CN115282996A - Preparation method and application of P, S, B backfill nitrogen vacancy carbon nitride material for efficient photolysis of water to produce hydrogen - Google Patents
Preparation method and application of P, S, B backfill nitrogen vacancy carbon nitride material for efficient photolysis of water to produce hydrogen Download PDFInfo
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- 125000005842 heteroatom Chemical group 0.000 claims abstract description 8
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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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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- 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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Abstract
The invention discloses a nonmetal element P, S, B backfill V N The preparation method and the application of the-CN have good application in the aspect of photolysis of water to produce hydrogen. The invention firstly uses melamine as raw material to prepare g-C by calcining in a muffle furnace 3 N 4 (ii) a Then, the prepared g-C 3 N 4 Secondary calcining under argon atmosphere to obtain carbon nitride (V) rich in nitrogen vacancy N -CN); taking a certain amount of V N adding-CN into a round-bottom flask, using a mixed solution of water and ethanol as a solvent, and respectively adding sodium hypophosphite (NaH) 2 PO 2 ·H 2 O), thiourea (CH) 4 N 2 S) and boric acid (H) 3 BO 3 ) Ultrasonic dispersing, treating with oil, and transferring to polytetrafluoroethylene under high pressureHydrothermal reaction in reactor, washing and drying to obtain P, S and B carbon nitride (P) with back-filled nitrogen vacancy Rf /S Rf /B Rf ‑V N -CN). The backfill method can effectively stabilize nitrogen vacancies on the surface of the carbon nitride, simultaneously changes the charge density of surrounding atoms by introducing the heteroatom, promotes the separation of photon-generated carriers, and shows higher activity and stability in the aspect of photolysis of water to produce hydrogen.
Description
Technical Field
The invention relates to a preparation method of P, S, B backfilled nitrogenized carbon-nitrogen vacancies and application thereof in hydrogen production by photolysis of water, belonging to the field of functional technical materials.
Background
The photocatalytic water decomposition hydrogen production is used as a clean energy production mode, and can effectively relieve serious energy crisis and greenhouse effect caused by overuse of fossil fuel. Semiconductor photocatalysts have received much attention for their excellent photocatalytic activity in hydrogen evolution, water oxidation, organic pollutant degradation, nitrogen fixation, and carbon dioxide reduction, among others. Graphitic carbonitrides (g-C) 3 N 4 ) It is considered one of the most promising photocatalysts due to its ease of preparation, ease of surface modification and inherent visible light absorption. However, original g-C 3 N 4 There is also a high recombination rate of photo-excited carriers and a limited visible light absorption range, resulting in undesirable photocatalytic activity.
To accelerate the separation of electrons and holes, g-C has been treated 3 N 4 Various modifications such as heteroatom doping, coupling to other semiconductors, cocatalyst loading, N/C vacancy preparation, and increased crystallinity are made. 5363 and the like, the doping of atoms such as S, P, B, F, O can not only effectively improve the visible light response, but also induce the electronic rearrangement, so that negative charges are concentrated around the doped atoms, and the adsorption of intermediates is facilitated. Generally, the heteroatom can be used as an active site of a photocatalytic reaction, and can effectively improve the photocatalytic activity of a sample. In particular, nitrogen vacancies have been extensively studied to enhance g-C by facilitating charge transfer 3 N 4 Photocatalytic activity of (2). Most of the reported nitrogen defects are surface defects, and have limited improvement in photocatalytic activity, while nitrogen vacancies in the framework also promote light absorption and carrier separation in the sample. It was found that the hydrogen evolution activity is not directly proportional to the nitrogen vacancy content, but increases and then decreases with increasing nitrogen vacancy content. An appropriate amount of nitrogen vacancies can capture electrons and accelerate the separation of carriers, and excessive vacancies can become carrier recombination centers and are not beneficial to photocatalysis. Although nitrogen vacancies exhibit good activity in hydrogen evolution, the stability of surface nitrogen vacancies should be considered, thus stabilizing g-C 3 N 4 V in N Is a significant challenge. Filling nitrogen vacancies of nitrogen-vacancy carbon nitride surfaces with heteroatoms may be a method of compensating for coordination numbersA good strategy to stabilize surface vacancies and even surprising activity is obtained due to the electronic interaction between surface heteroatoms and nitrogen vacancies within the surface structure.
Disclosure of Invention
In the invention, g-C 3 N 4 Preparing carbon nitride containing a large number of nitrogen vacancies as raw material, and then respectively using sodium hypophosphite (NaH) 2 PO 2 ·H 2 O), thiourea (CH) 4 N 2 S) and boric acid (H) 3 BO 3 ) The material is a P source, an S source and a B source, and is subjected to element backfilling through an oil bath and a hydrothermal process, and the material shows excellent hydrogen activity of photolysis water. Backfilling of P, S, B with nitrogen vacancy carbon nitride (P) Rf /S Rf /B Rf -V N -CN) comprises the following steps:
(1) Putting 3.0g of melamine into a 50mL crucible, and calcining for 4h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 。
(2) 0.3g of g-C prepared above was weighed 3 N 4 Calcining the mixture for 5 hours in a tube furnace at the temperature of 600 ℃ under the atmosphere of argon to obtain carbon nitride (V) rich in nitrogen vacancies N -CN)。
(3) 0.1g of the resulting nitrogen vacancy-containing carbon nitride (V) N -CN) was added to a mixed solution of 20mL of water and 50mL of ethanol, and then 1m mol of sodium hypophosphite (NaH) was added thereto, respectively 2 PO 2 ·H 2 O), thiourea (CH) 4 N 2 S) and boric acid (H) 3 BO 3 ) Ultrasonic dispersion, oil is left at 90 ℃ for 2h, and then the mixture is transferred into a liner of a 100mL polytetrafluoroethylene high-pressure reaction kettle for hydrothermal treatment at 160 ℃ for 5h. Washing with anhydrous ethanol and distilled water for 3 times, respectively, drying at 70 deg.C to obtain nitrogen vacancy-backfilled carbon nitride (P, S, B) Rf /S Rf /B Rf -V N -CN)。
The invention has the advantages that
1. Nonmetal P, nonmetal S and nonmetal B are adopted for backfilling, and the photocatalytic hydrogen production effect of the whole system is promoted. The raw materials are cheap and easy to obtain, and the cost is reduced.
2. The backfill can stabilize the nitrogen vacancy on the surface of the carbon nitride, so that the material keeps better stability.
3. The introduction of heteroatoms may make the electrons more prone to flow to the heteroatoms, thereby facilitating carrier separation.
Drawings
FIG. 1 (a) shows CN in example 1 and V in examples 5 to 8 N -CN,P Rf -V N -CN,S Rf -V N -CN and B Rf -V N XRD pattern of-CN, no significant change in characteristic peaks of carbon nitride was observed, FIG. 1 (B) is a partial enlarged view of FIG. 1 (a) showing that XRD peaks shifted to high angles after formation of N-vacancies and further shifted to high angles after P, S, B backfilling. The layer spacing is illustrated as shrinking.
FIGS. 2a-e show CN in example 1 and V in examples 5-8 N -CN,P Rf -V N -CN,S Rf -V N -CN and B Rf -V N -SEM picture of CN; f-j CN in example 1 and V in examples 5 to 8 N -CN,P Rf -V N -CN,S Rf -V N -CN and B Rf -V N TEM image of-CN. CN is in a multilayer sheet structure, and the sheet becomes thin after secondary calcination to form a plurality of small fragments.
FIG. 3 shows CN in example 1 and V in examples 5 to 8 N -CN,P Rf -V N -CN,S Rf -V N -CN and B Rf -V N The EPR diagram of-CN shows that the EPR signal after the secondary calcination is obviously enhanced, which indicates the formation of N vacancy, the EPR signal strength is weakened after the backfilling of P, S and B, and the sequence is P in sequence Rf -V N CN is greater than S Rf -V N -CN is greater than B Rf -V N -CN. A weakening of the EPR signal indicates successful backfilling of the element.
FIG. 4 (a) shows NiCo as a sample in examples 1 to 8 2 O 4 The figure (b) is a photocatalytic hydrogen production performance graph of the cocatalyst, and a photocatalytic hydrogen production cycle test graph of example 8. As can be seen from the figure, after the N vacancies are prepared, the photocatalytic hydrogen production activity of the sample is increased, and the performance of the sample is greatly increased after the P, S and B are backfilled. Wherein B is Rf -V N The hydrogen-generating activity of-CN is V N 7.2 times CN, 10.3 times CN, and remains stable after 20 hours of cycling.
Detailed Description
The present invention is further described in detail below with reference to examples.
Example 1
Putting 3.0g of melamine into a 50mL crucible, and calcining for 4h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 。
0.1g of the resulting g-C 3 N 4 Adding the mixture into a mixed solution of 20mL of water and 50mL of ethanol, performing ultrasonic dispersion, transferring the mixture into a liner of a 100mL polytetrafluoroethylene high-pressure reaction kettle after 2 hours of oil bath at 90 ℃, and performing hydrothermal treatment at 160 ℃ for 5 hours. Washing with anhydrous ethanol and distilled water for 3 times, respectively, and drying at 70 deg.C to obtain control group Carbon Nitride (CN).
Example 2
Putting 3.0g of melamine into a 50mL crucible, and calcining for 4h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 。
0.1g of the resulting g-C 3 N 4 Adding into a mixed solution of 20mL of water and 50mL of ethanol, and adding 1m mol of sodium hypophosphite (NaH) 2 PO 2 ·H 2 O) ultrasonic dispersion, transferring the mixture into a lining of a 100mL polytetrafluoroethylene high-pressure reaction kettle after oil is rich at 90 ℃ for 2 hours, and carrying out hydrothermal treatment at 160 ℃ for 5 hours. Washing with anhydrous ethanol and distilled water for 3 times, and drying at 70 deg.C to obtain P-doped carbon nitride (P-CN).
Example 3
Putting 3.0g of melamine into a 50mL crucible, and calcining for 4h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 。
0.1g of the resulting g-C 3 N 4 To a mixed solution of 20mL of water and 50mL of ethanol was added 1m mol of thiourea (CH) 4 N 2 S) ultrasonic dispersion, transferring the mixture into a lining of a 100mL polytetrafluoroethylene high-pressure reaction kettle after oil is rich at 90 ℃ for 2 hours, and performing hydrothermal treatment at 160 ℃ for 5 hours. Washing with anhydrous ethanol and distilled water for 3 times, and drying at 70 deg.C to obtain S-doped carbon nitride (S-CN).
Example 4
Putting 3.0g of melamine into a 50mL crucible, and calcining for 4h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 。
0.1g of the resulting g-C 3 N 4 To a mixed solution of 20mL of water and 50mL of ethanol was added 1m mol of boric acid (H) 3 BO 3 ) Ultrasonic dispersion, oil is left for 2h at 90 ℃, and then the mixture is transferred into a lining of a 100mL polytetrafluoroethylene high-pressure reaction kettle for hydrothermal reaction for 5h at 160 ℃. Washing with anhydrous ethanol and distilled water for 3 times respectively, and drying at 70 deg.C to obtain B-doped carbon nitride (B-CN).
Example 5
Putting 3.0g of melamine into a 50mL crucible, and calcining for 4h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 。
0.3g of g-C prepared above was weighed 3 N 4 And calcining the mixture for 5 hours in a tubular furnace at the temperature of 600 ℃ under the atmosphere of argon to obtain the carbon nitride rich in nitrogen vacancies.
0.1g of the nitrogen vacancy-rich carbon nitride is added into a mixed solution of 20mL of water and 50mL of ethanol for ultrasonic dispersion, and the mixture is transferred into a liner of a 100mL polytetrafluoroethylene high-pressure reaction kettle for hydrothermal treatment at 160 ℃ for 5 hours after being oil-rich at 90 ℃ for 2 hours. Washing with anhydrous ethanol and distilled water for 3 times, and drying at 70 deg.C to obtain control group nitrogen vacancy carbon nitride (V) N -CN)。
Example 6
Putting 3.0g of melamine into a 50mL crucible, and calcining for 4h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 。
0.3g of g-C prepared above was weighed 3 N 4 And calcining the mixture for 5 hours in a tubular furnace at the temperature of 600 ℃ under the atmosphere of argon to obtain the carbon nitride rich in nitrogen vacancies.
0.1g of the resulting nitrogen vacancy-rich carbon nitride was added to a mixed solution of 20mL of water and 50mL of ethanol, and 1m mol of sodium hypophosphite (NaH) was added 2 PO 2 ·H 2 O) ultrasonic dispersion, transferring the mixture into a lining of a 100mL polytetrafluoroethylene high-pressure reaction kettle after oil is rich at 90 ℃ for 2 hours, and carrying out hydrothermal treatment at 160 ℃ for 5 hours. Washing with anhydrous ethanol and distilled water for 3 times, respectively, and drying at 70 deg.C to obtain P-doped carbon nitride (P) Rf -V N -CN)。
Example 7
Putting 3.0g of melamine into a 50mL crucible, and calcining for 4h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 。
Weighing0.3g of g-C prepared as described above 3 N 4 And calcining the mixture for 5 hours in a tubular furnace at the temperature of 600 ℃ under the atmosphere of argon to obtain the carbon nitride rich in nitrogen vacancies.
0.1g of the resulting nitrogen vacancy-rich carbon nitride was added to a mixed solution of 20mL of water and 50mL of ethanol, and 1m mol of thiourea (CH) was added 4 N 2 S) ultrasonic dispersion, transferring the mixture into a lining of a 100mL polytetrafluoroethylene high-pressure reaction kettle after oil is rich at 90 ℃ for 2h, and carrying out hydrothermal treatment at 160 ℃ for 5h. Washing with anhydrous ethanol and distilled water for 3 times, respectively, and drying at 70 deg.C to obtain S-doped carbon nitride (S) Rf -V N -CN)。
Example 8
Putting 3.0g of melamine into a 50mL crucible, and calcining for 4h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 。
0.3g of g-C prepared above was weighed 3 N 4 And calcining the mixture for 5 hours in a tubular furnace at the temperature of 600 ℃ under the atmosphere of argon to obtain the carbon nitride rich in nitrogen vacancies.
0.1g of the resulting nitrogen vacancy-rich carbon nitride was added to a mixed solution of 20mL of water and 50mL of ethanol, and 1m mol of boric acid (H) was added 3 BO 3 ) Ultrasonic dispersion, oil is left for 2h at 90 ℃, and then the mixture is transferred into a lining of a 100mL polytetrafluoroethylene high-pressure reaction kettle for hydrothermal reaction for 5h at 160 ℃. Washing with anhydrous ethanol and distilled water for 3 times, respectively, and drying at 70 deg.C to obtain B-doped carbon nitride (B) Rf -V N -CN)。
Experiment and data
The activity investigation method for photocatalytic hydrogen production provided by the invention comprises the following steps:
the reaction system was evacuated to a pressure of about-0.13 MPa. Specifically, 20mg of catalyst, 90mL of distilled water, and 10mL of triethanolamine were added simultaneously to the reactor. Triethanolamine is used as a sacrificial agent. In the whole process, ar is used as H 2 And (4) precipitated carrier gas. The sample in the reactor was irradiated using a 300W Xe lamp with an AM 1.5 filter as a light source, taken every 0.5H, and the collected H was monitored by gas chromatography 2 The total reaction time was 4h.
Claims (8)
1. A non-metallic element P, S,b backfill V N The preparation method and application of the-CN are characterized in that the carbon nitride containing a large number of nitrogen vacancies is firstly prepared, and then sodium hypophosphite (NaH) is respectively added 2 PO 2 •H 2 O), thiourea (CH) 4 N 2 S) and boric acid (H) 3 BO 3 ) Ultrasonic dispersing, oil-rich treating, hydrothermal treating in high pressure PTFE reactor, washing, and drying to obtain P, S and B nitrogen vacancy-backfilled carbon nitride (P) Rf /S Rf /B Rf -V N The backfill of P, S and B can effectively stabilize nitrogen vacancies on the surface of carbon nitride, and simultaneously, the introduction of heteroatoms changes the charge density of surrounding atoms, promotes the separation of photon-generated carriers, and shows higher activity and stability in the aspect of photolysis of water to produce hydrogen, and the method specifically comprises the following steps:
the first step is as follows: putting a certain amount of melamine into a crucible, and putting the crucible into a muffle furnace for calcining to obtain g-C 3 N 4 ；
The second step is that: weighing a certain amount of the above prepared g-C 3 N 4 Calcining in a tube furnace in argon atmosphere to obtain carbon nitride (V) rich in nitrogen vacancy N -CN）；
The third step: a certain amount of the obtained nitrogen vacancy-containing carbon nitride (V) N -CN) is added into the mixed solution of water and ethanol, and sodium hypophosphite (NaH) is added respectively 2 PO 2 •H 2 O), thiourea (CH) 4 N 2 S) and boric acid (H) 3 BO 3 ) Ultrasonic dispersing, transferring into polytetrafluoroethylene high-pressure reactor liner for hydrothermal treatment after oil is rich, washing and drying to obtain P, S and B nitrogen vacancy backfilled carbon nitride (P) Rf /S Rf /B Rf -V N -CN）。
2. The preparation method and application of nonmetallic element P, S, B backfill nitrogen vacancy carbon nitride according to claim 1 are characterized in that: in the first step, melamine was added in an amount of 3.0g, at a calcination temperature of 550 ℃ for a time of 4h.
3. According to the rightThe preparation method and application of nonmetallic element P, S, B backfill nitrogen vacancy carbon nitride according to claim 1 are characterized in that: in the second step, g-C 3 N 4 The amount of (2) is 0.3g, the calcination temperature is 600 ℃ and the calcination time is 5h.
4. The preparation method and application of nonmetallic element P, S, B backfill nitrogen vacancy carbon nitride according to claim 1 are characterized in that: in the third step, nitrogen vacancy carbon nitride (V) N -CN) in an amount of 0.1g, sodium hypophosphite (NaH) 2 PO 2 •H 2 O), thiourea (CH) 4 N 2 S) and boric acid (H) 3 BO 3 ) The addition amounts of (A) and (B) were all 1 mmol.
5. The preparation method and application of nonmetallic element P, S, B backfilled nitrogen vacancy carbon nitride as claimed in claim 1, characterized in that: in the third step, the ratio of water to ethanol was 2:5 (water: 20mL, ethanol 50 mL).
6. The preparation method and application of nonmetallic element P, S, B backfill nitrogen vacancy carbon nitride according to claim 1 are characterized in that: in the third step, the oil bath temperature is 90 ℃ and the reaction time is 2 h.
7. The preparation method and application of nonmetallic element P, S, B backfill nitrogen vacancy carbon nitride according to claim 1 are characterized in that: in the third step, the hydrothermal temperature is 160 ℃ and the reaction time is 5h.
8. The preparation method and application of nonmetallic element P, S, B backfilled nitrogen vacancy carbon nitride as claimed in claim 1, characterized in that: the material can be used for simulating photocatalytic decomposition of water under sunlight to produce hydrogen.
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