A Sm 0.99 Eu 0.01 Preparation method and application of CoO3 / SBA-15 / GO supported Pt single-atom efficient water-gas shift reaction catalyst

Abstract

The application provides a kind of Sm 0.99 Eu 0.01 Preparation method and application of CoO3 / SBA-15 / GO supported Pt single-atom efficient water-gas shift reaction catalyst. First, Sm 0.99 Eu 0.01 CoO3 / SBA-15 composite material is prepared by using modified sol-gel method, then graphene oxide (GO) is put into deionized water and ultrasonic for 4h, then Sm 0.99 Eu 0.01 CoO3 / SBA-15 composite material is added, and after stirring uniformly, Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO composite material is obtained. Then Pt is loaded to obtain the catalyst, and the Pt loading amount is ≤1wt%. The prepared catalyst has very good catalytic effect on water-gas shift reaction CO in the temperature (150℃-400℃) range, the reaction gas composition is 2vol% CO+10vol% H2O+N2, the flow rate is 30mL / min, the space velocity is 18000mL / (gh), and the CO conversion rate is 77%-93% at 400℃. The catalyst has excellent catalytic activity and good thermal stability.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of for catalytic elimination of CO Sm 0.99 Eu 0.01 Preparation method of CoO3 / SBA-15 / GO supported Pt single-atom efficient water-gas shift reaction catalyst and its application in water-gas shift reaction. BACKGROUND

[0002] The speed of social development is accelerating, and the demand for energy is increasing. If the technology remains stagnant, humanity will face a situation where energy supply cannot keep up with development needs. The rational development and efficient use of energy is a crucial research direction. In recent years, although many countries are developing and using more non-fossil fuel energy, the main energy still comes from fossil fuel supply. The incomplete combustion of fossil fuels and carbon-containing substances is the main source of carbon monoxide. CO gas is a typical flammable, explosive, toxic and harmful gas that greatly harms the environment and human health. High levels of CO inhaled into the body with air can rapidly bind to hemoglobin in red blood cells, weaken hemoglobin's ability to carry oxygen, inhibit and reduce oxygen hemoglobin dissociation, cause tissue necrosis due to hypoxia, and even endanger human life. Therefore, the elimination of CO also has great practical significance. Currently, hydrogen energy is considered the most promising clean energy in the 21st century due to its cleanliness, efficiency, and renewability, so the development and application of hydrogen energy are also the main research focus of researchers. Water-gas shift reaction is a commonly used reaction in industry, which not only recycles CO waste gas but also is an important method for hydrogen production, with the dual advantages of environmental governance and energy saving and emission reduction. Water-gas shift reaction can effectively react equal amounts of CO and H2O to form CO2 and H2, so water-gas shift reaction has a wide application in the hydrogen production industry. In recent years, with the rapid development of proton exchange membrane fuel cell (PEMFC) technology, low-temperature water-gas shift reaction has a new application background. It can cause irreversible poisoning of the electrode in the proton exchange membrane fuel cell. Water-gas shift reaction can reduce the concentration of reforming gas and increase the content of H2, so low-temperature water-gas shift reaction has become a research hotspot again.

[0003] Single-atom catalysts (SACs) refer to metal atoms uniformly dispersed on a support. They offer significant economic advantages for precious metals, reducing the amount of precious metals used, improving metal utilization efficiency, and lowering catalyst costs. Since the concept of single atoms was proposed, SACs have rapidly gained popularity in academia, primarily due to the high activity exhibited by single atoms in both homogeneous and heterogeneous catalytic reactions. Perovskite oxides possess outstanding thermal stability, ionic conductivity, and oxidation resistance, exhibit good catalytic activity in alkaline media, and are low-cost, making them widely studied as catalysts. Graphite oxide (GO) has gained more attention in catalysis due to its unique structure and excellent electron transport capabilities. Ordered mesoporous material SBA-15 has attracted attention due to its excellent high specific surface area, tunable pore size, and ordered pore structure, which can be used as a template to increase the specific surface area of ​​the catalyst. In this patent, the high specific surface area mesoporous material SBA-15 is used as a template to disperse perovskite Sm... 0.99 Eu 0.01 A composite material Sm was prepared by combining CoO3 with GO and SBA-15. 0.99 Eu 0.01 CoO3 / SBA-15 / GO was used to load Pt single atoms and Pt nanoparticles onto Sm... 0.99 Eu 0.01 The composite material, consisting of CoO3 / SBA-15 / GO, exhibits high catalytic CO elimination performance and stability over a wide temperature range (150℃-400℃). This project was supported by the National Natural Science Foundation of China (Grant Nos. 21277008 and 20777005), the Beijing Natural Science Foundation (Grant No. 8082008), and the National Key Research and Development Program of China (No. 2017YFC0209905), and also encompasses the research content of these projects. Summary of the Invention

[0004] The purpose of this invention is to provide a Sm 0.99 Eu 0.01Preparation method of CoO3 / SBA-15 / GO supported Pt single-atom efficient water-gas shift reaction catalyst and application thereof in water-gas shift reaction.The provided catalyst has very high catalytic efficiency for CO in a water-gas shift reaction under the following conditions: temperature range (150 DEG C-400 DEG C), reaction gas composition 2vol% CO+10vol% H2O+N2, flow rate 30 mL / min, and space velocity 18000 mL / (gh). Moreover, the catalyst has good thermal stability at 400 DEG C. Raw materials of the catalyst widely exist in nature, and can effectively improve the atomic utilization rate of Pt noble metal and reduce the use amount of Pt noble metal.

[0005] The application provides a Sm 0.99 Eu 0.01 Preparation method of CoO3 / SBA-15 / GO supported Pt single-atom efficient water-gas shift reaction catalyst

[0006] 1、Sm 0.99 Eu 0.01 Preparation of CoO3 / SBA-15 / GO composite carrier

[0007] 1.7099g of samarium nitrate, 1.1309g of cobalt nitrate, 0.0173g of europium nitrate and 2.4498g of citric acid are dissolved in 100mL of deionized water, ammonia water is used to adjust the pH value of the solution to 7, and stirring is carried out at room temperature for 0.5h; then 1g of SBA-15 is dispersed into the nitrate solution; stirring is carried out under a water bath temperature of 80 DEG C until a gel is formed. The composite material precursor is dried in a 100 DEG C oven to obtain a composite material precursor; the composite material precursor is placed into a muffle furnace, calcination is carried out at 700 DEG C at a temperature increasing rate of 2 DEG C / min, and the temperature is kept for 3h. The calcined material is washed with a 2mol / L NaOH solution for 4h to remove the template SBA-15, and then filtration and drying are carried out to obtain Sm 0.99 Eu 0.01 CoO3 / SBA-15; then 10mg of GO is added into 100mL of deionized water and ultrasonic treatment is carried out for 4h, so that the GO is uniformly dispersed in the deionized water; 1g of Sm 0.99 Eu 0.01 CoO3 / SBA-15 is added into the above solution and ultrasonic treatment is continuously carried out for 2h, so that the GO is uniformly dispersed on the composite material; suction filtration is carried out and drying is carried out at 100 DEG C for 12h to obtain Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO.

[0008] 2、Sm 0.99 Eu 0.01 Preparation of CoO3 / SBA-15 / GO supported Pt single-atom catalyst

[0009] 1 g of Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO was added into 100 mL of deionized water and stirred for 1 h to make it fully dispersed in the solution, 1.25 mL of Pt(NO3)2 solution with a concentration of 0.4 g / L was added according to the mass ratio, then ammonia was used to adjust the pH value of the solution to 9, and the solution was stirred under ice water bath for 4 h and aged for 2 h; the aged solution was subjected to suction filtration and washing, and then dried at 100 ℃ for 12 h, and then calcined at 400 ℃ with a temperature rising rate of 4 ℃ / min and kept at this temperature for 2 h to obtain xPt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO; wherein x is the mass percentage of Pt in the catalyst.

[0010] 3、Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO supported Pt nanoparticle catalyst

[0011] Pt nanoparticles were supported on Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO by PVA protection reduction method; first, 20 mg of polyvinyl alcohol was weighed and added into 100 mL of deionized water and stirred for 10 min, and then an appropriate amount of Pt(NO3)2 solution with a concentration of 0.4 g / L was added according to the mass ratio, and after the addition of NaBH4, the solution was stirred for 30 min; then, 1 g of Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO was added into the above solution and stirred under ice water bath for 4 h and aged for 2 h; the aged solution was subjected to suction filtration and washing, and then dried at 100 ℃ for 12 h, and then calcined at 400 ℃ with a temperature rising rate of 4 ℃ / min and kept at this temperature for 2 h to obtain Pt nanoparticle xPt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO; wherein x is the mass percentage of Pt in the catalyst.

[0012] 4. The above catalyst was placed in a continuous flow fixed bed device and reacted with a reaction gas composition of 2 vol% CO + 10 vol% H2O + N2, the flow rate was 30 mL / min, the space velocity was 18000 mL / (gh), and the catalyst exhibited very high catalytic activity for the water gas shift reaction of CO at a reaction temperature of 150-400°C, and the CO conversion rate was 77-93%. The catalyst was investigated for activity at a reaction temperature of 400°C for 600 min with a reaction gas composition of 2 vol% CO + 10 vol% H2O + N2, the flow rate was 30 mL / min, the space velocity was 18000 mL / (gh), and the CO conversion rate did not decrease much at the temperature studied, and the catalyst exhibited high stability. BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO, 0.37Pt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO, 0.83Pt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO, 0.88Pt / Sm 0.99 Eu 0.01 XRD pattern of CoO3 / SBA-15 / GO catalyst.

[0014] Figure 2 Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO, 0.37Pt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO, 0.83Pt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO, 0.88Pt / Sm 0.99 Eu 0.01 N2-adsorption / desorption pattern of CoO3 / SBA-15 / GO catalyst.

[0015] Figure 3 Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO, 0.37Pt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO, 0.83Pt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO, 0.88Pt / Sm0.99 Eu 0.01 Activity graph of CoO3 / SBA-15 / GO catalyst.

[0016] Figure 4 0.37Pt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO, 0.83Pt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO, 0.88Pt / Sm 0.99 Eu 0.01 Stability graph of CoO3 / SBA-15 / GO catalyst. DETAILED DESCRIPTION

[0017] Example 1

[0018] 1, Sm 0.99 Eu 0.01 Preparation of CoO3 / SBA-15 / GO composite carrier

[0019] Dissolve 1.7099 g of samarium nitrate, 1.1309 g of cobalt nitrate, 0.0173 g of europium nitrate and 2.4498 g of citric acid in 100 mL of deionized water, adjust the pH value of the solution to 7 using ammonia water, and stir at room temperature for 0.5 h; then disperse 1 g of SBA-15 into the nitrate solution; stir at a water bath temperature of 80°C until a gel is formed. Dry the composite material precursor in an oven at 100°C; place the above-mentioned composite material precursor into a muffle furnace, and calcine at a temperature increasing rate of 2°C / min at 700°C, and maintain this temperature for 3 h. Wash the calcined material with a 2 mol / L NaOH solution for 4 h to remove the template SBA-15, and then filter and dry to obtain Sm 0.99 Eu 0.01 CoO3 / SBA-15; then add 10 mg of GO into 100 mL of deionized water and ultrasonically disperse for 4 h; add 1 g of Sm 0.99 Eu 0.01 CoO3 / SBA-15 into the above-mentioned solution and continue to ultrasonically disperse for 2 h, so that the GO is uniformly dispersed on the composite material; then perform suction filtration and dry at 100°C for 12 h to obtain Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO.

[0020] 2, Sm 0.99 Eu 0.01 Preparation of Pt monatomic catalyst supported by CoO3 / SBA-15 / GO

[0021] Dissolve 1 g of Sm 0.99 Eu0.01 CoO3 / SBA-15 / GO was added into 100 mL deionized water and stirred for 1 h to make it fully dispersed in the solution, 1.25 mL of Pt(NO3)2 solution with a concentration of 0.4 g / L was added according to the mass ratio, then the pH value of the solution was adjusted to 9 using ammonia water, and the solution was stirred under ice water bath for 4 h and aged for 2 h; the aged solution was subjected to suction filtration and washing, and then dried at 100 ℃ for 12 h, and then calcined at 400 ℃ with a temperature rising rate of 4 ℃ / min and kept at this temperature for 2 h to obtain 0.37Pt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO; wherein 0.37 is the mass percentage of Pt in the catalyst.

[0022] 3, The above catalyst was placed in a continuous flow fixed bed device and reacted with a reaction gas composition of 2vol% CO + 10vol% H2O + N2, the flow rate was 30 mL / min, the space velocity was 18000 mL / (gh), and the water gas shift reaction of CO showed very high catalytic activity at a reaction temperature of 150-400 ℃, the CO conversion rate was 77%. The catalyst was investigated for activity at a reaction temperature of 400 ℃ for 600 min with a reaction gas composition of 2vol% CO + 10vol% H2O + N2, the flow rate was 30 mL / min, the space velocity was 18000 mL / (gh), and the CO conversion rate was 69% at the temperature studied, showing high stability.

[0023] Example 2

[0024] 1, Sm 0.99 Eu 0.01 Preparation of CoO3 / SBA-15 / GO composite carrier

[0025] 1.7099 g of samarium nitrate, 1.1309 g of cobalt nitrate, 0.0173 g of europium nitrate and 2.4498 g of citric acid were dissolved in 100 mL deionized water, the pH value of the solution was adjusted to 7 using ammonia water, and the solution was stirred at room temperature for 0.5 h; then 1 g of SBA-15 was dispersed in the nitrate solution; stirring was carried out under water bath at 80 ℃ until a gel was formed. The composite material precursor was dried in an oven at 100 ℃; the above composite material precursor was placed in a muffle furnace and calcined at 700 ℃ with a temperature rising rate of 2 ℃ / min and kept at this temperature for 3 h. The calcined material was washed with 2 mol / L NaOH solution for 4 h to remove the template SBA-15, and then filtered and dried to obtain Sm 0.99 Eu 0.01 CoO3 / SBA-15; then 10 mg of GO was added into 100 mL deionized water and ultrasonicated for 4 h to make it uniformly dispersed in the deionized water; 1 g of Sm 0.99 Eu0.01 CoO3 / SBA-15 was added into the above solution and ultrasonic treatment was continued for 2 h to make GO uniformly dispersed on the composite, and then Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO.

[0026] 2、Sm 0.99 Eu 0.01 Preparation of Pt monatomic catalyst supported by CoO3 / SBA-15 / GO

[0027] 1 g of Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO was added into 100 mL of deionized water and stirred for 1 h to make it fully dispersed in the solution, 2.5 mL of Pt(NO3)2 solution with a concentration of 0.4 g / L was added according to the mass ratio, then ammonia was used to adjust the pH value of the solution to 9, and the solution was stirred under ice water bath for 4 h and aged for 2 h; the aged solution was filtered and washed, and then dried at 100 ℃ for 12 h, and calcined at 400 ℃ with a temperature rising rate of 4 ℃ / min and kept at this temperature for 2 h to obtain 0.83Pt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO; wherein 0.83 is the mass percentage of Pt in the catalyst.

[0028] 3、The above catalyst was placed in a continuous flow fixed bed device and reacted with a reaction gas composition of 2 vol% CO + 10 vol% H2O + N2, the flow rate was 30 mL / min, the space velocity was 18000 mL / (g h), and the water gas shift reaction of CO showed very high catalytic activity at a reaction temperature of 150-400 ℃, the CO conversion rate was 93%. The catalyst was investigated for activity at a reaction temperature of 400 ℃ for 600 min with a reaction gas composition of 2 vol% CO + 10 vol% H2O + N2, the flow rate was 30 mL / min, the space velocity was 18000 mL / (g h), and the CO conversion rate was 87% at the temperature studied, showing high stability.

[0029] Example 3

[0030] 1、Sm 0.99 Eu 0.01 Preparation of CoO3 / SBA-15 / GO composite carrier

[0031] 1.7099 g of samarium nitrate, 1.1309 g of cobalt nitrate, 0.0173 g of europium nitrate, and 2.4498 g of citric acid were dissolved in 100 mL of deionized water. The pH of the solution was adjusted to 7 using ammonia, and the mixture was stirred at room temperature for 0.5 h. Then, 1 g of SBA-15 was dispersed in the nitrate solution. The mixture was stirred in an 80 °C water bath until a gel was formed. The composite precursor was dried in an oven at 100 °C. The composite precursor was then placed in a muffle furnace and calcined at 700 °C with a heating rate of 2 °C / min for 3 h. The calcined material was washed with 2 mol / L NaOH solution for 4 h to remove the template agent SBA-15, and then filtered and dried to obtain Sm. 0.99 Eu 0.01 CoO3 / SBA-15; then 10 mg of GO was added to 100 mL of deionized water and sonicated for 4 hours to ensure uniform dispersion in the deionized water; 1 g of Sm 0.99 Eu 0.01 CoO3 / SBA-15 was added to the above solution and sonicated for 2 hours to uniformly disperse GO on the composite material. After filtration and drying at 100°C for 12 hours, Sm was obtained. 0.99 Eu 0.01 CoO3 / SBA-15 / GO.

[0032] 2. Sm 0.99 Eu 0.01 Preparation of CoO3 / SBA-15 / GO supported Pt nanoparticle catalyst

[0033] Pt nanoparticles loaded with Sm were prepared by PVA protection and reduction method. 0.99 Eu 0.01 CoO3 / SBA-15 / GO; First, weigh 20 mg of polyvinyl alcohol and add it to 100 mL of deionized water and stir for 10 min. Then, add 2.5 mL of 0.4 g / L Pt(NO3)2 solution according to the mass ratio, add NaBH4 and stir for 30 min; then add 1 g of Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO was added to the above solution, stirred in an ice-water bath for 4 hours, and aged for 2 hours. The aged solution was filtered and washed, dried at 100℃ for 12 hours, and then calcined at 400℃ with a heating rate of 4℃ / min and held at this temperature for 2 hours to obtain 0.88Pt / Sm. 0.99 Eu 0.01 CoO3 / SBA-15 / GO; where 0.88 is the mass percentage of Pt in the catalyst.

[0034] 3. The above catalyst was placed in a continuous flow fixed bed apparatus and reacted with a reaction gas composition of 2 vol% CO + 10 vol% H2O + N2 at a flow rate of 30 mL / min and a space velocity of 18000 mL / (gh). The catalyst exhibited high catalytic activity for CO in the water-gas shift reaction at a reaction temperature of 150℃-400℃, with a CO conversion rate of 82%. The catalyst activity was also investigated at 400℃ for 600 min with a reaction gas composition of 2 vol% CO + 10 vol% H2O + N2 at a flow rate of 30 mL / min and a space velocity of 18000 mL / (gh). At the investigated temperature, the CO conversion rate was 73%, demonstrating high stability.

Claims

1. A Sm 0.99 Eu 0.01 A method for preparing a Pt single-atom efficient water-gas shift reaction catalyst loaded on CoO3 / SBA-15 / GO, characterized in that, Comprising the following steps: (1) Sm 0.99 Eu 0.01 Preparation of CoO3 / SBA-15 / GO composite carrier Preparation of the composite support by modified sol-gel method: 1.7099 g of samarium nitrate, 1.1309 g of cobalt nitrate, 0.0173 g of europium nitrate and 2.4498 g of citric acid were dissolved in 100 mL of deionized water, the pH value of the solution was adjusted to 7 using ammonia water, and stirred at room temperature for 0.5 h; then 1 g of SBA-15 was dispersed into the nitrate solution; stirring was carried out at a water bath temperature of 80 °C until a gel was formed; the composite material precursor was dried in an oven at 100 °C; the above composite material precursor was placed in a muffle furnace and calcined at 700 °C at a temperature increasing rate of 2 °C / min, and maintained at this temperature for 3 h; The calcined material was washed with 2 mol / L NaOH solution for 4 h to remove the template SBA-15, and then filtered and dried to obtain Sm 0.99 Eu 0.01 CoO3 / SBA-15; then 10 mg of GO was added into 100 mL of deionized water and ultrasonicated for 4 h to uniformly disperse in the deionized water; 1 g of Sm 0.99 Eu 0.01 CoO3 / SBA-15 was added into the above solution and ultrasonicated for 2 h to uniformly disperse GO on the composite material, and then suction filtered and dried at 100 °C for 12 h to obtain Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO; (2) Sm 0.99 Eu 0.01 Preparation of Pt single-atom catalyst supported by CoO3 / SBA-15 / GO 1 g of Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO was added into 100 mL of deionized water, stirred for 1 h to make it fully dispersed in the deionized water, 1.25 mL - 2.5 mL of Pt(NO3)2 solution with a concentration of 0.4 g / L was added into the above solution according to the mass ratio, then the pH value of the solution was adjusted to 9 using ammonia water, stirred under ice water bath for 4 h, aged for 2 h; the aged solution was subjected to suction filtration and washing, and after drying at 100 °C for 12 h, calcination was carried out at 400 °C with a temperature rising rate of 4 ℃ / min and keeping the temperature for 2 h to obtain x Pt / Sm 0.99 Eu 0.01 CoO3 / SBA-15 / GO; wherein x is the mass percentage of Pt in the catalyst.

2. Sm obtained by the production process of claim 1 0.99 Eu 0.01 The application of the CoO3 / SBA-15 / GO supported Pt single-atom efficient water-gas shift reaction catalyst in the water-gas shift reaction is characterized in that: The above catalyst was placed in a continuous flow fixed bed device, and a reaction gas with a composition of 2 vol% CO + 10 vol% H2O + N2was introduced for reaction, the flow rate was 30 mL / min, the space velocity was 18000 mL / (g.h), and the reaction temperature was 150 °C-400 °C.

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