CN111514914A - Ag-Ni (OH)2-(g-C3N4) Composite photocatalyst and preparation method thereof - Google Patents
Ag-Ni (OH)2-(g-C3N4) Composite photocatalyst and preparation method thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
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- 238000000227 grinding Methods 0.000 claims description 28
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 20
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- 239000008098 formaldehyde solution Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
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- 238000001035 drying Methods 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 101710134784 Agnoprotein Proteins 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 4
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- 230000008569 process Effects 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 22
- 239000001257 hydrogen Substances 0.000 description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 21
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- 238000007146 photocatalysis Methods 0.000 description 3
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
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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
-
- B01J35/39—
-
- B01J35/60—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
Abstract
The invention discloses an Ag-Ni (OH)2‑(g‑C3N4) Composite photocatalyst of Ag and Ni (OH)2Attached to g-C3N41-9% of Ag in the composite photocatalyst, and Ni (OH)2The mass percentage of the composite photocatalyst is 1-9 percent, and the balance is g-C3N4The composite photocatalyst is in a porous and multi-sheet shape. The invention also provides a method for preparing the catalyst, which comprises (1) preparing g-C3N4；(2)g‑C3N4With Ni (NO)3)2·6H2O hydrothermal treatment to obtain Ni (OH)2/g‑C3N4A composite photocatalyst; (3) g-C3N4Obtaining Ag/g-C by silver mirror reaction3N4A composite photocatalyst; (4) weighing the Ni (OH) in the step (2)2‑g‑C3N4Obtaining Ag/Ni (OH) by silver mirror reaction2/g‑C3N4A composite photocatalyst is provided. The invention has the advantages of simple and easily controlled preparation method process, convenient operation, low cost and high visible light catalytic activity of the product.
Description
Technical Field
The invention belongs to the technical field of nano catalytic materials, and particularly relates to Ag-Ni (OH)2-(g-C3N4) A composite photocatalyst and a preparation method thereof.
Background
Graphite phase carbon nitride (g-C)3N4) Is a non-metal organic polymer semiconductor. Because of good chemical stability, thermal stability and semiconductor performance, the crystal has a proper forbidden band width (Eg ═ 2.7eV) and proper positions of a conduction band (CB ═ 1.3eV) and a valence band (VB ═ 1.4eV), and g-C3N4The photocatalyst is easy to prepare, harmless, good in stability and excellent in visible light response characteristic, and is widely applied to the field of photocatalysis, the aspects of removing pollutants W by photocatalysis, synthesizing organic compounds by photocatalysis and the like. The core goal of the photocatalytic technology is to prepare a cheap, efficient and stable photocatalyst. Pure g-C3N4Has not yet reached satisfactory levels in terms of efficiency and stability, mainly because of the pure g-C3N4There are various disadvantages. These disadvantages include; (1) g-C3N4The specific surface area is small, the visible light absorption rate is limited, and the light utilization efficiency is low; (2) the photon-generated carriers are easy to recombine, so that the number of effective photon-generated electrons or holes is small; (3) g-C3N4Is easily decomposed by self-generated photogenerated holes, resulting in g-C3N4The cycle stability of (2) is not good.
Ni(OH)2The photocatalyst is concerned by people due to the stability, the changeable morphology, the good reversible redox reaction, the environmental friendliness and certain photocatalytic performance. Ni (OH)2The p-type photocatalyst is a p-type photocatalyst and can be compounded with a host material to form a p-n heterojunction material, wherein a built-in electric field formed by the heterojunction can play a role in promoting the separation of electrons and holes.
Among all noble metals, Ag has good environmental compatibility and low cost.
Although all three materials can be used as photocatalytic materials or modified photocatalytic materials, how to further improve the photocatalytic efficiency is an important issue to be solved at present.
Disclosure of Invention
To solve the problem of the prior art with a single catalyst, e.g. g-C3N4、Ni(OH)2And Ag has defects in catalytic efficiency, stability, and the like. The invention provides Ag-Ni (OH)2-(g-C3N4) A composite photocatalyst and a preparation method thereof. The purpose is realized because Ag and Ni (OH)2And g-C3N4The heterojunction is directly formed between the two layers, and the direct Z-scheme can avoid the defects of an electronic transmission medium so as to realize the efficient utilization of light, so that the g-C3N4The electron hole separation rate can be improved, the separation efficiency of the photoelectric charges is improved, and the photocatalytic efficiency is effectively improved; deposition of Ag on Ni (OH) by silver mirror reaction2And g-C3N4On the formed complex, Ag, Ni (OH)2And g-C3N4And a ternary composite structure is formed cooperatively, so that the performance of the catalyst is obviously improved.
In order to achieve the purpose, the invention provides the following technical scheme: the invention provides Ag-Ni (OH)2-(g-C3N4) Composite photocatalyst of Ag and Ni (OH)2Attached to g-C3N41-9% of Ag in the composite photocatalyst, and Ni (OH)2The mass percentage of the composite photocatalyst is 1-9 percent, and the balance is g-C3N4The composite photocatalyst is in a porous and multi-sheet shape.
The invention also provides a method for preparing the Ag-Ni (OH)2-(g-C3N4) The method for compounding the photocatalyst comprises the following steps:
(1) preparation of g-C3N4；
(2)Ni(OH)2-g-C3N4The preparation of (1): the prepared g-C3N4Dissolving in 60mL distilled water at a ratio of 10mg/mL, ultrasonic dispersing for 0.5h, stirring at room temperature, adding g-C3N4And Ni (NO)3)2·6H2The mass ratio of O to O is 1: 0.0317-0.2853 Ni (NO)3)2·6H2O, stirring for 1h, adjusting the pH of the mixed solution to 9-10 by using ammonia water with the concentration of 0.05M and the volume of 3mL, and then stirring for 2 h; then transferring the stirred mixed solution to a reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 4h, naturally cooling to room temperature, alternately washing with distilled water and absolute ethyl alcohol for 6 times, carrying out vacuum drying at 60 ℃, and grinding a sample to obtain Ni (OH)2/g-C3N4A complex;
(3)Ag-Ni(OH)2-(g-C3N4) The preparation of (1) weighing the Ni (OH) obtained in the step (2)2-g-C3N4Dissolving in 20mL distilled water at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, placing in an oil bath, stirring, setting the temperature at 40 ℃, and weighing Ni (OH)2-g-C3N4And AgNO3The mass ratio of AgNO is 1: 0.016-0.1443Mixing AgNO3Preparing silver ammonium solution with 4.8-43.2 mul ammonia water, adding the prepared silver ammonium solution when the temperature in the flask reaches 40 ℃, stirring for 5min, adding 1.6-14.4 mul formaldehyde solution, and continuing stirring for 3 h; after the reaction is finished, the obtained solid is washed for 6 times by distilled water and absolute ethyl alcohol alternately, dried for 12 hours in vacuum at the temperature of 60 ℃, and the sample is ground to obtain Ag/Ni (OH)2/g-C3N4And (c) a complex.
Further, the method of step (1) is as follows: the temperature of the ground melamine is raised to 550 ℃ at the heating rate of 2 ℃/min, the temperature is preserved for 4h at 550 ℃, a muffle furnace is naturally cooled to the room temperature, and g-C is taken out3N4Grinding the crude sample, alternately washing with distilled water and anhydrous ethanol for 6 times, drying at 60 deg.C for 12 hr, and grinding again to obtain g-C3N4And is named CN.
By adopting the technical scheme, the invention has the following beneficial effects: in the invention, g-C3N4And Ni (NO)3)2·6H2O hydrothermal method for compounding to obtain Ni (OH)2/g-C3N4A composite photocatalyst prepared by mixing Ni (OH)2/g-C3N4The composite photocatalyst is compounded with Ag through a silver mirror reaction to form Ag/Ni (OH) with porous multi-sheet shape2/g-C3N4The nano composite photocatalyst is tested by adopting the prior art, and Ag and Ni (OH) are used independently under the irradiation of visible light2And g-C3N4The catalytic efficiency is remarkably improved. The preparation method adopted in the invention has the advantages of simple and easily controlled process, convenient operation, low cost and high visible light catalytic activity of the product.
Drawings
Figure 1 is an XRD spectrum of Ax-CN (x ═ 1, 3, 5, 7, 9; x is the percentage of Ag).
FIG. 2 shows CN, A5-CN, N5-CN and A5Ny-CN (y is 1, 3, 5, 7, 9; x is Ni (OH))2Percentage of (c) XRD spectrum.
FIG. 3 is an XRD spectrum of CN, A5-CN, N5-CN and AxN 5-CN.
FIG. 4 is a FT-IR spectrum of CN, A5-CN, N5-CN and A5N 5-CN.
FIG. 5 is a DRS spectrum of CN, A5-CN, N5-CN and A5N 5-CN.
FIG. 6 is an XPS survey of A5N 5-CN.
FIG. 7 is a high resolution XPS spectrum of C1s in A5N 5-CN.
FIG. 8 is a high resolution XPS spectrum of N1s in A5N 5-CN.
FIG. 9 is a high resolution XPS spectrum of Ag 3d in A5N 5-CN.
FIG. 10 is a high resolution XPS spectrum of Ni 2p in A5N 5-CN.
FIG. 11 is a high resolution XPS spectrum of O1s in A5N 5-CN.
FIG. 12 is a TEM image of A5-CN.
FIG. 13 is a TEM image of N5-CN.
FIG. 14 is a TEM image of A5N 5-CN.
FIG. 15 is a HRTEM image of A5N 5-CN.
FIG. 16 is a graph of Ax-CN hydrogen production data.
FIG. 17 is a graph of Ax-CN hydrogen production rate data.
FIG. 18 is a chart of hydrogen production data for CN, A5-CN, N5-CN and A5 Ny-CN.
FIG. 19 is a graph of hydrogen production data for CN, A5-CN, N5-CN, and AxN 5-CN.
FIG. 20 is a graph of hydrogen production rate data for CN, A5-CN, N5-CN, and A5 Ny-CN.
FIG. 21 is a graph of hydrogen production rate data for CN, A5-CN, N5-CN, and AxN 5-CN.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions. The starting materials or reagents used are all commercially available.
The first embodiment is as follows: the invention provides Ag-Ni (OH)2-(g-C3N4) Composite photocatalyst of Ag and Ni (OH)2Attached to g-C3N4The mass percent of Ag in the composite photocatalyst is 1 percent, and Ni (OH)2The mass percentage of the composite photocatalyst is 5 percent, and the balance is g-C3N4The composite photocatalyst is in a porous and multi-sheet shape.
The invention also provides a method for preparing the Ag-Ni (OH)2-(g-C3N4) The method for compounding the photocatalyst comprises the following steps:
(1) preparation of g-C3N4(ii) a g-C is prepared by any method in the prior art3N4Namely, the name is CN;
(2)Ni(OH)2-g-C3N4the preparation of (1): dissolving prepared CN in distilled water 60mL at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, adding CN and Ni (NO) under stirring at room temperature3)2·6H2Ni (NO) with O mass ratio of 1:0.15853)2·6H2O, stirring for 1h, adjusting the pH of the mixed solution to 9-10 by using ammonia water with the concentration of 0.05M and the volume of 3mL, and then stirring for 2 h. Then transferring the stirred mixed solution to a reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 4h, naturally cooling to room temperature, alternately washing with distilled water and absolute ethyl alcohol for 6 times, carrying out vacuum drying at 60 ℃, and grinding a sample to obtain a product containing 5% of Ni (OH)2The composite photocatalyst is named as N5-CN.
(3)Ag-Ni(OH)2-(g-C3N4) The preparation method comprises weighing the N5-CN obtained in the step (2) to dissolve in 20mL of distilled water at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, placing in an oil bath, stirring at 40 ℃, and weighing N5-CN and AgNO3AgNO with the mass ratio of 1:0.0163Mixing AgNO3And 4.8 mu L of ammonia water to prepare a silver ammonium solution, adding the prepared silver ammonium solution when the temperature in the flask reaches 40 ℃, stirring for 5min, adding 1.6 mu L of formaldehyde solution, and continuing stirring for 3 h. After the reaction is finished, the obtained solid is washed for 6 times by distilled water and absolute ethyl alcohol alternately, dried for 12 hours in vacuum at the temperature of 60 ℃, and the sample is ground to obtain the product containing 1 percent of Ag and 5 percent of Ni (OH)2The composite photocatalyst is named as A1N 5-CN.
Example two: the invention provides Ag-Ni (OH)2-(g-C3N4) Composite photocatalyst of Ag and Ni (OH)2Attached to g-C3N4The mass percent of Ag in the composite photocatalyst is 9 percent, Ni (OH)2The mass percentage of the composite photocatalyst is 5 percent, and the balance is g-C3N4The composite photocatalyst is in a porous and multi-sheet shape.
The invention also provides a method for preparing the Ag-Ni (OH)2-(g-C3N4) The method for compounding the photocatalyst comprises the following steps:
(1) preparation of g-C3N4: the temperature of the ground melamine is raised to 550 ℃ at the heating rate of 2 ℃/min, the temperature is preserved for 4h at 550 ℃, a muffle furnace is naturally cooled to the room temperature, and g-C is taken out3N4Grinding the crude sample, alternately washing with distilled water and anhydrous ethanol for 6 times, drying at 60 deg.C for 12 hr, and grinding again to obtain g-C3N4And is named CN.
(2)Ni(OH)2-g-C3N4The preparation of (1): dissolving prepared CN in distilled water 60mL at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, adding CN and Ni (NO) under stirring at room temperature3)2·6H2Ni (NO) with O mass ratio of 1:0.15853)2·6H2O, stirring for 1h, and adjusting the pH of the mixed solution to 9 with ammonia water with the concentration of 0.05M and the volume of 3mLAfter-10, stir for an additional 2 h. Then transferring the stirred mixed solution to a reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 4h, naturally cooling to room temperature, alternately washing with distilled water and absolute ethyl alcohol for 6 times, carrying out vacuum drying at 60 ℃, and grinding a sample to obtain a product containing 5% of Ni (OH)2The composite photocatalyst is named as N5-CN.
(3)Ag-Ni(OH)2-(g-C3N4) The preparation method comprises weighing the N5-CN obtained in the step (2) to dissolve in 20mL of distilled water at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, placing in an oil bath, stirring at 40 ℃, and weighing N5-CN and AgNO3In a mass ratio of 1:0.144 of AgNO3Mixing AgNO3Preparing silver ammonium solution with 43.2 mul ammonia water, adding the prepared silver ammonium solution when the temperature in the flask reaches 40 ℃, stirring for 5min, adding 14.4 mul formaldehyde solution, and continuing stirring for 3 h. After the reaction is finished, the obtained solid is washed for 6 times by distilled water and absolute ethyl alcohol alternately, dried for 12 hours in vacuum at the temperature of 60 ℃, and the sample is ground to obtain the product containing 9 percent of Ag and 5 percent of Ni (OH)2The composite photocatalyst is named as A9N 5-CN.
Example three: the invention provides Ag-Ni (OH)2-(g-C3N4) A composite photocatalyst, said Ag, Ni (OH)2Attached to g-C3N4The mass percent of Ag in the composite photocatalyst is 5 percent, Ni (OH)2The mass percentage of the composite photocatalyst is 1 percent, and the balance is g-C3N4The composite photocatalyst is in a porous and multi-sheet shape.
The invention also provides a method for preparing the Ag-Ni (OH)2-(g-C3N4) The method for compounding the photocatalyst comprises the following steps:
(1) preparation of g-C3N4: the temperature of the ground melamine is raised to 550 ℃ at the heating rate of 2 ℃/min, the temperature is preserved for 4h at 550 ℃, a muffle furnace is naturally cooled to the room temperature, and g-C is taken out3N4Grinding the crude sample, alternately washing with distilled water and anhydrous ethanol for 6 times, drying at 60 deg.C for 12 hr, and grinding again to obtain g-C3N4And is named CN.
(2)Ni(OH)2-g-C3N4The preparation of (1): dissolving prepared CN in distilled water 60mL at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, adding CN and Ni (NO) under stirring at room temperature3)2·6H2Ni (NO) with O mass ratio of 1:0.03173)2·6H2O, stirring for 1h, adjusting the pH of the mixed solution to 9-10 by using ammonia water with the concentration of 0.05M and the volume of 3mL, and then stirring for 2 h. Then transferring the stirred mixed solution to a reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 4h, naturally cooling to room temperature, alternately washing with distilled water and absolute ethyl alcohol for 6 times, carrying out vacuum drying at 60 ℃, and grinding a sample to obtain a product containing 1% of Ni (OH)2The composite photocatalyst is named as N1-CN.
(3)Ag-Ni(OH)2-(g-C3N4) The preparation method comprises weighing the N1-CN obtained in the step (2) to dissolve in 20mL of distilled water at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, placing in an oil bath, stirring at 40 ℃, and weighing N1-CN and AgNO3AgNO with the mass ratio of 1:0.083Mixing AgNO3And 24 mu L of ammonia water to prepare a silver ammonium solution, adding the prepared silver ammonium solution when the temperature in the flask reaches 40 ℃, stirring for 5min, adding 8 mu L of formaldehyde solution, and continuing stirring for 3 h. After the reaction is finished, the obtained solid is washed for 6 times by distilled water and absolute ethyl alcohol alternately, dried for 12 hours in vacuum at the temperature of 60 ℃, and the sample is ground to obtain the product containing 5 percent of Ag and 1 percent of Ni (OH)2The composite photocatalyst is named as A5N 1-CN.
Example four: the invention provides Ag-Ni (OH)2-(g-C3N4) A composite photocatalyst, said Ag, Ni (OH)2Attached to g-C3N4The mass percent of Ag in the composite photocatalyst is 5 percent, Ni (OH)2The mass percentage of the composite photocatalyst is 9 percent, and the rest is g-C3N4The composite photocatalyst is in a porous and multi-sheet shape.
The invention also provides a method for preparing the Ag-Ni (OH)2-(g-C3N4) The method for compounding the photocatalyst comprises the following steps:
(1) preparation of g-C3N4: the temperature of the ground melamine rises to 2 ℃/minKeeping the temperature at 550 ℃ for 4h, naturally cooling the muffle furnace to room temperature, and taking out the g-C3N4Grinding the crude sample, alternately washing with distilled water and anhydrous ethanol for 6 times, drying at 60 deg.C for 12 hr, and grinding again to obtain g-C3N4And is named CN.
(2)Ni(OH)2-g-C3N4The preparation of (1): dissolving prepared CN in distilled water 60mL at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, adding CN and Ni (NO) under stirring at room temperature3)2·6H2Ni (NO) with O mass ratio of 1:0.28533)2·6H2O, stirring for 1h, adjusting the pH of the mixed solution to 9-10 by using ammonia water with the concentration of 0.05M and the volume of 3mL, and then stirring for 2 h. Then transferring the stirred mixed solution to a reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 4h, naturally cooling to room temperature, alternately washing with distilled water and absolute ethyl alcohol for 6 times, carrying out vacuum drying at 60 ℃, and grinding a sample to obtain a product containing 9% of Ni (OH)2The composite photocatalyst is named as N9-CN.
(3)Ag-Ni(OH)2-(g-C3N4) The preparation method comprises weighing the N9-CN obtained in the step (2) to dissolve in 20mL of distilled water at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, placing in an oil bath, stirring at 40 ℃, and weighing N9-CN and AgNO3AgNO with the mass ratio of 1:0.083Mixing AgNO3And 24 mu L of ammonia water to prepare a silver ammonium solution, adding the prepared silver ammonium solution when the temperature in the flask reaches 40 ℃, stirring for 5min, adding 8 mu L of formaldehyde solution, and continuing stirring for 3 h. After the reaction is finished, the obtained solid is washed for 6 times by distilled water and absolute ethyl alcohol alternately, dried for 12 hours in vacuum at the temperature of 60 ℃, and the sample is ground to obtain the product containing 5 percent of Ag and 9 percent of Ni (OH)2The composite photocatalyst is named as A5N 9-CN.
Example five: the invention provides Ag-Ni (OH)2-(g-C3N4) A composite photocatalyst, said Ag, Ni (OH)2Attached to g-C3N4The mass percent of Ag in the composite photocatalyst is 3 percent, Ni (OH)2The mass percentage of the composite photocatalyst is 5 percent, and the balance is g-C3N4The composite photocatalyst is multiThe pores are multi-lamellar in shape.
The invention also provides a method for preparing the Ag-Ni (OH)2-(g-C3N4) The method for compounding the photocatalyst comprises the following steps:
(1) preparation of g-C3N4: the temperature of the ground melamine is raised to 550 ℃ at the heating rate of 2 ℃/min, the temperature is preserved for 4h at 550 ℃, a muffle furnace is naturally cooled to the room temperature, and g-C is taken out3N4Grinding the crude sample, alternately washing with distilled water and anhydrous ethanol for 6 times, drying at 60 deg.C for 12 hr, and grinding again to obtain g-C3N4And is named CN.
(2)Ni(OH)2-g-C3N4The preparation of (1): dissolving prepared CN in distilled water 60mL at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, adding CN and Ni (NO) under stirring at room temperature3)2·6H2Ni (NO) with O mass ratio of 1:0.15853)2·6H2O, stirring for 1h, adjusting the pH of the mixed solution to 9-10 by using ammonia water with the concentration of 0.05M and the volume of 3mL, and then stirring for 2 h. Then transferring the stirred mixed solution to a reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 4h, naturally cooling to room temperature, alternately washing with distilled water and absolute ethyl alcohol for 6 times, carrying out vacuum drying at 60 ℃, and grinding a sample to obtain a product containing 5% of Ni (OH)2The composite photocatalyst is named as N5-CN.
(3)Ag-Ni(OH)2-(g-C3N4) The preparation method comprises weighing the N5-CN obtained in the step (2) to dissolve in 20mL of distilled water at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, placing in an oil bath, stirring at 40 ℃, and weighing N5-CN and AgNO3In a mass ratio of 1:0.048 of AgNO3Mixing AgNO3Preparing silver ammonium solution with 14.4 mu L ammonia water, adding the prepared silver ammonium solution when the temperature in the flask reaches 40 ℃, stirring for 5min, adding 4.8 mu L formaldehyde solution, and continuing stirring for 3 h. After the reaction is finished, the obtained solid is washed for 6 times by distilled water and absolute ethyl alcohol alternately, dried for 12 hours in vacuum at the temperature of 60 ℃, and the sample is ground to obtain the product containing 3 percent of Ag and 5 percent of Ni (OH)2The composite photocatalyst is named as A3N 5-CN.
Example six: the invention provides Ag-Ni (OH)2-(g-C3N4) A composite photocatalyst, said Ag, Ni (OH)2Attached to g-C3N4The mass percent of Ag in the composite photocatalyst is 7 percent, and Ni (OH)2The mass percentage of the composite photocatalyst is 5 percent, and the balance is g-C3N4The composite photocatalyst is in a porous and multi-sheet shape.
The invention also provides a method for preparing the Ag-Ni (OH)2-(g-C3N4) The method for compounding the photocatalyst comprises the following steps:
(1) preparation of g-C3N4: the temperature of the ground melamine is raised to 550 ℃ at the heating rate of 2 ℃/min, the temperature is preserved for 4h at 550 ℃, a muffle furnace is naturally cooled to the room temperature, and g-C is taken out3N4Grinding the crude sample, alternately washing with distilled water and anhydrous ethanol for 6 times, drying at 60 deg.C for 12 hr, and grinding again to obtain g-C3N4And is named CN.
(2)Ni(OH)2-g-C3N4The preparation of (1): dissolving prepared CN in distilled water 60mL at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, adding CN and Ni (NO) under stirring at room temperature3)2·6H2Ni (NO) with O mass ratio of 1:0.15853)2·6H2O, stirring for 1h, adjusting the pH of the mixed solution to 9-10 by using ammonia water with the concentration of 0.05M and the volume of 3mL, and then stirring for 2 h. Then transferring the stirred mixed solution to a reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 4h, naturally cooling to room temperature, alternately washing with distilled water and absolute ethyl alcohol for 6 times, carrying out vacuum drying at 60 ℃, and grinding a sample to obtain a product containing 5% of Ni (OH)2The composite photocatalyst is named as N5-CN.
(3)Ag-Ni(OH)2-(g-C3N4) The preparation method comprises weighing the N5-CN obtained in the step (2) to dissolve in 20mL of distilled water at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, placing in an oil bath, stirring at 40 ℃, and weighing N5-CN and AgNO3In a mass ratio of 1:0.112 of AgNO3Mixing AgNO3Mixing with 33.6 μ L ammonia water to obtain silver ammonium solution, adding the prepared silver ammonium solution when the temperature in the flask reaches 40 deg.C, stirring for 5min, adding 11.2 μ L ammonia waterAfter L of the formaldehyde solution, stirring was continued for 3 h. After the reaction is finished, the obtained solid is washed for 6 times by distilled water and absolute ethyl alcohol alternately, dried for 12 hours in vacuum at the temperature of 60 ℃, and the sample is ground to obtain the product containing 7 percent of Ag and 5 percent of Ni (OH)2The composite photocatalyst is named as A7N 5-CN.
Example seven: the invention provides Ag-Ni (OH)2-(g-C3N4) A composite photocatalyst, said Ag, Ni (OH)2Attached to g-C3N4The mass percent of Ag in the composite photocatalyst is 5 percent, Ni (OH)2The mass percentage of the composite photocatalyst is 3 percent, and the balance is g-C3N4The composite photocatalyst is in a porous and multi-sheet shape.
The invention also provides a method for preparing the Ag-Ni (OH)2-(g-C3N4) The method for compounding the photocatalyst comprises the following steps:
(1) preparation of g-C3N4: the temperature of the ground melamine is raised to 550 ℃ at the heating rate of 2 ℃/min, the temperature is preserved for 4h at 550 ℃, a muffle furnace is naturally cooled to the room temperature, and g-C is taken out3N4Grinding the crude sample, alternately washing with distilled water and anhydrous ethanol for 6 times, drying at 60 deg.C for 12 hr, and grinding again to obtain g-C3N4And is named CN.
(2)Ni(OH)2-g-C3N4The preparation of (1): dissolving prepared CN in distilled water 60mL at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, adding CN and Ni (NO) under stirring at room temperature3)2·6H2Ni (NO) with O mass ratio of 1:0.09513)2·6H2O, stirring for 1h, adjusting the pH of the mixed solution to 9-10 by using ammonia water with the concentration of 0.05M and the volume of 3mL, and then stirring for 2 h. Then transferring the stirred mixed solution to a reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 4h, naturally cooling to room temperature, alternately washing with distilled water and absolute ethyl alcohol for 6 times, carrying out vacuum drying at 60 ℃, and grinding a sample to obtain a product containing 3% of Ni (OH)2The composite photocatalyst is named as N3-CN.
(3)Ag-Ni(OH)2-(g-C3N4) The preparation of (1) is that the N3-C obtained in the step (2) is weighedDissolving N in distilled water 20mL at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, placing in oil bath, stirring, setting temperature at 40 deg.C, and weighing N3-CN and AgNO3AgNO with the mass ratio of 1:0.083Mixing AgNO3And 24 mu L of ammonia water to prepare a silver ammonium solution, adding the prepared silver ammonium solution when the temperature in the flask reaches 40 ℃, stirring for 5min, adding 8 mu L of formaldehyde solution, and continuing stirring for 3 h. After the reaction is finished, the obtained solid is washed for 6 times by distilled water and absolute ethyl alcohol alternately, dried for 12 hours in vacuum at the temperature of 60 ℃, and the sample is ground to obtain the product containing 5 percent of Ag and 3 percent of Ni (OH)2The composite photocatalyst is named as A5N 3-CN.
Example eight: the invention provides Ag-Ni (OH)2-(g-C3N4) A composite photocatalyst, said Ag, Ni (OH)2Attached to g-C3N4The mass percent of Ag in the composite photocatalyst is 5 percent, Ni (OH)2The mass percentage of the composite photocatalyst is 7 percent, and the balance is g-C3N4The composite photocatalyst is in a porous and multi-sheet shape.
The invention also provides a method for preparing the Ag-Ni (OH)2-(g-C3N4) The method for compounding the photocatalyst comprises the following steps:
(1) preparation of g-C3N4: the temperature of the ground melamine is raised to 550 ℃ at the heating rate of 2 ℃/min, the temperature is preserved for 4h at 550 ℃, a muffle furnace is naturally cooled to the room temperature, and g-C is taken out3N4Grinding the crude sample, alternately washing with distilled water and anhydrous ethanol for 6 times, drying at 60 deg.C for 12 hr, and grinding again to obtain g-C3N4And is named CN.
(2)Ni(OH)2-g-C3N4The preparation of (1): dissolving prepared CN in distilled water 60mL at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, adding CN and Ni (NO) under stirring at room temperature3)2·6H2Ni (NO) with O mass ratio of 1:0.22193)2·6H2O, stirring for 1h, adjusting the pH of the mixed solution to 9-10 by using ammonia water with the concentration of 0.05M and the volume of 3mL, and then stirring for 2 h. Then transferring the stirred mixed solution to a reaction kettle at 120 DEG CPerforming hydrothermal treatment for 4h, naturally cooling to room temperature, alternately washing with distilled water and anhydrous ethanol for 6 times, vacuum drying at 60 deg.C, and grinding to obtain a sample containing 7% Ni (OH)2The composite photocatalyst is named as N7-CN.
(3)Ag-Ni(OH)2-(g-C3N4) The preparation method comprises weighing the N7-CN obtained in the step (2) to dissolve in 20mL of distilled water at a ratio of 10mg/mL, ultrasonically dispersing for 0.5h, placing in an oil bath, stirring at 40 ℃, and weighing N7-CN and AgNO3AgNO with the mass ratio of 1:0.083Mixing AgNO3And 24 mu L of ammonia water to prepare a silver ammonium solution, adding the prepared silver ammonium solution when the temperature in the flask reaches 40 ℃, stirring for 5min, adding 8 mu L of formaldehyde solution, and continuing stirring for 3 h. After the reaction is finished, the obtained solid is washed for 6 times by distilled water and absolute ethyl alcohol alternately, dried for 12 hours in vacuum at the temperature of 60 ℃, and the sample is ground to obtain the product containing 5 percent of Ag and 7 percent of Ni (OH)2The composite photocatalyst is named as A5N 7-CN.
The following is a list of some structural and morphological characterization of the experimental data to illustrate the use of Ag, Ni (OH) in the present invention2The optimum composite photocatalyst can be obtained by adding the compound photocatalyst.
Fig. 1-3 are XRD spectra of the photocatalyst. Fig. 1 is an XRD spectrum of Ax-CN (x ═ 1, 3, 5, 7, 9; x is the percentage of Ag), from which it can be seen that when no Ag is present in the photocatalyst, only the characteristic peaks of CN, two distinct peaks at 13.4 ° (100) and 27.5 ° (002), the peak at 13.4 ° being a tri-s-triazinyl unit and the peak at 27.5 ° being due to interlayer stacking of the conjugated aromatic system. When Ag is present, in addition to the two peaks of CN, there are four characteristic peaks of Ag, 38.1 ° (111), 44.3 ° (200), 64.4 ° (220), and 77.4 ° (311). It can also be seen from the figure that as the percentage content of Ag increases, the two characteristic peaks of CN gradually decrease, and the four characteristic peaks of Ag gradually increase, which proves that Ag exists in the composite photocatalyst Ax-CN. FIGS. 2 and 3 are CN, A5-CN, N5-CN, Ag and Ni (OH)2Ag-Ni (OH) of different mass ratios2-(g-C3N4) XRD spectrogram of the composite photocatalyst. As can be seen from the figure, the sample of AxNy-CN contains not only the characteristic peak of CN, but also Ag and Ni (OH)2Characteristic peaks of (A), indicating Ag and Ni (OH)2Successfully attached to the CN. As can be seen from FIG. 2, when the fixed Ag content is 5%, Ni (OH)2Diffraction intensity of three peaks with Ni (OH)2The content is increased. As can be seen from FIG. 3, when Ni (OH) is fixed2At 5%, the diffraction intensities of the four peaks of Ag increase with increasing Ag content. And with Ag and Ni (OH)2Gradually increased in CN and gradually decreased in the relative intensities of the peaks at 13.4 ℃ and 27.3 ℃, indicating Ag and Ni (OH)2So that the peak intensity of CN is reduced. This also shows that Ag exists in the ternary composite photocatalyst and Ni (OH) exists2。
FIG. 4 is a FT-IR spectrum of CN, A5-CN, N5-CN and A5N 5-CN. Pure CN is at 3000-3580cm-1The broad peak between is attributed to N-H or NH2The stretching mode and hydrogen bond interaction of (1) at 1200-1650cm-1The peak in between corresponds to the typical tensile vibration mode of the CN heterocycle at 810cm-1The nearby absorption peak is the bending vibration mode of the triazine unit. The characteristic peak attributed to Ag was not observed in the photocatalyst, and it was likely that the Ag content was small and was not exhibited. In the presence of Ni (OH)2Of the existing photocatalysts, a photocatalyst at 3645cm can be easily identified-1Infrared peak of (1), which belongs to Ni (OH)2Typical signal peaks. This illustrates Ni (OH)2Successful attachment to g-C3N4The above.
FIG. 5 is a DRS spectrum of CN, A5-CN, N5-CN and A5N 5-CN. As shown, CN exhibits a strong intrinsic absorption band from ultraviolet to visible, with an absorption edge at 460nm, due to electron transition from the valence band to the conduction band of CN. It was observed that when 5% Ag was introduced into CN to form a5-CN photocatalyst, the absorption edge was significantly red-shifted and the absorption of CN increased over the entire range from ultraviolet to infrared, with the increase in absorption in the visible region being primarily due to Surface Plasmon Resonance (SPR) absorption by Ag. When 5% Ni (OH)2When CN was introduced to form N5-CN photocatalyst, the absorption edge appeared slightly red-shifted, indicating that Ni (OH)2The addition of (2) enhances the utilization rate of the catalyst to light. From the figure can alsoIt was observed that 5% Ag and 5% Ni (OH)2When CN is introduced to form the A5N5-CN photocatalyst, the red shift of the absorption edge is more obvious, which shows that the catalyst has stronger utilization rate to visible light, and means that Ag and Ni (OH)2And simultaneously, more available photon-generated carriers can be generated by introducing the photocatalyst, which is very consistent with the improvement of the photocatalytic hydrogen production performance.
FIGS. 6-11 are XPS spectra of A5N5-CN, which analyzed the elemental composition and valence state of A5N 5-CN. Because of Ag-Ni (OH)2-(g-C3N4) In the ternary composite photocatalyst, regardless of Ag and Ni (OH)2The content ratio of (A) is more than or equal to that of (B), an XPS spectrum similar to that of A5N5-CN appears, so that the XPS spectrum of the composite photocatalyst A5N5-CN with the best photocatalytic performance is tested. As can be seen from the scanning spectrum of FIG. 6, five elements of C, N, Ag, O and Ni are present in A5N5-CN, which is very consistent with the EDS-mapping analysis. FIG. 7 is a high resolution XPS spectrum of C1s with three distinct peaks at 281.5eV, 282.6eV, and 284.5eV, corresponding to graphitic carbon, linked to-NH2Sp of a radical2With C atoms and N ═ C-N bound to the aromatic ring sp2A C atom. FIG. 8 is a high resolution XPS spectrum of N1s showing four asymmetric peaks at 395.2eV, 396.4 eV, 397.4eV and 401.3eV corresponding to periodic tris-s-triazine units, sp of the tertiary N atom2N atom (C ═ NC) (g-C)3N4N-C in substrates3) Residual amino groups (C-N-H) and pi excitation. FIG. 9 is a high resolution XPS spectrum of Ag 3d showing two major peaks at 364.5eV and 370.6eV, corresponding to Ag 3d due to metallic Ag, respectively5/2And Ag 3d3/2The 3d double peak of the two characteristic peaks is split into 6.1eV, which corresponds to the metal Ag0Species of the species. FIG. 10 is a high resolution spectrum of Ni 2p showing two peaks at 852.8eV and 858.5eV, corresponding to Ni 2p3/2Two peaks are shown at 873.4eV and 877eV, corresponding to Ni 2p1/2It was confirmed that Ni ions exist in the +2 valence state. FIG. 11 is a high resolution XPS spectrum of O1s showing two main peaks at 527.7eV and 529.3eV, the former due to hydroxyl oxygen (Ni-OH) and the latter related to adsorbed molecular water.
FIGS. 12-14 are TEM images of photocatalysts. FIG. 12 is a TEM image of A5-CN photocatalyst showing silver nanoparticles. FIG. 13 is a TEM image of N5-CN photocatalyst, showing Ni (OH)2Nanosheets. FIG. 14 is a TEM image of A5N5-CN photocatalyst showing both silver nanoparticles and Ni (OH)2Nanosheets, which indicate the presence of both silver nanoparticles and Ni (OH) in the ternary composite photocatalyst2Nanosheets.
FIG. 15 is an HRTEM image of A5N5-CN, which can detect a lattice spacing of 0.24nm, corresponding to Ag (111) plane, and a interplanar spacing of 0.336nm, corresponding to Ni (OH)2The (101) plane of (A), which indicates that both Ag and Ni (OH) exist in the composite photocatalyst2。
Photocatalytic activity test
FIGS. 16-21 are graphs of hydrogen production data for photocatalysts. As can be seen from FIG. 16, the hydrogen production of pure CN in 3 hours was 84.53mol g-1When Ag is added, the hydrogen production of the catalyst is obviously improved, wherein the catalyst containing 5 percent of Ag has the best hydrogen production activity, and the hydrogen production in 3 hours is 1557mol g-1. FIG. 17 is a graph of the hydrogen production rate of Ax-CN, from which it can be seen that the hydrogen production rate of A5-CN is 19.5 times that of CN. FIGS. 18, 19 show AxNy-CN photocatalyst with H over 3 hours2The amount produced. As can be seen from the figure, the hydrogen production of A5N5-CN in three hours is 59.75 times, 3.28 times and 12.53 times that of CN, A5-CN and N5-CN, respectively. Figures 20, 21 show the hydrogen production rate over three hours for different photocatalysts. As can be seen from the image, the hydrogen production rate of CN was 29.2mol g-1h-1The photocatalytic hydrogen release rate after loading Ag is 568.9mol g-1h-1In the presence of Ni (OH)2Then, the photocatalytic hydrogen release rate was 161.9mol g-1h-1. Of note, Ag and Ni (OH)2Common load is in g-C3N4The photocatalytic hydrogen production activity of the photocatalyst can be obviously improved, and the photocatalytic hydrogen release rate is 1663.2mol g-1h-1. H of pure CN compared to A5-CN, N5-CN and ternary AxNy-CN nanocomposites2The evolution activity is much lower, the reason for which can be attributed to the ultra-fast recombination of electrons and holes.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. Ag-Ni (OH)2-(g-C3N4) A composite photocatalyst, wherein Ag and Ni (OH) are contained in the photocatalyst2Attached to g-C3N41-9% of Ag in the composite photocatalyst, and Ni (OH)2The mass percentage of the composite photocatalyst is 1-9 percent, and the balance is g-C3N4The composite photocatalyst is in a porous and multi-sheet shape.
2. A process for preparing the Ag-Ni (OH) of claim 12-(g-C3N4) The method for compounding the photocatalyst is characterized by comprising the following steps of:
(1) preparation of g-C3N4；
(2)Ni(OH)2-g-C3N4The preparation of (1): the prepared g-C3N4Dissolving in 60mL distilled water at a ratio of 10mg/mL, ultrasonic dispersing for 0.5h, stirring at room temperature, adding g-C3N4And Ni (NO)3)2·6H2Ni (NO) with O mass ratio of 1: 0.0317-0.28533)2·6H2O, stirring for 1h, adjusting the pH of the mixed solution to 9-10 by using ammonia water with the concentration of 0.05M and the volume of 3mL, and then stirring for 2 h; then transferring the stirred mixed solution to a reaction kettle, carrying out hydrothermal treatment at 120 ℃ for 4h, naturally cooling to room temperature, alternately washing with distilled water and absolute ethyl alcohol for 6 times, carrying out vacuum drying at 60 ℃, and grinding a sample to obtain Ni (OH)2/g-C3N4A complex;
(3)Ag-Ni(OH)2-(g-C3N4) The preparation of (1) weighing the Ni (OH) obtained in the step (2)2-g-C3N4At 10mg/mDissolving L in 20mL of distilled water, ultrasonically dispersing for 0.5h, placing in an oil bath, stirring, setting the temperature to be 40 ℃, and weighing Ni (OH)2-g-C3N4And AgNO3The mass ratio of AgNO is 1: 0.016-0.1443Mixing AgNO3Preparing silver ammonium solution with 4.8-43.2 mul ammonia water, adding the prepared silver ammonium solution when the temperature in the flask reaches 40 ℃, stirring for 5min, adding 1.6-14.4 mul formaldehyde solution, and continuing stirring for 3 h; after the reaction is finished, the obtained solid is washed for 6 times by distilled water and absolute ethyl alcohol alternately, dried for 12 hours in vacuum at the temperature of 60 ℃, and the sample is ground to obtain Ag/Ni (OH)2/g-C3N4And (c) a complex.
3. The method of claim 2, wherein the method of step (1) is as follows: the temperature of the ground melamine is raised to 550 ℃ at the heating rate of 2 ℃/min, the temperature is preserved for 4h at 550 ℃, a muffle furnace is naturally cooled to the room temperature, and g-C is taken out3N4Grinding the crude sample, alternately washing with distilled water and anhydrous ethanol for 6 times, drying at 60 deg.C for 12 hr, and grinding again to obtain g-C3N4。
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