CN112973751A - Ru monoatomic and g-C3N4Composite photocatalyst and preparation method and application thereof - Google Patents
Ru monoatomic and g-C3N4Composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention provides a Ru monoatomic and g-C3N4A composite photocatalyst and a preparation method and application thereof, belonging to the technical field of nano material synthesis; in the invention, a simple and quick one-step calcination method is used for loading Ru single atoms on g-C3N4The surface of the material is formed by a Ru monoatomic atom and g-C3N4A composite photocatalyst; the photocatalyst can efficiently and stably photolyze water to produce hydrogen under visible light.
Description
Technical Field
The invention belongs to the technical field of nano material synthesis,in particular to a Ru monoatomic compound and g-C3N4A composite photocatalyst and a preparation method and application thereof.
Background
The photocatalytic technology is a green method for producing hydrogen by effectively photolyzing water, and the photocatalytic hydrogen production has the advantages of high efficiency, safety, environmental protection and the like, but the photocatalytic material developed and applied at present still has the defects of poor stability, incapability of fully utilizing solar energy, high recombination rate of photon-generated carriers and the like.
Graphite phase carbon nitride (g-C)3N4) Is an n-type semiconductor polymer, has a narrow forbidden band width (2.7 eV), can fully utilize visible light, is non-toxic and harmless, has the advantages of acid resistance, alkali resistance, photo-corrosion resistance and the like, but is pure g-C3N4Still has the defects of small specific surface area, high recombination rate of photo-generated electron-hole pairs and poor photocatalytic activity.
In g-C3N4The surface assembled noble metal nano particle can promote electrons from g-C3N4The surface is transferred to a noble metal cocatalyst to inhibit the recombination of photon-generated carriers, and the surface can also be used as an effective reaction active site to reduce the activation energy required by hydrogen production. Researches show that compared with noble metal nanoparticles, noble metals are loaded on the surface of the catalyst in an atomic form, the theoretical atomic utilization efficiency of 100 percent can be achieved, and the photocatalytic reaction activity is greatly improved. However, in the process of producing hydrogen by photolyzing water, the photocatalytic activity of the monatomic noble metal-supported photocatalyst is reduced along with the reaction, and the performance of the monatomic noble metal-supported photocatalyst cannot be kept stable, so that the use of the photocatalyst is seriously influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a Ru (ruthenium) monoatomic and g-C3N4A composite photocatalyst and a preparation method and application thereof. In the invention, a simple and quick one-step calcination method is used for loading Ru single atoms on g-C3N4The surface of the material is formed by a Ru monoatomic atom and g-C3N4The composite photocatalyst system realizes efficient and stable hydrogen production by water photolysis under visible light.
The invention firstly provides a Ru monoatomic and g-C3N4A composite photocatalyst of said Ru monoatomic with g-C3N4In the composite photocatalyst, Ru is loaded on g-C3N4The surface is of a two-dimensional nanosheet structure, and mesopores exist in the catalyst; the photocatalyst is marked as RuCN-a%, a =0.05-1.5, and a% is the amount of metal Ru in the catalyst and g-C3N4Percentage of the amount of (c).
The invention also provides the Ru monoatomic and g-C3N4The preparation method of the composite photocatalyst specifically comprises the following steps:
adding an ethanol solution containing ruthenium acetylacetonate into a urea aqueous solution, stirring and mixing uniformly, evaporating the mixed solution to dryness in an oil bath, putting a sample subjected to evaporation to dryness into a glass mortar, grinding the sample into powder, calcining at 500-550 ℃, and naturally cooling to room temperature to obtain Ru monoatomic ions and g-C3N4A composite photocatalyst is provided.
Furthermore, g-C generated by calcining metal Ru in the ruthenium acetylacetonate and urea3N4The mass ratio of (A) to (B) is 0.05-1.5: 100.
Further, the temperature of the oil bath is 90-100 ℃.
Further, the calcining temperature is 500 ℃, and the calcining time is 3-5 hours.
Further, the heating rate of the calcination is 5 ℃/min.
The invention also provides the Ru monoatomic and g-C3N4The composite photocatalyst is used in photocracking water to produce hydrogen.
Further, the application includes:
uniformly dispersing RuCN-a% in water solution containing Triethanolamine (TEOA), introducing nitrogen to exhaust air in the reactor, and measuring generated H with online gas chromatography system using 300W xenon lamp equipped with 420nm cut-off filter as visible light source2The amount of (c).
Further, the ratio of the RuCN-a% to the Triethanolamine (TEOA) containing aqueous solution is 50 mg: 100 mL.
Further, the volume fraction of triethanolamine in the triethanolamine-containing (TEOA) aqueous solution was 10%.
Compared with the prior art, the invention has the beneficial effects that:
g-C3N4the optical material has good optical performance and surface adsorption characteristic, and appropriate electronic energy band width can fully utilize visible light, is nontoxic and harmless, and is resistant to acid, alkali and photo corrosion. The invention applies the simple and rapid method of one-step calcination to prepare the high-efficiency and stable Ru monoatomic compound and g-C3N4The composite system obviously enhances the efficiency of the photocatalyst in decomposing water to produce hydrogen under visible light.
The invention successfully loads Ru monoatomic atom on g-C3N4On the surface, Ru monoatomic atoms and g-C are formed3N4Composite photocatalyst, without changing g-C3N4Original two-dimensional nanosheet structure characteristics, rich surface active sites are provided, and g-C is improved3N4The absorption capacity to visible light and the separation and transportation efficiency of carriers effectively prevent the recombination of photon-generated electron-hole pairs, and obviously improve the efficiency of hydrogen production by decomposing water under the visible light.
The invention controls g-C precisely3N4The ratio of Ru metal composition to the Ru monoatomic compound to the g-C3N4A composite photocatalytic system. Continuously adjusting the metal Ru and g-C by a photocatalytic hydrogen production test3N4The compounding ratio is finally determined3N4In a mass ratio of 0.05-1.5:100, wherein Ru and g-C3N4The mass ratio of the components is respectively 0.5:100, the photocatalytic hydrogen production performance is optimal, and the stability of the long-time hydrogen production performance is kept. It was found by experiment that pure g-C without addition of cocatalyst3N4The photocatalytic hydrogen production rate is basically zero, and the hydrogen production rate of the RuCN-0.5 percent composite photocatalyst in photocatalytic decomposition of water can reach 629.9 umol h at most-1 g-1. Under the irradiation of 420nm monochromatic light, RuCN-0.5% achieves the optimal quantum efficiency of 10.3%. In addition, RuCN-0.5% Complex was run in series for 25 groups 10After a 0h photolysis water hydrogen production cycle experiment, the hydrogen production amount is not obviously reduced, which shows that the RuCN-0.5% compound has stable performance and can be repeatedly used.
The method has simple process and low energy consumption, and does not need complex steps such as high pressure and the like; the required equipment cost is low, and the production process does not cause pollution to the environment, thereby meeting the environment-friendly requirement; the catalyst has stable performance and high hydrogen production activity, and is beneficial to practical production and application.
Drawings
FIG. 1 shows g-C3N4(a) TEM image of RuCN-0.5% (b).
FIG. 2 is a RuCN-0.5% HADDF map (a) and EDX element maps (b-d), where b is C, C is N, and d is Ru.
FIG. 3 is a RuCN-0.5% HADDF-STEM plot, where a is a picture taken at 2nm size and b is a picture taken at 5nm size.
FIG. 4 shows g-C3N4And RuCN-0.5% ultraviolet-visible diffuse reflectance absorption spectrum.
FIG. 5 is g-C3N4And a RuCN-0.5% water photolysis hydrogen production performance diagram (a), a RuCN-0.5% quantum efficiency under different monochromatic light (b) and a RuCN-0.5% sample continuous circulation 100 h water photolysis hydrogen production performance diagram (c).
FIG. 6 shows g-C3N4And RuCN-0.5% of transient photocurrent (a) and impedance spectrum (b).
FIG. 7 is g-C3N4And transient fluorescence lifetime spectrum (a) and polarization curve (b) of RuCN-0.5%.
FIG. 8 is g-C3N4And RuCN-0.5% of N2Adsorption and desorption curves.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1: preparation of RuCN-0.05% photocatalyst and hydrogen production by photolysis of water
Weighing 20g of urea, and dissolving the urea in deionized water to form a solution A; weighing a certain amount of ruthenium acetylacetonate, metal Ru andg-C3N4is 0.05:100, and is dissolved in ethanol to form a solution B; pouring the B into the A, stirring for 10min by magnetic force, stirring and drying the mixed solution in an oil bath at 90 ℃, putting the dried sample into a glass mortar after the mixed solution is completely dried, grinding the sample into powder, pouring the powder into a 50ml crucible, wrapping the crucible with tinfoil, raising the temperature from room temperature to 500 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and calcining for 3 h. Naturally cooling to room temperature to obtain RuCN-0.05% photocatalyst.
The photocatalytic reaction was carried out in a closed glass reaction system, in which 50mg of RuCN-0.05% composite catalyst was uniformly dispersed in 100ml of 10 vol% aqueous Triethanolamine (TEOA). In the reaction process, circulating water of 20 ℃ is used for maintaining the temperature of the reaction system, nitrogen is introduced for 20min to exhaust the air in the reactor, then a 300W xenon lamp provided with a 420nm cut-off filter is used as a visible light source, and an online gas chromatography system is used for measuring the generated H2The amount of (c).
Example 2: preparation of RuCN-0.1% photocatalyst and hydrogen production by photolysis of water
Weighing 20g of urea, and dissolving the urea in deionized water to form a solution A; weighing a certain amount of ruthenium acetylacetonate, metal Ru and g-C3N4Is 0.1:100, and is dissolved in ethanol to form a solution B; pouring the B into the A, stirring for 10min by magnetic force, stirring and drying the mixed solution in an oil bath at 90 ℃, putting the dried sample into a glass mortar after the mixed solution is completely dried, grinding the sample into powder, pouring the powder into a crucible of 50ml, wrapping the crucible with tinfoil, raising the temperature from room temperature to 525 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and calcining for 4 h. Naturally cooling to room temperature to obtain RuCN-0.1% photocatalyst.
The photocatalytic reaction was carried out in a closed glass reaction system, in which 50mg of RuCN-0.1% composite catalyst was uniformly dispersed in 100ml of 10 vol% aqueous Triethanolamine (TEOA). In the reaction process, circulating water of 20 ℃ is used for maintaining the temperature of the reaction system, nitrogen is introduced for 20min to exhaust the air in the reactor, then a 300W xenon lamp provided with a 420nm cut-off filter is used as a visible light source, and an online gas chromatography system is used for measuring the generated H2The amount of (c).
Example 3: preparation of RuCN-0.5% photocatalyst and hydrogen production by photolysis of water
Weighing 20g of urea, and dissolving the urea in deionized water to form a solution A; weighing a certain amount of ruthenium acetylacetonate, metal Ru and g-C3N4Is 0.5:100, and is dissolved in ethanol to form a solution B; pouring the B into the A, stirring for 10min by magnetic force, stirring and drying the mixed solution in an oil bath at 90 ℃, putting the dried sample into a glass mortar after the mixed solution is completely dried, grinding the sample into powder, pouring the powder into a 50ml crucible, wrapping the crucible with tinfoil, raising the temperature from room temperature to 500 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and calcining for 3 h. Naturally cooling to room temperature to obtain RuCN-0.5% photocatalyst.
The photocatalytic reaction was carried out in a closed glass reaction system, in which 50mg of RuCN-0.5% composite catalyst was uniformly dispersed in 100ml of 10 vol% aqueous Triethanolamine (TEOA). In the reaction process, circulating water of 20 ℃ is used for maintaining the temperature of the reaction system, nitrogen is introduced for 20min to exhaust the air in the reactor, then a 300W xenon lamp provided with a 420nm cut-off filter is used as a visible light source, and an online gas chromatography system is used for measuring the generated H2The amount of (c).
FIG. 1 is g-C3N4And TEM spectrogram of RuCN-0.5% composite photocatalyst. As can be seen from FIG. 1, both g-C and g-C3N4Or RuCN-0.5%, both exhibit a typical two-dimensional nanosheet structure; obvious mesopores can be observed on the surface, and the single atom of Ru on the surface is loaded at g-C3N4Surface, no change in g-C3N4The original structure.
FIG. 2 is a TEM EDX elemental mapping spectrum of RuCN-0.5% composite photocatalyst. As can be seen from the RuCN-0.5% High Angle Annular Dark Field (HAADF) image (2 a) and the element mapping (EDX) image (2 b-2 d), RuCN-0.5% is composed of C, N and Ru, and is distributed in characteristics, further showing that Ru monoatomic atoms and g-C3N4Successfully preparing the composite photocatalytic material.
FIG. 3 is a graph of the HAADF-SEDX spectrum of a RuCN-0.5% composite photocatalyst. Under different shooting scales of graphs (a and b), white bright spots of 0.2nm exist, the bright spots are proved to be Ru single atoms, and the successful preparation of the RuCN-a% composite photocatalytic material is further proved.
FIG. 4 is g-C3N4And a RuCN-0.5% ultraviolet-visible diffuse reflectance absorption spectrogram and a corresponding estimated band gap spectrogram. As can be seen from the figure, g-C3N4Has obvious visible light response compared with RuCN-0.5 percent composite photocatalyst sample3N4The RuCN-0.5% complex significantly enhanced the utilization of visible light.
FIG. 5a is g-C3N4And a performance diagram of hydrogen production by photodecomposition water of the RuCN-a% composite photocatalyst. From FIG. 5a it can be observed that pure g-C3N4The hydrogen production rate is basically zero, the hydrogen evolution rate of the RuCN-a% composite photocatalyst is gradually increased along with the increase of the single atom load of Ru in the catalyst, and when the load of Ru is 0.5% (RuCN-0.5%), the hydrogen production rate can reach the maximum value of 629.9 mu mol.h-1·g-1. However, as the loading amount of Ru increased, the hydrogen production tended to decrease, indicating that too much Ru loading would lead to g-C3N4The light absorption has shielding effect, and the photocatalytic hydrogen production performance is influenced.
FIG. 5b is a graph of the quantum efficiency of RuCN-0.5% under different monochromatic lights, where it can be observed that the highest quantum efficiency of 10.3% is reached at 420 nm. FIG. 5c is a graph of RuCN-0.5% continuously performed on 25 groups of hydrogen production by 100 h cycle, and it can be seen that the decrease degree of hydrogen production after 100 h is negligible, from which it is known that the RuCN-0.5% composite catalyst has good stability and reusability.
FIG. 6 is g-C3N4And a transient photocurrent-time response spectrum (a) and an impedance spectrum (b) of the RuCN-0.5% composite photocatalyst. As shown in FIG. 6 (a), comparative g-C3N4The RuCN-0.5% catalyst has a higher photocurrent response value, which indicates that the RuCN-0.5% catalyst has higher photo-generated carrier separation efficiency and mobility; in FIG. 6 (b), the diameter of the RuCN-0.5% Nyquist plot is much smaller than that of pure g-C3N4The RuCN-0.5% photocatalyst has lower interface charge migration resistance and is beneficial to improving the performance of photocatalytic hydrogen production.
FIG. 7a is g-C3N4And a transient life spectrogram of the RuCN-0.5% composite photocatalyst. Through calculation, the fluorescence lifetime of RuCN-0.5% is 2.38 ns and is less than pure g-C3N4(2.73 ns), indicating that there may be an additional non-radiative decay channel, increasing the efficiency of separation of photogenerated carriers. FIG. 7b is g-C3N4And a polarization curve spectrogram of the RuCN-0.5% composite photocatalyst. As shown in FIG. 7b, at 10 mA cm-2Where the overpotential (-0.68V) of the RuCN-0.5% complex is greater than g-C3N4The overpotential (-0.72V) shows that the loaded Ru single atom effectively reduces the overpotential and fundamentally promotes the performance of photocatalytic water decomposition.
FIG. 8 is g-C3N4And N of RuCN-0.5% composite photocatalyst2Adsorption and desorption curves. As seen from FIG. 8, the isothermal hysteresis loop was measured to be between 0.2 and 1.0 (P/P)0) Confirm that g-C3N4And RuCN-0.5% of the catalyst. Furthermore, RuCN-0.5% of BET specific surface area (81.8 m)2 g-1) Is obviously higher than pure g-C3N4（33.5m2 g-1) The larger specific surface area is beneficial to exposing more adsorption and surface reaction active sites, thereby further improving the hydrogen production activity of photocatalytic water decomposition.
Example 4: preparation of RuCN-1% photocatalyst and hydrogen production by photolysis of water
Weighing 20g of urea, and dissolving the urea in deionized water to form a solution A; weighing a certain amount of ruthenium acetylacetonate, metal Ru and g-C3N4The mass ratio of the components is 1:100, and the components are dissolved in ethanol to form a solution B; pouring the B into the A, stirring for 10min by magnetic force, stirring and drying the mixed solution in an oil bath at 90 ℃, putting the dried sample into a glass mortar after the mixed solution is completely dried, grinding the sample into powder, pouring the powder into a 50ml crucible, wrapping the crucible with tinfoil, raising the temperature from room temperature to 550 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and continuously calcining for 3 h. Naturally cooling to room temperature to obtain the RuCN-1% photocatalyst.
Carrying out photocatalytic reaction in a closed glass reaction system, uniformly dispersing 50mg of RuCN-1% composite catalyst in 100ml of 10 vol% Triethanolamine (TEOA) water solutionIn the liquid. In the reaction process, circulating water of 20 ℃ is used for maintaining the temperature of the reaction system, nitrogen is introduced for 20min to exhaust the air in the reactor, then a 300W xenon lamp provided with a 420nm cut-off filter is used as a visible light source, and an online gas chromatography system is used for measuring the generated H2The amount of (c).
Example 5: preparation of RuCN-1.5% photocatalyst and hydrogen production by photolysis of water
Weighing 20g of urea, and dissolving the urea in deionized water to form a solution A; weighing a certain amount of ruthenium acetylacetonate, metal Ru and g-C3N4The mass ratio of the components is 1:100, and the components are dissolved in ethanol to form a solution B; pouring the B into the A, stirring for 10min by magnetic force, stirring and drying the mixed solution in an oil bath at 90 ℃, putting the dried sample into a glass mortar after the mixed solution is completely dried, grinding the sample into powder, pouring the powder into a 50ml crucible, wrapping the crucible with tinfoil, raising the temperature from room temperature to 500 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and calcining for 5 h. Naturally cooling to room temperature to obtain RuCN-1.5% photocatalyst.
The photocatalytic reaction was carried out in a closed glass reaction system, in which 50mg of RuCN-1.5% composite catalyst was uniformly dispersed in 100ml of 10 vol% aqueous Triethanolamine (TEOA). In the reaction process, circulating water of 20 ℃ is used for maintaining the temperature of the reaction system, nitrogen is introduced for 20min to exhaust the air in the reactor, then a 300W xenon lamp provided with a 420nm cut-off filter is used as a visible light source, and an online gas chromatography system is used for measuring the generated H2The amount of (c).
Comparative example 1. g-C3N4Preparing a nano sheet:
taking out a certain amount of urea, drying in an oven at 80 deg.C overnight, weighing 20g of dried urea, grinding in a glass mortar to powder, pouring into a 50ml crucible with a cover, wrapping with tinfoil, and heating at room temperature for 5 deg.C for min in a muffle furnace-1The temperature rise rate of (2) is increased to 500 ℃, and the calcination is carried out for 3 hours. Naturally cooling to room temperature to obtain g-C3N4Nanoplatelets in a yield of 500mg.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. Ru monoatomic and g-C3N4The composite photocatalyst is characterized in that the Ru monoatomic group and g-C3N4In the composite photocatalyst, Ru is loaded on g-C3N4The surface is of a two-dimensional nanosheet structure, and mesopores exist in the catalyst; the photocatalyst is marked as RuCN-a%, a =0.05-1.5, and a% is the amount of metal Ru in the catalyst and g-C3N4Percentage of the amount of (c).
2. Ru monoatomic and g-C3N4The preparation method of the composite photocatalyst is characterized by comprising the following steps:
adding an ethanol solution containing ruthenium acetylacetonate into a urea aqueous solution, stirring and mixing uniformly, evaporating the mixed solution to dryness in an oil bath, putting a sample subjected to evaporation to dryness into a glass mortar, grinding the sample into powder, calcining at 500-550 ℃, and naturally cooling to room temperature to obtain Ru monoatomic ions and g-C3N4A composite photocatalyst is provided.
3. The Ru monatomic and g-C of claim 23N4The preparation method of the composite photocatalyst is characterized in that g-C generated by calcining metal Ru in ruthenium acetylacetonate and urea3N4The mass ratio of (A) to (B) is 0.05-1.5: 100.
4. The Ru monatomic and g-C of claim 23N4The preparation method of the composite photocatalyst is characterized in that the temperature of the oil bath is 90-100 ℃.
5. The Ru monatomic and g-C of claim 23N4The preparation method of the composite photocatalyst is characterized in that the calcining temperature is 500 ℃, and the calcining time is 3-5 hours.
6. The Ru monatomic and g-C of claim 23N4The preparation method of the composite photocatalyst is characterized in that the temperature rise rate of calcination is 5 ℃/min.
7. The Ru monoatomic bond of claim 1 and g-C3N4The composite photocatalyst is applied to the photocracking of water to produce hydrogen.
8. The use according to claim 7, comprising:
uniformly dispersing RuCN-a% in water solution containing Triethanolamine (TEOA), introducing nitrogen to exhaust air in the reactor, and measuring generated H with online gas chromatography system using 300W xenon lamp equipped with 420nm cut-off filter as visible light source2The amount of (c).
9. Use according to claim 8, wherein the ratio between the amount of said RuCN-a% and the amount of triethanolamine TEOA in aqueous solution is 50 mg: 100 mL.
10. Use according to claim 9, wherein the triethanolamine TEOA-containing aqueous solution has a triethanolamine volume fraction of 10%.
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