CN115155624A - Heterojunction composite material for visible light catalysis aldehyde removal, preparation method thereof and method for visible light catalysis degradation of VOCs - Google Patents
Heterojunction composite material for visible light catalysis aldehyde removal, preparation method thereof and method for visible light catalysis degradation of VOCs Download PDFInfo
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- 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
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- 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
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- 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
- B01D—SEPARATION
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- 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
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- B01D53/8687—Organic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J37/08—Heat treatment
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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
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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
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Abstract
The invention discloses a heterojunction composite material for visible light catalytic aldehyde removal, a preparation method thereof and a method for visible light catalytic degradation of VOCs (volatile organic compounds), wherein the general formula of the heterojunction composite material for visible light catalytic aldehyde removal is TiO 2‑x /BiO 1‑x Cl, said formula being represented by formula (I) to TiO 2 Or oxygen vacancy (O) is introduced into BiOCl crystal lattice v ). The heterojunction composite material provided by the invention can be used for visible lightThe utilization rate of the formaldehyde is higher, the degradation rate of the formaldehyde is higher in the air medium, and the stability is better.
Description
Technical Field
The invention relates to the technical field of photocatalytic nano composite materials and air purification, in particular to a heterojunction composite material for visible light catalysis aldehyde removal, a preparation method thereof and a method for visible light catalysis VOCs degradation.
Background
Volatile Organic Compounds (VOCs) are air pollutants generated from industrial gases, building and decorative materials, and automobile exhaust emissions, and pose great harm to air quality and human health. Among the various volatile organics, formaldehyde (HCHO) is one of the most hazardous and typical indoor air pollutants, and is also the major cause of Sick Building Syndrome (SBS). Numerous studies have shown that long-term exposure to high concentrations of formaldehyde can cause serious pathological effects on human health, mainly including skin and mucosal irritation, nasal tumors, chronic bronchitis, respiratory dysfunction, hepatotoxic lesions and even cancer. In recent years, various techniques for removing HCHO from indoor air, such as physical adsorption, plasma oxidation, thermal catalytic oxidation and photocatalytic oxidation, have been explored in view of potential health hazards, increasingly stringent environmental regulations and increasing public concerns. Of these treatment techniques, photocatalytic oxidation is due to the CO it produces under sunlight 2 And H 2 The environmentally friendly product of O is considered to be the most promising and effective method for removing HCHO indoors.
Titanium dioxide (TiO) 2 ) As one of the widely studied photocatalysts, the photocatalyst has the characteristics of no toxicity, good stability, high photocatalytic oxidation capacity and the like, is widely applied to photocatalytic treatment of gas pollutants, and has actual indoor application prospects. However, tiO 2 The wide bandgap (about 3.2 eV) and low quantum efficiency limit their practical indoor applications. Therefore, there is a need to improve quantum efficiency, expand visible light response, and tune the bandgap structure. Generally, the method for constructing a binary photocatalytic system by selecting a narrow-bandgap semiconductor photocatalyst with visible light activity is to adjust TiO 2 Bandgap is one of the most common and effective means. Recently, bismuth oxychloride/titanium dioxide (BiOCl/TiO) 2 ) The photocatalytic performance of heterojunction structures through the construction of p-n type heterostructures is receiving increasing attention.
Among various photocatalyst semiconductors, titanium dioxide (TiO) 2 ) Has been widely researched and accepted as eliminating indoor volatilization due to the advantages of low cost, excellent chemical stability, no toxicity, strong oxidizing power and the likeOrganic substances are one of the most promising choices. However, titanium dioxide generally exhibits low photocatalytic efficiency due to limited spectral response (only 5% of solar light) and rapid recombination of light-induced charges, which severely limits practical applications of photocatalytic removal of volatile organic compounds. To overcome these limitations, tiO has been used 2 Recombination with other semiconductors has been pursued to develop heterojunction structures to improve photocatalytic performance.
Therefore, how to pass through TiO 2 And BiOCl to obtain heterojunction composite materials for visible light catalyzed aldehyde removal have become the focus of research.
Disclosure of Invention
The invention mainly aims to provide a heterojunction composite material for visible light catalysis aldehyde removal, a preparation method thereof and a method for visible light catalysis degradation of VOCs, and aims to develop a heterojunction composite material capable of improving photocatalytic performance and further improving catalytic degradation of VOCs.
In order to achieve the purpose, the invention provides a heterojunction composite material for visible light catalysis aldehyde removal, and the general formula of the heterojunction composite material is TiO 2-x /BiO 1-x Cl, said formula being represented by formula II to TiO 2 Or oxygen vacancies (O) are introduced into the BiOCl lattice v )。
The invention also provides a preparation method of the heterojunction composite material for visible light catalysis aldehyde removal, which is characterized by comprising the following steps:
s1: preparation of TiO 2 /BiOCl；
S2: subjecting the TiO to a reaction 2 Calcining BiOCl to obtain a product TiO 2-x /BiO 1-x Cl。
Optionally, the step S1 includes:
s11: adding tetrabutyl titanate into absolute ethyl alcohol, adding ultrapure water, adding hydrochloric acid, and stirring to form a mixed solution;
s12: dropwise adding a transparent solution in which bismuth nitrate and potassium chloride are dissolved into the mixed solution, adjusting the pH to be neutral, stirring, standing to form sol-gel, drying in a drying oven to constant weight, and grinding to obtain TiO 2 /BiOCl。
Optionally, the volume ratio of the tetrabutyl titanate, the absolute ethyl alcohol, the ultrapure water and the hydrochloric acid is 1: (2-5): 1: (0.1-0.4).
Optionally, the mass concentration of the hydrochloric acid is 0.5 to 2mol/L.
Optionally, the mass ratio of the bismuth nitrate to the potassium chloride in the transparent solution is (4-5): 1.
optionally, the stirring time in the step S12 is 0.5 to 2 hours, the rotation speed is 600 to 1500r/min, and the standing time is 12 to 24 hours.
Optionally, the step S2 includes:
subjecting the TiO to a reaction 2 /BiOCl is calcined in inert gas or vacuum environment to obtain a product TiO 2-x /BiO 1-x Cl。
Optionally, the flow rate of the inert gas is 50-200 mL/min, the calcining temperature is 300-600 ℃, the heating rate is 1-10 ℃/min, and the calcining time is 1-3 h.
The invention also provides a method for degrading VOCs by visible light catalysis, which comprises the following steps: under the action of visible light, VOCs are catalytically degraded by using the heterojunction composite material with aldehyde removed by visible light catalysis, and the heterojunction composite material with aldehyde removed by visible light catalysis is prepared by the preparation method of the heterojunction composite material with aldehyde removed by visible light catalysis.
In the technical scheme provided by the invention, tiO 2-x /BiO 1-x Cl has an extremely excellent degradation effect on volatile organic compounds, particularly formaldehyde, under the photocatalysis condition. After the reaction has started, the TiO 2-x /BiO 1-x The Cl photocatalyst is easily excited by visible light due to a narrow band gap to generate a photo-generated electron hole pair, and in addition, due to a proper energy band position between the Cl photocatalyst and the bismuth oxychloride, electrons of a titanium dioxide conduction band can rapidly migrate to the bismuth oxychloride conduction band, and meanwhile, light-induced holes move in a reverse direction, and a built-in electric field is generated at an interface due to redistribution of charges, so that the carrier separation efficiency is effectively promoted. Finally, under the irradiation of visible light, the electron-hole pair is separated, and the electron converts-OH and water molecule into hydroxyl freeActive oxidizing substances such as superoxide radical and the like, thereby promoting the degradation of volatile organic compounds such as formaldehyde and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows TiO provided by the present invention 2-x /BiO 1-x SEM images of Cl nanoparticles;
FIG. 2 shows TiO provided by the present invention 2 ，BiOCl，TiO 2-x /BiO 1-x Cl ultraviolet diffuse reflection spectrogram;
FIG. 3 shows TiO provided by the present invention 2-x /BiO 1-x N of Cl 2 Adsorption-desorption isotherm plot;
FIG. 4 shows TiO provided by the present invention 2 ，BiOCl，TiO 2-x /BiO 1-x A Fourier diffuse reflectance infrared spectrogram of Cl;
FIG. 5 shows TiO provided by the present invention 2 ，BiOCl，TiO 2-x /BiO 1-x A comparison chart of the performance of Cl visible light catalytic degradation of formaldehyde;
FIG. 6 shows TiO provided by the present invention 2-x /BiO 1-x And (3) a reutilization experiment for degrading formaldehyde by Cl visible light catalysis.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B", including either A or B or both A and B. In addition, technical solutions between the various embodiments may be combined with each other, but must be based on the realization of the capability of a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Recently, bismuth oxychloride/titanium dioxide (BiOCl/TiO) 2 ) The photocatalytic performance of heterojunction structures through the construction of p-n type heterostructures is receiving increasing attention. The improvement in photoactivity is mainly due to the fact that the electric field inside the heterostructure accelerates the charge separation. In the utilization of TiO 2 In the process of constructing the heterojunction with BiOCl, the existing preparation method generally has the following problems: 1) TiO 2 2 And BiOCl has limited visible light absorption range and higher carrier recombination rate, and TiO is utilized 2 After BiOCl compounding, tiO 2 The efficiency of the/BiOCl degradation of formaldehyde is still low. 2) Built TiO 2 the/BiOCl heterojunction does not consider the influence of the introduction of oxygen vacancies on the band gap and the photocatalytic performance. For example, CN201911409702.4 discloses a TiO 2 A low-temperature liquid-phase one-step preparation method of the-BiOCl composite photocatalyst, although the TiO is successfully prepared by using a one-step method 2 BiOCl, but the process is relatively complicated, oxygen vacancies are not introduced, the light absorption of the composite material is not further expanded, and the improvement of the catalytic activity is not facilitated.
In view of the above, the invention provides a heterojunction composite material for visible light catalyzed aldehyde removal by adjusting BiOCl/TiO 2 The band gap of the material improves the absorptivity of visible light, and is more beneficial to removing aldehyde by photocatalysis. Fig. 1 shows SEM images of nanoparticles of an embodiment of the heterojunction composite material for visible-light catalyzed aldehyde removal provided by the present invention. The general formula of the heterojunction composite material is TiO 2-x /BiO 1-x Cl, said formula being represented by formula II to TiO 2 Or oxygen vacancies (O) are introduced into the BiOCl lattice v )。
It is understood that titanium dioxide (TiO) 2 ) Has the characteristics of no toxicity, good stability, high photocatalytic oxidation capability and the like, is widely applied to the photocatalytic treatment of gas pollutants, however, tiO 2 The wide bandgap (about 3.2 eV) and low quantum efficiency limit their practical indoor applications. Therefore, there is a need to improve quantum efficiency, expand visible light response, and tune the bandgap structure. Generally, the narrow band gap semiconductor photocatalyst with visible light activity is selected to construct a binary photocatalytic system by adjusting TiO 2 One of the most common and effective means of bandgap, bismuth oxychloride/titanium dioxide (BiOCl/TiO) 2 ) The heterojunction structure improves the photocatalytic activity by constructing a p-n type heterostructure, and the improvement of the photoactivity is mainly attributed to the fact that the electric field inside the heterostructure accelerates the charge separation. On the other hand, with alternating layers of bicl atoms and [ Bi 2 O 2 ] 2+ The unique layered tetragonal structure of the layer BiOCl helps to increase the photocatalytic activity, which can promote the efficient separation of photo-induced carriers. Furthermore, to TiO 2 Or oxygen vacancies (O) are introduced into the BiOCl lattice v ) To produce TiO 2-x Or BiO 1-x Cl, after introduction of oxygen vacancies, tiO 2 The band gap structure is adjusted, so that the absorption efficiency of the band gap structure on visible light is improved, and the formaldehyde removal efficiency of photocatalysis is improved.
Further, the invention also provides a preparation method of the heterojunction composite material for visible light catalysis aldehyde removal, which comprises the following steps:
step S1, preparing TiO 2 /BiOCl；
Step S2, adding the TiO 2 Calcining BiOCl to obtain product TiO 2-x /BiO 1-x Cl。
In the scheme, the heterojunction composite material for removing aldehyde by visible light catalysis is made of TiO 2 And BiOCl, so to obtain the product of the scheme, tiO is firstly utilized 2 Compounding BiOCl to obtain TiO 2 BiOCl, and TiO 2 The efficiency of VOCs degradation by BiOCl is very low, so that TiO is needed 2 The BiOCl is further reacted, namely is obtained by calciningProduct TiO 2-x /BiO 1-x Cl, said product TiO 2-x /BiO 1-x Cl to TiO 2 Or oxygen vacancies (O) are introduced into the BiOCl lattice v ) Thus reducing TiO 2 And BiOCl, tiO 2-x /BiO 1-x The Cl photocatalyst is easily excited by visible light due to a narrow band gap to generate a photo-generated electron hole pair, and in addition, due to a proper energy band position between the Cl photocatalyst and the bismuth oxychloride, electrons of a titanium dioxide conduction band can rapidly migrate to the bismuth oxychloride conduction band, and meanwhile, light-induced holes move in a reverse direction, and a built-in electric field is generated at an interface due to redistribution of charges, so that the carrier separation efficiency is effectively promoted. Finally, under the irradiation of visible light, the electron-hole pair is separated, and the electron converts-OH and water molecules into active oxidation substances such as hydroxyl free radicals and superoxide free radicals, so that the degradation of volatile organic compounds such as formaldehyde is promoted.
Further, in this embodiment, the step S1 includes:
step S11, adding tetrabutyl titanate into absolute ethyl alcohol, adding ultrapure water, adding hydrochloric acid, and stirring to form a mixed solution;
s12, dropwise adding the transparent solution dissolved with the bismuth nitrate and the potassium chloride into the mixed solution, adjusting the pH to be neutral, stirring, standing to form sol-gel, drying in a drying oven to constant weight, and grinding to obtain TiO 2 /BiOCl。
The reaction equation involved in step S12 is Bi (NO) 3 +3KCl→ BiOCl+3KNO 3 +2HCl, in the scheme, the preparation of the raw materials of tetrabutyl titanate, absolute ethyl alcohol, ultrapure water, hydrochloric acid, bismuth nitrate, potassium chloride and the like are common chemical substances, so that the TiO is prepared 2 the/BiOCl is convenient and simple.
Further, in this embodiment, tetrabutyl titanate is added to the absolute ethyl alcohol, and the tetrabutyl titanate is added according to a proper proportion, specifically, the volume ratio of tetrabutyl titanate to absolute ethyl alcohol is: 1: (2-5); adding ultrapure water, then adding hydrochloric acid, and stirring to form a mixed solution, wherein the hydrochloric acid is added according to a proportion, and the volume ratio of the absolute ethyl alcohol to the ultrapure water to the hydrochloric acid is 1: (2-5): 1: (0.1-0.4), the arrangement can ensure even mixing and does not waste raw materials.
In this embodiment, in step S11, after adding ultrapure water, hydrochloric acid is added and stirred, wherein the hydrochloric acid is diluted hydrochloric acid, specifically, the amount concentration of the hydrochloric acid is 0.5 to 2mol/L.
In this embodiment, further, in step S12, a transparent solution in which bismuth nitrate and potassium chloride are dissolved is added dropwise to the mixed solution, where the bismuth nitrate and the potassium chloride need to be mixed in a certain proportion, so as to perform a reaction, specifically, the mass ratio of the bismuth nitrate to the potassium chloride is (4-5): 1, the arrangement can ensure full reaction and does not waste raw materials.
In this embodiment, further, in step S12, the transparent solution in which the bismuth nitrate and the potassium chloride are dissolved is added dropwise into the mixed solution, the pH is adjusted to be neutral, the mixed solution is stirred and then stands to form a sol-gel, and in order to fully stir the mixed solution to form a sol-gel with good quality, sufficient stirring time is required and a suitable rotation speed is matched, specifically, the stirring time is 0.5 to 2 hours, the rotation speed is 600 to 1500r/min, and the standing time is 12 to 24 hours.
Further, in this embodiment, the step S2 includes:
mixing the TiO with a solution of a binder 2 Calcining BiOCl in inert gas or vacuum environment to obtain product TiO 2-x /BiO 1-x Cl。
In this scheme, to extend TiO 2 The visible light responds and adjusts the band gap structure to prepare the narrow band gap semiconductor photocatalyst with visible light activity, and the narrow band gap semiconductor photocatalyst is TiO 2 Or oxygen vacancies (O) are introduced into the BiOCl lattice v ) The specific steps are that the TiO is mixed 2 /BiOCl is calcined in inert gas or vacuum environment to obtain a product TiO 2-x /BiO 1-x Cl can ensure that other impurities cannot be generated under the inert gas or vacuum environment, so that the output efficiency is influenced.
Further, in this embodiment, it is preferable that the calcination treatment is performed in an inert gas atmosphere,the flow rate of the inert gas is 50-200 mL/min, the calcining temperature is 300-600 ℃, the heating rate is 1-10 ℃/min, and the calcining time is 1-3 h, so that the TiO can be calcined by the arrangement 2 the/BiOCl is in an inert gas environment, the calcination is sufficient, no impurity is generated, and the reaction efficiency is high.
The invention also provides a method for degrading VOCs by visible light catalysis, which comprises the following steps: under the action of visible light, VOCs are catalytically degraded by the heterojunction composite material with aldehyde removed by visible light catalysis, and the heterojunction composite material with aldehyde removed by visible light catalysis is prepared by the preparation method of the heterojunction composite material with aldehyde removed by visible light catalysis. The heterojunction composite material for removing aldehyde by visible light catalysis is made of TiO 2 And BiOCl by addition to TiO 2 Or oxygen vacancies (O) are introduced into the BiOCl lattice v ) To reduce TiO in the solution 2 And the band gap of BiOCl, thereby extending the visible light response, tiO 2-x /BiO 1-x The Cl is easily excited by visible light, and the VOCs are catalytically degraded by the heterojunction composite material for removing aldehyde by visible light catalysis under the action of the visible light, so that the efficiency is greatly improved, and the method has the advantages of no toxicity and good stability.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
First, 10mL of tetrabutyl titanate was slowly added to 40mL of stirred anhydrous ethanol, 10mL of ultrapure water was slowly added, and 2mL of 1mol/L HCl was immediately added thereto, and stirring was continued for 30min. Then, 20mL of dissolved Bi (NO) was added 3 ) 3 ·5H 2 A transparent solution of O (1.86 g) and KCl (0.43 g) was added dropwise to the above solution. The pH was adjusted to neutral and stirred at room temperature for 2h. Standing for 12h to form sol-gel, fully drying in a forced air dryer at 80 ℃, grinding, transferring the product into a crucible, and calcining in a tube furnace at 500 ℃ at a heating rate of 5 ℃/min for 3h under the protection of nitrogen. After cooling to room temperature, tiO is obtained 2-x /BiO 1-x Cl。
Example 2
First, 10mL of tetrabutyltitanate was slowly added to 20mL of stirred anhydrous ethanol, 10mL of ultrapure water was slowly added, and 1mL of 1mol/L HCl was immediately added thereto, and stirring was continued for 30min. Then, 20mL of dissolved Bi (NO) 3 ) 3 ·5H 2 A transparent solution of O (1.86 g) and KCl (0.43 g) was added dropwise to the above solution. The pH was adjusted to neutral and stirred at room temperature for 2h. Standing for 12h to form sol-gel, fully drying in a forced air dryer at 80 ℃, grinding, transferring the product into a crucible, and calcining in a tube furnace at 500 ℃ at a heating rate of 5 ℃/min for 3h under the protection of nitrogen. After cooling to room temperature, tiO is obtained 2-x /BiO 1-x Cl。
Example 3
First, 10mL of tetrabutyltitanate was slowly added to 50mL of stirred anhydrous ethanol, 10mL of ultrapure water was slowly added, and immediately 4mL of 1mol/L HCl was added, and stirring was continued for 30min. Then, 20mL of dissolved Bi (NO) 3 ) 3 ·5H 2 A transparent solution of O (1.86 g) and KCl (0.43 g) was added dropwise to the above solution. The pH was adjusted to neutral and stirred at room temperature for 2h. Standing for 12h to form sol-gel, drying in a forced air dryer at 80 deg.C, grinding, transferring the product into a crucible, and calcining in a tube furnace at 500 deg.C under nitrogen protection at a heating rate of 5 deg.C/min for 3 hr. After cooling to room temperature, tiO is obtained 2-x /BiO 1-x Cl。
Comparative example 1
First, 5mL of tetrabutyltitanate was slowly added to 20mL of stirred anhydrous ethanol, 5mL of ultrapure water was slowly added, and 0.5mL of 2mol/L HCl was immediately added thereto, and stirring was continued for 30min. Standing for 24h to form sol-gel, drying in 80 deg.C forced air drier, and grinding to obtain TiO 2 。
Comparative example 2
Adding Bi (NO) 3 ) 3 ·5H 2 O (1.86 g) and KCl (0.43 g) were dissolved in 10mL of ultrapure water, the pH was adjusted to neutral, and the mixture was stirred at room temperature for 2 hours. Standing for 18 hr to form sol-gel, and drying at 80 deg.C in a forced air drierDrying and grinding to obtain BiOCl.
Test methods and results
In a 1.5L quartz photocatalytic reactor, formaldehyde was removed photocatalytically with a 5W fan under visible light irradiation at room temperature. A350W xenon lamp was placed vertically outside the photoreactor. The ultraviolet rays were removed using an ultraviolet cut filter (420 nm). The average light intensity of the surface of the reaction solution in the reaction solution measured by a photon densitometer was 200mW/cm 2 I.e., 2 standard solar intensities (AM 3G), 0.2G of catalyst and 15mL of deionized water were sonicated in a petri dish (7.0 cm diameter) for 25 minutes to form a suspension. The dish was dried under vacuum at 60 ℃ for 1h and a uniform photocatalyst film was formed on the bottom of the dish. The dish was then placed in a photocatalytic reactor. A certain amount of 38% aqueous formaldehyde was injected into the reactor, and the initial concentration of HCHO evaporated after reaching adsorption-desorption equilibrium in the dark was 60mg/m 3 . Formaldehyde, CO in the reactor during irradiation 2 And H 2 The O concentration was monitored on-line by a photoacoustic infrared multi-gas monitor (inova Air Tech 95Instruments model 1412). The removal rate of formaldehyde (Y) was calculated as Y (%) = (1-C/C) 0 ) X 100% where C and C 0 The concentrations of formaldehyde at 0 and t min, respectively.
Continuous degradation experiments:
after the first degradation reaction is finished, drying the culture dish containing the photocatalyst at 60 ℃ for 0.5 hour, then putting the culture dish into the reactor again for the next formaldehyde removal reaction, wherein the reaction conditions except materials are consistent with those of the first time; and after the second reaction is finished, repeating the steps, carrying out a third degradation experiment, and repeating the steps in the same way for five times of cycle experiments.
The experimental results show that: visible light (lambda) at 2 standard solar intensities>420 nm), the dosage of the catalyst is 0.1g, and the initial concentration of formaldehyde is 60mg/m 3 At an initial temperature of room temperature, tiO 2-x /BiO 1-x The degradation efficiency of the Cl photocatalytic nano material to formaldehyde after 120 minutes is as high as 99.8%.
FIG. 1 shows TiO prepared in example 1 2-x /BiO 1-x SEM image of Cl nanoparticles, FIG. 1 shows TiO 2-x The nano particles are uniformly distributed in the BiO 1-x On the Cl nano-sheet, the reduction of particle agglomeration increases the exposure area, thereby being beneficial to the subsequent photocatalytic degradation process.
FIG. 2 shows TiO prepared in example 2 ，BiOCl，TiO 2-x /BiO 1-x Cl ultraviolet diffuse reflection spectrogram. It can be found that TiO alone 2 And BiOCl are both confined to the UV absorption region, and after oxygen vacancies are introduced by high temperature calcination, the TiO is oxidized to form a film 2-x /BiO 1-x The light absorption range of Cl is widened to a full visible light region, and the reduction of the band gap means that more photons can be transited under visible light, so that the photoelectric transfer efficiency is improved.
FIG. 3 shows TiO of the present invention 2-x /BiO 1-x N of Cl 2 An adsorption-desorption isotherm diagram, and the specific surface area of the composite material is 41.2m 2 G, indicates TiO 2-x /BiO 1-x Cl has relatively weak formaldehyde adsorption capacity, and is mainly degraded by the cooperation of persistent free radicals generated by photocatalysis after visible light is absorbed and formaldehyde is reacted.
FIG. 4 shows TiO prepared in example 2 ，BiOCl，TiO 2-x /BiO 1-x Fourier diffuse reflectance infrared spectrum of Cl. For TiO 2 Below 800cm -1 The peak of (a) is due to tensile vibration of Ti-O-Ti; 3415cm -1 And 1633cm -1 The peak at (A) may be the bending and stretching vibration of O-H, which may be due to TiO 2 Water and hydroxyl are adsorbed on the surface; for BiOCl,520-530cm -1 And 1050cm -1 The peaks are apparent due to tensile vibration of Bi-O and Bi-Cl bonds in the BiOCl structure, respectively. Noteworthy, tiO 2 And BiOCl exist in TiO 2-x /BiO 1-x In Cl samples, this further indicates TiO 2-x /BiO 1-x And (4) successfully synthesizing the Cl composite catalyst.
FIG. 5 is g-C 3 N 4 TiO prepared in example 2 ，BiOCl，TiO 2-x /BiO 1-x Visible light catalytic degradation formaldehyde of Cl nano composite materialPerformance is compared to the graph. It can be seen that due to TiO 2 And BiOCl does not absorb visible light, resulting in a low degradation rate of formaldehyde, only 9.5% and 3.3%, which may be caused by adsorption on the catalyst surface. When the two form a heterojunction and oxygen vacancies are introduced during high-temperature calcination, the two can absorb visible light, and the two have proper energy level difference, so that the transfer of photogenerated electrons at the heterojunction interface is facilitated, and the degradation rate of formaldehyde is greatly improved. Finally, tiO 2-x /BiO 1-x The Cl photocatalysis nano material has the degradation efficiency of 99.8 percent to formaldehyde under the action of free radicals generated by photocatalysis within 120 minutes.
FIG. 6 shows TiO 2-x /BiO 1-x The Cl photocatalysis nano material has stable photocatalysis performance. After the first degradation reaction is finished, drying the culture dish containing the photocatalyst at 60 ℃ for 0.5 hour, then putting the culture dish into the reactor again for the next formaldehyde removal reaction, wherein the reaction conditions except materials are consistent with those of the first time; and after the second reaction is finished, repeating the steps, carrying out a third degradation experiment, and so on. The formaldehyde degradation efficiency was above 90% in five consecutive degradation experiments, which indicates that TiO 2-x /BiO 1-x The photocatalytic activity of the Cl photocatalytic nanomaterial remains good after five cycles.
In conclusion, the heterojunction composite material TiO for visible light catalytic aldehyde removal provided by the invention 2-x /BiO 1-x The Cl has high formaldehyde degradation efficiency which reaches 99.8 percent under the action of free radicals generated by photocatalysis within 120 minutes, and has stable photocatalysis performance.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A kind ofThe heterojunction composite material for removing aldehyde by visible light catalysis is characterized in that the general formula of the heterojunction composite material is TiO 2-x /BiO 1-x Cl, said formula being represented by formula II to TiO 2 Or oxygen vacancies (O) are introduced into the BiOCl lattice v )。
2. A method for preparing a heterojunction composite material for visible-light catalyzed aldehyde removal according to claim 1, comprising the steps of:
s1: preparation of TiO 2 /BiOCl；
S2: mixing the TiO with a solution of a binder 2 Calcining BiOCl to obtain product TiO 2-x /BiO 1-x Cl。
3. The method for preparing a heterojunction composite material for visible light catalyzed aldehyde removal according to claim 2, wherein the step S1 comprises:
s11: adding tetrabutyl titanate into absolute ethyl alcohol, adding ultrapure water, adding hydrochloric acid, and stirring to form a mixed solution;
s12: dropwise adding the transparent solution dissolved with bismuth nitrate and potassium chloride into the mixed solution, adjusting the pH to be neutral, stirring, standing to form sol-gel, drying in a drying oven to constant weight, and grinding to obtain TiO 2 /BiOCl。
4. The method for preparing the heterojunction composite material for visible light catalytic aldehyde removal according to claim 3, wherein the volume ratio of the tetrabutyl titanate, the absolute ethyl alcohol, the ultrapure water and the hydrochloric acid is 1: (2-5): 1: (0.1-0.4).
5. The method of claim 3, wherein the hydrochloric acid is used in an amount of 0.5 to 2mol/L.
6. The method for preparing the heterojunction composite material for visible light catalytic aldehyde removal according to claim 3, wherein the mass ratio of the bismuth nitrate to the potassium chloride in the transparent solution is (4-5): 1.
7. the method for preparing the heterojunction composite material for visible light catalysis aldehyde removal according to claim 3, wherein the stirring time in the step S12 is 0.5 to 2 hours, the rotating speed is 600 to 1500r/min, and the standing time is 12 to 24 hours.
8. The method for preparing a heterojunction composite material for visible light catalyzed aldehyde removal according to claim 2, wherein the step S2 comprises:
subjecting the TiO to a reaction 2 /BiOCl is calcined in inert gas or vacuum environment to obtain a product TiO 2-x /BiO 1-x Cl。
9. The method for preparing the heterojunction composite material for visible light catalysis aldehyde removal according to claim 8, wherein the flow rate of the inert gas is 50-200 mL/min, the calcination temperature is 300-600 ℃, the temperature rise rate is 1-10 ℃/min, and the calcination time is 1-3 h.
10. A method for degrading VOCs by visible light catalysis is characterized by comprising the following steps: under the action of visible light, VOCs are catalytically degraded by using the heterojunction composite material with aldehyde removed by visible light catalysis, and the heterojunction composite material with aldehyde removed by visible light catalysis is prepared by the preparation method of the heterojunction composite material with aldehyde removed by visible light catalysis according to any one of claims 1 to 9.
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