CN100588018C - Preparation method for carbon supported ultra-low platinum catalytic electrode by indirect galvanic deposit - Google Patents
Preparation method for carbon supported ultra-low platinum catalytic electrode by indirect galvanic deposit Download PDFInfo
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- CN100588018C CN100588018C CN200810070245A CN200810070245A CN100588018C CN 100588018 C CN100588018 C CN 100588018C CN 200810070245 A CN200810070245 A CN 200810070245A CN 200810070245 A CN200810070245 A CN 200810070245A CN 100588018 C CN100588018 C CN 100588018C
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Abstract
The invention provides a method for preparing a carbon-supported ultra-low platinum catalytic electrode by means of indirect electrodeposition, which belongs to the fuel cell technique field. The method comprises the steps: transition metal M (such as: Cu, Co, Ni and the like) nano-particles in an aqueous solution are highly dispersed and deposited on a porous carbon electrode (PCE) bonded with perfluoro-sulfonated resin through a four-step electrodeposition method, then the obtained M/PCE electrode is immerged into a platinum salt solution for preparing the carbon-supported ultra-low platinumcatalytic electrode through displacement reaction. The invention has the advantages of simple process and low costs. The prepared carbon-supported ultra-low platinum catalytic electrode has the advantages of low platinum loading, high electro-catalytic performance, good dispersion of platinum nano-particles and controllable sizes, and can replace the existing commercial platinum carbon (Pt/C) catalyst.
Description
One, technical field:
The invention belongs to the fuel cell technology field, particularly a kind of indirect galvanic deposit prepares the method for carbon supported ultra-low platinum catalytic electrode.
Two, background technology:
As chemical energy being transformed into the most effective device of electric energy, Proton Exchange Membrane Fuel Cells (PEMFC) has been in business-like eve.Yet high cost is to perplex it to realize business-like key problem always, main a large amount of uses from eelctro-catalyst platinum that it is expensive.Since costing an arm and a leg of platinum, scarcity of resources, and under the situation of the non-precious metal catalyst that does not find its catalytic performance and stability and platinum to compare favourably at present yet, it is significant to reduce the consumption of platinum in PEMFC.USDOE is controlled at 0.05mg/cm with anode platinum loading in the pemfc stack of 50kW
2Below and can operational excellence classify a long term object as.And negative electrode platinum load amount is about 0.4mg/cm at present
2, head and shoulders above the scope that can bear of commercialization.
The reduction of platinum carrying capacity generally realizes by utilance and the catalytic activity that improves platinum.Chinese patent ZL031177786 discloses a kind of " proton exchange membrane fuel cell electrode novel preparation method ", promptly in containing the aqueous solution of platinum ion, method with electrochemical deposition, on the porous carbon electrodes that platinum directly is deposited on proton exchange membrane contacts, form the Proton Exchange Membrane Fuel Cells gas catalysis electrode of metal supported catalyst platinum.This method can directly optionally be deposited on existing electron channel with metallic catalyst platinum, have again on the ion transfer passage and the carrier that the proton film contacts, shown than traditional higher catalyst utilization of method with the bonding Pt/C catalyst of proton exchange membrane electrolyte solution.But this method still exists in prepared by electrodeposition Pt catalysis electrode process because of liberation of hydrogen causes the local hydrolysis of platinum salt, washes away the porous carbon-coating, and defective such as the platinum crystal grain that is deposited is thick.Chinese patent 200810069271.7 discloses a kind of " preparation method of ' nuclear/shell ' structure gas perforated electrode catalyst ", this method in the aqueous solution that contains non-platinum family transition metal M ion (as: Cu, Co, Ni etc.), at first with the method for two pace pulse electro-deposition with the transition metal M electro-deposition with porous carbon electrodes that proton exchange membrane contacts on; Then by the chemical replacement reaction between the institute non-platinum family transition metal that deposit and the solubility platinum salt, carry the platinum monoatomic layer that the surface formation of non-platinum family transition metal is replaced fully, formation " nuclear/shell " type catalyst for fuel cell M@Pt at carbon.Serial problems such as that this method has overcome to a certain extent is serious by the Direct Electrochemistry deposition liberation of hydrogen effect that platinum caused, electrolyte hydrolysis deterioration and platinum crystal grain are thick.But, when deposition M examines on porous carbon electrodes, this method is not considered the influence that the porous carbon electrodes electric double layer capacitance discharges and recharges, and makes that the high advantageous effect of instantaneous peak current can not be given full play in the pulse electrodeposition, thereby causes M nuclear crystal grain and M@Pt crystal grain is excessive, size is difficult to control.
Three, summary of the invention:
The objective of the invention is weak point, provide a kind of indirect galvanic deposit to prepare the method for carbon supported ultra-low platinum catalytic electrode at existing two pace pulse electro-deposition Pt.The present invention at first goes on foot the transition metal M (as: Cu of electrodeposition processes with high dispersive by four in the aqueous solution, Co, Ni etc.) nano particle is deposited on the porous carbon electrodes (PCE): the little electric current that at first applies a long period charges to the electric double layer of porous carbon electrodes, and with the M ion enrichment in the deep hole of PCE, adopt the big electric current of a short period to reduce M ion and in PCE, generate the M nucleus then, and then the little electric current that applies a long period once more in the deep hole of PCE, applies the M ion enrichment at last one and is not enough to generate new nucleus and but can makes the M particle growth to desired size by the electric current of reduction M ion on existing nucleus enough; Then resulting M/PCE electrode is immersed in the carbon supported ultra-low platinum catalytic electrode that obtains high dispersive in the platinum salting liquid of nitrogen protection by displacement reaction.When giving full play to the high advantage of the instantaneous peak current of pulse electrodeposition, overcome like this in the two pace pulse electrodeposition process by electric double layer capacitance and discharged and recharged the M nuclear crystal grain that is caused and M@Pt crystal grain is excessive, the unmanageable drawback of size.
The object of the present invention is achieved like this: a kind of indirect galvanic deposit prepares the method for carbon supported ultra-low platinum catalytic electrode, in the aqueous solution, go on foot electrodeposition processes (FSD) being deposited on the porous carbon electrodes (PCE) with transition metal M (as: Cu, Co, Ni etc.) nano particle high dispersive by four, then resulting M/PCE electrode is immersed in the carbon supported ultra-low platinum catalytic electrode that obtains high dispersive in the platinum salting liquid by displacement reaction, its concrete grammar step is as follows:
(1), preparation microporous layers
At first, carbon paper is immersed in the ethanol water, the 30min that vibrates under the ultrasonic wave condition, it being soaked 30min in 30% ptfe emulsion, to be placed on temperature be the diffusion layer that roasting 40min obtains hydrophobic in 340 ℃ the Muffle furnace again.By polytetrafluoroethylene: the mass ratio of Vulcan XC-72 carbon dust is to take by weighing polytetrafluoroethylene and Vulcan XC-72 carbon dust at 1: 1, be that solvent vibrates under the ultrasonic wave condition evenly then with ethanol, be coated on several times on the diffusion layer of hydrophobic, being placed on temperature at last is that roasting 45min obtains microporous layers in 340 ℃ of Muffle furnaces.
(2), the bonding porous carbon electrodes of preparation perfluorinated sulfonic resin
By perfluorinated sulfonic resin: the mass ratio of Vulcan XC-72 carbon dust is to take by weighing perfluorinated sulfonic resin at 1: 30, its mass concentration is 0.5% and Vulcan XC-72 carbon dust, be that solvent vibrates under the ultrasonic wave condition evenly then with ethanol, be coated on several times on the microporous layers of step (1) preparation, oven dry makes the bonding porous carbon electrodes PCE of perfluorinated sulfonic resin under 140 ℃ of conditions.
(3), four step electrodeposition processes prepare the M/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin for preparing with (2) step is a negative electrode, and metal M is an anode; Electrolyte is the acidic aqueous solution that contains the metal M water soluble salt of 0.001～1mol/L, and electrodeposition temperature is 10～50 ℃; Adopt four step electrodeposition processes to prepare the M/PCE electrode of high dispersive controllable size.
Wherein metal M is one of them of copper, cobalt, nickel.The metal M water soluble salt is one of them of sulfate, chlorate or nitrate of metal M.The technological parameter of four step electro-deposition is as follows:
The first step: peak current density is 0.1～1A/dm
2, ON time is 50～150s;
Second step: peak current density is 5～30A/dm
2, ON time is 1～5s;
The 3rd step: peak current density is 0.1～1A/dm
2, ON time is 20～120s;
The 4th step: peak current density is 2～20A/dm
2, ON time is 2～8s;
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, prepared M/PCE electrode cleaned up with ultra-pure water; replace in the platinum saline solution of immersion nitrogen protection; the pH value of control platinum saline solution is 0～8, and concentration is 0.1～30g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 0.5～3 hour.
Wherein the platinum saline solution is that chloroplatinic acid aqueous solution, dinitro four ammoniums close one of them that the platinum aqueous solution and dinitroso two ammoniums close the platinum aqueous solution.
After the present invention adopts technique scheme, mainly contain following effect:
(1), overcome in the present invention's advantage that instantaneous peak current is high in giving full play to pulse electrodeposition in the two pace pulse electrodeposition process by electric double layer capacitance and discharged and recharged the M nuclear crystal grain that is caused and M@Pt crystal grain is excessive, the unmanageable drawback of size.
(2), prepared carbon supported ultra-low platinum catalytic electrode nano platinum particle excellent dispersion and the particle size of the present invention is controlled.
(3), the prepared carbon supported ultra-low platinum catalytic electrode of the present invention has that the platinum carrying capacity is very low, the electrocatalysis characteristic advantages of higher.
It is electrolytical fuel cell that " carbon supported ultra-low platinum catalytic electrode " that adopts the present invention to prepare can be applicable to proton exchange membrane, as the gas electrode of hydrogen-oxygen proton exchange membrane fuel cell, direct methanol fuel cell etc.Fuel cell with the present invention makes is widely used in electric automobile, various spacecrafts, and portable electric appts, as video camera, notebook computer, electronic toy etc.
Four, description of drawings:
Fig. 1 is embodiment 1 and contrast experiment's 1 high power ESEM (SEM) photo.
Among the figure: Fig. 1-1 is Cu nano particle observed high power ESEM (SEM) photo when multiplication factor is 100000 times of embodiment 1 preparation.
Fig. 1-2 is Cu nano particle observed high power ESEM (SEM) photo when multiplication factor is 60000 times of contrast experiment's 1 preparation.
Fig. 2 is embodiment 2, contrast experiment 1 and contrast experiment's 2 high power ESEM (SEM) and transmission electron microscope (TEM) photo.
Among the figure: Fig. 2-1 is carbon supported ultra-low platinum catalytic electrode observed high power ESEM (SEM) photo when multiplication factor is 200000 times of embodiment 2 preparations, and wherein the Pt loading is 0.066mg/cm
2
Fig. 2-2 is carbon platinum carried catalysis electrode observed high power ESEM (SEM) photo when multiplication factor is 300000 times of contrast experiment's 1 preparation, and wherein the Pt loading is 0.20mg/cm
2
Fig. 2-3 is carbon platinum carried catalysis electrode observed high power transmission electron microscope (TEM) photo when multiplication factor is 73000 times of contrast experiment's 2 preparations, and wherein the Pt loading is 0.23mg/cm
2
Fig. 3 is embodiment 1,4 and 5 and current density-voltage curve of contrast experiment 1～3.
Among the figure: curve 1 is that the Pt loading for preparing with embodiment 4 is 0.095mg/cm
2Carbon supported ultra-low platinum catalytic electrode be work electrode, silver/silver chloride electrode is a reference electrode, platinum filament is to electrode, the 0.5mol/L aqueous sulfuric acid that oxygen is saturated is an electrolyte solution, sweep speed is the current density-voltage curve under the 2mV/s condition.
Curve 3 is that the Pt loading for preparing with embodiment 5 is 0.054mg/cm
2Carbon supported ultra-low platinum catalytic electrode be work electrode, silver/silver chloride electrode is a reference electrode, platinum filament is to electrode, the 0.5mol/L aqueous sulfuric acid that oxygen is saturated is an electrolyte solution, sweep speed is the current density-voltage curve under the 2mV/s condition.
Curve 4 is that the Pt loading for preparing with contrast experiment 1 is 0.20mg/cm
2The carbon platinum carried catalysis electrode be work electrode, silver/silver chloride electrode is a reference electrode, platinum filament is to electrode, the 0.5mol/L aqueous sulfuric acid that oxygen is saturated is an electrolyte solution, sweep speed is the current density-voltage curve under the 2mV/s condition.
Curve 5 is that the Pt loading for preparing with contrast experiment 3 is 0.27mg/cm
2The Pt/C catalysis electrode be work electrode, silver/silver chloride electrode is a reference electrode, platinum filament is to electrode, the 0.5mol/L aqueous sulfuric acid that oxygen is saturated is an electrolyte solution, sweep speed is the current density-voltage curve under the 2mV/s condition.
Curve 6 is that the Pt loading for preparing with contrast experiment 2 is 0.23mg/cm
2The Pt/C catalysis electrode be work electrode, silver/silver chloride electrode is a reference electrode, platinum filament is to electrode, the 0.5mol/L aqueous sulfuric acid that oxygen is saturated is an electrolyte solution, sweep speed is the current density-voltage curve under the 2mV/s condition.
Five, embodiment:
Below in conjunction with embodiment, further specify the present invention.
Embodiment 1
(1), preparation microporous layers
At first, carbon paper is immersed in the ethanol water, the 30min that vibrates under the ultrasonic wave condition, it being soaked 30min in 30% ptfe emulsion, to be placed on temperature be the diffusion layer that roasting 40min obtains hydrophobic in 340 ℃ the Muffle furnace again.By polytetrafluoroethylene: the mass ratio of Vulcan XC-72 carbon dust is to take by weighing polytetrafluoroethylene and Vulcan XC-72 carbon dust at 1: 1, be that solvent vibrates under the ultrasonic wave condition evenly then with ethanol, be coated on pretreated carbon paper surface several times, being placed on temperature at last is that roasting 45min obtains microporous layers in 340 ℃ of Muffle furnaces.
(2), the bonding porous carbon electrodes of preparation perfluorinated sulfonic resin
By perfluorinated sulfonic resin: the mass ratio of Vulcan XC-72 carbon dust is to take by weighing perfluorinated sulfonic resin at 1: 30, its mass concentration is 0.5% and Vulcan XC-72 carbon dust, be that solvent vibrates under the ultrasonic wave condition evenly then with ethanol, be coated on several times on the microporous layers of step (1) preparation, oven dry makes the bonding porous carbon electrodes PCE of perfluorinated sulfonic resin under 140 ℃ of conditions.
(3), four step electrodeposition processes prepare the Cu/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin for preparing with (2) step is a negative electrode, and metallic copper is an anode; Electrolyte is 62.5g/L copper sulphate and 196g/L sulfuric acid solution, and electrodeposition temperature is 25 ℃; Adopt four step electrodeposition processes to prepare the Cu/PCE electrode of high dispersive controllable size on the bonding porous carbon electrodes of perfluorinated sulfonic resin, the technological parameter of four step electro-deposition is:
The first step: peak current density is 1A/dm
2, ON time is 50s;
Second step: peak current density is 30A/dm
2, ON time is 1s;
The 3rd step: peak current density is 1A/dm
2, ON time is 20s;
The 4th step: peak current density is 20A/dm
2, ON time is 2s;
The Cu/PCE electrode for preparing obtains high power ESEM (SEM) photo among Fig. 1-1 with sem test.
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, the Cu/PCE electrode that makes cleaned up with ultra-pure water, immerse in the chloroplatinic acid aqueous solution of nitrogen protection and replace, the pH value of control chloroplatinic acid aqueous solution is 6, concentration is 0.5g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 2 hours.
(5), the hydrogen reduction performance evaluation of carbon supported ultra-low platinum catalytic electrode
Adopt three-electrode system, the carbon supported ultra-low platinum catalytic electrode that makes with (4) step is a work electrode, silver/silver chloride electrode is a reference electrode, platinum filament is to electrode, the 0.5mol/L aqueous sulfuric acid that oxygen is saturated is an electrolyte solution, (CH1660B, Shanghai occasion China instrument company) goes up the situation of change of record current density with voltage at electrochemical workstation, and curve 2 in the corresponding diagram 3.
Step (1)～(2) are with step (1)～(2) among the embodiment 1.
(3), four step electrodeposition processes prepare the Cu/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin that makes with (2) step is a negative electrode, and metallic copper is an anode; Electrolyte is 0.25g/L copper sulphate and 98g/L sulfuric acid solution, and electrodeposition temperature is 10 ℃, adopts four step electrodeposition processes to prepare the Cu/PCE electrode of high dispersive controllable size on the bonding porous carbon electrodes of perfluorinated sulfonic resin, and the technological parameter of four step electro-deposition is:
The first step: peak current density is 0.1A/dm
2, ON time is 150s;
Second step: peak current density is 5A/dm
2, ON time is 5s;
The 3rd step: peak current density is 0.1A/dm
2, ON time is 120s;
The 4th step: peak current density is 2A/dm
2, ON time is 8s;
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, the Cu/PCE electrode that makes cleaned up with ultra-pure water; dinitro four ammoniums that immerse nitrogen protection close in the platinum aqueous solution replaces; it is 8 that control dinitro four ammoniums close the platinum pH value of aqueous solution, and concentration is 30g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 1 hour.
The carbon supported ultra-low platinum catalytic electrode for preparing obtains high power ESEM (SEM) photo among Fig. 2-1 with sem test.
Embodiment 3
Step (1)～(2) are with step (1)～(2) among the embodiment 1.
(3), four step electrodeposition processes prepare the Cu/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin that makes with (2) step is a negative electrode, and metallic copper is an anode; Electrolyte is 188g/L copper nitrate and 196g/L sulfuric acid solution, and electrodeposition temperature is 25 ℃, adopts four step electrodeposition processes to prepare the Cu/PCE electrode of high dispersive controllable size on the bonding porous carbon electrodes of perfluorinated sulfonic resin, and the technological parameter of four step electro-deposition is:
The first step: peak current density is 0.5A/dm
2, ON time is 100s;
Second step: peak current density is 10A/dm
2, ON time is 3s;
The 3rd step: peak current density is 0.5A/dm
2, ON time is 60s;
The 4th step: peak current density is 5A/dm
2, ON time is 5s;
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, the Cu/PCE electrode that makes cleaned up with ultra-pure water; dinitroso two ammoniums that immerse nitrogen protection close in the platinum aqueous solution replaces; it is 0 that control dinitroso two ammoniums close the platinum pH value of aqueous solution, and concentration is 0.1g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 0.5 hour.
Embodiment 4
Step (1)～(2) are with step (1)～(2) among the embodiment 1.
(3), four step electrodeposition processes prepare the Ni/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin that makes with (2) step is a negative electrode, and metallic nickel is an anode; Electrolyte is 30g/L nickelous sulfate, 6g/L nickel chloride and 4g/L BAS, electrodeposition temperature is 50 ℃, adopt four step electrodeposition processes to prepare the Ni/PCE electrode of high dispersive controllable size on the bonding porous carbon electrodes of perfluorinated sulfonic resin, the technological parameter of four step electro-deposition is:
The first step: peak current density is 0.8A/dm
2, ON time is 80s;
Second step: peak current density is 20A/dm
2, ON time is 4s;
The 3rd step: peak current density is 0.8A/dm
2, ON time is 50s;
The 4th step: peak current density is 15A/dm
2, ON time is 6s;
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, the Ni/PCE electrode that makes cleaned up with ultra-pure water, immerse in the chloroplatinic acid aqueous solution of nitrogen protection and replace, the pH value of control chloroplatinic acid aqueous solution is 3, concentration is 2g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 3 hours.
(5), the hydrogen reduction performance evaluation of carbon supported ultra-low platinum catalytic electrode
Adopt three-electrode system, the carbon supported ultra-low platinum catalytic electrode that makes with (4) step is a work electrode, silver/silver chloride electrode is a reference electrode, platinum filament is to electrode, the 0.5mo1/L aqueous sulfuric acid that oxygen is saturated is an electrolyte solution, (CHI660B, Shanghai occasion China instrument company) goes up the situation of change of record current density with voltage at electrochemical workstation, and curve 1 in the corresponding diagram 3.
Embodiment 5
Step (1)～(2) are with step (1)～(2) among the embodiment 1.
(3), four step electrodeposition processes prepare the Co/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin that makes with (2) step is a negative electrode, and metallic cobalt is an anode; Electrolyte is 30g/L cobaltous sulfate, 2g/L sodium chloride and 5g/L BAS, electrodeposition temperature is 50 ℃, adopt four step electrodeposition processes to prepare the Co/PCE electrode of high dispersive controllable size on the bonding porous carbon electrodes of perfluorinated sulfonic resin, the technological parameter of four step electro-deposition is:
The first step: peak current density is 0.3A/dm
2, ON time is 120s;
Second step: peak current density is 15A/dm
2, ON time is 3s;
The 3rd step: peak current density is 0.3A/dm
2, ON time is 100s;
The 4th step: peak current density is 10A/dm
2, ON time is 5s;
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, the Co/PCE electrode that makes cleaned up with ultra-pure water; dinitro four ammoniums that immerse nitrogen protection close in the platinum aqueous solution replaces; it is 7 that control dinitro four ammoniums close the platinum pH value of aqueous solution, and concentration is 5g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 1.5 hours.
(5), the hydrogen reduction performance evaluation of carbon supported ultra-low platinum catalytic electrode
Adopt three-electrode system, the carbon supported ultra-low platinum catalytic electrode that makes with (4) step is a work electrode, silver/silver chloride electrode is a reference electrode, platinum filament is to electrode, the 0.5mol/L aqueous sulfuric acid that oxygen is saturated is an electrolyte solution, (CHI660B, Shanghai occasion China instrument company) goes up the situation of change of record current density with voltage at electrochemical workstation, and curve 3 in the corresponding diagram 3.The contrast experiment 1
Step (1)～(2) are with step (1)～(2) among the embodiment 1.
(3), two pace pulse electrodeposition processes prepare the Cu/PCE electrode
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin that makes with (2) step is a negative electrode, and metallic copper is an anode; Electrolyte is 0.25g/L copper sulphate and 98g/L sulfuric acid solution, and electrodeposition temperature is 10 ℃, and peak current density is 1A/dm
2, the pulse ON time is 0.1ms, and pulse turn-off time is 0.1ms, and sedimentation time is a prepared by electrodeposition Cu/PCE electrode under the 300s condition.
The Cu/PCE electrode for preparing obtains high power ESEM (SEM) photo among Fig. 1-2 with sem test.
(4), preparation carbon platinum carried catalysis electrode
After (3) step, the Cu/PCE electrode that makes cleaned up with ultra-pure water; dinitro four ammoniums that immerse nitrogen protection close in the platinum aqueous solution replaces; it is 8 that control dinitro four ammoniums close the platinum pH value of aqueous solution, and concentration is 30g/L, replaces and obtains the carbon platinum carried catalysis electrode after 2 hours.
(5), the hydrogen reduction performance evaluation of carbon platinum carried catalysis electrode
Adopt three-electrode system, the carbon platinum carried catalysis electrode that makes with (4) step is a work electrode, silver/silver chloride electrode is a reference electrode, platinum filament is to electrode, the 0.5mol/L aqueous sulfuric acid that oxygen is saturated is an electrolyte solution, (CHI660B, Shanghai occasion China instrument company) goes up the situation of change of record current density with voltage at electrochemical workstation, and curve 4 in the corresponding diagram 4.
The carbon platinum carried catalysis electrode for preparing obtains high power ESEM (SEM) photo among Fig. 2-2 with sem test.
The contrast experiment 2
The direct electro-deposition Pt of two pace pulses prepares the Pt/C catalysis electrode:
Step (1)～(2) are with step (1)～(2) among the embodiment 1.
(3), the direct electro-deposition Pt of two pace pulses prepares the Pt/C catalysis electrode
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin that makes with (2) step is a negative electrode, and platinum filament is an anode; Electrolyte is 10g/L chloroplatinic acid and 60g/L aqueous hydrochloric acid solution, and electrodeposition temperature is 25 ℃, and peak current density is 10A/dm
2, the pulse ON time is 0.2ms, and pulse turn-off time is 1ms, and sedimentation time is that pulse electrodeposition prepares the Pt/C catalysis electrode under the 30s condition.
(4), the structural characterization of Pt/C catalyst
The Pt/C catalyst of step (3) preparation scraped off from electrode be dissolved in the absolute ethyl alcohol, after being uniformly dispersed under the ultrasonic wave condition, drawing small volume of solution with suction pipe drips on stencil plate, then sample web is immersed wherein, treat that sample takes out nature attached to top back and dries, put into the transmission electron microscope photo that transmissioning electric mirror test obtains Fig. 2-3 at last.
(5), the hydrogen reduction performance evaluation of Pt/C catalysis electrode
Adopt three-electrode system, Pt/C catalysis electrode with the preparation of (3) step is a work electrode, silver/silver chloride electrode is a reference electrode, platinum filament is to electrode, the 0.5mol/L aqueous sulfuric acid that oxygen is saturated is an electrolyte solution, (CHI660B, Shanghai occasion China instrument company) goes up the situation of change of record current density with voltage at electrochemical workstation, and curve 6 in the corresponding diagram 3.The contrast experiment 3
The preparation of commercial Pt/C catalysis electrode:
Step (1) is with step (1) among the embodiment 1.
(2) preparation of commercial platinum carbon catalysis electrode
Be 40% commercial Pt/C catalyst (Johnson-matthey company) with mass percent: perfluorinated sulfonic resin (mass percent concentration is 5%) is that 3: 1 ratio takes by weighing platinum C catalyst and perfluorinated sulfonic resin in mass ratio, and the control platinum content is 0.3mg/cm
2, be that solvent vibrates under the ultrasonic wave condition evenly then with ethanol, be uniformly coated on several times on the prepared porous carbon electrodes of step (1) and obtain commercial Pt/C catalysis electrode.
(3), the hydrogen reduction performance evaluation of commercial Pt/C catalyst
Adopt three-electrode system, with prepared commercial Pt/C catalysis electrode of (2) step is work electrode, silver/silver chloride electrode is a reference electrode, platinum filament is to electrode, the 0.5mol/L aqueous sulfuric acid that oxygen is saturated is an electrolyte solution, (CHI660B, Shanghai occasion China instrument company) goes up the situation of change of record current density with voltage at electrochemical workstation, and curve 5 in the corresponding diagram 3.Result of the test of the present invention:
By stereoscan photograph (Fig. 1) as can be seen: adopt Cu nano particle (Fig. 1-1) particle diameter in the prepared Cu/PEC electrode of the present invention's four steps electrodeposition process between 30-60nm, and be uniformly dispersed, and adopt the prepared Cu particles of two pace pulse electro-deposition (Fig. 1-2) particle diameter that the hundreds of nanometer is arranged enough.
By ESEM and transmission electron microscope photo (Fig. 2) as can be seen: adopt nano platinum particle in the carbon supported ultra-low platinum catalytic electrode of the present invention's preparation be uniformly dispersed (Fig. 2-1), and serious agglomeration (Fig. 2-2) has appearred in the nano platinum particle that adopts two pace pulse prepared by electrodeposition, and the particle diameter of the direct electro-deposition Pt of two pace pulses gained platinum grain is especially about 200nm.
Adopt the catalytic oxidation-reduction performance of the carbon supported ultra-low platinum catalytic electrode that the present invention prepares obviously to be better than adopting two pace pulse electro-deposition, the Pt/C electrode of directly electrodeposition process preparation and the Pt/C electrode that makes by the commercialization catalyst as seen from Figure 3.As to adopt the prepared carbon supported ultra-low platinum catalytic electrode of the present invention be 0.095mg/cm in the platinum carrying capacity
2The time its hydrogen reduction electric current surpassed 90mA/cm
2(curve 1 among Fig. 3), and be 0.27mg/cm by the Pt/C electrode that the commercialization catalyst makes in its platinum carrying capacity
2The time its hydrogen reduction electric current only be 60mA/cm
2(curve 5 among Fig. 3), this just means and adopts the prepared carbon supported ultra-low platinum catalytic electrode of the present invention only to use 1/3 amount of commercialization platinum just to obtain 1.5 times to the catalytic oxidation-reduction performance of commercialization catalysis electrode, thereby has improved the utilance of platinum catalyst greatly.
Claims (8)
1, a kind of indirect galvanic deposit prepares the method for carbon supported ultra-low platinum catalytic electrode, and concrete method step comprises
(1), preparation microporous layers
At first, carbon paper is immersed in the ethanol water, the 30min that vibrates under the ultrasonic wave condition, it being soaked 30min in 30% ptfe emulsion, to be placed on temperature be the diffusion layer that roasting 40min obtains hydrophobic in 340 ℃ the Muffle furnace again; By polytetrafluoroethylene: the mass ratio of Vulcan XC-72 carbon dust is to take by weighing polytetrafluoroethylene and Vulcan XC-72 carbon dust at 1: 1, be that solvent vibrates under the ultrasonic wave condition evenly then with ethanol, be coated on several times on the diffusion layer of hydrophobic, being placed on temperature at last is that roasting 45min obtains microporous layers in 340 ℃ of Muffle furnaces;
(2), the bonding porous carbon electrodes of preparation perfluorinated sulfonic resin
By perfluorinated sulfonic resin: the mass ratio of Vulcan XC-72 carbon dust is to take by weighing perfluorinated sulfonic resin at 1: 30, its mass concentration is 0.5% and Vulcan XC-72 carbon dust, be that solvent vibrates under the ultrasonic wave condition evenly then with ethanol, be coated on several times on the microporous layers of step (1) preparation, oven dry makes the bonding porous carbon electrodes PCE of perfluorinated sulfonic resin under 140 ℃ of conditions;
It is characterized in that:
(3), four step electrodeposition processes prepare the M/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin for preparing with (2) step is a negative electrode, and metal M is an anode; Electrolyte is the acidic aqueous solution that contains the metal M water soluble salt of 0.001～1mol/L, and electrodeposition temperature is 10～50 ℃; Adopt four step electrodeposition processes to prepare the M/PCE electrode of high dispersive controllable size, the technological parameter of four step electro-deposition is:
The first step: peak current density is 0.1～1A/dm
2, ON time is 50～150s;
Second step: peak current density is 5～30A/dm
2, ON time is 1～5s;
The 3rd step: peak current density is 0.1～1A/dm
2, ON time is 20～120s;
The 4th step: peak current density is 2～20A/dm
2, ON time is 2～8s;
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, prepared M/PCE electrode cleaned up with ultra-pure water; replace in the platinum saline solution of immersion nitrogen protection; the pH value of control platinum saline solution is 0～8, and concentration is 0.1～30g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 0.5～3 hour.
2, the method for preparing carbon supported ultra-low platinum catalytic electrode according to the described a kind of indirect galvanic deposit of claim 1 is characterized in that described metal M is one of them of copper, cobalt, nickel; The metal M water soluble salt is one of them of sulfate, chlorate or nitrate of metal M.
3, the method for preparing carbon supported ultra-low platinum catalytic electrode according to the described a kind of indirect galvanic deposit of claim 1 is characterized in that described platinum saline solution is that chloroplatinic acid aqueous solution, dinitro four ammoniums close one of them that the platinum aqueous solution and dinitroso two ammoniums close the platinum aqueous solution.
4, the method for preparing carbon supported ultra-low platinum catalytic electrode according to the described a kind of indirect galvanic deposit of claim 1 is characterized in that concrete preparation method's step (3)～(4):
(3), four step electrodeposition processes prepare the Cu/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin for preparing with (2) step is a negative electrode, and metallic copper is an anode; Electrolyte is 62.5g/L copper sulphate and 196g/L sulfuric acid solution, and electrodeposition temperature is 25 ℃; Adopt four step electrodeposition processes to prepare the Cu/PCE electrode of high dispersive controllable size on the bonding porous carbon electrodes of perfluorinated sulfonic resin, the technological parameter of four step electro-deposition is:
The first step: peak current density is 1A/dm
2, ON time is 50s;
Second step: peak current density is 30A/dm
2, ON time is 1s;
The 3rd step: peak current density is 1A/dm
2, ON time is 20s;
The 4th step: peak current density is 20A/dm
2, ON time is 2s;
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, the Cu/PCE electrode that makes cleaned up with ultra-pure water, immerse in the chloroplatinic acid aqueous solution of nitrogen protection and replace, the pH value of control chloroplatinic acid aqueous solution is 6, concentration is 0.5g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 2 hours.
5, the method for preparing carbon supported ultra-low platinum catalytic electrode according to the described a kind of indirect galvanic deposit of claim 1 is characterized in that concrete preparation method's step (3)～(4):
(3), four step electrodeposition processes prepare the Cu/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin that makes with (2) step is a negative electrode, and metallic copper is an anode; Electrolyte is 0.25g/L copper sulphate and 98g/L sulfuric acid solution, and electrodeposition temperature is 10 ℃, adopts four step electrodeposition processes to prepare the Cu/PCE electrode of high dispersive controllable size on the bonding porous carbon electrodes of perfluorinated sulfonic resin, and the technological parameter of four step electro-deposition is:
The first step: peak current density is 0.1A/dm
2, ON time is 150s;
Second step: peak current density is 5A/dm
2, ON time is 5s;
The 3rd step: peak current density is 0.1A/dm
2, ON time is 120s;
The 4th step: peak current density is 2A/dm
2, ON time is 8s;
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, the Cu/PCE electrode that makes cleaned up with ultra-pure water; dinitro four ammoniums that immerse nitrogen protection close in the platinum aqueous solution replaces; it is 8 that control dinitro four ammoniums close the platinum pH value of aqueous solution, and concentration is 30g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 1 hour.
6, the method for preparing carbon supported ultra-low platinum catalytic electrode according to the described a kind of indirect galvanic deposit of claim 1 is characterized in that concrete preparation method's step (3)～(4):
(3), four step electrodeposition processes prepare the Cu/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin that makes with (2) step is a negative electrode, and metallic copper is an anode; Electrolyte is 188g/L copper nitrate and 196g/L sulfuric acid solution, and electrodeposition temperature is 25 ℃, adopts four step electrodeposition processes to prepare the Cu/PCE electrode of high dispersive controllable size on the bonding porous carbon electrodes of perfluorinated sulfonic resin, and the technological parameter of four step electro-deposition is:
The first step: peak current density is 0.5A/dm
2, ON time is 100s;
Second step: peak current density is 10A/dm
2, ON time is 3s;
The 3rd step: peak current density is 0.5A/dm
2, ON time is 60s;
The 4th step: peak current density is 5A/dm
2, ON time is 5s;
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, the Cu/PCE electrode that makes cleaned up with ultra-pure water; dinitroso two ammoniums that immerse nitrogen protection close in the platinum aqueous solution replaces; it is 0 that control dinitroso two ammoniums close the platinum pH value of aqueous solution, and concentration is 0.1g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 0.5 hour.
7, the method for preparing carbon supported ultra-low platinum catalytic electrode according to the described a kind of indirect galvanic deposit of claim 1 is characterized in that concrete preparation method's step (3)～(4):
(3), four step electrodeposition processes prepare the Ni/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin that makes with (2) step is a negative electrode, and metallic nickel is an anode; Electrolyte is 30g/L nickelous sulfate, 6g/L nickel chloride and 4g/L BAS, electrodeposition temperature is 50 ℃, adopt four step electrodeposition processes to prepare the Ni/PCE electrode of high dispersive controllable size on the bonding porous carbon electrodes of perfluorinated sulfonic resin, the technological parameter of four step electro-deposition is:
The first step: peak current density is 0.8A/dm
2, ON time is 80s;
Second step: peak current density is 20A/dm
2, ON time is 4s;
The 3rd step: peak current density is 0.8A/dm
2, ON time is 50s;
The 4th step: peak current density is 15A/dm
2, ON time is 6s;
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, the Ni/PCE electrode that makes cleaned up with ultra-pure water, immerse in the chloroplatinic acid aqueous solution of nitrogen protection and replace, the pH value of control chloroplatinic acid aqueous solution is 3, concentration is 2g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 3 hours.
8, the method for preparing carbon supported ultra-low platinum catalytic electrode according to the described a kind of indirect galvanic deposit of claim 1 is characterized in that concrete preparation method's step (3)～(4):
(3), four step electrodeposition processes prepare the Co/PCE electrode of high dispersive controllable size
Adopt two electrode systems, the bonding porous carbon electrodes of perfluorinated sulfonic resin that makes with (2) step is a negative electrode, and metallic cobalt is an anode; Electrolyte is 30g/L cobaltous sulfate, 2g/L sodium chloride and 5g/L BAS, electrodeposition temperature is 50 ℃, adopt four step electrodeposition processes to prepare the Co/PCE electrode of high dispersive controllable size on the bonding porous carbon electrodes of perfluorinated sulfonic resin, the technological parameter of four step electro-deposition is:
The first step: peak current density is 0.3A/dm
2, ON time is 120s;
Second step: peak current density is 15A/dm
2, ON time is 3s;
The 3rd step: peak current density is 0.3A/dm
2, ON time is 100s;
The 4th step: peak current density is 10A/dm
2, ON time is 5s;
(4), preparation carbon supported ultra-low platinum catalytic electrode
After (3) step, the Co/PCE electrode that makes cleaned up with ultra-pure water; dinitro four ammoniums that immerse nitrogen protection close in the platinum aqueous solution replaces; it is 7 that control dinitro four ammoniums close the platinum pH value of aqueous solution, and concentration is 5g/L, replaces and obtains carbon supported ultra-low platinum catalytic electrode after 1.5 hours.
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| CN102403516B (en) * | 2011-08-04 | 2013-11-06 | 重庆大学 | Preparation method of curved surface electrode catalyst layer |
| CN102517604B (en) * | 2011-12-15 | 2015-08-12 | 昆明理工大学 | Carbon-carrying core-shell type platinoid-platinum catalyst for indirect electrolytic hydrogen production and preparation method thereof |
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