CN114768786A - Binary composite material for visible light catalytic aldehyde removal and preparation method thereof - Google Patents
Binary composite material for visible light catalytic aldehyde removal and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000011218 binary composite Substances 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 19
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 86
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
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- 238000003756 stirring Methods 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 122
- 230000001699 photocatalysis Effects 0.000 abstract description 23
- 238000006731 degradation reaction Methods 0.000 abstract description 15
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J35/23—
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- B01J35/39—
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- B01J35/612—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
Abstract
The invention discloses a binary composite material for visible light catalytic aldehyde removal and a preparation method thereof, wherein the binary composite material for visible light catalytic aldehyde removal is represented by the following general formula: R-TiO2/rGO, wherein R group represents a basic group containing a lone pair of electrons, TiO2Represents titanium dioxide and rGO represents graphene oxide. The invention improves the photocatalyst by introducing the basic group containing lone pair electrons, preferably amino, which can be used as a chemical adsorption site to increase the concentration of formaldehyde on the surface of the catalystThe concentration of formaldehyde on the surface is an effective way for improving the catalytic performance, and is beneficial to improving the photocatalytic decomposition efficiency. Graphene is a crystalline structure consisting of sp in a hexagonal lattice2Doping graphene into TiO by using single-atom thick sheet consisting of hybridized carbon atoms2The photocatalytic performance can be further improved. The binary composite material is a photocatalytic composite material with higher formaldehyde degradation rate and better stability in an air medium.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a binary composite material for visible light catalysis aldehyde removal and a preparation method thereof.
Background
Formaldehyde (HCHO) is a common Volatile Organic Compound (VOC). The long-term exposure to formaldehyde of more than 0.08PPM can cause the health problems of the human body such as the damage of the respiratory system and the central nervous system. Therefore, the indoor formaldehyde content is one of the key factors influencing the health of people. In order to eliminate formaldehyde in indoor air, physical/chemical adsorption, plasma catalytic oxidation, thermal catalytic oxidation and other technologies are adopted, but the technologies have high energy consumption, may generate harmful byproducts and have undesirable removal effect. The photocatalytic oxidation is a low-cost, green and effective formaldehyde removal method, and the existing photocatalytic material has low formaldehyde removal efficiency.
TiO2Due to excellent photochemical stability, low cost, no toxicity and proper energy band position, the photocatalyst is one of the most potential formaldehyde degradation photocatalytic materials. However, TiO2The efficiency of the photocatalytic degradation of formaldehyde is low, and when the concentration of formaldehyde is lower than 1PPM, the photocatalytic decomposition efficiency of formaldehyde is obviously reduced due to the high film diffusion resistance.
Disclosure of Invention
The invention mainly aims to provide a binary composite material for visible light catalytic aldehyde removal, aiming at TiO in the prior art2The photocatalytic degradation efficiency of the photocatalytic material is low.
In order to achieve the purpose, the invention provides a binary composite material for visible light catalytic aldehyde removal, which is represented by the following general formula: R-TiO2/rGO, wherein R group represents a basic group containing a lone pair of electrons, TiO2Represents titanium dioxide, rGO represents graphene oxide.
Optionally, the lone pair of electron-containing basic group is an amino group.
The invention also provides a preparation method of the binary composite material for visible light catalytic aldehyde removal, which comprises the following steps:
preparation of R-TiO2：TiO2Reacting with a reagent providing a basic group containing a lone pair of electrons to produce R-TiO of positive surface potential2；
Preparation of R-TiO2/rGO: preparation of negative surface potential rGO, positive surface potential R-TiO2Mixing with negative surface potential rGO, adding a hole sacrificial agent, and reacting to obtain R-TiO2/rGO。
Alternatively, R-TiO preparation2Comprises the following steps:
adding TiO into the mixture2Dispersing in ethanol by ultrasonic treatment to obtain TiO2Ethanol solution;
to TiO 22Adding a reagent for providing an alkaline group containing lone pair electrons into the ethanol solution, and heating the mixture in a water bath;
the product was cooled to room temperature and filtered to recover the washings and dried thoroughly in an oven to obtain R-TiO of positive surface potential2。
Optionally, the agent providing the lone pair-containing basic group is selected from at least one of 3-aminopropyltriethoxysilane, phenylaminomethyltriethoxysilane;
and/or the agent for providing a basic group containing a lone pair of electrons and TiO2The volume ratio of the ethanol solution is 1: (180-220).
Alternatively, in the preparation of R-TiO2In the step (2), the ultrasonic treatment time is 30-60 min; the heating temperature of the water bath heating is 40-60 ℃, and the heating time is 3.5-4.5 hours; filtering, recovering, washing with ethanol for 6-10 times; the drying temperature for full drying is 40-80 deg.C, and the drying time is 10-24 hr.
Alternatively, R-TiO preparation2The steps of/rGO include:
preparation of rGO suspension: stirring powdered graphite and sodium nitrate in sulfuric acid to prepare rGO with negative surface potential;
stirring and mixing: mixing R-TiO2Adding the dispersion into the rGO suspension, and stirring and mixing for 0.8-1.2 hours under the condition that the pH value is 6.9-7.1;
and (3) illumination reaction: adding a hole sacrificial agent, and irradiating by ultraviolet to obtain R-TiO2/rGO。
Optionally, during the preparation of the rGO suspension, potassium permanganate is added to the rGO suspension while stirring, treated with a resin-type anion and cation exchanger to remove salt impurities, and dehydrated with phosphorus pentoxide.
Alternatively, in the preparation of R-TiO2In the step of rGO, the mass ratio of the powdery graphite to the sodium nitrate is 1: (1.8-2.2);
and/or the volume ratio of potassium permanganate to rGO suspension is 1: (18-22);
and/or, R-TiO2And rGO in a mass ratio of 50: (1-10).
Alternatively, in the step of the photoreaction, the hole sacrificial agent is selected from at least one of lactic acid, triethanolamine, EDTA-2Na, or sodium sulfite, and the ultraviolet light irradiation is performed for 2.5 to 3.5 hours using an ultraviolet lamp of 28 to 32W.
According to the technical scheme, the alkali group containing lone-pair electrons is introduced, preferably, the amino group is introduced, the alkali group containing lone-pair electrons can serve as a chemical adsorption site, so that the formaldehyde concentration on the surface of the catalyst is increased, the improvement of the formaldehyde concentration on the surface of the photocatalyst is an effective way for improving the catalytic performance, and the improvement of the photocatalytic decomposition efficiency is facilitated. Meanwhile, graphene is formed by sp in hexagonal lattice2Doping graphene into TiO by using single-atom thick sheet consisting of hybridized carbon atoms2The photocatalytic performance can be further improved. In conclusion, the preparation method is simple, and the photocatalytic composite material has higher formaldehyde degradation rate and better stability under an air medium and can be recycled.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 shows NH prepared according to example 1 of the present invention2-TiO2SEM images of/rGO;
FIG. 2 shows NH prepared in example 1 of the present invention2-TiO2UV diffuse reflectance spectrogram of/rGO;
FIG. 3 shows NH prepared according to example 1 of the present invention2-TiO2N2 adsorption-desorption isotherm plot for rGO;
FIG. 4 shows NH prepared in example 1 of the present invention2-TiO2A Fourier infrared spectrum of rGO;
FIG. 5 shows NH prepared in example 1 of the present invention2-TiO2rGO and TiO2A performance contrast diagram of photocatalytic degradation of formaldehyde;
FIG. 6 shows NH prepared according to example 1 of the present invention2-TiO2Data histogram of photocatalytic performance test of/rGO.
The implementation, functional features and advantages of the present invention will be further described with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a binary composite material for visible light catalytic aldehyde removal, which is represented by the following general formula: R-TiO2/rGO, wherein R group represents a basic group containing a lone pair of electrons, TiO2Represents titanium dioxide, rGO represents graphene oxide.
In a preferred embodiment of the invention, the lone pair of electrons-containing basic group is preferably an amino group.
The method introduces the basic group containing lone-pair electrons, preferably amino, and the basic group containing lone-pair electrons can serve as a chemical adsorption site, so that the concentration of formaldehyde on the surface of the catalyst is increased, and the improvement of the concentration of formaldehyde on the surface of the photocatalyst is an effective way for improving the catalytic performance and is beneficial to improving the photocatalytic decomposition efficiency. Meanwhile, graphene is a hexagonal structureSp in the lattice2Doping graphene into TiO by using single-atom thick sheet consisting of hybridized carbon atoms2The photocatalytic performance can be further improved. In conclusion, the preparation method is simple, and the photocatalytic composite material has higher formaldehyde degradation rate and better stability under the air medium and can be recycled.
The invention also provides a preparation method of the binary composite material for visible light catalytic aldehyde removal, which comprises the following steps:
preparation of R-TiO2：TiO2Reacting with a reagent providing a basic group containing a lone pair of electrons to produce R-TiO with a positive surface potential2；
Preparation of R-TiO2/rGO: preparation of negative surface potential rGO, positive surface potential R-TiO2Mixing with rGO with negative surface potential, adding hole sacrificial agent, reacting to obtain R-TiO2/rGO。
The preparation method is to prepare the R-TiO with high removal efficiency under low formaldehyde concentration (1PPM) by an electrostatic self-assembly method (ESSA), namely a material preparation method for spontaneously assembling a composite material by utilizing electrostatic attraction between opposite surface potentials of two substances2a/rGO photocatalyst.
In the examples of the present invention, R-TiO was prepared2Comprises the following steps:
adding TiO into the mixture2Dispersing in ethanol by ultrasonic treatment to obtain TiO2Ethanol solution;
to TiO2Adding a reagent for providing an alkaline group containing lone pair electrons into the ethanol solution, and heating the mixture in water bath;
the product was cooled to room temperature and filtered to recover the washings and dried thoroughly in an oven to obtain R-TiO of positive surface potential2。
In an embodiment of the present invention, the agent providing a basic group having a lone pair of electrons is selected from at least one of 3-aminopropyltriethoxysilane, phenylaminomethyltriethoxysilane; and/or the agent providing a basic group containing a lone pair of electrons and TiO2The volume ratio of the ethanol solution is 1: (180-220) havingIn particular, the ratio may be 1: 180 or 1: 220, more preferably 1: 200.
in the examples of the present invention, in the preparation of R-TiO2In the step (2), the ultrasonic treatment time is 30-60 min; the heating temperature of the water bath heating is 40-60 ℃, and the heating time is 3.5-4.5 hours; filtering, recovering, washing with ethanol for 6-10 times; the drying temperature for full drying is 40-80 deg.C, and the drying time is 10-24 hr.
In the examples of the present invention, R-TiO was prepared2The steps of/rGO include:
preparation of rGO suspension: stirring powdered graphite and sodium nitrate in sulfuric acid to prepare rGO with negative surface potential; specifically, the powdery graphite is preferably powdery natural graphite;
stirring and mixing: adding R-TiO2Adding the dispersion into the rGO suspension, and stirring and mixing for 0.8-1.2 hours under the condition that the pH value is 6.9-7.1; in a preferred embodiment of the present invention, the pH is more preferably 7, and the mixing time is 1 hour under stirring;
and (3) illumination reaction: adding a hole sacrificial agent, and irradiating by ultraviolet to obtain R-TiO2/rGO。
In the examples of the present invention, potassium permanganate was added to the rGO suspension while stirring during the preparation of the rGO suspension, treated with a resin-type anion and cation exchanger to remove salt impurities, and dehydrated with phosphorus pentoxide.
In the examples of the present invention, in the preparation of R-TiO2In the step of rGO, the mass ratio of the powdery graphite to the sodium nitrate is 1: (1.8-2.2), and/or the volume ratio of the potassium permanganate to the rGO suspension is 1: (18-22), and/or R-TiO2And rGO in a mass ratio of 50: (1-10).
In an embodiment of the present invention, in the step of the photoreaction, the hole sacrificial agent is selected from at least one of lactic acid, triethanolamine, EDTA-2Na, or sodium sulfite. The ultraviolet light irradiation is carried out for 2.5-3.5 hr by using 28-32W ultraviolet lamp, wherein the ultraviolet lamp power is 28W, 30W or 32W, and the irradiation time is 2.5 hr, 3 hr or 3.5 hr, so as to activate TiO2A photocatalytic material.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. The raw materials and reagents mentioned in the examples are all common commercial products, and the operations mentioned are all routine operations in the field unless otherwise specified. Deionized water was used for all water used in the examples.
Example 1
TiO2(commercial P25) and 3-aminopropyltriethoxysilane (C)9H23NO3Si, APTES) was purchased from Aladdin (shanghai, china).
Step 1: 1g of TiO2Dispersed in 200mL ethanol by sonication for 30min, 1mL APTES was added, and the solution was refluxed at 60 ℃ for 4 h. The product was then cooled to room temperature and recovered by filtration, washed with ethanol, and dried thoroughly in an oven at 60 ℃ to obtain the final positively charged NH2-TiO2。
Step 2: a flask was charged with 4g of powdered natural graphite and 0.75g of NaNO3The flask was placed in an ice-water bath and 75mL of concentrated sulfuric acid was added slowly with constant stirring. 4.5g of KMnO are added in portions in 1h4The reaction was stirred in an ice bath for 2 h. The flask was then removed from the ice bath and the reaction stirred for 20h at 35 ℃. Then transferring into a constant temperature water bath kettle, and adding 150mL of 5 wt% H in batches within 1H2SO4Then, the temperature was maintained at 98 ℃ and the mixture was stirred for 2 hours. After the reaction is finished, the temperature of the system is reduced to 60 ℃, and 10mL of 30% H is added2O2Stirring at normal temperature for 2 h. The mixture was then centrifuged, the supernatant removed, and 500mL of 3 wt% H added to the lower solids2SO4And 0.5 wt% H2O2Under the condition of strong stirring, the mixed solution is subjected to ultrasonic treatment at 140W for 30 min. To the lower layer solid, 500mL of 3 wt% HCl solution was added, sonicated, centrifuged, and repeated 3 times. And finally washing the product to be neutral by using deionized water to obtain the rGO.
And step 3: a proper amount of positive surface potential NH2-TiO2Dispersing according to TiO2In a weight ratio to rGO of50:1 was added to the negative surface potential rGO suspension. After continuously stirring and mixing at pH 7 for 1 hour, 10mL of lactic acid was added to the above solution as a hole-sacrificing agent, and 30W of ultraviolet light was irradiated for 3 hours to obtain NH2-TiO2/rGO。
FIG. 1 shows NH prepared in example 1 of the present invention2-TiO2SEM image of/rGO, FIG. 1 shows NH2-TiO2the/rGO material is in a nano-particle shape, and the clustering phenomenon among the materials is serious.
FIG. 2 shows NH prepared in example 1 of the present invention2-TiO2The ultraviolet diffuse reflection spectrogram of/rGO, wherein the Y axis is absorbance (absorbance) and the X axis is wavelength (wavelength). As shown in the figure, TiO2The light absorption edge of the photocatalyst is around 390 nm. And NH2-TiO2The light absorption boundary of/rGO extends significantly to 430nm and a larger absorption tail appears, indicating that it can utilize more visible light.
FIG. 3 shows NH in example 1 of the present invention2-TiO2N2 adsorption-desorption isotherm diagram of/rGO, and the specific surface area of the composite material is 9.4724m2The/g shows that the formaldehyde adsorption performance is weak, and the degradation is mainly caused by the reaction of persistent free radicals generated by photocatalysis on formaldehyde.
FIG. 4 shows NH in example 1 of the present invention2-TiO2Fourier infrared spectrum of/rGO. To study the composition and structure of the post-synthesis samples, FTIR analysis was used, as shown in FIG. 4, showing one for rGO at 3230cm-1Is a broad band centered, due to the O-H stretching vibration of the hydroxyl groups. At 1420 and 1720cm-1The peaks at the centers are respectively attributed to the O — C ═ O and C ═ O stretching vibrations of the carboxyl groups. For NH2-TiO2At 3120-3620cm-1Peaks observed in the range were assigned to N-H and O-H at 1650cm-1Observed at (A) is NH or NH2The bending vibration of (2). It is worth mentioning that NH2-TiO2And the major typical absorption peaks of rGO are all present in NH2-TiO2in/rGO samples, this further indicates NH2-TiO2Successful synthesis of/rGO composite catalyst.
Example 2
This example serves to verify the NH prepared in example 12-TiO2The degradation performance of the rGO photocatalytic nano material on formaldehyde.
Evaluation of photocatalytic activity:
the catalytic activity of the catalyst is measured by the removal of formaldehyde in a closed system and under UV irradiation (365 nm). In all tests, 200mg NH was added2-TiO2the/rGO was placed in a glass petri dish placed in a volume of about 216L (60X 60 cm)3) The formaldehyde release source (38% formaldehyde solution) was introduced into the reactor at the bottom of the reactor. The concentration of gaseous formaldehyde in the reactor was 1 PPM. The reactor was finally sealed with a glass plate to make a closed system. The photodegradation reaction of formaldehyde takes place at 25 ℃ and is terminated at a constant concentration of gaseous formaldehyde within half an hour under a 30W 365nm UV light source and a 5W fan at the bottom of the reactor. The formaldehyde removal rate (Y) was calculated as Y (%) ═ 1-C/C0) X 100% where C and C0The concentrations of formaldehyde at 0 and t min, respectively.
Continuous degradation experiments:
after the first degradation reaction is finished, drying the culture dish containing the photocatalyst at 60 ℃ for 0.5 hour, then putting the culture dish into the reactor again for the next formaldehyde removal reaction, wherein the reaction conditions except materials are consistent with those of the first time; and after the second reaction is finished, repeating the steps to carry out a third degradation experiment. Five degradation experiments were performed in total.
The experimental results show that: under the irradiation of 365nm ultraviolet light source, the adding amount of the catalyst is 0.2g, the initial concentration of formaldehyde is 1ppm, and the initial temperature is room temperature2-TiO2The degradation efficiency of the/rGO photocatalytic nano material to formaldehyde after 6 hours is as high as 92%. The formaldehyde elimination did not show any significant loss in each repeat cycle, indicating a higher durability of the catalyst.
FIG. 5 shows NH prepared according to example 1 of the present invention2-TiO2rGO and TiO2A contrast graph of the performance of degrading formaldehyde by photocatalysis, in particular, the Y axis in the graph is C/C0C and C0Concentration of formaldehyde at 0 and t min, respectively, and X-axis is test time. It can be seen that the single TiO species is responsible for2The absorbance is limited, the recombination rate of photo-generated electron and hole is higher, the degradation efficiency to formaldehyde is 39.6 percent within 6h, and the degradation efficiency to NH is higher2-TiO2The formaldehyde degradation efficiency of rGO reaches 92.1 percent in 6 hours.
FIG. 6 shows NH in example 1 of the present invention2-TiO2Data histogram of photocatalytic performance test of/rGO. In each repeated circulation, the elimination rate of formaldehyde does not have any obvious loss, and the degradation rate still reaches more than 85 percent after 5 cycles, which indicates that the catalyst has higher reutilization property.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A binary composite material for visible light catalytic aldehyde removal is characterized by being represented by the following general formula: R-TiO2/rGO, wherein R group represents a basic group containing a lone pair of electrons, TiO2Represents titanium dioxide, rGO represents graphene oxide.
2. The binary composite material for visible light catalyzed aldehyde removal according to claim 1 wherein the basic group containing a lone pair of electrons is an amino group.
3. The preparation method of the binary composite material for visible light catalytic aldehyde removal is characterized by comprising the following steps:
preparation of R-TiO2：TiO2Reacting with a reagent providing a basic group containing a lone pair of electrons to produce R-TiO with a positive surface potential2；
Preparation of R-TiO2/rGO: preparation of negative surface potential rGO, positive surface potential R-TiO2And negative surface electricityMixing the rGO at the position, adding a hole sacrificial agent, and reacting to obtain R-TiO2/rGO。
4. The method of claim 3, wherein the R-TiO is prepared as a binary composite for visible light catalyzed aldehyde removal2Comprises the following steps:
mixing TiO with2Dispersing in ethanol by ultrasonic treatment to obtain TiO2Ethanol solution;
to TiO 22Adding a reagent for providing an alkaline group containing lone pair electrons into the ethanol solution, and heating the mixture in a water bath;
the product was cooled to room temperature and filtered to recover the washings and dried thoroughly in an oven to obtain R-TiO of positive surface potential2。
5. The method for preparing the binary composite material for visible light catalytic aldehyde removal according to claim 3 or 4, wherein the reagent for providing the alkali group containing the lone pair of electrons is at least one selected from 3-aminopropyl triethoxysilane and phenylaminomethyl triethoxysilane;
and/or the agent for providing a basic group containing a lone pair of electrons and TiO2The volume ratio of the ethanol solution is 1: (180-220).
6. The method for preparing the binary composite material for visible light catalyzed aldehyde removal according to claim 4, wherein the R-TiO is prepared2In the step (2), the ultrasonic treatment time is 30-60 min; the heating temperature of the water bath heating is 40-60 ℃, and the heating time is 3.5-4.5 hours; filtering, recovering, washing with ethanol for 6-10 times; the drying temperature for full drying is 40-80 deg.C, and the drying time is 10-24 hr.
7. The method for preparing the binary composite material for visible light catalytic aldehyde removal according to claim 3 or 4, wherein R-TiO is prepared2The steps of/rGO include:
preparation of rGO suspension: stirring powdered graphite and sodium nitrate in sulfuric acid to prepare rGO with a negative surface potential;
stirring and mixing: adding R-TiO2Adding the dispersion into the rGO suspension, and stirring and mixing for 0.8-1.2 hours under the condition that the pH value is 6.9-7.1;
and (3) illumination reaction: adding a hole sacrificial agent, and irradiating by ultraviolet to obtain R-TiO2/rGO。
8. The method of claim 7, wherein during the preparation of the rGO suspension, potassium permanganate is added to the rGO suspension while stirring, a resin-type anion and cation exchanger is used to remove salt impurities, and phosphorus pentoxide is used for dehydration.
9. The method of claim 8, wherein the R-TiO is prepared in the step of preparing the binary composite material for visible light catalyzed aldehyde removal2In the step of rGO, the mass ratio of the powdery graphite to the sodium nitrate is 1: (1.8-2.2);
and/or the volume ratio of potassium permanganate to rGO suspension is 1: (18-22);
and/or, R-TiO2And rGO in a mass ratio of 50: (1-10).
10. The method of claim 7, wherein the hole sacrificial agent is at least one selected from the group consisting of lactic acid, triethanolamine, EDTA-2Na, and sodium sulfite, and the UV irradiation is performed for 2.5 to 3.5 hours using a 28 to 32W UV lamp in the step of the photo reaction.
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