CN112264076A - Photocatalyst for improving indoor VOCs removal efficiency and preparation method thereof - Google Patents
Photocatalyst for improving indoor VOCs removal efficiency and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
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- 238000002360 preparation method Methods 0.000 title abstract description 8
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention provides a photocatalyst for improving the removal efficiency of indoor VOCs and a preparation method thereof. The method comprises the steps of firstly adopting melamine as a precursor to prepare the carbon nitride photocatalyst, then introducing hydroxyl and amino on the surface of the material through alkaline water heat treatment, and finally utilizing the functional groups to induce Fe (III) to be uniformly attached on the surface of the material, so that the carbon nitride photocatalyst co-grafted by hydroxyl/amino and Fe (III) can be prepared. Compared with the traditional photocatalyst, the indoor VOCs purification material prepared by the invention can effectively capture VOC molecules in air and improve the adsorption quantity and adsorption rate of VOCs because the surface of the photocatalyst is rich in adsorption sites such as hydroxyl, amino and the like. In addition, Fe (III) as a co-catalyst is effective in promoting the formation of oxygen-containing active species. Due to the synergistic effect of hydroxyl/amino and Fe (III), the photocatalyst is applied to ppm levelAdsorption amount of gas phase isopropanol and mineralized product-CO2Compared with pure carbon nitride, the carbon nitride is respectively improved by 31 times and 23 times. Is particularly suitable for absorbing and degrading indoor VOCs.
Description
Technical Field
The invention belongs to the technical field of air purification materials, and provides a photocatalyst for improving the removal efficiency of indoor VOCs and a preparation method thereof.
Background
VOCs are an important indoor air pollutant, mainly including hydrocarbons, alcohols, aldehydes, ketones, lipids, amines, carboxylic acids, and the like, and most commonly mainly including formaldehyde, benzene, toluene, xylene, and the like. The indoor VOCs directly influence the health of human bodies and are one of important measurement standards for evaluating the indoor air quality.
At present, the main methods for treating indoor VOCs include an adsorption purification technology, an ionization technology, a photocatalytic oxidation technology, a biological purification technology and the like. The photocatalytic oxidation method is a novel efficient and green treatment method for VOCs (volatile organic compounds), and the principle of the photocatalytic oxidation method is that a photocatalyst excites a photon-generated carrier under the condition of illumination, the photocatalyst has strong oxidation reduction capability, and pollutants are decomposed into harmless small molecules through contact reaction with the pollutants and even mineralized into CO2And H2And O, thereby achieving the purpose of complete removal. The current photocatalyst semiconductor material is mainly inorganic semiconductor material (such as TiO)2BiOCl), organic semiconductor materials (e.g. g-C)3N4PDI). Wherein g-C3N4The material is an easily-obtained and nontoxic semiconductor material, and is concerned by scientific researchers in the field of environmental catalysis due to the advantages of appropriate band gap, quick response of visible light and the like. Generally, the photocatalytic reaction is carried out by first adsorbing the VOC molecules onto the surface of the material, while the bulk g-C is3N4The photocatalytic material has low adsorption capacity for low-concentration indoor VOCs due to the defects of low specific surface area, insufficient surface active sites and the like, and cannot exert the corresponding photocatalytic performance. Besides, photo-generated electrons and holes generated by light radiation are easy to recombine, and the photocatalytic activity of the material is greatly reduced.
Therefore, how to efficiently utilize natural light to perform photocatalytic reaction, develop a photocatalyst with excellent adsorption performance and high separation efficiency of photon-generated carriers, can effectively improve the treatment effect of VOCs, simplify the treatment process and the treatment difficulty, and have great attraction for enterprises.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a photocatalyst for improving the indoor VOCs removal efficiency and a preparation method thereof, and the prepared photocatalyst has the advantages of high adsorption capacity, excellent degradation efficiency, good stability, visible light response, mild reaction conditions, easiness in regeneration and recovery, capability of improving the VOCs treatment effect and simplifying the treatment process and treatment difficulty.
In order to meet the above requirements, the primary object of the present invention is to provide a hydroxyl/amino and fe (iii) co-grafted carbon nitride catalyst.
The invention also aims to provide a preparation method of the hydroxyl/amino and Fe (III) co-grafted carbon nitride catalyst.
The invention further aims to provide the application of the hydroxyl/amino and Fe (III) co-grafted carbon nitride catalyst in removing VOCs.
The purpose of the invention is realized by the following scheme:
in a first aspect, the present invention provides a method for preparing a photocatalyst, which is a hydroxyl-and amino-grafted carbon nitride, the method comprising: soaking original bulk-phase carbon nitride in alkaline solution, mixing, performing hydrothermal treatment at 80-160 ℃ for 2-12 h, and washing to neutrality to obtain hydroxyl-and amino-grafted carbon nitride, wherein the alkaline solution can be LiOH, NaOH, KOH and Ba (OH)2One kind of (1).
In a second aspect, the present invention provides a method of preparing a photocatalyst which is a hydroxyl/amino and fe (iii) co-grafted carbonitride catalyst, the method comprising: soaking original bulk-phase carbon nitride in an alkaline solution, mixing, performing hydrothermal treatment at 80-160 ℃ for 2-12 h, and washing to neutrality to obtain hydroxyl-and amino-grafted carbon nitride, wherein the alkaline solution can be LiOH, NaOH, KOH and Ba (OH)2One of (1); immersing hydroxyl-and-amino-grafted carbon nitride in Fe (III) solution, mixing, standing for adsorption for 1-24 h, then performing heat treatment at 0-90 ℃ for 30min, and finally washing and drying to obtain hydroxyl/amino-and Fe (III) -co-grafted carbon nitride, wherein the Fe (III) solution can be FeCl3、Fe(NO3)3、FeCl3·6H2O and Fe (NO)3)3·9H2And O is one of the compounds.
According to the technical scheme of the invention, the original carbon nitride is obtained by a high-temperature polymerization process of organic micromolecules rich in nitrogen and carbon.
According to the technical scheme description of the invention, the organic micromolecules containing nitrogen and carbon are at least one of melamine, urea and cyanamide.
According to the technical scheme of the invention, the high-temperature polymerization process is carried out for 4-8 hours at 450-600 ℃.
According to the technical scheme of the invention, the concentration of the alkaline solution is 0.05-1.5M.
According to the technical scheme of the invention, the ratio of the original carbon nitride to the alkaline solution is (0.05-2 g): (10-30 ml).
According to the technical scheme of the invention, the hydroxyl/amino and Fe (III) are co-grafted with the carbon nitride, wherein Fe (III) is loaded on the surface of the carbon nitride by amorphous FeOOH to form a new composite catalyst, and the mass percent of Fe (III) is 0.05-0.5 wt%.
The method comprises the steps of hydrolyzing carbon nitride in an alkaline solution to obtain hydroxyl-and amino-grafted carbon nitride, and then soaking and adsorbing the hydroxyl-and amino-grafted carbon nitride in Fe (III) solution to obtain hydroxyl/amino-and Fe (III) co-grafted carbon nitride. Specifically, on one hand, the surface chemical environment of the catalyst is optimized by introducing the functional groups as charge acceptors or donors, so that a good condition is provided for the attachment of pollutant molecules on the surface of the material; in addition, a transport channel of photo-generated charges is constructed, and carrier separation efficiency is improved; on the other hand, the grafted Fe (III) species can be used as a photon-generated electron acceptor, carrier separation is accelerated through an interface charge transfer effect, and the polarity reversal in the catalytic degradation process is realized by introducing a photo-Fenton reaction to regulate active species and quantity.
The method is simple and reliable, does not need expensive equipment, and has wide application prospect.
Drawings
Fig. 1 is a fourier infrared transmission spectrum of the photocatalyst produced in example 1 of the present invention.
FIG. 2 is an X-ray powder diffraction pattern of the photocatalyst prepared in example 2 of the present invention
FIG. 3 is a Fe element X-ray photoelectron spectrum of the photocatalyst prepared in example 2 of the present invention.
FIG. 4 is a graph showing the adsorption performance of the photocatalysts prepared in examples 1 and 2 of the present invention.
Fig. 5 is a graph showing the catalytic performance of the photocatalyst produced in example 1 of the present invention.
Fig. 6 is a graph showing the catalytic performance of the photocatalyst produced in example 2 of the present invention.
Fig. 7 is a uv-vis diffuse reflectance spectrum of the photocatalyst prepared in example 2 of the present invention.
FIG. 8 is a graph showing the performance test of hydrogen peroxide capture in examples 1 and 2 of the present invention.
FIG. 9 is a graph showing the experiment of the hydroxyl radical trapping performance of the preferred samples in examples 1 and 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples were carried out under the conventional conditions, unless otherwise specified. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
A preparation method of a carbon nitride photocatalyst for removing VOCs in a room comprises the following steps:
(1) 10g of melamine is placed in the center of a hearth of a tubular furnace, and the temperature is raised to 550 ℃ at the heating rate of 2.3 ℃/min and is kept for 4 hours. And naturally cooling the muffle furnace to room temperature, taking out the sample, grinding the sample into powder by using an agate crucible, and recording the powder as the graphite-phase carbon nitride CN.
(2) 1.0g of CN prepared above was weighed and immersed in 30ml of KOH solutions of 0.05, 0.20 and 0.70M, respectively, and stirred at room temperature for 30 min.
(3) And (3) filling the suspension obtained in the step (2) into a 50ml high-pressure reaction kettle, carrying out heat treatment at 140 ℃ for 12 hours, and then washing and drying to obtain hydroxyl-grafted and amino-grafted carbon nitride, which is respectively marked as CN-0.05, CN-0.20 and CN-0.70.
The structural characteristics and performance tests of the carbon nitride photocatalyst for removing VOCs are as follows:
fig. 1 is a fourier infrared transmission spectrum (FTIR) of a carbon nitride photocatalyst for removing VOCs in example 1. 1200-1600cm-1And 810cm-1The peak of (A) represents the stretching vibration and triazine structure of aromatic CN hybridization respectively, and is in the range of 3000-3500cm-1Clearly continuous enhanced vibrational peaks of hydroxyl and amino groups were found, meaning that the base treatment had successfully grafted hydroxyl and amino groups on the surface of the material, with the grafted functional group being the highest in the CN-0.70 sample. Therefore, CN-0.70 is preferably used as a representative sample for the next step of grafting and loading of Fe (III).
Example 2
A preparation method of a carbon nitride photocatalyst for removing VOCs in a room comprises the following steps:
(1) 0.5g of the above CN-0.70 was weighed out and placed in a clean beaker, and 30m L% ultra pure water was added thereto and ultrasonically dispersed for 10 min.
(2) 1.2, 3.6 and 12ml of 1mg/ml FeCl were added3Stirring the aqueous solution at normal temperature for 30min, standing and adsorbing for 24 h.
(3) Then heating for 30min at 90 ℃ under the stirring condition; after cooling to room temperature, washing and drying, the obtained powder is hydroxyl/amino and Fe (III) co-grafted carbon nitride. The weight percentages of the Fe (III) load are respectively 0.05, 0.15 and 0.50 percent, and the samples are respectively marked as 0.05Fe (III) CN-0.70, 0.15Fe (III) CN-0.70 and 0.50Fe (III) CN-0.70.
Fig. 2 is an X-ray powder diffraction pattern of the carbon nitride photocatalyst for removing VOCs prepared in example 2. As can be seen from the figure, the structural characteristics of the carbon nitride are not changed by the graft loading of fe (iii), and no diffraction peak occurs with respect to fe (iii) species, which indicates that fe (iii) exists in the form of amorphous clusters on the surface of the material.
Fig. 3 is an Fe element X-ray photoelectron spectrum of the carbon nitride photocatalyst for removing VOCs prepared in example 2. As can be seen from the figure, Fe (III) can be divided into two pairs of peaks, wherein the binding energy represents the characteristic peak of FeOOH at 711.6 eV. In addition, referring to FIG. 2, the grafted Fe (III) clusters are amorphous FeOOH. Fe (ii) is the product of fe (iii) reduction due to XPS characterization of the environment under vacuum.
Example 3
The carbon nitride prepared in examples 1 and 2 was used as a catalyst to test its adsorption performance to gas phase Isopropanol (IPA) by the following specific steps: 100mg of the catalyst was weighed out and spread evenly on a planar support with a diameter of 2cm, and placed in the center of a 600ml gas-solid phase reactor. And before the experiment is started, all-light pre-irradiation is carried out for 60min to remove the impurity carbon source adsorbed on the surface of the material. After the reaction, the reactor is closed, artificial compressed air is communicated from a side port for aeration for 30min, and a gas phase carbon source in the reactor is discharged, wherein the gas flow is 100 ml/min. Then, the concentration of IPA in the mixed gas contacted with the catalyst was made to be about 450ppm, and an adsorption test was performed under dark conditions, and 1ml of the mixed gas was taken out from the reactor every 20min and tested by gas chromatography to observe the change in concentration with time.
FIG. 4 is a graph showing adsorption performance of catalysts prepared in examples 1 and 2 of the present invention. It can be seen that the concentration of IPA remained unchanged under the blank condition, i.e., no catalyst, when the other conditions were identical. When the catalyst was added, the CN catalyst also had no effect on IPA removal under dark conditions. However, for the alkali treated samples, the IPA concentration dropped rapidly within 20min and almost equilibrated after 60 min. Wherein, the best adsorption property is CN-0.70, the adsorption removal rate is 93.27 percent and is 67 times higher than CN, which shows that the hydroxyl and amino grafted on the surface of the material play an important role in adsorbing VOCs. Then, the adsorption performance of the Fe (III) CN-0.70 series samples is examined, and as can be seen from FIG. 4, the adsorption performance is reduced after the Fe (III) is grafted, which is caused by that Fe (III) and hydroxyl or amino occupy part of adsorption sites through electrostatic interaction.
Example 4
The carbon nitride prepared in examples 1 and 2 was used as a catalyst to test the photocatalytic performance of the material on gas phase Isopropanol (IPA), and after the dark adsorption process of example 3, the material reached IPA adsorption and desorption equilibrium, i.e. the concentration of IPA was not changed, the IPA was removed in situ by photocatalysis under the irradiation of a 300W xenon lamp. Likewise, 1ml of mixed gas was taken from the reactor every 20min and tested by gas chromatography to observe the degrading species acetone and CO2The change in concentration with time.
FIG. 5 shows the present inventionThe catalytic performance of the photocatalyst prepared in example 1. It can be seen that acetone and CO were not detected under blank conditions, i.e., no catalyst was present or under dark conditions, other conditions were consistent2IPA, which is difficult to degrade and remove under natural conditions; after the catalyst and the visible light source are introduced simultaneously, acetone and CO2The concentration showed different degrees of increase. In which acetone and CO were generated in the catalytic system of the CN-0.70 sample2The highest amount, which should be attributed to its excellent adsorption properties and higher photogenerated carrier separation efficiency.
Fig. 6 is a graph showing the catalytic performance of the photocatalyst produced in example 2 of the present invention. As can be seen from the figure, when the material is loaded with Fe (III), acetone and CO2The amount of production of (b) increases to various degrees. Wherein, the best catalytic performance belongs to 0.15Fe (III) CN-0.70. The reason for this is that, in addition to the excellent adsorption performance of the sample, the interface electron transfer effect and the photo-induced fenton reaction introduced by the fe (iii) clusters play a crucial role. Therefore, the ultraviolet-visible diffuse reflection spectrum of the sample is characterized and active species such as hydrogen peroxide (o-tolidine molecular probe) and hydroxyl radical (terephthalic acid molecular probe) are detected.
FIG. 7 is a UV-VIS diffuse reflectance spectrum of a preferred sample of examples 1, 2 of the present invention. As can be seen from the UV-Vis diffuse reflectance spectrum of the preferred sample, after grafting Fe (III), the sample shows a new visible light absorption band at the wavelength of 460-580nm, which is the interface electron transfer effect caused by the Fe (III) cluster, corresponding to the above analysis. In addition, the UV-Vis spectrum of the captured hydrogen peroxide in the preferred sample (FIG. 8) shows that CN-0.70 has the highest absorbance, representing the highest amount of hydrogen peroxide catalyzed by the three catalysts. After Fe (III) clusters are loaded, the amount of hydrogen peroxide shows a great reduction, and Fe (III) is supposed to be used as an electron acceptor to receive a photo-generated electron to be converted into Fe (II), and Fe (II) and the photo-generated hydrogen peroxide rapidly react to generate hydroxyl radicals (Fe (II) + H) with strong oxidizing capability2O2→ Fe (III) +. OH + -OH). To further confirm this, hydroxyl radical probe experiments were performed. FromThe hydroxyl radical trapping photoluminescence spectrum (FIG. 9) shows that the preferred sample 0.15Fe (III) CN-0.70 has the highest fluorescence intensity, which indicates that the content of the photogenerated hydroxyl radicals is the highest.
Through high adsorption performance, fast carrier separation efficiency and the systematic coordination of the photo-Fenton reaction, the hydroxyl/amino and Fe (III) co-grafted carbon nitride can effectively eliminate VOCs, can comprehensively improve the air quality and optimize the living environment.
Claims (9)
1. The photocatalyst for improving the indoor VOCs removal efficiency is characterized by comprising a bulk catalytic material and a characteristic modifying species.
2. The photocatalyst for enhancing the removal efficiency of VOCs indoor as claimed in claim 1, wherein the carbon nitride surface-grafted with hydroxyl and amino groups comprises surface-grafted hydroxyl and amino functional groups and has excellent adsorption-photocatalytic synergy properties.
3. The photocatalyst for improving the removal efficiency of VOCs in a room as claimed in claim 1, wherein the photocatalyst comprises hydroxyl/amino groups grafted on the surface and Fe (III) and other modifying species, and further has more excellent adsorption-photocatalysis synergy performance.
4. The photocatalyst for enhancing the removal efficiency of VOCs from a room as claimed in claim 1, wherein the grafted functional groups are obtained by reaction under alkaline thermal conditions.
5. The photocatalyst for enhancing the removal of VOCs from a room as claimed in claim 1, wherein the grafted fe (iii) species is obtained by an immersion adsorption process.
6. The photocatalyst for enhancing removal of VOCs from a chamber as recited in claim 1, wherein the grafted fe (iii) species is present in the amorphous FeOOH form.
7. The photocatalyst for enhancing the removal of VOCs from a room as recited in claim 1, wherein the grafted hydroxyl and amino groups provide effective adsorption sites for VOCs.
8. The photocatalyst of claim 1, wherein the grafted fe (iii) species is effective in promoting molecular oxygen activation and the formation of active species.
9. The photocatalyst for enhancing the removal efficiency of VOCs in a room as claimed in claim 1, wherein the space is suitable for use in, but not limited to, residential environments, factory environments, hospitals, restaurants and the like.
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