CN111790421A - Graphite-phase carbon nitride modified fabric visible-light-driven photocatalyst and one-step preparation method and application thereof - Google Patents
Graphite-phase carbon nitride modified fabric visible-light-driven photocatalyst and one-step preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 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
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Abstract
The invention provides a graphite phase carbon nitride modified fabric visible light catalyst and a one-step preparation method and application thereof. When the prepared catalyst is used for indoor air purification, pollutants such as formaldehyde and the like can be rapidly degraded, and the removal rate of the pollutants can reach more than 99% within 90 minutes; and moreover, the catalyst has excellent recycling performance and can still have excellent catalytic performance after being washed by water.
Description
Technical Field
The invention relates to a chemical catalyst technology, in particular to a graphite phase carbon nitride modified fabric visible-light-induced photocatalyst, a one-step preparation method and application thereof, and specifically relates to graphite phase carbon nitride (g-C) for promoting decomposition of organic pollutants such as indoor formaldehyde gas and the like3N4) A modified fabric visible light catalyst and a preparation method thereof.
Background
The indoor harmful gas mainly comprises formaldehyde emitted by decorative materials and the like and methyl mercaptan, hydrogen sulfide, ammonia gas and the like generated in the living environment. The formaldehyde has the most serious harm to human bodies, becomes the pollutant with the largest harm in indoor pollution, has strong irritation to eyes, respiratory tracts, skin and the like of human bodies, and can cause symptoms of nausea, bronchitis, conjunctivitis and the like when contacting low-concentration formaldehyde for a long time. The nanometer titanium dioxide can decompose and oxidize air pollutants such as formaldehyde adsorbed on the surface through photocatalysis, so that the concentration of the formaldehyde in the air is reduced, and the uncomfortable feeling of the environment is relieved or eliminated.
As a cheap and environment-friendly material, nano titanium dioxide is widely used for treating harmful gases in the air environment. The nanometer titanium dioxide photocatalyst is applied to textiles, can effectively degrade toxic and harmful gases in the air under the action of illumination, can decompose and harmlessly treat toxins released by bacteria or fungi, and has the functions of deodorization, stain resistance and the like. However, the band gap of nano-titania is relatively wide (3-3.2 eV), and can only absorb about 3-5% of the UV light in sunlight, which greatly limits the application of nano-titania [ Zhang S, Li J, ZengM, ethyl. in situ synthesis of water-soluble magnetic carbon nitride and organic synthetic carbon performance [ J ]. ACS applied materials & interfaces.2013,5(23): 12735-. Therefore, it is very necessary to develop a catalyst having a high efficiency of visible light response.
In recent years, graphite phase carbon nitride (g-C)3N4) Because of its visible light response (band gap of 2.7e V), simple preparation method, wide raw material source, no toxicity, very good thermal stability, and little chemical corrosion by any acid, alkali, etc., it has become the hot door of photocatalytic material [ Wang X, Blechert S, Antonietti M.polymeric graphical carbon Nitride for Heterogeneous catalysis [ J ] J].ACS Catalysis.2012,2(8):1596-1606.]. However g-C3N4The catalyst is a powder catalyst, and the dispersion effect of the catalyst in aqueous solution is extremely poor due to the similar graphite phase structure, namely the van der Waals force action between single-layer carbon nitrides, so that the recombination between electron hole pairs is increased, and the photocatalytic performance is reduced. In addition, the powder catalysts all face the problem of difficult recycling, resulting in poor recycling and high cost. Modification and loading of the powder catalyst is currently a more efficient and feasible process. However, g-C3N4Generally, high catalytic activity can be achieved only by high-temperature calcination treatment, which is limited to the application of fiber materials and the like which are not resistant to high temperature.
Disclosure of Invention
The invention aims to provide a graphite-phase carbon nitride modified fabric visible-light-driven photocatalyst which has higher visible-light catalytic activity than the existing catalyst with nano titanium dioxide added, and g-C3N4Is not easy to fall off, can keep better catalytic performance even in visible light conditions indoors, and has excellent reusability.
The invention also aims to provide a one-step preparation method of the graphite-phase carbon nitride modified fabric visible-light-driven photocatalyst, which is simple in preparation method, low in energy consumption and environment-friendly.
Still another object of the present invention is to provide an application of a graphite-phase carbon nitride modified fabric visible light catalyst for catalyzing an oxidative degradation reaction of indoor formaldehyde gas, so as to enable organic pollutants such as formaldehyde in indoor air to undergo an oxidative degradation reaction more rapidly, thereby purifying indoor air.
The specific technical scheme of the invention is as follows:
a one-step preparation method of a graphite phase carbon nitride modified fabric visible light catalyst comprises the following steps:
1) mixing urea and transition metal salt, and heating to obtain modified liquid;
2) and (3) placing the fabric into the modification solution, and heating for reaction to obtain the graphite-phase carbon nitride modified fabric visible-light-driven photocatalyst.
The mass ratio of the urea to the transition metal salt in the step 1) is as follows: 0.5-1.5:1.
Further, the transition metal salt in the step 1) is zinc acetate, zinc sulfate, zinc nitrate, zinc chloride or copper acetate.
The heat treatment in the step 1) means treatment at 70 ℃ to 90 ℃ for 1 to 2 hours.
After the heating reaction in the step 1), carrying out vacuum drying, wherein the vacuum drying refers to vacuum drying for 12-24 hours at the temperature of 50-70 ℃. And (4) heating, and then drying in vacuum to remove water in the system.
Further, in the step 1), the modified liquid is stored in a sealed manner.
The fabric in step 2) is preferably a polyester fabric.
The dosage ratio of the fabric to the modification liquid in the step 2) is 1: 30-60 g/ml.
The heating reaction in the step 2) refers to a reaction for 12 to 36 hours at 180 to 240 ℃ under a sealed condition. Preferably, the reaction is carried out in a high temperature, high pressure autoclave with a polytetrafluoroethylene liner.
Further, the step 2) also comprises washing and vacuum drying the obtained product after the heating reaction is finished.
The invention provides a graphite-phase carbon nitride modified fabric visible-light-driven photocatalyst which is prepared by adopting the method. The graphite-phase carbon nitride modified fabric visible-light-induced photocatalyst is g-C loaded on fabric3N4The nano-sheet layer has the load of 20-60mg/g and the appearance of the product is light yellow.
The application of the graphite-phase carbon nitride modified fabric visible-light-driven photocatalyst provided by the invention is used for catalyzing the oxidative degradation reaction of formaldehyde, and is particularly used for catalyzing the oxidative degradation reaction of formaldehyde in indoor air; the specific application method comprises the following steps: the graphite phase carbon nitride modified fabric visible light photocatalyst is made into a curtain, and the curtain is placed indoors and used for catalytic degradation of formaldehyde in indoor air.
Furthermore, the visible-light-driven photocatalyst for the graphite-phase carbon nitride modified fabric can keep better catalytic performance under the condition of weak light radiation intensity.
According to the invention, urea and a transition metal salt compound can form a eutectic solvent system through heating and melting, and after the polyester fabric is placed in the system, the polyester fiber is slightly swelled, so that urea molecules can enter and permeate the surface layer of the polyester fiber, and thus graphite-phase carbon nitride is formed under the conditions of high temperature and high pressure and is more firmly fixed on the surface of the fiber. In addition, g-C not fixed to the surface of the fiber3N4Gradually form precipitate, and the formed eutectic solvent system can greatly promote g-C3N4Thereby promoting g-C3N4Combined with polyester fiber to increase g-C3N4Is fixed on the surface of the polyester fiber. In addition, g-C is formed in the reaction3N4The ammonia byproduct is generated in the process, so that the pressure in the sealed container is increased, the reaction is accelerated, the reaction is promoted to be carried out under the low-temperature condition, and the energy consumption and the production cost are further reduced. In addition, the glass transition temperature of the amorphous region of the polyester fiber is about 67 ℃, the glass transition temperature of the crystalline region is about 81 ℃, and the crystalline and oriented region is about 120 ℃. When the modification temperature exceeds the glass transition temperature of the polyester fiber, the molecular chain of the amorphous area of the fiber starts to move; when the temperature reaches above 120 ℃, the molecular chain motion is intensified, micropores in the amorphous region are opened to form instant holes, and the g-C size smaller than the hole size3N4The nano-sheet layer precursor (urea) also rapidly enters the instant holes to enter the fiber due to Brownian motion at high temperature, and reacts to generate g-C3N4Nanosheets, when the temperature is reduced, causing the g-C to shrink due to shrinkage of the micropores3N4The nanosheets are left behind in the amorphous regions of the fiber. Due to g-C3N4The modified polyester fabric catalyst is fixed on the surface of polyester fiber in the synthesis process, and the catalyst is synthesized by one-step reaction, so that the modified polyester fabric catalyst has excellent washing resistance, simple preparation process, moderate cost and easy operation, and is beneficial to industrial popularization. The obtained catalyst has higher catalytic activity for the oxidative degradation reaction of pollutants such as formaldehyde in indoor air. In addition, the catalyst of the invention can maintain better catalytic performance under the condition of weak light radiation intensity, can enable pollutants in indoor air such as formaldehyde and the like to carry out oxidation degradation reaction more quickly, and can be repeatedly utilized.
The invention can control g-C in the catalyst by adjusting the concentration of urea in the modification reaction, the reaction time and the temperature3N4And (4) preparing a series of catalyst products with different properties. In general, g-C3N4The load capacity of the modified polyester fabric catalyst is mainly controlled by using the initial concentration and the reaction time of urea in the synthetic reaction process, and the g-C of the obtained catalyst is obtained when the concentration of the urea is higher3N4The higher the content. For example, when a high-loading catalyst is used, the catalyst has the highest catalytic activity and is suitable for treating high-concentration indoor formaldehyde. The catalyst product actually prepared is not limited to this content range value as required. Meanwhile, the invention can be easily made into other shapes such as small particles or microparticles by a mechanical method.
Compared with the prior art, the catalyst prepared by the invention is used for promoting the oxidative degradation reaction of indoor formaldehyde gas, has higher catalytic activity than the existing nano titanium dioxide catalyst, and can maintain better catalytic performance even under the condition of weak light radiation intensity. And g-C3N4The catalyst is not easy to fall off, can keep better catalytic performance under the condition of indoor visible light, has excellent reusability, can enable organic pollutants such as formaldehyde in indoor air to carry out oxidative degradation reaction more quickly, and purifies the indoor air. When the air purifier is used for purifying indoor air, pollutants such as formaldehyde and the like can be rapidly degraded, and the removal rate of the pollutants can reach more than 99% within 90 minutes. Furthermore, due to g-C3N4At the same time of synthesisIs fixed on the surface of the polyester fiber, thus g-C3N4The modified polyester fabric visible-light-induced photocatalyst is prepared by a one-step method, so that the modified polyester fabric visible-light-induced photocatalyst has the advantages of excellent washing resistance, simple preparation process, low cost and easiness in operation, and is beneficial to industrial popularization; the catalyst has excellent recycling performance and can still have excellent catalytic performance after being washed by water.
Drawings
FIG. 1 shows the preparation of g-C according to examples 1, 2 and 3 of the present invention3N4A modified polyester fabric catalyst load variation graph;
FIG. 2 shows the preparation of g-C according to examples 1, 2 and 3 of the present invention3N4A comparison graph of the removal effect of the modified polyester fabric catalyst and the nano titanium dioxide loaded polyester fabric in the comparative example on formaldehyde;
FIG. 3 shows catalysts g-C according to the invention3N4-3 recycling properties for formaldehyde removal;
FIG. 4 shows catalysts g-C according to the invention3N4-3 and a comparison graph of formaldehyde removal effect before and after washing of the nano titanium dioxide loaded polyester fabric in the comparative example.
Detailed Description
Specific embodiments of the present invention are described below, but the claims of the present invention are not limited to these specific embodiments.
Example 1
The one-step preparation method of the graphite-phase carbon nitride modified fabric visible-light-induced photocatalyst comprises the following steps:
1) urea and copper acetate were mixed in a ratio of 0.5: 1, treating at 90 ℃ for 2 hours, then drying at 60 ℃ for 12 hours in vacuum, and finally sealing the obtained modified solution for later use;
2) immersing the polyester fabric into the modified solution prepared in the step 1), wherein the ratio of the weight of the polyester fabric to the volume of the modified solution is 1: 50 g/ml, then placing the mixture into a high-temperature high-pressure reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, carrying out modification reaction for 24 hours at the temperature of 180 ℃, naturally cooling the mixture to room temperature, and then using distilled water to react the obtained light yellow fabric-shaped g-C3N4Washing the modified polyester fabric for 3-5 times, and then drying the washed modified polyester fabric for 12 hours in vacuum at the temperature of 60 ℃ to obtain the graphite-phase carbon nitride modified fabric visible-light-induced photocatalyst prepared by the one-step method, which is abbreviated as g-C3N4-1。
Example 2
The one-step preparation method of the graphite-phase carbon nitride modified fabric visible-light-induced photocatalyst comprises the following steps:
the mass ratio of the urea to the copper acetate is 1: 1, otherwise as in example 1; obtaining the visible-light-driven photocatalyst of graphite-phase carbon nitride modified fabric prepared by one-step method, which is abbreviated as g-C3N4-2。
Example 3
The one-step preparation method of the graphite-phase carbon nitride modified fabric visible-light-induced photocatalyst comprises the following steps:
the mass ratio of the urea to the copper acetate is 1.5:1, the remainder of the same procedure as in example 1 gave a one-step preparation of a graphite-phase carbon nitride modified textile visible-light-induced photocatalyst, abbreviated as g-C3N4-3。
The invention adopts the following method to measure the loading capacity of the obtained catalyst: weighing and recording the weight of the fabric before the reaction is started, fully washing and drying the obtained fabric after the reaction is finished, weighing and recording, and further respectively calculating g-C in the obtained catalyst3N4The loading of (a) is in mg/g.
In FIG. 1 (examples 1-3), the g-C of the catalyst prepared increases with the urea concentration3N4The load amount gradually increases. This indicates that increasing the urea concentration can increase the g-C of the fabric3N4The amount of the supported. The reason is that the urea concentration increases, the more urea micromolecules enter the interior of the polyester fiber, and g-C is generated in the reaction process3N4The more so that the catalyst loading amount is gradually increased.
Comparative example
The nano titanium dioxide hydrosol modified polyester fabric comprises the following components:
1) preparing nano titanium dioxide hydrosol: firstly, dissolving 100 ml of butyl titanate in 130 ml of absolute ethyl alcohol at room temperature to form a butyl titanate ethanol solution; while adding 8.4 g of hydrochloric acid to 870 ml of distilled water to obtain a dilute aqueous hydrochloric acid solution; then dripping the butyl titanate ethanol solution into hydrochloric acid aqueous solution at room temperature under the stirring condition; after the dropwise addition is finished, stirring is continuously carried out for 5 hours to obtain milky white water dispersion; finally, the mixture is sealed, kept stand and aged for 5 to 7 days to form yellowish and semitransparent about 1100 ml of nano titanium dioxide hydrosol.
2) Soaking the polyester fabric into the nano titanium dioxide hydrosol prepared in the step 1), wherein the using amount ratio and the reaction conditions are the same as those of the example 1.
The visible-light-induced photocatalyst for graphite-phase carbon nitride modified fabric prepared by the one-step method in examples 1 to 3 and the nano titanium dioxide loaded polyester fabric prepared in the comparative example were measured in the aspect of formaldehyde degradation catalysis, specifically as follows:
purification experiment of formaldehyde in indoor air: the catalyst fabric samples obtained in the above examples and comparative examples, each having an area of 0.06 square meter, were first fixed on sample holders on both sides of the light source of a gas-phase photochemical reactor, at a distance of 6 cm, in which 36W energy-saving lamps (light intensity in the wavelength range of 400 nm to 1000 nm: 1.20 mW/cm) were placed. Then, under the conditions that the room temperature and the relative humidity are 45 +/-3%, 0.01 ml of formaldehyde is injected into the surface of a heating plate in the environmental chamber, and meanwhile, an axial flow fan is started, so that the formaldehyde gas is fully volatilized, and the adsorption balance on the surface of the sample is achieved. And then, turning on a light source to perform a formaldehyde photocatalytic degradation reaction in the air, measuring the change of the concentration of the formaldehyde gas by using a POT400 type formaldehyde gas detector (Shenzhen Wanandei science and technology Limited) at intervals, and calculating the removal rate of the formaldehyde. The structure of the gas-phase photochemical reactor is as shown in the utility model CN 206950982U.
The results of the above formaldehyde degradation effect are shown in fig. 2, and it can be found from fig. 2 (examples 1-3 and comparative example) that the formaldehyde removal rate of the modified polyester fabrics of the three examples of the invention gradually increases with the prolonging of the catalytic reaction time, the formaldehyde removal rate can reach more than 90% after 90 minutes of reaction, and the formaldehyde removal rate thereof is negativeThe loading increases and rises. And when the comparative example finished polyester fabric exists, the formaldehyde removal rate is only less than 20% after the reaction is carried out for 90 minutes. This shows that the formaldehyde removal rate of the catalyst of the example of the present invention is significantly higher than that of the catalyst of the comparative example. This is because the nano titanium dioxide can only absorb ultraviolet light to oxidize and decompose formaldehyde, so as to remove the formaldehyde, while the catalysts of examples 1 to 3 of the present invention can catalyze formaldehyde decomposition under the condition of visible light source, and the comparative example can only adsorb formaldehyde, but cannot oxidize and remove the formaldehyde. g-C in the catalyst of the invention3N4The formaldehyde remover can absorb visible light, generate electron migration and form an electron-hole pair, so that formaldehyde is subjected to oxidative decomposition reaction, and the formaldehyde removal rate is remarkably reduced. More importantly, when the finishing fabric of 3 embodiments of the invention exists, the formaldehyde removal rate in the test chamber can reach 99.9% after the load fabric exists for 2 hours, and the formaldehyde concentration is only 0.005 mg/L, which is far lower than the requirement of national indoor air quality standard.
The g-C obtained in example 3 is given in FIG. 33N4-3, the catalyst is repeatedly applied to the change of catalytic activity in the oxidation removal reaction of formaldehyde in the air under the visible light radiation condition, and the experimental conditions are consistent with the experimental conditions for purifying formaldehyde in the indoor air. The results show that the formaldehyde removal rate hardly changed when used repeatedly 5 times. This means that the catalyst still maintains high catalytic activity after being repeatedly used for five times, and can still well oxidize and remove formaldehyde in the air. The catalyst also has good reusability and wide application prospect.
The catalyst obtained in example 3 and the nano titanium dioxide-loaded polyester fabric obtained in the comparative example were washed with water, respectively, and then the formaldehyde gas-removing effect thereof was measured. Water washing experiment of the obtained catalyst: the catalyst described in the example obtained above and the nano titanium dioxide-loaded polyester fabric of the comparative example were immersed in 100 ml of 5.0 g/l soap powder aqueous solution and stirred continuously at 50 ℃ for 120 minutes, and then applied to the photocatalytic oxidation removal reaction of formaldehyde in indoor air according to the experimental conditions for purification of formaldehyde in indoor air described above, and the removal rates of formaldehyde of the samples before and after washing were respectively measured, and the results are shown in fig. 4.
FIG. 4 shows the formaldehyde removal effect of the catalyst after water washing. The results show that the removal effect of the loaded fabric on formaldehyde is hardly reduced in example 3 before and after washing, and the removal effect of the nano titanium dioxide loaded polyester fabric on formaldehyde is remarkably reduced. The result shows that the terylene visible light catalyst prepared by the invention has excellent washing fastness. This is mainly because of the g-C of the invention3N4The modified terylene photocatalyst is used for synthesizing g-C3N4Is prepared by3N4Slowly synthesized and gradually enlarged, and grows on the surface of the polyester fiber, and the polyester fiber can be firmly combined and are difficult to separate. When the nano titanium dioxide is loaded on the polyester fabric in the comparative example, the nano titanium dioxide is agglomerated before entering the interior of the fiber, particles become large, more particles are difficult to inlay on the surface of the fiber, and the bonding between the particles and the fiber is not firm, so that the nano titanium dioxide almost completely falls off from the surface of the fiber after washing, and the formaldehyde removal effect is obviously reduced.
In summary, a g-C of the present invention was used3N4The modified polyester fabric visible-light-driven photocatalyst and the preparation method thereof solve the problems that the common semiconductor catalyst contains heavy metal, can only absorb ultraviolet light, has low recycling rate, high energy consumption and the like. The urea and the transition metal salt used in the invention are easy for industrial production, low in toxicity and cost, easy for large-scale storage and transportation and industrial production, and have more excellent catalytic performance, high efficiency, low cost, environment-friendly performance and the like compared with semiconductor catalysts such as nano titanium dioxide, nano zinc oxide and the like.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several modifications can be made without departing from the inventive concept, and these modifications belong to the protective scope of the invention.
Claims (10)
1. A one-step preparation method of a graphite-phase carbon nitride modified fabric visible-light-induced photocatalyst is characterized by comprising the following steps:
1) mixing urea and transition metal salt, and heating to obtain modified liquid;
2) and (3) placing the fabric into the modification solution, and heating for reaction to obtain the graphite-phase carbon nitride modified fabric visible-light-driven photocatalyst.
2. The process according to claim 1, wherein the mass ratio of urea to transition metal salt in step 1) is: 0.5-1.5:1.
3. The method according to claim 1, wherein the transition metal salt in step 1) is zinc acetate, zinc sulfate, zinc nitrate, zinc chloride or copper acetate.
4. The method according to claim 1, wherein the heat treatment in step 1) is treatment at 70 ℃ to 90 ℃ for 1 to 2 hours.
5. The preparation method according to claim 1, wherein after the heating reaction in step 1), vacuum drying is performed, and the vacuum drying is performed at 50 ℃ to 70 ℃ for 12 to 24 hours.
6. The method of claim 1, wherein the fabric in step 2) is a polyester fabric.
7. The preparation method according to claim 1, wherein the ratio of the fabric to the modifying solution in step 2) is 1: 30-60 g/ml.
8. The preparation method of claim 1, wherein the heating reaction in step 2) is performed under a sealed condition at 180-240 ℃ for 12-36 hours.
9. A graphite-phase carbon nitride modified fabric visible-light-induced photocatalyst prepared by the preparation method of any one of claims 1 to 8.
10. Use of the graphite-phase carbon nitride modified fabric visible-light-induced photocatalyst prepared by the preparation method according to any one of claims 1 to 8, for catalyzing the oxidative degradation reaction of formaldehyde.
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