CN111957310A - Preparation method and application of silver-titanium dioxide-carbon nano composite material - Google Patents
Preparation method and application of silver-titanium dioxide-carbon nano composite material Download PDFInfo
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- CN111957310A CN111957310A CN202010786549.3A CN202010786549A CN111957310A CN 111957310 A CN111957310 A CN 111957310A CN 202010786549 A CN202010786549 A CN 202010786549A CN 111957310 A CN111957310 A CN 111957310A
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- butyl titanate
- silver
- silver nitrate
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 21
- MVTRSNDLGXMUHB-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4].[Ag+] Chemical compound [C+4].[O-2].[O-2].[Ti+4].[Ag+] MVTRSNDLGXMUHB-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 98
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 43
- 239000002028 Biomass Substances 0.000 claims abstract description 42
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 38
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 32
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 32
- 235000005822 corn Nutrition 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 241000209149 Zea Species 0.000 claims abstract 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 230000001699 photocatalysis Effects 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 49
- 230000033558 biomineral tissue development Effects 0.000 abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 52
- 239000000243 solution Substances 0.000 description 32
- 240000008042 Zea mays Species 0.000 description 28
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002060 nanoflake Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
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- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000013329 compounding Methods 0.000 description 3
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 3
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- 210000003041 ligament Anatomy 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
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- -1 polysaccharide compounds Chemical class 0.000 description 2
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- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 238000004887 air purification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 1
- HTRJDXQPCKIFIU-UHFFFAOYSA-N silver;ethanol;nitrate Chemical compound [Ag+].CCO.[O-][N+]([O-])=O HTRJDXQPCKIFIU-UHFFFAOYSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Images
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
-
- 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
Abstract
The invention relates to a preparation method of a silver-titanium dioxide-carbon nano composite material, which comprises the following steps: adding biomass corn stalks into a mixed ethanol solution of silver nitrate and butyl titanate, soaking for 24 hours in a dark place to enable the butyl titanate and the silver nitrate to be fully adsorbed on the biomass corn stalks, and then illuminating for 2 hours under sunlight to enable Ag ions to perform photochemical reduction reaction to form an Ag simple substance; finally, the supported TiO is2Taking out the biomass cornstalks of the nano particles and the Ag simple substance, naturally drying, calcining and cooling to room temperature to obtain the Ag/TiO2@ C nanocomposite. The invention also discloses an application of the composite material. The invention adopts two steps of photochemical reduction and high-temperature calcinationThe method prepares a series of Ag/TiO2The method is simple and easy to implement, and the obtained composite material can achieve the purpose of improving the removal rate and mineralization rate of phenol under visible light.
Description
Technical Field
The invention relates to the technical field of composite materials and environmental pollution treatment, in particular to a preparation method and application of a silver-titanium dioxide-carbon nano composite material.
Background
The photocatalytic oxidation technology can degrade organic matters in the environment into water, carbon dioxide and the like under the excitation of light, and has wide application prospects in the aspects of air purification, sterilization, deodorization, wastewater treatment and the like. In the photocatalytic oxidation technology, the photocatalytic material plays an important role. TiO 22The nano material has the advantages of strong oxidation capacity, good stability, low price, no toxicity, no harm and the like, has wide application potential, but the TiO2Belongs to a wide band gap semiconductor, can only absorb ultraviolet light, and the ultraviolet light only occupies about 4 percent in sunlight, thereby greatly limiting TiO2Popularization and application of the method.
To improve TiO2The research personnel research the methods of metal and nonmetal doping, dye sensitization, semiconductor compounding, noble metal compounding, carbon material compounding and the like. Wherein the noble metal is mixed with TiO2The composite material is one of means for effectively improving the visible light response and the photocatalytic activity of the composite material. Not only can effectively expand TiO by the plasma effect of noble metal2Can also promote TiO by inhibiting the separation of photogenerated electron holes2Photocatalytic activity of (1). The simple substance of noble metal silver as a less expensive noble metal has the characteristics of noble metal, and TiO2The phase recombination can better promote the visible light catalytic activity of the material, and a proper amount of carbon material is helpful for improving the separation efficiency of photo-generated electron holes.
Corn stalks are usually discarded as agricultural wastes, contain macromolecular polysaccharide compounds such as cellulose, hemicellulose, lignin and the like, are mutually crosslinked to form a regular natural micro-nano structure, are usually used for preparing porous carbon materials and are applied to adsorbing heavy metal ions and organic pollutants. On the other hand, the polysaccharide compounds contain a large number of hydroxyl, carboxyl and amino functional groups, can be used as a reactor of the nano material, provide utilization sites for the nucleation and growth of the nano material, and control the size of nano particles, thereby obtaining the nano material with special morphology and good dispersion.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a silver-titanium dioxide-carbon nano composite material, which is simple and easy to implement.
In order to solve the problems, the preparation method of the silver-titanium dioxide-carbon nano composite material is characterized by comprising the following steps: adding biomass corn stalks into a mixed ethanol solution of silver nitrate and butyl titanate, soaking for 24 hours in a dark place to enable the butyl titanate and the silver nitrate to be fully adsorbed on the biomass corn stalks, and then illuminating for 2 hours under sunlight to enable Ag ions to perform photochemical reduction reaction to form an Ag simple substance; finally, the supported TiO is2Taking out the biomass cornstalks of the nano particles and the Ag simple substance, naturally drying, calcining and cooling to room temperature to obtain the Ag/TiO2@ C nanocomposite.
The preparation method of the mixed ethanol solution of silver nitrate and butyl titanate is to firstly prepare a butyl titanate ethanol solution with the concentration of 0.0585 mol/L; and adding different amounts of silver nitrate into 50 mL of the solution to ensure that the molar ratio of the silver nitrate to the butyl titanate is 0.025/1-1.25/1, stirring for 10 minutes, and uniformly mixing to obtain the silver nitrate-butyl titanate nano-silver nano-particles.
The butyl titanate ethanol solution with the concentration of 0.0585 mol/L is a solution obtained by adding 1mL of butyl titanate into 49mL of absolute ethanol and uniformly mixing.
The biomass cornstalk is obtained by cutting dried corncobs into slices, soaking the slices in deionized water for 3-5 times to remove soluble substances, and drying the slices at room temperature.
The calcination condition is that the temperature is raised to 700 ℃ at the heating rate of 5 ℃/min in the atmosphere of air in a muffle furnace, and the temperature is kept for 2 h.
Ag/TiO prepared by the method2The application of the @ C nanocomposite is characterized in that: the Ag/TiO2The @ C nanocomposite is used for degrading organic substance phenol in wastewater under the photocatalytic condition.
Compared with the prior art, the invention has the following advantages:
1. the invention takes corn stalks as a template and a carbon source, soaks butyl titanate and silver nitrate ethanol solution in the corn stalks, and adopts a photochemical reduction-high temperature calcination two-step method to prepare a series of Ag/TiO2The @ C nanocomposite is simple in method and easy to implement.
2. The biomass cornstalk not only can be used as TiO2And Ag nanoparticles as template to form nano-flakes, and optionally high-temperature calcining to form carbon material as linked TiO2Ligaments of the nanoparticles.
3. The invention uses Ag simple substance and TiO2The nano-sheet phase is compounded to form a heterojunction to promote TiO2The separation of the photo-generated electron hole improves the visible light catalytic performance.
4. For the Ag/TiO obtained by the invention2The structure and performance of the @ C nanocomposite were evaluated:
fig. 1 shows Ag/TiO prepared under different Ag usage conditions2The XRD spectrum of the @ C composite material. As can be seen from FIG. 1, the different AgNO3In an amount corresponding to TiO2Can have an effect.
When AgNO3At lower dosages, the composite material is mainly anatase (JCPDS 21-1272), when AgNO is used3The rutile crystal form (JCPDS 21-1276) appears in the composite material in small quantity when the dosage is increased, and the dosage is along with AgNO3The proportion of rutile in the composite material is gradually increased by increasing the dosage, thereby showing AgNO3To TiO 22Has a certain influence on the formation of the crystal phase, and is beneficial to forming rutile TiO2. 0.025Ag/TiO prepared with lower Ag dosage2@ C and 0.25Ag/TiO2The @ C composite material has no obvious diffraction peak of noble metal Ag, and the reason is that the Ag content in the composite material is too low to be detected. 1.25Ag/TiO Ag of higher Ag content2The @ C composite material has a weak cubic phase crystal phase Ag elementary substance diffraction peak (JCPDS 03-0921) at an angle of 44.3 degrees of 2 theta, and the diffraction peak of Ag at an angle of 38.0 degrees and the diffraction peak of anatase are mutually overlapped, so that the diffraction peak intensity of Ag at an angle of 38.0 degrees is not obvious. Several materials have no diffraction peak of carbon, and may have less carbon contentFor the reason. Visible, Ag/TiO2@ C composite material mainly comprising TiO in different crystal forms2Mainly contains a small amount of Ag simple substance.
Secondly, FIG. 2 shows 0.25Ag/TiO with different magnifications2SEM image of @ C composite. As can be seen from FIG. 2a, the material has the morphology of nano-flakes, and the nano-flakes are well dispersed and do not form obvious agglomeration and accumulation; as can be seen from FIG. 2b, the thickness of the nano-flake is about 100 nm, and as can be seen from FIG. 2c with a larger magnification, the surface of the nano-flake shows more wrinkles, and the nano-flake is composed of uniform nano-particles, the size of the nano-particles is between 10 nm and 20 nm, and the nano-particles should be TiO2And Ag elementary substance nanoparticles, and carbon as a linkage TiO2The ligaments of the nanoparticles form a lamellar structure, thereby enabling the Ag/TiO2The @ C composite material maintains the morphology of the biomass. Most of biomass is gradually decomposed into CO in the high-temperature calcination process2And butyl titanate is converted to TiO during high temperature calcination2Nanoparticles, a small amount of biomass converted to carbon, becoming linked TiO2The prepared composite material well replicates the morphology of a biological template and forms a thin nanometer sheet morphology due to the ligament of the nanometer particles.
Thirdly, in order to further observe Ag/TiO2The morphology of the @ C composite material is tested and 0.25Ag/TiO2TEM and HRTEM images of the @ C composite material, electron diffraction and EDX elemental analysis were performed, and the results are shown in FIG. 3.
As can be seen from FIG. 3a, the composite material has a nanosheet shape, which is consistent with SEM picture analysis, spherical or cubic nanoparticles with a deep color are dispersed on the nanosheets, the size of the nanoparticles is about 10 nm, and the nanoparticles are dispersed on TiO2The Ag nanoparticles on the nanosheets, in addition to some feather-like material, should be agglomerated TiO2And (3) nano materials. From the HRTEM image of FIG. 3b, the TiO can be seen2And lattice fringes of Ag nanoparticles, wherein the lattice fringes of 0.35nm correspond to anatase TiO2(101) Crystal face, the lattice stripe is 0.24 nm, the lattice stripe corresponds to the (111) crystal face of the cubic phase Ag simple substance, and the composite material is proved to contain the Ag simple substance and anatase TiO2. While the electron diffraction pattern shows different diffraction points corresponding to anatase TiO2And diffraction points of different crystal faces of the Ag simple substance. EDX element analysis shows that the material mainly contains Ti, O, C and a small amount of Ag element.
The above characterization shows that the method synthesizes Ag/TiO2@ C composite material. Preparing Ag/TiO by biological template method2In the process of the @ C composite material, most of the biological templates are gradually decomposed into CO in the calcining process2And a small amount of biological templates containing hydroxyl and carbonyl provide oxygen atoms for titanium dioxide to become ligaments for linking titanium dioxide nanoparticles, so that the titanium dioxide nanoparticles are stacked to form a nanosheet structure, and the morphology of the biological templates is maintained. Ag ions are converted into Ag simple substances under illumination, the existence of carbon creates an anoxic environment for the Ag simple substances, the oxidation of Ag nano particles is inhibited, and the Ag nano particles are dispersed in TiO in the form of noble metal simple substances2Formation of Ag/TiO on @ C nanosheet layer2A heterojunction.
5. The invention takes phenol which is a common organic pollutant in industrial wastewater as a target degradation product, and evaluates the visible light catalytic activity of the composite material by the removal rate and mineralization rate of the phenol under visible light, thereby providing a new idea for the development of nano-photocatalyst.
FIG. 4 shows different AgNO3Ag/TiO prepared by using amount2@ C composite and TiO2@ C for the visible photocatalytic properties of phenol. As can be seen from FIG. 4, an appropriate amount of noble metal Ag promotes TiO2The visible light of (2) can catalyze the removal of phenol. Ag-free TiO2The removal rate of the @ C material to phenol is 80.80% in 300 minutes of visible light illumination; and the prepared Ag/TiO with the increase of the Ag content2The removal rate of the @ C composite material to phenol under visible light is gradually increased, and the removal rates to phenol are 91.24%, 92.18%, 94.90%, 99.84% and 98.38%, wherein 0.25Ag/TiO2The removal rate of the @ C composite material to phenol reaches 99.84%, and the composite material has the optimal visible light catalytic activity. Continuously increasing AgNO3Amount of 1.25Ag/TiO prepared2The removal rate of the @ C composite material to phenol was 67.27%, the removal rate to phenol was sharpDecrease to show proper amount of Ag and TiO2The composition of the @ C material is helpful for improving TiO2Visible light photocatalytic activity of (1).
FIG. 5 shows Ag/TiO mixtures with different Ag contents2@ C composite material and TiO without Ag2The ability of @ C to mineralize phenol under visible light is shown in FIG. 5, which shows that TiO without Ag2The mineralization rate of the @ C composite material to phenol is 61.14% when the visible light irradiates for 300 minutes. Several kinds of Ag/TiO2The @ C composite material has better mineralization capability on phenol, and the prepared Ag/TiO material is added with the content of Ag2The mineralization rate of the @ C composite material to phenol is gradually increased and is respectively 70.52%, 75.52%, 82.19%, 94.07% and 91.77%. Wherein 0.25Ag/TiO2The mineralization rate of the @ C composite material to phenol reaches 94.07%, and the composite material has the optimal mineralization capacity. When the content of Ag is continuously increased, the prepared Ag/TiO2The mineralization rate of the @ C composite material to phenol is 51.59%. Visible, Ag/TiO2The mineralization rate of the @ C composite material to phenol is basically consistent with the trend of the performance of removing phenol by photocatalysis.
According to the comparison of the mineralization rate and the removal rate of the composite material on the phenol, the mineralization rates of the composite materials on the phenol are slightly lower than the removal rate, the degradation of the composite material on the phenol is relatively thorough, and most of the phenol is completely mineralized into pollution-free CO2And water. Thus, the appropriate amounts of noble metals silver and TiO2The @ C material is compounded, so that not only can TiO be improved2The @ C composite material has the effect of removing phenol through photocatalysis and has a good mineralization effect.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows different Ag/TiO materials of the present invention2The XRD spectrum of the @ C composite material.
FIG. 2 shows 0.25Ag/TiO of the present invention2SEM picture of @ C.
FIG. 3 shows 0.25Ag/TiO of the present invention2TEM image (a), HRTEM image (b), electron diffraction image (C), and EDX elemental analysis (d) of @ C composite.
FIG. 4 shows Ag/TiO of the present invention2@ C composite materialThe visible light catalysis removal effect on phenol.
FIG. 5 shows Ag/TiO of the present invention2The mineralization performance of @ C composite material on phenol.
Detailed Description
Example 1a method of preparing a silver-titanium dioxide-carbon nanocomposite:
adding 0.75g of biomass corn stalks into 50 mL of mixed ethanol solution of silver nitrate and butyl titanate, soaking the biomass corn stalks for 24 hours in the dark to enable the butyl titanate and the silver nitrate to be fully adsorbed on the biomass corn stalks, and then illuminating the biomass corn stalks for 2 hours under sunlight to enable Ag ions to perform photochemical reduction reaction to form an Ag simple substance; finally, the supported TiO is2Taking out the biomass cornstalks of the nano particles and the Ag simple substance, naturally airing, putting into a crucible, heating to 700 ℃ at a heating rate of 5 ℃/min in a muffle furnace under the air atmosphere, calcining, preserving heat for 2h, and cooling to room temperature to obtain 0.025Ag/TiO2@ C nanocomposite.
Wherein: the preparation method of the mixed ethanol solution of silver nitrate and butyl titanate is to firstly prepare the butyl titanate ethanol solution with the concentration of 0.0585 mol/L; and then adding silver nitrate into 50 mL of the solution to ensure that the molar ratio of the silver nitrate to the butyl titanate is 0.025/1, stirring for 10 minutes, and uniformly mixing to obtain the silver nitrate-butyl titanate nano-silver/silver nitrate nano-silver titanate nano-silver oxide.
The composite material has the removal rate of 91.24% and the mineralization rate of 70.52% on phenol when being irradiated by visible light for 300 minutes.
Example 2a method of preparing a silver-titanium dioxide-carbon nanocomposite:
adding 0.75g of biomass corn stalks into 50 mL of mixed ethanol solution of silver nitrate and butyl titanate, soaking the biomass corn stalks for 24 hours in the dark to enable the butyl titanate and the silver nitrate to be fully adsorbed on the biomass corn stalks, and then illuminating the biomass corn stalks for 2 hours under sunlight to enable Ag ions to perform photochemical reduction reaction to form an Ag simple substance; finally, the supported TiO is2Taking out the biomass cornstalks of the nano particles and the Ag simple substance, naturally airing the cornstalks, putting the cornstalks in a crucible, heating the cornstalks to 700 ℃ at a heating rate of 5 ℃/min in a muffle furnace under the air atmosphere, calcining the cornstalks, preserving the heat for 2 hours, and cooling the cornstalks to room temperature to obtain 0.05Ag/TiO2@ C nanocomposite。
Wherein: the preparation method of the mixed ethanol solution of silver nitrate and butyl titanate is to firstly prepare the butyl titanate ethanol solution with the concentration of 0.0585 mol/L; then adding different amounts of silver nitrate into 50 mL of the solution to ensure that the molar ratio of the silver nitrate to the butyl titanate is 0.05/1, stirring for 10 minutes, and uniformly mixing to obtain the silver nitrate-butyl titanate aqueous solution.
The composite material has the removal rate of 92.18% and the mineralization rate of 75.52% on phenol when being irradiated by visible light for 300 minutes.
Example 3a method of preparing a silver-titanium dioxide-carbon nanocomposite:
adding 0.75g of biomass corn stalks into 50 mL of mixed ethanol solution of silver nitrate and butyl titanate, soaking the biomass corn stalks for 24 hours in the dark to enable the butyl titanate and the silver nitrate to be fully adsorbed on the biomass corn stalks, and then illuminating the biomass corn stalks for 2 hours under sunlight to enable Ag ions to perform photochemical reduction reaction to form an Ag simple substance; finally, the supported TiO is2Taking out the biomass cornstalks of the nano particles and the Ag simple substance, naturally airing the cornstalks, putting the cornstalks in a crucible, heating the cornstalks to 700 ℃ at a heating rate of 5 ℃/min in a muffle furnace under the air atmosphere, calcining the cornstalks, preserving the heat for 2 hours, and cooling the cornstalks to room temperature to obtain 0.1Ag/TiO2@ C nanocomposite.
Wherein: the preparation method of the mixed ethanol solution of silver nitrate and butyl titanate is to firstly prepare the butyl titanate ethanol solution with the concentration of 0.0585 mol/L; then adding different amounts of silver nitrate into 50 mL of the solution to ensure that the molar ratio of the silver nitrate to the butyl titanate is 0.1/1, stirring for 10 minutes, and uniformly mixing to obtain the silver nitrate-butyl titanate aqueous solution.
The composite material has a phenol removal rate of 94.90% and a mineralization rate of 82.19% under visible light illumination for 300 minutes.
Example 4 a method of preparing a silver-titanium dioxide-carbon nanocomposite:
adding 0.75g of biomass corn stalks into 50 mL of mixed ethanol solution of silver nitrate and butyl titanate, soaking the biomass corn stalks for 24 hours in the dark to enable the butyl titanate and the silver nitrate to be fully adsorbed on the biomass corn stalks, and then illuminating the biomass corn stalks for 2 hours under sunlight to enable Ag ions to perform photochemical reduction reaction to form an Ag simple substance; finally, the supported TiO is2Nano-particlesTaking out the biomass cornstalks with the particles and the Ag simple substance, naturally airing the cornstalks, putting the cornstalks in a crucible, heating the cornstalks to 700 ℃ at a heating rate of 5 ℃/min in a muffle furnace under the air atmosphere, calcining the cornstalks, preserving the heat for 2 hours, and cooling the cornstalks to room temperature to obtain 0.25Ag/TiO2@ C nanocomposite.
Wherein: the preparation method of the mixed ethanol solution of silver nitrate and butyl titanate is to firstly prepare the butyl titanate ethanol solution with the concentration of 0.0585 mol/L; then adding different amounts of silver nitrate into 50 mL of the solution to ensure that the molar ratio of the silver nitrate to the butyl titanate is 0.25/1, stirring for 10 minutes, and uniformly mixing to obtain the silver nitrate-butyl titanate aqueous solution.
The composite material has a phenol removal rate of 99.84% and a mineralization rate of 94.07% under visible light illumination for 300 minutes.
Example 5a method of preparing a silver-titanium dioxide-carbon nanocomposite:
adding 0.75g of biomass corn stalks into 50 mL of mixed ethanol solution of silver nitrate and butyl titanate, soaking the biomass corn stalks for 24 hours in the dark to enable the butyl titanate and the silver nitrate to be fully adsorbed on the biomass corn stalks, and then illuminating the biomass corn stalks for 2 hours under sunlight to enable Ag ions to perform photochemical reduction reaction to form an Ag simple substance; finally, the supported TiO is2Taking out the biomass cornstalks of the nano particles and the Ag simple substance, naturally airing the cornstalks, putting the cornstalks in a crucible, heating the cornstalks to 700 ℃ at a heating rate of 5 ℃/min in a muffle furnace under the air atmosphere, calcining the cornstalks, preserving the heat for 2 hours, and cooling the cornstalks to room temperature to obtain 0.5Ag/TiO2@ C nanocomposite.
Wherein: the preparation method of the mixed ethanol solution of silver nitrate and butyl titanate is to firstly prepare the butyl titanate ethanol solution with the concentration of 0.0585 mol/L; then adding different amounts of silver nitrate into 50 mL of the solution to ensure that the molar ratio of the silver nitrate to the butyl titanate is 0.5/1, stirring for 10 minutes, and uniformly mixing to obtain the silver nitrate-butyl titanate aqueous solution.
The composite material has a phenol removal rate of 98.38% and a mineralization rate of 91.77% under visible light illumination for 300 minutes.
Example 6 a method of preparing a silver-titanium dioxide-carbon nanocomposite:
0.75g of raw material was added to 50 mL of a mixed ethanol solution of silver nitrate and butyl titanateSoaking the substance corn stalks in the dark for 24 hours to enable butyl titanate and silver nitrate to be fully adsorbed on the substance corn stalks, and then illuminating the substance corn stalks under sunlight for 2 hours to enable Ag ions to perform photochemical reduction reaction to form Ag simple substances; finally, the supported TiO is2Taking out the biomass cornstalks of the nano particles and the Ag simple substance, naturally airing the cornstalks, putting the cornstalks in a crucible, heating the cornstalks to 700 ℃ at a heating rate of 5 ℃/min in a muffle furnace under the air atmosphere, calcining the cornstalks, preserving the heat for 2 hours, and cooling the cornstalks to room temperature to obtain 1.25Ag/TiO2@ C nanocomposite.
Wherein: the preparation method of the mixed ethanol solution of silver nitrate and butyl titanate is to firstly prepare the butyl titanate ethanol solution with the concentration of 0.0585 mol/L; then adding different amounts of silver nitrate into 50 mL of the solution to ensure that the molar ratio of the silver nitrate to the butyl titanate is 1.25/1, stirring for 10 minutes, and uniformly mixing to obtain the silver nitrate-butyl titanate aqueous solution.
The material has the removal rate of 67.27% and the mineralization rate of 51.59% on phenol when the material is illuminated by visible light for 300 minutes.
In examples 1 to 6, the butyl titanate ethanol solution having a concentration of 0.0585 mol/L was obtained by adding 1mL of butyl titanate to 49mL of anhydrous ethanol and mixing the mixture uniformly.
The biomass cornstalk is obtained by cutting dried corncobs into slices, soaking the slices in deionized water for 3-5 times to remove soluble substances, and drying the slices at room temperature.
Ag/TiO powders obtained in examples 1 to 62Application of @ C nanocomposites: the Ag/TiO2The @ C nanocomposite is used for degrading organic substance phenol in wastewater under the photocatalytic condition.
Claims (6)
1. A preparation method of a silver-titanium dioxide-carbon nano composite material is characterized by comprising the following steps: adding biomass corn stalks into a mixed ethanol solution of silver nitrate and butyl titanate, soaking for 24 hours in a dark place to enable the butyl titanate and the silver nitrate to be fully adsorbed on the biomass corn stalks, and then illuminating for 2 hours under sunlight to enable Ag ions to perform photochemical reduction reaction to form an Ag simple substance; finally, the supported TiO is2Taking out the biomass cornstalks of the nano particles and the Ag simple substance, and naturally treatingAir drying, calcining and cooling to room temperature to obtain Ag/TiO2@ C nanocomposite.
2. The method of preparing a silver-titanium dioxide-carbon nanocomposite as claimed in claim 1, wherein: the preparation method of the mixed ethanol solution of silver nitrate and butyl titanate is to firstly prepare a butyl titanate ethanol solution with the concentration of 0.0585 mol/L; and adding different amounts of silver nitrate into 50 mL of the solution to ensure that the molar ratio of the silver nitrate to the butyl titanate is 0.025/1-1.25/1, stirring for 10 minutes, and uniformly mixing to obtain the silver nitrate-butyl titanate nano-silver nano-particles.
3. The method of preparing a silver-titanium dioxide-carbon nanocomposite material according to claim 2, wherein: the butyl titanate ethanol solution with the concentration of 0.0585 mol/L is a solution obtained by adding 1mL of butyl titanate into 49mL of absolute ethanol and uniformly mixing.
4. The method of preparing a silver-titanium dioxide-carbon nanocomposite as claimed in claim 1, wherein: the biomass cornstalk is obtained by cutting dried corncobs into slices, soaking the slices in deionized water for 3-5 times to remove soluble substances, and drying the slices at room temperature.
5. The method of preparing a silver-titanium dioxide-carbon nanocomposite as claimed in claim 1, wherein: the calcination condition is that the temperature is raised to 700 ℃ at the heating rate of 5 ℃/min in the atmosphere of air in a muffle furnace, and the temperature is kept for 2 h.
6. Ag/TiO compounds produced by the method of claim 12The application of the @ C nanocomposite is characterized in that: the Ag/TiO2The @ C nanocomposite is used for degrading organic substance phenol in wastewater under the photocatalytic condition.
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