CN109201102B - Z-type heterojunction M-C3N4Preparation method of CdS composite photocatalyst - Google Patents
Z-type heterojunction M-C3N4Preparation method of CdS composite photocatalyst Download PDFInfo
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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
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- 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
- 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
-
- 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 provides a Z-type heterojunction M-C3N4The preparation method of the/CdS composite photocatalyst comprises the following steps: firstly, porous g-C is synthesized by a method of thermal polymerization of urea3N4Nanosheets, then photodepositing at g-C3N4The surface is pre-deposited with metal promoter M (Pt, Au, Ag), etc., to synthesize M (Pt, Au, Ag) -g-C3N4Finally, CdS quantum dots are grown in situ on the surface of the CdS quantum dots by a chemical bath deposition method to synthesize M-C3N4and/CdS. The invention realizes the effective regulation and control of a TypeII to Z-type heterojunction composite catalyst model by selectively depositing the metal cocatalyst by utilizing a step-by-step chemical synthesis method. M-C prepared by the invention3N4CdS and traditional TypeII type composite photocatalyst M-CdS/C3N4The comparison shows that the hydrogen production performance by photolysis of water is better.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by photocatalytic water decomposition, and particularly relates to a Z-type heterojunction M-C3N4A preparation method of a CdS composite photocatalyst.
Background
With the development of society, the demand of human beings for energy is gradually increased, but a great amount of fossil energy consumption brings energy and environmental problems, and governments and scientists of various countries vigorously develop and seek green ways for producing new energy in order to realize sustainable development of human society. At present, in the process of photocatalytic water decomposition, recombination of photogenerated electron holes is a key factor for limiting the efficiency of photolysis water hydrogen generation, wherein heterojunction-oriented electron hole separation is one of the most common and effective technical means for promoting photogenerated charge separation researched at present. In order to improve the efficiency of photocatalytic hydrogen production, more requirements are generally placed on the synthesized photocatalytic material.
The Z-type composite photocatalyst is a photocatalytic hydrogen production material with excellent performance, but the photoelectron transfer of most composite catalysts conforms to a TypeII heterojunction model, namely a semiconductor A with electrons having high conduction band positions is transferred to a semiconductor B with low conduction band positions, and holes are transferred from the semiconductor A with low conduction band positions to the semiconductor A with high conduction band positions, so that the oxidation and reduction capability of photo-generated charges is weakened to a great extent; in order to retain the redox abilities of electrons and holes, researchers in the prior art have developed Z-type heterojunction composite photocatalysts.
Compared with the traditional TypeII type composite catalyst, the composite photocatalyst with the Z model structure furthest reserves the oxidation-reduction capability of electrons and holes generated by a conduction band position and a valence band position, and therefore has more excellent photocatalytic performance.
At present, the synthesis of the Z-type composite photocatalyst is complex, and particularly, the existence of a metal capable of being stabilized between two semiconductors has a great challenge. Aiming at the problem, the method mainly adopts a step-by-step synthesis method, and the metal is selectively photo-deposited on the surfaces of different catalysts in advance and then is further compounded with another semiconductor, so that the deposition sites of the metal are controlled, and the structure of the composite photocatalyst is effectively regulated and controlled.
Disclosure of Invention
The invention aims to provide a Z-type heterojunction M-C3N4The preparation method of the/CdS composite photocatalyst realizes effective regulation and control from TypeII to Z-type heterojunction composite photocatalyst model by utilizing a step-by-step chemical synthesis method and selectively depositing a metal cocatalyst, and the synthesized Z-type heterojunction M-C3N4The CdS composite photocatalyst shows excellent hydrogen evolution effect when being used for photocatalytic water hydrogen evolution.
In order to achieve the above purpose, the invention provides the following technical scheme:
z-type heterojunction M-C3N4The preparation method of the/CdS composite photocatalyst comprises the following steps:
1)g-C3N4preparation of
Method for synthesizing nano-porous g-C by utilizing thermal polymerization of urea3N4；
2)M-C3N4Preparation of
Subjecting the g-C obtained in step 1)3N4Putting the powder into a beaker, adding deionized water, putting the powder into a photocatalytic reaction device after ultrasonic dispersion is uniform, and adding a sacrificial agent solution into the beaker to obtain a mixed solution; then, a certain amount of metal salt solution is measured by a pipette and added into the mixed solution to obtain a mixed solution I; under illumination, the mixed solution is subjected to reduction reactionShould form metal particles deposited in g-C3N4Centrifugal washing and drying to obtain M-C3N4；
3)M-C3N4Synthesis of CdS
Mixing M-C obtained in step 2)3N4Adding deionized water, and ultrasonically dispersing uniformly to obtain M-C3N4Mixing the solution with the mixture, and then adding to M-C3N4Adding cadmium chloride, ammonium chloride, thiourea and ammonia water into the mixed solution respectively, and stirring the obtained mixed solution for a certain time until the CdS is in M-C3N4The growth reaction on the surface is complete, and a second mixed solution is obtained;
4)M-C3N4cleaning of CdS materials
Washing the mixed solution II obtained in the step 3) to be neutral, and then centrifugally separating the precipitated particles of the mixed solution II to obtain the water-containing M-C3N4A CdS particle;
5)M-C3N4drying of CdS materials
The water content M-C in the step 4)3N4Drying the CdS granules in a vacuum drying oven to obtain M-C3N4/CdS。
In a Z-type heterojunction M-C as described above3N4Preferably, the metal salt solution in the step 2) is chloroplatinic acid, chloroauric acid or silver nitrate;
preferably, when the metal salt solution is chloroplatinic acid, the deposition is at g-C3N4The surface metal particles of (A) are correspondingly Pt, M-C3N4Represents Pt-C3N4M-C in Steps 3), 4) and 5)3N4/CdS for Pt-C3N4/CdS；
When the metal salt solution is chloroauric acid, the deposition is in g-C3N4The surface metal particles of (A) are correspondingly Au, M-C3N4Represents Au-C3N4M-C in Steps 3), 4) and 5)3N4/CdS for Au-C3N4/CdS；
When the metal salt is dissolvedWhen the liquid is silver nitrate, the deposition is in g-C3N4The surface metal particles of (A) are correspondingly Ag, M-C3N4Represents Ag-C3N4M-C in Steps 3), 4) and 5)3N4/CdS for Ag-C3N4/CdS。
In a Z-type heterojunction M-C as described above3N4Preferably, in the step 1), the nanoporous g-C is synthesized by a thermal polymerization method of urea3N4The method comprises the following specific steps: weighing 10g of urea, putting the urea into a crucible, and sintering in a muffle furnace to obtain the nano porous g-C3N4；
Preferably, the sintering temperature of the sintering treatment in the muffle furnace is 400-600 ℃, and the sintering time is 3-5 h;
preferably, the sintering temperature in the muffle furnace is 500 ℃ and the sintering time is 3 h.
In a Z-type heterojunction M-C as described above3N4Preferably, the sacrificial agent in the step 2) is methanol;
preferably, the addition amount of the methanol is 1-2 ml.
In a Z-type heterojunction M-C as described above3N4Preferably, the addition amount of the metal salt solution in the step 2) is g-C converted into the mass of the corresponding metal particles3N41-5% wt of the powder mass.
In a Z-type heterojunction M-C as described above3N4Preferably, in the step 3), the molar ratio of the cadmium chloride to the ammonium chloride to the thiourea to the ammonia water is 1: 2: 1-4: 10.
In a Z-type heterojunction M-C as described above3N4Preferably, the rotation speed in the centrifugal separation in the step 4) is 10000r/min, and the centrifugal time is 10 min.
In a Z-type heterojunction M-C as described above3N4The preparation method of the/CdS composite photocatalyst is preferably,the amount of the deionized water added in the steps 2) and 3) is 10-20 ml.
In a Z-type heterojunction M-C as described above3N4Preferably, in the step 5), the drying temperature for drying in the vacuum drying oven is 60 ℃, and the drying time is 12 hours.
In a Z-type heterojunction M-C as described above3N4Preferably, in the preparation method of the/CdS composite photocatalyst, the stirring time of the mixed solution in the step 3) is 3-5 hours.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
the invention adopts a step-by-step synthesis method, uses a photoreduction method to pre-deposit metals on the surfaces of different catalysts, and controls and synthesizes C with different heterojunction models3N4A CdS composite photocatalyst. Wherein the metal promoters respectively comprise three different metal sources of platinum, gold and silver, and cadmium sulfide quantum dots are further grown in situ by a chemical bath deposition method to finally obtain Pt-C3N4/CdS、Au-C3N4/CdS、Ag- C3N4the/CdS has a composite photocatalyst different from a Type II heterojunction structure in the traditional method.
The composite photocatalyst prepared by the invention has the advantages that the average hydrogen production rate is 31 mmoleg under the visible light through comparison of hydrogen production performance-1h-1、8.9mmolg-1h-1、5.3mmolg-1h-1The composite photocatalyst is greatly superior to a corresponding composite photocatalyst with a metal cocatalyst Type II heterojunction structure.
The technical scheme provided by the invention is that the simple composite catalyst of the metal deposition site regulation heterojunction model has good photocatalytic performance and Z-type M-C3N4The preparation method of the/CdS is simple and easy to synthesize.
Drawings
FIG. 1 shows Pt-C according to an embodiment of the present invention3N4CdS and Pt-CdS/C3N4XRD pattern of (a);
FIG. 2 shows Pt-C according to an embodiment of the present invention3N4CdS and Pt-CdS/C3N4Transmission electron microscopy images of;
FIG. 3 shows M-C of an embodiment of the present invention3N4CdS and M-CdS/C3N4And (3) photolyzing the water under the visible light to obtain a hydrogen performance comparison curve.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The Z-type heterojunction M-C provided by the invention3N4The preparation method of the CdS composite photocatalyst realizes effective regulation and control of a Type II to Z Type heterojunction composite photocatalyst model by selectively depositing a metal cocatalyst by utilizing a step-by-step chemical synthesis method. The synthesis principle is as follows: firstly, porous g-C is synthesized by a method of thermal polymerization of urea3N4Nanosheets, then photodepositing at g-C3N4The surface is pre-deposited with a metal cocatalyst M (Pt, Au, Ag), and M (Pt, Au, Ag) -g-C is synthesized3N4Finally growing CdS quantum dots on the surface of the CdS quantum dots in situ by a chemical bath deposition method, and finally synthesizing M-C3N4and/CdS. Z-type heterojunction M-C prepared by the invention3N4/CdS compared with Type II heterojunction M-CdS/C3N4The composite photocatalyst model has more excellent performance of photolysis of water to produce hydrogen.
The invention provides a Z-type heterojunction M-C3N4The preparation method of the/CdS composite photocatalyst comprises the following steps:
1)g-C3N4preparation of
Method for synthesizing nano-porous g-C by utilizing thermal polymerization of urea3N4；
2)M-C3N4Preparation of
Subjecting the g-C obtained in step 1)3N4Putting the powder into a beaker, adding deionized water, putting the powder into a photocatalytic reaction device after ultrasonic dispersion is uniform, and adding a sacrificial agent solution into the beaker to obtain a mixed solution; then, a certain amount of metal salt solution is measured by a pipette and added into the mixed solution to obtain a mixed solution I; under illumination, the mixed solution undergoes a reduction reaction to form metal particles deposited on g-C3N4Centrifugal washing and drying to obtain M-C3N4；
3)M-C3N4Synthesis of CdS
Mixing M-C obtained in step 2)3N4Adding deionized water, and ultrasonically dispersing uniformly to obtain M-C3N4Mixing the solution with the mixture, and then adding to M-C3N4Adding cadmium chloride, ammonium chloride, thiourea and ammonia water into the mixed solution respectively, and stirring the obtained mixed solution for a certain time until the CdS is in M-C3N4The growth reaction on the surface is complete, and a second mixed solution is obtained;
4)M-C3N4cleaning of CdS materials
Washing the mixed solution II obtained in the step 3) to be neutral, and then centrifugally separating the precipitated particles of the mixed solution II to obtain the water-containing M-C3N4A CdS particle;
5)M-C3N4drying of CdS materials
The water content M-C in the step 4)3N4Drying the CdS granules in a vacuum drying oven to obtain M-C3N4/CdS。
In the embodiment of the present invention, it is further preferable that the metal salt solution in step 2) is chloroplatinic acid, chloroauric acid, or silver nitrate;
preferably, when the metal salt solution is chloroplatinic acid, the deposition is at g-C3N4Surface metal particles of (1) arePt，M-C3N4Represents Pt-C3N4M-C in Steps 3), 4) and 5)3N4/CdS for Pt-C3N4/CdS；
When the metal salt solution is chloroauric acid, the deposition is in g-C3N4The surface metal particles of (A) are correspondingly Au, M-C3N4Represents Au-C3N4M-C in Steps 3), 4) and 5)3N4/CdS for Au-C3N4/CdS；
When the metal salt solution is silver nitrate, the deposition is in g-C3N4The surface metal particles of (A) are correspondingly Ag, M-C3N4Represents Ag-C3N4M-C in Steps 3), 4) and 5)3N4/CdS for Ag-C3N4/CdS。
In a specific embodiment of the present invention, it is further preferred that in step 1), nanoporous g-C is synthesized by thermal polymerization of urea3N4The method comprises the following specific steps: weighing 10g of urea, putting the urea into a crucible, and sintering in a muffle furnace to obtain the nano porous g-C3N4；
Preferably, the sintering temperature of the sintering treatment in the muffle furnace is 400-600 ℃ (such as 420 ℃, 440 ℃, 450 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃), and the sintering time is 3-5 h (such as 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8 h);
preferably, the sintering temperature in the muffle furnace is 500 ℃ and the sintering time is 3 h.
In a specific embodiment of the present invention, it is further preferred that the sacrificial agent in step 2) is methanol;
preferably, the amount of methanol added is 1-2 ml (e.g. 1.2ml, 1.4ml, 1.6ml, 1.8ml, 2 ml).
Preferably, the amount of methanol added is 2 ml.
In a specific embodiment of the present invention, it is further preferred that the metal salt solution in step 2) is added in an amount of g-C in terms of the mass of the corresponding metal particles3N4Powder of1 to 5% wt (for example, 1.5% wt, 2% wt, 2.5% wt, 3% wt, 3.5% wt, 4% wt, 4.5% wt) by mass.
In a specific embodiment of the present invention, it is further preferable that the molar ratio of the cadmium chloride, the ammonium chloride, the thiourea and the ammonia water in the step 3) is 1: 2: 1-4: 10 (for example, 1: 2: 1: 10, 1: 2: 1.5: 10, 1: 2: 10, 1: 2: 2.5: 10, 1: 2: 3: 10, 1: 2: 3.5: 10, 1: 2: 4: 10).
In the embodiment of the present invention, it is further preferable that the rotation speed in the centrifugal separation in the step 4) is 10000r/min, and the centrifugal time is 10 min.
In an embodiment of the present invention, it is further preferable that the deionized water is added in steps 2) and 3) in an amount of 10-20 ml (e.g. 12ml, 14ml, 16ml, 18ml, 20 ml).
In the embodiment of the present invention, it is further preferable that the drying in the vacuum drying oven in the step 5) is performed at a drying temperature of 60 ℃ for a drying time of 12 hours.
In the embodiment of the present invention, it is further preferable that the stirring time of the mixed solution in step 3) is 3 to 5 hours (for example, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, and 4.8 hours).
In an embodiment of the present invention, it is further preferable that the photocatalytic reaction device used in step 2) is a light source manufactured by beijing porfilly technologies ltd, and an optical filter of 420nm is additionally arranged.
Example 1
The specific embodiment of the invention provides a Z-type heterojunction M-C3N4The preparation method of the/CdS composite photocatalyst comprises the following steps:
1)g-C3N4preparation of
Weighing 10g of urea, putting the urea into a crucible, and sintering in a muffle furnace at 500 ℃ for 3h to obtain the nanoporous g-C3N4；
2)Pt-C3N4Preparation of
Subjecting the g-C obtained in step 1)3N4The powder was placed in a beaker and 10ml of deionised water was addedWater, after ultrasonic dispersion, putting into a photocatalysis reaction device, adding 2ml methanol as sacrificial agent solution into a beaker, then measuring 20 microliter chloroplatinic acid in the mixed solution by a liquid transfer gun, wherein the platinum metal accounts for g-C3N4The mass percent of the powder is 5%, and the concentration of the chloroplatinic acid aqueous solution is 270mg/ml, so as to obtain a mixed solution I; under illumination, the mixed solution undergoes a reduction reaction to form metal particles Pt which are deposited on g-C3N4Centrifugally washing and drying to obtain Pt-C3N4；
3)Pt-C3N4Synthesis of CdS
Subjecting the Pt-C obtained in the step 2)3N4Adding 10ml of deionized water, and uniformly dispersing by ultrasonic to obtain Pt-C3N4Mixed solution, respectively to Pt-C3N4Adding cadmium chloride, ammonium chloride, thiourea and ammonia water into the mixed solution at a molar ratio of 1: 2: 10, stirring the obtained mixed solution for 3h until the CdS is in Pt-C3N4The growth reaction on the surface is complete, and a second mixed solution is obtained;
4)Pt-C3N4cleaning of CdS materials
Washing the mixed solution II obtained in the step 3) until the pH value is about 7, then centrifugally separating precipitate particles in the mixed solution II, wherein the centrifugal speed is 10000r/min, and the centrifugal time is 10min, so as to obtain the water-containing Pt-C3N4A CdS particle;
5)Pt-C3N4drying of CdS materials
Mixing the water-containing Pt-C obtained in the step 4)3N4Drying the CdS granules in a vacuum drying oven at 60 ℃ for 12h to obtain Pt-C3N4/CdS。
The Z-type heterojunction Pt-C prepared in the example3N4Performing X-ray powder diffraction on the CdS composite photocatalyst and simultaneously performing Pt-C diffraction on the CdS composite photocatalyst3N4Performing X-ray powder diffraction with CdS, and comparing the obtained XRD diffraction pattern, as shown in FIG. 1, Pt-C3N4Crystalline diffraction peaks of/CdS and Pt-C3N4Corresponding to the crystal diffraction peak of CdSNo impurity peaks appear, indicating Pt-C3N4And CdS both form good composite catalysts.
The Z-type heterojunction Pt-C prepared in the example3N4Transmission electron microscope analysis is carried out on the/CdS composite photocatalyst, as shown in figure 2, and a projection electron microscope image is shown as C3N4After complexing with CdS, C3N4The porous structure effectively avoids the agglomeration of CdS quantum dots to form Pt-C3N4The CdS composite photocatalyst has good dispersibility.
The Z-type heterojunction Pt-C prepared in the example3N4The composite photocatalyst of the CdS is used for photolyzing the hydrogen production material, and the photocatalytic performance of the material is tested, and the specific method is as follows:
50mg of Pt-C was weighed3N4and/CdS is ultrasonically dispersed in 200ml of water solution, 20ml of lactic acid serving as a sacrificial agent solution is added after uniform dispersion, the mixture is placed in a photochemical reactor, Ar is introduced to purge the reactor for 20min under dark state stirring, after air in the reactor is removed, a circulating cooling water pump is turned on to keep the reaction temperature of the system at about 20 ℃, a 300W xenon lamp (a 420nm optical filter is used for removing the ultraviolet part) is turned on, and a photocatalysis experiment is carried out under stirring.
At intervals during the photocatalytic reaction, 1ml of gas was withdrawn from the photocatalytic reactor by means of a syringe, and the content of hydrogen produced was analyzed by means of gas chromatography. The chromatographic model for analyzing the gas product is Fuli 9700 of Fuli analytical instruments Ltd (Fuli, Zhejiang)
Molecular sieve, TCD, Ar as carrier gas).
The Pt-C prepared in this example was used3N4The hydrogen production amount of the/CdS composite photocatalyst is made into a curve under the illumination of 12h, as shown in a graph in figure 3, and Pt-C after the illumination of 12h3N4The hydrogen yield of the CdS reaches 366mmol-1。
Example 2
In this example, chloroplatinic acid in step 2) was replaced with chloroauric acid, and Au metal particles were deposited in g-C3N4The surface of the substrate is centrifugally washed and dried to obtain Au-C3N4The other method steps are the same as embodiment 1, and are not described herein again.
In this example, the method of photo-deposition is used at g-C3N4The surface of the catalyst is pre-deposited with a metal cocatalyst Au, and then CdS quantum dots are grown in situ on the surface of the catalyst by a chemical bath deposition method to synthesize Au-C3N4/CdS。
The prepared Z-type heterojunction Au-C3N4The composite photocatalyst of/CdS is used for photolyzing a hydrogen production material to test the photocatalytic performance, the specific method is the same as that in example 1, and Au-C prepared in the example is used3N4The hydrogen production amount of the/CdS composite photocatalyst is made into a curve under the illumination of 12h, as shown in a b diagram in figure 3, and Au-C is obtained after the illumination of 12h3N4The hydrogen yield of CdS reaches 107mmolg-1。
Example 3
In this example, the chloroplatinic acid in step 2) was replaced by silver nitrate, and Ag, a metal particle, was deposited in g-C3N4Centrifugally washing and drying to obtain Ag-C3N4The other method steps are the same as embodiment 1, and are not described herein again.
In this example, the method of photo-deposition is used at g-C3N4The Ag-C is synthesized by pre-depositing a metal cocatalyst Ag on the surface, and then growing CdS quantum dots on the surface in situ by a chemical bath deposition method3N4/CdS。
The prepared Z-type heterojunction Ag-C3N4The composite photocatalyst of/CdS is used for photolyzing a hydrogen production material, the photocatalytic performance of the material is tested, the specific method is the same as that in example 1, and Ag-C prepared in the example is used3N4The hydrogen production amount of the CdS composite photocatalyst is made into a curve under the illumination of 12h, as shown in a C diagram in figure 3, Ag-C after the illumination of 12h3N4The hydrogen yield of CdS reaches 63mmolg-1。
Example 4
In this embodiment, the temperature for sintering in the muffle furnace in step 1) is 450 ℃, the sintering time is 2 hours, and other method steps are the same as those in embodiment 1 and are not described herein again.
The Z-type heterojunction Pt-C prepared in the example3N4The composite photocatalyst of/CdS is used as a material for photolyzing hydrogen production to test the photocatalytic performance, the specific method is the same as that in example 1, and the Pt-C prepared in the example is used3N4The hydrogen yield of the/CdS composite photocatalyst under illumination for 12h is made into a curve (not shown in the figure), and Pt-C after illumination for 12h3N4The hydrogen yield of CdS reaches 350mmolg-1Explanation of Pt-C in example 43N4The hydrogen production of/CdS was lower than that of example 1, and varying the sintering temperature and sintering time in example 4 affected Pt-C3N4Hydrogen production by CdS.
Example 5
In this embodiment, the temperature for sintering in the muffle furnace in step 1) is 550 ℃, the sintering time is 4 hours, and other method steps are the same as those in embodiment 1 and are not described herein again.
The Z-type heterojunction Pt-C prepared in the example3N4The composite photocatalyst of/CdS is used as a material for photolyzing hydrogen production to test the photocatalytic performance, the specific method is the same as that in example 1, and the Pt-C prepared in the example is used3N4The hydrogen yield of the/CdS composite photocatalyst under illumination for 12h is made into a curve (not shown in the figure), and Pt-C after illumination for 12h3N4The hydrogen yield of CdS reaches 350mmolg-1Note that Pt-C in example 53N4The hydrogen production of/CdS was lower than that of example 1, and varying the sintering temperature and sintering time in example 5 affected Pt-C3N4Hydrogen production by CdS.
Example 6
In step 3) of this example, the other method steps are the same as example 1, and are not repeated herein, except that the molar ratio of cadmium chloride, ammonium chloride, thiourea and ammonia is 1: 2: 3: 10.
The Z-type heterojunction Pt-C prepared in the example3N4Composite photocatalyst of CdS used for photolyzing aquatic productsHydrogen material, the photocatalytic performance of which was tested in the same manner as in example 1, was prepared by subjecting Pt-C prepared in this example to3N4The hydrogen yield of the/CdS composite photocatalyst under illumination for 12h is made into a curve (not shown in the figure), and Pt-C after illumination for 12h3N4The hydrogen yield of CdS reaches 330mmolg-1Note that Pt-C in example 63N4The hydrogen production of CdS/CdS was lower than that of example 1, and the composition of the raw materials in example 6 was changed for Pt-C3N4The hydrogen production of/CdS will have an effect, and the raw material formulation in example 1 is superior.
Example 7
In this example, the amount of chloroplatinic acid added in step 2) was 10. mu.l, and the platinum metal accounted for g-C3N4The mass percent of the powder is 2.5%, and other method steps are the same as example 1 and are not repeated herein.
The Z-type heterojunction Pt-C prepared in the example3N4The composite photocatalyst of/CdS is used as a material for photolyzing hydrogen production to test the photocatalytic performance, the specific method is the same as that in example 1, and the Pt-C prepared in the example is used3N4The hydrogen yield of the/CdS composite photocatalyst under illumination for 12h is made into a curve (not shown in the figure), and Pt-C after illumination for 12h3N4The hydrogen production of CdS reaches 310mmolg-1Pt-C in example 73N4The hydrogen production data for the/CdS is lower than that of example 1, indicating that the amount of chloroplatinic acid added to Pt-C3N4The hydrogen production of the/CdS has great influence, and the inappropriate addition amount can reduce the Pt-C3N4The hydrogen evolution of/CdS, the chloroplatinic acid addition in example 1 was optimal.
Comparative example 1
The comparison example is used for preparing TypeII type composite photocatalyst Pt-CdS/C with different metal deposition sites3N4I.e. according to the conventional preparation method of type II composite catalysts, in the synthesis of C3N4The surface light deposition metal cocatalyst of the CdS composite catalyst comprises the following specific steps:
synthesis of C3N4catalyst/CdS complexAdding chloroplatinic acid solution before a photocatalyst hydrogen production experiment, carrying out in-situ photoreduction to deposit platinum on the surface of the composite catalyst, wherein the cadmium sulfide conduction band position is lower than that of carbon, nitrogen and nitrogen, and the platinum is deposited on the surface of the cadmium sulfide according to a traditional Type II structure.
The TypeII type heterojunction Pt-CdS/C prepared in the comparative example3N4Carrying out X-ray powder diffraction on the composite photocatalyst, and carrying out XRD diffraction pattern and Pt-C in example 13N4Comparison of/CdS, Pt-CdS/C as shown in FIG. 13N4Crystal diffraction peak and Pt-C of3N4The composite photocatalyst corresponds to a crystal diffraction peak of CdS, and no impurity peak appears, which indicates that the deposition site of Pt does not influence the crystal structure of the composite photocatalyst.
In this comparative example, i.e., according to the conventional preparation method of a TypeII type composite catalyst, in Synthesis C3N4Depositing a metal cocatalyst on the surface of the CdS composite catalyst, and preparing Type II heterojunction Pt-CdS/C from the control example3N4The composite photocatalyst is used for photolyzing the hydrogen production material to test the photocatalytic performance, the specific method is the same as that of the embodiment 1, and the Pt-CdS/C prepared by the comparative example is used3N4The hydrogen production capacity of the composite photocatalyst is manufactured into a curve under the condition of illumination for 12h, the curve is shown as a in figure 3, and Pt-CdS/C is obtained after the composite photocatalyst is illuminated for 12h3N4The hydrogen yield of (A) is up to 117mmol-1，Pt-C3N4The CdS is Pt-CdS/C3N43.1 times the amount of hydrogen produced.
Comparative example 2
The difference between the comparative example and the comparative example 1 is that chloroplatinic acid added before the photocatalytic hydrogen production experiment in the synthesis step is replaced by chloroauric acid, and other steps are the same as the comparative example 1 to prepare TypeII type composite photocatalysts Au-CdS/C with different metal deposition sites3N4。
The TypeII type heterojunction Au-CdS/C prepared in the comparative example3N4The composite photocatalyst is used for photolyzing the hydrogen production material to test the photocatalytic performance, the specific method is the same as that of the embodiment 1, and the Au-Cd prepared by the comparative exampleS/C3N4The hydrogen production capacity of the composite photocatalyst is made into a curve as shown in b in figure 3 under the condition of illumination for 12h, and the Au-CdS/C is obtained after the composite photocatalyst is illuminated for 12h3N4The hydrogen yield of the catalyst reaches 37 mmoleg-1，Au -C3N4/CdS is Au-CdS/C3N42.9 times the amount of hydrogen produced.
Comparative example 3
The difference between the comparative example and the comparative example 1 is that the chloroplatinic acid added before the photocatalytic hydrogen production experiment in the synthesis step is replaced by silver nitrate, and other steps are the same as the comparative example 1 to prepare the TypeII type composite photocatalyst Ag-CdS/C with different metal deposition sites3N4。
The TypeII type heterojunction Ag-CdS/C prepared in the comparative example3N4The composite photocatalyst is used for photolyzing the hydrogen production material to test the photocatalytic performance, the specific method is the same as that of the embodiment 1, and the Ag-CdS/C prepared by the comparative example is used3N4The hydrogen production capacity of the composite photocatalyst is manufactured into a curve as shown in a graph C in figure 3 under the condition of illumination for 12 hours, and Ag-CdS/C is obtained after the composite photocatalyst is illuminated for 12 hours3N4The hydrogen yield of the catalyst reaches 20mmol-1， Ag-C3N4The CdS is Ag-CdS/C3N43.2 times the amount of hydrogen produced.
As can be seen from examples 1-7 and comparative examples 1-3, the invention utilizes a distributed chemical synthesis method to realize effective regulation and control from Type II to Z-Type heterojunction composite photocatalyst model through selective deposition of a metal cocatalyst, and M-CdS/C synthesized in the comparative example3N4M-C of different metal deposition sites prepared according to the invention3N4The comparison of the/CdS shows that the Z-shaped heterojunction composite photocatalyst prepared by the invention is compared with the traditional M-CdS/C3N4The crystal form structure of the material is the same, and the material has more excellent photocatalytic water hydrogen production performance.
The research on the structure, the appearance and the performance of the two composite catalysts with different metal deposition sites proves the influence of the metal deposition sites on the transmission process of photo-generated electrons and the heterojunction structure of the composite catalyst. M-C obtained by the invention3N4CdS and M-CdS/C3N4The comparison shows that the hydrogen production performance by photolysis of water is better.
Through comparison of hydrogen production performance, Pt-C can be obtained under the irradiation of visible light3N4CdS and Pt-CdS/C3N4， Au-C3N4/CdS and Au-CdS/C3N4，Ag-C3N4CdS and Ag-CdS/C3N4The average hydrogen production rates of the two composite catalysts with different heterojunction structures are respectively 31 mmoleg-1h-1And 9.8 mmoleg-1h-1， 8.9mmolg-1h-1And 3.1 mmoleg-1h-1，5.3mmolg-1h-1And 1.6 mmoleg-1h-1。
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 (8)
1. Z-type heterojunction M-C3N4The preparation method of the/CdS composite photocatalyst is characterized by comprising the following steps of:
1)g-C3N4preparation of
Method for synthesizing nano-porous g-C by utilizing thermal polymerization of urea3N4；
In the step 1), the nano-porous g-C is synthesized by using a urea thermal polymerization method3N4The method comprises the following specific steps: weighing 10g of urea, putting the urea into a crucible, and sintering in a muffle furnace to obtain the nano porous g-C3N4；
The sintering temperature of the sintering treatment in the muffle furnace is 400-600 ℃, and the sintering time is 3-5 h;
2)M-C3N4preparation of
Subjecting the g-C obtained in step 1)3N4Putting the powder in a beaker, adding deionized water, and ultrasonically dispersingAfter being mixed, the mixture is put into a photocatalytic reaction device, and a sacrificial agent solution is added into a beaker to obtain a mixed solution; then, a certain amount of metal salt solution is measured by a pipette and added into the mixed solution to obtain a mixed solution I; under illumination, the mixed solution undergoes a reduction reaction to form metal particles deposited on g-C3N4Centrifugal washing and drying to obtain M-C3N4；
The metal salt solution in the step 2) is chloroplatinic acid or chloroauric acid;
the addition amount of the metal salt solution in the step 2) is converted into the mass of the corresponding metal particles as g-C3N41-5% wt of powder mass;
3)M-C3N4synthesis of CdS
Mixing M-C obtained in step 2)3N4Adding deionized water, and ultrasonically dispersing uniformly to obtain M-C3N4Mixing the solution with the mixture, and then adding to M-C3N4Adding cadmium chloride, ammonium chloride, thiourea and ammonia water into the mixed solution respectively, and stirring the obtained mixed solution for a certain time until the CdS is in M-C3N4The growth reaction on the surface is complete, and a second mixed solution is obtained;
the molar ratio of the cadmium chloride to the ammonium chloride to the thiourea to the ammonia water in the step 3) is 1: 2 to (1-4) to 10;
4)M-C3N4cleaning of CdS materials
Washing the mixed solution II obtained in the step 3) to be neutral, and then centrifugally separating the precipitated particles of the mixed solution II to obtain the water-containing M-C3N4A CdS particle;
5)M-C3N4drying of CdS materials
The water content M-C in the step 4)3N4Drying the CdS granules in a vacuum drying oven to obtain M-C3N4/CdS。
2. The Z-type heterojunction M-C of claim 13N4The preparation method of the/CdS composite photocatalyst is characterized in that when the metal salt solution is chloroplatinic acid, the metal salt solution is deposited on g-C3N4The surface metal particles of (A) are correspondingly Pt, M-C3N4Represents Pt-C3N4M-C in Steps 3), 4) and 5)3N4/CdS for Pt-C3N4/CdS；
When the metal salt solution is chloroauric acid, the deposition is in g-C3N4The surface metal particles of (A) are correspondingly Au, M-C3N4Represents Au-C3N4M-C in Steps 3), 4) and 5)3N4/CdS for Au-C3N4/CdS。
3. The Z-type heterojunction M-C of claim 13N4The preparation method of the/CdS composite photocatalyst is characterized in that in the step 1), the sintering temperature in a muffle furnace is 500 ℃, and the sintering time is 3 hours.
4. The Z-type heterojunction M-C of claim 13N4The preparation method of the/CdS composite photocatalyst is characterized in that the sacrificial agent in the step 2) is methanol;
the adding amount of the methanol is 1-2 mL.
5. The Z-type heterojunction M-C of claim 13N4The preparation method of the/CdS composite photocatalyst is characterized in that the rotation speed in the centrifugal separation in the step 4) is 10000r/min, and the centrifugal time is 10 min.
6. The Z-type heterojunction M-C of claim 13N4The preparation method of the/CdS composite photocatalyst is characterized in that the amount of the deionized water added in the steps 2) and 3) is 10-20 mL.
7. The Z-type heterojunction M-C of claim 13N4The preparation method of the/CdS composite photocatalyst is characterized in that in the step 5), the drying temperature for drying in the vacuum drying oven is 60 ℃, and the drying time is 12 hours.
8. The Z-type heterojunction M-C of claim 13N4The preparation method of the/CdS composite photocatalyst is characterized in that the stirring time of the mixed solution in the step 3) is 3-5 hours.
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