CN115920945A - Hydroxyl graphite phase carbon nitride photocatalyst and preparation method and application thereof - Google Patents
Hydroxyl graphite phase carbon nitride photocatalyst and preparation method and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention belongs to the technical field of nano photocatalytic materials, and particularly relates to a hydroxyl graphite phase carbon nitride photocatalyst as well as a preparation method and application thereof. The invention adopts ethanol and glycerol to react graphite-phase carbon nitride g-C 3 N 4 Surface hydroxylation modification, g-C obtained by this process 3 N 4 OH represents larger specific surface area, wherein hydroxyl can promote the transmission and separation of photogenerated electrons and improve the utilization efficiency of photogenerated charges, and more importantly, the hydroxyl can reduce g-C 3 N 4 The oxidation-reduction reaction energy barrier on the surface is favorable for realizing the hydrogen production by photocatalytic water decomposition compared with g-C 3 N 4 PhotocatalystSaid g-C 3 N 4 the-OH photocatalyst has more efficient activity of photocatalytic decomposition of seawater to produce hydrogen. The preparation method is simple, strong in operability and good in repeatability, can be used for carrying out amplification production, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of nano photocatalytic materials, and particularly relates to a hydroxyl graphite phase carbon nitride photocatalyst as well as a preparation method and application thereof.
Background
The shortage of fossil fuels and the environmental pollution are becoming more serious, and attention is paid to the development of new pollution-free sustainable energy. Due to the characteristics of high energy density and environmental friendliness, hydrogen gas has great potential in replacing fossil fuel energy sources. Current hydrogen storage materials mainly include: hydrogen-containing compounds (e.g. NaBH) 4 Hydrazine hydrate, organic hydrogen-containing compounds) and water, which are sources from which hydrogen gas is obtained. Hydrogen energy, as a secondary energy source, needs to be extracted by a hydrogen production technology. According to the production source of hydrogen energy and the discharge condition in the production process, people call the hydrogen energy as grey hydrogen, blue hydrogen and green hydrogen respectively. Wherein, the ash hydrogen is hydrogen generated by burning fossil fuel, carbon dioxide and the like are discharged in the production process, and the yield of the ash hydrogen accounts for about 95 percent of the global hydrogen yield; blue hydrogen is prepared from fossil fuels such as coal or natural gas, carbon dioxide byproducts are captured, utilized and stored ((Carbon Capture, deactivation and Storage, CCUS for short) in the preparation process of the blue hydrogen so as to realize Carbon neutralization, wherein the natural gas and the coal also belong to the fossil fuels and can generate greenhouse gases when the blue hydrogen is produced, but due to the use of advanced technologies such as the CCUS, the greenhouse gases are captured, the influence on the global environment is reduced, and low-emission production is realized.
N-type semiconductor TiO was discovered by Fujishima and Honda as early as 1972 2 Photoelectrocatalytic water decomposition hydrogen production (Electrochemical phos)Catalysis of water at a semiconductor electrode, nature,1972, 238,37-38), can utilize solar energy to achieve semiconductor-based photocatalytic hydrogen production, and this strategy has been considered to be the most effective approach to solving the current world energy problem. The key to the implementation of this strategy is the development of photocatalysts with highly efficient and stable photocatalytic performance.
In the photocatalyst, graphite phase carbon nitride (g-C) 3 N 4 ) The photocatalyst has the advantages of proper energy band position, chemical stability, good visible light response range and the like, and is widely used in the field of photocatalytic conversion; but g-C of bulk phase 3 N 4 The defects of small surface area, rapid recombination of photogenerated electron-hole pairs and the like exist, and the practical application of the photogenerated electron-hole pairs is severely limited. Many researchers have been working on finding efficient ways to modify g-C 3 N 4 For example: multiple thermal polycondensation processes (engineering of crystalline carbon nitride by defect engineering, chemSusChem,2019,12, 3257-3262), thermal polycondensation of different N-rich precursors (Synthesis of crystalline carbon nitride direct polymerization using differential precursors and applications in lithium-sulfur batteries, applied. PhysMa mater, 2018,124, 758), element doping (photoelecric and electrochemical reactions of polymeric C substrates) 3 N 4 and O-modified C 3 N 4 embedded for selective photosynthetical oxidation of alcohols to alcohols, total, 2019,328, 21-28) and morphology control (phosphorous-gated carbon nitride tubes with a layered micro-nano structure for enhanced visual-light photosynthetical hydrogen evolution, image.chem.int.ed., 2016,55, 1830-1834). Visible, porous g-C 3 N 4 Can increase the specific surface area and shorten the transmission distance of photogenerated carriers, but the g-C 3 N 4 The affinity between the photocatalyst and the reactant has been neglected and especially the bottleneck of low separation efficiency of the photo-generated carriers has not been solved.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the existing g-C 3 N 4 The defects and defects of low separation efficiency of photo-generated carriers, slow surface oxidation-reduction reaction kinetics and low photocatalysis efficiency of the photocatalyst provide a graphite-phase carbon nitride photocatalyst (g-C) which is rich in hydroxyl, porous, high in specific surface area, low in photo-generated charge recombination efficiency, low in cost and high in catalytic activity 3 N 4 -OH) is disclosed.
The invention aims to provide g-C prepared by the preparation method 3 N 4 -OH。
It is another object of the present invention to provide said g-C 3 N 4 Application of-OH in hydrogen production by photocatalytic water decomposition.
The above purpose of the invention is realized by the following technical scheme:
g-C 3 N 4 -OH photocatalyst, comprising the steps of:
g to C 3 N 4 Dispersing the nano-sheets in ethanol and glycerol, carrying out complete solvothermal reaction at 160-200 ℃, and carrying out post-treatment to obtain the nano-sheet.
The invention utilizes ethanol and glycerol to react g-C 3 N 4 Surface polarization to obtain g-C 3 N 4 the-OH not only exhibits a larger specific surface area, but also the hydroxyl group (-OH) therein can form an induced electric field in the surface region and raise the band gap edge, thereby improving the charge separation efficiency. In addition, the presence of-OH promotes the kinetics of the oxidation reaction of water, and therefore, with ordinary g-C 3 N 4 Comparative example g-C 3 N 4 The separation efficiency of photogenerated charges in-OH is high, the surface oxidation capacity is strong, and the enhanced activity of photocatalytic decomposition of water to produce hydrogen is shown.
Preferably, the volume ratio of the ethanol to the glycerol is 3:1-1:3.
Preferably, the solvothermal reaction is completed for 2 to 48 hours.
Further, the g-C 3 N 4 The nano-sheet is prepared by a conventional method or obtained by purchasing.
Preferably, said g-C 3 N 4 The nano-sheet is obtained by calcining urea at 450-560 ℃ for 2-5 h.
More preferably, said g-C 3 N 4 The nano-sheet is obtained by calcining urea at 550 ℃ for 2 h.
Further, the post-treatment includes cooling, centrifugation, washing and drying.
Still further, the drying is freeze drying.
Specifically, the post-treatment operation comprises the steps of naturally cooling the completely reacted substances to room temperature, centrifuging, thoroughly washing with deionized water, and freeze-drying to obtain the g-C 3 N 4 -OH。
The invention also provides g-C prepared by the preparation method 3 N 4 -OH。
In addition, the present invention also provides said g-C 3 N 4 Application of-OH in photocatalytic water hydrogen production. g-C 3 N 4 the-OH in the process of catalyzing water to produce hydrogen relates to the adsorption-dissociation process of water molecules on the surface of a catalyst, g-C 3 N 4 the-OH surface has a large number of hydroxyl groups, and the hydroxyl groups have hydrophilicity, so that the adsorption of water molecules on the surface is facilitated, and the water decomposition hydrogen production process is promoted.
Further, the photocatalytic hydrogen production requires the addition of a Pt metal catalyst as a promoter.
Preferably, the Pt metal catalyst includes chloroplatinic acid, platinum dichloride, and platinum nitrate. In the photocatalytic process, g-C 3 N 4 the-OH absorbs light to generate reducing photoelectrons, and the photoelectrons reduce platinum ions in the Pt metal catalyst to form g-C 3 N 4 And a Pt atom is used as an active site for photocatalytic water decomposition to produce hydrogen. While conventional Pt modified g-C 3 N 4 The composite photocatalyst has the structure that Pt nano particles are loaded on g-C 3 N 4 The Pt nanoparticles participating in the reaction.
More preferably, the Pt metal catalyst is chloroplatinic acid.
The invention has the following beneficial effects: the invention adopts ethanol and glycerol to g-C 3 N 4 Subjected to surface hydroxylation modification, and the methodg-C of 3 N 4 the-OH photocatalyst shows larger specific surface area, wherein hydroxyl (-OH) can promote the transmission and separation of photo-generated electrons and improve the utilization efficiency of photo-generated charges, and more importantly, the hydroxyl can reduce g-C 3 N 4 The oxidation-reduction reaction energy barrier on the surface is favorable for realizing the hydrogen production by decomposing water by photocatalysis compared with g-C 3 N 4 A photocatalyst of said g-C 3 N 4 the-OH photocatalyst has more efficient hydrogen production activity by photocatalytic decomposition of seawater. The preparation method is simple, strong in operability and good in repeatability, can be used for carrying out amplification production, and has a good application prospect.
Drawings
FIG. 1 is g-C prepared in comparative example 1 3 N 4 And g-C prepared in example 1 3 N 4 XRD pattern of-OH.
FIG. 2 is g-C prepared in comparative example 1 3 N 4 SEM image of (d).
FIG. 3 is g-C prepared in example 3 3 N 4 SEM image of-OH.
FIG. 4 is g-C prepared in comparative example 1 3 N 4 And g-C prepared in example 2 3 N 4 -infrared spectrum of OH.
FIG. 5 is g-C prepared in comparative example 1 3 N 4 And g-C prepared in example 1 3 N 4 -fluorescence emission spectrum of OH.
FIG. 6 is g-C prepared in comparative example 1 3 N 4 And g-C prepared in example 3 3 N 4 -photocurrent response plot of OH.
FIG. 7 is g-C prepared in comparative example 1 3 N 4 And g-C prepared in example 2 3 N 4 -electrocatalytic hydrogen evolution polarization diagram of OH.
FIG. 8 is g-C prepared in comparative example 1 3 N 4 And g-C prepared in examples 1, 2 and 3, respectively 3 N 4 Accumulation curve of total hydrogen production of-OH photocatalyst along with illumination time.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
The specific test method for characterization and performance test of the photocatalyst refers to the following steps:
(1) The instrument used for the analysis of the Scanning Electron Microscope (SEM) is a JSM-6700F type scanning electron microscope of Japan electronic company to observe the microscopic morphology of the surface of a sample, the sample is fixed on a sample table by conductive adhesive, and the microscopic morphology is directly observed after gold plating treatment, and the accelerating voltage is 2-20 kV.
(2) The apparatus used for photoluminescence spectroscopy (PL) was an Shimadzu RF-6000 spectrofluorometer, and the powder samples were pressed between two parallel pieces of quartz glass and placed on a sample-carrying stage. The excitation wavelength is set to 380nm, and the scanning wavelength range is 400-800 nm.
(3) The apparatus used for XRD analysis is Rigaku Ultima type IV X-ray diffractometer (XRD) for characterizing the crystalline phase structure material of the prepared final product. The test conditions are Cu target, K alpha radiation, 40kV,40mA, step width of 0.02 degree and scanning range of 10-80 degrees. The sample is powder and is placed in a groove of a sample table to be flattened, and direct detection is carried out.
(4) Preparing a working electrode: mu.L of Nafion (5 wt%) solution and 5.0mg of photocatalyst were added to 1.0mL of ethanol, and ultrasonically dispersed to obtain a suspension. 100 mul of the suspension was drop coated onto an FTO conductive glass substrate (2X 1 cm) 2 ) And naturally drying, and annealing at 150 ℃ for 60min in an argon atmosphere to obtain the working electrode.
(5) Photoelectrochemical tests were carried out on an electrochemical workstation (CHI 650E) equipped with a three-electrode system, with a platinum electrode and an Ag/AgCl (saturated KCl) electrode as counter and reference electrodes, respectively. With 0.5M Na 2 SO 4 The solution serves as an electrolyte. A300W xenon lamp is used as a light source, and a transient photocurrent curve (i-t) under bias voltage is recorded. At a scanning rate of 5mV s -1 In Na 2 SO 4 Testing polarization curves of electrocatalytic Hydrogen Evolution Reaction (HER) in solutionA wire.
(6) The photocatalytic water decomposition reaction is carried out in a Labsolar 6A photocatalytic reaction system (Beijing Pofely), and the whole system can be communicated with a vacuum pump. Adding 20mg of photocatalyst into a reactor filled with 100mL of seawater, carrying out ultrasonic dispersion for 3min, then adding 0.5mg of chloroplatinic acid, and uniformly stirring. The reactor was connected to the system and sealed, the whole system was evacuated to 2.0kPa by means of a vacuum pump, the reactor was kept at a constant temperature by means of 15 ℃ condensate water, and the suspension in the reactor was kept in suspension by means of magnetic stirring. The reactor is of a top-illuminated type, a 300W xenon lamp is used as a light source, the input voltage is 220V, and the current is 15A. After the reaction starts, sampling one sample every 60min by an automatic sampling system, and sending the sample into an online gas chromatograph to detect H generated by the reaction 2 。
Example 1A g-C 3 N 4 Preparation method of-OH photocatalyst
g-C 3 N 4 A method for preparing an-OH photocatalyst, comprising the steps of:
adding 50.0g of urea into a crucible with a cover and a volume of 100mL, and reacting for 2h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 Nanosheets. Mixing 0.5g g-C 3 N 4 Dispersing the nanosheets in a Teflon stainless steel autoclave containing 30mL of ethanol and 10mL of glycerol, carrying out heat treatment on the nanosheets in a solvent at 180 ℃ for 4h, naturally cooling to room temperature, centrifuging, then thoroughly cleaning with deionized water, and carrying out freeze drying to finally obtain g-C 3 N 4 -OH。
Example 2A g-C 3 N 4 Preparation method of-OH photocatalyst
g-C 3 N 4 A method for preparing an-OH photocatalyst, comprising the steps of:
50.0g of urea was added to a crucible having a cover and a volume of 100mL, and reacted at 550 ℃ in a muffle furnace for 2 hours to obtain g-C 3 N 4 Nanosheets. Mixing 0.5g g-C 3 N 4 Dispersing the nano-sheets in a Teflon stainless steel autoclave containing 30mL of ethanol and 10mL of glycerol, carrying out heat treatment on the nano-sheets in a solvent at 160 ℃ for 4h, naturally cooling to room temperature, centrifuging, then thoroughly cleaning with deionized water, and carrying out freeze drying to finally obtain g-C 3 N 4 -OH。
Example 3A g-C 3 N 4 Preparation method of-OH photocatalyst
g-C 3 N 4 A method for preparing an-OH photocatalyst, comprising the steps of:
adding 50.0g of urea into a crucible with a cover and a volume of 100mL, and reacting for 2h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 Nanosheets. Mixing 0.5g g-C 3 N 4 Dispersing the nanosheets in a Teflon stainless steel autoclave containing 30mL of ethanol and 10mL of glycerol, carrying out heat treatment on the nanosheets in a solvent at 180 ℃ for 20 hours, naturally cooling to room temperature, centrifuging, then thoroughly washing with deionized water, and carrying out freeze drying to finally obtain g-C 3 N 4 -OH。
Example 4A g-C 3 N 4 Preparation method of-OH photocatalyst
g-C 3 N 4 A method for preparing an-OH photocatalyst, comprising the steps of:
adding 50.0g of urea into a crucible with a cover and a volume of 100mL, and reacting for 2h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 A nanosheet. Mixing 0.5g g-C 3 N 4 Dispersing the nanosheets in a Teflon stainless steel autoclave containing 10mL of ethanol and 30mL of glycerol, carrying out heat treatment on the nanosheets in a solvent at 200 ℃ for 2 hours, naturally cooling to room temperature, centrifuging, then thoroughly washing with deionized water, and carrying out freeze drying to finally obtain g-C 3 N 4 -OH。
Example 5a g-C 3 N 4 Preparation method of-OH photocatalyst
g-C 3 N 4 -OH photocatalyst, comprising the steps of:
50.0g of urea was added to a crucible having a cover and a volume of 100mL, and reacted at 550 ℃ in a muffle furnace for 2 hours to obtain g-C 3 N 4 Nanosheets. Mixing 0.5g g-C 3 N 4 Dispersing the nano-sheets in a Teflon stainless steel autoclave containing 20mL of ethanol and 20mL of glycerol, carrying out heat treatment on the nano-sheets in a solvent at 160 ℃ for 48h, naturally cooling to room temperature, centrifuging, then thoroughly cleaning with deionized water, and carrying out freeze drying to finally obtain g-C 3 N 4 -OH。
Comparative example 1 a g to C 3 N 4 Method for preparing photocatalyst
g-C 3 N 4 The preparation method of the photocatalyst comprises the following steps:
adding 50.0g of urea into a crucible with a cover and a volume of 100mL, and reacting for 2h at 550 ℃ in a muffle furnace to obtain g-C 3 N 4 Nanosheets.
Experimental examples characterization and Performance testing of photocatalysts
Determination of g-C from comparative example 1 3 N 4 And g-C prepared in example 1 3 N 4 XRD pattern of-OH, results are shown in FIG. 1, g-C 3 N 4 The XRD data of (a) shows two strong diffraction peaks at 13.3 deg. and 27.6 deg. respectively, which correspond to g-C respectively 3 N 4 The (111) and (002) crystal planes of (a). After solvothermal treatment, g-C 3 N 4 XRD pattern of-OH and g-C 3 N 4 The XRD pattern of the compound has no obvious change, which shows that the g-C is not changed during the solvent heat treatment process 3 N 4 The crystal structure of (1). g-C prepared in examples 2 to 5 3 N 4 -OH has an XRD pattern substantially consistent with example 1.
Determination of g-C from comparative example 1 3 N 4 And g-C prepared in example 3 3 N 4 SEM pictures of-OH, the results are shown in FIGS. 2 and 3, respectively, and it is apparent that g-C was obtained 3 N 4 Is in the form of nano-flakes, the surface of which is relatively smooth, and g-C 3 N 4 OH is also in the form of nanoplatelets, but its surface is associated with g-C 3 N 4 Compared to being slightly rough, has more fine pores and thus has a larger specific surface area. g-C prepared in examples 1, 2, 4 and 5 3 N 4 The — OH had a SEM morphology substantially consistent with example 3.
Determination of g-C from comparative example 1 3 N 4 And g-C prepared in example 2 3 N 4 IR spectrum of-OH, results are shown in FIG. 4, and g-C 3 N 4 Comparative example g-C 3 N 4 OH at 3325cm -1 The intensity of the characteristic peak of hydroxyl group is higher, which indicates that the solvothermal process causes g-C 3 N 4 The surface of the-OH groups is grafted with hydroxyl groups. g-C prepared in examples 1, 3, 4 and 5 3 N 4 the-OH has an infrared spectrum which is basically consistent with that of the example 2, and the intensities of characteristic peaks of hydroxyl groups at corresponding positions are all stronger than those of g-C 3 N 4 。
Determination of g-C from comparative example 1 3 N 4 And g-C prepared in example 1 3 N 4 Fluorescence emission spectrum of-OH, shown in FIG. 5, with g-C 3 N 4 In contrast, g-C 3 N 4 The fluorescence emission peak intensity of-OH at 465nm is obviously reduced, which indicates that g-C 3 N 4 The photoproduction electron-hole separation efficiency of-OH is higher than that of g-C 3 N 4 . g-C prepared in examples 2 to 5 3 N 4 OH has a fluorescence emission spectrum substantially in accordance with example 1.
Determination of g-C from comparative example 1 3 N 4 And g-C prepared in example 3 3 N 4 Photocurrent response curve of-OH, results are shown in FIG. 6, g-C 3 N 4 Photocurrent density ratio of-OH g-C 3 N 4 Large, this indicates g-C 3 N 4 The hydroxyl on the-OH surface can accelerate charge transfer and improve the utilization efficiency of photo-generated electrons. g-C prepared in examples 1, 2, 4 and 5 3 N 4 OH has a photocurrent response curve substantially consistent with that of example 3, with a photocurrent density to g-C ratio 3 N 4 Is large.
Determination of g-C from comparative example 1 3 N 4 And g-C prepared in example 2 3 N 4 The polarization curve of electrocatalytic hydrogen evolution of-OH is shown in FIG. 7, compared to g-C 3 N 4 ，g-C 3 N 4 The hydrogen evolution overpotential of-OH becomes smaller, which says that g-C 3 N 4 The surface hydroxyl groups can reduce the potential barrier of the hydrogen evolution reaction and promote the hydrogen evolution reaction. g-C prepared in examples 1, 3, 4 and 5 3 N 4 the-OH has electrocatalytic hydrogen evolution polarization curve data substantially consistent with example 2, and hydrogen evolution overpotentials are all less than g-C 3 N 4 。
Determination of g-C from comparative example 1 3 N 4 And g-C prepared in examples 1 to 3 3 N 4 The accumulation curve of the total hydrogen production amount of-OH along with the illumination time shows that the result is shown in figure 8, and g-C is obtained after 3 hours of illumination 3 N 4 The total hydrogen production of the photocatalyst was 100.3. Mu. Mol/h. g-C prepared in examples 1 to 3 under the same conditions 3 N 4 The total hydrogen production of the-OH photocatalyst is 443.2, 215.6 and 311.25 mu mol/h respectively, and the hydrogen production and g-C 3 N 4 Compared with the prior art, particularly the g-C prepared in example 1 3 N 4 The hydrogen production rate of the-OH photocatalyst is g-C 3 N 4 4.42 times of the photocatalyst. This result demonstrates that surface hydroxyls can effectively increase g-C 3 N 4 The photocatalytic hydrogen evolution rate. g-C prepared in examples 4 and 5 3 N 4 The total hydrogen yield of the-OH photocatalyst is more than g-C 3 N 4 A photocatalyst.
In conclusion, the invention synthesizes hydroxyl-rich porous g-C by a simple method 3 N 4 -OH. g-C with reference 3 N 4 Comparison of samples, g-C 3 N 4 OH represents a larger specific surface area and a lower photogenerated charge recombination rate. g-C of supported Pt cocatalyst under irradiation of ultraviolet and visible light 3 N 4 The rate of hydrogen evolution from seawater by photocatalytic decomposition of-OH is as high as 148.2 mu mol/g/h. g-C under the same conditions 3 N 4 Almost has no activity of decomposing seawater by photocatalysis to generate hydrogen.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. g-C 3 N 4 A method for preparing an-OH photocatalyst, comprising the steps of:
g to C 3 N 4 Dispersing the nano-sheets in ethanol and glycerol, carrying out complete solvothermal reaction at 160-200 ℃, and carrying out post-treatment to obtain the nano-sheet.
2. The method according to claim 1, wherein the volume ratio of ethanol to glycerin is 3:1 to 1:3.
3. The method according to claim 1, wherein the solvothermal reaction is completed for 2 to 48 hours.
4. The method according to claim 1, wherein the g-C is 3 N 4 The nano-sheet is obtained by calcining urea at 450-560 ℃ for 2-5 h.
5. The method of claim 1, wherein the post-processing comprises cooling, centrifuging, washing, and drying.
6. The method of claim 1, wherein the drying is freeze-drying.
7. g-C obtained by the production method according to any one of claims 1 to 6 3 N 4 -OH photocatalyst.
8. g-C as claimed in claim 7 3 N 4 Application of-OH photocatalyst in photocatalytic water hydrogen production.
9. The application of claim 8, wherein the photocatalytic water hydrogen production requires the addition of a Pt metal catalyst as a promoter.
10. The use of claim 9, wherein the Pt metal catalyst comprises chloroplatinic acid, platinum dichloride, and platinum nitrate.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607228A (en) * | 2015-01-23 | 2015-05-13 | 哈尔滨工业大学 | Preparation method for alpha-Fe2O3 quantum dot/nitrogen-doped graphene composite material |
| US20160045908A1 (en) * | 2014-08-14 | 2016-02-18 | Council Of Scientific & Industrial Research | CuO - TiO2 NANOCOMPOSITE PHOTOCATALYST FOR HYDROGEN PRODUCTION, PROCESS FOR THE PREPARATION THEREOF |
| CN108927101A (en) * | 2018-07-06 | 2018-12-04 | 济南大学 | A kind of acicular nanometer FeOOH adsorbent and preparation method thereof |
| US20190321805A1 (en) * | 2018-04-23 | 2019-10-24 | King Abdulaziz University | Multi-walled carbon nanotube nanocomposite for hydrogen production |
| CN111333127A (en) * | 2020-03-05 | 2020-06-26 | 西北工业大学 | Hierarchical porous honeycomb nickel oxide microsphere and preparation method thereof |
| CN112090440A (en) * | 2020-09-22 | 2020-12-18 | 海南师范大学 | Oxygen-deficient titanium dioxide material of composite hydroxylated carbon nitride and preparation method thereof |
| CN112517043A (en) * | 2020-12-17 | 2021-03-19 | 中南大学 | Nitrogen vacancy and hydroxyl synergistically modified graphite-phase carbon nitride photocatalyst, preparation method thereof and application thereof in photocatalytic hydrogen production |
| CN113731466A (en) * | 2021-08-31 | 2021-12-03 | 岭南师范学院 | MoC/N-dot carbon/g-C3N4Composite photocatalyst and preparation and application thereof |
| CN114011440A (en) * | 2021-11-18 | 2022-02-08 | 三峡大学 | Preparation method of high-hydrophilicity bismuth oxybromide photocatalyst |
| CN114570424A (en) * | 2022-03-30 | 2022-06-03 | 东北石油大学 | Double-modified carbon nitride and preparation method and application thereof |
| CN114713264A (en) * | 2022-05-06 | 2022-07-08 | 重庆工商大学 | Photocatalytic carboxylation of chlorophenols and carbon dioxide on carbon nitride nanotubes |
-
2022
- 2022-12-28 CN CN202211708506.9A patent/CN115920945A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160045908A1 (en) * | 2014-08-14 | 2016-02-18 | Council Of Scientific & Industrial Research | CuO - TiO2 NANOCOMPOSITE PHOTOCATALYST FOR HYDROGEN PRODUCTION, PROCESS FOR THE PREPARATION THEREOF |
| CN104607228A (en) * | 2015-01-23 | 2015-05-13 | 哈尔滨工业大学 | Preparation method for alpha-Fe2O3 quantum dot/nitrogen-doped graphene composite material |
| US20190321805A1 (en) * | 2018-04-23 | 2019-10-24 | King Abdulaziz University | Multi-walled carbon nanotube nanocomposite for hydrogen production |
| CN108927101A (en) * | 2018-07-06 | 2018-12-04 | 济南大学 | A kind of acicular nanometer FeOOH adsorbent and preparation method thereof |
| CN111333127A (en) * | 2020-03-05 | 2020-06-26 | 西北工业大学 | Hierarchical porous honeycomb nickel oxide microsphere and preparation method thereof |
| CN112090440A (en) * | 2020-09-22 | 2020-12-18 | 海南师范大学 | Oxygen-deficient titanium dioxide material of composite hydroxylated carbon nitride and preparation method thereof |
| CN112517043A (en) * | 2020-12-17 | 2021-03-19 | 中南大学 | Nitrogen vacancy and hydroxyl synergistically modified graphite-phase carbon nitride photocatalyst, preparation method thereof and application thereof in photocatalytic hydrogen production |
| CN113731466A (en) * | 2021-08-31 | 2021-12-03 | 岭南师范学院 | MoC/N-dot carbon/g-C3N4Composite photocatalyst and preparation and application thereof |
| CN114011440A (en) * | 2021-11-18 | 2022-02-08 | 三峡大学 | Preparation method of high-hydrophilicity bismuth oxybromide photocatalyst |
| CN114570424A (en) * | 2022-03-30 | 2022-06-03 | 东北石油大学 | Double-modified carbon nitride and preparation method and application thereof |
| CN114713264A (en) * | 2022-05-06 | 2022-07-08 | 重庆工商大学 | Photocatalytic carboxylation of chlorophenols and carbon dioxide on carbon nitride nanotubes |
Non-Patent Citations (1)
| Title |
|---|
| PHUONG ANH NGUYEN ET AL.: ""Ethanol Solvothermal Treatment on Graphitic Carbon Nitride Materials for Enhancing Photocatalytic Hydrogen Evolution Performance"", 《NANOMATERIALS》, vol. 12, no. 2, 6 January 2022 (2022-01-06), pages 2 * |
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