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000005286 illumination Methods 0.000 abstract description 2
- 206010021143 Hypoxia Diseases 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 230000007954 hypoxia Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- 238000003756 stirring Methods 0.000 description 13
- 238000000227 grinding Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 241001330002 Bambuseae Species 0.000 description 5
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 4
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- 238000007873 sieving Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000004113 Sepiolite Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 235000019355 sepiolite Nutrition 0.000 description 3
- 229910052624 sepiolite Inorganic materials 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000000356 contaminant Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000001052 transient effect Effects 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
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a bismuth oxycarbonate/biochar composite photocatalyst with strong charge separation characteristic and a preparation method and application thereof. The invention firstly carbonizes the biomass under the condition of limited oxygen supply or complete hypoxia to generate porous biochar with high specific surface area, and carries out surface hydroxylation treatment on the porous biochar, and further adopts a simple chemical reaction method to prepare the bismuth oxycarbonate/biochar composite photocatalyst with strong charge separation characteristic. The photocatalytic material prepared by the invention has excellent and adjustable photocatalytic degradation activity under the condition of illumination, has strong degradation effect on organic pollutants in water, and has potential application value in the aspect of improving environmental problems.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a bismuth oxycarbonate/biochar composite photocatalyst and a preparation method and application thereof.
Background
The photocatalysis technology is based on clean energy solar energy, and can convert low-density solar energy into chemical energy through photochemical reaction, thereby realizing efficient degradation of organic pollutants with low energy consumption. The existing common photocatalyst is bismuth subcarbonate, the unique layered structure of the photocatalyst has a good photodegradation effect on organic pollutants in water, however, the photoinduced charge carrier recombination phenomenon caused by the inherent characteristics of the existing bismuth subcarbonate photocatalyst has a certain inhibition effect on the photocatalytic activity of the existing bismuth subcarbonate photocatalyst, and further, the existing bismuth subcarbonate photocatalyst has some limitations and defects in the catalytic degradation process of the organic pollutants. Therefore, the light-induced charge carrier separation rate of the lamellar bismuth oxycarbonate is promoted, the visible light absorption range is widened to improve the catalytic activity of the lamellar bismuth oxycarbonate under visible light, and high efficiency from the aquatic environment is realizedThe removal of organic contaminants is a problem that is currently in the spotlight. In recent years, many subject groups begin to develop corresponding researches, and finally provide some new materials and preparation methods, but the preparation process is complex and high in cost, and the catalytic effect of the prepared bismuth oxycarbonate-containing catalyst is not ideal. For example, patent CN112808287a discloses a magnetic core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst and a preparation method thereof, cetyl Trimethyl Ammonium Bromide (CTAB) is dissolved in Ethylene Glycol (EG) to prepare CTAB-EG solution as a template agent and a reducing agent, bismuth nitrate-ferric nitrate solution is used as a raw material, and after the pH value is adjusted, magnetic core-shell type Fe is sequentially added 3 O 4 @SiO 2 And fully mixing the microspheres and the purified sepiolite, and then carrying out hydrothermal reaction to generate the shape-controllable core-shell type bismuth oxycarbonate/sepiolite composite photocatalyst. Although the morphology of the catalyst provided in the patent is controllable and stable, on one hand, the specific surface area of the final catalyst per unit mass is small because the core in the core-shell coating is large, so that the catalytic effect is influenced to a certain extent, and meanwhile, the number of reactants involved in the preparation process is large, the preparation process is also complex, the reaction conditions are harsh, the cost is high, and large-scale production is difficult to realize.
Disclosure of Invention
In view of the defects and shortcomings of the bismuth oxycarbonate photocatalyst, the method aims to further overcome the technical problems that the bismuth oxycarbonate semiconductor material has high photoproduction electron-hole recombination rate and low photocatalytic degradation efficiency in photocatalysis. The invention provides a bismuth oxycarbonate/biochar composite photocatalyst with strong charge separation characteristic, wherein bismuth oxycarbonate in the photocatalyst is uniformly loaded on the surface of biochar, wherein the particle size of bismuth oxycarbonate is 50-300 nm, the biochar is in a porous shape, and the bismuth oxycarbonate is in a sheet shape. The prepared photocatalyst promotes the transfer of carriers through the interface interaction between the surface hydroxylation biochar and the bismuth oxycarbonate loaded on the surface of the surface hydroxylation biochar, and shows strong charge separation characteristics.
In the technical scheme provided by the invention, the charge transfer resistance of the bismuth oxycarbonate/biochar composite photocatalyst is 0.5-25 k omega; the photoresponse current intensity is 1.3 multiplied by 10 -7 ～4.0×10 -6 A/cm 2 (300W，0.8V vs.Ag/AgCl)。
In the technical scheme provided by the invention, the bismuth oxycarbonate/biochar composite photocatalyst is prepared by reacting a soluble bismuth-containing substance, a treated biomass raw material and carbonate; wherein:
the soluble bismuth-containing substance is at least one selected from bismuth nitrate, bismuth nitrate hydrate, bismuth chloride hydrate and bismuth oxide;
the biomass raw material is at least one of sunflower seed shells, bamboo shells, rice hulls, peanut shells and corn straws;
the treatment of the biomass raw material comprises pyrolysis carbonization treatment and hydroxylation treatment, and the biomass raw material is subjected to the pyrolysis carbonization treatment and the hydroxylation treatment to obtain charcoal powder;
the carbonate is at least one selected from sodium carbonate, sodium bicarbonate, potassium carbonate and ammonium bicarbonate.
In the technical scheme provided by the invention, the mass ratio of the soluble bismuth-containing substance, the biomass raw material and the carbonate used for preparing the bismuth oxycarbonate/biochar composite photocatalyst is (30-40) to (0.35-8) to (60-65).
The invention also provides a preparation method of the bismuth oxycarbonate/biochar composite photocatalyst, which comprises the following steps:
1) Carrying out pyrolysis carbonization treatment on a biomass raw material in a gas atmosphere, and then carrying out hydroxylation treatment to prepare charcoal powder;
2) Dissolving 0.35-8 parts of charcoal powder and 30-40 parts of soluble bismuth-containing substance in 1-2 mol/L nitric acid solution to prepare solution A;
3) Dissolving 60-65 parts of carbonate in water to prepare solution B;
4) And mixing the solution A and the solution B for reaction, and performing post-treatment after the reaction to obtain the final product, namely the bismuthyl carbonate/biochar composite photocatalyst.
In the preparation method provided by the invention, the pyrolysis carbonization treatment is continuously heating for 2-6 h at 400-700 ℃; the gas atmosphere of the pyrolysis carbonization treatment is pure inert gas or mixed gas of inert gas and oxygen; the hydroxylation treatment is ultrasonic washing in 0.1-1 mol/L acid solution for 0.5-60 min and then water washing to neutrality; the preparation conditions in the steps 2) and 3) are ultrasonic for 30-60 min at room temperature; the reaction condition in the step 4) is that the reaction is carried out for 1 to 6 hours at a temperature of between 25 and 40 ℃.
In the above preparation method provided by the present invention, in some embodiments, the gas atmosphere of the pyrolysis carbonization treatment reaction is prepared by mixing the following components in a volume ratio of 100: (10-25) a mixed gas of an inert gas and oxygen; in other embodiments, the gas atmosphere of the pyrolytic charring treatment reaction is a pure inert gas.
In the preparation method provided by the invention, the inert gas is at least one of nitrogen, argon and helium.
In the preparation method provided by the invention, the acidic solution is at least one of nitric acid, hydrochloric acid, sulfuric acid and hydrogen peroxide.
In the preparation method provided by the invention, the post-treatment mode in the step 4) comprises centrifugation, washing and drying; wherein:
the washing solution is at least one of absolute ethyl alcohol, isopropanol and distilled water, the washing times are 3-6 times, and the drying condition is drying for 8-12 h at 60-120 ℃.
The invention also provides application of the bismuthyl carbonate/biochar composite photocatalyst in visible light catalytic degradation of organic pollutants, in particular application in catalytic degradation of tetracycline antibiotic.
The centrifugation in the invention refers to solid-liquid separation in equipment such as a centrifuge; the drying is a process in which a solvent such as water is removed in a drying apparatus such as a vacuum dryer to leave a solid.
Compared with the prior art, the invention has the following beneficial effects:
(1) The bismuth oxycarbonate/biochar composite photocatalyst has high charge separation efficiency and wider photoresponse range, and the introduction of the biochar with strong adsorption effect greatly improves the activity of the biochar for photocatalytic degradation of organic pollutants.
(2) The one-step chemical reaction method is simple, convenient, effective, environment-friendly, mild, economical and efficient, and can realize composite in-situ growth so as to enhance the stability and activity of the composite catalyst.
(3) The catalytic activity of the bismuth oxycarbonate/biochar composite photocatalyst can be adjusted by adjusting and controlling the proportion of the powder.
(4) The chemical raw materials needed are few in variety, cheap raw materials are adopted, the preparation process is simple, complex equipment and harsh preparation conditions are not needed, the production cost is greatly reduced, and meanwhile, the method is beneficial to large-scale industrial production.
Drawings
FIG. 1 is a graph showing the evaluation of tetracycline degradation ability of the samples prepared in examples 1 to 5;
FIG. 2 is a transient photocurrent response spectrum of samples prepared in examples 1 to 4;
FIG. 3 is an electrochemical AC impedance spectrum of samples prepared in examples 1 to 4;
FIG. 4 is a scanning electron micrograph of a sample prepared in example 2;
FIG. 5 is a scanning electron micrograph of the sample prepared in example 4;
Detailed Description
The description is to be regarded as illustrative and explanatory only and should not be taken as limiting the scope of the invention in any way. Furthermore, those skilled in the art can combine features from the embodiments in this document and from different embodiments accordingly, based on the description in this document.
Example 1
1) Weighing 10.0000g of bamboo charcoal, uniformly grinding, washing and drying, thermally degrading for 4h in a nitrogen atmosphere at 600 ℃, cooling to room temperature, washing for 30min by 0.1mol/L hydrochloric acid, washing to neutrality, vacuum drying for 12h at 80 ℃, grinding and sieving for later use;
2) 14.5521g bismuth nitrate pentahydrate and 0.0728g biochar are dissolved in 30mL nitric acid solution (1 mol/L), ultrasonic stirring is carried out for 30min, and the obtained solution is marked as solution A;
3) Dissolving 25.4376g sodium carbonate in water, and ultrasonically stirring for 30min, wherein the obtained solution is marked as solution B;
4) Mixing and stirring the A, B solution at 30 ℃ and reacting for 1h; taking out the reaction solution, centrifuging, alternately washing with isopropanol and deionized water for 3 times, and vacuum drying at 60 ℃ for 12h to obtain the bismuthyl carbonate/biochar composite photocatalyst, which is marked as BOC/BC-0.5.
Example 2
1) Weighing 10.0000g of bamboo charcoal, uniformly grinding, washing and drying, thermally degrading for 4h in a nitrogen atmosphere at 600 ℃, cooling to room temperature, washing for 30min by 0.1mol/L hydrochloric acid, vacuum drying for 12h at 80 ℃, grinding and sieving for later use;
2) 14.5521g bismuth nitrate pentahydrate and 0.3638g biochar are dissolved in 30mL nitric acid solution (1 mol/L), ultrasonic stirring is carried out for 30min, and the obtained solution is marked as solution A;
3) Dissolving 25.4376g sodium carbonate in water, and ultrasonically stirring for 30min to obtain solution B;
4) Mixing and stirring the A, B solution at 30 ℃ and reacting for 1h; taking out the reaction solution, centrifuging, alternately washing with isopropanol and deionized water for 3 times, and vacuum drying at 60 deg.C for 12 hr to obtain bismuthyl carbonate/biochar composite photocatalyst, labeled BOC/BC-2.5
Example 3
1) Weighing 10.0000g of bamboo charcoal, uniformly grinding, washing and drying, thermally degrading for 4h in a nitrogen atmosphere at 600 ℃, cooling to room temperature, washing for 30min by 0.1mol/L hydrochloric acid, vacuum drying for 12h at 80 ℃, grinding and sieving for later use;
2) 14.5521g bismuth nitrate pentahydrate and 0.7276g biochar are dissolved in 30mL nitric acid solution (1 mol/L), ultrasonic stirring is carried out for 30min, and the obtained solution is marked as solution A;
3) Dissolving 25.4376g sodium carbonate in water, and ultrasonically stirring for 30min, wherein the obtained solution is marked as solution B;
4) Mixing and stirring the A, B solution at 30 ℃ and reacting for 1h; taking out the reaction solution, centrifuging, alternately washing with isopropanol and deionized water for 3 times, and vacuum drying at 60 ℃ for 12h to obtain the bismuthyl carbonate/biochar composite photocatalyst, which is marked as BOC/BC-5.0.
Example 4
Dissolving 14.5521g bismuth nitrate pentahydrate in 30mL nitric acid solution (1 mol/L), and ultrasonically stirring for 30min to obtain solution A; dissolving 25.4376g sodium carbonate in water, and ultrasonically stirring for 30min to obtain solution B; mixing and stirring the A, B solution at 30 ℃ and reacting for 1h; taking out the reaction solution, centrifuging, washing, and vacuum drying at 60 ℃ for 12h to obtain bismuth oxycarbonate powder marked as BOC.
Example 5
Weighing 10.0000g of bamboo charcoal, uniformly grinding, washing and drying, thermally degrading for 4h at 600 ℃ in a nitrogen atmosphere, cooling to room temperature, washing for 30min by using 0.1mol/L hydrochloric acid, vacuum-drying for 12h at 80 ℃, grinding and sieving to obtain charcoal powder marked as BC.
And (3) performance testing:
1. the samples prepared in examples 1 to 5 were tested for synergistic adsorption-photocatalytic activity using tetracycline as the simulated organic contaminant, and the specific operating steps were as follows: 60.00mg of samples prepared in examples 1-5 are weighed, ultrasonically dispersed in 100mL of tetracycline aqueous solution with the concentration of 70mg/L, placed under a 300W xenon lamp light source for continuous stirring, 5mL of solution is periodically taken out and filtered by using a 0.22 mu m filter, and the absorbance of the solution is measured by using an ultraviolet spectrophotometer, wherein the specific test result is shown in figure 1.
2. The photoelectrochemical measurements were performed on the samples prepared in examples 1-4 using a standard three-electrode system via an electrochemical workstation, using the following specific operating steps: 10.00mg of the samples prepared in examples 1 to 4 were weighed, respectively mixed with 0.2mL of ethanol and 15. Mu.L of a nafion solution with a mass fraction of 5%, the mixture was ground into slurry, and the slurry was uniformly coated on a substrate of 1X 1cm 2 The ITO conductive glass is dried for 12 hours at 60 ℃ and then used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and photoelectric test is carried out in 0.5mol/L sodium sulfate aqueous solution. Under the illumination of a 300W xenon lamp, a transient photocurrent response test is carried out on the samples prepared in the examples 1 to 4 under the voltage stabilization condition of 0.8V (vs. Ag/AgCl), and the specific test result is shown in figure 2; the samples prepared in examples 1 to 4 were subjected to electrochemical ac impedance testing in a frequency range of 100kHz to 1kHz, and the specific test results are shown in fig. 3.
As can be seen from fig. 1: the synergetic adsorption-photocatalytic degradation activity of the bismuth oxycarbonate/biochar composite photocatalytic materials prepared in examples 1-3 on tetracycline is better than that of the pure bismuth oxycarbonate prepared in example 4 and that of the pure biochar prepared in example 5, and the synergetic adsorption-photocatalytic degradation activity of the bismuth oxycarbonate/biochar composite photocatalytic materials prepared in examples 1-3 on tetracycline is adjustable along with the doping content of the biochar.
As can be seen from fig. 2: the photoresponse current intensity of the bismuth oxycarbonate/biochar composite photocatalytic materials prepared in the examples 1-3 is superior to that of the pure bismuth oxycarbonate prepared in the example 4, which shows that the photogenerated charge separation efficiency of the bismuth oxycarbonate/biochar composite photocatalytic materials prepared in the examples 1-3 is superior to that of the pure bismuth oxycarbonate prepared in the example 4, and the photogenerated carrier transfer efficiency of the bismuth oxycarbonate/biochar composite photocatalytic materials prepared in the examples 1-3 can be adjusted along with the doping content of the biochar.
As can be seen from fig. 3: the charge transfer resistances of the bismuth oxycarbonate/biochar composite photocatalytic materials prepared in examples 1-3 are all lower than that of the pure bismuth oxycarbonate prepared in example 4, which indicates that the photo-generated charge transfer efficiencies of the bismuth oxycarbonate/biochar composite photocatalytic materials prepared in examples 1-3 are better than that of the pure bismuth oxycarbonate prepared in example 4, and the photo-generated charge transfer efficiencies of the bismuth oxycarbonate/biochar composite photocatalytic materials prepared in examples 1-3 show adjustability along with the doping content of the biochar.
As can be seen from fig. 4 to 5: the pure bismuth subcarbonate prepared in example 4 is stacked in a flake-shaped disordered manner, and the flaky bismuth subcarbonate in the bismuth subcarbonate/biochar composite photocatalytic material prepared in example 2 is loaded on the surface of porous biochar, and the thickness of the flake is reduced.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention. The foregoing is illustrative of the preferred embodiments of the present invention only and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the appended claims are intended to be embraced therein.
In the description herein, references to the description of the terms "some embodiments," "other embodiments," "an embodiment," "an example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
While embodiments of the present invention and examples have been shown and described above, it is understood that the above embodiments, examples are illustrative and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations in the above embodiments, examples, can be made by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The bismuth oxycarbonate/biochar composite photocatalyst is characterized in that bismuth oxycarbonate is loaded on the surface of biochar, the particle size of the bismuth oxycarbonate is 50-300 nm, and the size of the biochar is 50-150 microns.
2. The bismuth oxycarbonate/biochar composite photocatalyst according to claim 1, wherein the biochar is porous, the bismuth oxycarbonate is in a sheet shape, and the bismuth oxycarbonate is bonded to the surface of the biochar through hydroxyl groups.
3. The bismuth oxycarbonate/biochar composite photocatalyst as claimed in claim 1, wherein the charge transfer resistance of the composite photocatalyst is 0.5-25 kq; the photoresponsive current intensity is 1.3 multiplied by 10 -7 ～4.0×10 -6 A/cm 2 。
4. The bismuth oxycarbonate/biochar composite photocatalyst as claimed in claim 1, which is prepared by reacting a soluble bismuth-containing substance, a treated biomass raw material and carbonate;
the soluble bismuth-containing substance is at least one selected from bismuth nitrate, bismuth nitrate hydrate, bismuth chloride hydrate and bismuth oxide;
the biomass raw material is at least one of sunflower seed shells, bamboo shells, rice hulls, peanut shells and corn straws;
the treatment of the biomass raw material comprises pyrolysis carbonization treatment and hydroxylation treatment;
the carbonate is at least one of sodium carbonate, sodium bicarbonate, potassium carbonate and ammonium bicarbonate.
5. The bismuth oxycarbonate/biochar composite photocatalyst as claimed in claim 4, wherein the mass ratio of the soluble bismuth-containing substance, the treated biomass raw material and the carbonate is (30-40): (0.35-8): (60-65).
6. A preparation method of the bismuth oxycarbonate/biochar composite photocatalyst as claimed in claims 1-5, which is characterized by comprising the following steps:
1) Carrying out pyrolysis carbonization treatment on a biomass raw material in a gas atmosphere, and then carrying out hydroxylation treatment to prepare charcoal powder;
2) Dissolving 0.35-8 parts of charcoal powder and 30-40 parts of soluble bismuth-containing substance in 1-2 mol/L nitric acid solution to prepare solution A;
3) Dissolving 60-65 parts of carbonate in water to prepare solution B;
4) And mixing the solution A and the solution B for reaction, and performing post-treatment after the reaction to obtain the final product, namely the bismuthyl carbonate/biochar composite photocatalyst.
7. The method for preparing the bismuth subcarbonate/biochar composite photocatalyst as claimed in claim 6, wherein the pyrolysis carbonization treatment is continuous heating at 400-700 ℃ for 2-6 h; the gas atmosphere is pure inert gas or mixed gas of inert gas and oxygen; the hydroxylation treatment is ultrasonic washing in 0.1-1 mol/L acid solution for 0.5-60 min and then washing to neutrality; the preparation conditions in the steps 2) and 3) are ultrasonic treatment for 30-60 min at room temperature; the reaction condition in the step 4) is that the reaction is carried out for 1 to 6 hours at a temperature of between 25 and 40 ℃, and the post-treatment mode comprises centrifugation, washing and drying, wherein: the washing solution is at least one of absolute ethyl alcohol, isopropanol and distilled water, the washing times are 3-6 times, and the drying condition is drying for 8-12 h at 60-120 ℃.
8. The method for preparing the bismuth oxycarbonate/biochar composite photocatalyst according to claim 6, wherein the inert gas is at least one of nitrogen, argon and helium; the volume ratio of the inert gas to the oxygen in the mixed gas is 100: (10-25); the acid solution is at least one of nitric acid, hydrochloric acid, sulfuric acid and hydrogen peroxide.
9. Use of the bismuth oxycarbonate/biochar composite photocatalyst of any one of claims 1-5 in visible light photocatalytic degradation of organic pollutants.
10. The use of the bismuth oxycarbonate/biochar composite photocatalyst of any one of claims 1-5 in the catalytic degradation of tetracycline.
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