CN111604063A - g-C3N4/In2Se3Composite photocatalyst and preparation method and application thereof - Google Patents
g-C3N4/In2Se3Composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011669 selenium Substances 0.000 claims abstract description 86
- 239000002131 composite material Substances 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 47
- 239000000725 suspension Substances 0.000 claims abstract description 38
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 229910052738 indium Inorganic materials 0.000 claims abstract description 17
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 16
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- 238000001354 calcination Methods 0.000 claims description 29
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000001699 photocatalysis Effects 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- 239000000463 material Substances 0.000 description 8
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000969 carrier Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/39—
-
- 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
-
- 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
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
Abstract
The invention relates to a g-C3N4/In2Se3A composite photocatalyst and a preparation method and application thereof. The method comprises the following steps: 1) mixing flakes g-C3N4Dissolving in a solvent to form a suspension; 2) adding an indium source to the suspension and stirring until dissolved; 3) continuously adding a selenium source and a reducing agent into the suspension, stirring, heating to 210-290 ℃ at a speed of 10-15 ℃/min, refluxing for 0-1h, and then cooling at a temperature of-5 to 5 ℃ to obtain the g-C3N4/In2Se3A composite photocatalyst is provided. The method obtains g-C with self-polarization capability3N4/In2Se3A two-dimensional-two-dimensional ultrathin composite photocatalyst. In addition, the invention also comprises g-C prepared by the method3N4/In2Se3A composite photocatalyst and application thereof.
Description
Technical Field
The invention relates to the field of nano photocatalysis, in particular to g-C3N4/In2Se3A composite photocatalyst and a preparation method and application thereof.
Background
In the present society, energy and environmental problems are two major problems that need to be solved urgently. Scientists are not left with the power to explore new energy to replace traditional fossil energy to deal with energy and environmental crisis. Among numerous new energy sources (solar energy, biomass energy, tidal energy, wind energy, nuclear energy and the like), solar energy is the most ideal clean energy source, has the advantages of inexhaustibility, safety, economy, cleanness and the like, and attracts great interest of scientific researchers. The problem of energy shortage faced by human society can be alleviated by converting solar energy into chemical energy. Photocatalytic hydrogen production is a technology for converting solar energy into hydrogen energy, however, the key of photocatalytic hydrogen production is a photocatalyst, and the photocatalysts developed at present are various in types, but the problem of low photocatalytic hydrogen production efficiency exists. Graphite phase carbon nitride (g-C)3N4) Is a relatively high-efficiency organic semiconductor photocatalyst which is just discovered in recent years, is favored by people due to the advantages of simple preparation method, cheap raw materials, no toxicity, no harm and the like, but g-C3N4The defects of easy recombination of photon-generated carriers, limited light absorption capacity and the like still exist, so that the two problems of improving the light absorption capacity and the recombination of the photon-generated carriers tend to greatly improve the g-C3N4The photocatalytic hydrogen production performance.
The method is an effective method for solving the problem that the compound is compounded with a narrow-bandgap semiconductor with self-polarization capability to form a compact heterojunction structure. Indium selenide is (In)2Se3) The IIIA-VIA type chalcogenide compound has a plurality of crystal forms and different electronic structures, is a very promising semiconductor material, and is endowed with self-polarization capability due to an asymmetric atom arrangement structure. When light irradiates the semiconductor, photo-generated carriers are generated to form a built-in electric field, and the separation of the photo-generated carriers is promoted.
Disclosure of Invention
Therefore, based on the background of the above studies, to solve how to obtain g-C with self-polarization capability3N4/In2Se3The invention provides a two-dimensional-two-dimensional ultrathin composite photocatalyst, and provides g-C3N4/In2Se3A composite photocatalyst and a preparation method and application thereof.
The invention provides a g-C3N4/In2Se3The preparation method of the composite photocatalyst comprises the following steps:
1) mixing flakes g-C3N4Dissolving in a solvent to form a suspension;
2) according to said g-C3N4/In2Se3In the composite photocatalyst2Se3And g-C3N4Adding an indium source into the suspension at a theoretical molar mass ratio of 1-10: 100, and stirring until the indium source is dissolved;
3) continuously adding a selenium source and a reducing agent into the suspension, stirring, heating to 210-290 ℃ at a speed of 10-15 ℃/min, refluxing for 0-1h, and then cooling at a temperature of-5 to 5 ℃ to obtain the g-C3N4/In2Se3A composite photocatalyst is provided.
Further, in step 1), the flake g-C is formed3N4Dissolving in triethylene glycol solvent to form suspension; then heating and distilling under the protection of nitrogen atmosphere to remove water.
Further, in the step 2), the indium source is one or two of indium chloride and indium nitrate.
Further, in step 3), the selenium source is selenium powder; and/or the reducing agent is sodium borohydride or hydrazine hydrate; and/or continuously adding the selenium source into the suspension according to the mol ratio of the indium source to the selenium source of 2-3: 3.
Further, in the step 3), the selenium source and the reducing agent are continuously added into the suspension, stirred and heated to 210-290 ℃ at the speed of 10-15 ℃/min and refluxed for 0-1h, and then cooled at the temperature of-5 to 5 ℃ to obtain the g-C3N4/In2Se3A composite photocatalyst is provided.
Further, in step 1), the flake-like g-C3N4Is prepared by the following steps:
s1, mixing g-C3N4Heating the precursor to 500-520 ℃ at the speed of 10-15 ℃/min, and calcining to obtain primary calcined g-C3N4(ii) a The g to C3N4The precursor is selected from one or more of urea, dicyandiamide, melamine, cyanamide and thiourea;
s2, calcining the primary g-C3N4Heating to 500-520 ℃ at the speed of 5-8 ℃/min for secondary calcination to obtain the flaky g-C3N4。
Further, in step 1), the flake g-C is subjected to3N4Dissolving in solvent, and ultrasonic treating for 30-120min to obtain suspension.
Further, in step 2), according to said g-C3N4/In2Se3In the composite photocatalyst2Se3And g-C3N4Adding the indium source into the suspension in a theoretical molar mass ratio of 1-10: 100, and stirring for 30-60min until dissolution.
The invention also provides g-C prepared by the preparation method3N4/In2Se3A composite photocatalyst is provided.
The invention also provides the above-mentioned g-C3N4/In2Se3The composite photocatalyst is applied to the aspect of photocatalytic hydrogen production.
Compared with the prior art, the invention has the advantages that: mixing flakes g-C3N4Dissolved in a solvent to form a suspension, g-C3N4Is in the form of flake to form flake g-C3N4/In2Se3Providing a substrate for the composite photocatalyst, and then preparing the composite photocatalyst according to the g-C3N4/In2Se3In the composite photocatalyst2Se3And g-C3N4Theoretical molar mass ofAdding an indium source into the suspension in a ratio of 1-10: 100 and stirring until the indium source is dissolved, g-C3N4Has negative charge, positive charge and mutual attraction of positive and negative charges, and is beneficial to loading indium at g-C3N4Then, a selenium source and a reducing agent are continuously added into the suspension, the mixture is stirred and heated to 210-290 ℃ at the speed of 10-15 ℃/min, the growth speed of the indium selenide on the graphite-phase carbon nitride is controlled by controlling the reaction temperature rise speed and the temperature, and the size and the thickness of the indium selenide growth are controlled by controlling the liquid phase reflux time to obtain the two-dimensional-two-dimensional ultrathin g-C3N4/In2Se3The composite photocatalyst is then cooled at-5 to 5 ℃, and g-C can be rapidly cooled under the low-temperature condition3N4/In2Se3Composite photocatalyst avoids g-C3N4/In2Se3The shape of the composite photocatalyst is changed, so that the final two-dimensional-two-dimensional ultrathin g-C can be obtained3N4/In2Se3Composite photocatalyst, In2Se3And g-C3N4Ultra-thin g-C with thickness within about 10nm3N4And ultra-thin In2Se3The composite photocatalyst is of a heterojunction structure, has the advantages of the heterojunction structure, and can further improve the separation efficiency of photo-generated carriers by establishing a polarization electric field inside, so that the photocatalytic efficiency is greatly improved.
Drawings
The features and advantages of the present invention will be more clearly understood by reference to the accompanying drawings, which are illustrative and not to be construed as limiting the invention in any way, and in which:
FIG. 1 shows the sheets g to C of example 1 of the present invention3N4A TEM image;
FIG. 2 shows g-C obtained in example 1 of the present invention3N4/In2Se3SEM picture of the composite photocatalyst;
FIG. 3 shows g-C obtained in example 1 of the present invention3N4/In2Se3XRD pattern of the composite photocatalyst;
FIG. 4 shows g-C obtained in example 1 of the present invention3N4/In2Se3A TEM image of the composite photocatalyst;
FIG. 5 shows g-C obtained in example 1 of the present invention3N4/In2Se3An infrared image of the composite photocatalyst;
FIG. 6 shows g-C obtained in example 1 of the present invention3N4/In2Se3The hydrogen production performance of the composite photocatalyst is compared with the hydrogen production performance of the catalysts obtained in comparative examples 1 and 2.
Detailed Description
The present embodiment provides a g-C3N4/In2Se3The preparation method of the composite photocatalyst comprises the following steps:
1) g to C3N4Heating the precursor to 500-520 ℃ at the speed of 10-15 ℃/min, and calcining to obtain primary calcined g-C3N4(ii) a The g to C3N4The precursor is selected from one or more of urea, dicyandiamide, melamine, cyanamide and thiourea;
2) subjecting said primary calcination g-C3N4Heating to 500-520 ℃ at the speed of 5-8 ℃/min for secondary calcination to obtain the flaky g-C3N4；
3) Mixing flakes g-C3N4Dissolving in solvent, and performing ultrasonic treatment for 30-120min to obtain suspension;
4) according to said g-C3N4/In2Se3In the composite photocatalyst2Se3And g-C3N4Adding an indium source into the suspension at a theoretical molar mass ratio of 1-10: 100, and stirring for 30-60min until dissolution; the indium source is one or two of indium chloride and indium nitrate;
5) continuously adding a selenium source and a reducing agent into the suspension according to the molar ratio of the indium source to the selenium source being 2-3: 3, stirring, heating to 210-290 ℃ at the speed of 10-15 ℃/min, refluxing for 0-1h, and cooling at the temperature of-5 to 5 ℃ to obtain the g-C3N4/In2Se3A composite photocatalyst is provided. The selenium source is selenium powder; and/or the reducing agent is sodium borohydride or hydrazine hydrate. The dosage of the reducing agent is 0.05mL-0.15 mL. Some embodiments further continue refluxing for 0-1h after heating to the temperature of 210-290 ℃ and then cooling at-5 to 5 ℃ to obtain the g-C3N4/In2Se3A composite photocatalyst; some embodiments provide the g-C by heating to the temperature of 210-290 ℃ and directly cooling at-5 to 5 DEG C3N4/In2Se3A composite photocatalyst is provided.
In this embodiment, the flake g-C is incorporated in step 3)3N4Dissolving in triethylene glycol solvent to form suspension; then heating and distilling under the protection of nitrogen atmosphere to remove moisture; the triethylene glycol solvent has a low boiling point if it contains water, so that the removal of water enables the temperature to rise to 210-290 ℃ after the selenium source and the reducing agent are added subsequently. The solvent in this embodiment may also be a high boiling point solvent such as oleylamine solvent, glycerin, and the like.
The specific embodiment also comprises g-C prepared by the preparation method3N4/In2Se3A composite photocatalyst is provided.
This embodiment also includes the above-mentioned g-C3N4/In2Se3The composite photocatalyst is applied to the aspect of photocatalytic hydrogen production.
To further illustrate the preparation methods proposed in this embodiment, the following examples are given.
Example 1
g-C3N4/In2Se3The preparation method of the composite photocatalyst comprises the following steps:
(1) weighing 15g of urea, placing the urea in a 30mL corundum crucible with a cover, heating to 520 ℃ at the heating rate of 10 ℃/min, and calcining for 150min to obtain primary calcined g-C3N4；
(2) Subjecting the primary calcined g-C obtained in the step (1)3N4(0.5g) was placed in a crucible and subjected to secondary calcination (rate of temperature rise 5 ℃/min, calcination temperature)Degree 500 ℃ C.), to give flake-like g-C3N4(ii) a As can be seen from the TEM image shown in FIG. 1, the g-C3N4Is in the shape of a sheet;
(3) weighing 0.5g of the flake g-C obtained in step (2)3N4Dissolving the mixture in 50mL of 99.5% (analytically pure) triethylene glycol solvent, and performing ultrasonic treatment for 1.5h to uniformly disperse the mixture to form uniform suspension;
(4) transferring the suspension into a quartz three-neck flask, heating to 95 ℃ under the protection of nitrogen atmosphere, distilling to remove water, cooling to room temperature under the protection of nitrogen, rapidly adding 0.2mmol of indium chloride, and stirring for 30min to completely dissolve the indium chloride;
(5) rapidly adding 0.3mmol selenium powder and 0.1mL 80% hydrazine hydrate, rapidly heating to 270 deg.C under vigorous stirring at 350 r/min, rapidly cooling to room temperature, centrifuging to obtain dark brown solid, washing with anhydrous ethanol for four times, washing with water for one time, and freeze drying to obtain g-C3N4/In2Se3A composite photocatalyst material, the catalyst is abbreviated as CNIS-6, In indicated by CNIS-62Se3And g-C3N4The theoretical content of (A) is 6%, and so on.
FIG. 2 is a scanning electron micrograph of CNIS-6, from which it can be seen that the prepared composite sample has a two-dimensional sheet structure and a partial pore structure distribution on the surface.
FIG. 3 is g-C prepared in comparative example 13N4Pure In prepared In comparative example 22Se3Comparing with XRD of composite structure CNIS-6, diffraction peak and In of composite structure CNIS-6 can be known from the figure2Se3，g-C3N4The diffraction peaks of (A) are completely corresponding to each other, which indicates that the prepared composite structure is In2Se3And g-C3N4The composite structure of (3) does not generate a heterogeneous phase.
FIG. 4 is a TEM image of the composite sample CNIS-6 prepared in example 1, in which black dotted boxes are shown grown on the substrate g-C3N4In of2Se3In is shown In the figure2Se3Intact growth of nanosheetsIn g-C3N4The above.
In the infrared image of FIG. 5, 810cm-1Wave number of g-C3N4Characteristic absorption peak of medium triazine ring structure, 1200-1700cm-1The wave number is the stretching vibration peak of the C-N ═ C heterocycle. As can be seen from the figure, in g-C3N4Overgrowth of In2Se3Then, there was no change affecting the absorption peak profile and position, indicating In2Se3The introduction of (A) has no influence on g-C3N4The structure of (1).
To examine g-C prepared in this example3N4/In2Se3The photocatalytic performance of the composite photocatalyst is used for a photocatalytic hydrogen production performance experiment, 20mg of the catalyst is weighed and placed in a 20% triethanolamine aqueous solution, the mixture is subjected to ultrasonic treatment for 20min to be uniformly dispersed, then nitrogen purging is performed for 30min to remove the influence of impurity gases, and the volume of the whole reactor is about 230 mL. A36 WLED lamp is used as a visible light source, hydrogen production performance test is carried out at the temperature of 20 ℃, and 0.5mL of gas is extracted from the reaction system at intervals of 1h and injected into a gas chromatograph for product analysis. In fig. 6, from left to right, the catalysts are: pure In2Se3The hydrogen production effect is almost 0; pure g-C3N4Hydrogen production is 0.94 mmol/g/h; the CNIS-6 produces 4.81mmol/g/h hydrogen which is far higher than that of the pure two compounds.
Example 2
g-C3N4/In2Se3The preparation method of the composite photocatalyst comprises the following steps:
(1) weighing 15g of urea, placing the urea in a 30mL corundum crucible with a cover, heating to 520 ℃ at the heating rate of 10 ℃/min, and calcining for 150min to obtain primary calcined g-C3N4；
(2) Subjecting the primary calcined g-C obtained in the step (1)3N4(0.5g) was placed in a crucible and subjected to secondary calcination (heating rate 5 ℃/min, calcination temperature 500 ℃ C.), to obtain flaky g-C3N4；
(3) Weighing 0.5g of the flake g-C obtained in step (2)3N4Dissolved in 99.5% (in part) of 50mLPurifying) triethylene glycol, and performing ultrasonic treatment for 1.5h to uniformly disperse the triethylene glycol to form uniform suspension;
(4) transferring the suspension into a quartz three-neck flask, heating to 95 ℃ under the protection of nitrogen atmosphere, distilling to remove water, cooling to room temperature under the protection of nitrogen, rapidly adding 0.1mmol of indium chloride, and stirring for 30min to completely dissolve the indium chloride;
(5) rapidly adding 0.15mmol selenium powder and 0.1mL 80% hydrazine hydrate, rapidly heating to 270 deg.C under vigorous stirring at 350 r/min, rapidly cooling to room temperature, centrifuging to obtain dark brown solid, washing with anhydrous ethanol for four times, washing with water for one time, and freeze drying to obtain g-C3N4/In2Se3A composite photocatalyst material is disclosed, and the catalyst is abbreviated as CNIS-2.
Example 3
g-C3N4/In2Se3The preparation method of the composite photocatalyst comprises the following steps:
(1) weighing 15g of urea, placing the urea in a 30mL corundum crucible with a cover, heating to 520 ℃ at the heating rate of 10 ℃/min, and calcining for 150min to obtain primary calcined g-C3N4；
(2) Subjecting the primary calcined g-C obtained in the step (1)3N4(0.5g) was placed in a crucible and subjected to secondary calcination (heating rate 5 ℃/min, calcination temperature 500 ℃ C.), to obtain flaky g-C3N4；
(3) Weighing 0.5g of the flake g-C obtained in step (2)3N4Dissolving the mixture in 50mL of 99.5% (analytically pure) triethylene glycol solvent, and performing ultrasonic treatment for 1.5h to uniformly disperse the mixture to form uniform suspension;
(4) transferring the suspension into a quartz three-neck flask, heating to 95 ℃ under the protection of nitrogen atmosphere, distilling to remove water, cooling to room temperature under the protection of nitrogen, rapidly adding 0.3mmol of indium chloride, and stirring for 30min to completely dissolve the indium chloride;
(5) rapidly adding 0.45mmol selenium powder and 0.1mL hydrazine hydrate with concentration of 80%, rapidly heating to 270 ℃ under vigorous stirring with stirring speed of 350 r/minThen quickly cooling to room temperature, centrifugally separating to obtain dark brown solid, washing with anhydrous ethanol for four times, washing with water for one time, and freeze-drying to obtain g-C3N4/In2Se3A composite photocatalyst material is disclosed, and the catalyst is abbreviated as CNIS-10.
Example 4
g-C3N4/In2Se3The preparation method of the composite photocatalyst comprises the following steps:
(1) weighing 15g of urea, placing the urea in a 30mL corundum crucible with a cover, heating to 520 ℃ at the heating rate of 10 ℃/min, and calcining for 150min to obtain primary calcined g-C3N4；
(2) Subjecting the primary calcined g-C obtained in the step (1)3N4(0.5g) was placed in a crucible and subjected to secondary calcination (heating rate 5 ℃/min, calcination temperature 500 ℃ C.), to obtain flaky g-C3N4；
(3) Weighing 0.5g of the flake g-C obtained in step (2)3N4Dissolving in 50ml of 99.5% (analytically pure) triethylene glycol solvent, and performing ultrasonic treatment for 1.5h to uniformly disperse the triethylene glycol solvent to form uniform suspension;
(4) transferring the suspension into a quartz three-neck flask, heating to 95 ℃ under the protection of nitrogen atmosphere, distilling to remove water, cooling to room temperature under the protection of nitrogen, rapidly adding 0.05mmol of indium chloride, and stirring for 30min to completely dissolve the indium chloride;
(5) rapidly adding 0.15mmol selenium powder and 0.1mL 80% hydrazine hydrate, rapidly heating to 270 deg.C under vigorous stirring at 350 r/min, rapidly cooling to room temperature, centrifuging to obtain dark brown solid, washing with anhydrous ethanol for four times, washing with water for one time, and freeze drying to obtain g-C3N4/In2Se3A composite photocatalyst material is disclosed, and the catalyst is abbreviated as CNIS-1.
Example 5
g-C3N4/In2Se3The preparation method of the composite photocatalyst comprises the following steps:
(1) weighing 15g of urea and placing in 30mLThe corundum crucible with the cover is heated to 520 ℃ at the heating rate of 10 ℃/min and calcined for 150min to obtain primary calcined g-C3N4；
(2) Subjecting the primary calcined g-C obtained in the step (1)3N4(0.5g) was placed in a crucible and subjected to secondary calcination (heating rate 5 ℃/min, calcination temperature 500 ℃ C.), to obtain flaky g-C3N4；
(3) Weighing 0.5g of the flake g-C obtained in step (2)3N4Dissolving the mixture in 60ml of 99.5 percent (analytically pure) triethylene glycol solvent, and performing ultrasonic treatment for 2 hours to uniformly disperse the mixture to form uniform suspension;
(4) transferring the suspension into a quartz three-neck flask, heating to 95 ℃ under the protection of nitrogen atmosphere, distilling to remove water, cooling to room temperature under the protection of nitrogen, rapidly adding 0.2mmol of indium chloride, and stirring for 30min to completely dissolve the indium chloride;
(5) rapidly adding 0.3mmol selenium powder and 0.15mL 80% hydrazine hydrate, rapidly heating to 270 deg.C under vigorous stirring at 350 r/min, rapidly cooling to room temperature, centrifuging to obtain dark brown solid, washing with anhydrous ethanol for four times, washing with water for one time, and freeze drying to obtain g-C3N4/In2Se3A composite photocatalyst material.
Example 6
g-C3N4/In2Se3The preparation method of the composite photocatalyst comprises the following steps:
(1) weighing 15g of urea, placing the urea in a 30mL corundum crucible with a cover, heating to 520 ℃ at the heating rate of 10 ℃/min, and calcining for 150min to obtain primary calcined g-C3N4；
(2) Subjecting the primary calcined g-C obtained in the step (1)3N4(0.5g) was placed in a crucible and subjected to secondary calcination (heating rate 5 ℃/min, calcination temperature 500 ℃ C.), to obtain flaky g-C3N4；
(3) Weighing 0.5g of the flake g-C obtained in step (2)3N4Dissolving in 50ml of 99.5% (analytically pure) triethylene glycol solvent, and performing ultrasonic treatment for 1.5hIt is uniformly dispersed to form a uniform suspension;
(4) transferring the suspension into a quartz three-neck flask, heating to 95 ℃ under the protection of nitrogen atmosphere, distilling to remove water, cooling to room temperature under the protection of nitrogen, rapidly adding 0.2mmol of indium chloride, and stirring for 30min to completely dissolve the indium chloride;
(5) adding 0.3mmol selenium powder and 0.1mL 80% hydrazine hydrate, rapidly heating to 270 deg.C under vigorous stirring at 350 r/min, reflux reacting for 10min, rapidly cooling to room temperature, centrifuging to obtain dark brown solid, washing with anhydrous ethanol for four times, washing with water for one time, and freeze drying to obtain g-C3N4/In2Se3A composite photocatalyst material.
Comparative example 1
Preparation of pure flake-form g-C3N4：
(1) Weighing 15g of urea, placing the urea in a 30mL corundum crucible with a cover, heating to 520 ℃ at the heating rate of 10 ℃/min, and calcining for 150min to obtain primary calcined g-C3N4；
(2) Subjecting the primary calcined g-C obtained in the step (1)3N4(0.5g) was placed in a crucible and subjected to secondary calcination (heating rate 5 ℃/min, calcination temperature 500 ℃ C.), to obtain flaky g-C3N4Abbreviated as U-CN.
Comparative example 2
Preparation of pure In2Se3：
Quickly measuring 50mL of triethylene glycol solvent, quickly transferring the triethylene glycol solvent into a quartz three-neck flask, quickly adding 0.2mmol of indium chloride under the protection of nitrogen atmosphere, stirring for 10min under a sealed condition to completely dissolve the indium chloride, quickly adding 0.2mmol of selenium powder and 0.1mL of hydrazine hydrate, quickly heating to 270 ℃ under the condition of violent stirring, quickly cooling to room temperature without reflux reaction, centrifugally separating to obtain dark brown solids, respectively washing with absolute ethyl alcohol for four times, washing with water once, and freeze-drying to obtain In2Se3A photocatalyst material.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope 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. The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
Claims (10)
1. g-C3N4/In2Se3The preparation method of the composite photocatalyst is characterized by comprising the following steps:
1) mixing flakes g-C3N4Dissolving in a solvent to form a suspension;
2) according to said g-C3N4/In2Se3In the composite photocatalyst2Se3And g-C3N4Adding an indium source into the suspension at a theoretical molar mass ratio of 1-10: 100, and stirring until the indium source is dissolved;
3) continuously adding a selenium source and a reducing agent into the suspension, stirring, heating to 210-290 ℃ at a speed of 10-15 ℃/min, refluxing for 0-1h, and then cooling at a temperature of-5 to 5 ℃ to obtain the g-C3N4/In2Se3A composite photocatalyst is provided.
2. The production method according to claim 1, wherein in step 1), the flake g is prepared-C3N4Dissolving in triethylene glycol solvent to form suspension; then heating and distilling under the protection of nitrogen atmosphere to remove water.
3. The production method according to claim 1, wherein in step 2), the indium source is one or both of indium chloride and indium nitrate.
4. The production method according to claim 1, wherein in step 3), the selenium source is selenium powder; and/or the reducing agent is sodium borohydride or hydrazine hydrate; and/or continuously adding the selenium source into the suspension according to the mol ratio of the indium source to the selenium source of 2-3: 3.
5. The method as claimed in claim 1, wherein in step 3), the selenium source and the reducing agent are added to the suspension, stirred and heated at 10-15 ℃/min to 210-290 ℃ and refluxed for 0-1h, and then cooled at-5 to 5 ℃ to obtain the g-C3N4/In2Se3A composite photocatalyst is provided.
6. The production method according to claim 1, wherein in step 1), the flake g-C3N4Is prepared by the following steps:
s1, mixing g-C3N4Heating the precursor to 500-520 ℃ at the speed of 10-15 ℃/min, and calcining to obtain primary calcined g-C3N4(ii) a The g to C3N4The precursor is selected from one or more of urea, dicyandiamide, melamine, cyanamide and thiourea;
s2, calcining the primary g-C3N4Heating to 500-520 ℃ at the speed of 5-8 ℃/min for secondary calcination to obtain the flaky g-C3N4。
7. The method according to claim 1, wherein in step 1), the mixture is subjected toThe flake form g-C3N4Dissolving in solvent, and ultrasonic treating for 30-120min to obtain suspension.
8. The method according to claim 1, wherein in step 2), the g-C is adjusted to3N4/In2Se3In the composite photocatalyst2Se3And g-C3N4Adding the indium source into the suspension in a theoretical molar mass ratio of 1-10: 100, and stirring for 30-60min until dissolution.
9. g-C prepared by the preparation method of any one of claims 1-83N4/In2Se3A composite photocatalyst is provided.
10. g-C as claimed in claim 93N4/In2Se3The composite photocatalyst is applied to the aspect of photocatalytic hydrogen production.
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| CN112062104A (en) * | 2020-09-08 | 2020-12-11 | 南京理工大学 | In2Se3Application of quantum dots and preparation method thereof |
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| CN115739193A (en) * | 2022-11-25 | 2023-03-07 | 华北电力大学 | Synthesis and application of carbon nitride/MOFs composite material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112062104A (en) * | 2020-09-08 | 2020-12-11 | 南京理工大学 | In2Se3Application of quantum dots and preparation method thereof |
| CN112062104B (en) * | 2020-09-08 | 2023-02-28 | 南京理工大学 | In 2 Se 3 Application of quantum dots and preparation method thereof |
| CN114602509A (en) * | 2022-04-13 | 2022-06-10 | 青岛科技大学 | S-rich defect ZnIn2S4/In2Se3Heterojunction photocatalyst and application |
| CN114602509B (en) * | 2022-04-13 | 2023-08-18 | 青岛科技大学 | S-rich defect ZnIn 2 S 4 /In 2 Se 3 Heterojunction photocatalyst and application thereof |
| CN115739193A (en) * | 2022-11-25 | 2023-03-07 | 华北电力大学 | Synthesis and application of carbon nitride/MOFs composite material |
| CN115739193B (en) * | 2022-11-25 | 2024-01-26 | 华北电力大学 | Synthesis and application of carbon nitride/MOFs composite material |
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Inventor after: An Changsheng Inventor after: Zhang Shumin Inventor after: Zhang Shiying Inventor after: Li Zhongfu Inventor after: Xu Kaiqiang Inventor before: Zhang Shumin Inventor before: Zhang Shiying Inventor before: Li Zhongfu Inventor before: Xu Kaiqiang |