CN116145171A - APTES modified CFP anode material and water oxidation electro-synthesis H using same 2 O 2 Is a method of (2) - Google Patents

APTES modified CFP anode material and water oxidation electro-synthesis H using same 2 O 2 Is a method of (2) Download PDF

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Publication number
CN116145171A
CN116145171A CN202310090976.1A CN202310090976A CN116145171A CN 116145171 A CN116145171 A CN 116145171A CN 202310090976 A CN202310090976 A CN 202310090976A CN 116145171 A CN116145171 A CN 116145171A
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carbon fiber
anode material
fiber paper
cfp
aptes
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李朝林
凌晨
王文辉
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Shenzhen Graduate School Harbin Institute of Technology
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Shenzhen Graduate School Harbin Institute of Technology
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • C25B11/042—Electrodes formed of a single material
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract

The invention provides an APTES modified CFP anode material and a water oxidation electro-synthesis method thereof for H 2 O 2 Is a method of (2). The anode material is obtained by depositing 3-aminopropyl-3-ethoxysilane on the surface of carbon fiber paper subjected to oxidation treatment. The material has the characteristic that APTES molecules self-assemble on the CFP surface to generate a monolayer film, can be used as an anode material for electro-oxidation catalytic reaction, and can participate in water oxidation electro-synthesis of H 2 O 2 When the H is increased 2 O 2 Selectivity and yield of (c).

Description

APTES modified CFP anode material and water oxidation electro-synthesis H using same 2 O 2 Is a method of (2)
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to an APTES modified CFP anode material and a water oxidation electrosynthesis H using the same 2 O 2 Is a method of (2).
Background
H 2 O 2 Is one of the most important basic chemicals in the fields of modern chemical industry, sustainable energy conversion/storage, environmental remediation and the like, and plays a vital role in production and life. Statistically, annual pair H worldwide 2 O 2 Is required to be more than 300 ten thousand tons. Anthraquinone process for producing H 2 O 2 The most mature method. Currently, 90% of the world's H 2 O 2 The anthraquinone method is adopted in the production, and the product concentration can reach 70 wt%. However, the anthraquinone process generates a large amount of waste, requires complex, large-scale infrastructure, consumes high energy, and is cumbersome in separation and purification procedures. In addition, H 2 O 2 Is a safety risk for transportation and storage of (a) and decentralized production of H 2 O 2 Is more attractive.
Electrochemical synthesis of H 2 O 2 Is a disperse production H 2 O 2 The method has good application prospect. Has the obvious advantages of simple equipment, controllable production scale, mild process conditions and the like. The production process is green and environment-friendly, takes electric energy generated by sustainable energy as energy, and takes H as energy 2 O/O 2 Is a raw material. H 2 O 2 The electrochemical synthesis of (c) can be carried out in two ways: cathodic two electron oxygen reduction reaction (2 e-ORR, formula 1) and anodic two electron water oxidation reaction (2 e-WOR, formula 2). Since the reaction potential of 2e-WOR is higher than that of the four-electron water oxidation reaction (OER, formula 3), the water is oxidized to H thermodynamically 2 O 2 Does not dominate. Current electrochemical synthesis of H 2 O 2 The study of (2) is mainly focused on 2 e-ORR. In recent years, CO has been found 3 2- /HCO 3- The electrolyte can improve the performance of 2e-WOR and has developed many carbon-based catalysts and metal oxides including BDD, PTFE-coated CFP, znO and CaSnO 3 Etc. But its application is generally over-potential high or H 2 O 2 Low yield.
O 2 +2H + +2e － →H 2 O 2 ，E o ＝0.67V vs.SHE， (1)；
2H 2 O→H 2 O 2 +2H + +2e － ，E o ＝1.76V vs.SHE， (2)；
2H 2 O→O 2 +4H + +4e － ，E o ＝1.23V vs.SHE， (3)；
*+H 2 O→OH*+(H + +e - )， (4)；
OH*+H 2 O→H 2 O 2 +(H + +e - )+*， (5)；
OH*→O*+(H + +e - ) (6)
O*+H 2 O→OOH*+(H + +e - ) (7)
OOH*→*+O 2 +(H + +e - ) (8)
* Indicating a smooth catalyst surface.
Self-assembled monolayers (SAMs) can form strong chemical bonds with substrates, spontaneously form on solid substrates at solid-liquid or solid-gas interfaces, and this process can introduce specific functional groups at the substrate surface at the same time. Since SAMs has limited impact on the intrinsic properties of the substrate, SAMs modifications are commonly used to study the impact of functional groups on the reaction process. If SAMs can be combined with electrochemistry to produce H 2 O 2 Combining will expand H 2 O 2 The new synthetic thought has high research value.
Disclosure of Invention
In view of this, to further explore SAMs and electrochemical synthesis of H 2 O 2 The invention provides an APTES modified CFP anode material and an electro-synthesis method for H by adopting the same 2 O 2 By using a SAMs-3-aminopropyl-3-ethoxysilane (APTES) to modify Carbon Fiber Paper (CFP), introducing specific functional groups on the surface of the CFP, thereby obtaining a modified CFP anode material, wherein the anode material can adjust the binding energy of an active site and a water oxidation intermediate OH, and improve the electrosynthesis of 2e-WOR into H 2 O 2 Selectivity and yield of (c).
In order to achieve the technical purpose, the technical scheme adopted by the application is as follows:
in a first aspect, the present invention provides an APTES modified CFP anode material obtained by depositing 3-aminopropyl-3-ethoxysilane (APTES) on the surface of oxidized Carbon Fiber Paper (CFP).
Further, the oxidized carbon fiber paper is obtained by oxidizing carbon fiber paper with an acidic oxidizing agent.
Further, the preparation method of the oxidized carbon fiber paper comprises the following steps: immersing the carbon fiber paper in an acidic oxidant, oxidizing for 2-3 hours at 50-60 ℃, and then washing the carbon fiber paper with deionized water and drying.
Further, the acidic oxidant is selected from concentrated nitric acid with the mass concentration of 50-60%, concentrated sulfuric acid with the mass concentration of 98% or concentrated sulfuric acid with the mass concentration of 98% and H with the mass concentration of 30% 2 O 2 The volume ratio of the solution is 7: 3.
Further, the carbon fiber paper is subjected to pretreatment before the oxidation treatment, the pretreatment comprising: cutting carbon fiber paper into 1X 2cm pieces, sequentially adding 0.5M NaOH solution and 0.5M H 2 SO 4 Ultrasonic cleaning is carried out on the solution, ethanol and deionized water for 20-30 min, and then drying is carried out.
Further, the control parameters of the drying are: vacuum is 100-133 Pa, temperature is 70-80 ℃, and drying time is not less than 10h.
Further, the depositing 3-aminopropyl-3-ethoxysilane (APTES) on the surface of the oxidized Carbon Fiber Paper (CFP) comprises:
placing the oxidized carbon fiber paper vertically in a hydrothermal reaction kettle, placing an open glass bottle filled with APTES in the hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle after filling with protective gas;
heating the hydrothermal reaction kettle to 160-200 ℃, preserving heat for 1-10 h, and naturally cooling to room temperature;
taking out the carbon fiber paper deposited with the 3-aminopropyl-3-ethoxysilane, and drying to obtain the carbon fiber paper.
Preferably, the hydrothermal reaction kettle is heated to 175-190 ℃, kept for 3.5-4.5 h and naturally cooled to room temperature.
Further, the control parameters of the drying are: vacuum is 100-133 Pa, temperature is 50-60 ℃ and drying time is 2-3 h.
In a second aspect, the present invention provides the use of an anode material as described above in an electro-oxidation catalytic reaction.
In a third aspect, the present invention provides a water oxidation electrosynthesis H 2 O 2 The method adopts the anode material, and comprises the following steps: with the anode materialThe material is used as anode, platinum sheet is used as cathode, and the electrolysis is carried out in electrolyte to prepare H 2 O 2 The reaction equation is: 2H (H) 2 O→H 2 O 2 +H 2 。
Further, the electrolyte is K with the concentration of 1-4M 2 CO 3 Solution, preferably 4M K 2 CO 3 A solution.
The invention develops an APTES-CFP material, which has the characteristic that APTES molecules self-assemble on the CFP surface to generate a monolayer film, can be used as an anode material for electro-oxidation catalytic reaction, and can participate in water oxidation electro-synthesis of H 2 O 2 When the H is increased 2 O 2 Selectivity and yield of (c).
Drawings
FIG. 1 is a microscopic morphology of APTES-CFP obtained in example 1 of the present invention, wherein FIG. a is an SEM image, FIG. b is an EDS image, and FIG. c is an AFM image.
FIG. 2 shows the reaction time and the reaction temperature versus H in example 2 of the present invention 2 O 2 The effect of selectivity, wherein plot a is the effect of different reaction times and plot b is the effect of different reaction temperatures.
FIG. 3 shows the concentration of the electrolyte versus H in example 3 of the present invention 2 O 2 The effect of rate of formation (panel a) and selectivity (panel b), and stability of APTES modified electrodes (panel c).
Detailed Description
In the description of the present invention, it is to be noted that the specific conditions are not specified in the examples, and the description is performed under the conventional conditions or the conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention will now be described in further detail with reference to the drawings and to specific examples, which are given by way of illustration and not limitation.
Example 1
The embodiment provides an APTES modified CFP anode material, which is obtained by depositing 3-aminopropyl-3-ethoxysilane (APTES) on the surface of oxidized Carbon Fiber Paper (CFP). The preparation method comprises the following steps:
1) Pretreatment of CFP
Cutting CFP into 1×2cm pieces, sequentially adding 0.5M NaOH and 0.5M H 2 SO 4 Ultrasonic cleaning in ethanol and deionized water for 30min, and drying in a vacuum oven at 80deg.C overnight.
2) Oxidation treatment of CFP
Concentrating the CFP obtained in the step 1) into concentrated HNO with the mass fraction of 60% at 60 DEG C 3 The CFP was thoroughly rinsed with deionized water and dried overnight at 80 ℃ in a vacuum oven with a vacuum of 100 to 133Pa. Concentrated HNO as strong acid oxidant in this step 3 Can also be replaced by 98% concentrated sulfuric acid or 98% concentrated sulfuric acid and 30% H 2 O 2 The volume ratio of the solution is 7: 3.
3) APTES modified CFP
The CFP obtained in the step 2) is vertically placed in a 50mL hydrothermal reaction kettle with a polytetrafluoroethylene lining, and a glass bottle with a volume of 2mL and containing 100 mu L of APTES is placed in the kettle. The reaction kettle is filled with argon, and then the stainless steel shell is covered and screwed. The entire hydrothermal kettle was placed in an oven and heated to 180 ℃. After 4h of preservation, naturally cooling to room temperature. Taking out the CFP, drying at 60 ℃ for 2 hours in a vacuum oven, and removing redundant APTES on the CFP to obtain an APTES modified CFP (APTES-CFP), wherein a microscopic morphology diagram of the material is shown in figure 1, a diagram a is an SEM image, a diagram b is an EDS image, and a diagram c is an AFM image, and the APTES is shown to successfully modify the CFP material.
Example 2
This example examined the APTES-CFP to water oxidation electrosynthesis of H obtained at different reaction times and different reaction temperatures in step 3) of example 1 2 O 2 The specific procedure of step 1) to 3) was as in example 1, and then the APTES-CFP material obtained with different reaction times and different reaction temperatures was used as anode, platinum sheet was used as cathode, and the reaction temperature was adjusted to 1M K 2 CO 3 Electrolytic preparation of H in solution 2 O 2 The voltage is 2.8V, when the total charge reaches 10C or the electrolysis time reachesThe electrolysis was terminated at 10 min.
Wherein, when the influence of the reaction time (2 h, 3h, 4h, 6h, 8 h) in the step 3) is examined, the reaction temperature adopted is 160 ℃; when the influence of the reaction temperature (140 ℃, 160 ℃, 180 ℃, 200 ℃) was examined, the reaction time employed was 4h.
H 2 O 2 Determination of the concentration: after the electrolytic reaction, 0.5mL of the electrolyte was taken and 0.5mL of 3M H was added 2 SO 4 Acidification was performed and 0.5ml of 0.05m potassium titanyl oxalate solution was added. After standing for 10min, the absorbance was measured and H was converted according to a standard curve 2 O 2 Concentration.
As a result, as shown in FIG. 2, it was revealed that the reaction time was about 4 hours and the reaction temperature was about 180℃as the optimal conditions for the preparation of APTES-modified CFP, so that the hydrothermal reaction vessel was preferably heated to 175 to 190℃and kept at a temperature of 3.5 to 4.5 hours in the present invention.
Example 3
The present example examines different K 2 CO 3 Electrolyte concentration pair adopts APTES-CFP electrode water oxidation electrosynthesis H 2 O 2 Is a function of (a) and (b). The optimal APTES modification CFP preparation conditions obtained in example 2 are adopted, and the APTES-CFP electrode is prepared by referring to the procedure of example 1, and is used as an anode, a platinum sheet is used as a cathode, and K with different concentrations is used 2 CO 3 Electrolytic synthesis of H in solution 2 O 2 The electrolysis was terminated when the total charge of the reaction reached 10C or the electrolysis time reached 10 min.
H 2 O 2 Determination of the concentration: after the reaction, 0.5mL of the electrolyte was taken and 0.5mL of 3M H was added 2 SO 4 Acidification was performed and 0.5ml of 0.05m potassium titanyl oxalate solution was added. After standing for 10min, the absorbance was measured and H was converted according to a standard curve 2 O 2 Concentration.
The results are shown in FIG. 3, which shows that with K 2 CO 3 Concentration increase, H 2 O 2 And the production rate and selectivity of the catalyst are improved. The maximum generation rate can reach 80 mu mol L -1 min -1 cm -2 (shown in a graph a), the selectivity can reach 83% (shown in a graph b). In addition, the electrode can stably operate12h (shown in the figure), and has good practical application prospect.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

  1. APTES modified CFP anode material, which is characterized in that: is obtained by depositing 3-aminopropyl-3-ethoxysilane on the surface of carbon fiber paper subjected to oxidation treatment.
  2. 2. The APTES modified CFP anode material according to claim 1, wherein: the oxidized carbon fiber paper is obtained by oxidizing carbon fiber paper with an acidic oxidant.
  3. 3. The APTES modified CFP anode material according to claim 1 or 2, characterized in that: the preparation method of the oxidized carbon fiber paper comprises the following steps: immersing the carbon fiber paper in an acidic oxidant, oxidizing for 2-3 hours at 50-60 ℃, and then washing the carbon fiber paper with deionized water and drying.
  4. 4. An APTES modified CFP anode material according to claim 3 wherein: the acidic oxidant is selected from concentrated nitric acid with the mass concentration of 50-60%, concentrated sulfuric acid with the mass concentration of 98% or concentrated sulfuric acid with the mass concentration of 98% and H with the mass concentration of 30% 2 O 2 The volume ratio of the solution is 7: 3.
  5. 5. The APTES modified CFP anode material according to claim 1, wherein: the carbon fiber paper is also subjected to a pretreatment prior to the oxidation treatment, the pretreatment comprising: cutting carbon fiber paper into 1X 2cm pieces, sequentially adding 0.5M NaOH and 0.5H of M 2 SO 4 Ultrasonic cleaning in ethanol and deionized water for 20-30 min, and drying.
  6. 6. The APTES modified CFP anode material according to claim 1, wherein: the method for depositing 3-aminopropyl-3-ethoxysilane on the surface of carbon fiber paper after oxidation treatment comprises the following steps:
    placing the oxidized carbon fiber paper vertically in a hydrothermal reaction kettle, placing an open glass bottle filled with APTES in the hydrothermal reaction kettle, and sealing the hydrothermal reaction kettle after filling with protective gas;
    heating the hydrothermal reaction kettle to 160-200 ℃, preserving heat for 1-10 h, and naturally cooling to room temperature;
    taking out the carbon fiber paper deposited with the 3-aminopropyl-3-ethoxysilane, and drying to obtain the carbon fiber paper.
  7. 7. The APTES modified CFP anode material according to claim 6, wherein: heating the hydrothermal reaction kettle to 175-190 ℃, preserving heat for 3.5-4.5 h, and naturally cooling to room temperature.
  8. 8. Use of an anode material according to any one of claims 1 to 7 in an electro-oxidation catalytic reaction.
  9. 9. Water oxidation electrosynthesis H 2 O 2 Is characterized in that: an anode material according to any one of claims 1 to 7, comprising: the anode material is used as an anode, a platinum sheet is used as a cathode, and the electrolysis is carried out in an electrolyte to prepare H 2 O 2 The reaction equation is: 2H (H) 2 O→H 2 O 2 +H 2 。
  10. 10. A water oxidation electrosynthesis H according to claim 9 2 O 2 Is characterized in that: the electrolyte is K with the concentration of 1-4M 2 CO 3 A solution.
CN202310090976.1A 2023-01-19 2023-01-19 APTES modified CFP anode material and water oxidation electro-synthesis H using same 2 O 2 Is a method of (2) Pending CN116145171A (en)

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