CN111468147A - Porous carbon composite titanium dioxide-oxyhalide photocatalyst and preparation method thereof - Google Patents
Porous carbon composite titanium dioxide-oxyhalide photocatalyst and preparation method thereof Download PDFInfo
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- CN111468147A CN111468147A CN202010449204.9A CN202010449204A CN111468147A CN 111468147 A CN111468147 A CN 111468147A CN 202010449204 A CN202010449204 A CN 202010449204A CN 111468147 A CN111468147 A CN 111468147A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 53
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- 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
-
- B01J35/39—
-
- B01J35/60—
Abstract
The invention relates to a porous carbon composite titanium dioxide-oxyhalide photocatalyst, in particular to a porous carbon composite titanium dioxide-oxyhalide photocatalyst, wherein the porous carbon composite titanium dioxide-oxyhalide is hydrolyzed and deposited on the surface of titanium dioxide through an oxyhalide precursor, a porous carbon material precursor (MOF) is prepared by adopting an in-situ growth method and then is carbonized at high temperature to obtain a porous carbon composite titanium dioxide-oxyhalide composite material, the titanium dioxide is calcined at different temperatures, the oxyhalide precursor is one of bismuth oxychloride, bismuth oxyiodide and bismuth oxyfluoride, and the porous carbon material precursor (MOF) is one of a zeolite imidazole framework material and a graphene-like framework material. The titanium dioxide-oxyhalide material prepared at the temperature of below 500 ℃ is compounded with the MOF carbon material porous carbon, so that the adsorption capacity of the material can be obviously enhanced, and the formaldehyde conversion efficiency is greatly improved.
Description
Technical Field
The invention belongs to the field of environmental protection photocatalysis, and particularly relates to a porous carbon composite titanium dioxide-oxyhalide photocatalyst for photocatalytic degradation of formaldehyde and a preparation method thereof.
Background
Indoor air pollution has been identified as one of the high environmental risks at present. Formaldehyde diffuses into the room from furniture, textiles, paints, wallpaper as one of the major air pollutants in the room, and the world health organization recommends that HCHO be harmful to health when its concentration is higher than 0.1 milligram per cubic meter. Prolonged exposure to air at high concentrations of HCHO increases the incidence of leukemia and cancer. Therefore, it is necessary to control HCHO contamination. Recently, many methods for removing HCHO from indoor air have been disclosed, such as absorption, plasma purification, biodegradation, thermocatalytic purification and photocatalytic purification. In the methods, the reaction conditions of the photocatalytic technology are moderate, the removal efficiency is high, no secondary pollution is caused, and the operation is simple, so that the method is the most economical and simple method.
The prior art, such as the Chinese patent with the publication number of CN 108609600B, discloses a novel three-dimensional carbon material and a preparation method thereof. The preparation method comprises the steps of treating the hardwood under the following temperature change conditions in an inert atmosphere or in the absence of oxygen; (a) heating from room temperature to 210-250 ℃ at a heating rate of 0.05-2 ℃/min; (b) heating from 210-250 ℃ to 760-850 ℃ at a heating rate of 0.1-3 ℃/min; (c) heating from 760-850 ℃ to 1100-1450 ℃ at a heating rate of 0.5-4 ℃/min, and preserving heat for 0.5-6.0 h; (d) cooling from 1100-1450 ℃ to room temperature at a cooling rate of 0.5-20 ℃/min. But the novel three-dimensional carbon material only plays an adsorption role and cannot effectively degrade formaldehyde gas in the air.
Titanium dioxide is considered one of the most promising photocatalysts for HCHO removal in many semiconductors because of its non-toxicity, excellent chemical stability and low cost. However, the original TiO2Absorbing ultraviolet rays only in the sun, limits its practical application. To enhance photocatalytic activity in visible light, many methods have been developed. For example, doping of metal/nonmetal elements, coupling of two or more semiconductors, surface modification of noble metals, and composite preparation by different materials have been increasingly gaining attention.
The prior art, such as the Chinese patent with the publication number of CN 108609600B, discloses a building decoration material with formaldehyde purification function and a preparation method thereof. The material consists of the following components in parts by weight: 1-20 parts of formaldehyde purifying agent, 100 parts of base material, 0.5-1 part of modified starch, 1-1.5 parts of adhesive, 0.6-1 part of lignocellulose, 0.01-0.1 part of foaming agent and 65-75 parts of water, wherein the formaldehyde purifying agent consists of the following components in parts by weight: 2-10 parts of polyvinylpyrrolidone, 1-6 parts of water-soluble macromolecular compound, 4-42 parts of chiral amino alcohol, 1-7 parts of titanium dioxide, 1-7 parts of tin dioxide, 1-7 parts of silicon dioxide, 2-6 parts of magnesium oxide, 1-13 parts of activated carbon, 1-9 parts of calcium chloride and 1-13 parts of soluble weak acid salt. The composite structure of the patent is complex, the photoelectric conversion efficiency is low, and the catalytic degradation of formaldehyde in the air can not be efficiently carried out.
However, the formaldehyde catalytic conversion efficiency in the prior art can not be ensured, and the problem of short service life of the formaldehyde catalytic conversion efficiency is still not effectively solved.
Disclosure of Invention
Aiming at the problems of low formaldehyde catalytic conversion efficiency, short service life and low recycling rate in the prior art, the invention provides a porous carbon composite titanium dioxide-oxyhalide photocatalyst with high conversion efficiency, long service life and high recycling rate and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a porous carbon composite titanium dioxide-oxyhalide photocatalyst is prepared through hydrolyzing and depositing a oxyhalide precursor on the surface of titanium dioxide, preparing a porous carbon material precursor (MOF) by using an in-situ growth method, carbonizing at high temperature to obtain the porous carbon composite titanium dioxide-oxyhalide photocatalyst, calcining titanium dioxide at different temperatures, wherein the oxyhalide precursor is one or more of bismuth oxychloride (BiOCl), bismuth oxyiodide (BiOI) and bismuth oxyfluoride (BiOF), and the porous carbon material precursor (MOF) is one of a zeolite imidazole framework material and a graphene-like framework material.
A porous carbon composite titanium dioxide-oxyhalide photocatalyst is characterized in that a stable MOF framework structure is provided for titanium dioxide-oxyhalide through porous carbon composite, structural change of the titanium dioxide-oxyhalide in a photoelectric conversion process is slowed down, the electron transmission efficiency of the titanium dioxide-oxyhalide is accelerated by utilizing the excellent conductivity of the MOF framework structure as a carbon structure, the catalytic conversion efficiency of the porous carbon composite titanium dioxide-oxyhalide photocatalyst on formaldehyde is improved, an oxyhalide precursor is deposited on the surface of titanium dioxide, the bonding rate of the oxyhalide and the titanium dioxide is improved, the photoelectric conversion efficiency of the porous carbon composite titanium dioxide-oxyhalide photocatalyst is improved, and the absorption conversion efficiency on the formaldehyde is improved.
Preferably, the porous carbon composite titanium dioxide-oxyhalide photocatalyst comprises the following components in percentage by weight: 30%, 20% -60% and 40% -70%. The titanium dioxide-oxyhalide plays an important role in the photoelectric conversion for the catalytic degradation of formaldehyde into water and carbon dioxide, and the absorption and conversion efficiency of the porous carbon composite titanium dioxide-oxyhalide photocatalyst to formaldehyde can be further promoted by adjusting the weight percentage of the titanium dioxide-oxyhalide.
Preferably, the porous carbon composite titanium dioxide-oxyhalide photocatalyst is prepared by using one of ZIF-5, ZIF-7, ZIF-8, ZIF-9, ZIF-21 and ZIF-67 as a zeolite imidazole framework material, and using Cu as a graphene framework material3(HHTP)2,Ni3(HITP)2The porous carbon has a porous structure, is high in specific surface area and stable in self-supporting framework, can be well combined with the titanium dioxide-oxyhalide, enhances the adsorption effect on formaldehyde in the air, and improves the absorption and conversion efficiency of the porous carbon composite titanium dioxide-oxyhalide photocatalyst on formaldehyde.
The specific preparation method of the invention comprises the following steps:
1) weighing titanyl sulfate and ammonia water, mixing and stirring, filtering and drying;
2) calcining the product of the step 1) at high temperature;
3) dripping a potassium chloride solution containing bismuth nitrate into the product obtained in the step 2), and stirring for 1-10 h;
4) separating and drying the product obtained in the step 3), putting the product into a container, vacuumizing, sealing and standing for 2-10 hours;
5) putting the product obtained in the step 4) into a hydrochloric acid solution, and soaking for 5-6 hours; separating, washing with deionized water, and drying;
6) putting the product obtained in the step 5) into an alcohol solution of a porous carbon precursor, and synthesizing the porous carbon material in situ;
7) standing the product obtained in the step 6) for 2-4 hours, and calcining;
8) washing and drying the product obtained in the step 7) to obtain the final product of the porous carbon composite titanium dioxide-oxyhalide.
Preferably, the calcination temperature of the product of the step 2) is: 100-300 ℃;
preferably, the calcination temperature of the product obtained in the step 6) is 300-800 ℃.
By modifying the calcination temperature of the product of step 2), such as: 150 ℃, 180 ℃, 200 ℃, 260 ℃, 300 ℃ and the like, and different calcining temperatures can improve the crystal grain structure of the titanium dioxide to ensure that TiO2Peripheral Ti3+、O2+The holes are increased, the absorption range of visible light is expanded, and the absorption range of the visible light is extended to an infrared region, so that the light conversion efficiency is enhanced, and the absorption conversion efficiency of the porous carbon composite titanium dioxide-halogen oxide photocatalyst to formaldehyde is improved.
By modifying the calcination temperature of the product of step 6), such as: the composite performance of the porous carbon composite titanium dioxide-oxyhalide photocatalyst can be enhanced at 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃ and 800 ℃, the porous carbon is not easy to separate when the porous carbon composite titanium dioxide-oxyhalide photocatalyst is subjected to an absorption conversion process, and the stability of the porous carbon composite titanium dioxide-oxyhalide photocatalyst can be improved.
Compared with other titanium dioxide photocatalytic materials, the invention has the following advantages:
1) the photocatalytic material prepared by combining a hydrolysis precipitation method with a calcination crystallization process is low in cost and environment-friendly, and has high photocatalytic absorption conversion rate on gaseous HCHO.
2) The appearance of the porous carbon composite titanium dioxide-oxyhalide photocatalyst is highest at the absorption conversion rate of 0.07685/min, and the unique layered quadrilateral structure of oxyhalide (such as BiOCl) has alternate double-halogen atomic layers and oxide layers, which is favorable for realizing high optical activity and promoting the effective separation of photoinduced carriers.
3) The composite material is compounded with a porous carbon material, so that the adsorption capacity of the composite material can be obviously enhanced, and the defects of weak adsorption performance, poor separation and recovery performance, poor dispersibility and the like are overcome.
4) The porous carbon material MOF has a stable carbon-carbon double bond and single bond composite framework structure, and the stability of the porous carbon material MOF in the using process is enhanced.
Drawings
FIG. 1 is pure TiO2SEM pictures of pure MOF carbon materials and porous carbon composite titanium dioxide-oxyhalide composite materials;
FIG. 2 is a diagram showing the formaldehyde conversion efficiency under irradiation of different light bands
FIG. 3 is pure TiO2Formaldehyde absorption and conversion diagram of pure MOF carbon material and porous carbon composite titanium dioxide-oxyhalide composite material
Detailed Description
Example 1:
a porous carbon composite titanium dioxide-oxyhalide photocatalyst is prepared by the following steps:
1) weighing titanyl sulfate and ammonia water with certain mass, mixing and stirring, filtering and drying;
2) calcining the product obtained in the step 1) at a high temperature of 100 ℃;
3) dripping a potassium chloride solution containing bismuth nitrate into the product obtained in the step 2), and stirring 1; controlling the temperature at 30 ℃;
4) separating and drying the product obtained in the step 3), putting the product into a container, vacuumizing, sealing, and standing at 500 ℃ for 2-4 h;
5) putting the product obtained in the step 4) into a hydrochloric acid solution, and soaking for 6 hours; separating, washing with deionized water, and drying;
6) putting the product obtained in the step 5) into an alcohol solution of a porous carbon material precursor, and growing a porous carbon intermediate carbon material in situ at 250 ℃;
7) standing the product obtained in the step 6) at 300 ℃ for 15 h;
the effect of the obtained porous carbon composite titanium dioxide-oxyhalide photocatalyst on HCHO photocatalytic absorption and conversion is tested, and the test method comprises the following steps:
8) washing and drying the product obtained in the step 7) to obtain the final product, namely the porous carbon composite titanium dioxide-oxyhalide.
And spraying gold on the calcined sample, and carrying out scanning electron microscope test.
Vertically placing a 300W xenon lamp with adjustable power outside a photoreactor, simulating whether a cut-off solar or visible light source and a filter (420nm) exist, and analyzing HCHO and CO on line by a GASERA ONE multi-gas analyzer provided with a closed-loop sampling and analyzing system2The concentration of (c). By monitoring changes in HCHO concentration and increased CO2The absorption and conversion efficiency of HCHO is evaluated by concentration, and the concentration of formaldehyde in the reaction process is from 66mg/m3Reduced to 17.8mg/m3。
Example 2: the calcination temperature of the product of step 6) of the preparation method of a porous carbon composite titania-oxyhalide catalyst described in example 1 was adjusted to 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, and the remaining part was completely the same as in example 1.
The results obtained are shown in the table below.
Example 3: the kind of the catalyst in the porous carbon composite titanium dioxide-oxyhalide catalyst in the embodiment 1 is adjusted, the adjusted catalyst is pure BiOCl catalyst, pure TiO2 catalyst, pure MOF, porous carbon composite titanium dioxide-oxyhalide catalyst, and the rest is completely consistent with the embodiment 1
FIG. 1 is pure TiO2The scanning electron microscope images of the pure MOFs carbon material and the porous carbon composite titanium dioxide-oxyhalide composite material show that the modified composite material has obvious change, surface cavities are increased, and an obvious rough structure with unevenness is formed, so that the adsorption capacity of the modified composite material is enhanced.
FIG. 2 is pure TiO2The parameter diagrams of the pure MOFs carbon material and the porous carbon composite titanium dioxide-oxyhalide composite material show that the integral performance of the porous carbon composite titanium dioxide-oxyhalide composite material is improved at 500 ℃, the pore volume size is increased,the adsorption capacity is enhanced.
FIG. 3 is a graph of formaldehyde conversion efficiency under irradiation of different light bands, and it can be seen that the visible light range at 500 ℃ is widest, the formaldehyde conversion efficiency is highest, and 500 ℃ shows the highest reaction rate constant (0.07685/min) under sunlight, which is about 3.59, 25.4 and 2.96 times of that of TiO2, BiOCl and MOFs carbon materials at the same temperature. Meanwhile, the photocatalytic capacity of the composite material under visible light is higher than that of other photocatalysts, the k value (0.00728/min is respectively 6.62 times, 7.43 times and 2.57 times of TiO2, BiOCl and T-B) of the porous carbon composite titanium dioxide-oxyhalide, when the MOFs material is loaded, the adsorption performance of the MOFs material is enhanced, so that the light conversion efficiency is enhanced, because HCHO molecules adsorbed on the surface of the catalyst are the first step of HCHO oxidation, the formaldehyde absorption and conversion efficiency graph of the porous carbon composite titanium dioxide-oxyhalide composite material is shown, the absorption and conversion efficiency and the carbon dioxide increment of the porous carbon composite titanium dioxide-oxyhalide composite material in sunlight with longer wave bands are obviously higher than those of other single materials, the visible composite material has wider energy band gap, can convert formaldehyde into water and carbon dioxide more, and convert toxic organic matters into non-toxic organic matters, the porous carbon composite titanium dioxide-oxyhalide composite material is favorable for adsorbing oxygen to form O2-Active substance and then generating holes to perform catalytic conversion on formaldehyde molecules to form nontoxic CO2And H2O。
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.
Claims (6)
1. The porous carbon composite titanium dioxide-oxyhalide photocatalyst is characterized in that an oxyhalide precursor is one of bismuth oxychloride, bismuth oxyiodide and bismuth oxyfluoride, and the porous carbon material precursor is one of a zeolite imidazole framework material and a graphene-like framework material. The weight percentages of the titanium dioxide, the porous carbon precursor and the oxyhalide precursor are respectively as follows: 30%, 20% -60%: 40% -70%, the zeolite imidazole framework material is one of ZIF-5, ZIF-7, ZIF-8, ZIF-9, ZIF-21 and ZIF-67, and the graphene-like framework material is one of Cu3(HHTP)2 and Ni3(HITP) 2.
2. The preparation method of the porous carbon composite titanium dioxide-oxyhalide photocatalyst according to claim 1, characterized in that the porous carbon composite titanium dioxide-oxyhalide is hydrolyzed and deposited on the surface of titanium dioxide by an oxyhalide precursor, the porous carbon material precursor is prepared by an in-situ growth method, and then high-temperature carbonization is performed to obtain the porous carbon composite titanium dioxide-oxyhalide composite material, and the titanium dioxide is calcined at different temperatures.
3. The preparation method of the porous carbon composite titanium dioxide-oxyhalide photocatalyst according to claim 2 comprises the following specific steps:
1) weighing titanyl sulfate and ammonia water, mixing and stirring, filtering and drying;
2) calcining the product of the step 1) at high temperature;
3) dripping a potassium halide solution containing bismuth nitrate into the product obtained in the step 2), and stirring for 1-10 h;
4) separating and drying the product obtained in the step 3), putting the product into a container, vacuumizing, sealing and standing for 2-10 hours;
5) putting the product obtained in the step 4) into a hydrochloric acid solution, and soaking for 5-6 hours; separating, washing with deionized water, and drying;
6) putting the product obtained in the step 5) into an alcohol solution of a porous carbon precursor, and synthesizing the porous carbon material in situ;
7) standing the product obtained in the step 6) for 2-4 hours, and calcining.
8) Washing and drying the product obtained in the step 7) to obtain the final product of the porous carbon composite titanium dioxide-oxyhalide.
4. The preparation method of the porous carbon composite titanium dioxide-oxyhalide photocatalyst according to claim 3, wherein the calcination temperature in the step 2) is stepwise calcination, the calcination is performed at 100-140 ℃ for 10-30 min, the calcination is performed at a temperature rise rate of 20 ℃/min to 260-300 ℃ for 20-40 min, and then the calcination is performed with furnace cooling.
5. The method for preparing the porous carbon composite titanium dioxide-oxyhalide photocatalyst according to claim 3, wherein the oxyhalide precursor in step 3) is one of bismuth oxychloride, bismuth oxyiodide and bismuth oxyfluoride.
6. The preparation method of the porous carbon composite titanium dioxide-oxyhalide photocatalyst according to claim 3, wherein the calcination temperature of the product obtained in the step 6) is 300-800 ℃.
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