CN102097640B - Method for manufacturing fuel cell capable of synthesizing acetic acid simultaneously - Google Patents

Abstract

The invention discloses a manufacturing method of a fuel cell capable of simultaneously synthesizing acetic acid. The main steps of the present invention are: adding complexing agent EDTA, reducing agent formaldehyde, PdCl ₂ or PdCl ₂ +RuCl ₃ solution into the hydrothermal reaction kettle, and cooling after heating and reacting to prepare PdRu or Pd nano catalyst particles; PdRu Or mix Pd nano catalyst particles with VulcanXC-72 to obtain carbon-supported PdRu or Pd catalyst particles; mix carbon-supported catalyst particles with polytetrafluoroethylene in ethanol, and ultrasonically disperse them into a paste; evenly coat the paste on Stainless steel mesh, dried and pressed to obtain Pd and PdRu nanoporous electrode sheets; the Pd electrode sheet is used as the cathode, and the PdRu electrode sheet is used as the anode to assemble the fuel cell. The electrolytes in the anode chamber and the cathode chamber are respectively sodium hydroxide of ethanol Solution, sulfuric acid solution of hydrogen peroxide, separated by a cationic membrane. The method of the invention is simple, the material is easy to obtain, and acetic acid can be simultaneously synthesized during use.

Description

A kind of manufacturing method of fuel cell capable of synthesizing acetic acid simultaneously

technical field

The invention belongs to the field of fuel cells, and in particular relates to a method for preparing nanoporous Pd-Ru and nanoporous Pd electrocatalysts and assembling an ethanol/hydrogen peroxide fuel cell capable of simultaneously synthesizing acetic acid.

Background technique

Direct Alcohol Fuel Cell (DAFC) has outstanding advantages such as small size, light weight, simple manufacture, and convenient use, and is especially suitable as a supporting power source for portable electronic devices. However, due to methanol’s easy permeation, low operating temperature, flammability, and volatile characteristics, and methanol has certain toxicity, the direct methanol fuel cell using methanol as fuel has great unsafety in the field of mobile power, so Finding new liquid fuels to replace methanol has important practical significance. As a common chemical substance, ethanol can be produced by fermentation of cellulose-containing sawdust and plant stems, etc., and can also be produced biologically. It has a wide range of sources, is a renewable energy source, and is non-toxic. Therefore, the development of new ethanol fuel cells is not only It has great theoretical significance and more potential wide application prospects.

At present, platinum is recognized as an efficient catalyst for the oxidation of alcohol molecules, but its high price seriously restricts the commercialization of DAFC. Compared with Pt, metal palladium is reasonably priced and has high electroactivity for the oxidation of alcohols in alkaline solutions such as NaOH and KOH. Pd/C, Pd-MWCNT, and Pd nanoparticles supported by carbonized TiO ₂ nanotubes all have excellent electrical activity for ethanol oxidation; bimetallic or trimetallic catalysts formed by some metals and Pd also greatly strengthen the palladium for ethanol oxidation. Electrocatalytic activity, such as Pt-Pd/C, Pd-MWCNT-Ni, binuclear Ru/Pd complexes, and Pd-Ag/C, etc.

On the other hand, the cathode reaction of DAFC is usually a reduction process of some oxidant such as oxygen or air. In the 1960s, Zaromb first proposed to use hydrogen peroxide instead of oxygen as the oxidant in the fuel cell, thus a new type of fuel cell using hydrogen peroxide as the oxidant appeared. Liquid hydrogen peroxide is convenient to store, has a higher density, and only transfers 2 electrons when reduced. Compared with the transfer of 4 electrons in the reduction reaction of oxygen, the reduction of hydrogen peroxide has a faster kinetic process. Hydrogen peroxide is used as a potential oxidant in the field of fuel cells. This fuel cell has a wide range of applications, not only in environments with air, but also in environments without air, such as underwater or space. middle. Hydrogen peroxide replaces oxygen as fuel cell cathode, and has received extensive attention. Among them, the catalyst materials that have been studied more are metal electrodes such as Au, Ag, Pt, and Pd. Nano-metal particles generally have higher electrochemical activity. Pournaghi-Azar et al. prepared a Prussian blue-modified palladium-aluminum electrode, and studied the electrocatalytic activity of the electrode for H ₂ O ₂ reduction. Cai et al. studied the electrocatalytic reaction of H ₂ O ₂ by nano-Pt particles dispersed on a polyphenylenediamine film. Others such as Au/C, Au/Ni, and Cu-Ni alloys have electrocatalytic activity for the reduction of hydrogen peroxide. Sun et al. prepared a Pd-Ru/C _binary catalyst by chemically reducing _PdCl2 and _RuCl3 , which exhibited high catalytic activity for the electroreduction of _H2O2 .

In summary, the development of ethanol/hydrogen peroxide fuel cells fueled by liquid ethanol is of great significance. Assuming that ethanol is completely oxidized to CO ₂ , the theoretical cell voltage of this ethanol/hydrogen peroxide fuel cell is about 2.614V, and its electrode reaction is as follows:

Anode reaction:

C ₂ H ₅ OH+12OH ^- → 2CO ₂ +9H ₂ O+12e E ₀ ＝-0.744V

Cathode reaction:

H ₂ O ₂ +2H ⁺ +2e→2H ₂ O E ₀ ＝1.87V

The overall reaction equation:

2C ₂ H ₅ OH+6H ₂ O ₂ →2CO ₂ +9H ₂ O

However, in fact, because the C-C bond in ethanol is difficult to break, the main product of ethanol oxidation on palladium electrode materials is acetic acid (acetate), and its electrode reaction is:

C ₂ H ₅ OH+5OH ^- →CH ₃ COO ^- +4H ₂ O+4e E ₀ ＝-0.925V

The theoretical battery voltage at this time is about 2.795V. Therefore, if such a fuel cell is discharging, the anode catalyst can selectively oxidize ethanol to acetic acid, and such a fuel cell can also recover acetic acid (salt) in the anode chamber while discharging, thereby achieving discharge and synthesis of organic products dual purpose.

Contents of the invention

The purpose of the present invention is to provide a kind of manufacture method of the ethanol/hydrogen peroxide fuel cell that can simultaneously synthesize acetic acid.

The present invention is realized by following method: the manufacture method of this fuel cell that can simultaneously synthesize acetic acid comprises the steps of following order:

(1) Manufacturing of electrodes:

(a) Add complexing agent EDTA, reducing agent formaldehyde, PdCl ₂ solution or PdCl ₂ +RuCl ₃ solution in sequence to the hydrothermal reaction kettle, then heat the reaction kettle to 150-200°C and keep it warm for 8-15 hours, after the reaction is completed Cool to room temperature, discard the upper hydrothermal reaction waste liquid, and wash the solid particles obtained by the reaction with pure water for 1 to 3 times to obtain PdRu nano-catalyst particles or Pd nano-catalyst particles;

Among them, the molar ratio of Pd ²⁺ or Pd ²⁺ +Ru ³⁺ to EDTA is 1:1, the molar ratio of formaldehyde to Pd ²⁺ or Pd ²⁺ +Ru ³⁺ is (30-80):1, Pd ^{2 +} The molar ratio of Pd ²⁺ and Ru ³⁺ in + +Ru ³⁺ is (95～50):(5～50);

(b) mixing the PdRu or Pd nano catalyst particles prepared by the hydrothermal method in the previous step with VulcanXC-72 to obtain carbon-supported PdRu or Pd catalyst particles, wherein the mass percentage of the catalyst is 40% to 60%;

(c) Mix the carbon-supported catalyst particles obtained in the previous step with polytetrafluoroethylene in ethanol, and ultrasonically disperse them into a paste; wherein, the mass percentage of the carbon-supported catalyst particles and polytetrafluoroethylene is 90% to 75%: 10%～25%, the concentration of polytetrafluoroethylene is: PTFE 30～60wt%;

(d) Finally, evenly coat the paste obtained in the previous step on a stainless steel mesh, dry it and press it under a pressure of 15 to 20 MPa for 1 min, thereby making a nanoporous Pd electrode sheet and a nanoporous PdRu electrode sheet, wherein The loading capacity of Pd or PdRu is 4-6 mg/cm ² ;

(2) Manufacture of fuel cells:

With the nanoporous Pd electrode sheet that step (1) makes is negative electrode, the nanoporous PdRu electrode sheet is anode, assembles fuel cell, and wherein, the electrolyte solution of anode compartment is the sodium hydroxide solution of ethanol, and the electrolyte solution of cathode compartment is the sodium hydroxide solution of ethanol. The sulfuric acid solution of hydrogen oxide, the cathode chamber and the anode chamber are separated by a cationic membrane;

(3) Recovery of acetic acid:

When the fuel cell prepared in step (2) is in use, the anode catalyst oxidizes ethanol to acetic acid, and the fuel cell can also recover acetic acid in the anode chamber while discharging.

As a preferred version, in step (1), the concentration of complexing agent EDTA is 0.005～0.01M, the concentration of reducing agent formaldehyde is 5%～15%, the concentration of _PdCl2 solution is 0.002～0.010M, the concentration of _RuCl3 solution 0.002-0.030M; in step (2), the concentration of ethanol is 0.1-3M, the concentration of sodium hydroxide is 0.5-1.5M, the concentration of hydrogen peroxide is 0.05-0.5M, and the concentration of sulfuric acid is 0.1-1.0M.

The invention provides the preparation method of the cathode and anode electrode materials of the ethanol/hydrogen peroxide fuel cell, as well as the synthesis method of acetic acid and the assembly method of the battery. The self-made catalyst particles in the invention are prepared in one step by a hydrothermal method, and the operation is convenient and the process is simple. The electro-oxidation activity of the nanoporous PdRu electrode to ethanol is high, the initial potential is low, and the oxidation peak current density is high. The acetic acid produced in the anode chamber can be recycled after long-term discharge. Nanoporous Pd has high reduction activity to hydrogen peroxide under acidic conditions, and liquid hydrogen peroxide is easy to carry and store, which simplifies the construction of the fuel cell system and improves the safety of the battery.

Description of drawings

Fig. 1 is a scanning electron microscope image of nanoporous palladium ruthenium catalyst particles and nanoporous palladium catalyst particles in an embodiment of the present invention.

Fig. 2 is a cyclic voltammogram of the nanoporous palladium ruthenium electrode in the embodiment of the present invention with different concentrations of C ₂ H ₅ OH added to 1M NaOH, with a scan rate of 50 mVs ^-1 .

Fig. 3 is a cyclic voltammogram of the nanoporous palladium electrode in an embodiment of the present invention in 0.5M H ₂ SO ₄ , with a scan rate of 50 mVs ^-1 .

Fig. 4 is a linear scan graph of adding different concentrations of H ₂ O ₂ into 0.5M H ₂ SO ₄ of the nanoporous palladium electrode in the embodiment of the present invention, with a scan rate of 1 mVs ^-1 .

Fig. 5 is a chronoampere diagram of the electrolysis of the nanoporous palladium electrode in 0.5M H ₂ SO ₄ +0.058M H ₂ O ₂ for 3600 s in the embodiment of the present invention.

Fig. 6 is a schematic structural diagram of an ethanol/hydrogen peroxide fuel cell according to an embodiment of the present invention.

Detailed ways

The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.

Example 1:

(1) Add 5mmolL ^-1 PdCl ₂ 10mL, 5mmolL ^-1 EDTA 10mL, 20mmolL ^-1 RuCl ₃ 0.6ml and 10% HCHO 1mL into the hydrothermal reaction kettle, put it in an infrared drying oven at 180°C for 10h, and the reaction is complete After cooling to room temperature, the upper reaction waste liquid was discarded, and the obtained solid catalyst particles were washed twice with pure water to obtain nanoporous PdRu particles.

The obtained PdRu nanoparticles were mixed with Vulcan XC-72 to obtain carbon-supported particles with a mass percentage of PdRu catalyst of 60%; then, the carbon-supported catalyst particles were uniformly mixed with polytetrafluoroethylene in ethanol, and ultrasonically dispersed into paste; wherein, the mass ratio of ethanol, carbon-supported catalyst particles and polytetrafluoroethylene is 18:90:10, and the concentration of polytetrafluoroethylene is: PTFE 60wt%; finally, this paste is evenly coated on stainless steel After drying, it was pressed under a pressure of 20 MPa for 1 min to make a nanoporous PdRu electrode sheet, wherein the loading capacity of PdRu was 6 mg/cm ² .

The surface morphology of the prepared electrode was characterized by JSM6380LV scanning electron microscope, and the scanning electron microscope image is shown in Figure 1a. Electrochemical tests were carried out on AutoLAB PGSTAT30/FRA, a three-chamber glass electrolytic cell, the working electrode was a nanoporous PdRu electrode, the counter electrode was a large-area Pt electrode, and the reference electrode was a saturated calomel electrode (SCE). Before the electrochemical test, the prepared PdRu electrode should be activated, and nitrogen gas should be passed into the electrolytic cell for 15 minutes to remove dissolved oxygen. During the test process, nitrogen gas should always be kept passing through the liquid surface. Scan at a scan rate of 100mVs ^-1 until stable. All electrochemical tests were performed at room temperature (22±2°C).

Fig. 2 is the cyclic voltammetry curve of the nanoporous PdRu catalyst electrode in 1M NaOH solution, adding different concentrations of C ₂ H ₅ OH, the potential range is -1.1V ~ 0.5V, and the sweep rate is 50mV/s. The oxidation of C ₂ H ₅ OH on this nanoporous PdRu catalyst electrode has a low onset potential and high current density, indicating that this nanoporous PdRu catalyst electrode has high catalytic activity for C ₂ H ₅ OH oxidation.

(2) In the hydrothermal reaction kettle, add 5mmolL ^-1 PdCl ₂ 10mL, 10mmolL ^-1 EDTA 5ml and 10% HCHO 1mL in sequence, place it in an infrared drying oven at 180°C for 10h, discard the hydrothermal reaction waste liquid , the resulting solid catalyst particles were washed twice with pure water to obtain nanoporous Pd particles.

Mix the obtained Pd nanoparticles with Vulcan XC-72 to obtain carbon-supported particles with a mass percentage of Pd catalyst of 60%; then, mix the carbon-supported catalyst particles with polytetrafluoroethylene in ethanol, and ultrasonically disperse them into paste; wherein, the mass ratio of ethanol, carbon-supported catalyst particles and polytetrafluoroethylene is 18:90:10, and the concentration of polytetrafluoroethylene is: PTFE 60wt%; finally, this paste is evenly coated on stainless steel After drying, it was pressed under a pressure of 20 MPa for 1 min to make a nanoporous Pd electrode sheet, wherein the Pd loading was 6 mg/cm ² .

The surface morphology of the prepared electrode was characterized by JSM6380LV scanning electron microscope, and the scanning electron microscope image is shown in Figure 1b. Electrochemical tests were carried out on AutoLAB PGSTAT30/FRA, a three-chamber glass electrolytic cell, the working electrode was a nanoporous Pd electrode, the counter electrode was a large-area Pt electrode, and the reference electrode was a saturated calomel electrode (SCE). Before the electrochemical test, nitrogen gas was passed into the electrolytic cell for 15 minutes to remove dissolved oxygen. During the test process, nitrogen gas was always kept passing through the liquid surface, and the prepared _{Pd electrode} was activated. Within the potential range, scan until stable at a scan rate of 100mVs ^-1 . All electrochemical tests were performed at room temperature (22±2°C).

Figure 3 is the cyclic voltammetry curve of the nanoporous Pd catalyst electrode in 0.5M H ₂ SO ₄ solution, the potential range is -0.225V to 1.2V, and the sweep rate is 50mV/s. The characteristic reduction peak current density of Pd in the figure is - 34.3 mA cm ^-2 .

Fig. 4 is a linear scan diagram of a nanoporous palladium electrode added with different concentrations of H ₂ O ₂ in 0.5M H ₂ SO ₄ , with a scan rate of 1 mVs ^-1 . The initial reduction potential of hydrogen peroxide under acidic conditions is about 0.53V. Within the tested concentration range, the reduction peak current tends to increase gradually with the increase of hydrogen peroxide concentration. It is shown that this nanoporous palladium electrode has high electrocatalytic activity for hydrogen peroxide reduction.

Figure 5 is the chronoamperometric diagram of the electrolysis of nanoporous palladium electrode in 0.5M H ₂ SO ₄ +0.058M H ₂ O ₂ for 3600s, the current is about -6.9mAcm ^-2 at 400s, and -6.56mAcm ^-2 at 3600s, indicating that this The nanoporous palladium electrode exhibits stable catalytic activity for hydrogen peroxide reduction.

(3) The nafion-117 membrane was boiled in a mixture of 3% H ₂ O ₂ and 5% H ₂ SO ₄ for 1 hour, and then soaked in pure water for 2 hours. The pretreated nafion-117 membrane was activated with 0.5M H ₂ SO ₄ for 1 h to prepare the ionic membrane. Referring to Fig. 6, the nanoporous Pd electrode sheet made by fixing step (2) is used as cathode 2 on the fixed rod 6, and the nanoporous PdRu electrode sheet made by fixing step (1) is used as anode 1 on the fixed rod 6, The ion membrane 3 is fixed between the anode chamber and the cathode chamber. Inject 1.0M sodium hydroxide solution containing 0.5M ethanol into the anode chamber through the electrolyte inlet 4, and inject 0.5M sulfuric acid solution containing 0.15M hydrogen peroxide into the cathode chamber through the electrolyte inlet 4. The electrolyte outlet 5 can recycle the acetic acid produced simultaneously when the battery is discharged, and the selectivity of converting ethanol into acetic acid is 90%.

Example 2:

(1) Add 10mmolL ^-1 PdCl ₂ 10mL, 10mmolL ^-1 EDTA 10mL, 20mmolL ^-1 RuCl ₃ 5ml and 10% HCHO 1mL in the hydrothermal reaction kettle, put it in an infrared drying oven at 150°C for 15h, after the reaction is completed After cooling to room temperature, the upper reaction waste liquid was discarded, and the obtained solid catalyst particles were washed once with pure water to obtain nanoporous PdRu particles.

Mix the obtained PdRu nanoparticles with Vulcan XC-72 to obtain carbon-supported particles with a mass percentage of PdRu catalyst of 40%; then, mix the carbon-supported catalyst particles with polytetrafluoroethylene in ethanol, and ultrasonically disperse them into paste; wherein, the mass ratio of ethanol, carbon-supported catalyst particles and polytetrafluoroethylene is 18:75:25, and the concentration of polytetrafluoroethylene is: PTFE 30wt%; finally, this paste is evenly coated on stainless steel After being dried, it was pressed under a pressure of 15 MPa for 1 min to make a nanoporous PdRu electrode sheet, wherein the loading capacity of PdRu was 4 mg/cm ² .

The characterization and electrochemical activity test of the nanoporous PdRu particles are the same as in Example 1.

(2) In the hydrothermal reaction kettle, add 10mmolL ^-1 PdCl ₂ 5mL, 5mmolL ^-1 EDTA 10ml and 10% HCHO 1mL in sequence, place it in an infrared drying oven at 150°C for 15h, discard the hydrothermal reaction waste liquid , the obtained solid catalyst particles were washed once with pure water to obtain nanoporous Pd particles.

The obtained Pd nanoparticles were mixed with Vulcan XC-72 to obtain carbon-supported particles with a mass percentage of PdRu catalyst of 40%; then, the carbon-supported catalyst particles were uniformly mixed with polytetrafluoroethylene in ethanol, and ultrasonically dispersed into paste; wherein, the mass ratio of ethanol, carbon-supported catalyst particles and polytetrafluoroethylene is 18:75:25, and the concentration of polytetrafluoroethylene is: PTFE 30wt%; finally, this paste is evenly coated on stainless steel After being dried, it was pressed under a pressure of 15 MPa for 1 min to make a nanoporous PdRu electrode sheet, wherein the loading capacity of PdRu was 4 mg/cm ² .

The characterization, electrochemical activity and stability tests of the nanoporous Pd particles are the same as in Example 1.

(3) The nafion-117 membrane was boiled in a mixture of 3% H ₂ O ₂ and 5% H ₂ SO ₄ for 1 hour, and then soaked in pure water for 2 hours. The pretreated nafion-117 membrane was activated with 0.5M H ₂ SO ₄ for 1 h to prepare the ionic membrane. Referring to Fig. 6, the nanoporous Pd electrode sheet made by fixing step (2) is used as cathode 2 on the fixed rod 6, and the nanoporous PdRu electrode sheet made by fixing step (1) is used as anode 1 on the fixed rod 6, The ion membrane 3 is fixed between the anode chamber and the cathode chamber. Inject 1.5M sodium hydroxide solution containing 1.0M ethanol into the anode chamber through the electrolyte inlet 4, and inject 1.0M sulfuric acid solution containing 0.25M hydrogen peroxide into the cathode chamber through the electrolyte inlet 4. The electrolyte outlet 5 can recycle the acetic acid produced simultaneously when the battery is discharged, and the selectivity of converting ethanol into acetic acid is 83%. .

Example 3:

(1) Add 2mmolL ^-1 PdCl ₂ 20mL, 5mmolL ^-1 EDTA 8mL, 2mmolL ^-1 RuCl ₃ 1ml and 10% HCHO 1mL into the hydrothermal reaction kettle, and place it in an infrared drying oven at 200°C for 8 hours. After the reaction is completed, After cooling to room temperature, the upper reaction waste liquid was discarded, and the obtained solid catalyst particles were washed three times with pure water to obtain nanoporous PdRu particles.

Mix the obtained PdRu nanoparticles with Vulcan XC-72 to obtain carbon-supported particles with a mass percentage of PdRu catalyst of 50%; then, mix the carbon-supported catalyst particles with polytetrafluoroethylene in ethanol, and ultrasonically disperse them into paste; wherein, the mass ratio of ethanol, carbon-supported catalyst particles and polytetrafluoroethylene is 18:85:20, and the concentration of polytetrafluoroethylene is: PTFE 40wt%; finally, this paste is evenly coated on stainless steel After drying, it was pressed under a pressure of 15 MPa for 1 min to make a nanoporous PdRu electrode sheet, wherein the PdRu loading capacity was 5 mg/cm ² .

The characterization and electrochemical activity test of the nanoporous PdRu particles are the same as in Example 1.

(2) In the hydrothermal reaction kettle, add 2mmolL ^-1 PdCl ₂ 10mL, 8mmolL ^-1 EDTA 2.5ml and 10% HCHO 1mL in sequence, place it in an infrared drying oven at 200°C for 8h, discard the hydrothermal reaction waste liquid, and the resulting solid catalyst particles were washed three times with pure water to obtain nanoporous Pd particles.

Mix the obtained Pd nanoparticles with Vulcan XC-72 to obtain carbon-supported particles with a mass percentage of Pd catalyst of 50%; then, mix the carbon-supported catalyst particles with polytetrafluoroethylene in ethanol, and ultrasonically disperse them into paste; wherein, the mass ratio of ethanol, carbon-supported catalyst particles and polytetrafluoroethylene is 18:85:20, and the concentration of polytetrafluoroethylene is: PTFE 40wt%; finally, this paste is evenly coated on stainless steel After being dried, it was pressed under a pressure of 15 MPa for 1 min to make a nanoporous Pd electrode sheet, wherein the loading of Pd was 5 mg/cm ² .

The characterization, electrochemical activity and stability tests of the nanoporous Pd particles are the same as in Example 1.

(3) The nafion-117 membrane was boiled in a mixture of 3% H ₂ O ₂ and 5% H ₂ SO ₄ for 1 hour, and then soaked in pure water for 2 hours. The pretreated nafion-117 membrane was activated with 0.5M H ₂ SO ₄ for 1 h to prepare the ionic membrane. Referring to Fig. 6, the nanoporous Pd electrode sheet made by fixing step (2) is used as cathode 2 on the fixed rod 6, and the nanoporous PdRu electrode sheet made by fixing step (1) is used as anode 1 on the fixed rod 6, The ion membrane 3 is fixed between the anode chamber and the cathode chamber. Inject 0.5M sodium hydroxide solution containing 0.1M ethanol into the anode chamber through the electrolyte inlet 4, and inject 0.1M sulfuric acid solution containing 0.05M hydrogen peroxide into the cathode chamber through the electrolyte inlet 4. The electrolyte outlet 5 can recycle the acetic acid produced simultaneously when the battery is discharged, and the selectivity of converting ethanol into acetic acid is 87%. .

Claims (2)

1. manufacture method of the fuel cell of synthesis of acetic acid simultaneously is characterized in that comprising the step of following order:

(1) manufacturing of electrode:

(a) in hydrothermal reaction kettle, add successively complexing agent EDTA, reducing agent formaldehyde, PdCl ₂Solution or PdCl ₂+ RuCl ₃Solution, then reactor is heated to 150 ~ 200 ℃ and be incubated 8 ~ 15h, is cooled to room temperature after reaction is finished, discard upper water thermal response waste liquid, the gained solid particle be will react with pure water washing 1～3 time, PdRu nanocatalyst particle or Pd nanocatalyst particle namely obtained;

Wherein, Pd ²⁺Perhaps Pd ²⁺+ Ru ³⁺With the mol ratio of EDTA be 1:1, formaldehyde and Pd ²⁺Perhaps Pd ²⁺+ Ru ³⁺Mol ratio be (30 ~ 80): 1, Pd ²⁺+ Ru ³⁺Middle Pd ²⁺With Ru ³⁺Mol ratio be (95 ~ 50): (5 ~ 50);

(b) PdRu or the Pd nanocatalyst particle that the previous step hydro thermal method are prepared gained mix with VulcanXC-72, obtain carbon and carry PdRu or Pd catalyst granules, and wherein the quality percentage composition of catalyst is 40% ~ 60%;

(c) in ethanol, carbon-supported catalyst particles and the polytetrafluoroethylene of previous step gained mixed the ultrasonic pasty state that is dispersed into; Wherein, the mass percent of carbon-supported catalyst particles and polytetrafluoroethylene is 90% ~ 75%:10% ~ 25%, and the concentration that polytetrafluoroethylene mixes with polytetrafluoroethylene in the formed pastel in ethanol, carbon-supported catalyst particles is: 30 ~ 60wt%;

(d) last, the pastel that previous step is made evenly is coated on the stainless (steel) wire, press down 1min in 15 ~ 20MPa pressure after being dried, thereby make nanoporous Pd electrode slice or nanoporous PdRu electrode slice, wherein the carrying capacity of Pd or PdRu is 4 ~ 6mg/cm ²

(2) manufacturing of fuel cell:

The nanoporous Pd electrode slice and the nanoporous PdRu electrode slice that make respectively with the method for step (1) are respectively negative electrode and anode, assembling fuel cell, wherein, the electrolyte of anode chamber is the sodium hydroxide solution of ethanol, the electrolyte of cathode chamber is the sulfuric acid solution of hydrogen peroxide, and cathode chamber and anode chamber separate with cationic membrane;

(3) recovery of acetic acid:

The fuel cell that step (2) makes is when using, and anode catalyst is acetic acid with oxidation of ethanol, and fuel cell can also reclaim acetic acid in the anode chamber in discharge.

2. the manufacture method of the fuel cell of simultaneously synthesis of acetic acid according to claim 1, it is characterized in that: in the step (1), the concentration of complexing agent EDTA is 0.005～0.01M, and the concentration of reducing agent formaldehyde is 5% ~ 15%, PdCl ₂The concentration of solution is 0.002 ~ 0.010M, RuCl ₃The concentration of solution is 0.002 ~ 0.030M; In the step (2), concentration of alcohol is 0.1 ~ 3M, and naoh concentration is 0.5 ~ 1.5M, and concentration of hydrogen peroxide is 0.05 ~ 0.5M, sulfuric acid concentration 0.1 ~ 1.0M.

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