Method for synthesizing hydrogen peroxide under mild condition
The use of defect-rich IV-VI group semiconductor nanomaterials as catalysts enables the synthesis of hydrogen peroxide from O2 and H2O at ambient conditions, addressing the inefficiencies of existing methods by providing a safe, green, and cost-effective solution.
Patent Information
- Application Number
- CN202510634655.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-16
- Publication Date
- 2025-07-15
AI Technical Summary
The existing hydrogen peroxide synthesis technology has problems such as high equipment investment, large energy consumption, high cost of generating organic waste, high cost of precious metal catalysts and large energy consumption, which limits its large-scale application.
Defectively rich IV-VI binary semiconductor nanomaterials are used as catalysts, O2 and H2O are used as raw materials at room temperature and pressure, and oxygen is dispersed by stirring or ultrasonic and oxygen is introduced to catalyze the synthesis of hydrogen peroxide, avoiding the use of precious metals and additional energy input.
It realizes safe, green and low-cost hydrogen peroxide synthesis under mild conditions, simplifies the operation process, reduces energy consumption, and has great potential for renewable catalysts.
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Figure CN120308915A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of preparation of hydrogen peroxide, and particularly relates to a method for synthesizing hydrogen peroxide under mild conditions, and more particularly to a method for synthesizing hydrogen peroxide using a defective IV-VI binary semiconductor material as a catalyst with O2 and H2O as raw materials. Background Art
[0002] Hydrogen peroxide (H2O2) is an important chemical with wide applications, and its synthesis technology has always been one of the key research areas in the field of chemistry and chemical engineering. The traditional industrial synthesis method of hydrogen peroxide is mainly the anthraquinone method. In this method, anthraquinone is used as a carrier, and under the action of a palladium catalyst, hydrogen peroxide is prepared by alternately performing hydrogenation and oxidation reactions. However, the anthraquinone method has some significant disadvantages. On the one hand, the process is relatively complex, involving multiple reaction steps and complex separation and purification operations, resulting in a high equipment investment cost; on the other hand, it has strict requirements for reaction conditions, requiring precise control of parameters such as temperature, pressure, and the concentration of reactants, and has high energy consumption during the production process, and at the same time generates a large amount of organic waste.
[0003] In recent years, with the continuous development of the concept of green chemistry, researchers have been committed to developing more environmentally friendly, efficient, and low-cost H2O2 synthesis technologies. Among them, the direct synthesis method based on noble metal catalysts has received extensive attention. For example, using noble metals such as palladium and gold as active components, by reasonably designing the structure and composition of the catalyst, it can directly catalyze the reaction of hydrogen and oxygen to generate hydrogen peroxide under mild conditions of low temperature and low pressure. This method simplifies the reaction process and reduces energy consumption, but the cost of noble metal catalysts is high, and flammable and explosive hydrogen needs to be used as a raw material. In addition, in recent years, photocatalytic and electrocatalytic methods have also provided very promising green reaction pathways, which can realize the synthesis of H2O2 from O2 and H2O, and are the most promising potential green synthesis means in the future. However, these methods require additional energy input (light energy, electrical energy, etc.) from the outside, increasing energy consumption, and the catalysts are all relatively complex and expensive, limiting their large-scale application. Summary of the Invention
[0004] Based on the problems existing in the prior art, the present invention provides a method for synthesizing hydrogen peroxide with mild, safe, green, and low-cost reaction conditions. Under mild conditions, using O2 and H2O as raw materials and a defective IV-VI binary semiconductor material as a catalyst, the synthesis of hydrogen peroxide can be achieved at normal temperature and normal pressure without additional energy input, and without using hydrogen, sacrificial agents, etc., providing a green, safe, and low-cost synthesis route.
[0005] The present invention provides a method for synthesizing hydrogen peroxide at room temperature, comprising the following steps:
[0006] Disperse the defect-rich group IV-VI binary semiconductor nanomaterials as catalysts in water, stir or ultrasonically disperse them, and continuously introduce air or oxygen into the water. Maintain the reaction system at a constant temperature of 0 to 80 °C for the reaction, and then catalytically produce hydrogen peroxide.
[0007] The defect-rich group IV-VI binary semiconductor nanomaterial catalyst is Sn 1-x Se, Sn 1-x Te, Sn 1-x S, Ge 1- x Te, Ge 1-x Se, Ge 1-x S, Pb 1-x Se, Pb 1-x S or Pb 1-x Te, with a defect concentration x of 0 to 0.99, having lattice vacancies; the defects include S vacancies, Sn vacancies, Se vacancies, Ge vacancies, Te vacancies, Pb vacancies or a combination thereof.
[0008] The morphology of the catalyst includes one or more of flakes, wires, particles or porous structures, with a size of 10 nm to 100 μm and a porosity range of 0 to 60%.
[0009] The dosage ratio of the catalyst to water is 10 mg to 1 g: 1 L.
[0010] Furthermore, the reaction temperature is 20 to 50 °C;
[0011] The reaction atmosphere is air or oxygen.
[0012] The water used for the reaction includes but is not limited to deionized water, seawater, domestic water or natural water.
[0013] The beneficial effects of the present invention are as follows:
[0014] The present invention provides a brand-new mild method for synthesizing hydrogen peroxide. Compared with all hydrogen peroxide production processes, the process described in this invention has mild reaction conditions and a simple operation process. It is a safe, green, low-energy-consuming and low-cost hydrogen peroxide production method, and the specific advantages are as follows:
[0015] (1) Green and environmentally friendly, without the need for additional energy or sacrificial agents;
[0016] (2) Simple operation, suitable for various environmental conditions;
[0017] (3) Low cost, without the need for precious metals, and the catalyst can be regenerated and commercialized;
[0018] (4) Flexible method, with wide applications of the product. Description of the Drawings
[0019] Figure 1 It is Sn 1-x Morphology diagrams of S catalysts, a-SnS, b-Sn 0.9 S, c-Sn 0.8 S, d-Sn 0.7 S.
[0020] Figure 2 It is Sn 1-x Performance comparison diagram of S catalysts.
[0021] Figure 3 It is Sn 0.8 Performance diagrams of S catalysts at different reaction temperatures.
[0022] Figure 4 Performance comparison diagram of IV-VI group binary semiconductor catalysts with different rich defects. Detailed implementation manners
[0023] To make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below.
[0024] The present invention provides a method for mild synthesis of hydrogen peroxide, using water and oxygen as reaction raw materials, and the required catalyst is a rich-defect IV-VI group binary semiconductor material, and the catalytic reaction is carried out at room temperature to synthesize hydrogen peroxide.
[0025] The technical solutions of the present invention will be described in detail below in conjunction with embodiments, but the scope of the present invention is not limited to the following embodiments.
[0026] All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.
[0027] Example 1:
[0028] (1) Sn 1-x Synthesis of SnS series catalysts by thermal injection method
[0029] Disperse 0.2 mmol of sulfur powder in 3 mL of oleylamine, and ultrasonically treat for 10 minutes to ensure uniform dispersion of sulfur to form a precursor solution. In a three-necked flask, dissolve 0.2 mmol of SnCl2·2H2O in 5 mL of oleylamine, stir at 60 °C for 30 minutes until completely dissolved, degas and purge with N2 for 1 h to remove dissolved oxygen. Heat to 180 °C at a rate of 5 °C / min and hold for 10 minutes. Then use a syringe to quickly inject the sulfur precursor solution into the three-necked flask. After the mixed solution turns black, react at a constant temperature for 1 hour under a N2 atmosphere. After cooling to room temperature, collect the obtained black powder SnS.
[0030] According to the designed stoichiometric ratio, adjust the amount of SnCl2 to 0.18 mmol following the same steps to synthesize the catalyst Sn 0.9 S;
[0031] Adjust the amount of SnCl2 to 0.16 mmol to synthesize the catalyst Sn 0.8 S;
[0032] Adjust the amount of SnCl2 to 0.14 mmol to synthesize the catalyst Sn 0.7 S.
[0033] Perform scanning electron microscopy (SEM) characterization on the catalytic system described in Example 1. As shown in the appendix Figure 1 are the morphology diagrams of a series of Sn 1-x S catalysts, presenting a two-dimensional flake structure. a-SnS, b-Sn 0.9 S, c-Sn 0.8 S, d-Sn 0.7 S.
[0034] (2) Catalytic performance of different Sn 1-x S catalysts
[0035] Respectively take 1 g of Sn 1-x S catalysts with different defect concentrations, add them to 1 L of deionized water, ultrasonicate for 10 s, continuously introduce oxygen, sample every 0.5 h at a constant water bath temperature of 30 °C, and measure the absorbance value with a UV spectrophotometer at a wavelength of 350 nm. Calculate the hydrogen peroxide concentration based on the pre-calibrated standard solution curve.
[0036] Compare the performance of the Sn 1-x S catalysts in the comparative implementation cases for hydrogen peroxide production. The performance of hydrogen peroxide production at 30 °C is shown in the appendix Figure 2 As shown, among them, the Sn 0.8 S catalyst has the best catalytic performance. At 3 h of the catalytic reaction, the yield of H2O2 produced by its catalysis reaches 950 μmol / g / h.
[0037] (3) Catalytic performance of Sn 0.8 S catalysts at different temperatures
[0038] Preferably, take 1 g of Sn 0.8 S catalyst, add it to 1 L of deionized water, ultrasonicate for 10 s, continuously introduce oxygen, and conduct catalytic experiments in constant temperature water baths at 0 °C, 10 °C, 20 °C, 30 °C, 40 °C, and 50 °C respectively. Sample every 0.5 h, measure the absorbance value with a UV spectrophotometer at a wavelength of 350 nm, and calculate the hydrogen peroxide concentration based on the pre-calibrated standard solution curve.
[0039] The Sn 0.8The S catalyst was evaluated according to the scheme in Example 2, and the catalytic performance of the catalysts in the comparative examples for producing hydrogen peroxide at different temperatures was compared. As shown in Figure 3 the figure, its catalytic performance is positively correlated with the reaction temperature. When the catalytic reaction temperature is 50 °C, the catalytic reaction rate can reach 1180 μmol / g / h, and it also has excellent performance at near room temperature.
[0040] Example 2: Catalytic experiments of different catalysts
[0041] (1) Preparation of catalysts
[0042] SnS and SnS2: SnS was prepared by the same method as in Example 1; in addition, according to the preparation method of Sn 1-x S in Example 1, keeping other steps unchanged, the amount of SnCl2 in Example 1 was adjusted to 0.05 mmol to synthesize the catalyst SnS2.
[0043] SnSe: 5 mmol of selenium powder was dissolved in 5 mL of trioctylphosphine (TOP) to form a transparent and homogeneous TOP-Se precursor solution; 0.5 mmol of SnCl2 was dissolved in 40 mL of oleylamine to form a homogeneous solution, and then purged with nitrogen for 1 hour to completely remove dissolved oxygen; 0.5 mL of the TOP-Se solution was mixed with 2 mL of hexamethyldisilazane to obtain the HMDS-TOP-Se solution. The Sn precursor solution was heated to 240 °C and quickly injected into the HMDS-TOP-Se solution. After the mixed solution turned black, it was further aged at 240 °C for 30 minutes under a N2 atmosphere, and the black powder SnSe was collected by centrifugation.
[0044] SnTe: 59.5 mg of tin acetate, 2 mL of oleic acid, and 0.5 mL of tri-n-octylphosphine were successively added to 10 mL of diphenyl ether. The mixture was stirred at 130 °C for 5 minutes, and then vacuum degassed at 80 °C for 1.5 h. Under nitrogen protection, 0.15 mL of 1-chlorotetradecane was added, and the system was heated to the reaction temperature of 210 °C. After 10 minutes, 0.8 m of a tri-n-octylphosphine-tellurium precursor solution with a concentration of 0.65 mol / L was quickly injected. At this time, the solution gradually changed from transparent yellow to grayish yellow. After the reaction proceeded for 1 minute, the heating was stopped, and the nanosheets were precipitated with toluene and then centrifuged and washed to collect the powder SnTe.
[0045] GeTe: First, dissolve 67 mg of polyvinylpyrrolidone and 50 mg of sodium caprylate in 250 mL of nonanoic acid solvent, and degas under vacuum at 110 °C. Subsequently, maintain at 110 °C under Ar, and add 120 mg of bis(trimethylsilyl)amino germanium Ge[N(SiMe3)2]2 using a syringe. The colorless solution gradually turns light yellow, and then the temperature is raised to 250 °C and 0.3 mL of tri-n-octylphosphine-tellurium (TOP-Te) precursor is injected. After about 5 minutes, a dark brown colloidal dispersion is formed. After aging for 20 minutes, it is cooled, diluted with an equal volume of hexane, centrifuged and washed, and the powder GeTe is collected.
[0046] PbTe: Dissolve 1 mmol of lead nitrate (Pb(NO3)2) and an appropriate amount of sodium hydroxide (NaOH) in 15 mL of deionized water, and stir magnetically until completely dissolved. Separately, dissolve 1 mmol of sodium tellurite (Na2TeO3) and 0.5 g of polyvinylpyrrolidone (PVP) in 10 mL of deionized water, and stir to form a homogeneous solution. After mixing the above two solutions, add 10 mL of hydrazine hydrate (N2H4·3H2O) and supplement deionized water to a total volume of 40 mL, and continuously stir for 5 minutes to ensure thorough mixing. Transfer the mixed solution to a 100 mL stainless steel autoclave with a polytetrafluoroethylene liner, seal it, and place it in an oven. React at 160 °C for 24 hours. After the reaction, naturally cool to room temperature, collect the gray precipitate product by vacuum filtration, wash it 3 times with deionized water and anhydrous ethanol in turn, and air-dry at room temperature for 12 hours to obtain the final sample PbTe.
[0047] (2) Catalytic performance experiment
[0048] Respectively take 1 g of the above catalysts SnS, SnS2, SnSe, SnTe, GeTe, PbTe and add them to 1 L of deionized water, ultrasonicate for 10 s, continuously introduce oxygen, and sample every 0.5 hours at a constant water bath temperature of 25 °C. Measure the absorbance value with a UV-visible spectrophotometer at a wavelength of 350 nm, and calculate the hydrogen peroxide concentration according to the pre-calibrated standard solution curve.
[0049] In Example 2, the catalytic performance of six defective group IV-VI binary semiconductor materials for hydrogen peroxide production was compared at 30 °C. As shown in the appendix Figure 4 Six catalysts all have the performance of catalytic hydrogen peroxide production at room temperature. Among them, the SnSe-based catalyst has more excellent performance, and the catalytic rate of H2O2 production is 1200 μmol / g / h when reacting at 30 °C for 3 h.
[0050] Although the present invention has been described in accordance with the preferred embodiments, various modifications can be made thereto without departing from the scope of the present invention, and the components thereof can be replaced with equivalents. In particular, as long as there is no structural conflict, the various technical features mentioned in each embodiment can be combined in any form. The present invention is not limited to the specific embodiments disclosed herein, but actually covers all technical solutions within the scope of the claims.
Claims
1. A method for synthesizing hydrogen peroxide under mild conditions, characterized in that, It includes the following steps: Disperse the defect-rich IV-VI binary semiconductor nanomaterial as a catalyst in water, stir or ultrasonically disperse it, continuously introduce air or oxygen into the water, and keep the reaction system at a constant temperature of 0-80 °C for reaction, thereby catalytically producing hydrogen peroxide.
2. The method for synthesizing hydrogen peroxide under mild conditions according to claim 1, wherein The catalyst of the defect-rich IV-VI binary semiconductor nanomaterial is Sn 1-x Se, Sn 1-x Te, Sn 1-x S, Ge 1-x Te, Ge 1-x Se, Ge 1-x S, Pb 1- x Se, Pb 1-x S or Pb 1-x Te, the defect concentration x is 0 to 0.99, and has lattice vacancies; the defects include S vacancies, Sn vacancies, Se vacancies, Ge vacancies, Te vacancies, Pb vacancies or combinations thereof.
3. The method for synthesizing hydrogen peroxide under mild conditions as claimed in claim 1, wherein The morphology of the catalyst includes one or more of flakes, wires, particles or porous structures, with a size of 10 nm to 100 μm and a porosity range of 0-60%.
4. The method for synthesizing hydrogen peroxide under mild conditions according to claim 1, wherein The dosage ratio of the catalyst to water is 10 mg to 1 g: 1 L.
5. The method for synthesizing hydrogen peroxide under mild conditions according to claim 1, wherein, The reaction temperature is 20-50 °C.
6. The method for synthesizing hydrogen peroxide under mild conditions as claimed in claim 1, wherein, The water used for the reaction includes but is not limited to deionized water, seawater, domestic water or natural water.