CN115445641A - Lead-free perovskite supported graphene-like carbon nitride visible-light-driven photocatalyst and preparation method thereof - Google Patents
Lead-free perovskite supported graphene-like carbon nitride visible-light-driven photocatalyst and preparation method thereof 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
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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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
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
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Abstract
The invention discloses a preparation method of a lead-free perovskite supported graphene-like carbon nitride visible-light-driven photocatalyst, which comprises the following steps: s1, adding CsCl and SnCl 2 Adding a medicine into a container, adding an HCl solution into the container for ultrasonic treatment, then putting the container into an oven for heating treatment, and washing and drying an obtained sample; s2, weighing melamine, placing the melamine in a crucible, placing the crucible in a muffle furnace for calcination, naturally cooling to room temperature after calcination, and collecting a sample C 3 N 4 (ii) a S3, mixing C 3 N 4 Putting into agate grinderAnd fully grinding in a bowl to obtain the photocatalyst. The lead-free perovskite load C prepared by the invention 3 N 4 Visible light performance ratio C of photocatalyst 3 N 4 The photocatalyst is improved by 20 percent. In addition, the invention provides a new idea for the combination of the lead-free halide perovskite and the photocatalytic material, has wide application prospect, has mild condition of the preparation method and simple operation, and is beneficial to commercial large-scale application.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to Cs 2 SnCl 6 Lead-free perovskite-supported graphene-like carbon nitride (C) 3 N 4 ) Visible light catalyst and its preparation process.
Background
At present, most of world energy supply is from fossil fuel, and a large amount of toxic and harmful gas is inevitably brought in the production and utilization process of the fossil fuel. Nitrogen oxides (NOx), a typical pollutant gas in our environment, are mainly derived from the overuse of fossil fuels and the emission of automobile exhaust. As industrial activities become more and more mobile exhaust gases on roads, the concentration of NO in the atmospheric environment rises sharply, which is closely related to the formation of photochemical smog, acid rain and ozone holes. More seriously, in the long-term life and work of people in such environments, concentrations of NO even below ppm or ppb levels can lead to respiratory and cardiopulmonary diseases.
In order to solve this problem of air pollution, a large number of researches are being conducted on the problem of nitrogen oxides in purified air. The development of environment-friendly and efficient purification technology is still a challenging subject, and the photocatalytic technology has the advantages of environmental protection and capability of directly utilizing sunlight, and has great potential to be paid attention to all the world. Therefore, the purification of air pollutants can be realized by exploring a novel high-efficiency photocatalyst.
Graphite carbon nitride (C) 3 N 4 ) The two-dimensional (2D) material has the advantages of excellent band gap structure and chemical stability, unique electronic structure, simple preparation method and the like, is widely paid attention to and researched, and is a promising photocatalyst. But C is 3 N 4 The hybridized arrangement of the mesographitic sp2 triazine units and the chemically inert stacking results in weaker inter-layer van der Waals (vdW) interaction forces, which allows C 3 N 4 The photocatalytic efficiency of (b) is not ideal. In recent years, C can be improved by modification methods such as precious metal deposition, nonmetal doping, heterojunction composition and the like 3 N 4 Is photocatalyticEfficiency. The heterojunction is formed to prevent electron-hole recombination so as to promote interface charge transfer, and the catalytic performance of the photocatalyst can be effectively improved. But C is 3 N 4 The properties of the base heterojunction are still in a non-ideal state, and C with excellent photocatalytic performance is constructed 3 N 4 The base heterojunction is still to be explored further.
Lead-free halogen perovskite Cs 2 SnCl 6 Has a binding to CsPbX 3 Similar configuration, not only has low toxicity but also shows excellent stability performance to water and oxygen in the environment. In addition, cs 2 SnX 6 Has a direct band gap and exhibits CsSnX 3 Similar optoelectronic properties, which have attracted a great deal of attention in the field of optoelectronics. Inspired by related research reports, the material can be applied to the main problem of photocatalytic air pollution purification, and is a potential photocatalytic material. Research reports that the perovskite and semiconductor material heterojunction can be constructed to better realize charge separation and maintain the stability of the photocatalyst. However, research on cesium-based lead-free perovskite heterojunction is reported less, and research on perovskite heterojunction is mostly applied to reduction, and a charge transfer mechanism and a photocatalytic mechanism of the perovskite heterojunction in a photocatalytic process cannot be deeply researched. Thus, by constructing novel Cs 2 SnCl 6 The solution of the main problem in air pollution by the base heterojunction remains a challenging issue.
Disclosure of Invention
The invention aims to provide a preparation method of a lead-free perovskite heterojunction photocatalyst, which can improve the photocatalytic activity under stable visible light and has the advantages of simple synthesis and mild reaction conditions, aiming at the defects of the existing research.
The invention invents a Cs by synthesizing a cesium-based perovskite heterojunction 2 SnCl 6 Lead-free perovskite-supported graphene-like carbon nitride (C) 3 N 4 ) The visible light catalyst has good stability and excellent activity when used for photocatalytic oxidation of NO under visible light.
The invention adopts the following technical scheme:
a kind ofThe lead-free perovskite supported graphene-like carbon nitride visible light catalyst is prepared from lead-free perovskite Cs 2 SnCl 6 And a two-dimensional material C 3 N 4 The two phases form a heterojunction.
The invention also provides a preparation method of the lead-free perovskite supported graphene-like carbon nitride visible-light-induced photocatalyst, which comprises the following steps:
s1, adding CsCl and SnCl 2 Sequentially adding medicines into a container, then adding an HCl solution into the container, carrying out ultrasonic treatment, then putting the container into an oven for heating treatment, cooling the oven to room temperature, standing, washing the obtained sample, drying in the oven, and collecting the sample Cs 2 SnCl 6 ；
S2, weighing melamine, placing the melamine in a crucible, covering a crucible cover, placing the crucible cover in a muffle furnace for calcining, wherein the calcining condition is that in static air, the calcining temperature, the calcining time and the heating rate are controlled, and after the temperature is naturally cooled to the room temperature, collecting a sample C 3 N 4 ；
S3, mixing C 3 N 4 Grinding in agate mortar, adding Cs after grinding until the sample is uniform 2 SnCl 6 Continuously grinding the lead-free perovskite, and collecting Cs after full grinding 2 SnCl 6 Lead-free perovskite load C 3 N 4 A photocatalyst.
Further, csCl and SnCl are added in step S1 2 The molar ratio of the drugs is 2:1.
Further, the ultrasonic treatment time in the step S1 is 5-10min, so that the medicine is fully and completely dissolved.
Further, after the reaction in the step S1 is finished, the reaction product can be centrifugally collected after standing for at least 20-24 hours.
Further, when the sample is collected in step S1, it may be washed several times with ethanol or isopropanol.
Further, the calcination temperature in step S2 is 450 to 550 ℃.
Furthermore, the calcination time in the step S2 is 2-4 h.
Further, the temperature rise rate in the step S2 is controlled to be 5-10 ℃/min.
Further, as described in step S3, cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 The mass ratio of (A) to (B) is 2 to 10 percent.
The invention has the following beneficial effects:
(1) Experimental analysis proves that the Cs obtained by the preparation method provided by the invention 2 SnCl 6 Lead-free perovskite and C 3 N 4 In the visible light catalyst, a heterojunction is constructed to accelerate the electron transmission between interfaces, and electrons pass through C 3 N 4 To Cs 2 SnCl 6 The lead-free perovskite is transferred upwards, so that the stability of the photocatalyst is enhanced, the electron-hole recombination is inhibited, the transfer of a current carrier is accelerated, the generation of free radicals is promoted, and the photocatalytic NO oxidation activity under visible light is improved.
(2) The invention provides a new idea for the combination of the lead-free halide perovskite and the photocatalytic material, has wide application prospect, has mild preparation method conditions and simple operation, and is beneficial to commercial large-scale application.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below. For a person skilled in the art, without inventive effort, further figures can be derived from these figures.
FIG. 1 shows Cs provided in examples 1, 2 and 3 of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 A flow chart of a preparation method of the visible light photocatalyst;
FIG. 2 shows three different mass ratios (Cs) prepared in examples 1, 2 and 3 of the present invention 2 SnCl 6 ：C 3 N 4 =2%, 5%, 10%) Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst and pure phase Cs 2 SnCl 6 And C 3 N 4 XRD pattern of (XRD is an abbreviation for X-ray diffraction, i.e. XRD is an abbreviation for X-ray diffraction)X-ray diffraction);
FIGS. 3, 4 and 5 show the 5% loading of Cs prepared in example 2 of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst and pure phase Cs 2 SnCl 6 XPS (XPS is an abbreviation for X-ray photoelectron spectroscopy, namely X-ray photoelectron spectroscopy);
FIGS. 6 and 7 show pure phase C prepared in example 1 of the present invention 3 N 4 And Cs 2 SnCl 6 TEM image of (TEM is an abbreviation of Transmission Electron Microscope, i.e., transmission Electron Microscope);
FIG. 8 is a 5% loading of Cs prepared in example 2 of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst and pure phase C prepared in example 3 N 4 And Cs 2 SnCl 6 The graph of UV-Vis DRS (UV-Vis DRS is UV-Visable Diffuse-reflection Spectra), and the graph of FIG. 9 is the band gap graph of two pure phase materials;
FIG. 10 is a graph of three different mass ratios (Cs) of three different mass ratios prepared in examples 1, 2, and 3 of the present invention 2 SnCl 6 ：C 3 N 4 =2%, 5%, 10%) Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst and pure phase Cs 2 SnCl 6 And C 3 N 4 Degradation efficiency for NO purification under visible light conditions is plotted versus the efficiency of the degradation, FIG. 11 is Cs prepared in example 2 2 SnCl 6 Lead-free perovskite load C 3 N 4 A cycle test chart of the visible light photocatalyst;
FIG. 12 shows the 5% loading by mass of Cs prepared in example 2 of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst and pure phase C prepared in example 3 N 4 And Cs 2 SnCl 6 ESR (. OH) diagram of (D);
FIG. 13 is a 5% loading of Cs prepared in example 2 of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst and example preparationPure phase C of 3 N 4 And Cs 2 SnCl 6 Time resolved fluorescence map of (a).
Detailed Description
Referring to FIG. 1, cs provided in embodiments 1, 2, and 3 of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 The preparation method of the visible light photocatalyst comprises the following steps:
s1. CsCl (2.4 mmol) and SnCl2 (1.2 mmol) were sequentially added to a 100mL Polytetrafluoroethylene (PTFE) container, and then HCl solution (6 mL) was added to the container. Further ultrasonic treatment was carried out, followed by placing in an oven and holding at 190 ℃ for 12 hours. Standing for 20-24 h after the oven is cooled to room temperature, washing the obtained sample with ethanol for 3 times, drying in an oven at 40 ℃ for 10-12 h, and collecting to obtain sample Cs 2 SnCl 6 ；
S2, weighing melamine (10 g) and placing the melamine in a crucible of 50 ml, covering a crucible cover, and placing the crucible cover in a muffle furnace for calcining. The calcining conditions are that in static air, the calcining temperature is 450-550 ℃, the calcining time is 2-4 h, the heating rate is 5-10 ℃/min, after the temperature is naturally cooled to the room temperature, a sample C is obtained by collection 3 N 4 ；
S3, mixing C 3 N 4 Grinding in agate mortar, adding Cs after grinding until the sample is uniform 2 SnCl 6 Continuously grinding the lead-free perovskite, and collecting Cs after fully grinding 2 SnCl 6 Lead-free perovskite load C 3 N 4 A photocatalyst.
The preparation method disclosed by the invention is exemplified by a plurality of specific examples, and the described examples are only a part of the examples in the invention. All embodiments obtained by persons skilled in the art based on the embodiments in the present invention without any creative efforts belong to the protection scope of the present invention.
Example 1
Cs (volatile organic Compounds) 2 SnCl 6 Lead-free perovskite load C 3 N 4 The preparation method of the visible light photocatalyst comprises the following steps:
CsCl (2.4 mmol) and SnCl 2 (1.2 mmol) of the drug substance was sequentially added to a 100mL Polytetrafluoroethylene (PTFE) container, and then HCl solution (6 mL) was added to the container. The ultrasonic treatment was then carried out and subsequently placed in an oven for 12h at 190 ℃. Standing for 24h after the oven is cooled to room temperature, washing the obtained sample with ethanol for 3 times, drying in an oven at 40 ℃ for 12h, and collecting to obtain sample Cs 2 SnCl 6 (ii) a Melamine (10 g) was weighed into a 50 ml crucible, covered with the crucible lid and placed in a muffle furnace for calcination. The calcining conditions are that in static air, the calcining temperature is 550 ℃, the calcining time is 4h, the heating rate is 5 ℃/min, when the temperature is naturally cooled to the room temperature, a sample C is obtained by collection 3 N 4 (ii) a 0.20g of C 3 N 4 Grinding in agate mortar until the sample is uniform, and adding 0.004g of Cs 2 SnCl 6 Grinding the lead-free perovskite, collecting the lead-free perovskite after sufficient grinding to obtain a content of Cs 2% 2 SnCl 6 Lead-free perovskite load C 3 N 4 A photocatalyst.
Cs prepared in the examples of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 The mass ratio of the visible-light-induced photocatalyst is 2% Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 The visible light catalyst degrades NO, and the specific process is as follows: 0.2g of 2 Cs-Cs prepared in the example was treated under conditions of a relative humidity of 60%, an oxygen content of 21%, a flow rate of the NO stream of 2.24L/min, and an initial concentration of NO of 500. Mu.g/kg 2 SnCl 6 Lead-free perovskite load C 3 N 4 The visible light catalyst is arranged on the glass disc; four small fans are arranged around the reactor; under dark conditions, UV light is filtered off with a 420nm cut-off filter, and when the NO concentration reaches equilibrium, 2% Cs is irradiated with a 150W tungsten halogen lamp 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst for 30min; and finally, turning off the lamp. Calculated 2% Cs prepared in the examples of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 The degradation rate of the visible light catalyst to NO is 43 percent, compared with the two catalystsEnd, 2% of Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 The degradation rate of the visible-light-driven photocatalyst to NO is improved.
Example 2
Cs (volatile organic Compounds) 2 SnCl 6 Lead-free perovskite load C 3 N 4 The preparation method of the visible light photocatalyst comprises the following steps:
CsCl (2.4 mmol) and SnCl 2 (1.2 mmol) of the drug substance was added sequentially to a 100mL Polytetrafluoroethylene (PTFE) container, and then HCl solution (6 mL) was added to the container. The ultrasonic treatment was then carried out and subsequently placed in an oven for 12h at 190 ℃. Standing for 24h after the oven is cooled to room temperature, washing the obtained sample with ethanol for 3 times, drying in an oven at 40 ℃ for 12h, and collecting to obtain sample Cs 2 SnCl 6 (ii) a Melamine (10 g) was weighed into a 50 ml crucible, covered with the crucible lid and placed in a muffle furnace for calcination. The calcining conditions are that in static air, the calcining temperature is 550 ℃, the calcining time is 4h, the heating rate is 5 ℃/min, when the temperature is naturally cooled to the room temperature, a sample C is obtained by collection 3 N 4 (ii) a 0.20g of C 3 N 4 Grinding in agate mortar until the sample is uniform, and adding 0.01g of Cs 2 SnCl 6 Grinding the lead-free perovskite, collecting the lead-free perovskite after sufficient grinding to obtain 5% of Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 A photocatalyst.
Cs prepared in the examples of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 The mass ratio of the visible-light-induced photocatalyst is 2% Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 The visible light catalyst degrades NO, and the specific process is the same as example 1. Calculated 5% Cs prepared according to an example of the invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst degradation of NO 61%, relative to two background, 5% Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 The degradation rate of the visible-light-driven photocatalyst to NO is improved.
Example 3
Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 The preparation method of the visible light photocatalyst comprises the following steps:
CsCl (2.4 mmol) and SnCl 2 (1.2 mmol) of the drug substance was sequentially added to a 100mL Polytetrafluoroethylene (PTFE) container, and then HCl solution (6 mL) was added to the container. Further ultrasonic treatment was carried out, followed by placing in an oven and holding at 190 ℃ for 12 hours. Standing for 24h after the oven is cooled to room temperature, washing the obtained sample with ethanol for 3 times, drying in an oven at 40 ℃ for 12h, and collecting to obtain sample Cs 2 SnCl 6 (ii) a Melamine (10 g) was weighed into a 50 ml crucible, covered with the crucible lid and calcined in a muffle furnace. The calcining conditions are that in static air, the calcining temperature is 550 ℃, the calcining time is 4h, the heating rate is 5 ℃/min, when the temperature is naturally cooled to the room temperature, a sample C is obtained by collection 3 N 4 (ii) a 0.20g of C 3 N 4 Grinding in agate mortar until the sample is uniform, and adding 0.02g of Cs 2 SnCl 6 Grinding the lead-free perovskite, collecting the lead-free perovskite after sufficient grinding to obtain 5% of Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 A photocatalyst.
Cs prepared in the examples of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 The mass ratio of the visible-light-induced photocatalyst is 2% Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 The visible light catalyst degrades NO, and the specific process is the same as example 1. Calculated to obtain 10% of Cs prepared in the examples of the invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst degradation rate of NO 55%, relative to two background, 10% Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 The degradation rate of the visible-light-driven photocatalyst to NO is improved.
As can be seen from the above examples, cs is passed 2 SnCl 6 Lead-free perovskite load C 3 N 4 Degradation of NO by visible light catalystRelative to pure phase Cs 2 SnCl 6 And C 3 N 4 For the degradation of NO, cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 The degradation rate of the visible-light-driven photocatalyst is obviously improved, and good stability is maintained. And the lead-free halide perovskite material is used in the field of photocatalysis, has few research reports and has further exploration and application values.
It should be noted that the Cs provided in the examples of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 The catalysis mechanism of the visible light catalyst on sulfides, volatile organic compounds, nitrogen oxides other than NO and other air pollutants is the same as that of NO, so that the visible light catalyst in the embodiment of the invention passes the NO degradation test representatively.
Experimental analysis proves that the Cs obtained by the preparation method provided by the invention 2 SnCl 6 Lead-free perovskite and C 3 N 4 In the visible light catalyst, the heterojunction is constructed to accelerate the electron transmission between interfaces, and electrons pass through C 3 N 4 To Cs 2 SnCl 6 The lead-free perovskite is transferred upwards, so that the stability of the photocatalyst is enhanced, the electron-hole recombination is inhibited, the migration of current carriers is accelerated, the generation of free radicals is promoted, and the photocatalytic NO oxidation activity under visible light is improved.
Cs prepared by the present invention in examples 1, 2 and 3 2 SnCl 6 Lead-free perovskite load C 3 N 4 The visible light photocatalyst is characterized, and the Cs is known 2 SnCl 6 Lead-free perovskite load C 3 N 4 The visible light catalyst has the following characteristics:
(1) Cs prepared in examples 1, 2 and 3 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst and pure phase Cs 2 SnCl 6 And C 3 N 4 XRD analysis (as shown in FIG. 2) was performed to confirm Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst and pure phase Cs 2 SnCl 6 And C 3 N 4 Has a complete crystal structure in Cs 2 SnCl 6 /C 3 N 4 Cs was also observed in the heterojunction material 2 SnCl 6 And C 3 N 4 Characteristic peak of (2).
(2) For Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst and pure phase Cs 2 SnCl 6 XPS analysis (shown in FIGS. 3, 4, and 5) was performed to confirm that Cs prepared in examples 1, 2, and 3 of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 Has pure phase Cs in visible light catalyst 2 SnCl 6 The same elements and no other impurity elements; for pure phase C 3 N 4 And Cs 2 SnCl 6 And Cs prepared in example 2 2 SnCl 6 Lead-free perovskite load C 3 N 4 TEM analysis of the visible-light-driven photocatalyst (as shown in FIGS. 6 and 7) confirms the successful preparation of the material.
(3) 5% by mass of Cs prepared in example 2 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst and pure phase C 3 N 4 And Cs 2 SnCl 6 UV-Vis DRS analysis (as shown in figure 8) is carried out, the light response range of the material is tested, and Cs is proved 2 SnCl 6 Introduction of energy to broaden C 3 N 4 Light absorption range of (1). The band gap of the material can be calculated by UV-vis DRS (as shown in FIG. 9), and C can be seen 3 N 4 Has a band gap of 2.54eV 2 SnCl 6 The band gap of (A) is 3.99eV.
Cs provided in examples 1, 2, and 3 by degrading purified NO 2 SnCl 6 Lead-free perovskite load C 3 N 4 The photocatalytic performance of the visible-light-driven photocatalyst is tested. The specific operation process of the test is as follows:
(1) 0.2g of Cs prepared in example 2 SnCl 6 Lead-free perovskite load C 3 N 4 The visible light catalyst is dispersed on the glass disc;
(2) Four small fans are arranged around the reactor;
(3) In the dark, when the NO concentration reaches equilibrium, cs is irradiated with 150W tungsten halogen lamp 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light photocatalyst is used for 30min.
The conditions of the above catalytic performance test process were: relative humidity 60%; the oxygen content is 21%; the flow rate of the NO gas flow is 2.24L/min; the initial concentration of NO was 500. Mu.g/kg; before the irradiation of the halogen tungsten lamp, a cut-off filter with the wavelength of 420nm is used for filtering ultraviolet light.
Cs provided by the embodiments of the present invention 2 SnCl 6 Lead-free perovskite load C 3 N 4 The visible light catalyst has the following effects on NO purification:
(1) Cs prepared in examples 1, 2, and 3 2 SnCl 6 Lead-free perovskite load C 3 N 4 The degradation rate of the visible light catalyst to NO is 43-61% (as shown in figure 10), which is higher than that of pure phase C 3 N 4 The degradation rate of the visible-light-driven photocatalyst to NO is 41 percent; the degradation rate is calculated by eta (%) = (1-C/C) 0 )×100％，C 0 C is the instantaneous concentration of NO. Cs prepared in example 2 2 SnCl 6 Lead-free perovskite load C 3 N 4 The cyclic degradation rate of the visible-light-driven photocatalyst on NO is shown in FIG. 11, and it can be seen that the supported material shows good stability.
(2) Hydroxyl ion (. OH) is Cs prepared in example 2 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalysts degrade the most dominant degrading radicals of NO under visible light conditions (as shown in fig. 12).
(3) For Cs prepared in example 2 2 SnCl 6 Lead-free perovskite load C 3 N 4 Visible light catalyst and pure phase C 3 N 4 And Cs 2 SnCl 6 Time-resolved fluorescence assay (as shown in FIG. 13) was performed to confirm Cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 The fluorescence lifetime of the visible light catalyst is increased, and the separation effect of the photo-generated electrons and the holes is enhanced.
Although the present invention has been described in terms of specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention as defined in the appended claims, and such changes and modifications are also encompassed within the scope of the invention.
Claims (9)
1. A lead-free perovskite supported graphene-like carbon nitride visible-light-driven photocatalyst is characterized in that: the catalyst is prepared from lead-free perovskite Cs 2 SnCl 6 And a two-dimensional material C 3 N 4 The two phases form a heterojunction.
2. The preparation method of the lead-free perovskite supported graphene-like carbon nitride visible-light-induced photocatalyst according to claim 1, characterized by comprising the following steps:
s1, adding CsCl and SnCl 2 Sequentially adding medicines into a container, then adding an HCl solution into the container, carrying out ultrasonic treatment, then putting the container into an oven for heating treatment, cooling the oven to room temperature, standing, washing the obtained sample, drying in the oven, and collecting the sample Cs 2 SnCl 6 ；
S2, weighing melamine, placing the melamine in a crucible, covering a crucible cover, placing the crucible cover in a muffle furnace for calcining, wherein the calcining condition is that in static air, the calcining temperature, the calcining time and the heating rate are controlled, and after the temperature is naturally cooled to the room temperature, collecting a sample C 3 N 4 ；
S3, mixing C 3 N 4 Grinding in agate mortar, adding Cs after grinding until the sample is uniform 2 SnCl 6 Continuously grinding the lead-free perovskite, and collecting Cs after fully grinding 2 SnCl 6 Lead-free perovskite load C 3 N 4 A photocatalyst.
3. The method for preparing the lead-free perovskite supported graphene-like carbon nitride visible-light-induced photocatalyst according to claim 2, characterized in that: csCl and SnCl in step S1 2 The molar ratio of the drugs is 2:1.
4. The method for preparing the lead-free perovskite supported graphene-like carbon nitride visible-light-induced photocatalyst according to claim 2, characterized in that: the ultrasonic treatment time in the step S1 is 5-10min, so that the medicine is fully and completely dissolved.
5. The preparation method of the lead-free perovskite supported graphene-like carbon nitride visible-light-induced photocatalyst according to claim 2, characterized by comprising the following steps: when the sample is collected in step S1, it may be washed several times with ethanol or isopropanol.
6. The method for preparing the lead-free perovskite supported graphene-like carbon nitride visible-light-induced photocatalyst according to claim 2, characterized in that: the calcination temperature in the step S2 is 450-550 ℃.
7. The method for preparing the lead-free perovskite supported graphene-like carbon nitride visible-light-induced photocatalyst according to claim 2, characterized in that: the calcination time in the step S2 is 2-4 h.
8. The method for preparing the lead-free perovskite supported graphene-like carbon nitride visible-light-induced photocatalyst according to claim 2, characterized in that: in the step S2, the temperature rise rate is controlled to be 5-10 ℃/min.
9. The preparation method of the lead-free perovskite supported graphene-like carbon nitride visible-light-induced photocatalyst according to claim 2, characterized by comprising the following steps: in step S3, as mentioned above, cs 2 SnCl 6 Lead-free perovskite load C 3 N 4 The mass ratio of (A) to (B) is 2 to 10 percent.
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| EP3848122A1 (en) * | 2020-01-09 | 2021-07-14 | Nankai University | Visible light catalytic material and preparation method and application thereof |
| CN114870879A (en) * | 2022-05-16 | 2022-08-09 | 电子科技大学长三角研究院(湖州) | Bimetal perovskite load graphene-like carbon nitride visible-light-induced photocatalyst and preparation method thereof |
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| EP3848122A1 (en) * | 2020-01-09 | 2021-07-14 | Nankai University | Visible light catalytic material and preparation method and application thereof |
| CN114870879A (en) * | 2022-05-16 | 2022-08-09 | 电子科技大学长三角研究院(湖州) | Bimetal perovskite load graphene-like carbon nitride visible-light-induced photocatalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| TIANQI TAN ET AL.: ""Highly active Cs2SnCl6/C3N4 heterojunction photocatalysts operating via interfacial charge transfer mechanism"", 《JOURNAL OF HAZARDOUS MATERIALS》, vol. 439, 30 July 2022 (2022-07-30), pages 129694 * |
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