CN111068735B - PtS quantum dot/g-C3N4Nanosheet composite photocatalyst and preparation method thereof - Google Patents
PtS quantum dot/g-C3N4Nanosheet composite photocatalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000002096 quantum dot Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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Abstract
The invention discloses a PtS quantum dot/g-C3N4A nanosheet composite photocatalyst and a preparation method thereof, belonging to the technical field of industrial catalysis, and the modified g-C is obtained by a high-temperature roasting technology of mixed atmosphere regulation and control3N4As a substrate, unique PtS quantum dots are grown by an in-situ ion adsorption assisted gas phase reduction method, thereby obtaining the PtS quantum dots/g-C3N4A nanosheet composite photocatalyst. The series of catalysts have simple preparation process, low raw material cost and high activity, and are suitable for further enlarged production and practical application.
Description
Technical Field
The invention belongs to the technical field of industrial catalysis, and particularly relates to PtS quantum dots/g-C3N4A nanosheet composite photocatalyst and a preparation method thereof.
Background
Hydrogen is used as an efficient clean raw material, plays an important role in economic construction and social development, is widely applied to various fields of petrochemical industry, electronic industry, food processing, metallurgical industry, aerospace and the like, and is praised as an ideal green carrier for constructing future energy patterns. At present, the hydrogen is mainly obtained by water gas conversion, hydrocarbon cracking, water electrolysis and other process methods. The processes are mature and occupy the main market, but the processes consume non-renewable resources too much and have the problems of environmental pollution, safety and the like. Therefore, how to realize low-cost green preparation of hydrogen is a major subject which must be considered preferentially in the ecological civilization construction of China.
The photocatalytic water splitting hydrogen production technology is called as 'fire ignition in water', and is considered as an important way for realizing clean and sustainable green and efficient hydrogen production. The technical mechanism is that when the photocatalytic material is excited by light, photo-generated electron-hole pairs (carriers) are generated; the photogenerated electrons transit from the valence band to the conduction band, leaving photogenerated holes in the valence band that can interact with H in aqueous solutions if they can migrate to the surface of the semiconductor material during its lifetime+Acts to produce hydrogen. And graphite phase carbon nitride (g-C) among the numerous photocatalytic materials3N4) As a novel two-dimensional non-metal photocatalytic material, the material has visible light absorption capacity and is easy to regulate and controlThe energy band structure, excellent chemical stability and thermal stability, greenness, no toxicity, rich sources and the like. But g-C3N4The practical application of the low carrier separation and migration efficiency in the field of photocatalytic hydrogen production is greatly limited.
The cocatalyst loading is to promote g-C3N4One of the effective approaches to carrier transport performance. However, the conventional cocatalyst has the problems of less exposed active sites, small specific surface area, less formed interfaces and the like, so that the g-C can not be greatly improved3N4The aim of photocatalytic hydrogen production activity is achieved. Therefore, the vigorous development of new cocatalysts with high efficiency and low cost is driving g-C3N4The key point of the practical application of the photocatalyst to hydrogen production is shown.
Disclosure of Invention
The invention aims to: aiming at the defects in the prior art, the PtS quantum dot/g-C with the photocatalytic performance remarkably improved compared with that of the existing photocatalyst is provided3N4A nanosheet composite photocatalyst and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
PtS quantum dot/g-C3N4The preparation method of the nanosheet composite photocatalyst comprises the following steps:
s1, placing melamine in H2Roasting the mixture for 3 to 6 hours at 500 to 600 ℃ in a tubular furnace in the Ar mixed atmosphere, and collecting the modified g-C after the tubular furnace is cooled to the room temperature3N4A bulk sample;
s2, modifying the g-C prepared in the step S13N4Ultrasonically dispersing the block in water, and adding H2PtCl6Stirring the aqueous solution for 4-8 h, centrifuging, collecting precipitate, drying, and grinding into powder;
s3, respectively placing the ceramic square boat containing the powder obtained in the step S2 and the ceramic square boat containing the sulfur powder at the central position and the upstream position of the tubular furnace, heating to 450-550 ℃ in Ar atmosphere, and then placing the ceramic square boat and the ceramic square boat in H2Heating to 500-600 ℃ in the mixed atmosphere of Ar and Ar, maintaining the temperature for 0.1-1 h, and finally cooling in the Ar atmosphereAnd (4) cooling to room temperature, and collecting the obtained sample.
The method obtains the modified g-C by the high-temperature roasting technology of mixed atmosphere regulation and control3N4Showing improved carrier separation efficiency and increased photocatalytic hydrogen production activity;
the invention can lead the PtS quantum dots to uniformly and tightly grow in g-C through the in-situ ion adsorption effect3N4Promoting g-C on the surface of the nanosheet3N4Interface channels capable of promoting rapid migration of electron-hole pairs are formed between the nanosheets and the PtS quantum dots, and the structure can realize main hydrogen production active substances g-C3N4The space of electron-hole pairs on the valence band and the conduction band is rapidly separated and transferred, so that photoproduction electrons are rapidly transferred to the PtS surface to participate in the photocatalytic water decomposition reaction, and the photocatalytic activity is greatly improved;
meanwhile, the g-C can be effectively stripped by the high-temperature gas-phase reduction treatment3N4The block is a nano-sheet.
Further, H in the mixed gas of steps S1 and S32The content is 5-30 vt%.
Further, in step S1, the temperature rise rate is 2-8 ℃/min.
Further, the Pt content in step S2 is modified g-C3N42-7 wt% of the block.
Further, drying at 70 ℃ for 20-30 h in step S2.
Further, in step S3, the temperature is increased to 450-550 ℃ at a temperature increasing rate of 30-60 ℃/min.
PtS quantum dot/g-C prepared by adopting preparation method3N4A nanosheet composite photocatalyst.
Further, the PtS quantum dots/g-C3N4Nanosheet composite photocatalyst, g-C3N4PtS quantum dots grow on the surfaces of the nanosheets.
The PtS quantum dot/g-C3N4The nanosheet composite photocatalyst is applied to photocatalytic decomposition of water to prepare hydrogen under irradiation of visible light and near infrared light.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the invention provides an in-situ ion adsorption assisted high-temperature gas phase reduction growth method, which realizes novel PtS quantum dots/g-C3N4The construction of the nanosheet composite photocatalyst (PtS/CN) provides a new method for preparing a novel two-dimensional heterojunction composite photocatalyst;
2. the invention adopts the high-temperature gas phase reduction growth technology assisted by in-situ ion adsorption to the g-C3N4Unique PtS quantum dots are grown on the surface, and an interface in close contact is formed between the unique PtS quantum dots and the surface. The interface can greatly promote the rapid separation of photon-generated carriers between the two, thereby promoting the photocatalytic performance of the composite material to be remarkably improved; experiments prove that the photocatalyst prepared by the invention has ultrahigh activity of decomposing hydrogen produced by water by photocatalysis, and is Pt/g-C with the same Pt content3N4The activity of the composite photocatalyst is 13.3 times that of the composite photocatalyst;
3. the raw materials such as melamine, sulfur powder and the like are cheap and easy to obtain, the reaction conditions are simple, the activity is high, and the method is suitable for further large-scale production.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a TEM image of the product of example 1;
FIG. 2 is a HRTEM image of the product of example 1;
FIG. 3 is an XRD pattern of PtS/CN and CN samples;
FIG. 4 is a UV-visible diffuse reflectance chart of PtS/CN and CN samples;
FIG. 5 is a PL profile for PtS/CN and CN samples;
FIG. 6 is a graph showing the performance of hydrogen production by photocatalytic water splitting of CN, PtS/CN and Pt/CN samples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It is noted that relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The preferred embodiment of the invention provides a PtS quantum dot/g-C3N4Nano sheet complexThe preparation method of the composite photocatalyst comprises the following steps:
s1, placing 2g of melamine in 20 vt% H2And 80 vt% Ar, roasting for 4h at 550 ℃, wherein the heating rate is 5 ℃/min; after the tube furnace is cooled to room temperature, collecting the modified g-C3N4A bulk sample;
s2, modifying the g-C prepared in the step S13N4The blocks were ultrasonically dispersed in 40mL of water, followed by dropwise addition of H2PtCl6Aqueous solution with modified Pt content g-C3N45 wt% of the block, stirring at room temperature for 6h, centrifuging, collecting precipitate, drying at 70 deg.C for 24h, and grinding into powder;
s3, respectively placing the ceramic square boat containing the powder obtained in the step S2 and the ceramic square boat containing excessive sulfur powder at the central position and the upstream position of the tubular furnace, heating to 500 ℃ in Ar atmosphere at the heating rate of 50 ℃/min, and then heating at 10 vt% H2And 90 vt% Ar are heated to 560 ℃ under the mixed atmosphere, the temperature is maintained for 0.5h, and finally, the temperature is reduced to room temperature under the Ar atmosphere, and the obtained sample is collected.
Example 2
The preferred embodiment of the invention provides a PtS quantum dot/g-C3N4The preparation method of the nanosheet composite photocatalyst comprises the following steps:
s1, placing 5g of melamine in 30 vt% H2And 70 vt% Ar, roasting for 3h at 570 ℃ in a tubular furnace under the mixed atmosphere, wherein the heating rate is 6 ℃/min; after the tube furnace is cooled to room temperature, collecting the modified g-C3N4A bulk sample;
s2, modifying the g-C prepared in the step S13N4The blocks were ultrasonically dispersed in 50mL of water, followed by dropwise addition of H2PtCl6Aqueous solution with modified Pt content g-C3N47 wt% of the block, stirring at room temperature for 8h, centrifuging, collecting precipitate, drying at 70 deg.C for 24h, and grinding into powder;
s3, respectively placing the ceramic square boat containing the powder obtained in the step S2 and the ceramic square boat containing excessive sulfur powder at the central position and the upstream position of the tube furnace, and adding the ceramic square boat and the ceramic square boat under Ar atmosphereHeating to 520 deg.C, heating at 60 deg.C/min, and then at 30 vt% H2And 70 vt% Ar, heating to 570 ℃, maintaining the temperature for 0.2h, finally cooling to room temperature under Ar, and collecting the obtained sample.
Example 3
The preferred embodiment of the invention provides a PtS quantum dot/g-C3N4The preparation method of the nanosheet composite photocatalyst comprises the following steps:
s1, 3g of melamine is placed in 5 vt% H2And a tube furnace in a mixed atmosphere of 95 vt% Ar, roasting for 3h at 520 ℃, wherein the heating rate is 3 ℃/min; after the tube furnace is cooled to room temperature, collecting the modified g-C3N4A bulk sample;
s2, modifying the g-C prepared in the step S13N4The blocks were ultrasonically dispersed in 20mL of water, followed by dropwise addition of H2PtCl6Aqueous solution with modified Pt content g-C3N42 wt% of the block, stirring at room temperature for 4h, centrifuging, collecting precipitate, drying at 70 deg.C for 24h, and grinding into powder;
s3, respectively placing the ceramic square boat containing the powder obtained in the step S2 and the ceramic square boat containing excessive sulfur powder at the central position and the upstream position of the tubular furnace, heating to 450 ℃ in Ar atmosphere at the temperature rise rate of 30 ℃/min, and then carrying out H reaction at 5vt percent2And 95 vt% Ar are heated to 530 ℃ under the mixed atmosphere, the temperature is maintained for 1h, and finally the temperature is reduced to room temperature under the Ar atmosphere, and the obtained sample is collected.
Experimental example 1
The product (PtS/CN) obtained in example 1 was observed by transmission electron microscopy, and the results are shown in FIG. 1;
the product obtained in example 1 was observed by a high-resolution transmission electron microscope, and the result is shown in fig. 2.
Experimental example 2
Modified g-C was obtained in step S1 of example 13N4A block (CN);
the products (PtS/CN and CN) obtained in example 1 were subjected to X-ray diffraction, and the diffraction patterns thereof are shown in FIG. 3, and it was found that,the XRD spectrum of the CN sample shows two significant characteristic peaks: one of the weaker diffraction peaks appears at 13.1 ° 2 θ, which corresponds to g-C3N4The (100) plane of (A) is derived from g-C3N4Diffraction of the in-plane repeating tris-triazine ring; a sharp and strong diffraction peak appears at 27.8 degrees 2 theta, which corresponds to g-C3N4The (002) face of (2) is derived from g-C3N4Diffraction of the aromatic-like ring structure stacked between layers (JCPDS # 87-1526). From the XRD spectrum of the PtS/CN sample, except g-C at 27.8 ° 2 θ was observed3N4(002) Except for the crystal plane peak, all other XRD diffraction peaks belong to PtS (JCPDS #18-0972) with a tetragonal crystal structure, and the successful construction of the PtS/CN binary heterojunction compound is shown.
The uv-vis diffuse reflectance spectra of the products (PtS/CN and CN) obtained in example 1 were measured, respectively, and as a result, as shown in fig. 4, it was analyzed that the CN sample could absorb the visible light with the maximum wavelength of 461nm, which corresponds to the forbidden bandwidth of 2.69eV, indicating the poor visible light absorption capability. Compared with the maximum absorption wavelength of a CN sample, the maximum absorption wavelength of the PtS/CN sample has obvious red shift and shows greatly improved visible light absorption capacity, which shows that the g-C is effectively improved by constructing the PtS/CN binary heterojunction composite system3N4The visible light absorption ability of (1).
The photoluminescence spectra of the products (PtS/CN and CN) obtained in example 1 were measured, respectively, and as a result, as shown in FIG. 5, it was found that a high-intensity signal peak appeared in the PL spectrum of the CN sample, indicating that g-C3N4The photon-generated carriers in the bulk are very easy to recombine. Compared with a CN sample, the PL signal peak intensity of the PtS/CN sample is obviously weakened, and the binary heterojunction structure can effectively promote the separation and the migration of photon-generated carriers.
Experimental example 3
Modified g-C was obtained in step S1 of example 13N4A block (CN); Pt/g-C having the same Pt content as the product of example 1 (PtS/CN) was obtained by using the steps S1, S2 and S3 of example 13N4A composite photocatalyst (Pt/CN);
the performance of CN, PtS/CN and Pt/CN samples for photocatalytic hydrogen production by water decomposition under the irradiation of visible light-near infrared light is respectively tested, and the result is shown in figure 6, and the result shows that the PtS/CN photocatalyst prepared by the invention has ultrahigh photocatalytic hydrogen production activity by water decomposition, which is far higher than that of the CN sample and is 13.3 times of that of a composite photocatalyst (Pt/CN) with the same Pt content.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. PtS quantum dot/g-C3N4The preparation method of the nanosheet composite photocatalyst is characterized by comprising the following steps:
s1, placing melamine in H2Roasting the mixture for 3 to 6 hours at 500 to 600 ℃ in a tubular furnace in the Ar mixed atmosphere, and collecting the modified g-C after the tubular furnace is cooled to the room temperature3N4A bulk sample;
s2, modifying the g-C prepared in the step S13N4Ultrasonically dispersing the block in water, and adding H2PtCl6Stirring the aqueous solution for 4-8 h, centrifuging, collecting precipitate, drying, and grinding into powder;
s3, respectively placing the ceramic square boat containing the powder obtained in the step S2 and the ceramic square boat containing the sulfur powder at the central position and the upstream position of the tubular furnace, heating to 450-550 ℃ at the temperature rising rate of 30-60 ℃/min under Ar atmosphere, and then heating in H2And heating to 500-600 ℃ in the mixed atmosphere of Ar, maintaining for 0.1-1 h at the temperature, finally cooling to room temperature in the atmosphere of Ar, and collecting the obtained sample.
2. The PtS quantum dot/g-C of claim 13N4The preparation method of the nanosheet composite photocatalyst is characterized in that H in the mixed gas of the steps S1 and S32The content is 5-30 vt%.
3. The method of claim 1PtS quantum dot/g-C3N4The preparation method of the nanosheet composite photocatalyst is characterized in that the temperature rise rate in the step S1 is 2-8 ℃/min.
4. The PtS quantum dot/g-C of claim 13N4The preparation method of the nanosheet composite photocatalyst is characterized in that the Pt content in the step S2 is modified g-C3N42-7 wt% of the block.
5. The PtS quantum dot/g-C of claim 13N4The preparation method of the nanosheet composite photocatalyst is characterized by comprising the step S2 of drying at 70 ℃ for 20-30 hours.
6. PtS quantum dot/g-C prepared by the preparation method of any one of claims 1 to 53N4A nanosheet composite photocatalyst.
7. The PtS quantum dot/g-C of claim 63N4The nanosheet composite photocatalyst is characterized by being g-C3N4PtS quantum dots grow on the surfaces of the nanosheets.
8. The PtS quantum dot/g-C of claim 63N4The nanosheet composite photocatalyst is applied to photocatalytic decomposition of water to prepare hydrogen under irradiation of visible light and near infrared light.
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