WO2024077411A1 - Bismuth titanate nanosheet/uio-66-nh2 heterojunction containing bismuth vacancies, preparation method therefor and use thereof - Google Patents
Bismuth titanate nanosheet/uio-66-nh2 heterojunction containing bismuth vacancies, preparation method therefor and use thereof Download PDFInfo
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- 229910002115 bismuth titanate Inorganic materials 0.000 title claims abstract description 111
- 239000002135 nanosheet Substances 0.000 title claims abstract description 96
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 82
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- 238000002360 preparation method Methods 0.000 title abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 36
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- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- PSVSZBOMJGAVRS-UHFFFAOYSA-N 2,3-diaminoterephthalic acid Chemical compound NC1=C(N)C(C(O)=O)=CC=C1C(O)=O PSVSZBOMJGAVRS-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 229910000416 bismuth oxide Inorganic materials 0.000 claims abstract description 8
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
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- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 16
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- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 239000001103 potassium chloride Substances 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 4
- 235000019743 Choline chloride Nutrition 0.000 claims description 4
- 229960003178 choline chloride Drugs 0.000 claims description 4
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical group [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 4
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- 239000003054 catalyst Substances 0.000 abstract description 14
- 239000013078 crystal Substances 0.000 abstract description 5
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- 238000002386 leaching Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
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- 238000001179 sorption measurement Methods 0.000 description 3
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
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- 150000001450 anions Chemical class 0.000 description 1
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- 150000001621 bismuth Chemical class 0.000 description 1
- 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 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
Definitions
- the invention relates to the technical field of inorganic/organic nanocomposite materials, and in particular to the preparation of bismuth titanate nanosheets/UiO-66- NH2 heterojunctions containing bismuth vacancies and their application in catalytic oxidation of formaldehyde.
- Formaldehyde is one of the main indoor pollutants and is widely present in various building and decoration materials. Long-term exposure to air with even very low formaldehyde gas content may cause irreversible adverse effects on the human respiratory system.
- the catalytic oxidation method can use active oxygen species to decompose formaldehyde gas into harmless carbon dioxide and water. Due to its long-term effectiveness, this method of purifying formaldehyde gas has attracted the attention of researchers.
- the current methods used for catalytic oxidation of formaldehyde gas are mainly photocatalysis and thermal catalysis. However, traditional photocatalysts have a narrow light absorption range and serious recombination of photogenerated electron-hole pairs, while thermal catalysts generally require the use of precious metals and are expensive.
- piezoelectric catalytic technology provides an efficient "green” method for utilizing these environmental mechanical energies. Under the action of mechanical stress, piezoelectric materials can generate piezoelectric potential, inducing free electrons and holes inside the piezoelectric material to reach the surface of the material to participate in redox reactions, thereby achieving the purpose of degrading pollutants.
- perovskite-type bismuth titanate has attracted the attention of researchers in the field of piezoelectric catalysis due to its unique layered crystal structure and good ferroelectric properties.
- the prior art discloses methods for improving the piezoelectric properties of bismuth titanate, such as increasing its piezoelectric coefficient by reducing the thickness of bismuth titanate nanosheets; enhancing the asymmetry of the crystal structure by introducing oxygen vacancies; strengthening ferroelectric polarization by coupling corona polarization and surface iodine ion grafting, and promoting the separation and transfer of carriers.
- the catalytic effect of modified bismuth titanate nanomaterials in the piezoelectric catalytic oxidation of formaldehyde gas needs to be improved.
- the purpose of the present invention is to provide a method for preparing a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies.
- Using bismuth titanate nanosheets containing bismuth vacancies as a substrate hydrothermally growing UiO-66- NH2 nanoparticles to construct a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies, a unique charged layer structure of alternating ( Bi2O2 ) 2+ layers and anion layers, so that the material forms an interlayer built-in electric field along the c-axis direction; it has high porosity and large specific surface area, and the introduction of amino groups further increases the catalytic performance of the material to formaldehyde gas.
- a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies and its preparation method comprises the following steps: (1) mixing titanium dioxide, bismuth oxide and inorganic salt and calcining to obtain bismuth titanate nanosheets, and then immersing the bismuth titanate nanosheets in an ionic eutectic solvent to obtain bismuth titanate nanosheets containing bismuth vacancies; (2) hydrothermally reacting a mixture of bismuth titanate nanosheets containing bismuth vacancies, diaminoterephthalic acid, zirconium chloride and acetic acid to obtain a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies.
- the preparation method is further described as follows: (1) titanium dioxide, bismuth oxide and inorganic salt are mixed and ground, and then calcined to prepare bismuth titanate nanosheets, and then the bismuth titanate nanosheets are immersed in an ionic eutectic solvent composed of a hydrogen bond donor and a hydrogen bond acceptor, and bismuth atoms are leached from the bismuth titanate lattice to form bismuth titanate nanosheets containing bismuth vacancies; (2) diaminoterephthalic acid, zirconium chloride and acetic acid are added to the bismuth titanate nanosheet solution containing bismuth vacancies, and a hydrothermal reaction is carried out to prepare a bismuth titanate nanosheet containing bismuth vacancies/UiO-66- NH2 heterojunction material.
- a method for catalytically oxidizing formaldehyde comprises the following steps: placing a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies into an environment containing formaldehyde, and achieving catalytic oxidation of formaldehyde under ultrasonic conditions.
- the inorganic salt is sodium chloride and potassium chloride; the molar ratio of titanium dioxide and bismuth oxide is 3:2, and the molar ratio of bismuth titanate, sodium chloride and potassium chloride is 1: (40-90): (40-90), preferably 1: 60: 60; the grinding time is 10 min to 60 min; the calcination temperature is 500°C to 1000°C, preferably 800°C, and the calcination time is 1 to 5 hours, preferably 2 h; preferably, after calcination, washing with water and then drying, such as vacuum drying at 60°C for 12 h, to obtain bismuth titanate nanosheets.
- the hydrogen bond donor is ethylene glycol
- the hydrogen bond acceptor is choline chloride
- the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is (1.5-3):1, preferably 2:1
- the hydrogen bond donor and the hydrogen bond acceptor are mixed to form an ionic eutectic solvent
- the bismuth titanate nanosheet is immersed in the ionic eutectic solvent, reacted at 70-90°C for 2 h-10 h, preferably at 80°C for 4 h, washed with water, and then dried, such as vacuum dried at 60°C for 12 h, to obtain a bismuth titanate nanosheet containing bismuth vacancies.
- the present invention adopts a simple ionic eutectic solvent soaking method to leach part of the bismuth atoms from the bismuth titanate nanosheet to obtain a bismuth titanate nanosheet containing bismuth vacancies, and the vacancies can effectively improve the piezoelectric catalytic performance.
- step (2) the mass ratio of bismuth titanate nanosheets containing bismuth vacancies, diaminoterephthalic acid, and zirconium chloride is (400-1500): (100-150): (80-100), preferably (900-1000): (100-130): (80-100), such as (950-1000): (110-120): (85-95).
- the bismuth titanate nanosheet solution containing bismuth vacancies is an aqueous solution with a concentration of 300-400 mg/mL; the hydrothermal reaction is 80°C-120°C for 20-30 hours, preferably 100°C for 24 hours, then washed with water and methanol, and then dried, such as 60°C vacuum drying for 12 hours, to obtain a bismuth titanate nanosheet containing bismuth vacancies/UiO-66- NH2 heterojunction.
- the present invention uses an ionic eutectic solvent to leach bismuth atoms from the bismuth titanate lattice to form cationic defects.
- the construction of vacancies changes the geometric structure of coordinated atoms, effectively improving the catalytic activity.
- the present invention combines bismuth titanate nanosheets containing bismuth vacancies with UiO-66- NH2 nanoparticles for the first time to construct bismuth titanate nanosheets containing bismuth vacancies/UiO-66- NH2 heterojunctions, which work together to greatly increase the material's treatment performance for formaldehyde gas, with a removal rate of 95.1% in 180 minutes at room temperature.
- FIG1 is a scanning electron microscope image of bismuth titanate nanosheets containing bismuth vacancies.
- Figure 2 shows the scanning electron microscope and transmission electron microscope images of the bismuth titanate nanosheets/UiO-66- NH2 heterojunction containing bismuth vacancies, with the transmission electron microscope image in the upper left corner.
- FIG. 3 is a curve diagram showing the piezoelectric catalytic oxidation of formaldehyde gas in the air by the catalyst.
- FIG4 is a cycle curve diagram of the piezoelectric catalytic oxidation of formaldehyde gas in the air by bismuth titanate nanosheets/UiO-66-NH 2 heterojunction containing bismuth vacancies.
- FIG5 is a graph showing the piezoelectric catalytic oxidation of formaldehyde gas for catalysts prepared by different preparation methods.
- FIG6 is a curve showing the effect of bismuth vacancies on the piezoelectric catalytic oxidation of formaldehyde gas.
- the present invention uses ionic eutectic solvent method, hydrothermal method and other preparation methods to construct a bismuth titanate nanosheet/UiO-66- NH2 heterogeneous material containing bismuth vacancies.
- Bismuth titanate can produce strong spontaneous polarization in the crystal, which is helpful for the separation of free carriers.
- the introduction of bismuth vacancies enhances the asymmetry of the crystal structure of the material and further improves the piezoelectric catalytic activity.
- UiO-66- NH2 has a high specific surface area, a developed microporous structure and outstanding chemical stability.
- the raw materials of the present invention are all commercially available products, and the specific preparation operations and performance tests are conventional techniques. Unless otherwise specified, the operations of the present invention are carried out at room temperature and in air.
- Example 1 Preparation of bismuth titanate nanosheets containing bismuth vacancies, the specific steps are as follows: 0.24 g titanium dioxide, 0.93 g bismuth oxide, 3.51 g sodium chloride, and 4.47 g potassium chloride are placed in a mortar, ground for 30 min, then calcined at 800 ° C for 2 h, then centrifuged and washed with deionized water, and finally dried in a vacuum oven at 60 ° C for 12 h to obtain bismuth titanate nanosheets, which are white powder solids. 2.64 g choline chloride is dissolved in 2.11 mL ethylene glycol to form an ionic eutectic solvent at room temperature.
- Figure 1 is a scanning electron microscope image of a bismuth titanate nanosheet containing bismuth vacancies. It can be seen from the above figure that the bismuth titanate nanosheet containing bismuth vacancies presents a layered structure, the thickness of the nanosheet is in the nanometer order, the plane size is in the micrometer order, and the specific surface area is large.
- Example 2 Preparation of bismuth titanate nanosheets containing bismuth vacancies/UiO-66- NH2 heterojunction, the specific steps are as follows: 980 mg of bismuth titanate nanosheets containing bismuth vacancies are dispersed in 3 ml of deionized water, and then 116.6 mg of zirconium chloride, 90.5 mg of diaminoterephthalic acid, and 2 ml of acetic acid are added, and then reacted at 100°C for 24 h, and then washed with deionized water 3 times, soaked and washed with methanol 3 times, and finally dried in a vacuum oven at 60°C for 12 h to obtain the final product, bismuth titanate nanosheets containing bismuth vacancies-10/UiO-66- NH2 heterojunction.
- Figure 2 shows the scanning electron microscope image and transmission electron microscope image of the above-mentioned bismuth titanate nanosheet-10/UiO-66- NH2 heterojunction containing bismuth vacancies. It can be seen from the above-mentioned figure that small-sized octahedral UiO-66- NH2 is uniformly grown on the surface of the bismuth titanate nanosheet containing bismuth vacancies.
- Example 3 Preparation of bismuth titanate nanosheets/UiO-66- NH2 heterojunctions containing bismuth vacancies in different molar ratios. The specific steps are as follows: 490 mg of bismuth titanate nanosheets containing bismuth vacancies are dispersed in 3 ml of deionized water, and then 116.6 mg of zirconium chloride, 90.5 mg of diaminoterephthalic acid, and 2 ml of acetic acid are added, and then reacted at 100°C for 24 h, and then washed with deionized water 3 times, soaked and washed with methanol 3 times, and finally dried in a vacuum oven at 60°C for 12 h to obtain the final product, bismuth titanate nanosheets containing bismuth vacancies-5/UiO-66- NH2 heterojunction.
- Example 4 Preparation of bismuth titanate nanosheets/UiO-66- NH2 heterojunctions containing bismuth vacancies in different molar ratios. The specific steps are as follows: 1470 mg of bismuth titanate nanosheets containing bismuth vacancies are dispersed in 3 ml of deionized water, and then 116.6 mg of zirconium chloride, 90.5 mg of diaminoterephthalic acid, and 2 ml of acetic acid are added, and then reacted at 100°C for 24 h, and then washed with deionized water 3 times, soaked and washed with methanol 3 times, and finally dried in a vacuum oven at 60°C for 12 h to obtain the final product, bismuth titanate nanosheets containing bismuth vacancies-15/UiO-66- NH2 heterojunction.
- Example 5 Formaldehyde gas piezoelectric catalytic oxidation experiment: 37% formaldehyde solution was diluted to 75 mg/mL formaldehyde solution, 20 ⁇ L of the prepared formaldehyde solution was placed in a 5 L gas generator, and the formaldehyde gas was volatilized by heating to form a simulated gas with a formaldehyde concentration of about 300 mg/m 3 .
- bismuth titanate nanosheets/UiO-66- NH2 heterojunction materials or other catalysts containing bismuth vacancies are placed in simulated gas containing formaldehyde gas, vibrated for a certain period of time using ultrasound as a mechanical source, and the change curve of formaldehyde concentration in the simulated gas with vibration time is measured to evaluate the effect of the composite material on piezoelectric catalytic oxidation of formaldehyde gas in the air under the action of mechanical force.
- the catalysts are bismuth titanate nanosheets, bismuth titanate nanosheets containing bismuth vacancies, and bismuth titanate nanosheets containing bismuth vacancies/UiO-66-NH 2 at different molar ratios.
- Figure 3 shows the piezoelectric catalytic oxidation curves of different catalysts for formaldehyde gas in simulated gas.
- the bismuth titanate nanosheet-10/UiO-66-NH 2 heterojunction containing bismuth vacancies of the present invention has the highest piezoelectric catalytic oxidation efficiency for formaldehyde gas in simulated gas, with a removal rate of 95.1% in 180 minutes; while the removal rate of the bismuth titanate nanosheet alone in 180 minutes is only 39.8%, indicating that the bismuth titanate nanosheet-10/UiO-66-NH 2 catalyst containing bismuth vacancies of the present invention has excellent catalytic performance.
- 75 mg of the catalyst (Example 2) was placed in 5 L of formaldehyde simulated gas with a concentration of 200 mg/m 3.
- Formaldehyde could be completely removed in 150 minutes.
- Example 3 required 180 minutes to completely remove formaldehyde. The remaining catalysts could not be completely removed in 180 minutes, and the residual amount exceeded 15 mg/m 3 .
- Example 6 Cyclic experiment of piezoelectric catalytic oxidation of formaldehyde in air by bismuth titanate nanosheet-10/UiO-66- NH2 heterojunction containing bismuth vacancies: The composite material recovered after 180 min of ultrasound in Example 5 was washed with deionized water, placed in a vacuum oven for drying, and then added to a newly prepared 5 L formaldehyde simulation gas with a concentration of 300 mg/ m3 , ultrasound (480 W, 45 Hz), 5 mL was sampled every 30 min, injected into the developer, and the absorbance of the sample at a wavelength of 630 nm was detected by a UV-visible spectrophotometer and the concentration of residual formaldehyde was calculated by the formaldehyde concentration-absorbance standard curve.
- Comparative Example 1 Replace the molten salt method of Example 1 with a solvent thermal method: Dissolve 12 g of sodium hydroxide in 30 mL of deionized water, and dissolve by ultrasonic dispersion to form a sodium hydroxide solution; Add 0.84 g of tetrabutyl titanate and 2.79 g of bismuth nitrate pentahydrate to the sodium hydroxide aqueous solution under stirring, continue stirring for 2 h, and then transfer to a 50 ml polytetrafluoroethylene-lined stainless steel autoclave after ultrasonication for 30 min, and heat at 180 ° C for 20 hours; After the reaction, wash the sample with deionized water and ethanol 3 times each, and vacuum dry at 60 ° C for 12 h to obtain bismuth titanate nanospheres.
- Example 5 a piezoelectric catalytic oxidation experiment of formaldehyde gas at room temperature was carried out. The results are shown in FIG5 .
- the catalyst obtained by the solvent thermal reaction has poor piezoelectricity, and its maximum removal rate is 64.1%, which is difficult to improve even if the time is extended.
- Comparative Example 2 The bismuth titanate nanosheet of Example 1 was taken and the method of Example 2 was referred to obtain a bismuth titanate nanosheet/UiO-66-NH 2 heterojunction.
- a room temperature formaldehyde gas piezoelectric catalytic oxidation experiment was carried out with reference to Example 5. The results are shown in FIG6 , and bismuth vacancies significantly improve the catalytic performance.
- Comparative Example 3 Take the bismuth titanate nanosheets of Example 1, place them in a tubular furnace, and anneal them at 260°C for 15 minutes under vacuum to obtain bismuth titanate nanosheets containing oxygen vacancies.
- Example 5 for a room temperature formaldehyde gas piezoelectric catalytic oxidation experiment.
- the piezoelectric catalytic performance of the bismuth titanate nanosheets containing oxygen vacancies is worse than that of the bismuth titanate nanosheets containing bismuth vacancies, and the formaldehyde removal rate at 180 minutes is 46.9%.
- the present invention uses bismuth titanate nanosheets containing bismuth vacancies as a substrate, and hydrothermally grows UiO-66- NH2 nanoparticles to construct bismuth titanate nanosheets containing bismuth vacancies/UiO-66- NH2 heterojunctions.
- the electronic structure is effectively modulated, the charge transfer properties are improved, and the charge diffusion coefficient is significantly improved, thereby improving the charge transfer efficiency; it has an ultra-high specific surface area and permanent porosity, and the introduction of -NH2 increases the adsorption performance of the material for gaseous formaldehyde.
- the skeleton structure of UiO-66- NH2 can withstand a mechanical pressure of 1MPa and has good chemical stability.
- the bismuth titanate nanosheets containing bismuth vacancies/UiO-66- NH2 heterojunction prepared by the present invention realizes efficient piezoelectric catalytic oxidation of formaldehyde gas through the synergistic effect of adsorption catalysis, which is the first example of pure piezoelectric catalytic removal of formaldehyde.
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Abstract
The present invention discloses a bismuth titanate nanosheet/UiO-66-NH2 heterojunction containing bismuth vacancies, a preparation method therefor and a use thereof. Titanium dioxide, bismuth oxide and inorganic salt are mixed and calcined to obtain a bismuth titanate nanosheet, and the bismuth titanate nanosheet is then immersed in an ionic cocrystal solvent to obtain the bismuth titanate nanosheet containing bismuth vacancies; and a mixture of the bismuth titanate nanosheet containing bismuth vacancies, diaminoterephthalic acid, zirconium chloride and acetic acid is subjected to hydrothermal reaction to obtain the bismuth titanate nanosheet/UiO-66-NH2 heterojunction containing bismuth vacancies. Bismuth vacancies are constructed on the bismuth titanate nanosheet by adopting a simple ionic cocrystal solvent leaching method so as to effectively increase the asymmetry of the crystal structure of the bismuth titanate nanosheet. A catalyst constructed by using the bismuth titanate nanosheet containing bismuth vacancies as a substrate and hydrothermally growing UiO-66-NH2 nanoparticles has excellent piezoelectric catalytic performance.
Description
本发明涉及无机/有机纳米复合材料技术领域，具体涉及含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结的制备及其在催化氧化甲醛中的应用。
The invention relates to the technical field of inorganic/organic nanocomposite materials, and in particular to the preparation of bismuth titanate nanosheets/UiO-66- NH2 heterojunctions containing bismuth vacancies and their application in catalytic oxidation of formaldehyde.
甲醛是目前主要的室内污染物之一，广泛存在于各种建筑和装饰材料中。长期暴露在即使甲醛气体含量极小的空气中，也可能对人体呼吸系统造成不可逆转的不良影响。催化氧化法可以利用活性氧物种将甲醛气体分解成无害的二氧化碳和水，由于其长效性，这种净化甲醛气体的方法受到研究者们的关注。目前用于催化氧化甲醛气体的方法主要是光催化和热催化。然而，传统的光催化剂光吸收范围窄、光生电子-空穴对复合严重，而热催化剂一般需要使用贵金属负载、成本较高。除了太阳能和热能外，自然界中还存在许多其他的可再生能源，如风能、潮汐能、水能等。如何利用这些机械能解决环境污染问题成为了人们关注的热点，压电催化技术的诞生为利用这些环境机械能提供了高效的“绿色”方法。在机械应力的作用下，压电材料能够产生压电势，诱导压电材料内部的自由电子和空穴到达材料表面参与氧化还原反应，达到降解污染物的目的。随着纳米技术的发展，钙钛矿型钛酸铋因其独特的层状晶体结构和良好的铁电性能，在压电催化领域受到研究者的关注。现有技术公开了提升钛酸铋压电性能的方法，如通过减小钛酸铋纳米片的厚度来提升其压电系数；通过引入氧空位来增强晶体结构的不对称性；通过耦合电晕极化和表面碘离子接枝来加强铁电极化，促进载流子的分离和转移等。纵观现有技术，改性钛酸铋纳米材料在压电催化氧化甲醛气体时，催化效果还需改善。Formaldehyde is one of the main indoor pollutants and is widely present in various building and decoration materials. Long-term exposure to air with even very low formaldehyde gas content may cause irreversible adverse effects on the human respiratory system. The catalytic oxidation method can use active oxygen species to decompose formaldehyde gas into harmless carbon dioxide and water. Due to its long-term effectiveness, this method of purifying formaldehyde gas has attracted the attention of researchers. The current methods used for catalytic oxidation of formaldehyde gas are mainly photocatalysis and thermal catalysis. However, traditional photocatalysts have a narrow light absorption range and serious recombination of photogenerated electron-hole pairs, while thermal catalysts generally require the use of precious metals and are expensive. In addition to solar energy and thermal energy, there are many other renewable energy sources in nature, such as wind energy, tidal energy, and hydropower. How to use these mechanical energies to solve environmental pollution problems has become a hot topic of concern. The birth of piezoelectric catalytic technology provides an efficient "green" method for utilizing these environmental mechanical energies. Under the action of mechanical stress, piezoelectric materials can generate piezoelectric potential, inducing free electrons and holes inside the piezoelectric material to reach the surface of the material to participate in redox reactions, thereby achieving the purpose of degrading pollutants. With the development of nanotechnology, perovskite-type bismuth titanate has attracted the attention of researchers in the field of piezoelectric catalysis due to its unique layered crystal structure and good ferroelectric properties. The prior art discloses methods for improving the piezoelectric properties of bismuth titanate, such as increasing its piezoelectric coefficient by reducing the thickness of bismuth titanate nanosheets; enhancing the asymmetry of the crystal structure by introducing oxygen vacancies; strengthening ferroelectric polarization by coupling corona polarization and surface iodine ion grafting, and promoting the separation and transfer of carriers. Looking at the prior art, the catalytic effect of modified bismuth titanate nanomaterials in the piezoelectric catalytic oxidation of formaldehyde gas needs to be improved.
本发明的目的是提供一种含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结的制备方法。以含铋空位的钛酸铋纳米片为基底，水热生长UiO-66-NH
2纳米颗粒构建含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结，独特的(Bi
2O
2)
2+层和阴离子层交错的带电层结构，使材料沿c轴方向形成层间内建电场；具有高孔隙率、大比表面积，同时氨基的引入进一步加大了材料对甲醛气体的催化性能。
The purpose of the present invention is to provide a method for preparing a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies. Using bismuth titanate nanosheets containing bismuth vacancies as a substrate, hydrothermally growing UiO-66- NH2 nanoparticles to construct a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies, a unique charged layer structure of alternating ( Bi2O2 ) 2+ layers and anion layers, so that the material forms an interlayer built-in electric field along the c-axis direction; it has high porosity and large specific surface area, and the introduction of amino groups further increases the catalytic performance of the material to formaldehyde gas.
为了达到上述目的，本发明采用如下具体技术方案：一种含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结，其制备方法包括以下步骤：（1）将二氧化钛、氧化铋、无机盐混合后煅烧，得到钛酸铋纳米片，然后将钛酸铋纳米片浸入离子共晶溶剂中，得到含铋空位的钛酸铋纳米片；（2）将含铋空位的钛酸铋纳米片、二氨基对苯二甲酸、氯化锆和乙酸的混合物水热反应，得到含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结。
In order to achieve the above-mentioned purpose, the present invention adopts the following specific technical scheme: a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies, and its preparation method comprises the following steps: (1) mixing titanium dioxide, bismuth oxide and inorganic salt and calcining to obtain bismuth titanate nanosheets, and then immersing the bismuth titanate nanosheets in an ionic eutectic solvent to obtain bismuth titanate nanosheets containing bismuth vacancies; (2) hydrothermally reacting a mixture of bismuth titanate nanosheets containing bismuth vacancies, diaminoterephthalic acid, zirconium chloride and acetic acid to obtain a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies.
上述制备方法进一步描述如下：（1）将二氧化钛、氧化铋、无机盐混合研磨，然后煅烧，制备钛酸铋纳米片，然后将钛酸铋纳米片浸入由氢键供体和氢键受体组成的离子共晶溶剂中，通过从钛酸铋晶格中浸出铋原子，从而形成含铋空位的钛酸铋纳米片；（2）向含有铋空位的钛酸铋纳米片溶液中加入二氨基对苯二甲酸、氯化锆和乙酸，水热反应，制备含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结材料。
The preparation method is further described as follows: (1) titanium dioxide, bismuth oxide and inorganic salt are mixed and ground, and then calcined to prepare bismuth titanate nanosheets, and then the bismuth titanate nanosheets are immersed in an ionic eutectic solvent composed of a hydrogen bond donor and a hydrogen bond acceptor, and bismuth atoms are leached from the bismuth titanate lattice to form bismuth titanate nanosheets containing bismuth vacancies; (2) diaminoterephthalic acid, zirconium chloride and acetic acid are added to the bismuth titanate nanosheet solution containing bismuth vacancies, and a hydrothermal reaction is carried out to prepare a bismuth titanate nanosheet containing bismuth vacancies/UiO-66- NH2 heterojunction material.
一种催化氧化甲醛的方法，包括以下步骤：将含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结置入含有甲醛的环境中，在超声条件下实现甲醛的催化氧化。
A method for catalytically oxidizing formaldehyde comprises the following steps: placing a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies into an environment containing formaldehyde, and achieving catalytic oxidation of formaldehyde under ultrasonic conditions.
上述技术方案中，步骤（1）中，无机盐为氯化钠、氯化钾；二氧化钛、氧化铋的摩尔比为3∶2，钛酸铋、氯化钠、氯化钾的摩尔比为1∶（40～90）∶（40～90），优选1∶60∶60；研磨的时间为10 min～60min；煅烧的温度为500℃～1000℃，优选800℃，煅烧的时间为1～5小时，优选2 h；优选的，煅烧之后，用水洗涤，然后干燥，比如60℃真空干燥12 h，得到钛酸铋纳米片。In the above technical scheme, in step (1), the inorganic salt is sodium chloride and potassium chloride; the molar ratio of titanium dioxide and bismuth oxide is 3:2, and the molar ratio of bismuth titanate, sodium chloride and potassium chloride is 1: (40-90): (40-90), preferably 1: 60: 60; the grinding time is 10 min to 60 min; the calcination temperature is 500°C to 1000°C, preferably 800°C, and the calcination time is 1 to 5 hours, preferably 2 h; preferably, after calcination, washing with water and then drying, such as vacuum drying at 60°C for 12 h, to obtain bismuth titanate nanosheets.
上述技术方案中，步骤（1）中，氢键供体为乙二醇，氢键受体为氯化胆碱，优选的，氢键供体和氢键受体的摩尔比为（1.5～3）∶1，优选2∶1，在室温下，氢键供体和氢键受体混合形成离子共晶溶剂，将钛酸铋纳米片浸入离子共晶溶剂中，70～90℃反应2 h～10 h，优选80℃反应4 h后，用水洗涤，然后干燥，比如60℃真空干燥12 h，获得含铋空位的钛酸铋纳米片。本发明采用简单的离子共晶溶剂浸泡的方法，将部分铋原子从钛酸铋纳米片中浸出，获得含铋空位的钛酸铋纳米片，空位能够有效提升压电催化性能。In the above technical scheme, in step (1), the hydrogen bond donor is ethylene glycol, the hydrogen bond acceptor is choline chloride, preferably, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is (1.5-3):1, preferably 2:1, at room temperature, the hydrogen bond donor and the hydrogen bond acceptor are mixed to form an ionic eutectic solvent, the bismuth titanate nanosheet is immersed in the ionic eutectic solvent, reacted at 70-90°C for 2 h-10 h, preferably at 80°C for 4 h, washed with water, and then dried, such as vacuum dried at 60°C for 12 h, to obtain a bismuth titanate nanosheet containing bismuth vacancies. The present invention adopts a simple ionic eutectic solvent soaking method to leach part of the bismuth atoms from the bismuth titanate nanosheet to obtain a bismuth titanate nanosheet containing bismuth vacancies, and the vacancies can effectively improve the piezoelectric catalytic performance.
上述技术方案中，步骤（2）中，含有铋空位的钛酸铋纳米片、二氨基对苯二甲酸、氯化锆的质量比为（400～1500）∶（100～150）∶（80～100），优选为（900～1000）∶（100～130）∶（80～100），比如（950～1000）∶（110～120）∶（85～95）。优选的，含铋空位的钛酸铋纳米片溶液为水溶液，浓度为300～400mg/mL；水热反应为80℃～120℃反应20～30小时，优选100℃反应24 h后用水、甲醇洗涤，然后干燥，比如60℃真空干燥12 h，得到含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结。
In the above technical scheme, in step (2), the mass ratio of bismuth titanate nanosheets containing bismuth vacancies, diaminoterephthalic acid, and zirconium chloride is (400-1500): (100-150): (80-100), preferably (900-1000): (100-130): (80-100), such as (950-1000): (110-120): (85-95). Preferably, the bismuth titanate nanosheet solution containing bismuth vacancies is an aqueous solution with a concentration of 300-400 mg/mL; the hydrothermal reaction is 80°C-120°C for 20-30 hours, preferably 100°C for 24 hours, then washed with water and methanol, and then dried, such as 60°C vacuum drying for 12 hours, to obtain a bismuth titanate nanosheet containing bismuth vacancies/UiO-66- NH2 heterojunction.
本发明的优点：本发明使用离子共晶溶剂从钛酸铋晶格中浸出铋原子以形成阳离子缺陷。空位的构建改变了配位原子的几何结构，有效提高催化活性。尤其是，本发明首次将含铋空位的钛酸铋纳米片与UiO-66-NH
2纳米颗粒结合，构建含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结，共同作用极大增加了材料对甲醛气体的处理性能，常温下180分钟去除率达到95.1%。
Advantages of the present invention: The present invention uses an ionic eutectic solvent to leach bismuth atoms from the bismuth titanate lattice to form cationic defects. The construction of vacancies changes the geometric structure of coordinated atoms, effectively improving the catalytic activity. In particular, the present invention combines bismuth titanate nanosheets containing bismuth vacancies with UiO-66- NH2 nanoparticles for the first time to construct bismuth titanate nanosheets containing bismuth vacancies/UiO-66- NH2 heterojunctions, which work together to greatly increase the material's treatment performance for formaldehyde gas, with a removal rate of 95.1% in 180 minutes at room temperature.
图1为含铋空位的钛酸铋纳米片的扫描电镜图。FIG1 is a scanning electron microscope image of bismuth titanate nanosheets containing bismuth vacancies.
图2为含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结的扫描电镜图与透射电镜图，其中左上角为透射电镜图。
Figure 2 shows the scanning electron microscope and transmission electron microscope images of the bismuth titanate nanosheets/UiO-66- NH2 heterojunction containing bismuth vacancies, with the transmission electron microscope image in the upper left corner.
图3为催化剂对空气中甲醛气体压电催化氧化的曲线图。FIG. 3 is a curve diagram showing the piezoelectric catalytic oxidation of formaldehyde gas in the air by the catalyst.
图4为含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结对空气中甲醛气体压电催化氧化的循环曲线图。
FIG4 is a cycle curve diagram of the piezoelectric catalytic oxidation of formaldehyde gas in the air by bismuth titanate nanosheets/UiO-66-NH 2 heterojunction containing bismuth vacancies.
图5为不同制备方法制备的催化剂的甲醛气体压电催化氧化的曲线图。FIG5 is a graph showing the piezoelectric catalytic oxidation of formaldehyde gas for catalysts prepared by different preparation methods.
图6为铋空位对甲醛气体压电催化氧化的影响关系曲线。FIG6 is a curve showing the effect of bismuth vacancies on the piezoelectric catalytic oxidation of formaldehyde gas.
针对现有纳米压电催化材料实际应用中存在的缺陷，本发明利用离子共晶溶剂法，水热法等制备方法构筑了一种含铋空位的钛酸铋纳米片/ UiO-66-NH
2异质。钛酸铋能在晶体中产生强烈的自发极化，有助于自由载流子的分离。铋空位的引入增强了材料晶体结构的不对称性，进一步提升了压电催化活性。UiO-66-NH
2具有较高的比表面积，发达的微孔结构和突出的化学稳定性，此外，氨基的引入进一步加大了材料对甲醛气体的处理性能。通过复合材料吸附和压电催化协同作用，实现了催化氧化空气中甲醛污染物的目的。
In view of the defects existing in the practical application of existing nano-piezoelectric catalytic materials, the present invention uses ionic eutectic solvent method, hydrothermal method and other preparation methods to construct a bismuth titanate nanosheet/UiO-66- NH2 heterogeneous material containing bismuth vacancies. Bismuth titanate can produce strong spontaneous polarization in the crystal, which is helpful for the separation of free carriers. The introduction of bismuth vacancies enhances the asymmetry of the crystal structure of the material and further improves the piezoelectric catalytic activity. UiO-66- NH2 has a high specific surface area, a developed microporous structure and outstanding chemical stability. In addition, the introduction of amino groups further increases the material's treatment performance for formaldehyde gas. Through the synergistic effect of composite material adsorption and piezoelectric catalysis, the purpose of catalytic oxidation of formaldehyde pollutants in the air is achieved.
本发明的原料都是市售产品，具体制备操作以及性能测试为常规技术，如无特殊说明，本发明操作在室温、空气中进行。The raw materials of the present invention are all commercially available products, and the specific preparation operations and performance tests are conventional techniques. Unless otherwise specified, the operations of the present invention are carried out at room temperature and in air.
实施例一：含铋空位的钛酸铋纳米片的制备，具体步骤如下：将0.24 g二氧化钛、0.93 g 氧化铋、3.51 g 氯化钠、4.47 g 氯化钾放入研钵中，研磨30min，然后在800℃下煅烧2 h，之后用去离子水离心洗涤，最后在60℃真空烘箱中干燥12 h，得到钛酸铋纳米片，为白色粉末状固体。将2.64 g氯化胆碱溶于2.11 mL乙二醇中，在室温下形成离子共晶溶剂。向离子共晶溶剂中加入1 g钛酸铋纳米片，80℃反应4 h，之后用去离子水离心洗涤3次，最后在60℃真空烘箱中干燥12 h，得到含铋空位的钛酸铋纳米片。Example 1: Preparation of bismuth titanate nanosheets containing bismuth vacancies, the specific steps are as follows: 0.24 g titanium dioxide, 0.93 g bismuth oxide, 3.51 g sodium chloride, and 4.47 g potassium chloride are placed in a mortar, ground for 30 min, then calcined at 800 ° C for 2 h, then centrifuged and washed with deionized water, and finally dried in a vacuum oven at 60 ° C for 12 h to obtain bismuth titanate nanosheets, which are white powder solids. 2.64 g choline chloride is dissolved in 2.11 mL ethylene glycol to form an ionic eutectic solvent at room temperature. 1 g bismuth titanate nanosheets are added to the ionic eutectic solvent, reacted at 80 ° C for 4 h, then centrifuged and washed with deionized water 3 times, and finally dried in a vacuum oven at 60 ° C for 12 h to obtain bismuth titanate nanosheets containing bismuth vacancies.
附图1为含铋空位的钛酸铋纳米片的扫描电镜图，从上述图中可以看出含铋空位的钛酸铋纳米片呈现层状结构，纳米片厚度在纳米量级，平面尺寸大小在微米级别，比表面积较大。Figure 1 is a scanning electron microscope image of a bismuth titanate nanosheet containing bismuth vacancies. It can be seen from the above figure that the bismuth titanate nanosheet containing bismuth vacancies presents a layered structure, the thickness of the nanosheet is in the nanometer order, the plane size is in the micrometer order, and the specific surface area is large.
实施例二：含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结的制备，具体步骤如下：将980 mg含铋空位的钛酸铋纳米片分散于3 ml去离子水中，然后加入116.6 mg 氯化锆、90.5 mg 二氨基对苯二甲酸、2 ml乙酸，再于100℃反应24 h，然后用去离子水洗涤3次，甲醇浸泡洗涤3次，最后在60℃真空烘箱中干燥12 h，得到最终产物含铋空位的钛酸铋纳米片-10/UiO-66-NH
2异质结。
Example 2: Preparation of bismuth titanate nanosheets containing bismuth vacancies/UiO-66- NH2 heterojunction, the specific steps are as follows: 980 mg of bismuth titanate nanosheets containing bismuth vacancies are dispersed in 3 ml of deionized water, and then 116.6 mg of zirconium chloride, 90.5 mg of diaminoterephthalic acid, and 2 ml of acetic acid are added, and then reacted at 100°C for 24 h, and then washed with deionized water 3 times, soaked and washed with methanol 3 times, and finally dried in a vacuum oven at 60°C for 12 h to obtain the final product, bismuth titanate nanosheets containing bismuth vacancies-10/UiO-66- NH2 heterojunction.
附图2为上述含铋空位的钛酸铋纳米片-10/ UiO-66-NH
2异质结的扫描电镜图和透射电镜图，从上述图中可以看出小尺寸的八面体UiO-66-NH
2均匀生长在含铋空位的钛酸铋纳米片表面。
Figure 2 shows the scanning electron microscope image and transmission electron microscope image of the above-mentioned bismuth titanate nanosheet-10/UiO-66- NH2 heterojunction containing bismuth vacancies. It can be seen from the above-mentioned figure that small-sized octahedral UiO-66- NH2 is uniformly grown on the surface of the bismuth titanate nanosheet containing bismuth vacancies.
实施例三：不同摩尔比含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结的制备，具体步骤如下：将490 mg含铋空位的钛酸铋纳米片分散于3 ml去离子水中，然后加入116.6 mg 氯化锆、90.5 mg 二氨基对苯二甲酸、2 ml乙酸，再于100℃反应24 h，然后用去离子水洗涤3次，甲醇浸泡洗涤3次，最后在60℃真空烘箱中干燥12 h，得到最终产物含铋空位的钛酸铋纳米片-5/UiO-66-NH
2异质结。
Example 3: Preparation of bismuth titanate nanosheets/UiO-66- NH2 heterojunctions containing bismuth vacancies in different molar ratios. The specific steps are as follows: 490 mg of bismuth titanate nanosheets containing bismuth vacancies are dispersed in 3 ml of deionized water, and then 116.6 mg of zirconium chloride, 90.5 mg of diaminoterephthalic acid, and 2 ml of acetic acid are added, and then reacted at 100°C for 24 h, and then washed with deionized water 3 times, soaked and washed with methanol 3 times, and finally dried in a vacuum oven at 60°C for 12 h to obtain the final product, bismuth titanate nanosheets containing bismuth vacancies-5/UiO-66- NH2 heterojunction.
实施例四：不同摩尔比含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结的制备，具体步骤如下：将1470 mg含铋空位的钛酸铋纳米片分散于3 ml去离子水中，然后加入116.6 mg 氯化锆、90.5 mg 二氨基对苯二甲酸、2 ml乙酸，再于100℃反应24 h，然后用去离子水洗涤3次，甲醇浸泡洗涤3次，最后在60℃真空烘箱中干燥12 h，得到最终产物含铋空位的钛酸铋纳米片-15/UiO-66-NH
2异质结。
Example 4: Preparation of bismuth titanate nanosheets/UiO-66- NH2 heterojunctions containing bismuth vacancies in different molar ratios. The specific steps are as follows: 1470 mg of bismuth titanate nanosheets containing bismuth vacancies are dispersed in 3 ml of deionized water, and then 116.6 mg of zirconium chloride, 90.5 mg of diaminoterephthalic acid, and 2 ml of acetic acid are added, and then reacted at 100°C for 24 h, and then washed with deionized water 3 times, soaked and washed with methanol 3 times, and finally dried in a vacuum oven at 60°C for 12 h to obtain the final product, bismuth titanate nanosheets containing bismuth vacancies-15/UiO-66- NH2 heterojunction.
实施例五 甲醛气体压电催化氧化实验：将37%甲醛溶液稀释成75 mg/mL的甲醛溶液，取20μL配置的甲醛溶液置于5 L气体发生器中，加热使甲醛气体挥发，形成甲醛浓度约为300 mg/m
3的模拟气。
Example 5 Formaldehyde gas piezoelectric catalytic oxidation experiment: 37% formaldehyde solution was diluted to 75 mg/mL formaldehyde solution, 20 μL of the prepared formaldehyde solution was placed in a 5 L gas generator, and the formaldehyde gas was volatilized by heating to form a simulated gas with a formaldehyde concentration of about 300 mg/m 3 .
室温下，将含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结材料或者其他催化剂置入含甲醛气体的模拟气中，以超声为机械源振动一定的时间，并测定模拟气中甲醛浓度随振动时间的变化曲线，以评价该复合材料在机械力作用下对空气中甲醛气体压电催化氧化的效果。
At room temperature, bismuth titanate nanosheets/UiO-66- NH2 heterojunction materials or other catalysts containing bismuth vacancies are placed in simulated gas containing formaldehyde gas, vibrated for a certain period of time using ultrasound as a mechanical source, and the change curve of formaldehyde concentration in the simulated gas with vibration time is measured to evaluate the effect of the composite material on piezoelectric catalytic oxidation of formaldehyde gas in the air under the action of mechanical force.
取75 mg催化剂置于5 L浓度为300 mg/m
3的甲醛模拟气中，超声（480 W，45 Hz），每隔30 min取样5 mL，注入显色剂中，使用紫外-可见分光光度计检测样品在630 nm波长下的吸光度并通过甲醛浓度-吸光度标准曲线计算得到的残留甲醛的浓度。随着压电催化的进行，甲醛残留浓度逐渐下降，从而得到具体的甲醛压电催化氧化曲线。
75 mg of catalyst was placed in 5 L of formaldehyde simulated gas with a concentration of 300 mg/m 3 , and ultrasonic (480 W, 45 Hz) was used. 5 mL of sample was taken every 30 min and injected into the color developer. The absorbance of the sample at a wavelength of 630 nm was detected by a UV-visible spectrophotometer and the concentration of residual formaldehyde was calculated by the formaldehyde concentration-absorbance standard curve. As the piezoelectric catalysis proceeded, the residual formaldehyde concentration gradually decreased, thus obtaining a specific formaldehyde piezoelectric catalytic oxidation curve.
催化剂分别为钛酸铋纳米片、含铋空位的钛酸铋纳米片、不同摩尔比含铋空位的钛酸铋纳米片/UiO-66-NH
2。附图3为不同催化剂对模拟气中甲醛气体的压电催化氧化曲线，可以看出，本发明含铋空位的钛酸铋纳米片-10/UiO-66-NH
2异质结对模拟气中甲醛气体的压电催化氧化效率最高，180分钟去除率达到95.1%；而单独的钛酸铋纳米片180分钟去除率仅为39.8%；说明本发明含铋空位的钛酸铋纳米片-10/UiO-66-NH
2催化剂的催化性能优异。尤其是，取75 mg催化剂（实施例二）置于5 L浓度为200 mg/m
3的甲醛模拟气中，150min可完全去除甲醛，对应的，实施例三需要180分钟可完全去除，其余催化剂在180分钟时都无法完全去除，残留超过15mg/m
3。
The catalysts are bismuth titanate nanosheets, bismuth titanate nanosheets containing bismuth vacancies, and bismuth titanate nanosheets containing bismuth vacancies/UiO-66-NH 2 at different molar ratios. Figure 3 shows the piezoelectric catalytic oxidation curves of different catalysts for formaldehyde gas in simulated gas. It can be seen that the bismuth titanate nanosheet-10/UiO-66-NH 2 heterojunction containing bismuth vacancies of the present invention has the highest piezoelectric catalytic oxidation efficiency for formaldehyde gas in simulated gas, with a removal rate of 95.1% in 180 minutes; while the removal rate of the bismuth titanate nanosheet alone in 180 minutes is only 39.8%, indicating that the bismuth titanate nanosheet-10/UiO-66-NH 2 catalyst containing bismuth vacancies of the present invention has excellent catalytic performance. In particular, 75 mg of the catalyst (Example 2) was placed in 5 L of formaldehyde simulated gas with a concentration of 200 mg/m 3. Formaldehyde could be completely removed in 150 minutes. Correspondingly, Example 3 required 180 minutes to completely remove formaldehyde. The remaining catalysts could not be completely removed in 180 minutes, and the residual amount exceeded 15 mg/m 3 .
实施例六 含铋空位的钛酸铋纳米片-10/UiO-66-NH
2异质结对空气中甲醛压电催化氧化的循环实验：实施例五中经超声180 min后回收的复合材料用去离子水洗涤，置于真空烘箱中烘干，再重新加入到新配制的5 L浓度为300 mg/m
3的甲醛模拟气中，超声（480 W，45 Hz），每30 min取样5 mL，注入显色剂中，使用紫外-可见分光光度计检测样品在630 nm波长下的吸光度并通过甲醛浓度-吸光度标准曲线计算得到的残留甲醛的浓度。依照上述步骤重复5次，分别测试并记录数据，其结果如附图4所示。从中可以看出，在五次重复过程中，本发明的压电催化剂始终保持着优良的压电催化性能。因此，该催化剂可以重复使用，具有良好的稳定性。
Example 6 Cyclic experiment of piezoelectric catalytic oxidation of formaldehyde in air by bismuth titanate nanosheet-10/UiO-66- NH2 heterojunction containing bismuth vacancies: The composite material recovered after 180 min of ultrasound in Example 5 was washed with deionized water, placed in a vacuum oven for drying, and then added to a newly prepared 5 L formaldehyde simulation gas with a concentration of 300 mg/ m3 , ultrasound (480 W, 45 Hz), 5 mL was sampled every 30 min, injected into the developer, and the absorbance of the sample at a wavelength of 630 nm was detected by a UV-visible spectrophotometer and the concentration of residual formaldehyde was calculated by the formaldehyde concentration-absorbance standard curve. Repeat the above steps 5 times, test and record the data respectively, and the results are shown in Figure 4. It can be seen that during the five repetitions, the piezoelectric catalyst of the present invention always maintains excellent piezoelectric catalytic performance. Therefore, the catalyst can be reused and has good stability.
对比例一：将实施例一的熔盐法替换为溶剂热法：将12 g氢氧化钠溶于30 mL去离子水中，超声分散溶解，形成氢氧化钠溶液；搅拌下，向氢氧化钠水溶液中加入0.84 g钛酸四丁酯和2.79 g五水合硝酸铋，持续搅拌2 h，再超声30 min后转移到50ml聚四氟乙烯衬里的不锈钢高压反应釜中，并在180℃下加热20小时；反应结束后用去离子水和乙醇各洗涤样品3次，并在60℃下真空干燥12 h，得到钛酸铋纳米球。将2.64 g氯化胆碱溶于2.11 mL乙二醇中，在室温下形成离子共晶溶剂。向离子共晶溶剂中加入1 g钛酸铋纳米球，80℃反应4 h，之后用去离子水离心洗涤3次，最后在60℃真空烘箱中干燥12 h，得到含铋空位的钛酸铋纳米球。然后根据实施例二，制备含铋空位的钛酸铋纳米球-10/UiO-66-NH
2异质结。
Comparative Example 1: Replace the molten salt method of Example 1 with a solvent thermal method: Dissolve 12 g of sodium hydroxide in 30 mL of deionized water, and dissolve by ultrasonic dispersion to form a sodium hydroxide solution; Add 0.84 g of tetrabutyl titanate and 2.79 g of bismuth nitrate pentahydrate to the sodium hydroxide aqueous solution under stirring, continue stirring for 2 h, and then transfer to a 50 ml polytetrafluoroethylene-lined stainless steel autoclave after ultrasonication for 30 min, and heat at 180 ° C for 20 hours; After the reaction, wash the sample with deionized water and ethanol 3 times each, and vacuum dry at 60 ° C for 12 h to obtain bismuth titanate nanospheres. Dissolve 2.64 g of choline chloride in 2.11 mL of ethylene glycol to form an ionic eutectic solvent at room temperature. Add 1 g of bismuth titanate nanospheres to the ionic eutectic solvent, react at 80 ° C for 4 h, then centrifuge and wash 3 times with deionized water, and finally dry in a vacuum oven at 60 ° C for 12 h to obtain bismuth titanate nanospheres containing bismuth vacancies. Then, according to Example 2, a bismuth titanate nanosphere-10/UiO-66- NH2 heterojunction containing bismuth vacancies was prepared.
参照实施例五进行室温甲醛气体压电催化氧化实验，结果见图5，溶剂热反应得到的催化剂压电性差，其最大去除率在64.1%，延长时间也很难提升。Referring to Example 5, a piezoelectric catalytic oxidation experiment of formaldehyde gas at room temperature was carried out. The results are shown in FIG5 . The catalyst obtained by the solvent thermal reaction has poor piezoelectricity, and its maximum removal rate is 64.1%, which is difficult to improve even if the time is extended.
对比例二：取实施例一的钛酸铋纳米片，参照实施例二的方法，得到钛酸铋纳米片/UiO-66-NH
2异质结。参照实施例五进行室温甲醛气体压电催化氧化实验，结果见图6，铋空位对催化性能有明显提升。
Comparative Example 2: The bismuth titanate nanosheet of Example 1 was taken and the method of Example 2 was referred to obtain a bismuth titanate nanosheet/UiO-66-NH 2 heterojunction. A room temperature formaldehyde gas piezoelectric catalytic oxidation experiment was carried out with reference to Example 5. The results are shown in FIG6 , and bismuth vacancies significantly improve the catalytic performance.
对比例三：取实施例一的钛酸铋纳米片，将其置于管式炉中，真空下260℃退火15分钟，得到含氧空位的钛酸铋纳米片，参照实施例五进行室温甲醛气体压电催化氧化实验，含氧空位的钛酸铋纳米片压电催化性能较含铋空位的钛酸铋纳米片差，180分钟时的甲醛去除率在46.9%。Comparative Example 3: Take the bismuth titanate nanosheets of Example 1, place them in a tubular furnace, and anneal them at 260°C for 15 minutes under vacuum to obtain bismuth titanate nanosheets containing oxygen vacancies. Refer to Example 5 for a room temperature formaldehyde gas piezoelectric catalytic oxidation experiment. The piezoelectric catalytic performance of the bismuth titanate nanosheets containing oxygen vacancies is worse than that of the bismuth titanate nanosheets containing bismuth vacancies, and the formaldehyde removal rate at 180 minutes is 46.9%.
本发明以含铋空位的钛酸铋纳米片为基底，水热生长UiO-66-NH
2纳米颗粒构建含铋空位的钛酸铋纳米片/UiO-66-NH
2异质结。有效调制电子结构，改善了电荷传输性质，同时显著提升了电荷扩散系数，从而提高了电荷传输效率；具有超高的比表面积和永久性的孔隙率，同时-NH
2的引入加大了材料对气态甲醛的吸附性能，此外，UiO-66-NH
2的骨架结构可承受1MPa的机械压力，具有良好的化学稳定性。本发明制备的含铋空位的钛酸铋纳米片/ UiO-66-NH
2异质结通过吸附催化的协同作用，实现甲醛气体的高效压电催化氧化，这是纯压电催化去除甲醛的第一例。
The present invention uses bismuth titanate nanosheets containing bismuth vacancies as a substrate, and hydrothermally grows UiO-66- NH2 nanoparticles to construct bismuth titanate nanosheets containing bismuth vacancies/UiO-66- NH2 heterojunctions. The electronic structure is effectively modulated, the charge transfer properties are improved, and the charge diffusion coefficient is significantly improved, thereby improving the charge transfer efficiency; it has an ultra-high specific surface area and permanent porosity, and the introduction of -NH2 increases the adsorption performance of the material for gaseous formaldehyde. In addition, the skeleton structure of UiO-66- NH2 can withstand a mechanical pressure of 1MPa and has good chemical stability. The bismuth titanate nanosheets containing bismuth vacancies/UiO-66- NH2 heterojunction prepared by the present invention realizes efficient piezoelectric catalytic oxidation of formaldehyde gas through the synergistic effect of adsorption catalysis, which is the first example of pure piezoelectric catalytic removal of formaldehyde.
Claims (10)
- 一种含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结的制备方法，其特征在于，包括以下步骤：（1）将二氧化钛、氧化铋、无机盐混合后煅烧，得到钛酸铋纳米片，然后将钛酸铋纳米片浸入离子共晶溶剂中，得到含铋空位的钛酸铋纳米片；（2）将含铋空位的钛酸铋纳米片、二氨基对苯二甲酸、氯化锆和乙酸的混合物水热反应，得到含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结。 A method for preparing a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies, characterized in that it comprises the following steps: (1) mixing titanium dioxide, bismuth oxide, and an inorganic salt and calcining the mixture to obtain bismuth titanate nanosheets, and then immersing the bismuth titanate nanosheets in an ionic eutectic solvent to obtain bismuth titanate nanosheets containing bismuth vacancies; (2) hydrothermally reacting a mixture of the bismuth titanate nanosheets containing bismuth vacancies, diaminoterephthalic acid, zirconium chloride, and acetic acid to obtain a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies.
- 根据权利要求1所述含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结的制备方法，其特征在于，包括以下步骤：（1）将二氧化钛、氧化铋、无机盐混合研磨，然后煅烧，制备钛酸铋纳米片，然后将钛酸铋纳米片浸入由氢键供体和氢键受体组成的离子共晶溶剂中，形成含铋空位的钛酸铋纳米片； （2）向含有铋空位的钛酸铋纳米片溶液中加入二氨基对苯二甲酸、氯化锆和乙酸，水热反应，制备含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结材料。 The method for preparing the bismuth titanate nanosheets/UiO-66- NH2 heterojunction containing bismuth vacancies according to claim 1 is characterized in that it comprises the following steps: (1) mixing and grinding titanium dioxide, bismuth oxide, and an inorganic salt, and then calcining to prepare bismuth titanate nanosheets, and then immersing the bismuth titanate nanosheets in an ionic eutectic solvent composed of a hydrogen bond donor and a hydrogen bond acceptor to form bismuth titanate nanosheets containing bismuth vacancies; (2) adding diaminoterephthalic acid, zirconium chloride, and acetic acid to the bismuth titanate nanosheet solution containing bismuth vacancies, and performing a hydrothermal reaction to prepare a bismuth titanate nanosheet/UiO-66- NH2 heterojunction material containing bismuth vacancies.
- 根据权利要求2所述含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结的制备方法，其特征在于，步骤（1）中，氢键供体为乙二醇，氢键受体为氯化胆碱。 The method for preparing the bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies according to claim 2 is characterized in that in step (1), the hydrogen bond donor is ethylene glycol and the hydrogen bond acceptor is choline chloride.
- 根据权利要求1所述含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结的制备方法，其特征在于，步骤（1）中，无机盐为氯化钠、氯化钾；二氧化钛、氧化铋的摩尔比为3∶2，钛酸铋、氯化钠、氯化钾的摩尔比为1∶（40～90）∶（40～90）；煅烧的温度为500℃～1000℃，煅烧的时间为1～5小时。 The method for preparing the bismuth titanate nanosheets/UiO-66- NH2 heterojunction containing bismuth vacancies according to claim 1 is characterized in that in step (1), the inorganic salt is sodium chloride and potassium chloride; the molar ratio of titanium dioxide and bismuth oxide is 3:2, and the molar ratio of bismuth titanate, sodium chloride and potassium chloride is 1: (40-90): (40-90); the calcination temperature is 500°C to 1000°C, and the calcination time is 1 to 5 hours.
- 根据权利要求1所述含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结的制备方法，其特征在于，步骤（1）中，氢键供体和氢键受体混合形成离子共晶溶剂，将钛酸铋纳米片浸入离子共晶溶剂中，70～90℃反应2 h～10 h，得到含铋空位的钛酸铋纳米片。 The method for preparing a bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies according to claim 1 is characterized in that, in step (1), a hydrogen bond donor and a hydrogen bond acceptor are mixed to form an ionic eutectic solvent, the bismuth titanate nanosheet is immersed in the ionic eutectic solvent, and the reaction is carried out at 70 to 90° C. for 2 h to 10 h to obtain a bismuth titanate nanosheet containing bismuth vacancies.
- 根据权利要求1所述含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结的制备方法，其特征在于，步骤（2）中，含有铋空位的钛酸铋纳米片、二氨基对苯二甲酸、氯化锆的质量比为（400～1500）∶（100～150）∶（80～100）；水热反应为80℃～120℃反应20～30小时。 The method for preparing a bismuth titanate nanosheet containing bismuth vacancies/UiO-66- NH2 heterojunction according to claim 1 is characterized in that, in step (2), the mass ratio of the bismuth titanate nanosheet containing bismuth vacancies, diaminoterephthalic acid, and zirconium chloride is (400-1500): (100-150): (80-100); and the hydrothermal reaction is carried out at 80°C-120°C for 20-30 hours.
- 根据权利要求1所述含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结的制备方法制备的含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结。 A bismuth titanate nanosheet containing bismuth vacancies/UiO-66- NH2 heterojunction prepared according to the method for preparing a bismuth titanate nanosheet containing bismuth vacancies/UiO-66- NH2 heterojunction according to claim 1.
- 一种催化氧化甲醛的方法，包括以下步骤：将权利要求7所述含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结置入含有甲醛的环境中，在超声条件下实现甲醛的催化氧化。 A method for catalytic oxidation of formaldehyde comprises the following steps: placing the bismuth titanate nanosheet/UiO-66- NH2 heterojunction containing bismuth vacancies according to claim 7 into an environment containing formaldehyde, and achieving catalytic oxidation of formaldehyde under ultrasonic conditions.
- 权利要求7所述含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结在处理污染物中的应用。 The use of the bismuth titanate nanosheets/UiO-66- NH2 heterojunction containing bismuth vacancies as described in claim 7 in treating pollutants.
- 权利要求7所述含铋空位的钛酸铋纳米片/UiO-66-NH 2异质结在压电催化去除甲醛中的应用。 Application of the bismuth titanate nanosheets/UiO-66- NH2 heterojunction containing bismuth vacancies as described in claim 7 in piezoelectric catalytic removal of formaldehyde.
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| CN110252415A (en) * | 2019-07-11 | 2019-09-20 | 佛山科学技术学院 | For eliminating the preparation method of the amino functional MOFs of indoor formaldehyde |
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