CN114108009B - Method for preparing and activating hydrogen peroxide in situ based on water oxidation and application thereof - Google Patents

Method for preparing and activating hydrogen peroxide in situ based on water oxidation and application thereof Download PDF

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CN114108009B
CN114108009B CN202110743713.7A CN202110743713A CN114108009B CN 114108009 B CN114108009 B CN 114108009B CN 202110743713 A CN202110743713 A CN 202110743713A CN 114108009 B CN114108009 B CN 114108009B
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hydrogen peroxide
cathode
carbon fiber
anode
fiber paper
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CN114108009A (en
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胡卓锋
胡睿婷
郑宁超
何茜
周泉
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Sun Yat Sen University
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Abstract

The invention provides a method for preparing and activating hydrogen peroxide in situ based on water oxidation, which comprises the steps of taking carbon fiber paper loaded with nano zero-valent iron as a cathode, forming an electrolytic circuit with an anode, connecting a power supply, and synchronously activating hydrogen peroxide in the process of preparing hydrogen peroxide by electrolyzing water. The method provided by the invention not only can be used for efficiently preparing the hydrogen peroxide, but also can be used for synchronously and efficiently activating the prepared hydrogen peroxide. When CFP-PTFE was used as an anode and a platinum electrode was used as a cathode, H was produced after 2 hours of electrolysis of water 2 O 2 Up to 4.97mmol/L. And not activate H 2 O 2 Compared with the method, the removal efficiency of the activated hydrogen peroxide prepared by the method for methyl blue with the concentration of 20mg/L is improved1.31×10 6 The removal rate is up to 100% within 12 min; and the removal rate of the triethyl phosphate with the concentration of 10mg/L in 2 hours is 50 percent.

Description

Method for preparing and activating hydrogen peroxide in situ based on water oxidation and application thereof
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a method for preparing and activating hydrogen peroxide in situ based on water oxidation and application thereof.
Background
Hydrogen peroxide is one of the most important chemicals in modern industry and environmental processes, global H 2 O 2 The annual demand of (2) is about 400 ten thousand tons. The currently prevailing hydrogen peroxide production process is the Anthraquinone Oxidation (AO) process. However, this method requires high energy consumption, large-scale facilities, a hydrogen raw material and a noble metal catalyst such as palladium. At the same time, a large amount of high-concentration H 2 O 2 And also constitutes a safety hazard. Few industries, other than the special aerospace industry, require H in concentrated form 2 O 2 . Thus, to avoid H 2 O 2 There is a potential safety hazard in storage and transportation, and efforts are underway to develop a process that is more energy efficient, resource efficient, and suitable for on-site production of H at dilute concentrations 2 O 2 Is a method of (2).
Electrocatalytic synthesis of H 2 O 2 Is a green method with application prospect, and H produced by the method 2 O 2 Can be continuously accumulated in the electrolysis process. Typically H 2 O 2 Both raw materials and products of electrocatalytic synthesis of (a) are non-toxic green materials, such as: air and water, the portability of which reduces H 2 O 2 The construction and transportation costs of the storage facility. Currently, the two-electron Oxygen Reduction Reaction (ORR) is an electrocatalytic synthesis of H 2 O 2 Is widely studied. For example: the Chinese patent publication No. CN 111472018A discloses a method for preparing hydrogen peroxide by SPE electrolysis, which comprises the following steps: medium water is introduced into the electrolysis system at the water inlet of the anode; introducing reaction O into an electrolysis system at a cathode gas inlet 2 The method comprises the steps of carrying out a first treatment on the surface of the Connecting the anode and the cathode with an external power supply to form an electrolysis path; the medium water is decomposed into a product O on the anode through electrolytic reaction 2 And H + Product O 2 Is discharged through a water outlet on the anode end plate; h + Reach the cathode through the proton exchange membrane and react with the introduced reaction O 2 Combining to form the product H 2 O 2 Product H 2 O 2 Is discharged through an exhaust port on the cathode end plate and collected. However, in the dual-electron ORR method, an aeration process of high-purity oxygen is required to increase the concentration of dissolved oxygen in the solution, the aeration process consumes high energy, and the high-purity oxygen is inconvenient in use, and also has a safety hazard. In order to avoid the consumption of high purity oxygen and the safety problems that exist, more recently researchers have developed hydrogen peroxide production processes based on electrochemical two-electron water oxidation, such as: the Chinese patent with publication number of CN101054677A discloses a method for preparing hydrogen and hydrogen peroxide by electrolyzing water, and specifically discloses the method comprising the following steps: in an acidic aqueous solution containing a surfactant, a carbon electrode is used as an anode and a cathode, and direct current is applied to the electrode end to prepare hydrogen and hydrogen peroxide by electrolysis. The double-electron water oxidation process has the following advantages: (1) Only water is needed as a reactant, so that an aeration process is avoided, and the production cost is reduced; (2) The two-electron water oxidation process can be used in anaerobic environments, such as water treatment in a cave; (3) The cathode in the water oxidation system can reduce water into hydrogen, and the hydrogen energy is a green energy source. However, current research on electrocatalytic synthesis of hydrogen peroxide is generally concerned with how to increase the efficiency and activity of the anode material to increase the yield of hydrogen peroxide, for example: the Chinese patent publication No. CN107200384A discloses a preparation method of a carbon fiber electrode for efficiently producing hydrogen peroxide to treat organic wastewater, and specifically discloses a preparation method of a carbon fiber electrode, which is prepared by immersing a carbon fiber material in a mixed solution of carbon nanotube particles and polytetrafluoroethylene for 20-40 min, performing ultrasonic treatment for 1-3 h to obtain pretreated carbon fibers, and drying and annealing the pretreated carbon fibers. The electrode can efficiently generate hydrogen peroxide, and under the condition of current of 100 mApH=7, H is generated for 3H 2 O 2 The yield reaches 900mg/L to 1050mg/L. HoweverThe effect of hydrogen peroxide on treating organic wastewater is poor. The oxidation capability of hydrogen peroxide is not strong, and in practical application, although only water is needed as a raw material for producing hydrogen peroxide by water oxidation, the production of hydrogen peroxide by a water oxidation method has no good effect on a plurality of organic wastewater. Therefore, it is very critical to develop a highly efficient contaminant removal technology based on hydrogen peroxide production by water oxidation.
Disclosure of Invention
The present invention aims to overcome the above-mentioned drawbacks and disadvantages of the prior art and to provide a method for in situ preparation and activation of hydrogen peroxide based on water oxidation.
A second object of the present invention is to provide the use of the above method for treating dye and/or organophosphorus wastewater.
A third object of the present invention is to provide a method for treating dye and/or organophosphorus wastewater.
The above object of the present invention is achieved by the following technical solutions:
a method for preparing and activating hydrogen peroxide in situ based on water oxidation comprises taking carbon fiber paper loaded with nano zero-valent iron as a cathode, forming an electrolytic circuit with an anode, connecting a power supply, and synchronously activating hydrogen peroxide in the process of preparing hydrogen peroxide by electrolyzing water.
In the invention, the anode electrolyzes water into hydrogen peroxide and hydrogen ions in the process of water electrolysis, and the carbon fiber paper loaded with nano zero-valent iron is used as a cathode, so that the carbon fiber paper can convert the hydrogen ions into hydrogen. In addition, the hydrogen peroxide is activated to obtain OH free radical by using nano zero-valent iron as a catalyst. The activity of the activated hydrogen peroxide is obviously improved, and the dye and the organophosphorus pollutants can be effectively removed.
Preferably, the anode is polytetrafluoroethylene carbon fiber paper.
Preferably, the preparation method of the polytetrafluoroethylene carbon fiber paper comprises the steps of diluting polytetrafluoroethylene suspension to obtain polytetrafluoroethylene suspension with the mass fraction of 5% -60%, immersing carbon fiber paper in the polytetrafluoroethylene suspension, taking out and drying, and calcining the dried carbon fiber paper in nitrogen atmosphere to obtain the polytetrafluoroethylene-coated carbon fiber paper (CFP-PTFE) anode.
More preferably, the mass fraction of polytetrafluoroethylene in the diluted polytetrafluoroethylene suspension is 20%, and the CFP-PTFE20% anode is obtained.
More preferably, the soaking time is 5-20 min; the drying temperature is 100-120 ℃ and the drying time is 5-10 min; the calcination temperature is 320-370 ℃ and the time is 0.5-1 h.
Preferably, the preparation method of the carbon fiber paper loaded with nano zero-valent iron comprises the steps of adding nano zero-valent iron powder into Nafion solution, performing ultrasonic treatment to obtain nano zero-valent iron suspension, coating the nano zero-valent iron suspension on the lower half part of the hydrophobic surface of the carbon fiber paper, and drying to obtain the carbon fiber paper (CFP-NZVI) cathode loaded with nano zero-valent iron carbon.
More preferably, the mass ratio of the nano zero-valent iron powder to Nafion is (1-2): (0.001-0.004).
More preferably, the mass concentration of the Nafion solution is 0.05g/L to 0.1g/L.
Further preferably, the Nafion solution has a mass concentration of 0.1g/L.
Preferably, in any of the above methods, the anode and the cathode are connected with an external power supply, an electrolytic path is formed in the electrolyte, and the hydrogen peroxide can be prepared and activated in situ by introducing a bias voltage of 2.24-3.66V vs RHE under stirring.
More preferably, the bias voltage is 3.66V vs RHE.
More preferably, the electrolyte is KHCO 3 A solution.
Further preferably, the KHCO 3 The concentration of the solution is 1-2 mol/L;
more preferably, a reference electrode is added to the electrolytic path.
Further preferably, the reference electrode is a silver chloride electrode.
More preferably, the stirring speed is 60 to 80rpm.
As a preferred embodiment, a method for in situ preparation and activation of hydrogen peroxide based on water oxidation comprises the steps of:
s1: preparation of CFP-PTFE anode: diluting the polytetrafluoroethylene suspension with ultrapure water to obtain polytetrafluoroethylene suspension with mass fraction of 20%, and concentrating the polytetrafluoroethylene suspension at 2×4cm 2 Immersing carbon fiber paper in polytetrafluoroethylene suspension for 10min, taking out, drying at 120 ℃ for 10min, calcining the dried carbon fiber paper in nitrogen atmosphere at 350 ℃ for 0.5h to obtain a CFP-PTFE anode;
s2: preparation of CFP-NZVI cathode: adding 0.1mL Nafion solution with mass concentration of 0.1g/L into 10mg nanometer zero-valent iron powder, performing ultrasonic treatment for 5min to obtain nanometer zero-valent iron suspension, and coating on 2×4cm 2 The lower half of the hydrophobic surface of the carbon fiber paper is coated with an area of 2X 2cm 2 Drying at 25 ℃ for 3min to obtain the CFP-NZVI cathode.
S3: the CFP-PTFE20% anode, the CFP-NZVI cathode and the silver chloride reference electrode in the step S1 and the step S2 are formed into a three-electrode system, and are added into an electrolytic cell with the capacity of 100mL, and 50mL of KHCO with the concentration of 2mol/L is added 3 The electrolyte is used for connecting the anode and the cathode with an external power supply to form an electrolytic path, and the hydrogen peroxide can be prepared and activated in situ by introducing a bias voltage of 3.66V vs RHE under the stirring condition of the rotating speed of 80rpm.
The invention also provides the application of any of the methods for preparing and activating hydrogen peroxide in situ based on water oxidation in treating dye and/or organophosphorus wastewater.
The invention also provides a method for treating dye and/or organophosphorus wastewater, which comprises taking the anode and the cathode in any one of the above methods as electrode materials, forming a three-electrode system with a reference electrode, and adding KHCO 3 The electrolyte connects the anode and the cathode with an external power supply to form an electrolytic path, and the biased electrolytic dye and/or the organophosphorus wastewater of 2.24-3.66V vs RHE is introduced. Preferably, any one of the dyes mentioned above is methyl blue; any one of the above organic phosphorus is triethyl phosphate.
More preferably, the concentration of the methyl blue is 20-500 mg/L; the concentration of the triethyl phosphate is 10-20 mg/L.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention uses CFP-NZVI as a cathode, and the cathode converts hydrogen ions generated by an anode into hydrogen in the process of preparing hydrogen peroxide in situ by oxidizing electrolyzed water. In addition, hydrogen peroxide generated by the anode is activated to obtain OH free radical by taking nano zero-valent iron as a catalyst. The activity of the activated hydrogen peroxide is obviously improved, and the dye and the organophosphorus pollutants can be effectively removed.
(2) The invention further uses CFP-PTFE as an anode, and the CFP-NZVI cathode is matched for use, so that hydrogen peroxide can be efficiently prepared, and the prepared hydrogen peroxide can be synchronously activated. Further, H was produced by electrolysis of water for 2 hours using CFP-PTFE20% as an anode and a platinum electrode as a cathode 2 O 2 Up to 4.97mmol/L; hydrogen peroxide was prepared and activated at a 3.66V vs RHE bias with CFP-PTFE20% as anode and CFP-NZVI as cathode. And not activate H 2 O 2 Compared with the method, the removal efficiency of the activated hydrogen peroxide prepared by the method for methyl blue with the concentration of 20mg/L is improved by 1.31 multiplied by 10 6 The removal rate is up to 100% in 12 minutes, and the removal rate of the organic phosphorus pollutant triethyl phosphate with the concentration of 10mg/L in 2 hours is 50%.
Drawings
Fig. 1 is an X-ray diffraction pattern of different anode materials.
FIG. 2 is a graph showing the effect of different anode materials on hydrogen peroxide production.
Fig. 3 is an X-ray diffraction pattern of different cathode materials.
FIG. 4 is a graph of hydroxyl accumulation over time for different cathodes used in a single cell.
Figure 5 is a graph of electron paramagnetic resonance before and after one hour of energization in a single cell using a CFP-NZVI cathode.
FIG. 6 is a graph showing the effect of different bias voltages on hydrogen peroxide production.
Fig. 7 is a graph showing the results of the removal of methyl blue from hydrogen peroxide activated by different cathode materials.
Fig. 8 is a graph of the removal rate results for methyl blue removal by hydrogen peroxide activated by different cathode materials.
Fig. 9 shows the removal efficiency of methyl blue by activated hydrogen peroxide and unactivated hydrogen peroxide.
FIG. 10 is a graph of the results of removal of methyl blue using CFP-NZVI cathode activated hydrogen peroxide at various bias voltages.
FIG. 11 is a graph of the removal rate results for removal of methyl blue using CFP-NZVI cathode activated hydrogen peroxide at various bias voltages.
FIG. 12 is a graph showing the results of removal of organophosphorus from a single cell using CFP-NZVI cathode activated hydrogen peroxide.
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1 optimization of anode materials
The effect of different polytetrafluoroethylene suspension concentrations on the yield of hydrogen peroxide produced by the anode is investigated, and the specific experimental steps are as follows:
preparation of CFP-PTFE anode: diluting polytetrafluoroethylene suspension with ultrapure water to obtain polytetrafluoroethylene suspension with mass fraction of 0%, 5%, 20%, 60%, and concentrating at 2×4cm 2 Immersing the carbon fiber paper in polytetrafluoroethylene suspension for 10min, taking out, drying for 10min at 120 ℃, calcining the dried carbon fiber paper in nitrogen atmosphere at 350 ℃ for 0.5h to obtain four different CFP-PTFE anodes of polytetrafluoroethylene carbon fiber paper, which are respectively marked as CFP, CFP-PTFE5% CFP-PTFE20% and CFP-PTFE60%.
S2, taking a platinum electrode as a cathode, respectively forming a three-electrode system by the 4 anodes and the platinum electrode in the step S1 and a silver chloride reference electrode, and adding the three-electrode system into an electrolytic cell with the capacity of 100mL, wherein a proton semipermeable membrane is arranged in the middle of the electrolytic cell, so as to prevent hydrogen peroxide from migrating to the cathode to be activated, and further accurately measuring the yield of the hydrogen peroxide. 50mL of the solution having a concentration of 2mol/L was added to the electrolytic cellKHCO 3 The electrolyte, the anode and the cathode are connected with an external power supply to form an electrolytic path, the bias voltage of 3.66Vvs RHE is introduced for electrolysis for 2 hours under the stirring condition of the rotating speed of 80rpm, and the yield of hydrogen peroxide is measured.
Analysis of results: the results of the X-ray diffraction tests on CFP, CFP-PTFE5% CFP-PTFE20% and CFP-PTFE60% are shown in FIG. 1. As can be seen from FIG. 1, a new diffraction peak appears at 17.991 ℃for CFP-PTFE5% CFP-PTFE20% and CFP-PTFE60%, demonstrating PTFE loading on CFP-PTFE5% CFP-PTFE20% and CFP-PTFE60%. The effect of different anodes on hydrogen peroxide production is shown in figure 2. As can be seen from fig. 2: the CFP-PTFE20% produced hydrogen peroxide at 3.66V vs RHE bias in an amount of 5% higher than CFP-PTFE and 60% higher than CFP-PTFE, up to 4.97mmol/L.
Example 2 optimization of cathode materials
The influence of different cathode materials on activated hydrogen peroxide is explored, and the specific experimental steps are as follows:
preparation of CFP-PTFE20% anode: diluting the polytetrafluoroethylene suspension with ultrapure water to obtain polytetrafluoroethylene suspension with mass fraction of 20%, and concentrating the polytetrafluoroethylene suspension at 2×4cm 2 Immersing the carbon fiber paper in polytetrafluoroethylene suspension for 10min, taking out, drying at 120 ℃ for 10min, calcining the dried carbon fiber paper in nitrogen atmosphere at 350 ℃ for 0.5h, and obtaining the CFP-PTFE20% anode of the polytetrafluoroethylene carbon fiber paper.
Preparation of CFP-NZVI cathode: preparing a nano zero-valent iron carbon fiber paper CFP-NZVI cathode: adding 0.1mL Nafion solution with mass concentration of 0.1g/L into 10mg nanometer zero-valent iron powder, performing ultrasonic treatment for 5min to obtain nanometer zero-valent iron suspension, and coating on 2×4cm 2 The lower half of the hydrophobic surface of the carbon fiber paper is coated with an area of 2X 2cm 2 Drying at 25 ℃ for 3min to obtain the CFP-NZVI cathode.
S3, respectively forming a three-electrode system by the CFP-PTFE20% anode prepared in the step S1, carbon Fiber Paper (CFP), a platinum sheet (Pt) and the CFP-NZVI cathode prepared in the step S2 and a silver chloride reference electrode, adding into an electrolytic cell with the capacity of 100mL, and adding 50mL of KHCO with the concentration of 2mol/L 3 Electrolyte, anode and cathode are connected withThe external power supply is connected to form an electrolysis passage, and the biased electrolysis of 3.66V vs RHE is conducted for 2 hours under the stirring condition of the rotating speed of 80rpm, so that the in-situ preparation and the activation of hydrogen peroxide can be realized.
In order to prove which free radical is converted from hydrogen peroxide in a single electrolytic cell in the electrolytic process, 1mL of electrolyte containing activated hydrogen peroxide is taken, 0.02mL of 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) solution with the concentration of 100mmol/L is added, the mixture is sufficiently and uniformly shaken to obtain a liquid sample to be detected, a sample application capillary is used for rapidly taking the liquid sample, an electron paramagnetic resonance tester (EPR) is used for detecting the free radical generation condition in the solution, and the hydroxyl free radical content in the electrolytic cells of different cathode materials is tested by a coumarin method.
Analysis of results: the X-ray diffraction patterns of CFP and CFP-NZVI cathodes are shown in FIG. 3. As can be seen from FIG. 3, a new diffraction peak appears at 44.765 ℃for CFP-NZVI, demonstrating that zero-valent iron is supported on CFP-NZVI. In order to prove which free radical is converted from hydrogen peroxide in a single electrolytic cell in the electrolytic process, 1mL of electrolyte containing activated hydrogen peroxide is taken, 0.02mL of 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) solution with the concentration of 100mmol/L is added, the mixture is sufficiently and uniformly shaken to obtain a liquid sample to be detected, the liquid sample is rapidly taken by a sample application capillary, and the generation condition of the free radical in the solution is detected by an electron paramagnetic resonance tester (EPR). The graph of hydroxyl accumulation over time for the use of different cathodes in a single cell is shown in FIG. 4, where a typical 1:2:2:1 graph of hydroxyl groups appears in the EPR image, which can determine that hydrogen peroxide generated at the anode has been activated to hydroxyl groups. The hydroxyl content of the cells of the different cathode materials is shown in figure 5. As can be seen from fig. 5, the hydroxyl content in the system using CFP-NZVI cathodes was significantly higher than in the systems using other cathodes.
Example 3 optimization of bias
The effect of different bias voltages on hydrogen peroxide production was investigated, and the specific experimental procedure was as follows:
preparation of CFP-PTFE20% anode: diluting the polytetrafluoroethylene suspension with ultrapure water to obtain polytetrafluoroethylene suspension with mass fraction of 20%, and concentrating the polytetrafluoroethylene suspension at 2×4cm 2 Immersing carbon fiber paper of (2) in polytetrafluoroethylene suspension, immersing 1Taking out the carbon fiber paper after 0min, drying the carbon fiber paper at 120 ℃ for 10min, calcining the dried carbon fiber paper in nitrogen atmosphere at 350 ℃ for 0.5h, and obtaining the CFP-PTFE20% anode of the polytetrafluoroethylene carbon fiber paper.
S2: the platinum electrode is used as a cathode, the anode and the platinum electrode in the step S1 and the silver chloride reference electrode form a three-electrode system respectively, and the three-electrode system is added into an electrolytic cell with the capacity of 100mL, and a proton semipermeable membrane is arranged in the middle of the electrolytic cell, so that the purpose of preventing hydrogen peroxide from migrating to the cathode to be activated is achieved, and the yield of the hydrogen peroxide can be measured more accurately. 50mL of KHCO with a concentration of 2mol/L was added to the electrolytic cell 3 The electrolyte, the anode and the cathode are connected with an external power supply to form an electrolytic path, and the electrolyte is respectively introduced with 3.66Vvs RHE,2.66V vs RHE,2.16V vs RHE and 1.66V vs RHE bias voltage for electrolysis for 2h under the stirring condition of the rotating speed of 80rpm, so as to measure the yield of the hydrogen peroxide.
Analysis of results: the effect of different bias voltages on hydrogen peroxide production results are shown in FIG. 6. It can be seen from the figure that the hydrogen peroxide yield is much higher at bias 3.66V vs RHE than at other bias, and therefore the most hydrogen peroxide is available for activation, so bias 3.66V vs RHE is the most preferred.
Example 4A method for in situ preparation and activation of Hydrogen peroxide based on Water Oxidation
Preparation of CFP-PTFE20% anode: diluting the polytetrafluoroethylene suspension with ultrapure water to obtain polytetrafluoroethylene suspension with mass fraction of 20%, and concentrating the polytetrafluoroethylene suspension at 2×4cm 2 Immersing the carbon fiber paper in polytetrafluoroethylene suspension for 10min, taking out, drying at 120 ℃ for 10min, calcining the dried carbon fiber paper in nitrogen atmosphere at 350 ℃ for 0.5h, and obtaining the CFP-PTFE20% anode.
Preparation of CFP-NZVI cathode: preparing a nano zero-valent iron carbon fiber paper CFP-NZVI cathode: adding 0.1mL Nafion solution with mass concentration of 0.1g/L into 10mg nanometer zero-valent iron powder, performing ultrasonic treatment for 5min to obtain nanometer zero-valent iron suspension, and coating with 2×4cm 2 The lower half of the hydrophobic surface of the carbon fiber paper is coated with an area of 2X 3cm 2 Drying at 25 ℃ for 3min to obtain the CFP-NZVI cathode.
S3, step S1 and stepThe CFP-PTFE20% anode, CFP-NZVI cathode and silver chloride reference electrode in S2 form a three-electrode system, and are added into an electrolytic cell with the capacity of 100mL, and 50mL of KHCO with the concentration of 2mol/L is added 3 The electrolyte is used for connecting the anode and the cathode with an external power supply to form an electrolytic path, and the hydrogen peroxide can be prepared and activated in situ by introducing a bias voltage of 3.66V vs RHE under the stirring condition of the rotating speed of 80rpm.
Comparative example 1
Only the "CFP-NZVI cathode" in example 4 was replaced with a "Carbon Fiber Paper (CFP) cathode", and the other steps were the same as in example 4.
Comparative example 2
Only the "CFP-NZVI cathode" in example 4 was replaced with a "platinum sheet (Pt) cathode", and the other steps were the same as in example 4.
Comparative example 3
The bias voltages in example 4 were replaced with 1.66V vs RHE and 2.16V vs RHE, respectively, and the other steps were the same as in example 4.
Comparative example 4
The unactivated hydrogen peroxide was prepared in the same manner as in example 4 except that only the CFP-NZVI cathode of example 4 was replaced with a "platinum (Pt) cathode" and the cell was replaced with a cell with a proton semipermeable membrane in between.
Test example 1 evaluation of removal Performance of methyl blue by activated Hydrogen peroxide
The performance of activated hydrogen peroxide to remove Methyl Blue (MB) was measured on a CFP-PTFE20% anode and CFP-NZVI cathode prepared in steps S1 and S2 of example 4, and compared with comparative examples 1 and 2; the test steps are as follows:
s1, preparing 10mL of MB solution with initial concentration of 1000mg/L, taking 1mL of MB solution with concentration of 1000mg/L, and adding 50mL of KHCO with concentration of 2mol/L 3 The electrolyte was charged into a 100mL cell to obtain a solution having a MB concentration of 20mg/L.
S2, using a saturated silver chloride electrode as a reference electrode to be added into the solution in the step S1, connecting an anode and a cathode with an external power supply to form an electrolytic path, introducing bias voltage of 3.66V vs RHE, continuously stirring at room temperature at a speed of 80rpm by using a magnetic stirrer, and sequentially sampling 1.5mL at different moments (0, 20,40,60,80,100,120 min).
S3, detecting the concentration of the water sample MB obtained in the step S2 by using an ultraviolet spectrophotometer (UV), and calculating the removal rate and the removal rate of the MB.
The present invention also compares the removal performance of methyl blue by activated hydrogen peroxide prepared in example 4 with unactivated hydrogen peroxide prepared in comparative example 4.
Analysis of results:
1. MB removal performance with respect to different cathode material activated hydrogen peroxide: the methyl blue removal results of example 4, comparative example 1, and comparative example 2 were compared. The results of the hydrogen peroxide activation to remove methyl blue for the different cathode materials are shown in fig. 7, and as can be seen from fig. 7, the system using CFP-NZVI cathode has excellent MB removal capability. The system using CFP-NZVI cathode is used for treating MB solution with initial concentration of 20mg/L, and the removal rate can reach 100% after 12 min. The results of methyl blue removal rates for different cathode material activated hydrogen peroxide are shown in fig. 8, where the system using CFP-NZVI cathode had the highest methyl blue removal rates, 44.29 and 80.76 times that of the system using CFP and Pt cathodes, respectively.
2. The removal efficiency of MB by activated hydrogen peroxide (example 4) and non-activated hydrogen peroxide (comparative example 4) is shown in FIG. 9. As can be seen from FIG. 9, the removal rate of MB by the activated hydrogen peroxide (example 8) is significantly improved by 1.31X10% compared with the unactivated hydrogen peroxide (comparative example 4) 6 Multiple times.
Test example 2 effect of different bias voltages on the performance of activated hydrogen peroxide to remove methyl blue
The performance effect of different biases on the removal of methyl blue by activated hydrogen peroxide was measured with the CFP-PTFE20% anode and CFP-NZVI cathode prepared in steps S1, S2 of example 4, and compared with comparative example 3; the test steps are as follows:
s1, preparing 10mL of MB solution with initial concentration of 1000mg/L, taking 1mL of MB solution with concentration of 1000mg/L, adding 50mL of electrolyte with concentration of 2mol/L, and adding the solution into an electrolytic cell with capacity of 100mL to obtain the MB solution with concentration of 20mg/L.
S2, adding a saturated silver chloride electrode serving as a reference electrode into the solution in the step S1, connecting an anode and a cathode with an external power supply to form an electrolytic path, respectively introducing 2.66V vs RHE,3.16V vs RHE and bias voltage of 3.66V vs RHE, continuously stirring at room temperature at a speed of 80rpm by using a magnetic stirrer, and sequentially sampling 1.5mL at different moments (0, 20,40 and 60 min).
S3, detecting the concentration of the MB of the water sample obtained in the step S2 by using an ultraviolet spectrophotometer (UV), and calculating the removal rate and the removal rate of the MB under different bias voltages.
Analysis of results: effect of different bias voltages on activated hydrogen peroxide removal MB: the methyl blue removal results of example 4 and comparative example 2 were compared. The results of the different bias voltages on the removal of methyl blue by activated hydrogen peroxide are shown in figure 10. As can be seen from FIG. 10, the activated hydrogen peroxide removed MB with the worst effect when the bias was 1.66V vs RHE, and the higher the efficiency of the activated hydrogen peroxide to remove MB with the increasing bias. When the bias voltage is 2.66V vs RHE-3.66V vs RHE, the removal rate of the activated hydrogen peroxide to MB with the initial concentration of 20mg/L is 100% in 40min, wherein the most rapid removal rate can be achieved by using 3.66V vs RHE, and the removal rate of MB reaches 100% in 15 min. The removal rates of methyl blue from activated hydrogen peroxide by different bias voltages are shown in figure 11. As can be seen from fig. 11, the removal efficiency of activated hydrogen peroxide on methyl blue is significantly better than the removal rates of 1.66V vs RHE and 2.16V vs RHE when the bias voltage is 2.66V vs RHE to 3.66V vs RHE, wherein the removal rate of methyl blue is highest at the bias voltage of 3.66V vs RHE.
Test example 3 evaluation of the Performance of activated Hydrogen peroxide to remove organic phosphorus
The removal of organic phosphorus (triethyl phosphate) by activated hydrogen peroxide was measured with the CFP-PTFE20% anode and CFP-NZVI cathode prepared in steps S1 and S2 of example 4, as follows:
s1, preparing 10mL of triethyl phosphate solution with initial concentration of 1000mg/L by using pure triethyl phosphate liquid, and adding 50mL of KHCO with concentration of 2mol/L into 0.5mL of triethyl phosphate solution with concentration of 1000mg/L 3 Pouring the electrolyte into a 100mL electrolytic cell to obtain 10mg/L triethyl phosphateA solution.
S2, 20% of CFP-PTFE and CFP-NZVI prepared in the steps S1 and S2 in the example 4 are respectively used as an anode and a cathode, a saturated silver chloride electrode is used as a reference electrode to be added into the solution in the step S1, a bias voltage of 3.66V vs RHE is applied to the system, the mixture is continuously stirred at the room temperature at the speed of 80rpm by a magnetic stirrer, and 1mL of the mixture is sampled at different moments (0, 20,40,60,80,100 and 120 min).
S3, adding 0.2mL of pure ethyl acetate liquid into the sample, vibrating and extracting for 10min, standing for 30s, and waiting for solution layering.
S4, sucking 10 mu L of upper ethyl acetate liquid by using a special gas chromatography needle, and pouring the liquid into the gas chromatography, so as to measure the residual amount of the triethyl phosphate at different time points.
Results CFP-PTFE20% anode and CFP-NZVI cathode were tested for the removal of organophosphorus (triethyl phosphate) by activated hydrogen peroxide as shown in fig. 12. The results of fig. 12 demonstrate that the use of CFP-PTFE20% anode and CFP-NZVI cathode systems has good removal of organophosphorus contaminants. The activated hydrogen peroxide prepared by using the CFP-PTFE20% anode and the CFP-NZVI cathode system is used for treating the organophosphorus solution with the initial concentration of 10mg/L, and the removal rate can reach 50% after 2 hours.

Claims (7)

1. A method for preparing and activating hydrogen peroxide in situ based on water oxidation is characterized by comprising the steps of taking carbon fiber paper loaded with nano zero-valent iron as a cathode, forming a passage with an anode, and using KHCO 3 The solution is electrolyte, and the bias voltage of 2.66-3.66V vs RHE is introduced under the stirring condition, so that the hydrogen peroxide can be synchronously activated in the process of preparing the hydrogen peroxide; the anode is made of polytetrafluoroethylene carbon fiber paper.
2. The method of claim 1, wherein the polytetrafluoroethylene carbon fiber paper is prepared by diluting polytetrafluoroethylene suspension to obtain polytetrafluoroethylene suspension with a mass fraction of 5% -60%, immersing carbon fiber paper in polytetrafluoroethylene suspension, taking out and drying, and calcining the dried carbon fiber paper in nitrogen atmosphere to obtain the polytetrafluoroethylene-coated carbon fiber paper anode.
3. The method of claim 1, wherein the preparation method of the carbon fiber paper loaded with nano zero-valent iron comprises the steps of adding nano zero-valent iron powder into Nafion solution, performing ultrasonic treatment to obtain nano zero-valent iron suspension, coating the nano zero-valent iron suspension on the lower half part of the hydrophobic surface of the carbon fiber paper, and drying to obtain the carbon fiber paper cathode loaded with nano zero-valent iron.
4. A method according to claim 3, wherein the mass ratio of nano zero-valent iron powder to Nafion is (1-2): (0.001-0.004).
5. A method for treating dye and/or organophosphorus wastewater, which is characterized by taking an anode and a cathode in the method as electrode materials, connecting the anode and the cathode with an external power supply, forming a passage in electrolyte, and introducing a bias voltage of 2.66-3.66V vs RHE to degrade the dye and/or organophosphorus wastewater.
6. The method of claim 5, wherein the dye is methyl blue.
7. The method of claim 5, wherein the organophosphorus is triethyl phosphate.
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