CN114749149A - Carbon material for formaldehyde purification and preparation method thereof - Google Patents

Carbon material for formaldehyde purification and preparation method thereof Download PDF

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CN114749149A
CN114749149A CN202210414342.2A CN202210414342A CN114749149A CN 114749149 A CN114749149 A CN 114749149A CN 202210414342 A CN202210414342 A CN 202210414342A CN 114749149 A CN114749149 A CN 114749149A
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formaldehyde
plant extract
plant
gqds
leaves
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CN114749149B (en
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刘协
朱明山
林晓瑜
董浩杰
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Guangzhou Quangao Environmental Protection Technology Co ltd
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    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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Abstract

The invention belongs to the technical field of air purification, and particularly relates to a carbon material for purifying formaldehyde and a preparation method thereof. The invention takes plant leaves as raw materials, and firstly adopts a physical method to obtain plant extract. Then, the plant extract, a nitrogen source and dimethyl sulfoxide are used as raw materials, and the sulfur-nitrogen co-doped graphite quantum dot (S, N-GQDs) nano material is synthesized in one step through a solvothermal method. The powder of S, N-GQDs is applied to formaldehyde adsorption experiments, and the powder is found to have higher adsorption performance and higher adsorption capacity to formaldehyde. The method has the advantages of cheap raw materials, simple synthesis method and wide application prospect. The preparation method has the advantages of simple preparation process, mild reaction conditions and low cost, and is suitable for batch production.

Description

Carbon material for formaldehyde purification and preparation method thereof
Technical Field
The invention belongs to the technical field of air purification, and particularly relates to a carbon material for purifying formaldehyde and a preparation method thereof.
Background
People live and work indoors most of the time, and indoor air quality is closely related to human health. The excessive gaseous formaldehyde content caused by indoor decoration has become a social problem. Scientifically proves that formaldehyde and other polluted gases have great influence on human bodies and are easy to cause respiratory tracts. Diseases, cancer, leukemia and neurological disorders are particularly harmful to pregnant women, children and the elderly. Therefore, the problem of overproof indoor gaseous formaldehyde is urgently solved.
Physical adsorption techniques are often used to purify air of low concentrations of harmful substances. The adsorbing material generally requires huge specific surface area, large adsorption capacity and good adsorbability to target gas. It is known that carbon nanomaterials have the characteristics of large specific surface area, rich surface functional groups, strong adsorption capacity and the like, and are excellent physical adsorption materials. Graphene Quantum Dots (GQDs) are a novel fluorescent carbon nanomaterial composed of multilayer graphene with small lateral dimensions. The size of GQD is less than 10nm, has excellent large specific surface area and stability, and furthermore, due to similar atomic size and the ability to bond with five valence electrons of carbon atoms, heteroatom doping becomes one of effective means for improving intrinsic characteristics of nanomaterials. And the rich functional groups on the surface of the GQD can further modify the GQD according to the needs, so that the adsorption performance of the GQD on target gas molecules is effectively improved. Therefore, the development of S, N-GQDs carbon nanomaterials and the application thereof in formaldehyde purification become one of the hot spots of research.
Disclosure of Invention
The invention aims to provide a low-cost and simple-preparation-process synthesis method for removing formaldehyde nano carbon material, which uses organic matters containing nitrogen as a carbon source and a nitrogen source, dimethyl sulfoxide as a reducing agent and a sulfur source, plant extract as a stabilizing agent and a supplementary carbon source, and adopts simple hydrothermal synthesis to obtain S, N-GQDs (quantum dots) with good water solubility, stability and uniform dispersion.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a carbon material for formaldehyde purification specifically comprises the following steps:
(1) mechanically treating plant leaves to obtain plant leaf extract, filtering the extract to obtain clear and transparent plant extract, and refrigerating for later use;
(2) weighing plant extract solid and nitrogen source, dissolving in dimethyl sulfoxide, and stirring to obtain clear solution;
(3) and (3) heating the clarified solution obtained in the step (2) to 160-200 ℃, keeping the temperature for 8-15 hours, and cooling to room temperature to obtain the sulfur and nitrogen co-doped graphene quantum dot carbon nano material S, N-GQDs, namely the carbon material for formaldehyde purification.
The plant leaves in the step (1) are one or more of chlorophytum comosum leaves, aloe leaves and succulent leaves.
The mechanical treatment in the step (1) is that firstly, the plant leaves are ground into juice by adopting a grinding method, then the juice is soaked by using excessive ethanol/water solution, the filtration is carried out, the ethanol in the clarified filtrate is removed by adopting a rotary evaporation mode, and then the juice is dried. Preferably, the concentration of the ethanol/water solution is 60% ethanol; the rotary evaporation temperature is 60-80 ℃, the drying temperature is 40-60 ℃, and the drying time is 4-8 hours.
And (3) in the step (2), the nitrogen source is at least one of triethanolamine, melamine, thiourea and urea.
In the step (2), the mass ratio of the plant extract solid to the nitrogen source is 1:0.2 to 1, preferably 1:0.2 to 0.6;
the mass-volume ratio of the plant extract solid to the dimethyl sulfoxide in the step (2) is 1 g: 10-20 mL; preferably 1 g: 12-18 mL.
Preferably, the temperature after the temperature rise in the step (3) is 170-190 ℃, and the holding time is 10-13 h.
Preferably, acetone is added after the reaction in the step (3) is completed, and then centrifugal drying is performed to obtain the sulfur-nitrogen co-doped graphene quantum dot carbon nanomaterial.
Preferably, the solvent reagents are all analytically pure.
A carbon material for formaldehyde purification is prepared by the method.
The carbon material for formaldehyde purification is applied to formaldehyde adsorption and photocatalytic degradation.
Compared with the prior art, the invention has the following advantages:
the invention uses plant extract as carbon source and stabilizer, and obtains S, N-GQDs nano material by one step through solvothermal method. The preparation method has the advantages of abundant sources, low cost, simple and controllable operation, and short time consumption; the prepared nano material has good water solubility and is beneficial to coating of products; and the stability is strong, and the specific surface area is large.
Drawings
FIG. 1 is a schematic diagram showing the structure of S, N-GQDs produced in example 1 of the present invention.
FIG. 2 is a photograph (a) of the sol of S, N-GQDs prepared in example 1 of the present invention, a TEM image (b) of the sol of S, N-GQDs and a distribution chart (c) of particle sizes thereof.
FIG. 3 is an SEM photograph of a carbon material synthesized in comparative example 2 without the presence of plant extract solids.
FIG. 4 is the FT-IR chart of the S, N-GQDs nano-material prepared by the example 1 of the invention.
Detailed Description
The present invention is further described in detail with reference to the following examples, and the technical solution of the present invention is not limited to the specific embodiments listed below, but includes any combination of the specific embodiments. The room temperature and the unspecified temperature are both 20-35 ℃.
Example 1
(1) Taking 50g of cleaned folium Aloe, oven drying, and cutting with scissors to 2cm2And putting the fragments into a mortar, grinding for 30min, transferring the fragments into 50mL of 60% ethanol/water solution, soaking for 30min, performing suction filtration, removing precipitates, performing rotary evaporation at 80 ℃ to remove ethanol, and then putting the fragments into a vacuum drying oven for vacuum drying at 40 ℃ to obtain a transparent plant extracting solution. Placing the obtained plant extract in refrigerator, refrigerating at 0 deg.C, And (4) standby.
(2) Dissolving 1.0g of the plant extract solid obtained in the step (1) and 3.0mmol (0.448g) of triethanolamine in 15mL of dimethyl sulfoxide, stirring for 30min to obtain a clear solution, transferring the solution to a 20mL high-pressure reaction kettle, reacting at 180 ℃ for 12 hours, cooling to room temperature, adding acetone to generate a precipitate, performing centrifugal separation on the precipitate, washing the precipitate with absolute ethanol for 3-5 times, and performing vacuum drying at 40 ℃ to obtain sulfur-nitrogen co-doped graphene quantum dots, which are abbreviated as S, N-GQDs.
Example 2
(1) Taking 100g of cleaned succulent leaf, oven drying, and cutting into 2cm with scissors2And (3) putting the fragments into a mortar, grinding for 30min, transferring the fragments into 50mL of 60% ethanol/water solution, soaking for 30min, performing suction filtration, removing precipitates, performing rotary evaporation at the temperature of 80 ℃ to remove ethanol, and then putting the fragments into a vacuum drying oven to perform vacuum drying at the temperature of 40 ℃ to obtain a transparent plant extracting solution. Placing the obtained plant extract in refrigerator, and refrigerating at 0 deg.C for use.
(2) Dissolving 1.0g of the plant extract solid obtained in the step (1) and 2.0mmol of melamine in 15mL of dimethyl sulfoxide, stirring for 30min to obtain a clear solution, transferring the solution to a 20mL high-pressure reaction kettle, reacting at 180 ℃ for 16 h, cooling to room temperature, adding acetone to generate a precipitate, centrifugally separating the precipitate, washing the precipitate for 3-5 times with absolute ethyl alcohol, and drying in vacuum at 40 ℃ to obtain sulfur-nitrogen co-doped graphene quantum dots, which are abbreviated as S and N-GQDs.
Example 3
(1) Taking 100g of cleaned succulent leaf, oven drying, and cutting into 2cm with scissors2And (3) putting the fragments into a mortar, grinding for 30min, transferring the fragments into 50mL of 60% ethanol/water solution, soaking for 30min, performing suction filtration, removing precipitates, performing rotary evaporation at the temperature of 80 ℃ to remove ethanol, and then putting the fragments into a vacuum drying oven to perform vacuum drying at the temperature of 40 ℃ to obtain a transparent plant extracting solution. Placing the obtained plant extract in refrigerator, and refrigerating at 0 deg.C for use.
(2) Dissolving 1.0g of the plant extract solid obtained in the step (1) and 0.2g of thiourea in 15mL of dimethyl sulfoxide, ultrasonically stirring for 30min to obtain a clear solution, then transferring the solution to a 20mL high-pressure reaction kettle, reacting for 16 h at 180 ℃, cooling to room temperature, adding acetone to generate a precipitate, centrifugally separating the precipitate, washing the precipitate for 3-5 times by using absolute ethyl alcohol, and drying in vacuum at 40 ℃ to obtain sulfur-nitrogen co-doped graphene quantum dots, which are abbreviated as S, N-GQDs.
FIG. 1 is a schematic structural diagram of S, N-GQDs, wherein a part of S, N elements replace the position of C in graphene quantum dots. FIG. 2a is a photograph of an S, N-GQDs sol, and it can be seen that the obtained sol is a brown clear solution; FIG. 2b is TEM of S, N-GQDs, and the results show that the prepared quantum dots are uniformly dispersed, and the particle sizes of the quantum dots are all between 2 and 10nm (FIG. 2 c). FIG. 3 is an SEM image of a carbon material synthesized without the participation of plant extract solids (comparative example 2), and it can be seen that the resulting carbon material is an aggregated bulk material, demonstrating the stabilizer function of the plant extract solids. The functional groups on the surface of the prepared S, N-GQDs nano-material are tested by Fourier Infrared (FTIR), and figure 4 is a characteristic peak of the functional groups on the surface of the S, N-GQDs nano-material.
Formaldehyde adsorption test with the carbon nanomaterial prepared in example 1:
selecting formaldehyde gas with a certain concentration (1 mg/m)3) Static formaldehyde adsorption experiments were performed as the contaminant source gas. The adsorption device is a self-made closed gas experimental box (the total volume is 0.008 m)3) A certain mass (0.2g) of the S, N-GQDs nano-material prepared in the example 1(2) is placed in a box, the experimental environment temperature is 25 +/-1 ℃, the relative humidity is (30 +/-5)%, and the illumination condition is a dark state. The formaldehyde concentration is monitored in real time by a formaldehyde concentration tester, and the sampling frequency is 1 time/10 min. The experimental time was 2 hours. After the adsorption experiment is finished, the content of formaldehyde in the experimental box is reduced by 35.08%, which shows that the S, N-GQDs nano material has better adsorption capacity to formaldehyde gas.
The carbon nanomaterial prepared in example 1 was used for photocatalytic degradation of formaldehyde:
0.2g of the S, N-GQDs powder sample prepared in example 1(2) was uniformly placed in a petri dish, and the petri dish was placed at the bottom of a self-made airtight gas experimental box for experimentThe box is made of quartz glass and covered with black paper to prevent light. The formaldehyde concentration in the experimental box is monitored by a formaldehyde concentration tester in real time. Before the reaction, 2mg/m3The formaldehyde gas is injected into the gas experiment box, and when the concentration of the formaldehyde in the gas experiment box does not change any more, the adsorption-desorption process of the S, N-GQDs to the formaldehyde is balanced. Taking away the black paper covered on the surface of the quartz glass, and adopting a 300W xenon lamp for illumination, so that the photocatalytic reaction starts. The sampling frequency of the formaldehyde concentration tester to formaldehyde gas is 1 time/10 min, and the experimental time is 2 hours. After the adsorption experiment is finished, the content of formaldehyde in the experimental box is reduced by 52.81%, which shows that the S, N-GQDs nano material has better photocatalysis removal capability to formaldehyde gas.
Example 4
The difference from example 1 as a comparison is that the amount of added plant extract solids was varied in step (2) as follows:
dissolving 0.5g of the plant extract solid obtained in the step (1) and 3.0mmol (0.448g) of triethanolamine in 15mL of dimethyl sulfoxide, stirring for 30min to obtain a clear solution, transferring the solution to a 20mL high-pressure reaction kettle, reacting at 180 ℃ for 12 hours, cooling to room temperature, adding acetone to generate a precipitate, performing centrifugal separation on the precipitate, washing the precipitate for 3-5 times with absolute ethyl alcohol, and performing vacuum drying at 40 ℃ to obtain the sulfur-nitrogen co-doped graphene quantum dot.
The prepared carbon nano material is used for adsorbing formaldehyde for testing:
selecting formaldehyde gas with a certain concentration (1 mg/m)3) Static formaldehyde adsorption experiments were performed as the contaminant source gas. The absorption device is a self-made closed gas experimental box (the total volume is 0.008 m)3) The S, N-GQDs nano material prepared by a certain mass (0.2g) is put into a box, the experimental environment temperature is 25 +/-1 ℃, the relative humidity is (30 +/-5)%, and the illumination condition is a dark state. The formaldehyde concentration is monitored in real time by a formaldehyde concentration tester, and the sampling frequency is 1 time/10 min. The experimental time was 2 hours. After the adsorption experiment was completed, the formaldehyde content in the experimental box was found to be reduced by 30.34%.
0.2g of the prepared S, N-GQDs powder sample is uniformly placed in a culture mediumIn the culture dish, the culture dish is placed at the bottom of a self-made airtight gas experiment box, quartz glass is used as a material above the experiment box, and black paper is used for covering the experiment box to prevent light. The formaldehyde concentration in the experimental box is monitored by a formaldehyde concentration tester in real time. Before the reaction, 2mg/m3The formaldehyde gas is injected into the gas experiment box, and the formaldehyde concentration in the gas experiment box does not change any more, which shows that the adsorption-desorption process of S, N-GQDs to formaldehyde is balanced. Taking away the black paper covered on the surface of the quartz glass, and adopting a 300W xenon lamp for illumination, so that the photocatalytic reaction starts. The sampling frequency of the formaldehyde concentration tester to formaldehyde gas is 1 time/10 min, and the experimental time is 2 hours. After the adsorption experiment was completed, the formaldehyde content in the experimental box was found to have decreased by 41.62%.
Comparative example 1
The difference from example 1 in comparison is that no plant extract solids are added in step (2), and the specific procedure is as follows: dissolving 0.448g of triethanolamine in 15mL of dimethyl sulfoxide, stirring for 30min to obtain a clear solution, transferring the solution to a 20mL high-pressure reaction kettle, reacting at 180 ℃ for 12 hours, cooling to room temperature, adding acetone to generate a precipitate, centrifugally separating the precipitate, washing the precipitate with absolute ethyl alcohol for 3-5 times, and drying in vacuum at 40 ℃ to obtain a product.
The prepared carbon nano material is used for formaldehyde adsorption test:
selecting formaldehyde gas with a certain concentration (1 mg/m)3) Static formaldehyde adsorption experiments were performed as the contaminant source gas. The adsorption device is a self-made closed gas experimental box (the total volume is 0.008 m)3) The nano material prepared in a certain mass (0.2g) is put into a box, the experimental environment temperature is 25 +/-1 ℃, the relative humidity is (30 +/-5)%, and the illumination condition is in a dark state. The formaldehyde concentration is monitored in real time by a formaldehyde concentration tester, and the sampling frequency is 1 time/10 min. The experimental time was 2 hours. After the adsorption experiment was completed, the formaldehyde content in the experimental box was found to decrease by 22.18%.
The prepared carbon nano material is used for photocatalytic degradation of formaldehyde for testing:
taking 0.2g of the prepared powder sample, uniformly placing the powder sample in a culture dish, and placing the culture dish into a self-made closed gas containerThe bottom of the test box, the material of the upper part of the test box is quartz glass, and the upper part of the test box is covered by black paper to avoid light. The formaldehyde concentration in the experimental box is monitored by a formaldehyde concentration tester in real time. Before the reaction, 2mg/m3The formaldehyde gas is injected into the gas experiment box, and when the concentration of the formaldehyde in the gas experiment box does not change any more, the result shows that the adsorption-desorption process of the sample obtained in the comparative example on the formaldehyde is balanced. Taking away the black paper covered on the surface of the quartz glass, and adopting a 300W xenon lamp for illumination, so that the photocatalytic reaction starts. The sampling frequency of the formaldehyde concentration tester to formaldehyde gas is 1 time/10 min, and the experimental time is 2 hours. After the adsorption experiment was completed, the formaldehyde content in the experimental box was found to be reduced by 33.04%.
Comparative example 2
The preparation method of the unmodified carbon quantum dot comprises the following specific steps: dissolving 1.05g of citric acid monohydrate solid and 335mL of ethylenediamine in 15mL of deionized water, mechanically stirring for 10 minutes, transferring the solution into a 25mL high-pressure reaction kettle, reacting for 5 hours at 180 ℃, dialyzing the obtained brown solution by using a semipermeable membrane, and drying to obtain the carbon quantum dots, which are abbreviated as GQDs.
The prepared carbon nano material is used for photocatalytic degradation of formaldehyde for testing:
and (3) uniformly placing 0.2g of the prepared GQDs powder sample into a culture dish, placing the culture dish into the bottom of a self-made airtight gas experiment box, wherein the material above the experiment box is quartz glass, and covering the experiment box with black paper to prevent light. The formaldehyde concentration in the experimental box is monitored by a formaldehyde concentration tester in real time. Before the reaction, 2mg/m3The formaldehyde gas is injected into the gas experiment box, and the formaldehyde concentration in the gas experiment box does not change any more, which shows that the adsorption-desorption process of the GQDs to the formaldehyde is balanced. Taking away the black paper covered on the surface of the quartz glass, and adopting a 300W xenon lamp for illumination, so that the photocatalytic reaction starts. The sampling frequency of the formaldehyde concentration tester to formaldehyde gas is 1 time/10 min, and the experimental time is 2 hours. After the adsorption experiment was completed, the formaldehyde content in the experimental box was found to have decreased by 18.04%.
The prepared carbon nano material is used for formaldehyde adsorption test:
selecting formaldehyde gas (1) with a certain concentrationmg/m3) Static formaldehyde adsorption experiments were performed as the contaminant source gas. The adsorption device is a self-made closed gas experimental box (the total volume is 0.008 m)3) The GQDs nano material prepared by a certain mass (0.2g) is put into a box, the experimental environment temperature is 25 +/-1 ℃, the relative humidity is (30 +/-5)%, and the illumination condition is in a dark state. The formaldehyde concentration is monitored in real time by a formaldehyde concentration tester, and the sampling frequency is 1 time/10 min. The experimental time was 2 hours. After the adsorption experiment was completed, the formaldehyde content in the experimental box was determined to have decreased by 30.51%.
Comparative example 3
This comparative example differs from example 1 in that triethanolamine and dimethyl sulfoxide were not added.
The prepared carbon nano material is used for testing the photocatalytic degradation of formaldehyde, the testing method is the same as that of the example 1, and the content of formaldehyde in an experimental box is reduced by 28.3 percent.
The prepared carbon nano material is used for adsorbing formaldehyde, and the test method is the same as that of the example 1, and the content of the formaldehyde in the experimental box is reduced by 10.32 percent.

Claims (10)

1. A preparation method of a carbon material for formaldehyde purification is characterized by comprising the following steps:
(1) mechanically treating plant leaves to obtain plant leaf extract, filtering the extract for multiple times to obtain clear and transparent plant extract, and refrigerating for later use;
(2) Weighing plant extract solid and nitrogen source, dissolving in dimethyl sulfoxide, and stirring to obtain clear solution;
(3) and (3) heating the clarified solution obtained in the step (2) to 160-200 ℃, keeping the temperature for 8-15 hours, and cooling to room temperature to obtain the sulfur and nitrogen co-doped graphene quantum dot carbon nano material S, N-GQDs, namely the carbon material for formaldehyde purification.
2. The method of claim 1, wherein: the plant leaves in the step (1) are one or more of chlorophytum comosum leaves, aloe leaves and succulent leaves.
3. The method of claim 1, wherein:
and (3) the nitrogen source in the step (2) is at least one of triethanolamine, melamine, thiourea and urea.
4. The method of claim 1, wherein: in the step (2), the mass ratio of the plant extract solid to the nitrogen source is 1: 0.2 to 1.
5. The method of claim 1, wherein: in the step (2), the mass ratio of the plant extract solid to the nitrogen source is 1: 0.2 to 0.6.
6. The method of claim 1, wherein: the mass-volume ratio of the plant extract solid to the dimethyl sulfoxide in the step (2) is 1 g: 10-20 mL.
7. The production method according to claim 1, characterized in that: the mechanical treatment in step (1) is that firstly the plant leaves are ground into juice by a grinding method, then the juice is soaked by excessive ethanol/water solution, the suction filtration is carried out, the ethanol in the clear filtrate is removed by a rotary evaporation mode, and then the juice is dried.
8. The production method according to claim 1, characterized in that: the temperature after the temperature rise in the step (3) is 170-190 ℃, and the holding time is 10-13 h.
9. A carbon material for formaldehyde purification, which is produced by the method according to any one of claims 1 to 8.
10. Use of the carbon material for formaldehyde purification according to claim 9 for adsorbing and photocatalytically degrading formaldehyde.
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