WO2023272413A1 - Application of tin disulfide nanocatalyst in production of hydrogen by piezoelectric catalytic decomposition of water - Google Patents

Application of tin disulfide nanocatalyst in production of hydrogen by piezoelectric catalytic decomposition of water Download PDF

Info

Publication number
WO2023272413A1
WO2023272413A1 PCT/CN2021/102591 CN2021102591W WO2023272413A1 WO 2023272413 A1 WO2023272413 A1 WO 2023272413A1 CN 2021102591 W CN2021102591 W CN 2021102591W WO 2023272413 A1 WO2023272413 A1 WO 2023272413A1
Authority
WO
WIPO (PCT)
Prior art keywords
tin
tin disulfide
nanoflowers
water
catalyst
Prior art date
Application number
PCT/CN2021/102591
Other languages
French (fr)
Chinese (zh)
Inventor
路建美
李娜君
Original Assignee
苏州大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 苏州大学 filed Critical 苏州大学
Priority to PCT/CN2021/102591 priority Critical patent/WO2023272413A1/en
Publication of WO2023272413A1 publication Critical patent/WO2023272413A1/en

Links

Classifications

    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to the technical field of inorganic nanomaterials and piezoelectric catalysis, in particular to a preparation method of copper ion/silver ion doped tin disulfide nanoflowers and its application in piezoelectric catalytic decomposition of water to produce hydrogen.
  • Hydrogen is an efficient and clean green energy. As a fuel, it has the advantages of rich raw materials, high combustion value, and clean and pollution-free combustion products.
  • the existing technology uses solar energy to realize the photocatalytic water decomposition of semiconductors to produce hydrogen.
  • perovskite oxide With unique physical and chemical properties, it is widely used in water splitting to produce hydrogen to realize the development of new energy and the purification of the environment. It is a green and environmentally friendly photocatalytic material with good development prospects.
  • the conditions required for photocatalysis are more complicated and the energy consumption is larger.
  • the prior art discloses the application of tin disulfide/carbon nanofiber composite materials in the degradation of organic pollutants.
  • Precursor solution dry after reaction to obtain tin disulfide/carbon nanofiber composite material, put tin disulfide/carbon nanofiber composite material into water containing organic pollutants, and then ultrasonically treat organic pollutants in water remove.
  • the application effect of the catalyst in hydrogen production from water splitting is not disclosed.
  • the invention provides an inorganic nanometer material of copper ion/silver ion doped tin disulfide nanoflowers and a preparation method thereof, which realizes the purpose of catalytically decomposing water to produce hydrogen through ultrasonic treatment under the condition of not needing light.
  • the present invention adopts the following specific technical scheme: the application of tin disulfide nano-catalyst in decomposing water to produce hydrogen.
  • the method for decomposing water with a tin disulfide nano catalyst to produce hydrogen comprises the following steps: placing the tin disulfide nano catalyst in water added with a sacrificial agent, and then performing ultrasonic treatment to realize decomposing water to produce hydrogen, and detecting the generation of hydrogen through gas chromatography.
  • the sacrificial agent is sodium sulfite.
  • the tin disulfide nano catalyst is copper ion doped tin disulfide nanoflower or silver ion doped tin disulfide nanoflower.
  • the precursor solution containing tin source and sulfur source is subjected to solvothermal reaction, centrifuged, washed, and dried to obtain tin disulfide nanoflowers.
  • a copper source is placed in a precursor solution containing a tin source and a sulfur source, centrifuged and washed after solvothermal reaction, and dried to obtain copper ion-doped tin disulfide nanoflowers.
  • a silver source is placed in a precursor solution containing a tin source and a sulfur source, centrifuged and washed after solvothermal reaction, and dried to obtain silver ion-doped tin disulfide nanoflowers.
  • pure tin disulfide nanoflowers SnS 2
  • copper ion doped tin disulfide nanoflowers Cu-SnS 2
  • silver ion doped tin disulfide nanoflowers Ag-SnS 2
  • the copper ion or silver ion doped tin disulfide nanoflowers provided by the present invention improve the utilization rate of free carriers, and can also promote the separation of free carriers to realize the catalytic reaction under the condition of no light.
  • tin tetrachloride pentahydrate (SnCl 4 5H 2 O) is used as the tin source
  • thioacetamide (CH 3 CSNH 2 ) is used as the sulfur source
  • the molar ratio of SnCl 4 ⁇ 5H 2 O to CH 3 CSNH 2 is 1: (1-10), such as 1:1-1:8, preferably, SnCl 4 ⁇ 5H 2 O and CH 3 CSNH 2
  • the molar ratio is 1:4.
  • the solvothermal reaction is carried out in a reactor at 100-160° C. for 6-24 hours, preferably at 120° C. for 12 hours.
  • a copper source is added as a dopant to prepare copper ion-doped tin disulfide nanoflowers (Cu-SnS 2 ).
  • copper nitrate trihydrate Cu(NO 3 ) 2 ⁇ 3H 2 O
  • the molar fraction of copper ions relative to tin ions is 1%-15%, preferably 3%-6%.
  • a silver source is added as a dopant to prepare silver ion-doped tin disulfide nanoflowers (Ag-SnS 2 ).
  • silver nitrate (AgNO 3 ) is selected as the silver source, and the mole fraction of silver ions relative to tin ions is 1%-15%, preferably 3%-6%.
  • sodium sulfite Na 2 SO 3
  • the frequency of ultrasonic treatment is 40-60KHz
  • the power is 400-800W, preferably 45KHz, 600W. Further, during the ultrasonic treatment, no light is used, and it is carried out under the condition of completely avoiding light.
  • the present invention discloses a preparation method of an inorganic nanometer material that decomposes water and produces hydrogen by using mechanical energy vibration without illumination.
  • the central symmetry of the crystal structure is a key factor affecting piezoelectricity, and ion doping is currently a feasible way to improve piezoelectricity.
  • the present invention utilizes the difference in ionic radius and the formation of an amorphous layer, and incorporates copper ions or silver ions into tin disulfide nanoflowers through a simple solvothermal method to improve the piezoelectricity of SnS 2 , and the two synergistically improve piezoelectric catalytic performance.
  • Figure 1 is a scanning electron microscope image of pure SnS 2 nanoflowers.
  • Figure 2 is a scanning electron microscope image of 3% Cu-SnS 2 nanoflowers.
  • Figure 3 is a scanning electron microscope image of 3%Ag-SnS 2 nanoflowers.
  • Figure 4 is the PFM piezoelectric response butterfly curve of SnS 2 .
  • Fig. 5 is Cu-SnS 2 PFM piezoelectric response butterfly curve.
  • Fig. 6 is the piezoelectric response butterfly curve of Ag-SnS 2 PFM.
  • Fig. 7 is an effect diagram of SnS 2 , Cu-SnS 2 , Ag-SnS 2 piezoelectric catalytic decomposition of water to produce hydrogen.
  • the present invention obtains simple SnS 2 nanoflowers, copper ion or silver ion doped SnS 2 nanoflowers (Cu-SnS 2 , Ag-SnS 2 ) through a simple solvothermal method, and realizes decomposing aquatic products without light. purpose of hydrogen.
  • the copper ion or silver ion doped tin disulfide nanoflower inorganic nanomaterial provided by the invention improves the utilization rate of free carriers, and realizes catalytic reaction efficiently under the condition of no light.
  • the mole fraction of copper ions or silver ions relative to tin ions is taken as a percentile.
  • Example 1 The preparation of pure SnS 2 nanoflowers, the specific steps are as follows: the molar ratio of SnCl 4 5H 2 O to CH 3 CSNH 2 is 1:4, and 0.5 mmol (175.3 mg) SnCl 4 5H 2 O and 2 Mmol (150.0 mg) CH 3 CSNH 2 were dissolved in 20 mL of absolute ethanol respectively, the two solutions were mixed evenly and placed in a 50 mL reactor liner, and reacted at 120°C for 12 hours. After the reaction, the obtained product was washed with deionized water and ethanol three times in sequence, and finally dried at 60°C for 12 hours to obtain SnS 2 nanoflowers.
  • Accompanying drawing 1 is the scanning electron microscope picture of above-mentioned simple SnS 2 nanoflower. It can be seen from the figure that pure SnS 2 is interspersed with large nanosheets to form a nanoflower morphology.
  • Example 2 Preparation of 3% Cu-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of copper ions is 3% of Sn 4+ , and 0.015 mmol (3.62 mg) Cu(NO 3 ) 2 ⁇ 3H 2 O is dissolved In 5 mL absolute ethanol, 0.48 mmol (170.0 mg) SnCl 4 ⁇ 5H 2 O was dissolved in 15 mL absolute ethanol, 150 mg (2 mmol) CH 3 CSNH 2 was dissolved in 20 mL absolute ethanol, and the above three The two solutions were mixed evenly and placed in a 50 mL reactor liner, and reacted at 120 °C for 12 hours.
  • Example 3 Preparation of 6% Cu-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of copper ions is 6% of Sn 4+ , and 0.03 mmol (7.25 mg) Cu(NO 3 ) 2 ⁇ 3H 2 O is dissolved In 5 mL absolute ethanol, 0.47 mmol (164.8 mg) SnCl 4 ⁇ 5H 2 O was dissolved in 15 mL absolute ethanol, 150 mg (2 mmol) CH 3 CSNH 2 was dissolved in 20 mL absolute ethanol, and the above After the three solutions were mixed evenly, they were placed in a 50 mL reactor liner and reacted at 120 °C for 12 hours. After the reaction, the obtained product was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Cu-SnS 2 nanoflowers.
  • Example 4 Preparation of 9% Cu-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of copper ions is 9% of Sn 4+ , and 0.045 mmol (10.87 mg) Cu(NO 3 ) 2 ⁇ 3H 2 O is dissolved In 5 mL absolute ethanol, 0.455 mmol (159.5 mg) SnCl 4 ⁇ 5H 2 O was dissolved in 15 mL absolute ethanol, 150 mg (2 mmol) CH 3 CSNH 2 was dissolved in 20 mL absolute ethanol, the above three The two solutions were mixed evenly and placed in a 50 mL reactor liner, and reacted at 120 °C for 12 hours. After the reaction, the obtained product was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Cu-SnS 2 nanoflowers.
  • Example 5 The preparation of 1% Ag-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of silver ions is 1% of Sn 4+ , 0.005 mmol (0.85 mg) AgNO 3 is dissolved in 5 mL of absolute ethanol, 0.495 mmol (173.6 mg) SnCl 4 5H 2 O was dissolved in 15 mL of absolute ethanol, 150 mg (2 mmol) of CH 3 CSNH 2 was dissolved in 20 mL of absolute ethanol, the above three solutions were mixed uniformly and placed in In a 50 mL reactor liner, react at 120°C for 12 hours. After the reaction, the product obtained was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Ag-SnS 2 nanoflowers.
  • Example 6 The preparation of 3% Ag-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of silver ions is 3% of Sn 4+ , 0.015 mmol (2.55 mg) AgNO 3 is dissolved in 5 mL of absolute ethanol, 0.48 mmol (170.0 mg) SnCl 4 5H 2 O was dissolved in 15 mL of absolute ethanol, 150 mg (2 mmol) of CH 3 CSNH 2 was dissolved in 20 mL of absolute ethanol, the above three solutions were mixed uniformly and placed in In a 50 mL reactor liner, react at 120°C for 12 hours.
  • Example 7 The preparation of 6% Ag-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of silver ions is 6% of Sn 4+ , 0.03 mmol (5.10 mg) AgNO 3 is dissolved in 5 mL of absolute ethanol, 0.47 mmol (164.8 mg) SnCl 4 5H 2 O was dissolved in 15 mL of absolute ethanol, 150 mg (2 mmol) of CH 3 CSNH 2 was dissolved in 20 mL of absolute ethanol, the above three solutions were mixed uniformly and placed in In a 50 mL reactor liner, react at 120°C for 12 hours. After the reaction, the product obtained was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Ag-SnS 2 nanoflowers.
  • Example 8 The preparation of 9% Ag-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of silver ions is 9% of Sn 4+ , 0.045 mmol (7.64 mg) AgNO 3 is dissolved in 5 mL of absolute ethanol, 0.455 mmol (159.5) SnCl 4 5H 2 O was dissolved in 15 mL of absolute ethanol, 150 mg (2 mmol) of CH 3 CSNH 2 was dissolved in 20 mL of absolute ethanol, the above three solutions were mixed uniformly and placed in 50 In the liner of a mL reactor, react at 120°C for 12 hours. After the reaction, the product obtained was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Ag-SnS 2 nanoflowers.
  • Embodiment 9 In order to study the difference among the three, the piezoelectricity of the three samples is characterized by PFM testing.
  • the results of accompanying drawings 4 to 6 show that the three samples have obtained typical Butterfly rings, these results confirm the piezoelectric properties of the three samples synthesized. From Figures 4 to 6, it can be seen that the maximum amplitudes of SnS 2 , 3%Cu-SnS 2 and 3%Ag-SnS 2 are 15 pm, 30 pm and 45 pm respectively. Obviously, Ag-SnS 2 exhibits the highest Piezoelectric response magnitude.
  • Example 10 SnS 2 piezoelectric catalytic decomposition of water to produce hydrogen: 10 mg of SnS 2 nanoflowers were dispersed in 10 mL of Na 2 SO 3 aqueous solution (0.05 M), and Na 2 SO 3 was used as a sacrificial agent. Seal the above suspension in a 30 mL borosilicate tube to evacuate and purge with Ar for about 5 min to completely remove the air. Then place the borosilicate tube in the center of the ultrasonic cleaner, and turn on the ultrasound (45 KHz, 600 W) in the dark to decompose water and produce hydrogen.
  • 10 mg of SnS 2 nanoflowers were dispersed in 10 mL of Na 2 SO 3 aqueous solution (0.05 M), and Na 2 SO 3 was used as a sacrificial agent. Seal the above suspension in a 30 mL borosilicate tube to evacuate and purge with Ar for about 5 min to completely remove the air. Then place the borosilicate tube in the center of the ultra
  • Example 11 Cu-SnS 2 piezoelectric catalytic decomposition of water to produce hydrogen: 10 mg 3% Cu-SnS 2 nanoflowers were dispersed in 10 mL Na 2 SO 3 aqueous solution (0.05 M), and Na 2 SO 3 was used as a sacrificial agent. Seal the above suspension in a 30 mL borosilicate tube to evacuate and purge with Ar for about 5 min to completely remove the air. Then place the borosilicate tube in the center of the ultrasonic cleaner, and turn on the ultrasound (45 KHz, 600 W) in the dark to decompose water and produce hydrogen.
  • 10 mg 3% Cu-SnS 2 nanoflowers were dispersed in 10 mL Na 2 SO 3 aqueous solution (0.05 M), and Na 2 SO 3 was used as a sacrificial agent. Seal the above suspension in a 30 mL borosilicate tube to evacuate and purge with Ar for about 5 min to completely remove the air. Then place the borosilicate tube
  • Example 12 Ag-SnS 2 piezoelectric catalyzed water splitting hydrogen production experiment: 10 mg 3% Ag-SnS 2 nanoflowers were dispersed in 10 mL Na 2 SO 3 aqueous solution (0.05 M), and Na 2 SO 3 was used as a sacrificial agent. Seal the above suspension in a 30 mL borosilicate tube to evacuate and purge with Ar for about 5 min to completely remove the air. Then place the borosilicate tube in the center of the ultrasonic cleaner, and turn on the ultrasound (45 KHz, 600 W) in the dark to decompose water and produce hydrogen.
  • 10 mg 3% Ag-SnS 2 nanoflowers were dispersed in 10 mL Na 2 SO 3 aqueous solution (0.05 M), and Na 2 SO 3 was used as a sacrificial agent. Seal the above suspension in a 30 mL borosilicate tube to evacuate and purge with Ar for about 5 min to completely remove the air. Then place the borosilicate tube in
  • Comparative example 1 Take the 0.5-SnS 2 /CNFs (10 mg) composite material prepared in Example 3 of the prior art CN202010815126X to replace the 10 mg Ag-SnS 2 in Example 12, and keep the rest unchanged. As a comparative experiment, the results show that in The amount of H 2 generated in 4 hours was 275 ⁇ mol g -1 .
  • Comparative example 2 using photoreduction reaction to deposit silver nanoparticles on the surface of SnS 2 nanoflowers. Put 0.5 g of SnS into a beaker filled with 25 mL of AgNO solution (0.02 M ). Place the beaker under UV light with constant stirring. Then the powder was washed and separated by a centrifuge and dried at room temperature to prepare SnS 2 nanoflowers deposited by silver nanoparticles. Take 10 mg to replace the 10 mg Ag-SnS 2 in Example 12, and keep the rest unchanged as a comparative experiment , the results showed that the amount of H 2 generated within 4 hours was 285 ⁇ mol g -1 .
  • the catalytic performance is not significantly affected by replacing the metal dopant copper salt with copper acetate monohydrate (Cu(CO 2 CH 3 ) 2 ⁇ H 2 O).
  • the 3% Cu-SnS 2 prepared in Reference Example 2 produced 307 ⁇ mol g -1 of H 2 within 4 hours.
  • the piezoelectric effect builds a built-in electric field, realizes the effective separation of carriers, and improves the piezoelectric catalytic efficiency.
  • the present invention prepares tin disulfide nanoflowers (Cu-SnS 2 , Ag-SnS 2 ) doped with copper ions or silver ions by a simple solvothermal method and applies them to the field of piezoelectric catalysis for the first time.
  • the doping synergistically increases the sensitivity of the material to sense mechanical energy, improves the piezoelectricity, and thus enhances the catalytic performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

Disclosed is an application of a tin disulfide nanocatalyst in production of hydrogen by piezoelectric catalytic decomposition of water. In the prior art, solar energy is utilized to achieve photocatalytic decomposition of water of a semiconductor to produce hydrogen, but conditions required by photocatalysis are relatively complex and energy consumption is relatively high. The present invention provides an inorganic nanomaterial of a copper ion- or silver ion- doped tin disulfide nanoflower. The purpose of catalytically decomposing water to produce hydrogen is achieved by means of ultrasonic treatment without the need for illumination.

Description

二硫化锡纳米催化剂在压电催化分解水产氢中的应用Application of tin disulfide nanocatalysts in piezoelectric catalytic water splitting for hydrogen production 技术领域technical field
本发明涉及无机纳米材料及压电催化技术领域，具体涉及铜离子/银离子掺杂二硫化锡纳米花的制备方法及其在压电催化分解水产氢中的应用。The invention relates to the technical field of inorganic nanomaterials and piezoelectric catalysis, in particular to a preparation method of copper ion/silver ion doped tin disulfide nanoflowers and its application in piezoelectric catalytic decomposition of water to produce hydrogen.
背景技术Background technique
氢气是一种高效清洁的绿色能源,作为燃料具有原料丰富、燃烧值高、燃烧产物洁净无污染等优越特性，现有技术利用太阳能实现半导体的光催化分解水制氢，其中钙钛矿氧化物具有独特的物理和化学性质被广泛应用于分解水制氢实现新能源的开发和环境的净化，是具有良好开发前景的绿色环保光催化材料。但是光催化需要的条件较复杂以及能量消耗较大，现有技术公开了二硫化锡/碳纳米纤维复合材料在降解有机污染物中的应用，将碳纳米纤维膜置于含有锡源与硫源的前驱体溶液中，反应后干燥，得到二硫化锡/碳纳米纤维复合材料，将二硫化锡/碳纳米纤维复合材料置入含有有机污染物的水中，然后超声处理，完成水中有机污染物的去除。但是没有公开该催化剂在分解水制氢中的应用效果。Hydrogen is an efficient and clean green energy. As a fuel, it has the advantages of rich raw materials, high combustion value, and clean and pollution-free combustion products. The existing technology uses solar energy to realize the photocatalytic water decomposition of semiconductors to produce hydrogen. Among them, perovskite oxide With unique physical and chemical properties, it is widely used in water splitting to produce hydrogen to realize the development of new energy and the purification of the environment. It is a green and environmentally friendly photocatalytic material with good development prospects. However, the conditions required for photocatalysis are more complicated and the energy consumption is larger. The prior art discloses the application of tin disulfide/carbon nanofiber composite materials in the degradation of organic pollutants. Precursor solution, dry after reaction to obtain tin disulfide/carbon nanofiber composite material, put tin disulfide/carbon nanofiber composite material into water containing organic pollutants, and then ultrasonically treat organic pollutants in water remove. However, the application effect of the catalyst in hydrogen production from water splitting is not disclosed.
技术问题technical problem
本发明提供一种铜离子/银离子掺杂二硫化锡纳米花的无机纳米材料及其制备方法，在无需光照的条件下，通过超声处理，实现催化分解水产氢的目的。The invention provides an inorganic nanometer material of copper ion/silver ion doped tin disulfide nanoflowers and a preparation method thereof, which realizes the purpose of catalytically decomposing water to produce hydrogen through ultrasonic treatment under the condition of not needing light.
技术解决方案technical solution
为了达到上述目的，本发明采用如下具体技术方案：二硫化锡纳米催化剂在分解水产氢中的应用。In order to achieve the above object, the present invention adopts the following specific technical scheme: the application of tin disulfide nano-catalyst in decomposing water to produce hydrogen.
二硫化锡纳米催化剂分解水产氢的方法，包括以下步骤：将二硫化锡纳米催化剂置于加入牺牲剂的水中，然后超声处理，实现分解水产氢，通过气相色谱检测氢气的产生。优选的，牺牲剂为亚硫酸钠。The method for decomposing water with a tin disulfide nano catalyst to produce hydrogen comprises the following steps: placing the tin disulfide nano catalyst in water added with a sacrificial agent, and then performing ultrasonic treatment to realize decomposing water to produce hydrogen, and detecting the generation of hydrogen through gas chromatography. Preferably, the sacrificial agent is sodium sulfite.
本发明中，二硫化锡纳米催化剂为铜离子掺杂二硫化锡纳米花或者银离子掺杂二硫化锡纳米花。In the present invention, the tin disulfide nano catalyst is copper ion doped tin disulfide nanoflower or silver ion doped tin disulfide nanoflower.
本发明中，将含有锡源和硫源的前驱体溶液进行溶剂热反应后离心洗涤，干燥后得到二硫化锡纳米花。In the present invention, the precursor solution containing tin source and sulfur source is subjected to solvothermal reaction, centrifuged, washed, and dried to obtain tin disulfide nanoflowers.
本发明中，将铜源置于含有锡源和硫源的前驱体溶液中，溶剂热反应后离心洗涤，干燥后得到铜离子掺杂二硫化锡纳米花。In the present invention, a copper source is placed in a precursor solution containing a tin source and a sulfur source, centrifuged and washed after solvothermal reaction, and dried to obtain copper ion-doped tin disulfide nanoflowers.
本发明中，将银源置于含有锡源和硫源的前驱体溶液中，溶剂热反应后离心洗涤，干燥后得到银离子掺杂二硫化锡纳米花。In the present invention, a silver source is placed in a precursor solution containing a tin source and a sulfur source, centrifuged and washed after solvothermal reaction, and dried to obtain silver ion-doped tin disulfide nanoflowers.
本发明中，通过简单的溶剂热的方法得到单纯的二硫化锡纳米花（SnS 2）、铜离子掺杂二硫化锡纳米花（Cu-SnS 2）和银离子掺杂二硫化锡纳米花（Ag-SnS 2），作为对比。本发明提供的铜离子或者银离子掺杂二硫化锡纳米花提高了自由载流子的利用率，在无光照条件下，也能促进自由载流子的分离实现催化反应。 In the present invention, pure tin disulfide nanoflowers (SnS 2 ), copper ion doped tin disulfide nanoflowers (Cu-SnS 2 ) and silver ion doped tin disulfide nanoflowers ( Ag-SnS 2 ), as a comparison. The copper ion or silver ion doped tin disulfide nanoflowers provided by the present invention improve the utilization rate of free carriers, and can also promote the separation of free carriers to realize the catalytic reaction under the condition of no light.
本发明中，使用五水合四氯化锡（SnCl 4·5H 2O）作为锡源，使用硫代乙酰胺（CH 3CSNH 2）作为硫源，溶解于无水乙醇得到含有硫源与锡源的前驱体溶液；SnCl 4·5H 2O与CH 3CSNH 2的摩尔比为1∶（1～10）比如1∶1～1∶8，优选的，SnCl 4·5H 2O与CH 3CSNH 2的摩尔比为1∶4。 In the present invention, tin tetrachloride pentahydrate (SnCl 4 5H 2 O) is used as the tin source, thioacetamide (CH 3 CSNH 2 ) is used as the sulfur source, and dissolved in absolute ethanol to obtain the sulfur source and tin source precursor solution; the molar ratio of SnCl 4 ·5H 2 O to CH 3 CSNH 2 is 1: (1-10), such as 1:1-1:8, preferably, SnCl 4 ·5H 2 O and CH 3 CSNH 2 The molar ratio is 1:4.
本发明中，溶剂热反应在反应釜中100～160℃下反应6～24小时，优选的条件为120℃下12小时。In the present invention, the solvothermal reaction is carried out in a reactor at 100-160° C. for 6-24 hours, preferably at 120° C. for 12 hours.
本发明中，在单纯二硫化锡纳米花制备方法的基础上，加入铜源作为掺杂剂制备铜离子掺杂二硫化锡纳米花（Cu-SnS 2）。具体的，选用三水合硝酸铜（Cu(NO 3) 2·3H 2O）作为铜源，铜离子相对于锡离子的摩尔分数为1%～15%，优选为3%～6%。 In the present invention, on the basis of the simple preparation method of tin disulfide nanoflowers, a copper source is added as a dopant to prepare copper ion-doped tin disulfide nanoflowers (Cu-SnS 2 ). Specifically, copper nitrate trihydrate (Cu(NO 3 ) 2 ·3H 2 O) is selected as the copper source, and the molar fraction of copper ions relative to tin ions is 1%-15%, preferably 3%-6%.
本发明中，在单纯二硫化锡纳米花制备方法的基础上，加入银源作为掺杂剂制备银离子掺杂二硫化锡纳米花（Ag-SnS 2）。具体的，选用硝酸银（AgNO 3）作为银源，银离子相对于锡离子的摩尔分数为1%～15%，优选为3%～6%。 In the present invention, on the basis of the simple preparation method of tin disulfide nanoflowers, a silver source is added as a dopant to prepare silver ion-doped tin disulfide nanoflowers (Ag-SnS 2 ). Specifically, silver nitrate (AgNO 3 ) is selected as the silver source, and the mole fraction of silver ions relative to tin ions is 1%-15%, preferably 3%-6%.
本发明中，在分解水产氢的过程中，加入亚硫酸钠（Na 2SO 3）作为牺牲剂，超声处理的频率为40～60KHz，功率为400～800W，优选45KHz，600 W。进一步的，超声处理时不进行光照，在完全避光的条件下进行。 In the present invention, sodium sulfite (Na 2 SO 3 ) is added as a sacrificial agent in the process of decomposing water to produce hydrogen, the frequency of ultrasonic treatment is 40-60KHz, and the power is 400-800W, preferably 45KHz, 600W. Further, during the ultrasonic treatment, no light is used, and it is carried out under the condition of completely avoiding light.
有益效果Beneficial effect
本发明的优点：本发明公开了一种无需光照、利用机械能振动进行分解水产氢的无机纳米材料的制备方法。晶体结构的中心对称性是影响压电性的关键因素，通过离子掺杂的手段改善压电性是目前可行的方式。本发明利用离子半径的不同以及形成非晶层，通过简便的溶剂热法将铜离子或者银离子掺入二硫化锡纳米花中，改善SnS 2的压电性，二者协同提高了压电催化性能。 The advantages of the present invention: the present invention discloses a preparation method of an inorganic nanometer material that decomposes water and produces hydrogen by using mechanical energy vibration without illumination. The central symmetry of the crystal structure is a key factor affecting piezoelectricity, and ion doping is currently a feasible way to improve piezoelectricity. The present invention utilizes the difference in ionic radius and the formation of an amorphous layer, and incorporates copper ions or silver ions into tin disulfide nanoflowers through a simple solvothermal method to improve the piezoelectricity of SnS 2 , and the two synergistically improve piezoelectric catalytic performance.
附图说明Description of drawings
图1为单纯的SnS 2纳米花的扫描电镜图。 Figure 1 is a scanning electron microscope image of pure SnS 2 nanoflowers.
图2为3%Cu-SnS 2纳米花的扫描电镜图。 Figure 2 is a scanning electron microscope image of 3% Cu-SnS 2 nanoflowers.
图3为3%Ag-SnS 2纳米花的扫描电镜图。 Figure 3 is a scanning electron microscope image of 3%Ag-SnS 2 nanoflowers.
图4为SnS 2的PFM压电响应蝶形曲线。 Figure 4 is the PFM piezoelectric response butterfly curve of SnS 2 .
图5为Cu-SnS 2 PFM压电响应蝶形曲线。 Fig. 5 is Cu-SnS 2 PFM piezoelectric response butterfly curve.
图6为Ag-SnS 2 PFM压电响应蝶形曲线。 Fig. 6 is the piezoelectric response butterfly curve of Ag-SnS 2 PFM.
图7为SnS 2、Cu-SnS 2、Ag-SnS 2压电催化分解水产氢的效果图。 Fig. 7 is an effect diagram of SnS 2 , Cu-SnS 2 , Ag-SnS 2 piezoelectric catalytic decomposition of water to produce hydrogen.
本发明的实施方式Embodiments of the present invention
本发明通过简便的溶剂热法得到单纯的SnS 2纳米花、铜离子或银离子掺杂的SnS 2纳米花（Cu-SnS 2、Ag-SnS 2），在无需光照的条件下，实现分解水产氢的目的。本发明提供的铜离子或银离子掺杂二硫化锡纳米花的无机纳米材料提高了自由载流子的利用率，在无光照条件下，高效实现催化反应。本发明中，铜离子或者银离子相对于锡离子的摩尔分数取百分位计。 The present invention obtains simple SnS 2 nanoflowers, copper ion or silver ion doped SnS 2 nanoflowers (Cu-SnS 2 , Ag-SnS 2 ) through a simple solvothermal method, and realizes decomposing aquatic products without light. purpose of hydrogen. The copper ion or silver ion doped tin disulfide nanoflower inorganic nanomaterial provided by the invention improves the utilization rate of free carriers, and realizes catalytic reaction efficiently under the condition of no light. In the present invention, the mole fraction of copper ions or silver ions relative to tin ions is taken as a percentile.
实施例一：单纯SnS 2纳米花的制备，具体步骤如下：SnCl 4·5H 2O与CH 3CSNH 2的摩尔比为1：4，将0.5 mmol（175.3 mg ）SnCl 4·5H 2O和2 mmol（150.0 mg） CH 3CSNH 2分别溶解于20 mL无水乙醇中，两种溶液混合均匀后置于50 mL反应釜内胆中，120℃下反应12小时。反应结束后得到的产物依次用去离子水和乙醇洗涤三次，最后在60℃下干燥12小时得到SnS 2纳米花。附图1为上述单纯SnS 2纳米花的扫描电镜图。从图中可以看到单纯的SnS 2由大的纳米片穿插形成纳米花形貌。 Example 1 : The preparation of pure SnS 2 nanoflowers, the specific steps are as follows: the molar ratio of SnCl 4 5H 2 O to CH 3 CSNH 2 is 1:4, and 0.5 mmol (175.3 mg) SnCl 4 5H 2 O and 2 Mmol (150.0 mg) CH 3 CSNH 2 were dissolved in 20 mL of absolute ethanol respectively, the two solutions were mixed evenly and placed in a 50 mL reactor liner, and reacted at 120°C for 12 hours. After the reaction, the obtained product was washed with deionized water and ethanol three times in sequence, and finally dried at 60°C for 12 hours to obtain SnS 2 nanoflowers. Accompanying drawing 1 is the scanning electron microscope picture of above-mentioned simple SnS 2 nanoflower. It can be seen from the figure that pure SnS 2 is interspersed with large nanosheets to form a nanoflower morphology.
实施例二：3% Cu-SnS 2纳米花的制备，具体步骤如下：铜离子的摩尔分数为Sn 4+的3%，将0.015 mmol（3.62 mg）Cu(NO 3) 2·3H 2O 溶解于5 mL无水乙醇中，0.48 mmol（170.0 mg） SnCl 4·5H 2O溶解于15 mL无水乙醇中，150mg（2 mmol）CH 3CSNH 2溶解于20 mL无水乙醇中，将以上三种溶液混合均匀后置于50 mL反应釜内胆中，120℃下反应12小时。反应结束后得到的产物依次用去离子水和乙醇洗涤三次，最后在60℃下干燥12小时得到Cu-SnS 2纳米花。附图2为上述Cu-SnS 2纳米花的扫描电镜图。从图中可以看到铜离子的掺入对SnS 2的形貌没有产生大的改变，仍保持为纳米花状。 Example 2 : Preparation of 3% Cu-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of copper ions is 3% of Sn 4+ , and 0.015 mmol (3.62 mg) Cu(NO 3 ) 2 ·3H 2 O is dissolved In 5 mL absolute ethanol, 0.48 mmol (170.0 mg) SnCl 4 ·5H 2 O was dissolved in 15 mL absolute ethanol, 150 mg (2 mmol) CH 3 CSNH 2 was dissolved in 20 mL absolute ethanol, and the above three The two solutions were mixed evenly and placed in a 50 mL reactor liner, and reacted at 120 °C for 12 hours. After the reaction, the obtained product was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Cu-SnS 2 nanoflowers. Accompanying drawing 2 is the scanning electron micrograph of above-mentioned Cu-SnS 2 nanometer flower. It can be seen from the figure that the doping of copper ions does not change the morphology of SnS 2 greatly, and it still maintains the shape of nanoflowers.
实施例三：6% Cu-SnS 2纳米花的制备，具体步骤如下：铜离子的摩尔分数为Sn 4+的6%，将0.03 mmol（7.25 mg）Cu(NO 3) 2·3H 2O 溶解于5 mL无水乙醇中，0.47 mmol（164.8 mg） SnCl 4·5H 2O溶解于15 mL无水乙醇中，150 mg（2 mmol）CH 3CSNH 2溶解于20 mL无水乙醇中，将以上三种溶液混合均匀后置于50 mL反应釜内胆中，120℃下反应12小时。反应结束后得到的产物依次用去离子水和乙醇洗涤三次，最后在60℃下干燥12小时得到Cu-SnS 2纳米花。 Example 3: Preparation of 6% Cu-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of copper ions is 6% of Sn 4+ , and 0.03 mmol (7.25 mg) Cu(NO 3 ) 2 ·3H 2 O is dissolved In 5 mL absolute ethanol, 0.47 mmol (164.8 mg) SnCl 4 ·5H 2 O was dissolved in 15 mL absolute ethanol, 150 mg (2 mmol) CH 3 CSNH 2 was dissolved in 20 mL absolute ethanol, and the above After the three solutions were mixed evenly, they were placed in a 50 mL reactor liner and reacted at 120 °C for 12 hours. After the reaction, the obtained product was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Cu-SnS 2 nanoflowers.
实施例四：9% Cu-SnS 2纳米花的制备，具体步骤如下：铜离子的摩尔分数为Sn 4+的9%，将0.045 mmol（10.87 mg）Cu(NO 3) 2·3H 2O 溶解于5 mL无水乙醇中，0.455 mmol（159.5 mg） SnCl 4·5H 2O溶解于15 mL无水乙醇中，150mg（2 mmol）CH 3CSNH 2溶解于20 mL无水乙醇中，将以上三种溶液混合均匀后置于50 mL反应釜内胆中，120℃下反应12小时。反应结束后得到的产物依次用去离子水和乙醇洗涤三次，最后在60℃下干燥12小时得到Cu-SnS 2纳米花。 Example 4 : Preparation of 9% Cu-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of copper ions is 9% of Sn 4+ , and 0.045 mmol (10.87 mg) Cu(NO 3 ) 2 ·3H 2 O is dissolved In 5 mL absolute ethanol, 0.455 mmol (159.5 mg) SnCl 4 ·5H 2 O was dissolved in 15 mL absolute ethanol, 150 mg (2 mmol) CH 3 CSNH 2 was dissolved in 20 mL absolute ethanol, the above three The two solutions were mixed evenly and placed in a 50 mL reactor liner, and reacted at 120 °C for 12 hours. After the reaction, the obtained product was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Cu-SnS 2 nanoflowers.
实施例五：1% Ag-SnS 2纳米花的制备，具体步骤如下：银离子的摩尔分数为Sn 4+的1%，将0.005 mmol（0.85 mg）AgNO 3 溶解于5 mL无水乙醇中，0.495 mmol（173.6 mg）SnCl 4·5H 2O溶解于15 mL无水乙醇中，150 mg（2 mmol）CH 3CSNH 2溶解于20 mL无水乙醇中，将以上三种溶液混合均匀后置于50 mL反应釜内胆中，120℃下反应12小时。反应结束后得到的产物依次用去离子水和乙醇洗涤三次，最后在60℃下干燥12小时得到Ag-SnS 2纳米花。 Example 5: The preparation of 1% Ag-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of silver ions is 1% of Sn 4+ , 0.005 mmol (0.85 mg) AgNO 3 is dissolved in 5 mL of absolute ethanol, 0.495 mmol (173.6 mg) SnCl 4 5H 2 O was dissolved in 15 mL of absolute ethanol, 150 mg (2 mmol) of CH 3 CSNH 2 was dissolved in 20 mL of absolute ethanol, the above three solutions were mixed uniformly and placed in In a 50 mL reactor liner, react at 120°C for 12 hours. After the reaction, the product obtained was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Ag-SnS 2 nanoflowers.
实施例六：3% Ag-SnS 2纳米花的制备，具体步骤如下：银离子的摩尔分数为Sn 4+的3%，将0.015 mmol（2.55 mg）AgNO 3 溶解于5 mL无水乙醇中，0.48 mmol（170.0 mg）SnCl 4·5H 2O溶解于15 mL无水乙醇中，150 mg（2 mmol）CH 3CSNH 2溶解于20 mL无水乙醇中，将以上三种溶液混合均匀后置于50 mL反应釜内胆中，120℃下反应12小时。反应结束后得到的产物依次用去离子水和乙醇洗涤三次，最后在60℃下干燥12小时得到Ag-SnS 2纳米花。附图3为上述Ag-SnS 2纳米花的扫描电镜图。从图中可以看到银离子的掺入明显使纳米片的尺寸减小，但仍保持纳米花的形貌。 Example 6: The preparation of 3% Ag-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of silver ions is 3% of Sn 4+ , 0.015 mmol (2.55 mg) AgNO 3 is dissolved in 5 mL of absolute ethanol, 0.48 mmol (170.0 mg) SnCl 4 5H 2 O was dissolved in 15 mL of absolute ethanol, 150 mg (2 mmol) of CH 3 CSNH 2 was dissolved in 20 mL of absolute ethanol, the above three solutions were mixed uniformly and placed in In a 50 mL reactor liner, react at 120°C for 12 hours. After the reaction, the product obtained was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Ag-SnS 2 nanoflowers. Accompanying drawing 3 is the scanning electron micrograph of above-mentioned Ag-SnS 2 nanometer flower. It can be seen from the figure that the incorporation of silver ions significantly reduces the size of the nanosheets, but still maintains the shape of the nanoflowers.
实施例七：6% Ag-SnS 2纳米花的制备，具体步骤如下：银离子的摩尔分数为Sn 4+的6%，将0.03 mmol（5.10 mg）AgNO 3 溶解于5 mL无水乙醇中，0.47 mmol（164.8 mg）SnCl 4·5H 2O溶解于15 mL无水乙醇中，150 mg（2 mmol）CH 3CSNH 2溶解于20 mL无水乙醇中，将以上三种溶液混合均匀后置于50 mL反应釜内胆中，120℃下反应12小时。反应结束后得到的产物依次用去离子水和乙醇洗涤三次，最后在60℃下干燥12小时得到Ag-SnS 2纳米花。 Example 7: The preparation of 6% Ag-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of silver ions is 6% of Sn 4+ , 0.03 mmol (5.10 mg) AgNO 3 is dissolved in 5 mL of absolute ethanol, 0.47 mmol (164.8 mg) SnCl 4 5H 2 O was dissolved in 15 mL of absolute ethanol, 150 mg (2 mmol) of CH 3 CSNH 2 was dissolved in 20 mL of absolute ethanol, the above three solutions were mixed uniformly and placed in In a 50 mL reactor liner, react at 120°C for 12 hours. After the reaction, the product obtained was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Ag-SnS 2 nanoflowers.
实施例八：9% Ag-SnS 2纳米花的制备，具体步骤如下：银离子的摩尔分数为Sn 4+的9%，将0.045 mmol（7.64 mg）AgNO 3 溶解于5 mL无水乙醇中，0.455 mmol（159.5）SnCl 4·5H 2O溶解于15 mL无水乙醇中，150 mg（2 mmol）CH 3CSNH 2溶解于20 mL无水乙醇中，将以上三种溶液混合均匀后置于50 mL反应釜内胆中，120℃下反应12小时。反应结束后得到的产物依次用去离子水和乙醇洗涤三次，最后在60℃下干燥12小时得到Ag-SnS 2纳米花。 Example 8: The preparation of 9% Ag-SnS 2 nanoflowers, the specific steps are as follows: the molar fraction of silver ions is 9% of Sn 4+ , 0.045 mmol (7.64 mg) AgNO 3 is dissolved in 5 mL of absolute ethanol, 0.455 mmol (159.5) SnCl 4 5H 2 O was dissolved in 15 mL of absolute ethanol, 150 mg (2 mmol) of CH 3 CSNH 2 was dissolved in 20 mL of absolute ethanol, the above three solutions were mixed uniformly and placed in 50 In the liner of a mL reactor, react at 120°C for 12 hours. After the reaction, the product obtained was washed with deionized water and ethanol three times in sequence, and finally dried at 60° C. for 12 hours to obtain Ag-SnS 2 nanoflowers.
实施例九：为研究三者的差异，通过PFM测试来表征三个样品的压电性，附图4～6的结果表明，三个样品在±10 V DC偏置场下均获得了典型的蝶形环，这些结果证实了合成的三个样品的压电性质。从附图4～6可看出，SnS 2，3%Cu-SnS 2和3%Ag-SnS 2的最大振幅分别为15 pm、30 pm、45 pm，显然，Ag-SnS 2表现出最高的压电响应幅度。 Embodiment 9: In order to study the difference among the three, the piezoelectricity of the three samples is characterized by PFM testing. The results of accompanying drawings 4 to 6 show that the three samples have obtained typical Butterfly rings, these results confirm the piezoelectric properties of the three samples synthesized. From Figures 4 to 6, it can be seen that the maximum amplitudes of SnS 2 , 3%Cu-SnS 2 and 3%Ag-SnS 2 are 15 pm, 30 pm and 45 pm respectively. Obviously, Ag-SnS 2 exhibits the highest Piezoelectric response magnitude.
实施例十：SnS 2压电催化分解水产氢实验：取10 mg SnS 2纳米花分散在 10 mL Na 2SO 3 水溶液（0.05 M）中，Na 2SO 3用作牺牲剂。将以上悬浮液密封在 30 mL 硼硅酸盐管中抽真空并用 Ar 吹扫约5分钟以完全去除空气。然后将硼硅酸盐管置于超声清洗器的中心，避光下开启超声（45 KHz，600 W）进行分解水产氢。为了检测产氢量，将硼硅酸盐管内的 5 mL气体组分间歇性地提取并注入带有热导检测器的气相色谱仪（7890B，美国）中。使用氢气摩尔数与峰面积的校准曲线计算产生的氢气量。 Example 10: SnS 2 piezoelectric catalytic decomposition of water to produce hydrogen: 10 mg of SnS 2 nanoflowers were dispersed in 10 mL of Na 2 SO 3 aqueous solution (0.05 M), and Na 2 SO 3 was used as a sacrificial agent. Seal the above suspension in a 30 mL borosilicate tube to evacuate and purge with Ar for about 5 min to completely remove the air. Then place the borosilicate tube in the center of the ultrasonic cleaner, and turn on the ultrasound (45 KHz, 600 W) in the dark to decompose water and produce hydrogen. To detect the amount of hydrogen produced, 5 mL of gas components in borosilicate tubes were intermittently extracted and injected into a gas chromatograph (7890B, USA) with a thermal conductivity detector. The amount of hydrogen produced was calculated using a calibration curve of hydrogen moles versus peak area.
实施例十一：Cu-SnS 2压电催化分解水产氢实验：取10 mg 3%Cu-SnS 2纳米花分散在 10 mL Na 2SO 3 水溶液（0.05 M）中，Na 2SO 3用作牺牲剂。将以上悬浮液密封在 30 mL 硼硅酸盐管中抽真空并用 Ar 吹扫约5分钟以完全去除空气。然后将硼硅酸盐管置于超声清洗器的中心，避光下开启超声（45 KHz，600 W）进行分解水产氢。为了检测产氢量，将硼硅酸盐管内的 5 mL气体组分间歇性地提取并注入带有热导检测器的气相色谱仪（7890B，美国）中。使用氢气摩尔数与峰面积的校准曲线计算产生的氢气量。 Example 11: Cu-SnS 2 piezoelectric catalytic decomposition of water to produce hydrogen: 10 mg 3% Cu-SnS 2 nanoflowers were dispersed in 10 mL Na 2 SO 3 aqueous solution (0.05 M), and Na 2 SO 3 was used as a sacrificial agent. Seal the above suspension in a 30 mL borosilicate tube to evacuate and purge with Ar for about 5 min to completely remove the air. Then place the borosilicate tube in the center of the ultrasonic cleaner, and turn on the ultrasound (45 KHz, 600 W) in the dark to decompose water and produce hydrogen. To detect the amount of hydrogen produced, 5 mL of gas components in borosilicate tubes were intermittently extracted and injected into a gas chromatograph (7890B, USA) with a thermal conductivity detector. The amount of hydrogen produced was calculated using a calibration curve of hydrogen moles versus peak area.
实施例十二：Ag-SnS 2压电催化分解水产氢实验：取10 mg 3%Ag-SnS 2纳米花分散在 10 mL Na 2SO 3 水溶液（0.05 M）中，Na 2SO 3用作牺牲剂。将以上悬浮液密封在 30 mL 硼硅酸盐管中抽真空并用 Ar 吹扫约5分钟以完全去除空气。然后将硼硅酸盐管置于超声清洗器的中心，避光下开启超声（45 KHz，600 W）进行分解水产氢。为了检测产氢量，将硼硅酸盐管内的 5 mL气体组分间歇性地提取并注入带有热导检测器的气相色谱仪（7890B，美国）中。使用氢气摩尔数与峰面积的校准曲线计算产生的氢气量。 Example 12: Ag-SnS 2 piezoelectric catalyzed water splitting hydrogen production experiment: 10 mg 3% Ag-SnS 2 nanoflowers were dispersed in 10 mL Na 2 SO 3 aqueous solution (0.05 M), and Na 2 SO 3 was used as a sacrificial agent. Seal the above suspension in a 30 mL borosilicate tube to evacuate and purge with Ar for about 5 min to completely remove the air. Then place the borosilicate tube in the center of the ultrasonic cleaner, and turn on the ultrasound (45 KHz, 600 W) in the dark to decompose water and produce hydrogen. To detect the amount of hydrogen produced, 5 mL of gas components in borosilicate tubes were intermittently extracted and injected into a gas chromatograph (7890B, USA) with a thermal conductivity detector. The amount of hydrogen produced was calculated using a calibration curve of hydrogen moles versus peak area.
附图7为SnS 2，3%Cu-SnS 2和3%Ag-SnS 2压电催化分解水产氢的效果图。SnS 2，3%Cu-SnS 2和3%Ag-SnS 2在4小时内的H 2生成量分别为126 μmol g -1，300 μmol g -1，520 μmol g -1。 Accompanying drawing 7 is the effect diagram of SnS 2 , 3%Cu-SnS 2 and 3%Ag-SnS 2 piezoelectric catalytic decomposition of water to produce hydrogen. The amounts of H 2 generated by SnS 2 , 3%Cu-SnS 2 and 3%Ag-SnS 2 within 4 hours were 126 μmol g -1 , 300 μmol g -1 , and 520 μmol g -1 , respectively.
将上述压电催化分解水的实验中避光下打开超声更改为300W氙灯照射（仅光照），其余不变，发现SnS 2，Cu-SnS 2和Ag-SnS 2在4小时内的H 2生成量分别为120 μmol g -1，137 μmol g -1，156 μmol g -1。进一步的，超声基础上加光照，未对超声产氢效果有提升。 In the above piezoelectric catalytic water splitting experiment, turn on the ultrasound in the dark and change it to 300W xenon lamp irradiation (only light), and the rest remain unchanged. It is found that SnS 2 , Cu-SnS 2 and Ag-SnS 2 generate H 2 within 4 hours The amounts are 120 μmol g -1 , 137 μmol g -1 , and 156 μmol g -1 , respectively. Furthermore, the addition of light on the basis of ultrasound did not improve the hydrogen production effect of ultrasound.
不同掺杂量的催化剂进行同样的实验，4小时的产氢结果如下：
Figure 84133dest_path_image001
。 The same experiment was carried out on catalysts with different doping amounts, and the results of hydrogen production in 4 hours were as follows:
Figure 84133dest_path_image001
.
对比例一：取现有技术CN202010815126X实施例三制备的0.5-SnS 2/CNFs（10 mg）复合材料替换实施例十二的10 mg Ag-SnS 2，其余不变，作为对比实验，结果显示，在4小时内的H 2生成量为275 μmol g -1。 Comparative example 1: Take the 0.5-SnS 2 /CNFs (10 mg) composite material prepared in Example 3 of the prior art CN202010815126X to replace the 10 mg Ag-SnS 2 in Example 12, and keep the rest unchanged. As a comparative experiment, the results show that in The amount of H 2 generated in 4 hours was 275 μmol g -1 .
对比例二：使用光还原反应将银纳米颗粒沉积在SnS 2纳米花的表面。 将 0.5 g SnS 2 放入装有 25 mL AgNO 3 溶液（0.02 M）的烧杯中。在不断搅拌下将烧杯置于紫外光照射下。然后将粉末通过离心机洗涤和分离并在室温下干燥，制备了银纳米颗粒沉积的SnS 2纳米花，取10 mg替换实施例十二的10 mg Ag-SnS 2，其余不变，作为对比实验，结果显示，在4小时内的H 2生成量为285 μmol g -1。 Comparative example 2: using photoreduction reaction to deposit silver nanoparticles on the surface of SnS 2 nanoflowers. Put 0.5 g of SnS into a beaker filled with 25 mL of AgNO solution (0.02 M ). Place the beaker under UV light with constant stirring. Then the powder was washed and separated by a centrifuge and dried at room temperature to prepare SnS 2 nanoflowers deposited by silver nanoparticles. Take 10 mg to replace the 10 mg Ag-SnS 2 in Example 12, and keep the rest unchanged as a comparative experiment , the results showed that the amount of H 2 generated within 4 hours was 285 μmol g -1 .
拓展实施例：将金属掺杂剂铜盐更换为一水合乙酸铜（Cu(CO 2CH 3) 2·H 2O），催化性能未受到明显的影响。参考实施例二制备的3%Cu-SnS 2在4小时内的H 2生成量为307 μmol g -1。 Extended example: the catalytic performance is not significantly affected by replacing the metal dopant copper salt with copper acetate monohydrate (Cu(CO 2 CH 3 ) 2 ·H 2 O). The 3% Cu-SnS 2 prepared in Reference Example 2 produced 307 μmol g -1 of H 2 within 4 hours.
本发明公开的二硫化锡纳米催化剂中，压电效应构建内建电场，实现载流子的有效分离，提高压电催化效率。本发明利用简便的溶剂热法制备了铜离子或者银离子掺杂的二硫化锡纳米花（Cu-SnS 2，Ag-SnS 2）并首次将其应用于压电催化领域，纳米片形貌以及掺杂协同提高材料感应机械能的灵敏度，改善压电性，从而提高催化性能。 In the tin disulfide nano-catalyst disclosed by the present invention, the piezoelectric effect builds a built-in electric field, realizes the effective separation of carriers, and improves the piezoelectric catalytic efficiency. The present invention prepares tin disulfide nanoflowers (Cu-SnS 2 , Ag-SnS 2 ) doped with copper ions or silver ions by a simple solvothermal method and applies them to the field of piezoelectric catalysis for the first time. The doping synergistically increases the sensitivity of the material to sense mechanical energy, improves the piezoelectricity, and thus enhances the catalytic performance.

Claims (10)

  1. 二硫化锡纳米催化剂在分解水产氢中的应用，其特征在于，所述二硫化锡纳米催化剂为二硫化锡纳米花、铜离子掺杂二硫化锡纳米花或者银离子掺杂二硫化锡纳米花。The application of tin disulfide nano-catalysts in decomposing water to produce hydrogen is characterized in that the tin disulfide nano-catalysts are tin disulfide nanoflowers, copper ion doped tin disulfide nanoflowers or silver ion doped tin disulfide nanoflowers .
  2. 根据权利要求1所述二硫化锡纳米催化剂在分解水产氢中的应用，其特征在于，铜离子相对于锡离子的摩尔分数为1%～15%；银离子相对于锡离子的摩尔分数为1%～15%。According to the application of the tin disulfide nano-catalyst in splitting water to produce hydrogen according to claim 1, it is characterized in that the molar fraction of copper ions relative to tin ions is 1% to 15%; the molar fraction of silver ions relative to tin ions is 1 %~15%.
  3. 根据权利要求1所述二硫化锡纳米催化剂在分解水产氢中的应用，其特征在于，分解水产氢在超声下进行。The application of the tin disulfide nano-catalyst in splitting water to produce hydrogen according to claim 1, characterized in that the splitting of water to produce hydrogen is carried out under ultrasound.
  4. 一种二硫化锡纳米催化剂的制备方法，其特征在于，将含有锡源和硫源的前驱体溶液进行溶剂热反应后离心洗涤，干燥后得到二硫化锡纳米催化剂；或者将铜源置于含有锡源和硫源的前驱体溶液中，溶剂热反应后离心洗涤，干燥后得到二硫化锡纳米催化剂；或者将银源置于含有锡源和硫源的前驱体溶液中，溶剂热反应后离心洗涤，干燥后得到二硫化锡纳米催化剂。A kind of preparation method of tin disulfide nano-catalyst, it is characterized in that, the precursor solution that contains tin source and sulfur source is subjected to solvothermal reaction, centrifuges and washes, and obtains tin disulfide nano-catalyst after drying; Or copper source is placed in containing In the precursor solution of tin source and sulfur source, centrifuge and wash after solvothermal reaction, and obtain tin disulfide nanocatalyst after drying; or place silver source in the precursor solution containing tin source and sulfur source, centrifuge after solvothermal reaction After washing and drying, the tin disulfide nanometer catalyst is obtained.
  5. 根据权利要求4所述二硫化锡纳米催化剂的制备方法，其特征在于，锡源和硫源的摩尔比为1∶（1～10）。The preparation method of the tin disulfide nano-catalyst according to claim 4, characterized in that the molar ratio of the tin source and the sulfur source is 1: (1-10).
  6. 根据权利要求4所述二硫化锡纳米催化剂的制备方法，其特征在于，溶剂热反应在反应釜中100～160℃下反应6～24小时。The preparation method of the tin disulfide nano-catalyst according to claim 4, characterized in that the solvothermal reaction is carried out in a reactor at 100-160°C for 6-24 hours.
  7. 一种二硫化锡纳米催化剂分解水产氢的方法，其特征在于，包括以下步骤：将二硫化锡纳米催化剂置于加入含有牺牲剂的水中，然后超声处理，实现分解水产氢。A method for decomposing water with a tin disulfide nano-catalyst to produce hydrogen, characterized in that it comprises the following steps: placing the tin disulfide nano-catalyst in water containing a sacrificial agent, and then performing ultrasonic treatment to realize decomposing water to produce hydrogen.
  8. 根据权利要求7所述二硫化锡纳米催化剂分解水产氢的方法，其特征在于，所述二硫化锡纳米催化剂为二硫化锡纳米花、铜离子掺杂二硫化锡纳米花或者银离子掺杂二硫化锡纳米花。According to claim 7, the method for decomposing water with a tin disulfide nanocatalyst to produce hydrogen is characterized in that the tin disulfide nanocatalyst is tin disulfide nanoflowers, copper ion doped tin disulfide nanoflowers or silver ion doped disulfide nanoflowers. Tin sulfide nanoflowers.
  9. 根据权利要求7所述二硫化锡纳米催化剂分解水产氢的方法，其特征在于，超声处理的频率为40～60KHz，功率为400～800W。The method for decomposing water with a tin disulfide nanocatalyst to produce hydrogen according to claim 7, characterized in that the frequency of the ultrasonic treatment is 40-60KHz, and the power is 400-800W.
  10. 根据权利要求7所述二硫化锡纳米催化剂分解水产氢的方法，其特征在于，超声处理在避光的条件下进行。The method for decomposing water and producing hydrogen by the tin disulfide nano catalyst according to claim 7, characterized in that the ultrasonic treatment is carried out under the condition of avoiding light.
PCT/CN2021/102591 2021-06-27 2021-06-27 Application of tin disulfide nanocatalyst in production of hydrogen by piezoelectric catalytic decomposition of water WO2023272413A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/102591 WO2023272413A1 (en) 2021-06-27 2021-06-27 Application of tin disulfide nanocatalyst in production of hydrogen by piezoelectric catalytic decomposition of water

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/102591 WO2023272413A1 (en) 2021-06-27 2021-06-27 Application of tin disulfide nanocatalyst in production of hydrogen by piezoelectric catalytic decomposition of water

Publications (1)

Publication Number Publication Date
WO2023272413A1 true WO2023272413A1 (en) 2023-01-05

Family

ID=84690890

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/102591 WO2023272413A1 (en) 2021-06-27 2021-06-27 Application of tin disulfide nanocatalyst in production of hydrogen by piezoelectric catalytic decomposition of water

Country Status (1)

Country Link
WO (1) WO2023272413A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116099551A (en) * 2023-02-07 2023-05-12 昆明理工大学 Preparation method and application of carbon nano tube composite material
CN116395751A (en) * 2023-03-29 2023-07-07 哈尔滨理工大学 Preparation and piezoelectric catalysis application of samarium-doped bismuth ferrite nano material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105709780A (en) * 2016-01-22 2016-06-29 中南大学 Sn1-0.5xCuxS2 nanoflower and preparation method and application thereof
CN111268720A (en) * 2020-01-13 2020-06-12 信阳师范学院 Preparation method of large interlayer spacing tin disulfide nanoflower sodium ion battery negative electrode material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105709780A (en) * 2016-01-22 2016-06-29 中南大学 Sn1-0.5xCuxS2 nanoflower and preparation method and application thereof
CN111268720A (en) * 2020-01-13 2020-06-12 信阳师范学院 Preparation method of large interlayer spacing tin disulfide nanoflower sodium ion battery negative electrode material

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CUI XIAODAN, XU WANGWANG, XIE ZHIQIANG, WANG YING: "High-performance dye-sensitized solar cells based on Ag-doped SnS 2 counter electrodes", JOURNAL OF MATERIALS CHEMISTRY A, ROYAL SOCIETY OF CHEMISTRY, GB, vol. 4, no. 5, 1 January 2016 (2016-01-01), GB , pages 1908 - 1914, XP093017732, ISSN: 2050-7488, DOI: 10.1039/C5TA10234K *
LIU YUE; ZHOU YANSONG; ZHOU XIN; JIN XIAOLI; LI BEIBEI; LIU JINGYUAN; CHEN GANG: "Cu doped SnS2 nanostructure induced sulfur vacancy towards boosted photocatalytic hydrogen evolution", CHEMICAL ENGENEERING JOURNAL, ELSEVIER, AMSTERDAM, NL, vol. 407, 30 September 2020 (2020-09-30), AMSTERDAM, NL , XP086432129, ISSN: 1385-8947, DOI: 10.1016/j.cej.2020.127180 *
PATIL SUPRIYA A.; SHRESTHA NABEEN K.; HUSSAIN SAJJAD; JUNG JONGWAN; LEE SANG-WHA; BATHULA CHINNA; KADAM ABHIJIT N.; IM HYUNSIK; KI: "Catalytic decontamination of organic/inorganic pollutants in water and green H2 generation using nanoporous SnS2 micro-flower structured film", JOURNAL OF HAZARDOUS MATERIALS, ELSEVIER, AMSTERDAM, NL, vol. 417, 12 May 2021 (2021-05-12), AMSTERDAM, NL , XP086677897, ISSN: 0304-3894, DOI: 10.1016/j.jhazmat.2021.126105 *
RAJWAR BIRENDRA KUMAR, SHARMA SHAILENDRA KUMAR: "Structural, optical and electrical properties of Ag-doped SnS 2 nano-flowers synthesized by solvothermal method", MATERIALS RESEARCH EXPRESS, vol. 6, no. 7, pages 075524, XP093017734, DOI: 10.1088/2053-1591/ab18b4 *
TIAN WENROU, QIU JIAHAO, LI NAJUN, CHEN DONGYUN, XU QINGFENG, LI HUA, HE JINGHUI, LU JIANMEI: "Efficient piezocatalytic removal of BPA and Cr(VI) with SnS2/CNFs membrane by harvesting vibration energy", NANO ENERGY, ELSEVIER, NL, vol. 86, 1 August 2021 (2021-08-01), NL , pages 106036, XP093017729, ISSN: 2211-2855, DOI: 10.1016/j.nanoen.2021.106036 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116099551A (en) * 2023-02-07 2023-05-12 昆明理工大学 Preparation method and application of carbon nano tube composite material
CN116395751A (en) * 2023-03-29 2023-07-07 哈尔滨理工大学 Preparation and piezoelectric catalysis application of samarium-doped bismuth ferrite nano material
CN116395751B (en) * 2023-03-29 2024-08-13 哈尔滨理工大学 Preparation and piezoelectric catalysis application of samarium-doped bismuth ferrite nano material

Similar Documents

Publication Publication Date Title
Liu et al. Template-free preparation of non-metal (B, P, S) doped g-C3N4 tubes with enhanced photocatalytic H2O2 generation
Fajrina et al. Engineering approach in stimulating photocatalytic H2 production in a slurry and monolithic photoreactor systems using Ag-bridged Z-scheme pCN/TiO2 nanocomposite
Li et al. Atomic defects in ultra-thin mesoporous TiO2 enhance photocatalytic hydrogen evolution from water splitting
CN112521618B (en) Bismuth-based metal organic framework material and preparation method and application thereof
CN113387326B (en) Application of tin disulfide nano catalyst in piezocatalysis decomposition of water to produce hydrogen
CN110975918B (en) Indium zinc sulfide-nitrogen doped graphene foam composite photocatalytic material and preparation method and application thereof
CN110252352B (en) Carbon quantum dot modified bismuth tungstate/ordered macroporous fluorine-doped tin oxide composite photocatalyst and preparation method and application thereof
WO2022041852A1 (en) Ni-mof thin-film photocatalyst grown in-situ on foamed nickel surface, preparation method therefor, and use thereof
CN108404960B (en) Preparation method of sulfur-indium-zinc-gold carbon nitride two-dimensional layered composite photocatalyst
CN111203231B (en) Indium zinc sulfide/bismuth vanadate composite material and preparation method and application thereof
CN110252346B (en) MoS2/SnS2Preparation method and application of/r-GO composite photocatalyst
Dai et al. Carbon nanotube exfoliated porous reduced graphene oxide/CdS-diethylenetriamine heterojunction for efficient photocatalytic H2 production
CN112756000B (en) Method for preparing sulfide semiconductor/metal nano particles by sulfur vacancy defects and application thereof
WO2023272413A1 (en) Application of tin disulfide nanocatalyst in production of hydrogen by piezoelectric catalytic decomposition of water
CN107552072B (en) graphene-CuInS2Nano composite photocatalyst
Li et al. Hollow cadmium sulfide tubes with novel morphologies for enhanced stability of the photocatalytic hydrogen evolution
Wang et al. Effects of NH4F quantity on N-doping level, photodegradation and photocatalytic H2 production activities of N-doped TiO2 nanotube array films
Lv et al. Construction of N-doped TiO 2/SnO 2 heterostructured microspheres with dominant {001} facets for enhanced photocatalytic properties
Shi et al. N-doped graphene-based CuO/WO3/Cu composite material with performances of catalytic decomposition 4-nitrophenol and photocatalytic degradation of organic dyes
Lin et al. High-performance α-Bi2O3/CdS heterojunction photocatalyst: innovative design, electrochemical performance and DFT calculation
Zhang et al. Highly efficient photocatalytic H 2 O 2 production on core–shell CdS@ CdIn 2 S 4 heterojunction in non-sacrificial system
Lin et al. One-pot microwave-assisted synthesis of In2S3/In2O3 nanosheets as highly active visible light photocatalysts for seawater splitting
Zhang et al. Hydrogen pressure-assisted rapid recombination of oxygen vacancies in WO3 nanosheets for enhanced N2 photofixation
WO2022198766A1 (en) In-situ synthesized all-solid-state z-type heterostructured photocatalyst and preparation method therefor, and application in photoelectrocatalytic synthesis of h2o2
Wang et al. Recent advances in CdS heterojunctions: morphology, synthesis, performances and prospects

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21947379

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21947379

Country of ref document: EP

Kind code of ref document: A1