CN112760598A - Porous noble metal-based membrane electrode and preparation method and application thereof - Google Patents
Porous noble metal-based membrane electrode and preparation method and application thereof Download PDFInfo
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Images
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/46—Sputtering by ion beam produced by an external ion source
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8867—Vapour deposition
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- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
The invention provides a porous noble metal-based membrane electrode and a preparation method and application thereof, wherein the method comprises the following steps: noble metal is used as a main catalytic phase, a transition metal element is used as an alloy phase, a noble metal-based thin film catalyst is prepared on the surface of a carbonaceous carrier, and dealloying treatment is carried out through mechanical and electrochemical double-field coupling to obtain the pore-type noble metal-based membrane electrode. The method for preparing the pore type noble metal-based membrane electrode based on the double-field coupling effect comprises the steps of synthesizing and preparing a carbon-supported noble metal-based catalyst film, carrying out ultrasonic-assisted electrochemical corrosion on the carbon-supported noble metal-based catalyst film, and controlling the oxidation precipitation atomic weight of alloy on the surface of the catalyst by adjusting the concentration, temperature, time and ultrasonic power density of a corrosive liquid to obtain an open pore structure, so that the electrochemical activity specific surface area of the surface of the membrane electrode can be remarkably increased, and the pore type noble metal-based membrane electrode directly applied to the technical field is prepared.
Description
Technical Field
The invention belongs to the technical field of water electrolysis-organic matter electrocatalytic reduction coupling and the technical field of conversion of low-carbon oxides into fuels, and particularly relates to a porous noble metal-based membrane electrode prepared based on a double-field coupling effect, and a preparation method and application thereof.
Background
The organic matter hydrogenation reaction is an important process in the production fields of food, chemical industry, energy and the like, hydrogen production by combining the organic matter hydrogenation reaction with electrolyzed water is possible to become a main hydrogen production mode in the future, and the organic matter hydrogenation process realized by utilizing the water electrolysis-organic matter electrocatalytic reduction coupling process has the characteristics of mild reaction conditions and no need of additionally providing a hydrogen source; electrochemical reduction of low carbon oxides (e.g. CO)2Etc.) not only can store intermittent renewable energy sources, but also can be converted into important raw materials (such as CH) in chemical fuel production4Etc.) meets the requirement of green chemistry and has great social and economic benefits and is extremely important. Because the above process is in a non-neutral reaction environment, carbon carriers resistant to acid and alkali erosion and noble metal-based (such as Pt, Au, etc.) catalysts with excellent catalytic activity and stability are often used to synthesize a long catalyst with high current densityAn active working electrode.
Based on the comprehensive consideration of the cost and the use efficiency of raw materials, processing and the like, the synthesized noble metal-based catalyst not only reduces the consumption of noble metal, but also improves the catalytic activity and the stability, and becomes one of the research and development focuses of novel working electrodes. For example, transition metals such as Ni and Ti are doped into Pt or Au, wherein Ni has good oxidation corrosion resistance and thermal and electrical conductivity and can absorb a certain amount of monocyclic aromatic hydrocarbon, Ti has the characteristics of excellent corrosion resistance and high adsorption capacity to hydrogen, the two have synergistic effect with Pt or Au to show excellent CO resistance and electrocatalytic activity, and the electron cloud density of the main catalytic phase is increased to reduce the energy barrier required by combining oxygen atoms.
In addition, the noble metal-based catalyst needs to be improved in catalytic reaction selectivity and stability, for example, the application of the carbon-supported PtNi alloy catalyst in the water electrolysis-organic electro-catalytic reduction coupling reaction process is hindered, and the control mechanism and the technical bottleneck are originated from, because the catalytic activity depends on the concentration and preferred orientation of the catalytic main phase, the catalyst energy band width taking Pt as the main phase near the fermi level is smaller, the Pt (111) crystal face has higher state density than other orientations and has optimal catalytic performance, and the Pt concentration change on the surface of the catalyst causes the surface defect of the thin film to influence the in-situ control of the catalytic activity.
At present, aiming at the improvement of the atom concentration gradient control technology, for example, a method for preparing a carrier catalyst by mixing VIB group and VIII group metal salts with ammonia water, adding the ammonia water to regulate the pH value to a certain value, heating to prepare a metal solution, saturating and soaking the metal solution on a carrier, drying and roasting has the defects that active metal components are uniformly distributed on the carrier, and the atom concentration gradient is not obvious and is difficult to control; for example, European patent EP0204314 adopts a stepwise multiple dipping, water washing, drying and roasting method to carry metal components, so that the concentration of the metal components in the carrier catalyst is higher than that of the metal components on the surface, and uneven distribution exists, the service life of the catalyst is correspondingly prolonged, and the cost is greatly increased due to the complex preparation process; for example, the Chinese patent CN99113273.4 adopts an unsaturated spray-dipping method to prepare a carrier catalyst with uneven active metal components, which reduces the manufacturing cost of the catalyst but has the defects of poor gradient distribution of the active metal components and difficult control of the gradient distribution of the active metal components in catalyst particles; for example, chinese patents CN200910086745.3 and CN200910086740.0 both adopt a method of impregnating a carrier in a saturated metal solution by gradually increasing the concentration of the metal solution or sequentially impregnating a carrier from low to high concentration of the metal impregnation solution, and then the carrier catalyst with active metal components and/or acidic auxiliary agents whose concentrations are increased in a gradient manner is obtained through multiple drying and roasting treatments, which has better activity and stability, but the active metal components in the catalyst particles are distributed in a multi-step manner.
Therefore, a new method is urgently needed to be provided to solve the problems of too long reaction time, complex treatment process, difficulty in removing intermediate reactants, high precious metal loss, poor uniformity and the like existing in the preparation method of the porous precious metal-based membrane electrode.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing a porous noble metal-based membrane electrode based on a double-field coupling effect, which solves the problems of overlong reaction time, complex treatment process, difficulty in removing intermediate reactants, high noble metal loss, poor uniformity and the like in the preparation method of the porous noble metal-based membrane electrode.
In a first aspect, the invention provides a method for preparing a porous noble metal-based membrane electrode based on a double-field coupling effect, which comprises the following steps: noble metal is used as a main catalytic phase, a transition metal element is used as an alloy phase, a noble metal-based thin film catalyst is prepared on the surface of a carbonaceous carrier, and dealloying treatment is carried out through mechanical and electrochemical double-field coupling to obtain the pore-type noble metal-based membrane electrode.
The invention relates to a method for preparing a pore type noble metal-based membrane electrode based on double-field coupling, which adopts a mechanical and electrochemical double-field coupling dealloying treatment method, namely, a carbon-loaded noble metal-based catalyst film is synthesized and prepared firstly, then the carbon-loaded noble metal-based catalyst film is subjected to ultrasonic-assisted electrochemical corrosion, and the oxidation precipitation atomic weight of alloy on the surface of the catalyst is controlled by adjusting the concentration, temperature, time and ultrasonic power density of a corrosive liquid to obtain an open pore structure, so that the electrochemical activity specific surface area on the surface of the membrane electrode can be obviously increased, and the pore type noble metal-based membrane electrode directly applied to the technical field is prepared.
As a specific embodiment of the invention, the mechanical and electrochemical double-field coupling effect comprises the following steps: and carrying out electrochemical corrosion under the ultrasonic vibration condition.
As a specific embodiment of the present invention, the power density of the ultrasonic wave is 0.2W/cm2-1.0W/cm2E.g. 0.2W/cm2，0.4W/cm2，0.6W/cm2，0.8W/cm2，1.0W/cm2And any combination thereof.
In one embodiment of the present invention, the concentration of the etching solution during the electrochemical etching operation is in the range of 0.1mol/L to 2.0mol/L, such as 0.1mol/L, 1.0mol/L, 2.0mol/L, and any combination thereof.
Preferably, the corrosion temperature is in the range of 20 ℃ to 60 ℃, e.g., 20 ℃, 40 ℃, 60 ℃, and any combination thereof.
Further preferably, the etching time is in the range of 15min to 120min, such as 15min, 50min, 75min, 100min, 120min and any combination thereof.
As a specific embodiment of the invention, the carbon carrier (carbon carrier has a high specific surface area, which is beneficial to high dispersion of the loaded catalytic active substance, such as high-strength fiber cloth with graphitized carbon content of more than 95%, conductive carbon paper, etc.) is at least selected from graphite fiber cloth and conductive carbon paper.
As a specific embodiment of the present invention, a noble metal-based thin film catalyst is prepared by an ion beam sputtering method.
For example, the carbonaceous carrier can be placed in an ion beam sputtering apparatus, heated to 250 deg.C-350 deg.C, and maintained at 8.0 × 10-3-2.0×10-2Introducing high-purity Ar of 7.0sccm-8.5sccm in the vacuum degree of Pa, controlling the sputtering screen pressure to be 2.0kV-3.0kV, the beam current to be 50mA-100mA, sputtering a noble metal target containing transition group metal by ion beams for 10min-30min, and naturally cooling in the same vacuum degreeCooling to room temperature to obtain the carbon-supported noble metal-based catalyst, wherein the noble metal target containing the transition group metal is characterized by comprising but not limited to splicing of the noble metal and the transition group metal, a mosaic target and a prefabricated alloy target.
The noble metal and the transition metal element are not particularly limited in the present invention, and are within the scope of the present invention as long as the present invention can be realized. As a specific embodiment of the present invention, the noble metal is at least one selected from Pt and Au; and/or, the transition metal element is at least one selected from Ti, Ni, Co, Cu and Fe.
As a specific implementation mode of the invention, the method for preparing the porous noble metal-based membrane electrode based on the double-field coupling effect further comprises the following steps: and pretreating the carbonaceous carrier.
The surface cleaning and activating pretreatment are carried out on the carbon carrier in advance, so that the interface combination state of the catalyst active metal and the carbon carrier can be obviously improved, and the stability of the catalytic activity is enhanced.
Preferably, the pretreatment step comprises washing with a sulfuric acid solution, deionized water and ethanol in sequence and drying.
More preferably, the concentration of the sulfuric acid solution is in the range of 0.5mol/L to 1mol/L, such as 0.5mol/L, 0.7mol/L, 1mol/L, and any combination thereof.
The temperature and time of drying can be adjusted according to actual conditions. For example, the drying temperature can range from 50 ℃ to 80 ℃, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃ and any combination thereof, and the drying time can range from 10min to 20 min.
The preparation method for preparing the porous noble metal-based membrane electrode based on the double-field effect comprises the following specific steps of:
(1) soaking the carbon carrier in 0.5-1.0 mol/L L H solution at 30-50 deg.c2SO4Washing and dehydrating the solution for 5-10 min by deionized water and absolute ethyl alcohol at room temperature, and drying the solution at 50-80 ℃ under normal pressure for 10-20 min to obtain the pretreated carbonaceous carrier.
(2) Placing the carbonaceous carrier obtained in the step (1) in ion beam sputteringHeating to 250-350 deg.C in a jetting device, and maintaining at 8.0 × 10-3-2.0×10-2Introducing high-purity Ar of 7.0sccm-8.5sccm into Pa in vacuum degree, controlling sputtering screen pressure to be 2.0kV-3.0kV, beam current to be 50mA-100mA, sputtering a noble metal target containing transition group metal by ion beams for 10min-30min, and naturally cooling to room temperature in the same vacuum degree to obtain the carbon-supported noble metal-based catalyst, wherein the noble metal target containing the transition group metal is characterized by comprising but not limited to splicing, inlaying and pre-alloying of noble metal and the transition group metal.
(3) Immersing the carbon-supported noble metal-based catalyst obtained in the step (2) in an electrolytic cell filled with 0.1-2.0 mol/L inorganic acid (oxyacid and/or oxyacid) at room temperature to 60 ℃ for electrochemical corrosion for 15-120 min, and keeping the ultrasonic power density in the electrolytic cell at 0.2W/cm2-1.0W/cm2(ii) a And then the porous noble metal-based membrane electrode is obtained after the membrane electrode is cleaned by deionized water at room temperature.
In a second aspect, the invention provides the porous noble metal-based membrane electrode prepared by the method.
As a specific embodiment of the invention, the specific surface area of the porous noble metal-based membrane electrode is 9.327-18.045m2/g。
The porous carbon-supported noble metal-based membrane electrode has the characteristics of low noble metal content, high catalytic activity and the like, and has important significance in the technical field of hydrogen storage of unsaturated organic matters and conversion of low-carbon oxides into fuels.
In a third aspect, the invention provides a cathode material of a hydrogen-oxygen fuel cell and/or an unsaturated organic matter circulating hydrogenation energy storage device, which comprises the porous noble metal-based membrane electrode.
The method for preparing the porous noble metal-based membrane electrode based on the double-field coupling effect has the following beneficial effects:
(1) the porous noble metal-based membrane electrode prepared by the invention has important significance in the technical field of unsaturated organic hydrogen storage and low-carbon oxide conversion into fuel.
(2) The invention adopts the technologies including but not limited to ion beam sputtering deposition and vacuum heat treatment, and a mechanical and electrochemical double-field coupling dealloying treatment method, namely, a carbon-supported noble metal-based catalyst film is synthesized and prepared firstly, then is subjected to ultrasonic-assisted electrochemical corrosion, and the oxidation precipitation atomic weight of the alloy on the surface of the catalyst is controlled by adjusting the concentration, the temperature, the time and the ultrasonic power density of a corrosive solution so as to obtain an open pore structure. The electrochemical active specific surface area of the membrane electrode surface can be obviously increased, thereby preparing the porous noble metal-based membrane electrode directly applied to the technical field.
(3) The carbon carrier adopted by the invention can be subjected to surface cleaning and activation pretreatment in advance so as to enhance the stability of the catalytic activity of the membrane electrode.
(4) The porous carbon-supported noble metal-based membrane electrode prepared by the method has the characteristics of low noble metal content, high catalytic activity and the like, and the preparation method has the advantages of short flow, low cost, no pollution of intermediate reactants and the like.
Drawings
FIG. 1 is an XRD overlay pattern (30 DEG 2 theta 100 DEG) of a porous carbon-supported noble metal-based membrane electrode, wherein a, b and c represent comparative example, example 3 and example 4, respectively;
fig. 2, 3 and 4 correspond to SEM images of the surface of a porous carbon supported noble metal based membrane electrode prepared in comparative example, example 3 and example 4, respectively;
FIGS. 5 and 6 are comparative graphs showing CV and LSV curves of a carbon-supported noble metal-based membrane electrode, wherein a represents a comparative example, and b to g represent examples 1 to 6, respectively;
FIG. 7 is a comparison of i-t curves of a carbon-supported noble metal-based membrane electrode, wherein a represents a comparative example, and b-d represent example 1, example 3 and example 6, respectively.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
In the embodiments and the comparative examples of the invention, the phase structure, the surface micro-morphology, the content of active metal components, the electrochemical activity specific surface area, the catalytic activity and the stability of the porous noble metal-based membrane electrode are represented by detection means such as X-ray diffraction (XRD), Scanning Electron Microscope (SEM), inductively coupled plasma emission spectrometry (ICP-OES), Cyclic Voltammetry (CV), Linear Scanning Voltammetry (LSV) and i-t test, and the test method is as follows:
1. cyclic Voltammetry (CV), Linear Sweep Voltammetry (LSV), and i-t curves
Detecting the electrochemical activity specific surface area and the catalytic activity of the pore type noble metal-based membrane electrode by adopting CV and LSV of a three-electrode single-sealed electrolytic cell system, wherein the pore type noble metal-based membrane electrode is a working electrode, the reference electrode is a saturated calomel electrode, and the counter electrode is a platinum sheet electrode; the electrolyte used in the CV test was 0.5mol/L H from which dissolved oxygen had been removed2SO4The scanning range of the solution is-0.3-1.2V (relative to a saturated calomel electrode), the potential scanning rate is 50mV/s, the detection instrument is a CHI660D electrochemical workstation, the integral area of the oxidation and desorption peak of hydrogen in a stable CV curve directly reflects the quantity of surface active reaction sites, and the electrochemical active specific surface area of unit mass of noble metal (such as Pt) can be obtained:
in the formula: ESA-specific surface area of electrochemical activity per unit mass of Pt, integral area of S-hydrogen oxidation desorption peak, m-1cm2Pt content on the working electrode, v-scan rate, C-Pt specific adsorption capacitance to hydrogen (0.21 mC/cm)2)。
The LSV testing device and the flow are the same as CV, the LSV curve of a non-overlapped region of-0.40 to-0.28V (relative saturated calomel electrode) in the cathode region is taken in the scanning range, the potential scanning speed is 50mV/s, the curve of the current of the working electrode changing along with the linear potential is detected, the exchange current density of the working electrode is calculated according to the formula (2), and the capability of the working electrode for transmitting the oxidation reduction reaction current is quantitatively described, namely the hydrogen evolution catalytic activity of the pore noble metal-based membrane electrode as the cathode.
lgA＝KΔE+lgi0 (2)
Wherein
In the formula: z-number of charges; F-Faraday constant; r-gas constant; t-electrode reaction temperature; a K-constant; Δ E-overpotential; i.e. i0-exchange current density.
The i-t testing device and the flow are the same as LSV, the current changes with time under the constant voltage of 1.5V, the testing time is 1000s, the current density rapidly decreases (initial section) and gradually reaches a stable (gradually stable section) state along with the time extension, and the slope of a connecting line formed by the intersection point of tangent lines of the initial section and the gradually stable section and the origin represents the stability of the catalytic activity of the membrane electrode.
2. Inductively coupled plasma emission spectroscopy (ICP-OES) (PS 1000): and (3) quantitatively determining the active metal content of the thin film catalyst in unit apparent area by adopting ICP-OES.
3. X-ray diffraction (XRD) (D/Max 2200, X-ray source using Cu)KαScanning step width is 0.02 degree, tube current is 20mA, tube voltage is 40 kV): the 2 theta of the diffraction pattern is controlled within 30-100 degrees.
4. Scanning Electron Microscope (SEM) (ZEISS EVO 18): and (4) visually representing the change of the microscopic morphology of the surface of the thin film catalyst by adopting SEM.
5. Nitrogen adsorption specific surface area analyzer (BET) (Quadrasorb SI): the specific surface area of the membrane electrode was measured by BET.
The graphite fiber cloth in the following examples and comparative examples is a carbon fiber cloth CFS-I-300; the conductive carbon paper is TGP-H-060 of TORAY.
[ example 1 ]
A. Soaking graphite fiber cloth in 0.5mol/L H solution at 30 deg.C2SO4Washing and dehydrating the solution for 5min by deionized water and absolute ethyl alcohol at room temperature, and drying the solution for 10min at 50 ℃ under normal pressure to obtain a pretreated carbonaceous carrier;
B. placing the carbon carrier obtained in the step A in an ion beam sputtering device, heating to 350 ℃, and preserving heat at 8.0 multiplied by 10- 3Introducing high-purity Ar of 7.5sccm into Pa vacuum, controlling the sputtering screen pressure to be 2.5kV and the beam current to be 70mA, and sputtering P containing Ni by ion beamst, targeting for 20min, and naturally cooling to room temperature in the same vacuum degree to obtain the carbon-supported PtNi alloy catalyst;
C. immersing the carbon-loaded PtNi composite catalyst obtained in the step B into an electrolytic cell filled with 0.5mol/L HCl solution at 60 ℃ for electrochemical corrosion for 60 min; then washing with deionized water at room temperature to obtain the porous noble metal-based membrane electrode;
D. and D, randomly selecting 2 parts of the porous carbon-supported PtNi alloy membrane electrode obtained in the step C, and respectively adopting CV, LSV, i-t and ICP-OES to carry out electrochemical activity specific surface area, catalytic activity and stability and active metal quantitative test.
As a result: the ESA value of the porous carbon-supported PtNi alloy membrane electrode obtained in the embodiment is 9.638m2/g；i0The value was 4.822mA/cm2(ii) a The Pt content was 0.019812mg/cm2(ii) a The specific surface area of the membrane electrode was 15.037m2/g。
[ example 2 ]
A. Soaking graphite fiber cloth in 0.8mol/L H solution at 40 deg.C2SO4Washing and dehydrating the solution for 10min by deionized water and absolute ethyl alcohol at room temperature, and drying the solution for 20min at the normal pressure of 60 ℃ to obtain a pretreated carbonaceous carrier;
B. placing the carbon carrier obtained in the step A in an ion beam sputtering device, heating to 250 ℃, and keeping the temperature at 1.5 multiplied by 10- 2Introducing high-purity Ar of 8.5sccm into the vacuum of Pa, controlling the sputtering screen pressure to be 2.0kV and the beam current to be 50mA, sputtering a Pt target containing Ti for 30min by using an ion beam, and naturally cooling to room temperature in the same vacuum degree to obtain the carbon-supported PtTi alloy catalyst;
C. immersing the carbon-supported PtTi composite catalyst obtained in the step B into an electrolytic cell filled with 1.0mol/L HCl solution at 50 ℃ for electrochemical corrosion for 90min, and keeping the ultrasonic power density in the electrolytic cell at 0.6W/cm2(ii) a Then washing with deionized water at room temperature to obtain the porous noble metal-based membrane electrode;
D. and D, randomly selecting 2 parts of the pore type carbon-supported PtTi alloy membrane electrode obtained in the step C, and respectively adopting CV, LSV, i-t and ICP-OES to carry out electrochemical activity specific surface area, catalytic activity and stability and active metal quantitative test.
As a result: pt exists in the porous carbon-supported PtTi alloy membrane electrode obtained in the embodiment5Ti3(111) And a Pt (111) phase; ESA value of 9.850m2/g；i0The value was 5.125mA/cm2(ii) a The Pt content was 0.021260mg/cm2(ii) a The specific surface area of the membrane electrode was 16.536m2/g。
[ example 3 ]
A. Soaking conductive carbon paper in 1.0mol/L H solution at 50 deg.C2SO4Washing and dehydrating the solution for 5min by deionized water and absolute ethyl alcohol at room temperature, and drying the solution for 15min at 80 ℃ under normal pressure to obtain a pretreated carbonaceous carrier;
B. placing the carbon carrier obtained in the step A in an ion beam sputtering device, heating to 350 ℃, and preserving heat at 1.0 multiplied by 10- 2Introducing high-purity Ar of 8.0sccm into Pa vacuum, controlling the sputtering screen pressure to be 3.0kV and the beam current to be 100mA, sputtering a Pt target containing Ni by using an ion beam for 15min, and naturally cooling to room temperature in the same vacuum degree to obtain the carbon-supported PtNi alloy catalyst;
C. immersing the carbon-supported PtNi composite catalyst obtained in the step B into an electrolytic cell filled with 0.2mol/L HCl solution at 40 ℃ for electrochemical corrosion for 30min, and keeping the ultrasonic power density in the electrolytic cell at 0.5W/cm2(ii) a Then washing with deionized water at room temperature to obtain the porous noble metal-based membrane electrode;
D. and D, randomly selecting 4 parts of the porous carbon-supported PtNi alloy membrane electrode obtained in the step C, and performing phase structure, electrochemical activity specific surface area, catalytic activity and stability, surface micro-morphology characterization and active metal quantitative test by respectively adopting XRD, CV, LSV, i-t, SEM and ICP-OES.
As a result: the porous carbon-supported PtNi alloy film electrode obtained in this example had (NiPt) (111) and Pt (111) phases; ESA value of 10.67m2/g；i0The value was 5.326mA/cm2(ii) a The Pt content was 0.023080mg/cm2(ii) a The specific surface area of the membrane electrode was 18.045m2/g。
[ example 4 ]
A. Soaking graphite fiber cloth in 0.6mol/L H solution at 35 deg.C2SO4Washing and dehydrating the solution for 8min by deionized water and absolute ethyl alcohol at room temperature, and drying the solution for 20min at the normal pressure of 60 ℃ to obtain a pretreated carbonaceous carrier;
B. placing the carbon carrier obtained in the step A in an ion beam sputtering device, heating to 300 ℃, and preserving heat at 2.0 multiplied by 10- 2Introducing high-purity Ar of 8.5sccm into Pa vacuum, controlling the sputtering screen pressure to be 3.0kV and the beam current to be 100mA, sputtering a Pt target containing Ni by using an ion beam for 30min, and naturally cooling to room temperature in the same vacuum degree to obtain the carbon-supported PtNi alloy catalyst;
C. immersing the carbon-supported PtNi composite catalyst obtained in the step B in 2.0mol/L HClO filled with the catalyst at 60 DEG C4Performing electrochemical corrosion in the electrolytic cell for 120min while maintaining the ultrasonic power density in the electrolytic cell at 1.0W/cm2(ii) a Then washing with deionized water at room temperature to obtain the porous noble metal-based membrane electrode;
D. and D, randomly selecting 4 parts of the porous carbon-supported PtNi alloy membrane electrode obtained in the step C, and performing phase structure, electrochemical activity specific surface area, catalytic activity and stability, surface micro-morphology characterization and active metal quantitative test by respectively adopting XRD, CV, LSV, i-t, SEM and ICP-OES.
As a result: the porous carbon-supported PtNi alloy film electrode obtained in this example had (NiPt) (111) and Pt (111) phases; ESA value of 10.32m2/g；i0The value was 4.139mA/cm2(ii) a The Pt content was 0.017940mg/cm2(ii) a The specific surface area of the membrane electrode was 17.345m2/g。
[ example 5 ]
A. Soaking graphite fiber cloth in 0.5mol/L H solution at 45 deg.C2SO4Washing with deionized water and anhydrous ethanol at room temperature for 10min, dewatering, and oven drying at 55 deg.C under normal pressure for 20min to obtain pretreated carbonaceous carrier;
B. placing the carbon carrier obtained in the step A in an ion beam sputtering device, heating to 300 ℃, and preserving heat at 9.0 multiplied by 10- 3Introducing high-purity Ar of 7.0sccm into Pa vacuum, controlling sputtering screen pressure to be 3.0kV and beam current to be 75mA, sputtering Pt target containing Ni by ion beam for 25min, and naturally treating in the same vacuum degreeCooling to room temperature to obtain the carbon-supported PtTi alloy catalyst;
C. immersing the carbon-supported PtTi composite catalyst obtained in the step B in a container filled with 0.1mol/L HClO at 60 DEG C4Performing electrochemical corrosion in the electrolytic cell for 15min while maintaining the ultrasonic power density in the electrolytic cell at 0.2W/cm2(ii) a Then washing with deionized water at room temperature to obtain the porous noble metal-based membrane electrode;
D. and D, randomly selecting 2 parts of the pore type carbon-supported PtTi alloy membrane electrode obtained in the step C, and respectively adopting CV, LSV, i-t and ICP-OES to carry out electrochemical activity specific surface area, catalytic activity and stability and active metal quantitative test.
As a result: the ESA value of the porous carbon-supported PtTi alloy membrane electrode obtained in the embodiment is 10.100m2/g；i0The value was 3.720mA/cm2(ii) a The Pt content was 0.017420mg/cm2(ii) a The specific surface area of the membrane electrode was 17.013m2/g。
[ example 6 ]
A. Soaking conductive carbon paper in 0.8mol/L H solution at 35 deg.C2SO4Washing and dehydrating the solution for 8min by deionized water and absolute ethyl alcohol at room temperature, and drying the solution for 10min at 70 ℃ under normal pressure to obtain a pretreated carbonaceous carrier;
B. placing the carbon carrier obtained in the step A in an ion beam sputtering device, heating to 330 ℃, and keeping the temperature at 1.0 multiplied by 10- 2Introducing high-purity Ar of 7.5sccm into Pa vacuum, controlling the sputtering screen pressure to be 2.5kV and the beam current to be 100mA, sputtering a Pt target containing Ni by using an ion beam for 10min, and naturally cooling to room temperature in the same vacuum degree to obtain the carbon-supported PtNi alloy catalyst;
C. immersing the carbon-supported PtNi composite catalyst obtained in the step B in 0.5mol/L HClO at room temperature4Naturally corroding with ultrasonic wave in electrolytic cell for 120min while maintaining the power density of ultrasonic wave in electrolytic cell at 0.6W/cm2(ii) a Then washing with deionized water at room temperature to obtain the porous noble metal-based membrane electrode;
D. and D, randomly selecting 2 parts of the porous carbon-supported PtNi alloy membrane electrode obtained in the step C, and respectively adopting CV, LSV, i-t and ICP-OES to carry out electrochemical activity specific surface area, catalytic activity and stability and active metal quantitative test.
As a result: the ESA value of the porous carbon-supported PtNi alloy membrane electrode obtained in the embodiment is 4.656m2/g；i0The value was 3.557mA/cm2(ii) a The Pt content was 0.034004mg/cm2(ii) a The specific surface area of the membrane electrode was 9.327m2/g。
[ COMPARATIVE EXAMPLES ]
A. Same as example 1, step A;
B. same as example 1, step B;
C. and D, randomly selecting 4 parts of the carbon-supported PtNi alloy catalyst obtained in the step B, and performing phase structure, electrochemical activity specific surface area, catalytic activity and stability, surface micro-morphology characterization and active metal quantitative test by respectively adopting XRD, CV, LSV, i-t, SEM and ICP-OES.
As a result: the carbon-supported PtNi alloy thin film catalyst obtained in the comparative example has (NiPt) (111) and Pt (111) phases; ESA value of 4.448m2/g；i0The value was 3.384mA/cm2(ii) a The Pt content was 0.038462mg/cm2(ii) a The specific surface area of the membrane electrode was 8.824m2/g。
Comparing examples 1-6 with comparative example 1, it can be seen that:
the XRD overlay pattern shown in FIG. 1 has excluded the influence of the characteristic diffraction peaks of the carbonaceous support, with (NiPt) (111) and Pt (111) phases present in a, c and d, and Pt present in b5Ti3(111) And Pt (111) phase, which shows that the catalyst is directly loaded on the surface of the clean graphite fiber cloth, no pollution of intermediate reactant exists, and the content of each phase can be regulated and controlled.
As can be seen from fig. 2 to 4, the membrane electrode surface of the comparative example was relatively uniform and smooth, with a few large particles present; the surface micro-topography of the embodiment 4 has an obvious hole structure, and more particles are distributed on the hole wall; the carbon-supported PtNi alloy membrane electrode of the pore type structure prepared in example 3 had higher surface roughness without any doubt.
As can be seen from fig. 5 to 7, the comparative example has a very low hydrogen evolution activity due to the presence of a large amount of elemental Ni; peak area and current for hydrogen oxidation and desorption of the membrane electrode in examples 3 and 4The density values are obviously increased compared with the comparative examples, and the catalytic activity is enhanced; compared with a comparative example, the Pt content and the ESA value of the embodiments 1-6 both show that the porous carbon-supported PtNi alloy catalyst prepared by the invention realizes the application purpose of low Pt content and high ESA value, and has the advantages of short flow, low cost and high Pt utilization rate; as can be seen from fig. 7, the slopes of example 1, example 3, example 6 and comparative example are 3.492 × 10, respectively-5、3.911×10-5、3.167×10-5And 3.084 × 10-5The results show that the dealloying treatment performed by the mechanical and electrochemical double-field coupling action is beneficial to enhancing the stability of the hydrogen evolution reaction.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for preparing a porous noble metal-based membrane electrode based on double-field coupling effect is characterized by comprising the following steps: noble metal is used as a main catalytic phase, a transition metal element is used as an alloy phase, a noble metal-based thin film catalyst is prepared on the surface of a carbonaceous carrier, and dealloying treatment is carried out through mechanical and electrochemical double-field coupling to obtain the pore-type noble metal-based membrane electrode.
2. The method for preparing a porous noble metal-based membrane electrode based on double field coupling according to claim 1, wherein the mechanical and electrochemical double field coupling comprises the following steps: and carrying out electrochemical corrosion under the ultrasonic vibration condition.
3. The method for preparing a porous noble metal-based membrane electrode based on double-field coupling according to claim 2, wherein the power density of the ultrasonic wave is 0.2W/cm2-1.0W/cm2。
4. The method for preparing a porous noble metal-based membrane electrode based on the double-field coupling effect according to claim 2 or 3, wherein the concentration of the etching solution is 0.1mol/L to 2.0mol/L during the electrochemical etching operation; preferably, the corrosion temperature is 20-60 ℃; further preferably, the etching time is 15min to 120 min.
5. The method for preparing a porous noble metal-based membrane electrode based on the double-field coupling effect according to claim 1, wherein the carbon carrier is at least one selected from graphite fiber cloth and conductive carbon paper; and/or, preparing the noble metal-based thin film catalyst by an ion beam sputtering method.
6. The method for preparing a porous noble metal-based membrane electrode assembly based on two-field coupling according to claim 1, wherein the noble metal is at least one selected from Pt and Au; and/or, the transition metal element is at least one selected from Ti, Ni, Co, Cu and Fe.
7. The method for preparing a porous noble metal-based membrane electrode based on the double-field coupling effect according to claim 1, further comprising the steps of: pretreating the carbonaceous carrier; preferably, the pretreatment step comprises sequentially washing with a sulfuric acid solution, deionized water and ethanol and drying; more preferably, the concentration of the sulfuric acid solution is 0.5mol/L to 1 mol/L; further preferably, the drying temperature is from 50 ℃ to 80 ℃.
8. A porous noble metal-based membrane electrode prepared by the method of any one of claims 1 to 7.
9. The porous noble metal-based membrane electrode of claim 8, having a specific surface area of 9.327-18.045m2/g。
10. A cathode material for hydrogen-oxygen fuel cells and/or an unsaturated organic compound recycling hydrogenation energy storage device, comprising the porous noble metal-based membrane electrode of claim 8 or 9.
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