CN111569909B - Preparation method of oxidation/reduction-double-promoter compounded CdS-based multielement photocatalytic composite material and hydrogen production application thereof - Google Patents
Preparation method of oxidation/reduction-double-promoter compounded CdS-based multielement photocatalytic composite material and hydrogen production application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 68
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 66
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 58
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 30
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- 238000000034 method Methods 0.000 claims abstract description 28
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- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000006303 photolysis reaction Methods 0.000 claims abstract description 19
- 230000015843 photosynthesis, light reaction Effects 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 14
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- RXHMDIUZIJSGAI-UHFFFAOYSA-J n,n-dimethylcarbamodithioate;molybdenum(4+) Chemical group [Mo+4].CN(C)C([S-])=S.CN(C)C([S-])=S.CN(C)C([S-])=S.CN(C)C([S-])=S RXHMDIUZIJSGAI-UHFFFAOYSA-J 0.000 claims abstract description 5
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- UDWCKMMKPOGURO-UHFFFAOYSA-N 1,2-dihydropyrazolo[3,4-b]pyridin-4-one Chemical compound O=C1C=CNC2=C1C=NN2 UDWCKMMKPOGURO-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
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- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 2
- VQNPSCRXHSIJTH-UHFFFAOYSA-N cadmium(2+);carbanide Chemical compound [CH3-].[CH3-].[Cd+2] VQNPSCRXHSIJTH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 60
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 57
- 239000000463 material Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 27
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical compound [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 24
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- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- -1 CdS compound Chemical class 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
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- C01B3/042—Decomposition of water
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Abstract
The invention relates to a preparation method of an oxidation/reduction-double-promoter compounded CdS-based multielement photocatalytic composite material and hydrogen production application thereof, wherein the preparation method comprises the following steps: s1: the sulfur-containing molybdenum source is molybdenum dimethyldithiocarbamate; s2: preparing a sodium tetrachloropalladate glycol solution as a palladium source; s3: adding the sulfur-containing molybdenum source precursor and the cadmium source precursor into an organic solvent, fully stirring, and uniformly mixing to obtain a precursor reaction solution; s4: carrying out one-step liquid phase microwave-assisted rapid synthesis reaction on the precursor reaction solution; s5: in the reaction process of S4, sodium tetrachloropalladate glycol solution serving as a palladium source is injected in a hot manner, so that the double-promoter composite CdS-based multielement photocatalytic composite material is obtained. The preparation method obtains the CdS-based multielement photocatalytic composite material with excellent hydrogen production performance by selecting and combining specific process steps and process parameters, can be used in the field of hydrogen production through water photolysis, and has good application prospect and industrialization potential.
Description
Technical Field
The invention belongs to the field of inorganic semiconductor materials and energy materials, and particularly relates to a multi-component sulfide photocatalytic composite material, a preparation method thereof and hydrogen production application.
Background
The solar photocatalytic hydrogen production technology not only meets the effective utilization and conversion of solar energy, but also realizes the safe, clean and low-cost hydrogen preparation, thereby becoming one of important approaches for solving the environmental pollution and developing novel renewable energy sources. In the research of solar photocatalytic hydrogen production technology, it is most important to develop and create a novel and efficient photocatalytic hydrogen production system, find a novel visible light-driven photocatalyst with a special energy band structure, and improve the efficiency and stability of photocatalyst hydrogen production.
Among many visible light-responsive semiconductor photocatalyst materials, cadmium sulfide is paid much attention by scientists because of its typical II-VI direct band gap structure (band gap width is 2.40eV), high in solar energy utilization rate and oxidation-reduction potential closest to water decomposition, namely suitable valence band potential (1.50eV) and conduction band potential (-0.87eV vs NHE), satisfy the condition of hydrogen production by photolysis of water. The single-component semiconductor CdS is easy to generate a photo-corrosion phenomenon, namely after a certain illumination time, a CdS compound can generate a photo-decomposition phenomenon to decompose bivalent cadmium ions with toxicity, so that the photo-catalytic activity is reduced. On the other hand, the photo-generated electron-hole pairs on the single-component CdS are easy to recombine, so that the hydrogen production efficiency of photocatalytic hydrolysis is low. By controlling the appearance of the catalyst, doping metal ions or forming a heterojunction material by utilizing a composite cocatalyst, the efficiency of photocatalytic hydrolysis hydrogen production of CdS and the light corrosion resistance can be improved. Among them, a heterostructure formed by loading a cocatalyst on CdS is one of effective methods for reducing recombination of photo-generated electron-hole pairs. When the double promoters (the reduction type promoter and the oxidation type promoter) are compounded at the same time, the best photo-generated carrier separation effect can be achieved.
Two-dimensional molybdenum sulfide (MoS)2) The catalyst is an excellent reduction type cocatalyst, and the surface of the catalyst has a plurality of exposed active centers, so that the catalyst has excellent optical performance and catalytic performance, and the photocatalytic reduction reaction is promoted. The band gap of palladium sulfide (PdS) is 1.60eV, the conduction band and the valence band are close to those of CdS, and the palladium sulfide has excellent optical properties. And PdS is an excellent oxidation type catalyst promoter, and can capture holes from the CdS catalyst, so that electron-hole pairs are better separated. CdS/MoS as described in CN103566953A and CN201610162861.92The composite material has good photocatalytic efficiency. CN201210370370.5, the preparation of PdS/CdS composite material is introduced, and the prepared PdS/CdS nanocomposite material can be applied to the fields of visible light photocatalysis, photoelectric materials, hydrogen storage and the like.
CN201811245436.1 introduces that a microwave-assisted synthesis method is utilized to load a promoter MoS on CdS nano-particles2、WS2And the hydrogen production performance of the particle material obtained by the Pt nanocrystalline is obviously improved, and the superiority of loading multiple promoters on the CdS is also proved.
Disclosure of Invention
In order to solve the problems and the defects in the prior art, the invention aims to provide a preparation method of an oxidation/reduction-double-promoter compounded CdS-based multielement photocatalytic composite material and hydrogen production application thereof. The preparation method is simple, rapid, economic and environment-friendly, and the prepared multi-component sulfide photocatalytic composite material has the advantages of regularity and controllable morphology, and the application of the composite material in the field of photocatalysis is researched.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing an oxidation/reduction-double-promoter composited CdS-based multielement photocatalytic composite material, comprising the steps of:
s1: preparing molybdenum dimethyldithiocarbamate as a sulfur-containing molybdenum source;
s2: preparing a sodium tetrachloropalladate glycol solution as a palladium source;
s3: adding the sulfur-containing molybdenum source precursor and the cadmium source precursor into an organic solvent, fully stirring, and uniformly mixing to obtain a precursor reaction solution;
s4: carrying out one-step liquid phase microwave-assisted rapid synthesis reaction on the precursor reaction solution;
s5: in the above reaction process of S4, a sodium tetrachloropalladate glycol solution as a palladium source was thermally injected, thereby obtaining a multi-component sulfide photocatalytic composite material.
It is further provided that the molybdenum dimethyldithiocarbamate in S1 is obtained by reacting molybdenum chloride, sodium ferbamate and absolute ethanol. In the preparation method of the oxidation/reduction-double-promoter composite CdS-based multi-element photocatalytic composite material of the present invention, in step S1, the amount of ethanol used is not particularly limited, for example, the amount may be an amount that is easy to react and/or perform post-treatment, and those skilled in the art can make appropriate selections and determinations, and thus details are not repeated herein. In step S1, the reaction temperature is preferably room temperature.
It is further provided that in step S3, the cadmium source precursor is selected from any one or a mixture of any more of cadmium diethyldithiocarbamate, cadmium acetate, and cadmium dimethyl. Most preferred is cadmium diethyldithiocarbamate (CED).
It is further provided that in step S3, the organic solvent is C1-6Alcohol, C2-6Any one of glycol, N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone. Preferably a C2-6 diol, most preferably ethylene glycol.
In the preparation method of the oxidation/reduction-double-promoter compounded CdS-based multi-element photocatalytic composite material of the present invention, in step S3, the amount of the organic solvent used is not particularly limited, for example, may be an amount that is easy to react and/or perform post-treatment, and those skilled in the art can make appropriate selection and determination, and details are not repeated here.
It is further provided that in step S3, the mass ratio of the cadmium source precursor to the sulfur-containing molybdenum source is 2: 1.
It is further provided that in step S3, the stirring is: stirring at normal temperature for 40min, and performing ultrasonic treatment for 20 min.
It is further set that the step S4 is as follows:
s4-1: setting a temperature-time program under the microwave power of ultrasonic stirring of 200W, heating the precursor reaction solution obtained in the step S3 from room temperature to 90 ℃, wherein the process needs 3-5 minutes, and keeping the temperature for 10 minutes to obtain a first reaction solution;
s4-2: and continuously heating the first reaction solution to 160 ℃, wherein the process needs 3-5 minutes, and keeping the temperature for 5 minutes to obtain a second reaction solution.
It is further set that the step S5 is as follows:
s5-1: injecting a palladium source into the second reaction solution obtained in the step S4 at 160 ℃, and keeping stirring to obtain a third reaction solution;
s5-2: continuing to heat the third reaction solution at 160 ℃ for 5 minutes, and keeping stirring;
s5-3: and naturally cooling the third reaction solution to room temperature, centrifuging at the centrifugal speed of 18000 rpm for 5 minutes, washing the obtained precipitate with absolute ethyl alcohol for 3-4 times in sequence, and then drying in vacuum to obtain the CdS-based multielement photocatalytic composite material.
The inventor finds that when the preparation method is adopted, the CdS-based multielement photocatalytic composite material with specific appearance forms (both granular and flaky) can be obtained, and when certain process parameters such as raw material dosage ratio, microwave power, constant temperature time and the like are changed, the photocatalytic composite material with the forms cannot be obtained.
In addition, the invention also provides an oxidation/reduction-double-promoter compounded CdS-based multi-element photocatalytic composite material prepared by the method, and the CdS-based multi-element photocatalytic composite material is marked as PdS-CdS-MoS2。
In addition, the invention also provides the application of the oxidation/reduction-double-promoter compounded CdS-based multi-element photocatalytic composite material as photocatalysis in hydrogen production by photolysis of water, and the oxidation/reduction-double-promoter compounded CdS-based multi-element photocatalytic composite material has good application prospect and industrialization potential.
The method specifically comprises the following steps: adding the CdS-based multi-element photocatalytic composite material into a mixture consisting of lactic acid and water, continuously irradiating by using a 300W xenon lamp, filtering by using an optical filter below 420nm, and photolyzing the water to obtain hydrogen.
The method is further characterized in that in the photolysis hydrogen production method, the mass-to-volume ratio of the CdS-based multi-element photocatalytic composite material to a mixture composed of lactic acid and water is 1:1-3 mg/mL. In the photolytic hydrogen production method, the volume ratio of the lactic acid to the water is 1:8-12, and may be, for example, 1:8, 1:9, 1:10, 1:11 or 1: 12.
The oxidation/reduction-double-promoter compounded CdS-based multi-element photocatalytic composite material has excellent photocatalytic hydrogen evolution efficiency, high-efficiency hydrogen evolution performance after continuous long-time reaction, high stability and capability of effectively solving the problems caused by photo-corrosion.
The inventor finds that the oxidation/reduction-double-promoter compounded CdS-based multi-element photocatalytic composite material obtained by the invention can prepare hydrogen by photolysis of water under the illumination condition, has very excellent hydrogen production performance and high stability, and effectively improves the problems caused by light corrosion. Provides a brand-new and high-efficiency photolysis composite material for photolysis hydrogen production, and has huge application potential and industrial value in the industrial field. See the example data for details.
Different from patent CN201811245436.1 are: in the material design, the patent specifically selects promoters with different functions, namely oxidized PdS and reduced MoS2Rather than simply compounding the same type of promoter, separation of photogenerated carriers is more likely to be achieved; in addition, this patent is directed to synthesizing two-dimensional structures of MoS2Amorphous nano-sheet, the obtained PdS-CdS particles are uniformly dispersed in MoS2On the nano-sheet, the particle structure is not agglomerated together, so that the dispersity and the specific surface area of the catalyst are increased to a certain extent, the absorption and utilization of a light source are enhanced, and the composition of a photon-generated carrier is inhibited; in the synthesis method, the CdS-MoS is obtained by utilizing a microwave-assisted synthesis method2After the heterojunction, the palladium source is injected at high temperature by combining a hot injection method, so that the PdS is prevented from independently nucleating in the previous synthesis, the PdS microcrystal is only loaded on the CdS particles, and simultaneously, the PdS microcrystal and the reduced MoS are simultaneously loaded2The nanosheets are spatially separated; therefore, the catalyst promoter with different shapes and different functions, namely the reduction type catalyst promoter MoS, is loaded on the CdS at the same time2When the catalyst is mixed with an oxidized cocatalyst PdS, a CdS-based multielement composite photolysis water catalyst with a multiple heterojunction structure is constructed, multiple synergistic effects are expected to be formed, the separation of photo-generated charges on space is achieved, the photocatalytic hydrolysis hydrogen production efficiency and stability driven by visible light are promoted, and PdS-CdS-MoS is formed2The multielement photocatalytic composite material is a good way to improve the photocatalytic hydrogen production performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a CdS-based multi-element photocatalytic composite material compounded by oxidation/reduction-double promoters prepared in example 1 of the present invention;
FIG. 2 is a Transmission Electron Microscope (TEM) image (FIGS. 2a-2b), a local high resolution TEM image (FIG. 2c) and an elemental energy spectrum (EDS) image (FIGS. 2d-2h) of an oxidized/reduced-double promoted CdS-based multi-element photocatalytic composite material prepared in example 1 of the present invention;
FIG. 3 is an X-ray diffraction pattern (XRD) of a CdS-based multi-element photocatalytic composite material composited by oxidation/reduction-double promoters and prepared in example 1 of the present invention;
FIG. 4 is an X-ray photoelectron spectrum (XPS) of a CdS-based multi-element photocatalytic composite material composited by oxidation/reduction-double promoters and prepared in example 1 of the present invention;
FIG. 5 is a graph showing the diffuse reflection of ultraviolet light (FIG. 5a) and the fluorescence emission (FIG. 5b) of the oxidation/reduction-double-promoter composite CdS-based multi-element photocatalytic composite material prepared in example 1 of the present invention;
fig. 6 is a graph showing a comparison relationship between the irradiation time and the hydrogen production amount in the hydrogen production by photolysis of water between the oxidation/reduction-dual-promoter composite CdS-based multi-component photocatalytic composite material prepared in example 1 of the present invention and different components (fig. 6a), a comparison graph showing the hydrogen production of materials obtained at different heat injection temperatures (fig. 6b), a comparison graph showing the hydrogen production of composite materials with different PdS loading amounts (fig. 6c), and a 12-hour hydrogen production stability graph showing the multi-component sulfide photocatalytic composite material prepared in example 1 (fig. 6 d).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
Example 1
S1: dissolving molybdenum chloride MoCl with the mass ratio of 1:1.5 in 200mL of ethanol5Mixing with sodium dimethyl dithiocarbamate, stirring with magnetic stirrer, mixing, standing for 6 hr, filtering, washing, and vacuum drying for 12 hr to obtain molybdenum source containing sulfur, i.e. molybdenum dimethyl dithiocarbamate Mo (dedc)5。
S2: dissolving 1.00g of sodium tetrachloropalladate solid in 100mL of ethylene glycol to obtain 33.989mmol/L palladium source-sodium tetrachloropalladate solution, and taking 5mL of the solution to dilute to 3.3989 mmol/L;
s3: adding a cadmium source and a molybdenum source into an organic solvent ethylene glycol (500mL) according to a mass ratio of (0.5:0.25), fully stirring by using a magnetic stirring device and an ultrasonic cleaner for 40-50 minutes, and uniformly mixing to obtain a precursor reaction solution;
s4: the precursor reaction solution is rapidly synthesized by a one-step liquid phase microwave-assisted method to obtain a binary sulfide precursor material, and the specific steps are as follows:
s4-1: setting a temperature-time program under the microwave power of ultrasonic stirring of 200W, heating the precursor reaction liquid obtained in the step S3 from room temperature to 90 ℃, wherein the process needs 5 minutes, and keeping the temperature for 10 minutes to obtain a first reaction liquid;
s4-2: continuously heating the first reaction solution to 160 ℃, wherein the process needs 5 minutes, and keeping the temperature for 5 minutes to obtain a second reaction solution;
s5: in the reaction process, a palladium source-sodium tetrachloropalladate solution is injected into the reaction kettle in a hot way, so that the multi-component sulfide photocatalytic composite material is obtained, and the specific steps are as follows:
s5-1: injecting 3.3989mmol/L sodium tetrachloropalladate-glycol solution 8.295mL into the second reaction solution obtained in the step S4 at 160 ℃, and keeping stirring to obtain a third reaction solution;
s5-2: continuing to heat the third reaction solution at 160 ℃ for 5 minutes, and keeping stirring;
s5-3: naturally cooling the third reaction solution to room temperature, centrifuging at the centrifugal speed of 18000 rpm for 5 minutes, washing the obtained precipitate with absolute ethyl alcohol for 3-4 times, and then drying in vacuum to obtain the multi-component sulfide composite material, namely 3% -PdS-CdS-MoS2。
EXAMPLES 2-4 examination of the Material compositions
The sulphides of the different material components shown in table 1 below, except for the three raw materials used in S4, S5, which resulted in ternary sulphide composites. The other operations were the same as in example 1, thus carrying out examples 2-4, and the different composites obtained were named as shown in table 1 below.
TABLE 1 composite materials of different material compositions
EXAMPLES 5-9 examination of Heat injection temperature
Except that a heat injection temperature of 160 ℃ was used in step S5, the palladium source was added at different temperatures as shown in table 2 below: examples 5-9 were carried out using the same procedure as example 1 for the temperature of the sodium tetrachloropalladate/ethylene glycol solution, and the heat injection temperatures and composite material nomenclature used are given in table 2 below.
TABLE 2 composite materials made at different thermal injection temperatures
Examples 10 to 13: investigation of different PdS load amounts
Examples 10 to 13: examples 10-13 were carried out using the same procedure as in example 1 except for the 3 w% PdS loading used in step S5-1 for the different PdS loadings of the multi-sulfide composite shown in Table 3 below.
TABLE 3 multicomponent sulfide composites made at different PdS loadings
Microscopic characterization
The oxidation/reduction-double-promoter compounded CdS-based multielement photocatalytic composite material obtained in example 1 is subjected to microscopic characterization by a plurality of different means, and the results are as follows:
1. as can be seen from a low-power Scanning Electron Microscope (SEM) image of figure 1, the CdS-based multi-element photocatalytic composite material has two shapes, namely granular shapes and flaky shapes. The particle surface is provided with convex thorn shape, and the diameter of the particles is 250-300 nm. The lamellar structures are uniformly distributed in the particles and have a length of about 1.5 μm.
2. As can be seen from the TEM images (fig. a and b) of the transmission electron microscope in fig. 2, the observed sample morphology is consistent with the profile of the sample morphology observed on the SEM, and the figures have granular heterojunction, the granular morphology surface is rough, and it can be observed that the granular composite material is formed by stacking dozens of small particles with nanometer size, and the particle surface has protrusions. The lamellar structure is distributed with a particle structure, consistent with SEM results.
Fig. 2c is a high resolution transmission electron microscope image (HRTEM) of the circled portion in fig. 2 b. Very clear lattice fringes can be seen in fig. 2c, which have widths of 0.242nm and 0.229nm, respectively, measured in correspondence with the faces of the hexagonal phase CdS (102), PdS (202), respectively, in which the sheet structure has no lattice parameter. The small graph in fig. 2c is a selected area electron diffraction pattern (SAED pattern) of the sheet structure, indicating an amorphous structure.
Fig. 2d-2h are the distribution diagrams of the elements of the obtained material, and it can be seen that Cd and Pd are mainly distributed on the particle structure, Mo is mainly distributed on the sheet structure, and S is uniformly distributed on the two structures.
3. As can be seen from the X-ray diffraction pattern (XRD) of FIG. 3, a characteristic main peak of CdS appears atIn different materials, the peak signals do not change obviously, and the other components do not have obvious peak signals in the figure, which is caused by the low content of the Pd source (1)<5％)，MoS2In an amorphous form.
4. As can be seen from the X-ray photoelectron spectroscopy (XPS) chart of FIG. 4, the elements Cd, Mo, Pd and S are respectively represented by Cd2+、Mo2+、Pd2+、S2-The form exists, and the combination of HRTEM can prove PdS/CdS/MoS2The existence of the multi-component sulfide photocatalytic composite material is verified.
Therefore, by combining the above material characteristics, it can be known that the invention successfully synthesizes the multi-component sulfide photocatalytic composite material, namely PdS-CdS-MoS, by a specific preparation method2。
5. FIG. 5 shows the comparison of light absorption intensity and fluorescence emission peak of CdS-based multi-photocatalytic composite material obtained in example 1 of the present invention with pure cadmium sulfide (CdS) and two-component sulfide material. The PdS-CM shown in fig. 5a has the strongest light absorption intensity in the visible range, which is better than the light absorption of single-component and two-component sulfides. The fluorescence emission peak of PdS-CM shown in fig. 5b is the weakest, and it can be considered that the recombination rate of the photo-generated electron-hole pairs is the lowest, which is beneficial to improving the photocatalytic hydrogen production efficiency. FIG. 5 demonstrates that PdS-MoS is associated with a cocatalyst2The compound positive effect of the formula (I).
6. FIG. 6 shows PdS-CdS-MoS obtained in example 1 of the present invention2The hydrogen production performance and stability of the multi-element composite photocatalyst material and other materials are shown. FIG. 6a is a graph comparing the performance of the material with pure cadmium sulfide (CdS), two-component sulfide, three-component sulfide, as MoS2And the hydrogen production performance of the material is greatly improved by compounding the PdS. When two promoters are compounded at the same time, the hydrogen production performance of the material is best, 6610 mu mol/(g.h), and is increased by 82 times compared with single-component CdS; FIG. 6b is a comparison graph of the hydrogen production performance of ternary sulfide obtained by thermally injecting Pd source at different temperatures, and it can be seen that the material obtained by thermally injecting Pd source at the highest temperature (160 ℃) set by microwave reaction has the best hydrogen production performance; FIG. 6c is a graph showing the hydrogen production rate of ternary sulfide composite materials with different PdS loading amounts in hydrogen production by photolysis of water, wherein when the ternary sulfide composite materials are loaded with 3wWhen the percentage of PdS is higher, the hydrogen production performance of the multi-component sulfide composite material is optimal; FIG. 6d shows a ternary sulfide composite PdS-CdS-MoS2The hydrogen production stability of the material is good, and the hydrogen production performance is still kept at a high value after the continuous illumination reaction for 12 hours, and the trend of obvious decline is not generated.
Therefore, the oxidation/reduction-double-promoter compounded CdS-based multi-element photocatalytic composite material has excellent photocatalytic hydrogen production performance and can be applied to the technical field of photocatalytic hydrogen production.
Characterization of the composite materials obtained in the other examples
1. SEM characteristics of the materials obtained in examples 2-13 show that the single-component CdS and the binary sulfide material PdS-CdS are single particle shapes and do not have sheet structures. CM and the materials obtained in examples 5 to 13 exhibit a granular and lamellar structure, but the morphological regularity is inferior to that of the material in example 1.
2. XRD characterization of the materials obtained in examples 10-13 shows that the PdS loading does not change the crystal form change of the composite material.
Photolysis water hydrogen production performance test
1. The CdS-based multi-element photocatalytic composite material obtained in the embodiment 1 is used for hydrogen production by photolysis of water, and the specific treatment method comprises the following steps:
adding 35mg sample into a mixture of 8ml lactic acid and 72ml water, irradiating with solar simulator, filtering with a filter below 420nm, and detecting H produced by gas chromatography2。
When the samples used were the CdS-based multi-photocatalytic composite material prepared in example 1 and the photocatalysts prepared in examples 2-13, respectively, the relationship between the hydrogen production amounts is shown in FIG. 6. From the figure, it can be seen that the photocatalytic hydrogen production performance of pure CdS is the weakest, and the hydrogen production rate is only 80 μmol/(g.h), while the CdS-based multi-element photocatalytic composite material 3 w% -PdS-CdS-MoS in the embodiment 1 of the invention2Has the best hydrogen production performance: the hydrogen production rate is 6610 mu mol/(g.h), which is about 82 times higher than the pure CdS hydrogen production rate and is much higher than the hydrogen production rate of two-component sulfide,And the ternary sulfide composite photocatalyst is obtained under other conditions.
Therefore, the CdS-based multi-element photocatalytic composite material has excellent performance of hydrogen production by water photolysis and can be used in the field of hydrogen production by water photolysis.
2. The hydrogen production by photolysis of water was performed in the same manner as described above, and the specific hydrogen production efficiencies of examples 2 to 13 were shown in the following table.
It can be seen that the cocatalyst MoS2The presence or absence of the PdS has larger appearance, and the addition and the loading amount of the PdS have little influence on the appearance of the material. But the addition of the two improves the hydrogen production performance of the material to a certain extent, and in addition, the Pd source is injected under high temperature (160 ℃) and is loaded with 3.0w percent of PdS to obtain PdS-CdS-MoS2The photocatalytic hydrolysis hydrogen production efficiency of the multielement composite material is optimal.
In summary, it can be seen from all the above embodiments that the preparation method of the present invention obtains the CdS-based multi-element photocatalytic composite material with a unique morphology through the synergistic combination and coordination of specific process steps, process parameters, etc., and the CdS-based multi-element photocatalytic composite material has good hydrogen production performance through photolysis of water.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (8)
1. A preparation method of an oxidation/reduction-double-promoter compounded CdS-based multielement photocatalytic composite material is characterized by comprising the following steps of:
s1: preparing molybdenum dimethyldithiocarbamate as a sulfur-containing molybdenum source;
s2: preparing a sodium tetrachloropalladate glycol solution as a palladium source;
s3: adding the sulfur-containing molybdenum source precursor and the cadmium source precursor into an organic solvent, fully stirring, and uniformly mixing to obtain a precursor reaction solution;
s4: carrying out one-step liquid phase microwave-assisted rapid synthesis reaction on the precursor reaction solution;
s5: in the reaction process of S4, thermally injecting sodium tetrachloropalladate glycol solution serving as a palladium source to obtain the CdS-based multielement photocatalytic composite material;
the step S4 is specifically as follows:
s4-1: setting a temperature-time program under the microwave power of ultrasonic stirring of 200W, heating the precursor reaction solution obtained in the step S3 from room temperature to 90 ℃, wherein the process needs 3-5 minutes, and keeping the temperature for 10 minutes to obtain a first reaction solution;
s4-2: continuously heating the first reaction solution to 160 ℃, wherein the process needs 3-5 minutes, and keeping the temperature for 5 minutes to obtain a second reaction solution;
the step S5 is specifically as follows:
s5-1: injecting a palladium source into the second reaction solution obtained in the step S4 at 160 ℃, loading 3.0w% of PdS, and keeping stirring to obtain a third reaction solution;
s5-2: continuing to heat the third reaction solution at 160 ℃ for 5 minutes, and keeping stirring;
s5-3: naturally cooling the third reaction solution to room temperature, centrifuging for 5 minutes at the centrifugal speed of 18000 rpm, washing the obtained precipitate with absolute ethyl alcohol for 3-4 times in sequence, and then drying in vacuum to obtain the multi-component sulfide composite material.
2. The method for preparing an oxidation/reduction-double-promoter compounded CdS-based multielement photocatalytic composite material as claimed in claim 1, characterized in that: the molybdenum dimethyldithiocarbamate in S1 is obtained by reacting molybdenum chloride, sodium ferbamate, and absolute ethanol, and in step S3, the cadmium source precursor is selected from any one or a mixture of any more of cadmium diethyldithiocarbamate, cadmium acetate, and dimethyl cadmium.
3. The method for preparing an oxidation/reduction-double-promoter compounded CdS-based multielement photocatalytic composite material as claimed in claim 1, characterized in that: in step S3, the organic solvent is C1-6Alcohol, C2-6Any one of glycol, N-dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone.
4. The method for preparing an oxidation/reduction-double-promoter compounded CdS-based multielement photocatalytic composite material as claimed in claim 1, characterized in that: in step S3, the mass ratio of the cadmium source precursor to the sulfur-containing molybdenum source is 2: 1.
5. An oxidation/reduction-double promoter compounded CdS-based multi-photocatalytic composite material as prepared by the method as claimed in any one of claims 1-4, wherein the CdS-based multi-photocatalytic composite material is marked as PdS-CdS-MoS2。
6. Use of the oxidation/reduction-double cocatalyst-composited CdS-based multi-photocatalytic composite material as defined in claim 5 as a photocatalyst in the photolysis of water to produce hydrogen.
7. A method for producing hydrogen by photolysis comprises the following steps: the CdS-based multi-element photocatalytic composite material as defined in claim 5 is added into a mixture consisting of lactic acid and water, and is continuously irradiated by a 300W xenon lamp, filtered by using an optical filter below 420nm, and water is photolyzed to obtain hydrogen.
8. The method of claim 7, wherein: in the photolytic hydrogen production method, the mass-to-volume ratio of the multi-component sulfide photocatalytic composite material to a mixture composed of lactic acid and water is 1:1-3 mg/mL.
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