CN107349937B - Preparation method of graphene-based bimetallic sulfide nano composite photocatalyst - Google Patents
Preparation method of graphene-based bimetallic sulfide nano composite photocatalyst Download PDFInfo
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- CN107349937B CN107349937B CN201710508676.5A CN201710508676A CN107349937B CN 107349937 B CN107349937 B CN 107349937B CN 201710508676 A CN201710508676 A CN 201710508676A CN 107349937 B CN107349937 B CN 107349937B
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- salt compound
- graphene
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- cadmium
- bimetallic sulfide
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- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims 1
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- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 claims 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims 1
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- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims 1
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- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 claims 1
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- 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
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- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- 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
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- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a graphene-based bimetallic sulfide nano composite photocatalyst, which is characterized in that a series of graphene-based bimetallic sulfide composite photocatalysts are synthesized by a simple and mild one-step hydrothermal method, and the morphology size and the oriented growth on the surface of graphene of bimetallic sulfide are regulated and controlled by controlling the hydrothermal reaction temperature, the reaction time, the addition amount of graphene and the content of a metal salt compound in a composite system; in addition, the preparation method provided by the invention is simple in process operation, low in raw material price and suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a bimetallic sulfide nano composite photocatalyst with graphene as a carrier, a preparation method thereof and application of the bimetallic sulfide nano composite photocatalyst in photocatalytic hydrolysis hydrogen production.
Background
Environmental pollution and energy shortage have become serious challenges facing the human society in the 21 st century. Therefore, the development and utilization of a novel, pollution-free and economic renewable energy source have profound significance for the sustainable development of the human society. The hydrogen is an ultra-clean secondary energy source, and has the advantages of high energy density, reproducibility, no pollution, storage, transportability and the like. In addition, hydrogen is used as an important chemical raw material and industrial protective gas and widely applied to the industries of metallurgy, fine organic synthesis, aerospace, petrochemical industry and the like. At present, the hydrogen energy is mainly from water gas conversion, hydrocarbon cracking, water electrolysis hydrogen production and the like, and the methods consume a large amount of non-renewable resources and cause pollution. Economic and green production of hydrogen energy is an urgent technical need. Since 1972, Japanese academician Fujishima and Honda successfully utilized TiO2Photo-anode material catalytically decomposes water into H2And O2Therefore, the solar photocatalytic hydrogen production by water decomposition becomes one of the most promising hydrogen production technologies at present, and has great social and economic values. Therefore, the rapid development of a high-performance, low-cost and environment-friendly solar photocatalytic material is one of the key problems to be solved in the technical field of hydrogen production by solar photocatalytic water decomposition. In the last half century, a variety of semiconductor photocatalytic materials such as oxides, sulfides, phosphides, halides, and nitrides, which have hydrogen production activity, have been developed. However, due to the physicochemical properties of these semiconductor materials themselves, defects such as: the material has larger forbidden band width, easy recombination of photo-generated electron-hole pairs, difficult recovery of the catalyst and the like, so that the semiconductor photocatalytic material catalyst is difficult to effectively utilize sunlight and has low photocatalytic hydrolysis hydrogen production activity, thereby limiting the practical application of the material in large-scale industrial production. Therefore, the key to realizing the large-scale industrial application of photocatalytic hydrolysis hydrogen production lies in developing and obtaining a novel photocatalyst with high sunlight utilization rate and high light quantum conversion efficiency.
Among the numerous semiconductor catalytic materials, sulfides, particularly CdS, have become the most widely studied photocatalysts. Due to the narrow forbidden bandwidth, the CdS has high hydrogen production activity under the irradiation of visible light. However, the CdS photocatalytic solution is very easy to generate light corrosion and autoxidation reaction phenomena in the hydrogen production reaction process by photolysis of water, so that the activity and stability of the whole photocatalytic system are not high, and the application of the CdS photocatalytic solution in the hydrogen production field by photolysis is greatly limited. Through deep exploration of the reaction mechanism of hydrogen production by hydrolysis of semiconductor photocatalytic materials and the intrinsic factors influencing catalytic activity, people find various effective ways to solve the bottleneck problem limiting improvement of photocatalytic efficiency, including single ion doping or co-doping, semiconductor compounding based on an energy band theory, surface photosensitization and precious metal cocatalyst loading. However, a large number of literature reports are combined to show that the sulfide semiconductor photocatalyst synthesized based on the improved method does not show remarkable activity of photocatalytic hydrogen production by water decomposition. In addition, due to the use of a large amount of noble metal promoters such as Pt, Au, etc., the preparation cost of the sulfide semiconductor photocatalyst is increased, and the large-scale industrial application is not facilitated.
Therefore, compounding the multi-component semiconductor nano material with graphene is one of effective strategies for improving hydrogen production by photocatalytic hydrolysis in a visible light region of a photocatalyst. The graphene has more excellent electric conduction and heat conduction performances, and the surface of the graphene has numerous oxygen-containing groups and defects, so that a plurality of chemically active sites can be brought, and anchoring sites can be provided for metal ions; in addition, the graphene can play a role in structural support and a conductive channel in a photocatalyst system, so that the directional separation and transmission efficiency of photo-generated charges in the photocatalyst system are greatly improved. Finally, the large specific surface area and the good stability of the graphene can also effectively improve the light absorption efficiency and the service life of the catalyst.
Disclosure of Invention
The invention aims to take two-dimensional material graphene with excellent conductivity as a substrate, and bimetallic sulfide grows in situ on the surface of the substrate, so that the graphene-based bimetallic sulfide nano composite photocatalyst is constructed. By coupling the large specific surface area and the high conductivity of graphene, the high carrier mobility of heterojunction materials with different dimensions is captured and absorbed by strong photons, a nano-channel for high-speed transmission of photo-generated carriers is established, a novel efficient photo-catalytic system is further constructed, and the photo-generated charge separation efficiency and the quantum efficiency of a visible light region of the system are remarkably improved.
The invention also aims to provide a preparation method of the graphene-based bimetallic sulfide nano composite photocatalyst, which is simple, mild, efficient and suitable for large-scale production. Compared with the existing preparation method of the graphene-based catalyst, the preparation method has the advantages of low reaction temperature, short reaction time, uniform dispersion of the bimetallic sulfide on the surface of the graphene, adjustable size and green and controllable whole synthesis process. In addition, the invention uses cheap non-noble metal sulfide to replace noble metals pt, Au and the like, thereby greatly reducing the production cost of the catalyst and simultaneously obviously improving the catalytic activity of the photocatalyst for hydrogen production by water photolysis. In addition, the graphene-based bimetallic sulfide composite photocatalyst prepared by the invention has excellent recycling performance and has potential commercial development prospect.
The invention relates to a preparation method of a graphene-based bimetallic sulfide nano composite photocatalyst, which comprises the following steps:
firstly, preparing graphite oxide powder by adopting a modified Hummer's method, weighing 0.1-1.0g of the graphite oxide powder, dispersing the graphite oxide powder into water, and preparing the graphite oxide powder with the concentration of 1-10 mg.m L-1The graphite oxide solution is prepared into a uniformly dispersed Graphene Oxide (GO) nanosheet suspension by an ultrasonic stripping method, wherein the ultrasonic power is 100-800W, and the ultrasonic time is 2-8 h;
secondly, adding metal salt precursors of bimetallic sulfide, namely a tin salt compound and a cadmium salt compound (or a molybdenum salt compound and a cadmium salt compound; or a nickel salt compound, a zinc salt compound and a cadmium salt compound) into 60m L deionized water according to a certain molar ratio, measuring 1-10m L of GO aqueous solution, dropwise adding the GO aqueous solution into the mixed metal salt aqueous solution, performing ultrasonic dispersion uniformly to form a mixed solution A, then adding 0-0.6mg of citric acid monohydrate, 0-0.8mg of anhydrous glucose, 0-1mg of polyvinylpyrrolidone and 0-0.6mg of hexadecyl trimethyl ammonium bromide into the mixed solution A respectively to form a mixed solution B, and finally magnetically stirring the mixed solution B at normal temperature for 6 hours for later use;
wherein the molar ratio of the metal salt precursor cadmium salt compound and the tin salt compound of the bimetallic sulfide in the step two is 6-1: 3; the molar ratio of the molybdenum salt compound to the cadmium salt compound is 0.01-0.3: 1; the molar ratio of the nickel salt compound to the zinc salt compound to the cadmium salt compound is 0.05-1: 1: 4.
Weighing L-cysteine with the molar weight of 1.0-8.0mmo L, adding the weighed L-cysteine into the mixed solution B in the step two, performing ultrasonic dissolution to form a mixed solution C, magnetically stirring the mixed solution C for 1 hour at normal temperature, transferring the mixed solution C into a stainless steel reaction kettle with a liner of 100m L, performing hydrothermal reaction for 1-20 hours at the temperature of 120-220 ℃, naturally cooling the reaction temperature to room temperature after the reaction is ended, centrifuging the obtained corresponding graphene-based bimetallic sulfide nano composite photocatalyst for 5 minutes on a centrifuge with the rotation speed of 4000r/min, respectively washing the product for multiple times by using water and ethanol, drying the product after centrifugal washing and separation for 24 hours at the temperature of 60 ℃, and finally obtaining the corresponding graphene-based bimetallic sulfide nano composite photocatalyst.
And step four, weighing 0.05g of the graphene-based bimetallic sulfide composite photocatalyst synthesized in the step three, ultrasonically dispersing the graphene-based bimetallic sulfide composite photocatalyst into 50m L of water, adding 5-20m L of organic acid or organic amine as a cavity sacrificial agent, purging with nitrogen for 5min, taking a 300W xenon lamp as a light source, simultaneously filtering out ultraviolet light and far ultraviolet light with the wavelength of less than 420nm by using an optical filter, carrying out hydrogen production reaction by decomposing water under visible light catalysis, and detecting the generation amount of hydrogen by using a gas chromatograph.
Wherein, the organic acid can be any one of lactic acid, malic acid or citric acid, and the organic amine can be any one of diethanolamine, n-propanolamine or triethanolamine; and the volume ratio of the addition amount of the cavity sacrificial agent to water is 0.1-0.5: 1.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method of the graphene-based bimetallic sulfide nano composite photocatalyst is simple and effective and has universality. Synthesizing a series of graphene-based bimetallic sulfide composite photocatalysts by a simple and mild one-step hydrothermal method, and controlling the morphology size and the oriented growth on the surface of graphene of bimetallic sulfide by controlling the hydrothermal reaction temperature, the reaction time, the addition amount of graphene and the content of a metal salt compound in a composite system; in addition, the preparation method has simple process operation and low raw material price, and is suitable for large-scale industrial production;
(2) the design idea of the graphene-based bimetallic sulfide nano composite photocatalyst is reasonable and novel. The invention combines the research hotspot and difficulty problem of the current photocatalytic hydrolysis hydrogen production, starts from the semiconductor energy band theory, takes the crystallography theory as an entry point, takes GO which has large specific surface area and high conductivity and is rich in oxygen-containing functional groups as a conductive substrate and an electronic transmission channel, and anchors and grows a uniformly dispersed bimetal sulfide composite photocatalyst on the surface of the GO. Photoexcited electrons generated by the light absorption active center can be transferred to an electron acceptor through the electron transmission channel graphene, so that the space separation and transfer of photo-generated electron-hole pairs are realized, and the activity of the composite catalyst for preparing hydrogen by photo-hydrolysis is improved to the maximum extent; in addition, the strategy inhibits the agglomeration and the photo-corrosion of the metal sulfide in the reaction process, and ensures the structural stability and the high-efficiency catalytic circulation activity of the graphene-based bimetal sulfide composite photocatalyst;
(3) by introducing small amounts of non-noble metal sulfides (e.g. Sn)2S3，NiS，Ni3S4，Ni7S6，MoS2And ZnS and the like) to replace common noble metals such as Pt, Au and the like as cocatalyst, not only improves the photocatalytic performance of the catalyst, but also greatly saves the preparation cost of the catalyst to a certain extent, and is beneficial to realizing the practical application of large-scale photolysis water hydrogen production of the series of products.
Drawings
FIG. 1(a) shows Sn prepared by the present invention2S3-SEM image of CdS/rGO composite nanoflake photocatalyst;
FIG. 1(b) is Sn prepared by the present invention2S3-TEM images of CdS/rGO composite nanoflake photocatalysts;
FIG. 2 shows pure Sn prepared by hydrothermal method of the present invention2S3Pure CdS and Sn2S3-XRD pattern of CdS/rGO composite nanoflake photocatalyst;
FIG. 3(a) is a graph of the rate of hydrogen production by visible light hydrolysis for hydrothermal methods of preparing catalyst samples according to the present invention (. lamda. >420 nm);
FIG. 3(b) is Sn prepared by the present invention2S3-CdS/rGO composite nanosheet visible light hydrolysis hydrogen production cyclic activity diagram (lambda)>420nm)；
FIG. 4(a) shows NiSx/Cd prepared by the present invention0.8Zn0.2S/rGO composite nano-filmsSEM pictures of the sheet;
FIG. 4(b) shows NiSx/Cd prepared by the present invention0.8Zn0.2TEM image of S/rGO composite nanoplatelets;
FIG. 5(a) is an XRD pattern of NiSx/rGO samples prepared by the hydrothermal method of the present invention;
FIG. 5(b) shows NiSx/Cd prepared by hydrothermal method of the present invention0.8Zn0.2XRD patterns of S/rGO samples;
FIG. 5(c) shows Cd prepared by hydrothermal method of the present invention0.8Zn0.2An XRD pattern of the S sample;
FIG. 6(a) is a graph of the rate of hydrogen production by visible light hydrolysis for hydrothermal methods of preparing catalyst samples according to the present invention (. lamda. >420 nm);
FIG. 6(b) shows NiSx/Cd prepared by the present invention0.8Zn0.2Visible light hydrolysis hydrogen production cycle activity diagram (lambda) of S/rGO composite nano sheet>420nm)；
FIG. 7(a) is a MoS prepared according to the invention2SEM image of/CdS/rGO composite nanosheet catalyst;
FIG. 7(b) is a MoS prepared according to the present invention2TEM image of/CdS/rGO composite nanoflake catalyst;
FIG. 8(a) shows MoS prepared by hydrothermal method of the present invention2XRD patterns of/CdS/rGO samples;
FIG. 8(b) is an XRD pattern of a sample of pure CdS prepared by a hydrothermal method according to the present invention;
FIG. 8(c) is a diagram of pure MoS prepared by hydrothermal method of the present invention2Sample XRD pattern;
FIG. 9(a) is a graph of visible light hydrolysis hydrogen production activity (λ >420nm) for a catalyst sample prepared by a hydrothermal method according to the present invention;
FIG. 9(b) is a MoS prepared according to the present invention2Visible light hydrolysis hydrogen production cycle activity diagram (lambda) of/CdS/rGO composite nano sheet>420nm).
Detailed Description
The preparation method of the graphene-based bimetallic sulfide nano-composite photocatalyst is further described in detail by the following examples. It should not be understood that the scope of the above-described subject matter is limited to the following examples, and any techniques implemented based on the above-described subject matter are within the scope of the present invention.
Example 1
(1) Weighing 60mg of dry graphite oxide powder, ultrasonically dispersing the powder into 20m L deionized water, and ultrasonically crushing the powder for 4 hours by using an ultrasonic crusher with the power of 800W to obtain the graphite oxide powder with the concentration of 3 mg.m L-1The aqueous solution of graphene oxide of (a);
(2) 0.2g of glucose, 0.11g of stannic chloride pentahydrate and 0.24g of 2.5 g of cadmium chloride hydrate are respectively weighed and placed in a clean 100m L small beaker, 60m L deionized water is added into the beaker for ultrasonic dissolution to form a mixed solution A, and then 4m L3 mg.m L is added into the mixed solution A-1Magnetically stirring the graphene oxide aqueous solution for 4 hours at normal temperature to form a mixed solution B;
(3) weighing L-cysteine 0.56g, adding into the mixed solution B, ultrasonically dissolving to form a mixed solution C, magnetically stirring at normal temperature for 1h, transferring the mixed solution C into a stainless steel reaction kettle with a liner of 100m L and polytetrafluoroethylene, carrying out hydrothermal reaction at 180 ℃ for 2h, naturally cooling to room temperature after the reaction is ended and the reaction temperature is naturally cooled, centrifuging the obtained precipitate on a centrifuge with the rotation speed of 4000r/min for 5min, washing the product with water and ethanol for multiple times, drying the product after centrifugal washing and separation at 60 ℃ for 24h to finally obtain Sn2S3-a CdS/rGO composite nanoflake photocatalyst;
(4) weighing 0.05g of Sn synthesized in the step (3)2S3Ultrasonically dispersing a CdS/rGO composite nano sheet photocatalyst into 50m L water, respectively adding 5m L of lactic acid and 3.0% of Pt serving as a hole sacrificial agent and a cocatalyst into the suspension, purging with nitrogen for 5min, filtering out ultraviolet light and far ultraviolet light with the wavelength of less than 420nm by using an optical filter, performing hydrogen production reaction by catalytically decomposing water with visible light, and detecting the generation amount of hydrogen by using a gas chromatograph.
FIG. 1 shows the synthesized "island" Sn2S3the-CdS symbiotic nano-crystals are uniformly dispersed on the surface of a reduced graphene oxide (rGO) nano-sheet, and Sn is2S3-the size of the CdS intergrown nanocrystals is between 16.7nm and 27.8 nm.
FIG. 2XRD spectrumThe samples prepared are shown to be highly crystalline and the synthesized CdS is in the hexagonal phase, while Sn2S3Is in an orthorhombic phase. In addition, the figure further shows that Sn is successfully synthesized by a simple one-pot hydrothermal method2S3-CdS/rGO composite nanoflake photocatalyst.
Fig. 3a shows: with pure Sn2S3、Sn2S3Synthetic Sn compared with/rGO and CdS/rGO composite nano material2S3the-CdS/rGO composite nano-flake photocatalyst has the highest capacity of producing hydrogen by decomposing water under the catalysis of visible light, the visible light irradiates for 6 hours, and the hydrogen production amount is up to 994.4 mu mol g-1. Furthermore, Sn can be seen from FIG. 3b2S3the-CdS/rGO composite nano-sheet has continuously increased hydrogen production circulation activity, visible light irradiates for 60h, and the hydrogen production rate is still up to 1671 mu mol.h-1·g-1Showing that Sn2S3the-CdS/rGO composite nano sheet has excellent hydrogen production performance by visible light catalytic hydrolysis and high stability.
Example 2
(1) Weighing 60mg of dry graphite oxide powder, ultrasonically dispersing the powder into 20m L deionized water, and ultrasonically crushing the powder for 6h by using an ultrasonic crusher with the power of 520W to obtain the graphite oxide powder with the concentration of 3 mg.m L-1The aqueous solution of graphene oxide of (a);
(2) respectively weighing 0.2g of glucose, 0.01g of nickel nitrate hexahydrate, 0.06g of zinc nitrate hexahydrate and 0.18g of 2.5 g of cadmium chloride hydrate, placing the weighed materials in a clean 100m L small beaker, adding 60m L deionized water into the beaker, carrying out ultrasonic dissolution to form a mixed solution A, and then adding 5m L3 mg.m L into the mixed solution A-1Magnetically stirring the graphene oxide aqueous solution for 6 hours at normal temperature to form a mixed solution B;
(3) weighing L-cysteine 0.54g, adding the L-cysteine into the mixed solution B, performing ultrasonic dissolution to form a mixed solution C, magnetically stirring the mixed solution C for 1h at normal temperature, transferring the mixed solution C into a 100m L stainless steel reaction kettle with a polytetrafluoroethylene lining, performing hydrothermal reaction at 160 ℃ for 2h, naturally cooling the reaction temperature to room temperature after the reaction is ended, centrifuging the obtained precipitate on a centrifuge with the rotation speed of 4000r/min for 5min, washing the product for multiple times by using water and ethanol respectively, drying the product after centrifugal washing and separation at 60 ℃ for 24h, and finally obtaining the NiSx/Cd0.8Zn0.2S/rGO composite nanosheet photocatalyst;
(4) weighing 0.05g of NiSx/Cd synthesized in the step (3)0.8Zn0.2Ultrasonically dispersing the S/rGO composite nano sheet photocatalyst into 50m L water, respectively adding 5m L of lactic acid serving as a cavity sacrificial agent into the suspension, purging with nitrogen for 5min, taking a 300W xenon lamp as a light source, simultaneously filtering ultraviolet light and far ultraviolet light with the wavelength less than 420nm by using an optical filter, performing hydrogen production reaction by visible light catalytic decomposition of water, and detecting the generation amount of hydrogen by using a gas chromatograph.
FIG. 4 shows the synthesized zero-dimensional NiSx/Cd0.8Zn0.2The S composite nano-microspheres are firmly anchored on the surface of a reduced graphene oxide (rGO) nano-sheet, and NiSx/Cd0.8Zn0.2The S composite nano microspheres have uniform size and good dispersibility, and the size of the microspheres is between 30nm and 60 nm.
FIG. 5XRD pattern shows that the prepared sample is highly crystalline and the synthesized Cd0.8Zn0.2S is a hexagonal phase and NiSx contains a cubic phase Ni3S4And orthorhombic phase Ni7S6. In addition, the figure further shows that the simple one-pot hydrothermal method is used for successfully synthesizing the ternary NiSx/Cd0.8Zn0.2S/rGO composite nano-sheet photocatalyst.
FIG. 6 shows that: with pure NiSx, Cd0.8Zn0.2S, NiSx/rGO and Cd0.8Zn0.2S/rGO comparison, NiSx/Cd0.8Zn0.2The S/rGO composite nano-sheet photocatalyst has the highest hydrogen production capacity by decomposing water under the catalysis of visible light, the irradiation of the visible light is 5 hours, and the hydrogen production rate is as high as 7.84 mmol.h-1·g-1Is obviously higher than Cd0.8Zn0.2Hydrogen production rate (5.84 mmol. h) of S/rGO + Pt catalyst-1·g-1) It shows that the promoter NiSx can completely replace the noble metal Pt. At the same time, NiSx/Cd0.8Zn0.2The S/rGO composite nano-sheet photocatalyst has stable hydrogen production performance by visible light catalytic hydrolysis, the visible light irradiates for 25h, and the hydrogen production amount is still as high as 36.79mmol·g-1。
Example 3
(1) Weighing 60mg of dry graphite oxide powder, ultrasonically dispersing the powder into 20m L deionized water, and ultrasonically crushing the powder for 6h by using an ultrasonic crusher with the power of 520W to obtain the graphite oxide powder with the concentration of 3 mg.m L-1The aqueous solution of graphene oxide of (a);
(2) 0.2g of glucose, 0.2g of citric acid monohydrate, 0.2g of hexadecyl trimethyl ammonium bromide, 0.072g of sodium molybdate dihydrate and 0.46g of 2.5 g of cadmium chloride hydrate are respectively weighed and placed in a clean 100m L small beaker, 60m L deionized water is added into the beaker for ultrasonic dissolution to form a mixed solution A, and then 3m L3 mg.m L is added into the mixed solution A-1Magnetically stirring the graphene oxide aqueous solution for 4 hours at normal temperature to form a mixed solution B;
(3) weighing L-cysteine 0.54g, adding into the mixed solution B, ultrasonically dissolving to form a mixed solution C, magnetically stirring at normal temperature for 1h, transferring the mixed solution C into a stainless steel reaction kettle with a liner of 100m L and polytetrafluoroethylene, carrying out hydrothermal reaction at 200 ℃ for 12h, naturally cooling to room temperature after the reaction is ended and the reaction temperature is naturally cooled, centrifuging the obtained precipitate on a centrifuge with the rotation speed of 4000r/min for 5min, washing the product with water and ethanol for multiple times, drying the product after centrifugal washing and separation at 60 ℃ for 24h, and finally obtaining MoS2a/CdS/rGO composite nanoflake photocatalyst;
(4) 0.05g of MoS synthesized in step (3) was weighed2Ultrasonically dispersing a/CdS/rGO composite nano sheet photocatalyst into 50m L water, respectively adding 5m L of lactic acid serving as a cavity sacrificial agent and a cocatalyst into the suspension, purging with nitrogen for 5min, using a 300W xenon lamp as a light source, simultaneously filtering out ultraviolet light and far ultraviolet light with the wavelength less than 420nm by using an optical filter, carrying out hydrogen production reaction by decomposing water under the catalysis of visible light, and detecting the generation amount of hydrogen by using a gas chromatograph.
FIG. 7 shows a synthetic zero-dimensional MoS2the/CdS composite nano-microspheres are firmly anchored on the surface of a reduced graphene oxide (rGO) nano-sheet and MoS2the/CdS composite nano-microspheres have uniform size and good dispersibility, and the size of the microspheres is between 125nm and 235 nm.
FIG. 8XRD pattern shows that the prepared sample is highly crystalline and the synthesized CdS is cubic and the promoter MoS is2Is in an orthorhombic phase. In addition, the figure further demonstrates the successful synthesis of ternary MoS by a simple one-pot hydrothermal method2a/CdS/rGO composite nano-flake photocatalyst.
FIG. 9 shows that: with pure MoS2CdS comparison, MoS2the/CdS/rGO composite nano-flake photocatalyst has the highest capability of producing hydrogen by decomposing water under the catalysis of visible light, and the hydrogen production amount is up to 8.1 mmol/g after the visible light irradiates for 5 hours-1. At the same time, MoS2the/CdS/rGO composite nano-sheet photocatalyst has stable hydrogen production performance by visible light catalytic hydrolysis, the visible light irradiates for 30 hours, and the hydrogen production amount is still as high as 7.7 mmol/g-1。
Claims (3)
1. A preparation method of a graphene-based bimetallic sulfide nano composite photocatalyst is characterized by comprising the following preparation steps:
(1) firstly, preparing graphite oxide powder by adopting a modified Hummer's method, then weighing 0.1-1.0g of the graphite oxide powder, dispersing the graphite oxide powder into water, and preparing the graphite oxide powder with the concentration of 1-10mg ∙ m L-1The uniformly dispersed graphene oxide nanosheet suspension is prepared from the graphite oxide solution by an ultrasonic stripping method, wherein the ultrasonic power is 100-800W, and the ultrasonic time is 2-8 h;
(2) adding metal salt precursors of a bimetallic sulfide, namely a tin salt compound and a cadmium salt compound, or a molybdenum salt compound and a cadmium salt compound, or a nickel salt compound, a zinc salt compound and a cadmium salt compound into 60m L deionized water according to a molar ratio, then measuring 1-10m L of graphene oxide aqueous solution, dropwise adding the graphene oxide aqueous solution into the mixed metal salt aqueous solution, performing ultrasonic dispersion uniformly to form a mixed solution A, then adding 0-0.6mg of citric acid monohydrate, 0-0.8mg of anhydrous glucose, 0-1mg of polyvinylpyrrolidone and 0-0.6mg of hexadecyl trimethyl ammonium bromide into the mixed solution A respectively to form a mixed solution B, and finally magnetically stirring the mixed solution B at normal temperature for 6 hours for standby application, wherein the molar ratio of the metal salt precursors of the bimetallic sulfide to the cadmium salt compound is 6-1: 3, the molar ratio of the molybdenum salt compound to the cadmium salt compound is 0.01-0.3: 1, and the molar ratio of the nickel salt compound, the zinc salt compound and the cadmium salt compound is 0.05: 1: 4;
(3) weighing L-cysteine with the molar weight of 1.0-8.0mmo L, adding the weighed L-cysteine into the mixed solution B in the step (2), performing ultrasonic dissolution to form a mixed solution C, magnetically stirring the mixed solution C for 1 hour at normal temperature, transferring the mixed solution C into a stainless steel reaction kettle with a liner of 100m L, performing hydrothermal reaction for 1-20 hours at the temperature of 120-220 ℃, naturally cooling the reaction temperature to room temperature after the reaction is ended, centrifuging the obtained corresponding graphene-based bimetallic sulfide nano composite photocatalyst for 5 minutes on a centrifuge with the rotation speed of 4000r/min, respectively washing the product for multiple times by using water and ethanol, drying the product after centrifugal washing and separation for 24 hours at the temperature of 60 ℃, and finally obtaining the corresponding graphene-based bimetallic sulfide nano composite photocatalyst;
(4) weighing 0.05g of the graphene-based bimetallic sulfide composite photocatalyst synthesized in the step (3), ultrasonically dispersing the graphene-based bimetallic sulfide composite photocatalyst into 50m L water, adding 5-20m L of organic acid or organic amine as a cavity sacrificial agent, purging with nitrogen for 5min, using a 300W xenon lamp as a light source, simultaneously filtering out ultraviolet light and far ultraviolet light with the wavelength of less than 420nm by using an optical filter, performing hydrogen production reaction by visible light catalytic decomposition of water, and detecting the generation amount of hydrogen by using a gas chromatograph.
2. The method for preparing the graphene-based bimetallic sulfide nano-composite photocatalyst as claimed in claim 1, wherein in the step (2), the metal salt precursor tin salt compound of the metal sulfide is tin tetrachloride; the cadmium salt compound is one or more of cadmium sulfate, cadmium carbonate, cadmium nitrate or cadmium acetate; the molybdenum salt compound is one or more of ammonium molybdate, bismuth molybdate, ammonium heptamolybdate, potassium molybdate or sodium molybdate; the nickel salt compound is one or more of nickel chloride, nickel nitrate, nickel acetate, nickel ammonium sulfate or nickel sulfamate; the zinc salt compound is one or more of zinc sulfate, zinc acetate or zinc nitrate.
3. The method for preparing the graphene-based bimetallic sulfide nano-composite photocatalyst according to claim 1, wherein in the step (4), an organic acid or an organic amine is selected as a hole sacrificial agent, wherein the organic acid is any one of lactic acid, malic acid or citric acid, and the organic amine is any one of diethanolamine, n-propanolamine or triethanolamine; and the volume ratio of the addition amount of the cavity sacrificial agent to water is 0.1-0.5: 1.
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