CN110813347B - Molecular doping modified graphite phase carbon nitride photocatalyst with three-dimensional loose structure and preparation method and application thereof - Google Patents
Molecular doping modified graphite phase carbon nitride photocatalyst with three-dimensional loose structure and preparation method and application thereof Download PDFInfo
- Publication number
- CN110813347B CN110813347B CN201910974433.XA CN201910974433A CN110813347B CN 110813347 B CN110813347 B CN 110813347B CN 201910974433 A CN201910974433 A CN 201910974433A CN 110813347 B CN110813347 B CN 110813347B
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- phase carbon
- graphite
- molecular
- modified graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 163
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 30
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 33
- BGRDGMRNKXEXQD-UHFFFAOYSA-N Maleic hydrazide Chemical compound OC1=CC=C(O)N=N1 BGRDGMRNKXEXQD-UHFFFAOYSA-N 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 28
- 239000005983 Maleic hydrazide Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 17
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000000919 ceramic Substances 0.000 claims description 12
- 238000003892 spreading Methods 0.000 claims description 12
- 230000007480 spreading Effects 0.000 claims description 10
- 239000002135 nanosheet Substances 0.000 claims description 9
- 239000011812 mixed powder Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 56
- 239000010439 graphite Substances 0.000 abstract description 56
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 5
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 description 34
- 230000000694 effects Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000011161 development Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000969 carrier Substances 0.000 description 8
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000206607 Porphyra umbilicalis Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- -1 carbon nitrides Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Images
Classifications
-
- 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
-
- B01J35/39—
-
- B01J35/60—
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a molecular doping modified graphite phase carbon nitride photocatalyst with a three-dimensional loose structure, a preparation method and application thereof. The three-dimensional loose structure molecule doped modified graphite phase carbon nitride photocatalyst prepared by the invention is obtained by taking hydrazide organic compounds as organic monomers for the first time. The preparation method effectively improves the visible light catalytic hydrogen production performance of the graphite phase carbon nitride. The method has simple operation and good repeatability, and expands the modification mode of graphite-phase carbon nitride and the application of the graphite-phase carbon nitride in photocatalysis and electrochemistry.
Description
Technical Field
The invention belongs to the field of hydrogen energy preparation, relates to a photocatalytic clean preparation technology of hydrogen energy, namely a photocatalytic hydrogen production technology taking water as a raw material under the condition of simulating sunlight visible light irradiation, and particularly relates to a molecular doping modified graphite phase carbon nitride photocatalyst with a three-dimensional loose structure, and a preparation method and application thereof.
Background
With the gradual depletion of traditional fossil energy such as petroleum, coal and natural gas and the increasing severity of environmental problems, mankind will face an unprecedented energy crisis. Therefore, the development and development of clean and renewable energy sources are effective ways to solve the crisis, and governments around the world also pay great attention to the research direction. The new energy sources with potential at present are solar energy, geothermal energy, wind energy, ocean energy, nuclear energy, biomass energy and the like which exist in nature. The solar energy is an energy which can be inexhaustible in theory and does not pollute the environment, and has great development space. But the utilization of solar energy is also greatly limited due to the characteristics of instability, strong dispersibility, discontinuity, unevenness and the like of the solar energy. Therefore, how to efficiently convert solar energy into chemical energy or electric energy is a difficult problem to overcome at the present stage and is the biggest bottleneck of marketization application. China insists on a sustainable development road, develops new energy according with the sustainable development strategy of China, and can play a great role in promoting future economic development of China if solar energy can be fully utilized.
Because hydrogen gas directly produces water by burning, energy density is high, and a large amount of water resources exist on the earth and can be recycled, and hydrogen has the advantages of storage, transportability, no pollution and the like, and hydrogen energy is considered as an ideal secondary energy source. With the rapid development of various hydrogen energy utilization technologies represented by fuel cells, the demand for hydrogen energy in the future will rise greatly. It is anticipated that the hydrogen economy age may come into the future. However, there are some problems restricting the development of hydrogen energy, such as to really realize the use of hydrogen as energy, and a series of key problems of hydrogen mass production, storage and transportation need to be solved. According to the energy conservation theorem, the hydrogen production process inevitably needs to consume energy, and researches show that substances such as water, biomass, natural gas, coal and the like can be used as hydrogen production raw materials. In consideration of factors such as sustainable development and renewable energy sources, water and biomass are used as raw materials, and hydrogen production by solar energy is a relatively good hydrogen production way. The solar photocatalytic water splitting hydrogen production provides a possible realization way for the hydrogen energy conversion of solar energy, and is a high salary technology which has the most potential to realize industrial production and obtain cheap hydrogen at present and even in the future.
The principle of photocatalytic water splitting hydrogen production is as follows: under the irradiation of certain energy light, the catalyst is excited to generate electron and hole pairs. The electron and hole pairs migrate to the surface of the catalyst where the electrons and water react to form hydrogen gas and the holes are consumed by the appropriate sacrificial agent added to the system. The key to realize the solar photocatalytic water decomposition is to find a high-efficiency, low-cost and stable visible light photocatalyst. Although a large number of visible light-responsive photocatalysts are reported internationally, the requirements of high efficiency, low cost and the like are still far away.
Organic semiconductor graphite phase carbon nitride (g-C)3N4) Has the advantages of low cost, easy preparation, stable structure and proper belt edge positionAnd the like, and is one of the visible light catalysts with great prospect. However, the absorption and utilization of visible light are quite limited, the recombination of photon-generated carriers is serious, and the smaller specific surface area cannot provide more photocatalytic reaction sites, so that the photocatalytic hydrogen production performance is poorer.
Disclosure of Invention
In order to solve the problem of poor hydrogen production performance of photocatalytic decomposition of water by graphite-phase carbon nitride in the prior art, the invention aims to provide a molecular-doped modified graphite-phase carbon nitride photocatalyst with a three-dimensional loose structure and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical means:
a preparation method of a molecular doping modified graphite phase carbon nitride photocatalyst with a three-dimensional loose structure comprises the following steps:
at room temperature, melamine and maleic hydrazide are ground and mixed evenly to obtain mixed powder, and the mixed powder is placed in a furnace body for primary heat treatment at the temperature of 5 ℃ for min-1The temperature rising rate is raised to 520-550 ℃, and the temperature is preserved to ensure that the mixture fully reacts; then cooling to obtain graphite-phase carbon nitride powder subjected to molecular doping modification;
uniformly spreading the molecular doped modified graphite-phase carbon nitride powder in a ceramic square boat, and carrying out secondary heat treatment: at 5 ℃ min-1The temperature rising rate is increased to 500-530 ℃, and the temperature is preserved to ensure that the mixture fully reacts; and then cooling to obtain the molecular doping modified graphite phase carbon nitride photocatalyst with a three-dimensional loose structure.
In the whole heating process of one-time heat treatment, the mixed powder is placed in a crucible, and the crucible needs to be covered so as to ensure that the whole calcining process is carried out in static air.
The mass ratio of the melamine to the maleic hydrazide is (200-25): 1.
The primary heat treatment heat preservation time is 2-6 h.
The cooling is natural cooling.
The heat preservation time of the secondary heat treatment is 3-6 h.
The photocatalyst has a three-dimensional nanosheet structure.
An application of a molecular doping modified graphite phase carbon nitride photocatalyst with a three-dimensional loose structure in photocatalytic hydrogen production.
Compared with the prior art, the invention has the following advantages:
according to the invention, the hydrazide compound is used as an organic monomer to be introduced into the photocatalyst for preparation and modification for the first time, and the prepared catalyst has a special three-dimensional loose nano structure, so that the photocatalytic hydrogen production activity of graphite-phase carbon nitride is greatly improved. On one hand, the introduction of the maleic hydrazide is subjected to copolymerization with melamine to promote charge separation, namely, part of heptazine ring structural units are replaced by organic groups of the maleic hydrazide in the molecular doping process to participate in the construction of valence band tops, so that band gaps are narrowed, the generation of more photo-generated carriers is promoted, the transfer of photo-generated electrons from the organic groups of the maleic hydrazide to adjacent heptazine ring structural units is enhanced, and the effective separation of the photo-generated carriers is realized; on the other hand, the molecular-doped modified graphite-phase carbon nitride nanosheet with the three-dimensional loose structure, which is obtained through secondary heat treatment, has rich pores, is beneficial to light capture, and enhances the light absorption.
The molecular doping modified graphite-phase carbon nitride with the three-dimensional loose structure effectively improves the visible light catalytic hydrogen production performance of the graphite-phase carbon nitride, and the visible light catalytic hydrogen production activity of the molecular doping modified graphite-phase carbon nitride reaches 7689.6 mu mol h-1g-1Is 31.5 times of pure graphite phase carbon nitride, and has an apparent quantum efficiency of 8.53% at 425 nm. The method has simple operation and good repeatability, and expands the modification mode of graphite-phase carbon nitride and the application of the graphite-phase carbon nitride in photocatalysis.
Drawings
Fig. 1 is (a) (b) SEM images and (c) micro-nano structure schematic diagrams and (d) TEM images of three-dimensional loose-structure molecule-doped modified graphite-phase carbon nitride.
FIG. 2 is (a) (b) SEM and (c) (d) TEM of pure graphite phase carbon nitride and molecular-doped modified graphite phase carbon nitride.
FIG. 3 is N of pure graphite phase carbon nitride, molecular doped graphite phase carbon nitride, and three-dimensional loose structure molecular doped modified graphite phase carbon nitride2Adsorption and desorption curves.
FIG. 4 shows XRD (a) and FT-IR (850 to 750 cm) of pure graphite-phase carbon nitride, molecularly-doped graphite-phase carbon nitride, and molecularly-doped modified graphite-phase carbon nitride having a three-dimensional loose structure-1) And (c) Uv-vis spectra.
Fig. 5 shows (a) XPS broad spectrum, (b) C1 s spectrum, (C) N1s spectrum, and (d) valence band spectrum of pure graphite-phase carbon nitride and molecular-doped modified graphite-phase carbon nitride.
Fig. 6 is a super cell model of (a) graphite phase carbon nitride and (b) molecular doped graphite phase carbon nitride for DFT calculations.
Fig. 7(a) is a graph of calculated band structure curve and state density of graphite-phase carbon nitride, fig. 7(b) is a graph of calculated band structure curve and state density of molecular-doped graphite-phase carbon nitride, and MH represents a curve of state density of the organic group of maleic acid hydrazide introduced.
Fig. 8 is (a) a steady state PL spectrum and (b) a time resolved transient PL spectrum of pure graphite phase carbon nitride, molecular doped graphite phase carbon nitride, and three-dimensional loose structure molecular doped modified graphite phase carbon nitride.
FIG. 9 shows (a) the curves of the photocurrent density with time (scan bias: 0.62V vs Ag/AgCl) and (b) the electrochemical impedance spectroscopy (scan bias: 0.15V vs Ag/AgCl, 100 kHz-0.1 Hz) for pure graphite-phase carbon nitride, molecularly-doped graphite-phase carbon nitride, and three-dimensional loose-structured molecularly-doped modified graphite-phase carbon nitride.
Fig. 10 shows (a) hydrogen production activity curves of pure graphite phase carbon nitride, molecular-doped graphite phase carbon nitride, and three-dimensional loose-structure molecular-doped modified graphite phase carbon nitride, and (b) photocatalytic hydrogen production stability test results of three-dimensional loose-structure molecular-doped modified graphite phase carbon nitride.
Fig. 11 is a schematic diagram of hydrogen production activity columns, (a) is a schematic diagram of hydrogen production activity columns of pure graphite phase carbon nitride, molecular-doped graphite phase carbon nitride, and three-dimensional loose-structure molecular-doped modified graphite phase carbon nitride, and (b) is a schematic diagram of quantum efficiency columns of three-dimensional loose-structure molecular-doped modified graphite phase carbon nitride at different excitation wavelengths.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of protection of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention relates to a preparation method of a molecular doping modified graphite phase carbon nitride photocatalyst with a three-dimensional loose structure, which comprises the following steps:
the method comprises the following steps: under the condition of room temperature, 200-25 parts of melamine and 1 part of maleic hydrazide are ground and uniformly mixed, then the mixture is transferred into a crucible, and the crucible is placed into a high-temperature furnace body at the temperature of 5 ℃ per minute-1The temperature rising rate is increased to 520-550 ℃, and the temperature is kept for 2-6 h. During the entire heating process, the crucible needs to be covered to ensure that the entire calcination process is carried out in still air. And naturally cooling to room temperature to obtain the graphite-phase carbon nitride modified by molecular doping.
Step two: get 10g of prepared molecular doping modified g-C3N4Spreading the powder in ceramic square boat at 5 deg.C/min-1The temperature rise rate is increased to 500-530 ℃, and the temperature is kept for 3-6 h. After naturally cooling to room temperature, the three-dimensional loose structure molecule doped modified graphite phase carbon nitride can be obtained.
The principle is as follows: the method comprises the steps of carrying out copolymerization reaction on maleic hydrazide and melamine and carrying out secondary heat treatment to obtain the three-dimensional loose structure molecule doped modified graphite phase carbon nitride photocatalyst, wherein maleic hydrazide is selected as an organic monomer, melamine is selected as a graphite phase carbon nitride precursor, and a direct calcination method is adopted to obtain the product. The hydrazide organic compound is used as an organic monomer for the first time to obtain the three-dimensional loose structure molecule doped modified graphite-phase carbon nitride photocatalyst, and the visible light catalytic hydrogen production activity of the photocatalyst reaches 7689.6 mu mol h-1g-1The method is 31.5 times of pure graphite phase carbon nitride, and the apparent quantum efficiency at 425nm can reach 8.53 percent, so the preparation method effectively improves the visible light catalytic hydrogen production performance of the graphite phase carbon nitride.
Example 1:
the method comprises the following steps: at room temperature, 4.0g of melamine and 50mg of maleic hydrazide are ground and mixed uniformly, then the mixture is transferred into a crucible and put into a high-temperature furnace body at the temperature of 5 ℃ for min-1The temperature rising rate of the temperature rising device is increased to 520 ℃, and the temperature is kept for 4 hours. During the entire heating process, the crucible needs to be covered to ensure that the entire calcination process is carried out in still air. And naturally cooling to room temperature to obtain the modified molecular doped graphite phase carbon nitride.
Step two: uniformly spreading 1.0g of prepared molecular doped graphite phase carbon nitride powder in a ceramic square boat by 5℃·min-1The temperature rising rate of the temperature rising device is increased to 520 ℃, and the temperature is kept for 5 hours. After naturally cooling to room temperature, the three-dimensional loose structure molecule doped modified graphite phase carbon nitride can be obtained.
Example 2:
the method comprises the following steps: 4.0g of melamine and 50mg of maleic hydrazide are ground and mixed uniformly at room temperature, then the mixture is transferred into a crucible and put into a high-temperature furnaceIn vivo, at 5 ℃ min-1The temperature rising rate of the temperature rising device is increased to 520 ℃, and the temperature is kept for 4 hours. During the entire heating process, the crucible needs to be covered to ensure that the entire calcination process is carried out in still air. And naturally cooling to room temperature to obtain the modified molecular doped graphite phase carbon nitride.
Step two: spreading 2.0g of the prepared molecular doped graphite phase carbon nitride powder in a ceramic square boat uniformly at 5 deg.C/min-1The temperature rising rate of the temperature rising device is increased to 520 ℃, and the temperature is kept for 5 hours. After naturally cooling to room temperature, the three-dimensional loose structure molecule doped modified graphite phase carbon nitride can be obtained.
Example 3:
the method comprises the following steps: at room temperature, 5.0g of melamine and 50mg of maleic hydrazide are ground and mixed uniformly, then the mixture is transferred into a crucible and put into a high-temperature furnace body at the temperature of 5 ℃ for min-1The temperature rising rate of the temperature rising device is increased to 520 ℃, and the temperature is kept for 4 hours. During the entire heating process, the crucible needs to be covered to ensure that the entire calcination process is carried out in still air. And naturally cooling to room temperature to obtain the modified molecular doped graphite phase carbon nitride.
Step two: uniformly spreading 1.0g of the prepared molecular doped graphite phase carbon nitride powder in a ceramic square boat at 5 ℃ for min-1The temperature rising rate of the temperature rising device is increased to 520 ℃, and the temperature is kept for 5 hours. After naturally cooling to room temperature, the three-dimensional loose structure molecule doped modified graphite phase carbon nitride can be obtained.
Example 4:
the method comprises the following steps: at room temperature, 4.0g of melamine and 40mg of maleic hydrazide are ground and mixed uniformly, then the mixture is transferred into a crucible and put into a high-temperature furnace body at the temperature of 5 ℃ for min-1The temperature rising rate of the temperature rising device is increased to 520 ℃, and the temperature is kept for 4 hours. During the entire heating process, the crucible needs to be covered to ensure that the entire calcination process is carried out in still air. And naturally cooling to room temperature to obtain the modified molecular doped graphite phase carbon nitride.
Step two: 1.0g of the prepared molecule is doped with g-C3N4Spreading the powder in ceramic square boat at 5 deg.C/min-1Speed of temperature riseThe rate is increased to 520 ℃, and the temperature is preserved for 5 h. After naturally cooling to room temperature, the three-dimensional loose structure molecule doped modified graphite phase carbon nitride can be obtained.
Example 5:
the method comprises the following steps: at room temperature, 4.0g of melamine and 50mg of maleic hydrazide are ground and mixed uniformly, then the mixture is transferred into a crucible and put into a high-temperature furnace body at the temperature of 5 ℃ for min-1The temperature rising rate of the temperature rising device is increased to 520 ℃, and the temperature is kept for 4 hours. During the entire heating process, the crucible needs to be covered to ensure that the entire calcination process is carried out in still air. And naturally cooling to room temperature to obtain the modified molecular doped graphite phase carbon nitride.
Step two: uniformly spreading 1.0g of the prepared molecular doped graphite phase carbon nitride powder in a ceramic square boat at 5 ℃ for min-1The temperature rising rate of the temperature rising device is increased to 520 ℃, and the temperature is kept for 4 hours. After naturally cooling to room temperature, the three-dimensional loose structure molecule doped modified graphite phase carbon nitride can be obtained.
Example 6:
the method comprises the following steps: at room temperature, 4.0g of melamine and 50mg of maleic hydrazide are ground and mixed uniformly, then the mixture is transferred into a crucible and put into a high-temperature furnace body at the temperature of 5 ℃ for min-1The temperature rising rate is increased to 550 ℃, and the temperature is kept for 4 hours. During the entire heating process, the crucible needs to be covered to ensure that the entire calcination process is carried out in still air. And naturally cooling to room temperature to obtain the modified molecular doped graphite phase carbon nitride.
Step two: uniformly spreading 1.0g of the prepared molecular doped graphite phase carbon nitride powder in a ceramic square boat at 5 ℃ for min-1The temperature rising rate of the temperature rising device is increased to 520 ℃, and the temperature is kept for 5 hours. After naturally cooling to room temperature, the three-dimensional loose structure molecule doped modified graphite phase carbon nitride can be obtained.
Example 1 is a standard preparation method used in the present invention;
example 3 is a preparation process with a modified melamine dosage;
example 4 is a preparation with varying amounts of maleic acid hydrazide;
example 5 is a preparation method with the time for holding the heat for the secondary heat treatment changed;
example 6 is a preparation method in which the temperature for keeping the copolymerization reaction is changed.
Example 7:
the method comprises the following steps: under the condition of room temperature, 1.25g of melamine and 50mg of maleic hydrazide are ground and mixed uniformly, then the mixture is transferred into a crucible and put into a high-temperature furnace body at the temperature of 5 ℃ for min-1The temperature rising rate of the temperature rising device is increased to 520 ℃, and the temperature is kept for 2 hours. During the entire heating process, the crucible needs to be covered to ensure that the entire calcination process is carried out in still air. And naturally cooling to room temperature to obtain the modified molecular doped graphite phase carbon nitride.
Step two: uniformly spreading 1.0g of the prepared molecular doped graphite phase carbon nitride powder in a ceramic square boat at 5 ℃ for min-1The temperature rising rate of the temperature rising device is increased to 510 ℃, and the temperature is kept for 3 hours. After naturally cooling to room temperature, the three-dimensional loose structure molecule doped modified graphite phase carbon nitride can be obtained.
Example 8:
the method comprises the following steps: at room temperature, 10.0g of melamine and 50mg of maleic hydrazide are ground and mixed uniformly, then the mixture is transferred into a crucible and put into a high-temperature furnace body at the temperature of 5 ℃ for min-1The temperature rising rate of the temperature rising device is increased to 540 ℃, and the temperature is kept for 6 hours. During the entire heating process, the crucible needs to be covered to ensure that the entire calcination process is carried out in still air. And naturally cooling to room temperature to obtain the modified molecular doped graphite phase carbon nitride.
Step two: uniformly spreading 1.0g of the prepared molecular doped graphite phase carbon nitride powder in a ceramic square boat at 5 ℃ for min-1The temperature rising rate is increased to 500 ℃, and the temperature is kept for 6 hours. After naturally cooling to room temperature, the three-dimensional loose structure molecule doped modified graphite phase carbon nitride can be obtained.
Example 9:
the method comprises the following steps: at room temperature, 6.0g of melamine and 50mg, grinding and uniformly mixing the maleic hydrazide, transferring the mixture into a crucible, and putting the crucible into a high-temperature furnace body at the temperature of 5 ℃ for min-1The temperature rising rate is increased to 550 ℃, and the temperature is kept for 4 hours. During the entire heating process, the crucible needs to be covered to ensure that the entire calcination process is carried out in still air. And naturally cooling to room temperature to obtain the modified molecular doped graphite phase carbon nitride.
Step two: uniformly spreading 1.0g of the prepared molecular doped graphite phase carbon nitride powder in a ceramic square boat at 5 ℃ for min-1The temperature rising rate of the temperature rising device is increased to 510 ℃, and the temperature is kept for 4 hours. After naturally cooling to room temperature, the three-dimensional loose structure molecule doped modified graphite phase carbon nitride can be obtained.
The following is a description of the drawings:
fig. 1 and fig. 2 show SEM and TEM photographs of three samples, and it can be seen from fig. 2 that pure graphite phase carbon nitride and the molecule-doped three-dimensional loose structure molecule-doped graphite phase carbon nitride have similar microscopic morphologies and are both composed of agglomerated thick nanosheets, and the morphology of the molecule-doped graphite phase carbon nitride having the three-dimensional loose structure after the secondary heat treatment in fig. 1 is significantly changed to show an obvious loose special structure similar to the structure of laver.
FIG. 3 shows N for three samples2The absorption and desorption curves from which it is clearly observed that the three-dimensional loose-structured molecularly-doped modified graphite-phase carbon nitride is at a relatively high pressure (P/P) compared to pure graphite-phase carbon nitride and molecularly-doped modified graphite-phase carbon nitride0>0.8) has ultrahigh absorption capacity, which indicates that the material has rich mesopores and macropores and has the same result as the result of microscopic morphology analysis. Meanwhile, the specific surface area of the graphite-phase carbon nitride doped and modified by the three-dimensional loose-structure molecules is 287.37m2 g-1The specific surface areas of the pure graphite phase carbon nitride and the molecular doping modified graphite phase carbon nitride are respectively 8.95 m and 12.06m2 g-1The method shows that the formation of the special three-dimensional loose structure formed by the thinned graphite-phase carbon nitride nanosheets greatly improves the surface area of the graphite-phase carbon nitride in the molecular doping process, and can provide more reaction sites for the photocatalytic reactionAnd (4) point.
In fig. 4, (a) shows XRD spectra of three graphite-phase carbon nitrides, which shows that both pure graphite-phase carbon nitride and the molecularly-doped modified graphite-phase carbon nitride have diffraction characteristic peaks of graphite-phase carbon nitride. The diffraction peak corresponding to the crystal face does not obviously move, which shows that the molecular doping process based on maleic hydrazide has no obvious influence on the interlayer structure of the graphite-phase carbon nitride nanosheet. (100) The weakening of characteristic peaks of crystal faces indicates that the molecular doping process of maleic hydrazide causes local disorder of crystal structures in graphite phase carbon nitride planes, and the interlayer structures of graphite phase carbon nitride nanosheets are not obviously affected. The three-dimensional loose-structured molecular-doped modified graphite-phase carbon nitride shows a similar XRD spectrum as the molecular-doped modified graphite-phase carbon nitride, which indicates that the crystal structure of the molecular-doped graphite-phase carbon nitride is not changed in the secondary heat treatment process, but the characteristic peak of the molecular-doped graphite-phase carbon nitride is widened and the peak strength of the molecular-doped graphite-phase carbon nitride is weakened, which is caused by the three-dimensional loose structure formed by the thinned graphite-phase carbon nitride nanosheets in the secondary heat treatment process. In fig. 4 (b), infrared absorption spectra of three samples are shown, and the peak corresponding to the heptazine ring structure is blue-shifted, which indicates that the heptazine ring structure is bent, corresponding to local disorder of the crystal structure in the graphite phase carbon nitride plane caused by molecular doping in the XRD pattern. In fig. 4, (c) shows the ultraviolet-visible absorption spectra of the three samples, the visible light absorption performance of the molecular-doped modified graphite-phase carbon nitride and the three-dimensional loose-structure molecular-doped modified graphite-phase carbon nitride is superior to that of pure graphite-phase carbon nitride, and the three-dimensional loose-structure molecular-doped graphite-phase carbon nitride has better light utilization performance.
FIG. 5 shows the XPS analysis of pure graphite-phase carbon nitride and molecularly-doped modified graphite-phase carbon nitride, and it can be seen that the structural units corresponding to the C-NH bond and the sp in the graphite-phase carbon nitride heptazine ring are shown2The characteristic peak of hybridized C (N ═ C-N) is slightly shifted after molecular doping, which indicates that the molecular doping has influence on the surrounding chemical environment of C in the graphite phase carbon nitride in-plane structure. The characteristic peaks of N1s corresponding to the molecular doped graphite phase carbon nitride all move to the high binding energy position, which shows that the surrounding chemistry of the molecular doping to N of the graphite phase carbon nitride in-plane structureThe environment is affected. By analyzing the content change of the phase key, N types (N- (C) can be obtained through molecular doping3) The content ratios to the N species (C ═ N-C), (π excitation) and (N-H) were all slightly decreased, indicating N- (C) in the in-plane structure of the molecularly doped graphite-phase carbonitride3Is destroyed. The results in table 1 show that the atomic ratio of C and N in the graphite phase carbon nitride is slightly increased by the molecular doping, and the content of H and O is slightly increased, and it is presumed that the slight increase in the atomic ratio of C and N should be due to the presence of more C than N atoms in the structure of the molecularly doped maleic acid hydrazide, resulting in a slight increase in the atomic ratio of C and N in the structure of the molecularly doped graphite phase carbon nitride, and the slight increase in the content of H and O is due to the introduction of H and O atoms in the structure of the maleic acid hydrazide. The above results can be summarized to show that maleic hydrazide-based molecular doping causes the change of the in-plane structure of graphite-phase carbon nitride, and further causes the change of the surrounding state density of C and N atoms in the graphite-phase carbon nitride, which are formed by the conduction band bottom and the valence band top, resulting in the movement of the valence band top position of the graphite-phase carbon nitride, and the maleic hydrazide structural monomer replaces part of the heptazine ring structural units of the graphite-phase carbon nitride, thereby causing the local disorder of the arrangement of the heptazine ring structural units in the graphite-phase carbon nitride plane.
Fig. 6 shows the super cell model for (a) graphite phase carbon nitride and (b) molecular doped graphite phase carbon nitride for DFT calculations, i.e., the model used for the calculations in fig. 7.
The calculated band structure curve and the state density graph of graphite phase carbon nitride are given in fig. 7(a), the calculated band structure curve and the state density graph of graphite phase carbon nitride molecule-doped in fig. 7(b), and MH represents the state density curve of the organic group of the introduced maleic acid hydrazide. From the band structure curves, the calculated band gap value of the graphite phase carbon nitride is 1.64eV, which is much smaller than the actual band gap value, and is mainly caused by the intrinsic energy calculation defect of the PBE exchange correlation functional in the GGA framework in the density functional theory. The calculated band gap value of the molecular doped graphite phase carbon nitride is 1.57eV, and compared with the graphite phase carbon nitride, the band gap is reduced and is consistent with the experimental structure, thereby showing the rationality of the electronic structure of the molecular doped graphite phase carbon nitride. Meanwhile, by comparing the state density diagrams of the graphite-phase carbon nitride and the molecular-doped graphite-phase carbon nitride, the organic group of the maleic acid hydrazide participates in the construction of the graphite-phase carbon nitride valence band top and does not participate in the construction of the conduction band bottom.
In fig. 8 (a), the pure graphite-phase carbon nitride has a strong PL characteristic peak, which indicates that the photogenerated carriers therein are seriously compounded, while the PL characteristic peak intensities of the molecular-doped modified graphite-phase carbon nitride and the molecular-doped modified graphite-phase carbon nitride with a three-dimensional loose structure are both obviously weakened, which indicates that the molecular-doped modification effectively inhibits the photogenerated carriers from being compounded and promotes the separation thereof. Meanwhile, the three-dimensional loose structure formed by the nano sheets shortens the migration distance of photon-generated carriers and further promotes the separation of the photon-generated carriers. The time-resolved transient PL spectrum in fig. 8 (b) shows that the increase in the surface area of the three-dimensional loose-structure molecule-doped graphite-phase carbon nitride facilitates the increase in the photocatalytic reaction sites to capture photo-generated carriers more easily, resulting in a shorter carrier lifetime of the graphite-phase carbon nitride.
In fig. 9, (a) and (b) of the three-dimensional loose-structure molecule-doped modified graphite-phase carbon nitride have the highest photocurrent density and the smallest impedance radius, and the next step is the molecule-doped graphite-phase carbon nitride which is not subjected to secondary heat treatment, which shows that both the molecule doping and the three-dimensional loose structure are beneficial to improving the photoelectrochemical properties of the graphite-phase carbon nitride.
Fig. 10 (a) shows a comparison of photocatalytic hydrogen production activities of several samples, and it can be seen that the photocatalytic hydrogen production performance of the molecule-doped graphite-phase carbon nitride is greatly improved by the special three-dimensional porous structure obtained by the secondary heat treatment. The stability test in (b) of fig. 10 shows that the visible light catalytic hydrogen production activity of the three-dimensional loose-structure molecule-doped modified graphite-phase carbon nitride is slightly reduced after three-cycle test. In order to eliminate the factors of hydrogen production activity reduction caused by consumption of the sacrificial agent, a proper amount of the sacrificial agent is supplemented before the fourth cycle test, and the result shows that the visible light catalytic hydrogen production activity of the three-dimensional loose structure molecule doped modified graphite phase carbon nitride is recovered to the activity level of the first cycle test, even slightly increased, which shows that the three-dimensional loose structure molecule doped modified graphite phase carbon nitride has good visible light catalytic hydrogen production stability.
Fig. 11 (a) shows a column diagram of hydrogen production activity of three samples, which shows that the secondary heat treatment greatly improves the photocatalytic hydrogen production performance of graphite-phase carbon nitride, and fig. 11 (b) shows that the three-dimensional loose-structure molecule-doped graphite-phase carbon nitride has the highest quantum efficiency under 425nm light irradiation, which reaches 8.53%, and is in the international leading level.
TABLE 1 Elemental Analysis (EA) results for graphite phase carbon nitride and molecularly doped graphite phase carbon nitride.
aIs the atomic ratio of the elements C and N.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (7)
1. A preparation method of a molecular doping modified graphite phase carbon nitride photocatalyst with a three-dimensional loose structure is characterized by comprising the following steps:
at room temperature, melamine and maleic hydrazide are ground and mixed uniformly to obtain mixed powder, and the mixed powder is placed in a furnace body to be subjected to primary heat treatment, wherein the primary heat treatment is carried out by 5oC• min-1Is increased to 520 oC ~550 oC, preserving heat to enable the mixture to react fully; then cooling to obtain graphite-phase carbon nitride powder subjected to molecular doping modification;
the mass ratio of the melamine to the maleic hydrazide is (200-25) to 1;
uniformly spreading the molecular doped modified graphite-phase carbon nitride powder in a ceramic square boat, and carrying out secondary heat treatment: by 5oC• min-1The temperature rise rate of (2) is increased to 500 oC ~530 oC, preserving heat to enable the mixture to react fully; then cooling to obtain the molecular doping modified graphite phase nitrogen with a three-dimensional loose structureA carbon-decomposing photocatalyst.
2. The method for preparing the molecular-doped modified graphite-phase carbon nitride photocatalyst with a three-dimensional loose structure as claimed in claim 1, wherein the mixed powder is placed in a crucible during one-time heat treatment and the whole heating process, and the crucible needs to be covered to ensure that the whole calcining process is carried out in static air.
3. The preparation method of the molecular doping modified graphite phase carbon nitride photocatalyst with the three-dimensional loose structure according to claim 1, characterized in that the heat preservation time of one-time heat treatment is 2-6 h.
4. The method for preparing the molecular doping modified graphite phase carbon nitride photocatalyst with the three-dimensional loose structure according to claim 1, characterized in that the cooling is natural cooling.
5. The preparation method of the molecular doping modified graphite phase carbon nitride photocatalyst with the three-dimensional loose structure according to claim 1, characterized in that the heat preservation time of the secondary heat treatment is 3-6 h.
6. The molecular-doped modified graphite-phase carbon nitride photocatalyst prepared by the preparation method of any one of claims 1 to 5, wherein the photocatalyst has a three-dimensional nanosheet structure.
7. The application of the molecular doping modified graphite phase carbon nitride photocatalyst with the three-dimensional loose structure in the claim 6 in photocatalytic hydrogen production.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910974433.XA CN110813347B (en) | 2019-10-14 | 2019-10-14 | Molecular doping modified graphite phase carbon nitride photocatalyst with three-dimensional loose structure and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910974433.XA CN110813347B (en) | 2019-10-14 | 2019-10-14 | Molecular doping modified graphite phase carbon nitride photocatalyst with three-dimensional loose structure and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110813347A CN110813347A (en) | 2020-02-21 |
| CN110813347B true CN110813347B (en) | 2021-01-19 |
Family
ID=69549139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910974433.XA Active CN110813347B (en) | 2019-10-14 | 2019-10-14 | Molecular doping modified graphite phase carbon nitride photocatalyst with three-dimensional loose structure and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110813347B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111330620A (en) * | 2020-03-11 | 2020-06-26 | 中国科学技术大学 | Intercalation type graphite-like carbon nitride composite material, preparation method and application thereof |
| CN115155641B (en) * | 2022-07-22 | 2023-07-25 | 东北大学 | Oxygen atom in-situ self-doped high-crystallization type carbon nitride photocatalyst and preparation method thereof |
| CN115678124B (en) * | 2022-11-28 | 2024-01-26 | 中国重汽集团济南动力有限公司 | Natural rubber composite material for heavy-duty truck spring rubber support and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5804251B2 (en) * | 2011-06-03 | 2015-11-04 | 国立研究開発法人物質・材料研究機構 | Porous carbon nitride film, method for producing the same, and use thereof |
| CN103272639B (en) * | 2013-06-09 | 2015-02-04 | 福州大学 | Copolymerization modified graphite-phase carbon nitride nanosheet visible-light-driven photocatalyst |
| WO2019130983A1 (en) * | 2017-12-25 | 2019-07-04 | 国立大学法人山形大学 | Carbon nitride, method for producing same, and semiconductor material |
| CN108394875B (en) * | 2018-02-12 | 2019-07-16 | 中国科学院化学研究所 | A kind of carbon nitride material and preparation method thereof that combined polymerization is modified |
| CN109876841B (en) * | 2019-01-22 | 2020-06-19 | 西安交通大学 | Method for preparing graphite-phase carbon nitride visible-light-driven photocatalyst by copolymerization of 2-amino terephthalic acid and amine compound |
-
2019
- 2019-10-14 CN CN201910974433.XA patent/CN110813347B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110813347A (en) | 2020-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mei et al. | Step-scheme porous g-C3N4/Zn0. 2Cd0. 8S-DETA composites for efficient and stable photocatalytic H2 production | |
| CN107297217B (en) | Porous thin-layer graphite-phase carbon nitride-supported platinum photocatalyst and preparation method and application thereof | |
| Guo et al. | Synthesis of Z-scheme α-Fe2O3/g-C3N4 composite with enhanced visible-light photocatalytic reduction of CO2 to CH3OH | |
| CN110813347B (en) | Molecular doping modified graphite phase carbon nitride photocatalyst with three-dimensional loose structure and preparation method and application thereof | |
| Osterloh et al. | Recent developments in solar water-splitting photocatalysis | |
| Yin et al. | Ultrathin graphitic carbon nitride nanosheets with remarkable photocatalytic hydrogen production under visible LED irradiation | |
| CN110694648B (en) | Photocatalytic water-splitting hydrogen-production molybdenum-doped indium-zinc sulfide hollow hierarchical structure photocatalyst and preparation method thereof | |
| Wang et al. | A facile synthesis of nano-layer structured g-C3N4 with efficient organic degradation and hydrogen evolution using a MDN energetic material as the starting precursor | |
| CN112427045A (en) | CdS/g-C synthesized by hydrothermal method and having Z-shaped heterojunction3N4Preparation method of composite photocatalyst material | |
| CN105618098A (en) | Platinum supported nitrogen-doped molybdenum disulfide photocatalyst and preparation method thereof | |
| CN113680372B (en) | Heat-assisted preparation method and application of graphite-phase carbon nitride nanosheets | |
| Shen et al. | NiSe 2/CdS composite nanoflakes photocatalyst with enhanced activity under visible light | |
| Sun et al. | Preparation of corn stover hydrothermal carbon sphere-CdS/g-C3N4 composite and evaluation of its performance in the photocatalytic co-reduction of CO2 and decomposition of water for hydrogen production | |
| Dong et al. | Built-in electric field intensified by photothermoelectric effect drives charge separation over Z-scheme 3D/2D In2Se3/PCN heterojunction for high-efficiency photocatalytic CO2 reduction | |
| CN115007174A (en) | Two-dimensional CdIn 2 S 4 Nanosheet and preparation method and application thereof | |
| Wang et al. | A facile template synthesis of phosphorus-doped graphitic carbon nitride hollow structures with high photocatalytic hydrogen production activity | |
| Hou et al. | Precise defect engineering on graphitic carbon nitrides for boosted solar H2 production | |
| CN114054066A (en) | Doped g-C3N4Nanotube photocatalyst, preparation method and application | |
| CN111349915B (en) | CoSe with controllable appearance2/Ti composite material and preparation method thereof | |
| CN113957458A (en) | g-C3N4Preparation and electrocatalytic properties of/two-dimensional porphyrin MOF material | |
| CN115090318B (en) | Preparation method and application of high specific surface area intermolecular heterojunction carbon nitride photocatalyst | |
| Hu et al. | Fabricate dual interface build-in electric fields by introducing Au nanospecies into Z-scheme heterojunction to propel photocatalytic CO2 reduction | |
| CN111807336B (en) | Amorphous molybdenum oxide nanodot/two-dimensional carbon nitride nanosheet with photocatalysis and photothermal conversion performances and preparation method thereof | |
| CN115055199B (en) | Sulfur-doped honeycomb nano sheet g-C 3 N 4 Preparation method and application thereof | |
| CN113522298A (en) | Perovskite oxide/Ti3C2MXene/foamed nickel composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |