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CN116371425B - CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of composite catalyst - Google Patents

CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of composite catalyst Download PDF

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CN116371425B
CN116371425B CN202310325815.6A CN202310325815A CN116371425B CN 116371425 B CN116371425 B CN 116371425B CN 202310325815 A CN202310325815 A CN 202310325815A CN 116371425 B CN116371425 B CN 116371425B
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CN116371425A (en
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马江权
朱斌
李楠
黄勇
黄良琪
董迁
霍兰兰
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Changzhou University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J27/045—Platinum group metals
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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
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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
    • 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
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Abstract

The invention belongs to the field of piezoelectricity photocatalysts, and in particular relates to CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of the composite catalyst. The invention synthesizes cadmium sulfide material by hydrothermal method, and uses NaBH 4 Etching to prepare cadmium sulfide nano rod (CdS-Vs) with sulfur vacancy, and then using cobalt ruthenium sulfide (Co) 2 RuS 6 ) Preparation of CdS-Vs/Co rich in sulphur vacancies as promoters by simple impregnation 2 RuS 6 Under the synergistic effect of solar light irradiation and ultrasonic vibration, the composite material is subjected to piezoelectric photocatalysis to produce H 2 . The invention has the advantages of simple synthesis, green pollution-free and simple operation. The prepared catalyst has the characteristics of rich active sites, excellent stability, no secondary pollution and the like.

Description

CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of composite catalyst
Technical Field
The invention belongs to the technical field of piezoelectro-optic catalysis, and in particular relates to CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of the composite catalyst.
Background
Hydrogen, one of the most promising energy sources for replacing fossil fuels, is a clean renewable energy source, which plays a vital role in global carbon emission reduction and sustainable development. Photocatalytic water splitting to produce hydrogen is receiving a great deal of attention as a potential method for producing hydrogen directly by solar energy. It is reported that a photocatalyst containing defects (such as sulfur vacancies, oxygen vacancies, etc.) has a great application prospect in hydrogen production compared with conventional materials. For example, patent CN 107649150A discloses a preparation method of a Cd/CdS heterojunction visible light catalyst rich in sulfur vacancies, and the obtained catalyst has excellent photocatalytic water splitting activity and stability. Patent CN 109569657A discloses a sulfur-indium-zinc photocatalyst rich in surface sulfur vacancy defect state structure and a preparation method thereof, and after high-temperature high-pressure hydrogenation treatment is carried out on the sulfur-indium-zinc photocatalyst, a large number of sulfur vacancy defect state structures exist on the surface, which can effectively promote separation of photo-generated charges, reduce recombination of photo-generated electron-hole pairs and improve hydrogen production performance of the photocatalyst. However, the method for preparing sulfur vacancy is very complicated and has high cost, and the obtained sample has low hydrogen production efficiency, which limits the application of the sample in practical industry.
Disclosure of Invention
The invention aims to provide a CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation method of composite catalyst and application of composite catalyst in piezoelectric light H production 2 Has high catalytic activity and better stability.
CdS is widely used for photocatalysis due to its narrow bandgap (about 2.4 eV) and the advantage of visible response. However, photocatalytic hydrogen production of pure CdS is still unsatisfactory due to rapid recombination of photogenerated charges and photo-corrosion problems. Vacancy engineering (e.g., S-vacancies) is considered an effective strategy for improving photocatalytic efficiency. The device can capture photo-generated electrons to effectively inhibit the recombination of carriers, thereby improving the hydrogen production performance of water decomposition. In addition, the problem of photo-corrosion of CdS can be improved by constructing different nano structures, so that the application potential of the CdS is further expanded. No CdS-Vs/Co rich in sulfur vacancies has been reported yet 2 RuS 6 Preparation of composite catalyst and its application in piezoelectric photocatalysis.
Here we synthesized a CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Piezoelectric electro-optic catalyst capable of greatly raising H yield 2 Efficiency is improved. Under the combined action of sunlight and ultrasonic waves, cdS-Vs/Co 2 RuS 6 Piezoelectricity photo-catalyst to produce H 2 The amount was 24.3 times that of pure CdS. This work demonstrates that CdS-Vs/Co 2 RuS 6 The composite material can introduce polarized electric field under the synergistic effect of piezoelectric and photocatalysis, so that the piezoelectric catalysis performance is greatly improved.
The technical scheme of the invention is as follows: cdS-Vs/Co rich in sulfur vacancies 2 RuS 6 The preparation method of the composite catalyst comprises the following steps:
CdS (abbreviated as CdS-Vs) and Co containing sulfur vacancies 2 RuS 6 Dispersing in distilled water, fully dispersing, reacting, filtering, washing and drying at room temperature after the reaction is finished to obtain dark green powdery CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 A composite catalyst;
co in composite catalyst 2 RuS 6 The mass is 3% -15% of the mass of CdS-Vs.
Further, co 2 RuS 6 The preparation of (C) comprises first preparing CoCl 2 ·6H 2 O and RuCl 3 Dispersing the aqueous solution in distilled water, stirring, adding TAA (thioacetamide) and PVP (polyvinylpyrrolidone), stirring, transferring the mixture to a reaction kettle lined with polytetrafluoroethylene, standing in a 160 deg.C oven for 36 hr, separating solid at room temperature, washing, drying, and adding into N 2 Annealing at 650 ℃ for 1.9-2.1h under the atmosphere.
The CdS-Vs/Co provided by the invention 2 RuS 6 In the preparation of the composite catalyst, preferably, the reaction time in the preparation of the composite catalyst is 22-24 hours; and/or Co in the composite catalyst 2 RuS 6 The mass is 9.5% -10.5% of the mass of CdS-Vs.
Further, cdS-Vs preparation involves reacting CdCl 2 ·2.5H 2 Adding O and thiourea into ethylenediamine, mixing thoroughly, performing hydrothermal reaction, collecting the precipitate after the reaction, washing with distilled water and ethanol for several times, vacuum drying to obtain CdS free of sulfur vacancy, and mixing with CdS and NaBH 4 Dispersing in water solution, ultrasonic to obtain enough bubbles to ensure high-efficiency preparation of CdS-Vs (ultrasonic time is preferably 30min+1min), separating solid at room temperature after reaction, washing and drying to obtain CdS-Vs.
More specifically, cdS-Vs were prepared by reacting 2.312g of CdCl 2 ·2.5H 2 O and 2.312g thiourea were added to 50mL ethylenediamine. Mixing the mixed solutionTransferring into a reaction kettle lined with polytetrafluoroethylene, performing hydrothermal reaction in an oven at 160 ℃ for 48h, centrifugally collecting the obtained precipitate, washing with distilled water and ethanol for multiple times, vacuum drying at 60 ℃ for 12h, and grinding to obtain CdS powder without sulfur vacancies. 0.3g of CdS powder free of sulfur vacancies and 1.1349g of NaBH 4 Dispersing in water solution, ultrasonic treating for 30min, centrifuging after reaction, washing, and drying to obtain yellow CdS-Vs powder.
Further, co 2 RuS 6 The heating rate of the tube furnace in the preparation is set to be 4.9-5.1 ℃/min, and the heating time is set to be 2+/-2.2 h.
More specifically, co 2 RuS 6 Preparation of (A) 0.1190g CoCl 2 ·6H 2 O and 1035. Mu.L RuCl 3 Aqueous solution (53.33 mg. ML) -1 RuCl 3 ·χH 2 O) was dispersed in 35mL distilled water, stirred for 0.5h, then 0.1503g TAA and 0.0175g PVP were added and stirred for 0.5h. Transferring the mixed solution into a polytetrafluoroethylene-lined reaction kettle, performing hydrothermal reaction in an oven at 160 ℃ for 36 hours, centrifugally washing with ethanol for several times, and drying in a vacuum oven at 60 ℃ overnight. Co to be obtained 2 RuS 6 Transferring the sample into a quartz tube of a tube furnace, setting the heating rate to be 5 ℃/min, setting the heating time to be 2.1h, and adding the sample into N 2 Annealing for 2h at 650 ℃.
Furthermore does not contain CoCl 2 ·6H 2 O and RuCl 3 In the case of aqueous solutions, pure Co was prepared according to the above procedure 9 S 8 And RuS (Rus) 2 。
The CdS-Vs/Co 2 RuS 6 Composite catalyst for producing H by piezoelectricity light 2 Including: cdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Adding the composite catalyst into distilled water, fully dispersing, adding lactic acid, and introducing N 2 Finally, performing airtight reaction under the irradiation of ultrasound and sunlight;
preferably, the sunlight is generated based on a solar lamp with a solar lamp power of 55W and an ultrasonic power of 240W. Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst provided by the invention is CdS-Vs/Co 2 RuS 6 The composite catalyst has the characteristics of simple synthesis conditions, easy operation, high speed, high efficiency, good stability and the like.
(2)Co 2 RuS 6 The introduction of the catalyst did not change the crystal structure of CdS-Vs, and no other diffraction peaks appeared, indicating that CdS-Vs/Co 2 RuS 6 The composite material has excellent crystallinity and purity. Co in composite catalyst 2 RuS 6 When the mass is 3-15% of the mass of CdS-Vs, the hydrogen production capacity under the action of piezoelectricity-light can be obviously improved by cooperating with ultrasound and sunlight illumination, and the hydrogen production rate is obviously improved.
Drawings
FIG. 1 is a CdS-Vs/Co synthesized in example 1 2 RuS 6 Transmission electron microscopy of the catalyst.
FIG. 2 shows Co synthesized in example 1, comparative example 4 and comparative example 5 2 RuS 6 、Co 9 S 8 And RuS (Rus) 2 XRD pattern of the catalyst.
FIG. 3 is a graph showing the different ratios of CdS-Vs/Co synthesized in examples 1, 4, 7, 10, 13 and comparative example 1 2 RuS 6 XRD patterns of composite and CdS-Vs.
FIG. 4 is Co prepared in example 1 and example 7 2 RuS 6 And 10% CdS-Vs/Co 2 RuS 6 X-ray photoelectron spectroscopy of (c).
FIG. 5 shows the synthesis of different ratios of CdS-Vs/Co in examples 1, 4, 7, 10, 13 and comparative example 1 under simultaneous irradiation of sunlight and ultrasonic vibration 2 RuS 6 Composite material and CdS-Vs produce H 2 Is a performance graph of (a).
FIG. 6 is a graph showing the ratio of CdS-Vs/Co in different ratios under the action of ultrasonic vibration 2 RuS 6 Composite material and CdS-Vs produce H 2 Is a performance graph of (a).
FIG. 7 is a graph showing the ratio of CdS-Vs/Co in different ratios under sunlight 2 RuS 6 Composite material and CdS-Vs produce H 2 Is a performance graph of (a).
FIG. 8 is a graph showing the simultaneous irradiation of sunlight and ultrasonic vibrationComparative examples 1, 4 and 5 synthesized CdS-Vs, 10% CdS-Vs/Co 9 S 8 And 10% CdS-Vs/RuS 2 H production 2 Is a performance graph of (a).
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The H production 2 The efficiency is calculated according to the following formula:
r: h production 2 Rate, unit: mu mol/(g.h)
V: hydrogen volume, unit: mu L (mu L)
m: catalyst mass, unit: g
t: reaction time, unit: h is a
Example 1
0.1190g of CoCl is first added 2 ·6H 2 O and 1035. Mu.L RuCl 3 Aqueous solution (53.33 mg. ML) -1 RuCl 3 ·χH 2 O) was dispersed in 35mL distilled water, stirred for 0.5h, then 0.1503g TAA and 0.0175g PVP were added and stirred for 0.5h. Transferring the mixed solution into a polytetrafluoroethylene-lined reaction kettle, performing hydrothermal reaction in an oven at 160 ℃ for 36 hours, centrifugally washing with ethanol for several times, and drying in a vacuum oven at 60 ℃ overnight. Co to be obtained 2 RuS 6 Transferring the sample into a quartz tube of a tube furnace, setting the heating rate to be 5 ℃/min, setting the heating time to be 2.1h, and adding the sample into N 2 Annealing for 2h at 650 ℃.
Co as described above 2 RuS 6 Catalyst and CdS-Vs catalyst of comparative example 1 were dissolved in distilled waterUltrasonic treatment is carried out for 1h, stirring is carried out for 20h, and the materials are uniformly mixed. Centrifuging, washing and drying at room temperature to obtain dark green powder, namely CdS-Vs/Co 2 RuS 6 A composite catalyst. Co addition 2 RuS 6 The mass was 5% of the mass of CdS-Vs.
2mg of the composite catalyst was weighed, 18mL of deionized water was added, and the mixture was sonicated for 30min. Adding 2mL of lactic acid, and introducing 30min N 2 Finally, sealing for 1h under the irradiation of ultrasonic and sunlight. After the experiment was completed, the gas in the 0.5mL tube was extracted, the peak area was detected by a gas chromatograph, and H production was calculated 2 The rate is analyzed and calculated to obtain the H production 2 The rate was 62.89 mmol/(g.h).
Example 2
Compared with example 1, the difference is that: the conditions in the application method were changed to ultrasound, otherwise the same as in example 1.CdS-Vs/Co 2 RuS 6 Catalyst production H 2 The rate was 246.64. Mu. Mol/(g.h).
Example 3
Compared with example 1, the difference is that: the conditions in the application method were changed to solar light, and the same as in example 1 was repeated. CdS-Vs/Co 2 RuS 6 Catalyst production H 2 The rate was 50311.23. Mu. Mol/(g.h).
Example 4
Compared with example 1, the difference is that: co addition during the preparation process 2 RuS 6 The mass was 7% of that of CdS-Vs, and the other preparation methods were the same as in example 1.
The method of application is the same as in example 1, example 4, cdS-Vs/Co 2 RuS 6 H production by composite catalyst 2 The rate was 92.54 mmol/(g.h).
Example 5
Compared with example 4, the difference is that: the conditions in the application method were changed to ultrasound, otherwise the same as in example 4.CdS-Vs/Co 2 RuS 6 H production by composite catalyst 2 The rate was 540.73. Mu. Mol/(g.h).
Example 6
Compared with example 4, the difference is that: the conditions in the application method were changed to solar light, and the same as in example 4 was repeated. CdS-Vs/Co 2 RuS 6 Catalyst production H 2 The rate was 60740.98. Mu. Mol/(g.h).
Example 7
Compared with example 1, the difference is that: co addition during the preparation process 2 RuS 6 The mass was 10% of that of CdS-Vs, and the other preparation methods were the same as in example 1.
The method of application is the same as in example 1, example 7, cdS-Vs/Co 2 RuS 6 H production by composite catalyst 2 The rate was 110.66 mmol/(g.h) which was 18.35 times that of the CdS-Vs catalyst.
Under the same conditions, co is adjusted 2 RuS 6 The mass is 9.5% of the mass of CdS-Vs, and the hydrogen production rate is 107 mmol/(g.h); the mass of CdS-Vs was adjusted to 10.5% of the mass of CdS-30, and the hydrogen production rate was 101 mmol/(g.h).
Example 8
Compared with example 7, the difference is that: the conditions in the application method were changed to ultrasound, otherwise the same as in example 7.CdS-Vs/Co 2 RuS 6 H production by composite catalyst 2 The rate was 856.39. Mu. Mol/(g.h).
Example 9
Compared with example 7, the difference is that: the conditions in the application method were changed to solar light, and the same as in example 7 was repeated. CdS-Vs/Co 2 RuS 6 Catalyst production H 2 The rate was 72969.27. Mu. Mol/(g.h).
Example 10
Compared with example 1, the difference is that: co addition during the preparation process 2 RuS 6 The mass was 12% of that of CdS-Vs, and the other preparation methods were the same as in example 1.
The method of application is the same as in example 1, example 7, cdS-Vs/Co 2 RuS 6 H production by composite catalyst 2 The rate was 86.46 mmol/(g.h).
Example 11
Compared with example 10, the difference is that: the conditions in the application method were changed to ultrasound, otherwise the same as in example 10.CdS-Vs/Co 2 RuS 6 H production by composite catalyst 2 The rate was 445.87. Mu. Mol/(g.h).
Example 12
Compared with example 10, the difference is that: the conditions in the application method were changed to solar light, and the same as in example 10 was repeated. CdS-Vs/Co 2 RuS 6 Catalyst production H 2 The rate was 64641.72. Mu. Mol/(g.h).
Example 13
Compared with example 1, the difference is that: co addition during the preparation process 2 RuS 6 The mass was 15% of that of CdS-Vs, and the other preparation methods were the same as in example 1.
The method of application was the same as in example 1, example 13, cdS-Vs/Co 2 RuS 6 H production by composite catalyst 2 The rate was 80.84 mmol/(g.h).
Example 14
Compared with example 13, the difference is that: the conditions in the application method were changed to ultrasound, otherwise the same as in example 13.CdS-Vs/Co 2 RuS 6 H production by composite catalyst 2 The rate was 179.55. Mu. Mol/(g.h).
Example 15
Compared with example 13, the difference is that: the conditions in the application method were changed to solar light, and the same as in example 13.CdS-Vs/Co 2 RuS 6 Catalyst production H 2 The rate was 59457.69. Mu. Mol/(g.h).
Comparative example 1
Will be 2.312g CdCl 2 ·2.5H 2 O and 2.312g thiourea were added to 50mL ethylenediamine. Transferring the mixed solution into a reaction kettle lined with polytetrafluoroethylene, performing hydrothermal reaction in an oven at 160 ℃ for 48 hours, centrifugally collecting the obtained precipitate, and washing with distilled water and ethanol for multiple times. Finally, vacuum drying is carried out for 12 hours at 60 ℃, and CdS without sulfur vacancy is obtained by grinding. 0.3g CdS and 1.1349g NaBH 4 Dispersing in water solution, ultrasonic treating for 30min, centrifuging, washing, drying, and grinding to obtain CdS-Vs yellow powder containing sulfur vacancy.
2mg of CdS-Vs catalyst was weighed, 18mL of water was added, and sonicated for 30min. Then adding 2mL of lactic acid, and then introducing 30min N 2 Finally, sealing for 1h under the irradiation of ultrasonic and sunlight. After the experiment is completed, the air is pumpedTaking gas in 0.5mL tube, detecting peak area by gas chromatograph, and calculating H production 2 The rate is analyzed and calculated to obtain the H production 2 The rate was 6.03 mmol/(g.h).
Comparative example 2
Compared with comparative example 1, the difference is that: the conditions in the application method were changed to ultrasound, and the other was the same as in comparative example 1.CdS-Vs catalysts to produce H 2 The rate was 109.12. Mu. Mol/(g.h).
Comparative example 3
Compared with comparative example 1, the difference is that: the conditions in the application method are changed to sun light, and the other conditions are the same as those in comparative example 1.CdS-Vs catalysts to produce H 2 The rate was 2450.89. Mu. Mol/(g.h).
Comparative example 4
0.1190g CoCl 2 ·6H 2 O was dispersed in 35mL distilled water and stirred for 0.5h, followed by addition of 0.1503g TAA and 0.0175g PVP and stirring for 0.5h. Transferring the mixed solution into a polytetrafluoroethylene-lined reaction kettle, performing hydrothermal reaction in an oven at 160 ℃ for 36 hours, centrifugally washing with ethanol for several times, and drying in a vacuum oven at 60 ℃ overnight. Co to be obtained 9 S 8 Transferring the sample into a quartz tube of a tube furnace, setting the heating rate to be 5 ℃/min, setting the heating time to be 2.1h, and adding the sample into N 2 Annealing for 2h at 650 ℃.
Co as described above 9 S 8 The catalyst and the CdS-Vs catalyst of comparative example 1 were dissolved in distilled water, sonicated for 1h, stirred for 20h, and mixed well. Centrifuging, washing and drying at room temperature to obtain dark green powder, namely CdS-Vs/Co 9 S 8 A composite catalyst. Co addition 9 S 8 The mass was 10% of the mass of CdS-Vs.
2mg of the composite catalyst was weighed, 18mL of deionized water was added, and the mixture was sonicated for 30min. Adding 2mL of lactic acid, and introducing 30min N 2 Finally, sealing for 1h under the irradiation of ultrasonic and sunlight. After the experiment was completed, the gas in the 0.5mL tube was extracted, the peak area was detected by a gas chromatograph, and H production was calculated 2 The rate is analyzed and calculated to obtain the H production 2 The rate was 7.50 mmol/(g.h).
Comparative example 5
1035 mu L RuCl 3 Aqueous solution (53.33 mg. ML) -1 RuCl 3 ·χH 2 O) was dispersed in 35mL distilled water, stirred for 0.5h, then 0.1503g TAA and 0.0175g PVP were added and stirred for 0.5h. Transferring the mixed solution into a polytetrafluoroethylene-lined reaction kettle, performing hydrothermal reaction in an oven at 160 ℃ for 36 hours, centrifugally washing with ethanol for several times, and drying in a vacuum oven at 60 ℃ overnight. RuS to be obtained 2 Transferring the sample into a quartz tube of a tube furnace, setting the heating rate to be 5 ℃/min, setting the heating time to be 2.1h, and adding the sample into N 2 Annealing for 2h at 650 ℃.
The RuS is processed by 2 The catalyst and the CdS-Vs catalyst of comparative example 1 were dissolved in distilled water, sonicated for 1h, stirred for 20h, and mixed well. Centrifuging, washing and drying at room temperature to obtain dark green powder, namely CdS-Vs/RuS 2 A composite catalyst. Adding RuS 2 The mass was 10% of the mass of CdS-Vs.
2mg of the composite catalyst was weighed, 18mL of deionized water was added, and the mixture was sonicated for 30min. Adding 2mL of lactic acid, and introducing 30min N 2 Finally, sealing for 1h under the irradiation of ultrasonic and sunlight. After the experiment was completed, the gas in the 0.5mL tube was extracted, the peak area was detected by a gas chromatograph, and H production was calculated 2 The rate is analyzed and calculated to obtain the H production 2 The rate was 6.99 mmol/(g.h).
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.

Claims (6)

1.CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 The preparation method of the composite catalyst is characterized by comprising the following steps: the method comprises the following steps: cdS-Vs and Co 2 RuS 6 Dispersing in distilled water, fully dispersing, reacting, filtering, washing and drying at room temperature after the reaction is finished to obtain dark green powder CdS-Vs/Co 2 RuS 6 A composite catalyst;
co in composite catalyst 2 RuS 6 The mass is 5% -15% of the mass of CdS-Vs;
Co 2 RuS 6 the preparation of (C) comprises first preparing CoCl 2 ·6H 2 O and RuCl 3 Dispersing the aqueous solution in distilled water, stirring, adding TAA and PVP, stirring, transferring the mixture to a reaction kettle lined with polytetrafluoroethylene, standing in an oven at 160deg.C for 36 hr, separating solid at room temperature, washing, drying, and adding into N 2 Annealing at 650 ℃ for 1.9-2.1h under the atmosphere;
CdS-Vs preparation involves reacting CdCl 2 ·2.5H 2 Adding O and thiourea into ethylenediamine, mixing thoroughly, performing hydrothermal reaction, collecting the precipitate after the reaction, washing with distilled water and ethanol for multiple times, vacuum drying to obtain CdS free of sulfur vacancy, and mixing CdS and NaBH 4 Dispersing in water solution, ultrasonic to obtain enough bubbles to provide conditions for obtaining CdS-Vs, separating out solid at room temperature after the reaction is finished, washing and drying to obtain CdS-Vs.
2. The sulfur vacancy rich CdS-Vs/Co of claim 1 2 RuS 6 The preparation method of the composite catalyst is characterized by comprising the following steps: co (Co) 2 RuS 6 The annealing step is carried out in a tube furnace, the heating rate is controlled to be 4.9-5.1 ℃/min, and the heating time is controlled to be 2-2.2h.
3. The sulfur vacancy rich CdS-Vs/Co of claim 1 2 RuS 6 The preparation method of the composite catalyst is characterized by comprising the following steps: the reaction time in the preparation of the composite catalyst is 22-24 hours; and/or Co in the composite catalyst 2 RuS 6 The mass is 9.5% -10.5% of the mass of CdS-Vs.
4.CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 The composite catalyst is characterized in that: a sulfur vacancy rich CdS-Vs/Co according to any one of claims 1 to 3 2 RuS 6 The preparation method of the composite catalyst is adopted.
5. The sulfur vacancy rich CdS-Vs/Co of claim 4 2 RuS 6 Composite catalyst for producing H by piezoelectricity light 2 Is characterized by comprising: cdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Adding the composite catalyst into distilled water, fully dispersing, adding lactic acid, and introducing N 2 Finally, the reaction is closed under the irradiation of ultrasound and sunlight.
6. The sulfur vacancy rich CdS-Vs/Co of claim 5 2 RuS 6 Composite catalyst for producing H by piezoelectricity light 2 Is characterized in that: the solar lamp power was 55W and the ultrasonic power was 240W.
CN202310325815.6A 2023-03-30 2023-03-30 CdS-Vs/Co rich in sulfur vacancies 2 RuS 6 Preparation and application of composite catalyst Active CN116371425B (en)

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