CN111530487A - Preparation method of bismuth tungstate nitrogen sulfur co-modified biochar - Google Patents
Preparation method of bismuth tungstate nitrogen sulfur co-modified biochar Download PDFInfo
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- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 34
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 34
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 80
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000011259 mixed solution Substances 0.000 claims abstract description 43
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims abstract description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 22
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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 claims abstract description 14
- 239000000376 reactant Substances 0.000 claims abstract description 13
- 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 abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 240000008042 Zea mays Species 0.000 claims description 48
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 48
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 48
- 235000005822 corn Nutrition 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- QXTCFDCJXWLNAP-UHFFFAOYSA-N sulfidonitrogen(.) Chemical compound S=[N] QXTCFDCJXWLNAP-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 10
- 238000012986 modification Methods 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000003610 charcoal Substances 0.000 abstract 1
- 239000010902 straw Substances 0.000 description 44
- 239000002131 composite material Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 13
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000005012 migration Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 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 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 229960003405 ciprofloxacin Drugs 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000004298 light response Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
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- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000010907 stover Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RFHAOTPXVQNOHP-UHFFFAOYSA-N fluconazole Chemical compound C1=NC=NN1CC(C=1C(=CC(F)=CC=1)F)(O)CN1C=NC=N1 RFHAOTPXVQNOHP-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- B01J27/24—Nitrogen compounds
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/22—Organic substances containing halogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/40—Inorganic substances
- A62D2101/43—Inorganic substances containing heavy metals, in the bonded or free state
Abstract
A preparation method of bismuth tungstate nitrogen sulfur co-modified biochar comprises the following steps: s1, soaking and modifying the biochar raw material by using thiourea, and placing the modified material in nitrogen for reaction to obtain nitrogen-sulfur doped modified biochar; s2, preparing a mixed solution of sodium oleate and pentahydrate bismuth nitrate by using ethylene glycol as a solvent; s3, adding sodium tungstate dihydrate into the sodium oleate bismuth nitrate mixed solution; s4, adding the nitrogen and sulfur doped modified biochar obtained in the step S1 into the mixed solution obtained in the step S3; s5, reacting the mixed solution obtained in the step S4; s6, obtaining a reactant solid obtained after the reaction in the step S5; and S7, drying the reactant solid to obtain the bismuth tungstate nitrogen sulfur co-modified biochar. The bismuth tungstate nitrogen sulfur co-modified charcoal subjected to nitrogen sulfur co-modification can promote adsorption of organic matters and heavy metals and improve photocatalytic performance.
Description
Technical Field
The invention relates to a method for modifying biochar, in particular to a method for preparing bismuth tungstate nitrogen sulfur co-modified biochar.
Background
Along with the continuous improvement of agricultural mechanization, the grain yield in the world is increasingly improved, the accompanying agricultural waste treatment faces a great challenge, and the condition that the straws are strictly burned in situ exists in northeast China, so that the resource utilization of the straws is widely concerned. Biochar has a large specific surface area, abundant surface optical energy groups (such as hydroxyl and carboxyl groups) and a large number of pore structures, and thus many studies are focused on the adsorption of heavy metals by biochar. The nitrogen element can adjust the electronic characteristics of the biochar to improve the migration capability of electrons on the biochar.
Bismuth tungstate (Bi)2WO6) Due to its typical perovskite structure and a certain photoresponsive ability, it is of interest to the outside world. However, a single bismuth tungstate material has a wider band gap and a low photon-generated carrier migration and transfer speed, so that the photocatalytic performance of pure bismuth tungstate is limited, and in recent years, p-n heterojunction, carbon load and doping (noble metal and inorganic non-metal ions) are constructed on bismuth tungstate, so that the photocatalytic activity of the composite material is improved. Bi can be prepared by constructing a sodium oleate/ethylene glycol system2WO6a/NSBC composite material to realize Bi2WO6The carbon load, the visible light response of the composite material are enhanced, the recombination of photo-generated electrons and holes is inhibited by enhancing the migration rate of electrons on NSBC, and the photocatalytic performance is further improved. However, Bi is present2WO6The photo-generated electrons and holes are easy to be combined to cause the problems of poor photo-catalytic activity and the like.
Disclosure of Invention
The invention mainly aims to make up the defects of the prior art and provides a preparation method of bismuth tungstate nitrogen sulfur co-modified biochar.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of bismuth tungstate nitrogen sulfur co-modified biochar comprises the following steps:
s1, soaking and modifying the biochar raw material by using thiourea, and placing the modified material in nitrogen for reaction to obtain nitrogen-sulfur doped modified biochar NSBC;
s2, preparing a mixed solution of sodium oleate and pentahydrate bismuth nitrate by using ethylene glycol as a solvent;
s3, adding sodium tungstate dihydrate into the sodium oleate bismuth nitrate mixed solution;
s4, adding the nitrogen-sulfur doped modified biochar NSBC obtained in the step S1 into the mixed solution obtained in the step S3;
s5, reacting the mixed solution obtained in the step S4;
s6, obtaining a reactant solid obtained after the reaction in the step S5;
s7, drying the reactant solid to obtain bismuth tungstate nitrogen sulfur co-modified biochar Bi2WO6/NSBC。
Further:
the biochar raw material is corn straw.
In step S1, the biochar raw material is crushed and then soaked in dilute nitric acid to remove surface organic matters, the affinity of the biochar raw material surface to nitrogen and sulfur elements is improved, the biochar raw material is dried, and is soaked and modified by thiourea, the modified biochar raw material is dried, reacts in a vacuum muffle furnace with nitrogen introduced, at the temperature of 600 ℃ for 3 hours, and is cooled to obtain nitrogen and sulfur doped modified biochar NSBC.
In step S2, sodium oleate is dissolved in ethylene glycol, and bismuth nitrate pentahydrate is added when the sodium oleate is completely dissolved.
In step S3, sodium tungstate dihydrate is dissolved in ethylene glycol at 60 ℃, and after the sodium tungstate is completely dissolved, the sodium tungstate is added to the mixed solution of sodium oleate and bismuth nitrate and stirred for 30 min.
In step S4, the nitrogen-sulfur doped modified biochar NSBC is dissolved in ethylene glycol for ultrasonic treatment for 20min, and then added into the mixed solution obtained in step S3, and is stirred for 1.5h and then uniformly mixed.
In step S5, the mixed solution obtained in step S4 is reacted in a reaction kettle at 200 ℃ for 24 hours.
In step S6, after cooling to room temperature, the reactant solid is taken out, and the reactant solid is washed with a mixed solution of ethanol and water by suction filtration.
In the step S7, the washed reactant solid is dried for 4 hours at the temperature of 80 ℃ to obtain the bismuth tungstate nitrogen sulfur co-modified biochar Bi2WO6/NSBC。
In step S1, the weight ratio of thiourea to the raw material of biochar is 2: 1-1: 1, for example 3: 2.
In steps S2-S7, the following proportioning relations are adopted: 0.1-0.05g of 4mmol of sodium oleate, 4mmol of bismuth nitrate pentahydrate, 2mmol of sodium tungstate dihydrate and nitrogen-sulfur doped modified biochar NSBC.
The invention has the following beneficial effects:
the invention provides a preparation method of bismuth tungstate nitrogen sulfur co-modified biochar, aiming at Bi2WO6The problem of poor photocatalytic activity caused by easy recombination of photogenerated electrons and holes is solved by adding Bi2WO6The composite material is loaded on the biochar modified by nitrogen and sulfur together, so that the transfer of photoproduction electrons is accelerated while the biochar loading of the photocatalytic material is realized, and the photocatalytic activity of the composite material is further enhanced. Among them, nitrogen can regulate the electronic characteristics of biochar to improve the migration capacity of electrons thereon, while sulfur can induce biochar to produce high chemical reactivity, such as excitation of free radicals to improve oxidative decomposition of organic pollutants and reduction of heavy metal ions. More importantly, the nitrogen-sulfur co-doped catalyst shows better synergistic effect compared with the single nitrogen element or sulfur element doped catalyst. Meanwhile, the adsorption of the catalyst on organic matters and heavy metals can be promoted after the nitrogen and sulfur are jointly modified, so that electrons in a conduction band of the catalyst are promoted to directly reduce heavy metal ions and holes in a valence band to directly oxidize the organic matters. Therefore, thisThe invention starts from the resource utilization of biochar such as corn stalks, the biochar is subjected to nitrogen and sulfur co-modification to prepare nitrogen and sulfur doped modified biochar NSBC, and then Bi is loaded on a sodium oleate/ethylene glycol system2WO6To obtain the bismuth tungstate loaded nitrogen-sulfur co-modified composite material Bi2WO6the/NSBC improves the visible light response capability of the composite material, improves the electron transport capability of the composite material, improves the photocatalytic performance of the composite material, can be effectively used for removing and adsorbing organic matters and heavy metals, and particularly can be used for degrading rhodamine B and ciprofloxacin and reducing Cr (VI).
Drawings
FIG. 1 shows the preparation of Bi according to examples 1 to 4 of the present invention2WO6Flow diagram for/NSBC.
FIG. 2 shows the preparation of Bi according to examples 1 to 4 of the present invention2WO6XRD pattern of/NSBC.
FIG. 3 shows the preparation of Bi according to examples 1 and 4 of the present invention2WO6FT-IR plot for/NSBC.
FIG. 4 shows the preparation of Bi according to examples 1 to 4 of the present invention2WO6Photocatalytic oxidation rhodamine B curve graph of NSBC
FIG. 5 shows the preparation of Bi according to examples 1 to 4 of the present invention2WO6Graph of ciprofloxacin removal by photocatalytic oxidation of/NSBC.
FIG. 6 shows the preparation of Bi according to examples 1 to 4 of the present invention2WO6Cr (VI) curve of photocatalytic reduction of/NSBC.
FIG. 7 shows the preparation of Bi according to example 3 of the present invention2WO6The test chart is repeated by the aid of/NSBC on rhodamine B.
Detailed Description
The embodiments of the present invention will be described in detail below. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
The embodiment of the invention provides a preparation method of bismuth tungstate nitrogen sulfur co-modified biochar, which comprises the following steps:
s1, soaking and modifying the biochar raw material by using thiourea, and placing the modified material in nitrogen for reaction to obtain nitrogen-sulfur doped modified biochar NSBC;
s2, preparing a mixed solution of sodium oleate and pentahydrate bismuth nitrate by using ethylene glycol as a solvent;
s3, adding sodium tungstate dihydrate into the sodium oleate bismuth nitrate mixed solution;
s4, adding the nitrogen-sulfur doped modified biochar NSBC obtained in the step S1 into the mixed solution obtained in the step S3;
s5, reacting the mixed solution obtained in the step S4;
s6, obtaining a reactant solid obtained after the reaction in the step S5;
s7, drying the reactant solid to obtain bismuth tungstate nitrogen sulfur co-modified biochar Bi2WO6/NSBC。
The embodiment of the invention provides a preparation method of bismuth tungstate nitrogen sulfur co-modified biochar, aiming at Bi2WO6The problem of poor photocatalytic activity caused by easy recombination of photogenerated electrons and holes is solved by adding Bi2WO6The composite material is loaded on the nitrogen-sulfur co-doped modified biochar, so that the migration of photoproduction electrons is accelerated while the load of the photo-catalytic biochar is realized, and the photo-catalytic activity of the composite material is further enhanced. Among them, nitrogen can regulate the electronic characteristics of biochar to improve the migration capacity of electrons thereon, while sulfur can induce biochar to produce high chemical reactivity, such as excitation of free radicals to improve oxidative decomposition of organic pollutants and reduction of heavy metal ions. More importantly, the nitrogen-sulfur co-doped catalyst shows better synergistic effect compared with the single nitrogen element or sulfur element doped catalyst. Meanwhile, the adsorption of the catalyst on organic matters and heavy metals can be promoted after the nitrogen and sulfur are jointly modified, so that electrons in a conduction band of the catalyst are promoted to directly reduce heavy metal ions and holes in a valence band to directly oxidize the organic matters. Therefore, the embodiment of the invention starts from resource utilization of biochar such as corn stalks, the biochar is subjected to nitrogen and sulfur co-modification to prepare nitrogen and sulfur doped modified biochar NSBC, and then Bi is loaded on a sodium oleate/ethylene glycol system2WO6To obtain the bismuth tungstate loaded nitrogen-sulfur co-modified compositeMaterial Bi2WO6The NSBC improves the visible light response capability of the composite material, improves the electron transport capability of the composite material, improves the photocatalytic performance of the composite material, can be effectively used for removing and adsorbing organic matters and heavy metals, and particularly can be used for degrading rhodamine B and ciprofloxacin and reducing Cr (VI).
In a preferred embodiment, the biochar feedstock is corn stover.
In a preferred embodiment, the weight ratio of the thiourea to the biochar raw material, especially corn stalks, is 2: 1-1: 1, preferably one of 2:1, 1:1 and 3: 2.
In a preferred embodiment, in steps S2-S7, the following formulation is prepared: 0.1-0.05g of 4mmol of sodium oleate, 4mmol of bismuth nitrate pentahydrate, 2mmol of sodium tungstate dihydrate and nitrogen-sulfur doped modified biochar NSBC. Preferably, 0.05g of NSBC is used.
Features and advantages of particular embodiments of the present invention are described further below.
An embodiment of a preparation method of bismuth tungstate nitrogen sulfur co-modified biochar is shown as figure 1, and the method comprises the following steps:
the method comprises the following steps: preparation of NSBC
Collecting and crushing corn straws, sequentially soaking the corn straws with dilute nitric acid to remove surface organic matters, improving the affinity of the surface of the biochar raw material to nitrogen and sulfur elements, drying, performing infiltration modification with thiourea, drying, placing the modified material in a ceramic crucible, reacting for 3 hours at 600 ℃ in a vacuum muffle furnace with introduced nitrogen, and cooling to obtain nitrogen-sulfur-doped modified biochar NSBC;
step two: preparation of Bi2WO6/NSBC
Firstly, dissolving sodium oleate in ethylene glycol, and adding bismuth nitrate pentahydrate when the sodium oleate is completely dissolved; simultaneously dissolving sodium tungstate dihydrate in ethylene glycol at 60 ℃, adding the sodium tungstate dihydrate into the mixed solution of sodium oleate and bismuth nitrate after the sodium tungstate dihydrate is completely dissolved, and stirring for 30 min; dissolving the NSBC prepared in the first step in ethylene glycol, performing ultrasonic treatment for 20min, adding the mixed solution, stirring for 1.5h, and transferring the uniformly mixed solution to a reaction kettleReacting for 24 hours at the temperature of 200 ℃; after cooling to room temperature, reserving a solid at the bottom of the container, and washing the composite material in a suction filtration mode by adopting a mixed solution of ethanol and water; then drying for 4 hours at the temperature of 80 ℃ to obtain the composite material Bi2WO6/NSBC。
In some preferred embodiments, the weight ratio of thiourea to corn stover in step one is 2:1 or 3:2 or 1:1, respectively.
Example 1:
collecting fresh corn straws, cleaning silt on the surface of the corn straws with distilled water, drying the corn straws, crushing the corn straws by a crusher, sieving the corn straws by a 60-mesh sieve, dripping two drops of dilute nitric acid into the corn straws to soak the corn straws for 20 hours, drying the corn straws in an oven at 80 ℃, dissolving 8g of thiourea in 50mL of distilled water, adding 4g of completely dried corn straws, fully stirring the mixture for 1 hour, drying the mixture at 80 ℃, placing the modified material in a ceramic crucible, reacting the modified material for 3 hours at 600 ℃ in a vacuum muffle furnace with nitrogen introduced, and cooling the reaction product to obtain NSBC-1; simultaneously dissolving 4mmol of sodium oleate into 40mL of ethylene glycol, and adding 4mmol of bismuth nitrate pentahydrate when the sodium oleate is completely dissolved; dissolving 2mmol of sodium tungstate dihydrate in 20mL of ethylene glycol at 60 ℃, adding the sodium tungstate dihydrate into the mixed solution of sodium oleate and bismuth nitrate after the sodium tungstate is completely dissolved, and stirring for 30 min; dissolving 10.05 g of NSBC-prepared in the first step in 10mL of glycol, performing ultrasonic treatment for 20min, adding the mixed solution, stirring for 1.5h, transferring the uniformly mixed solution to a reaction kettle, and reacting for 24h at 200 ℃; after cooling to room temperature, reserving a solid at the bottom of the container, and washing the composite material in a suction filtration mode by adopting a mixed solution of ethanol and water; then drying for 4 hours at the temperature of 80 ℃ to obtain the composite material Bi2WO6/NSBC-1。
The composite prepared in example 1 was subjected to FT-IR characterization as shown in fig. 3. From the infrared spectrum, the sample can be found from 500-1000cm-1The wavelength of the absorption peak is W-O, Bi-O and W-O-W stretching vibration once, thereby fully proving the existence of bismuth tungstate. At 649 and 1381cm-1And (3) stretching vibration at the absorption wavelength of C ═ S and N-O. From this, it is presumed that nitrogen and sulfur elements modify the biochar by forming a chemical bond.
Example 2:
collecting fresh corn straws, cleaning silt on the surface of the fresh corn straws with distilled water, drying the fresh corn straws, crushing the dried corn straws by using a crusher, sieving the crushed corn straws by using a 60-mesh sieve, dripping two drops of dilute nitric acid into the crushed corn straws to soak the corn straws for 20 hours, drying the corn straws in an oven at 80 ℃, dissolving 6g of thiourea in 50mL of distilled water, adding 4g of completely dried corn straws, fully stirring the mixture for 1 hour, drying the mixture at 80 ℃, placing the modified material in a ceramic crucible, reacting the modified material for 3 hours at 600 ℃ in a vacuum muffle furnace with nitrogen introduced, and cooling the reaction product to obtain NSBC-2; simultaneously dissolving 4mmol of sodium oleate into 40mL of ethylene glycol, and adding 4mmol of bismuth nitrate pentahydrate when the sodium oleate is completely dissolved; dissolving 2mmol of sodium tungstate dihydrate in 20mL of ethylene glycol at 60 ℃, adding the sodium tungstate dihydrate into the mixed solution of sodium oleate and bismuth nitrate after the sodium tungstate is completely dissolved, and stirring for 30 min; dissolving the NSBC-20.05 g prepared in the first step in 10mL of glycol, performing ultrasonic treatment for 20min, adding the mixed solution, stirring for 1.5h, transferring the uniformly mixed solution to a reaction kettle, and reacting for 24h at 200 ℃; after cooling to room temperature, reserving a solid at the bottom of the container, and washing the composite material in a suction filtration mode by adopting a mixed solution of ethanol and water; then drying for 4 hours at the temperature of 80 ℃ to obtain the composite material Bi2WO6/NSBC-2。
Example 3:
collecting fresh corn straws, cleaning silt on the surface of the fresh corn straws with distilled water, drying the fresh corn straws, crushing the dried corn straws by using a crusher, sieving the crushed corn straws by using a 60-mesh sieve, dripping two drops of dilute nitric acid into the crushed corn straws to soak the corn straws for 20 hours, drying the corn straws in an oven at 80 ℃, dissolving 4g of thiourea in 50mL of distilled water, adding 4g of completely dried corn straws, fully stirring the mixture for 1 hour, drying the mixture at 80 ℃, placing the modified material in a ceramic crucible, reacting the modified material for 3 hours at 600 ℃ in a vacuum muffle furnace with nitrogen introduced, and cooling the reaction product to obtain NSBC-3; simultaneously dissolving 4mmol of sodium oleate into 40mL of ethylene glycol, and adding 4mmol of bismuth nitrate pentahydrate when the sodium oleate is completely dissolved; dissolving 2mmol of sodium tungstate dihydrate in 20mL of ethylene glycol at 60 ℃, adding the sodium tungstate dihydrate into the mixed solution of sodium oleate and bismuth nitrate after the sodium tungstate is completely dissolved, and stirring for 30 min; dissolving 30.05 g of NSBC-prepared in the first step in 10mL of glycol, performing ultrasonic treatment for 20min, adding the mixed solution, stirring for 1.5h, and uniformly mixingThe solution is transferred into a reaction kettle and reacts for 24 hours at the temperature of 200 ℃; after cooling to room temperature, reserving a solid at the bottom of the container, and washing the composite material in a suction filtration mode by adopting a mixed solution of ethanol and water; then drying for 4 hours at the temperature of 80 ℃ to obtain the composite material Bi2WO6/NSBC-3。
Four replicates of the composite material prepared in example 3 were run as shown in figure 7. The composite material is found to be capable of being repeatedly and stably used, which indicates that the catalyst has industrial production value.
Example 4:
collecting fresh corn straws, cleaning silt on the surface of the fresh corn straws with distilled water, drying the fresh corn straws, crushing the corn straws by using a crusher, sieving the crushed corn straws by using a 60-mesh sieve, dripping two drops of dilute nitric acid into the crushed corn straws to soak the corn straws for 20 hours, drying the corn straws in an oven at the temperature of 80 ℃, placing the corn straws in a ceramic crucible, reacting the corn straws for 2 hours at the temperature of 550 ℃ in a vacuum muffle furnace with introduced nitrogen, and cooling the corn straws to obtain pure corn straw Biochar (BC); simultaneously dissolving 4mmol of sodium oleate into 40mL of ethylene glycol, and adding 4mmol of bismuth nitrate pentahydrate when the sodium oleate is completely dissolved; dissolving 2mmol of sodium tungstate dihydrate in 20mL of ethylene glycol at 60 ℃, adding the sodium tungstate dihydrate into the mixed solution of sodium oleate and bismuth nitrate after the sodium tungstate is completely dissolved, and stirring for 30 min; dissolving 0.05g of the BCG prepared in the first step in 10mL of glycol, performing ultrasonic treatment for 20min, adding the mixed solution, stirring for 1.5h, transferring the uniformly mixed solution to a reaction kettle, and reacting for 24h at 200 ℃; after cooling to room temperature, reserving a solid at the bottom of the container, and washing the composite material in a suction filtration mode by adopting a mixed solution of ethanol and water; then drying for 4 hours at the temperature of 80 ℃ to obtain the composite material Bi2WO6/BC。
XRD powder characterization of the composites prepared in examples 1-4 was performed, as shown in FIG. 2, it is evident from XRD that the composites maintain good crystallinity, and all peak intensities are orthorhombic Bi2WO6And from the composite material Bi2WO6Diffraction peaks for graphitic carbon were found in NSBC-1.
FIGS. 4, 5 and 6 are graphs of the degradation of rhodamine B, ciprofloxacin and reduction of Cr (VI) of the prepared composite material under visible light for the first time. Can be used forCan see Bi2WO6the/NSBC-3 has the best photocatalytic performance, the degradation efficiency to 10mg/L rhodamine B is 99.7 percent (figure 4), the degradation efficiency to 5mg/L ciprofloxacin is 93.9 percent (figure 5), and the reduction efficiency to 10mg/L Cr (VI) is 99.7 percent (figure 6) within 75 min.
The background of the present invention may contain background information related to the problem or environment of the present invention and does not necessarily describe the prior art. Accordingly, the inclusion in the background section is not an admission of prior art by the applicant.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and it is not intended that the specific embodiments of the invention be limited to these descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and these substitutions and modifications should be construed as falling within the scope of the invention. In the description herein, references to the description of the term "one embodiment," "some embodiments," "preferred embodiments," "an example," "a specific example," or "some examples" or the like are intended to 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. Various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction. Although embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope of the claims.
Claims (10)
1. A preparation method of bismuth tungstate nitrogen sulfur co-modified biochar is characterized by comprising the following steps:
s1, soaking and modifying the biochar raw material by using thiourea, and placing the modified material in nitrogen for reaction to obtain nitrogen-sulfur co-modified biochar NSBC;
s2, preparing a mixed solution of sodium oleate and pentahydrate bismuth nitrate by using ethylene glycol as a solvent;
s3, adding sodium tungstate dihydrate into the sodium oleate bismuth nitrate mixed solution;
s4, adding the nitrogen and sulfur co-modified biochar NSBC obtained in the step S1 into the mixed solution obtained in the step S3;
s5, reacting the mixed solution obtained in the step S4;
s6, obtaining a reactant solid obtained after the reaction in the step S5;
s7, drying the reactant solid to obtain bismuth tungstate nitrogen sulfur co-modified biochar Bi2WO6/NSBC。
2. The method for preparing bismuth tungstate, nitrogen sulfide co-modified biochar as claimed in claim 1, wherein the biochar raw material is corn stalks.
3. The method for preparing bismuth tungstate nitrogen sulfur co-modified biochar as claimed in claim 1 or 2, wherein in step S1, the biochar raw material is crushed, soaked in dilute nitric acid to remove surface organic matters, improve the affinity of the biochar raw material surface to nitrogen sulfur elements, dried, soaked and modified with thiourea, dried, and the modified material is reacted in a vacuum muffle furnace with nitrogen gas at 600 ℃ for 3h, and then cooled to obtain nitrogen sulfur co-modified biochar NSBC.
4. The method for preparing bismuth tungstate nitrogen sulfur co-modified biochar as claimed in any one of claims 1 to 3, wherein in step S2, sodium oleate is dissolved in ethylene glycol, and bismuth nitrate pentahydrate is added when the sodium oleate is completely dissolved.
5. The method for preparing bismuth tungstate nitrogen sulfur co-modified biochar as claimed in any one of claims 1 to 4, wherein in step S3, sodium tungstate dihydrate is dissolved in ethylene glycol at 60 ℃, and after complete dissolution, the sodium tungstate dihydrate is added into the mixed solution of sodium oleate and bismuth nitrate and stirred for 30 min.
6. The method for preparing bismuth tungstate nitrogen sulfur co-modified biochar as claimed in any one of claims 1 to 5, wherein in step S4, nitrogen sulfur doped modified biochar NSBC is dissolved in ethylene glycol and subjected to ultrasonic treatment for 20min, then added to the mixed solution obtained in step S3, and stirred for 1.5h before being uniformly mixed.
7. The method for preparing bismuth tungstate nitrogen sulfur co-modified biochar as claimed in any one of claims 1 to 6, wherein in step S5, the mixed solution obtained in step S4 is reacted in a reaction kettle at 200 ℃ for 24 h.
8. The method for preparing bismuth tungstate nitrogen sulfur co-modified biochar as claimed in any one of claims 1 to 7, wherein in step S6, after cooling to room temperature, the reactant solid is taken out and washed with a mixed solution of ethanol and water by suction filtration.
9. The method for preparing bismuth tungstate nitrogen sulfur co-modified biochar as claimed in any one of claims 1 to 8, wherein in step S7, the washed reactant solid is dried at 80 ℃ for 4h to obtain bismuth tungstate nitrogen sulfur co-modified biochar Bi2WO6/NSBC。
10. The preparation method of bismuth tungstate nitrogen sulfur co-modified biochar as claimed in any one of claims 1 to 9, wherein in step S1, the weight ratio of thiourea to the biochar raw material is 2: 1-1: 1, such as 3: 2; preferably, in steps S2-S7, the following proportioning relationship is adopted: 0.1-0.05g of 4mmol of sodium oleate, 4mmol of bismuth nitrate pentahydrate, 2mmol of sodium tungstate dihydrate and nitrogen-sulfur doped modified biochar NSBC.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113181889A (en) * | 2021-06-11 | 2021-07-30 | 清华大学深圳国际研究生院 | Preparation method of sodium polyacrylate dispersed ferrous sulfide grafted nitrogen-doped biochar |
| CN113198431A (en) * | 2021-06-12 | 2021-08-03 | 清华大学深圳国际研究生院 | Preparation and application of carbonized sodium alginate-coated or iron/manganese cross-linked modified biochar |
| CN113413870A (en) * | 2021-05-17 | 2021-09-21 | 中国科学院青海盐湖研究所 | Magnesium oxide-metal sulfide-biomass charcoal composite material and preparation method and application thereof |
| CN115501858A (en) * | 2022-10-19 | 2022-12-23 | 辽宁大学 | Magnetic sulfur-nitrogen doped biochar composite material, preparation method thereof and application thereof in co-adsorption of antibiotics and heavy metal ions |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110172092A1 (en) * | 2010-01-13 | 2011-07-14 | Ut-Battelle, Llc | Biochar Production Method and Composition Therefrom |
| US20150251172A1 (en) * | 2012-09-21 | 2015-09-10 | Toto Ltd. | Composite photocatalyst, and photocatalyst material |
| CN107497455A (en) * | 2017-09-28 | 2017-12-22 | 福州大学 | A kind of preparation method and applications of the ultra-thin Bismuth tungstate nano-sheet photochemical catalyst of Determination of Trace Sulfur surface modification |
| CN107537469A (en) * | 2016-06-27 | 2018-01-05 | 张家港市杨舍丝印工艺厂 | A kind of preparation method of bismuth tungstate Quito member heterojunction photocatalyst |
| CN108940191A (en) * | 2018-06-05 | 2018-12-07 | 西北农林科技大学 | A kind of sulphur N doping multiporous biological charcoal, preparation method and application |
| CN111036273A (en) * | 2019-12-30 | 2020-04-21 | 吉林农业大学 | Corn straw biochar and Bi for efficiently degrading organic pollutants2WO6Method for preparing photocatalyst |
-
2020
- 2020-04-29 CN CN202010358073.3A patent/CN111530487A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110172092A1 (en) * | 2010-01-13 | 2011-07-14 | Ut-Battelle, Llc | Biochar Production Method and Composition Therefrom |
| US20150251172A1 (en) * | 2012-09-21 | 2015-09-10 | Toto Ltd. | Composite photocatalyst, and photocatalyst material |
| CN107537469A (en) * | 2016-06-27 | 2018-01-05 | 张家港市杨舍丝印工艺厂 | A kind of preparation method of bismuth tungstate Quito member heterojunction photocatalyst |
| CN107497455A (en) * | 2017-09-28 | 2017-12-22 | 福州大学 | A kind of preparation method and applications of the ultra-thin Bismuth tungstate nano-sheet photochemical catalyst of Determination of Trace Sulfur surface modification |
| CN108940191A (en) * | 2018-06-05 | 2018-12-07 | 西北农林科技大学 | A kind of sulphur N doping multiporous biological charcoal, preparation method and application |
| CN111036273A (en) * | 2019-12-30 | 2020-04-21 | 吉林农业大学 | Corn straw biochar and Bi for efficiently degrading organic pollutants2WO6Method for preparing photocatalyst |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113413870A (en) * | 2021-05-17 | 2021-09-21 | 中国科学院青海盐湖研究所 | Magnesium oxide-metal sulfide-biomass charcoal composite material and preparation method and application thereof |
| CN113413870B (en) * | 2021-05-17 | 2022-11-25 | 中国科学院青海盐湖研究所 | Magnesium oxide-metal sulfide-biomass charcoal composite material and preparation method and application thereof |
| CN113181889A (en) * | 2021-06-11 | 2021-07-30 | 清华大学深圳国际研究生院 | Preparation method of sodium polyacrylate dispersed ferrous sulfide grafted nitrogen-doped biochar |
| CN113181889B (en) * | 2021-06-11 | 2023-02-24 | 清华大学深圳国际研究生院 | Preparation method of sodium polyacrylate dispersed ferrous sulfide grafted nitrogen-doped biochar |
| CN113198431A (en) * | 2021-06-12 | 2021-08-03 | 清华大学深圳国际研究生院 | Preparation and application of carbonized sodium alginate-coated or iron/manganese cross-linked modified biochar |
| CN115501858A (en) * | 2022-10-19 | 2022-12-23 | 辽宁大学 | Magnetic sulfur-nitrogen doped biochar composite material, preparation method thereof and application thereof in co-adsorption of antibiotics and heavy metal ions |
| CN115501858B (en) * | 2022-10-19 | 2023-12-08 | 辽宁大学 | Magnetic sulfur-nitrogen doped biochar composite material, preparation method thereof and application thereof in co-adsorption of antibiotics and heavy metal ions |
| CN116532084A (en) * | 2023-04-28 | 2023-08-04 | 淮安兴淮消防设备有限公司 | Nd-doped Bi 2 WO 6 Preparation and application of nanoflower-biomass porous carbon material |
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