CN111905787A - Carbon nitride nanotube-platinum composite material with semi-chemical interaction and preparation method thereof - Google Patents
Carbon nitride nanotube-platinum composite material with semi-chemical interaction and preparation method thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 230000003993 interaction Effects 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000126 substance Substances 0.000 title claims abstract description 18
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002071 nanotube Substances 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910002804 graphite Inorganic materials 0.000 claims abstract 2
- 239000010439 graphite Substances 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 23
- 239000001257 hydrogen Substances 0.000 abstract description 23
- 230000001699 photocatalysis Effects 0.000 abstract description 23
- 239000004065 semiconductor Substances 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a carbon nitride nanotube/platinum composite material with a semi-chemical interaction and a preparation method thereof, which reduce the charge transmission energy barrier between a semiconductor and noble metal, realize the quick transmission and transfer of photogenerated charge, achieve the high-efficiency photocatalytic activity and the high-efficiency utilization of the noble metal, design and synthesize a heterostructure (Pt-CNNT) with the semi-chemical interaction between a graphite phase Carbon Nitride Nanotube (CNNT) and the noble metal platinum (Pt), and the conversion frequency (TOF) of catalyst hydrogen production is up to 918 per hour and is 200 times of that of Pt nanoparticles under the excitation of visible light; the invention has the advantages that: 1. the catalyst of the invention can greatly improve the effect of the noble metal cocatalyst, reduce the cost of the catalyst and meet the condition of enlarging production; 2. the catalyst has good and stable photocatalytic water splitting performance.
Description
The technical field is as follows:
the invention relates to the field of photocatalysis, in particular to a carbon nitride nanotube/platinum composite material with semi-chemical interaction and a preparation method thereof.
Background
The national sustainable development demands on clean energy more and more, the photocatalytic energy conversion technology provides a new scheme for the preparation of clean energy, and the photocatalytic water splitting hydrogen production technology adopts sustainable solar energy and water with rich reserves as raw materials, so that the photocatalytic water splitting hydrogen production becomes a research hotspot. In the photocatalytic hydrogen production technology, the design and preparation of a high-efficiency, stable and low-cost photocatalyst are the key for restricting the popularization and application of the technology, so that a great amount of photocatalysts are designed and developed by scientific researchers for photocatalytic hydrogen production, wherein graphite-phase carbon nitride (g-C)3N4) The method is a hot spot for researching photocatalytic hydrogen production materials due to the fact that the method has visible light activity, is low in price, is simple to prepare and the like. However, g-C3N4The excessive hydrogen-generating overpotential and the serious carrier recombination problem make noble metal promoters (such as platinum and gold) become necessary components for improving the photocatalytic hydrogen-generating efficiency; although noble metal promoters can reduce hydrogen generation overpotentials, g-C3N4Weak van der Waals interactions with the cocatalyst will prevent the transmission of photogenerated charges and even become new recombination centers, thus increasing g-C3N4Interaction with the promoter will favor photogenerated charge from g-C3N4Migration to the cocatalyst and reduction of recombination are realized, so that the photocatalytic hydrogen production activity is improved.
The loading mode of the promoter has important influence on the magnitude of the interaction force between the semiconductor and the promoter, the in-situ photoreduction method is the most common and simple method for depositing the noble metal nanoparticles on the specific surface of the semiconductor, and the deposition sites have certain selectivity, so that the photocatalytic hydrogen production activity is improved. Chemical reduction is also a common noble gold-loaded materialThe method belongs to a cocatalyst mode, the deposited cocatalyst has good dispersibility and uniformity, more active sites are provided for photocatalytic hydrogen production, in addition, the adsorption effect is a mode of loading the prepared cocatalysts with different shapes and sizes on the surface of a semiconductor, and therefore, the method can study the influence of the cocatalyst shape and size factors on the photocatalytic hydrogen production performance. However, these methods support only weak van der waals interactions between the noble metal promoters and the semiconductor. Of course, there are also some studies on the strong interaction between the co-catalyst and the semiconductor. The researchers have utilized g-C3N4Adsorption of Pt4+And preparing Pt monoatomic supported g-C by a thermal reduction two-step method3N4Photocatalyst, platinum and g-C realized by coordination of Pt-N3N4By changing the surface capture state, the lifetime of the photo-generated charge is increased. In addition, some researchers have also achieved coordination between Pt and N by simple solution-impregnation adsorption, and this strong interaction significantly alters g-C3N4The electronic structure of (2) accelerates the charge transfer rate. Although the strong interaction can accelerate charge migration, experiments and theoretical calculation show that the catalytic hydrogen production promoting effect of the ionic Pt is obviously different from that of the metallic Pt, so that part of Pt atoms in the Pt nanoparticles and a semiconductor form strong interaction, the other part of Pt keeps the metallic state, and the semi-chemical interaction between the Pt and the semiconductor can realize quick transfer of photo-generated charges and simultaneously keep the efficient catalytic hydrogen production promoting effect, thereby realizing efficient photocatalytic hydrogen production.
Disclosure of Invention
The invention aims to provide a carbon nitride nanotube/platinum composite material with semi-chemical interaction and a preparation method thereof.
A composite carbon nitride nanotube/platinum material with semi-chemical interaction prepared by high-pressure solvothermal method is composed of noble metal platinum and graphite-phase carbon nitride, and the two components are connected by semi-chemical interaction.
Preferably, the carbon nitride nanotube/platinum composite material with the semi-chemical interaction is prepared by adopting high-pressure solvothermal method, and the synthesis steps are as follows:
(1) weighing 1 g of melamine, dissolving the melamine in 50-100 ml of water, adding 0.05-0.8 g of sodium hydroxide solid, and stirring for 30-60 minutes to obtain a clear solution;
(2) transferring the solution obtained in the step (1) to a hydrothermal reaction kettle, preserving the heat for 5-15 hours in an oven at 180 ℃, cooling, then carrying out suction filtration, washing and drying to obtain a supramolecular precursor;
(3) placing the supramolecular precursor prepared in the step (2) in a tube furnace, heating to 500-700 ℃ at the heating rate of 5-20 ℃ per minute under the protection of atmosphere, and preserving heat for 1-4 hours to obtain the graphite-phase carbon nitride nanotube;
(4) weighing 50-100 mg of the graphite-phase carbon nitride nanotube prepared in the step (3) and dispersing in 15-50 ml of 25-40% isopropanol solution, carrying out ultrasonic dispersion for 30 minutes, adding 10-2000 microliter of noble metal salt solution, continuing ultrasonic treatment for 5 minutes, transferring to a polytetrafluoroethylene sleeve, sealing, placing in a high-pressure reaction container, heating to 150-200 ℃ at a heating rate of 1-5 ℃ per minute, setting the pressure to be 100-200 MPa, carrying out heat preservation for 10-20 hours, and directly drying the suspension after cooling to obtain the composite material.
The X-ray diffraction, fluorescence spectrum and high-resolution transmission electron microscope test results show that the high-pressure solvent heat can improve the crystallinity of the CNNT and form an in-plane heterojunction; the X-ray photoelectron spectrum of Pt and the valence band spectrum of the sample confirm that a semi-chemical interaction is formed between Pt and CNNT; in addition, photoelectrochemical tests indicate that the in-plane heterojunction of CNNTs and the semi-chemical interaction thereof with Pt can significantly improve the separation and migration of photo-generated charges of samples. Therefore, the conversion frequency of 918 per hour is realized by photocatalytic hydrogen production under the irradiation of Pt-CNNT visible light, which is reported at presentg-C3N4The method provides a new research idea and a preparation method for improving the effect of the noble metal cocatalyst and realizing high-efficiency photocatalytic hydrogen production.
The invention has the advantages that: 1. the catalyst of the invention can greatly improve the effect of the noble metal cocatalyst, reduce the cost of the catalyst and meet the requirement of expanded production; 2. the catalyst has good and stable photocatalytic water splitting performance.
Drawings
FIG. 1 is a graph of a, b, X-ray powder diffraction pattern (XRD), c, fluorescence spectrum (PL), d, half-height peak width of sample (002) peak, Transmission Electron Microscope (TEM) graph of e, CNNT and TEM graph of f, Pt-CNNT prepared by high pressure hydrothermal (S-CNNT) and high pressure hydrothermal preparation of CNNT and chloroplatinic acid in the presence of CNNT and chloroplatinic acid.
FIG. 2 shows the a, Fourier transform infrared spectra of CNNTs, S-CNNTs and Pt-CNNTs prepared according to the present invention, the C1S spectra of b, CNNTs and Pt-CNNTs, the Pt4f spectra of C, Pt-CNNTs, and the valence band spectra of d, CNNTs, Pt/S-CNNTs and Pt-CNNTs.
FIG. 3 shows the a, UV-VIS absorption spectra, b, Tacu curves, c, photocurrent, and d, time-resolved fluorescence spectra of the CNNTs, S-CNNTs, and Pt-CNNTs prepared by the present invention.
FIG. 4 is a graph showing the conversion frequency of the CNNTs, S-CNNTs and Pt-CNNTs prepared by the present invention by a photocatalytic hydrogen production, b, and g-C reported in literature3N4A comparison graph of the hydrogen production conversion frequency of the base photocatalyst and the hydrogen production conversion frequency of the invention, and a test effect graph of the hydrogen production period of c and Pt-CNNT photocatalysis.
Detailed Description
1) Synthesizing 0.01% of Pt-CNNT heterogeneous composite material;
(1) weighing 1 g of melamine, dissolving the melamine in 50-100 ml of water, adding 0.05-0.8 g of sodium hydroxide solid, and stirring for 30-60 minutes to obtain a clear solution;
(2) transferring the solution in the step (1) to a hydrothermal reaction kettle, preserving heat for 5-15 hours in an oven at 180 ℃, cooling, then carrying out suction filtration, washing and drying to obtain a supramolecular precursor;
(3) placing the supramolecular precursor obtained in the step (2) in a tube furnace, heating to 500-700 ℃ at the heating rate of 5-20 ℃ per minute under the protection of atmosphere, and preserving heat for 1-4 hours to obtain a graphite-phase Carbon Nitride Nanotube (CNNT);
(4) weighing 60 mg of CNNT, dispersing in 15-50 ml of 25-40% isopropanol solution, ultrasonically dispersing for 30 min, adding 16 microliters of 1 mg/ml chloroplatinic hexahydrate solution, continuing to ultrasonically treat for 5 min, then transferring to a polytetrafluoroethylene sleeve, sealing, placing into a high-pressure reaction container, heating to 150-200 ℃ at the heating rate of 1-5 ℃ per min, setting the pressure to 100-200 MPa, preserving heat for 10-20 h, and directly drying the suspension after cooling to obtain the composite material.
2) Synthesizing 0.05% of Pt-CNNT heterogeneous composite material;
(1) weighing 1 g of melamine, dissolving the melamine in 50-100 ml of water, adding 0.05-0.8 g of sodium hydroxide solid, and stirring for 30-60 minutes to obtain a clear solution;
(2) transferring the solution in the step (1) to a hydrothermal reaction kettle, preserving heat for 5-15 hours in an oven at 180 ℃, cooling, then carrying out suction filtration, washing and drying to obtain a supramolecular precursor;
(3) placing the supramolecular precursor obtained in the step (2) in a tube furnace, heating to 500-700 ℃ at the heating rate of 5-20 ℃ per minute under the protection of atmosphere, and preserving heat for 1-4 hours to obtain a graphite-phase Carbon Nitride Nanotube (CNNT);
(4) weighing 60 mg of CNNT, dispersing in 15-50 ml of 25-40% isopropanol solution, ultrasonically dispersing for 30 min, adding 80 microliter of 1 mg/ml chloroplatinic acid hexahydrate solution, continuing to ultrasonically disperse for 5 min, then transferring to a polytetrafluoroethylene sleeve, sealing, placing into a high-pressure reaction container, heating to 150-200 ℃ at the heating rate of 1-5 ℃ per minute, setting the pressure to 100-200 MPa, preserving the heat for 10-20 h, and directly drying the suspension after cooling to obtain the composite material.
3) Synthesizing 0.1% of Pt-CNNT heterogeneous composite material;
(1) weighing 1 g of melamine, dissolving the melamine in 50-100 ml of water, adding 0.05-0.8 g of sodium hydroxide solid, and stirring for 30-60 minutes to obtain a clear solution;
(2) transferring the solution in the step (1) to a hydrothermal reaction kettle, preserving heat for 5-15 hours in an oven at 180 ℃, cooling, then carrying out suction filtration, washing and drying to obtain a supramolecular precursor;
(3) placing the supramolecular precursor obtained in the step (2) in a tube furnace, heating to 500-700 ℃ at the heating rate of 5-20 ℃ per minute under the protection of atmosphere, and preserving heat for 1-4 hours to obtain a graphite-phase Carbon Nitride Nanotube (CNNT);
(4) weighing 60 mg of CNNT, dispersing in 15-50 ml of 25-40% isopropanol solution, ultrasonically dispersing for 30 min, adding 160 microliters of 1 mg/ml chloroplatinic hexahydrate solution, continuing to ultrasonically treat for 5 min, then transferring to a polytetrafluoroethylene sleeve, sealing, placing into a high-pressure reaction container, heating to 150-200 ℃ at the heating rate of 1-5 ℃ per min, setting the pressure to 100-200 MPa, preserving heat for 10-20 h, and directly drying the suspension after cooling to obtain the composite material.
4) Synthesizing 0.5% Pt-CNNT heterogeneous composite material;
(1) weighing 1 g of melamine, dissolving the melamine in 50-100 ml of water, adding 0.05-0.8 g of sodium hydroxide solid, and stirring for 30-60 minutes to obtain a clear solution;
(2) transferring the solution in the step (1) to a hydrothermal reaction kettle, preserving heat for 5-15 hours in an oven at 180 ℃, cooling, then carrying out suction filtration, washing and drying to obtain a supramolecular precursor;
(3) placing the supramolecular precursor obtained in the step (2) in a tube furnace, heating to 500-700 ℃ at the heating rate of 5-20 ℃ per minute under the protection of atmosphere, and preserving heat for 1-4 hours to obtain a graphite-phase Carbon Nitride Nanotube (CNNT);
(4) weighing 60 mg of CNNT, dispersing in 15-50 ml of 25-40% isopropanol solution, ultrasonically dispersing for 30 min, adding 800 microliter of 1 mg/ml chloroplatinic hexahydrate solution, continuing to ultrasonically treat for 5 min, then transferring to a polytetrafluoroethylene sleeve, sealing, placing into a high-pressure reaction container, heating to 150-200 ℃ at the heating rate of 1-5 ℃ per minute, setting the pressure to 100-200 MPa, preserving the heat for 10-20 h, and directly drying the suspension after cooling to obtain the composite material.
5) Synthesizing 1% Pt-CNNT heterogeneous composite material;
(1) weighing 1 g of melamine, dissolving the melamine in 50-100 ml of water, adding 0.05-0.8 g of sodium hydroxide solid, and stirring for 30-60 minutes to obtain a clear solution;
(2) transferring the solution in the step (1) to a hydrothermal reaction kettle, preserving heat for 5-15 hours in an oven at 180 ℃, cooling, then carrying out suction filtration, washing and drying to obtain a supramolecular precursor;
(3) placing the supramolecular precursor obtained in the step (2) in a tube furnace, heating to 500-700 ℃ at the heating rate of 5-20 ℃ per minute under the protection of atmosphere, and preserving heat for 1-4 hours to obtain a graphite-phase Carbon Nitride Nanotube (CNNT);
(4) weighing 60 mg of CNNT, dispersing in 15-50 ml of 25-40% isopropanol solution, adding 1600 microliter of 1 mg/ml chloroplatinic acid hexahydrate solution after ultrasonic dispersion for 30 minutes, continuing ultrasonic treatment for 5 minutes, then transferring to a polytetrafluoroethylene sleeve, sealing, placing in a high-pressure reaction container, heating to 150-200 ℃ at the heating rate of 1-5 ℃/minute, setting the pressure to 100-200 MPa, preserving the heat for 10-20 hours, and directly drying the suspension after cooling to obtain the composite material.
As shown in fig. 1a and 1b, XRD test results show that after high-pressure solvothermal treatment, the in-plane repeating unit of CNNT is significantly changed, and three in-plane structural units with different intervals appear; in FIG. 1c, two new fluorescence peaks of S-CNNT and Pt-CNNT prepared by the present invention show that different in-plane structural units have different energy band structures; the smaller peak widths at half heights and the more distinct lattice fringes of S-CNNT and Pt-CNNT in FIGS. 1d-1f indicate that high pressure solvent heat can improve the crystallinity of CNNT.
As shown in FIG. 2a, the Fourier transform infrared spectrum of the Pt-CNNT prepared by the invention has no obvious change relative to the CNNT, which indicates that the Pt-CNNT still maintains g-C3N4Short range ordered structure and thus possess g-C3N4The nature of (c); the C1s spectrum of Pt-CNNT in FIG. 2b shows a new peak at 289 eVg-C3N4Better crystallinity is caused by pi electron delocalization; the spectrum of Pt4f for Pt-CNNT in FIG. 2c shows that Pt has two valence states, while the spectrum of valence band for the sample in FIG. 2d shows that Pt-CNNT prepared by the present invention has higher density of states, and the above results show that Pt and CNNT in Pt-CNNT form semi-chemical interaction, a part of Pt exists in metallic state, and the other part of Pt and CNNT have strong interaction and show ionic state.
As shown in FIGS. 3a and b, the Pt-CNNT prepared by the invention has larger band gap, which is caused by quantum confinement effect to increase the band gap due to different repeating units formed in the surface of the CNNT by high-pressure solvent heat; as shown in fig. 3c, d, the photocurrent of Pt-CNNT was significantly increased and the fluorescence lifetime was also increased, indicating that the semi-chemical interaction of Pt and CNNT favors the migration of photo-generated charges.
As shown in FIGS. 4a and 4b, the conversion frequency (TOF) of Pt-CNNT visible light catalysis hydrogen production prepared by the invention is improved by 200 times compared with CNNT, and is obviously improved compared with that reported in literature, and meanwhile, FIG. 4c shows that Pt-CNNT has good stability of photocatalytic hydrogen production, and shows that the semi-chemical interaction between Pt and CNNT can obviously improve the efficiency and stability of visible light catalysis hydrogen production.
The invention develops a new method for preparing the heterogeneous composite material with strong interaction between the semiconductor and the noble metal cocatalyst through high-pressure solvothermal, and provides a new thought for designing and preparing the semiconductor/cocatalyst composite material with excellent photocatalytic performance. The catalyst has the advantages of simple synthesis method, low production cost, high synthetic yield, high purity and good repeatability, and meets the requirement of expanded production; the catalyst has good and stable performance of photocatalytic water decomposition.
While embodiments of the present invention have been described herein, it will be understood by those skilled in the art that changes may be made to the embodiments herein without departing from the spirit of the invention. The above examples are merely illustrative and should not be taken as limiting the scope of the invention.
Claims (2)
1. A carbon nitride nanotube/platinum composite material with semi-chemical interaction, which is characterized in that: consists of noble metal platinum and graphite phase carbon nitride, and the two components are connected through semi-chemical interaction.
2. The carbon nitride nanotube/platinum composite material with semi-chemical interaction of claim 1, wherein: the preparation method adopts high-pressure solvothermal preparation, and comprises the following preparation steps:
(1) weighing 1 g of melamine, dissolving the melamine in 50-100 ml of water, adding 0.05-0.8 g of sodium hydroxide solid, and stirring for 30-60 minutes to obtain a clear solution;
(2) transferring the solution obtained in the step (1) to a hydrothermal reaction kettle, preserving the heat for 5-15 hours in an oven at 180 ℃, cooling, then carrying out suction filtration, washing and drying to obtain a supramolecular precursor;
(3) placing the supramolecular precursor prepared in the step (2) in a tube furnace, heating to 500-700 ℃ at the heating rate of 5-20 ℃ per minute under the protection of atmosphere, and preserving heat for 1-4 hours to obtain the graphite-phase carbon nitride nanotube;
(4) weighing 50-100 mg of the graphite-phase carbon nitride nanotube prepared in the step (3) and dispersing in 15-50 ml of 25-40% isopropanol solution, carrying out ultrasonic dispersion for 30 minutes, adding 10-2000 microliter of noble metal salt solution, continuing ultrasonic treatment for 5 minutes, transferring to a polytetrafluoroethylene sleeve, sealing, placing in a high-pressure reaction container, heating to 150-200 ℃ at a heating rate of 1-5 ℃ per minute, setting the pressure to be 100-200 MPa, carrying out heat preservation for 10-20 hours, and directly drying the suspension after cooling to obtain the composite material.
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