CN110438528A - A kind of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode and preparation method thereof - Google Patents
A kind of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode and preparation method thereof Download PDFInfo
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- CN110438528A CN110438528A CN201910753997.0A CN201910753997A CN110438528A CN 110438528 A CN110438528 A CN 110438528A CN 201910753997 A CN201910753997 A CN 201910753997A CN 110438528 A CN110438528 A CN 110438528A
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/04—Pretreatment of the material to be coated
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to a kind of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode and preparation method thereof, steps are as follows: (1) pre-process nickel foam；(2) using pretreated nickel foam as anode, using platinized platinum as cathode, using the alcohol water mixed solution of ammonium salt as electrolyte, anodic oxidation reprocessing is carried out, obtains modified nickel foam matrix；(3) modified nickel foam matrix is placed in the presoma homogeneous phase solution containing precious metal element, is heated, by precious metal element growth in situ in modified nickel foam surface.Nickel foam abundance used in the present invention, technology for preparing electrode is simple, controllable, and equipment requirement is lower；The noble metal catalyst particles size being prepared is smaller, is uniformly dispersed and is firmly combined with matrix；Load capacity of the noble metal granule on modified nickel foam matrix is lower, saves cost of material；Prepared electrode shows excellent electrocatalytic hydrogen evolution activity and stability to water decomposition, with important application prospects.
Description
Technical field
The invention belongs to electrocatalytic hydrogen evolution technical field of material, and in particular to a kind of modified nickel foam carried noble metal
Catalyst hydrogen-precipitating electrode and preparation method thereof.
Background technique
Hydrogen Energy has been widely regarded as solving because its is from a wealth of sources, energy density is high, environmental-friendly and the features such as can regenerate
One of certainly current energy crisis and the alternative clean energy resource of environmental pollution.In numerous hydrogen producing technologies, electro-catalysis water decomposition
Liberation of hydrogen can convert electrical energy into stable chemical energy, can obtain purified hydrogen without generating other by-products, be sustainable energy
The solution of one great competitiveness of source hydrogen storage.Efficient catalyst is needed in electro-catalysis water splitting processes to reduce analysis
Hydrogen reacts overpotential, improves rate of catalysis reaction, therefore research liberation of hydrogen catalyst electrode material has promotion Hydrogen Technology development
Important meaning.
Electro-catalysis water decomposition liberation of hydrogen catalyst is broadly divided into base metal and noble metal two major classes, base metal elctro-catalyst
The semiconductor materials such as transient metal sulfide, selenides, phosphide, carbide, nitride are concentrated on, catalytic activity is temporarily gone back
It is difficult to fully meet industrial requirement, therefore, the elctro-catalyst based on noble metal design efficient stable is imperative.The original of noble metal
There are more empty d track in sub-track, energy level spacing is smaller, is easy to be coordinated with hydrogen atom, thus in electro-catalysis water decomposition
There is higher hydrogen evolution activity.However, noble metal electrocatalyst is limited to its price and storage capacity, industry is limited indirectly and produces hydrogen
Extensive development.To solve this problem, its catalytically active surface product is usually improved as far as possible, and noble metal nano particles are loaded
In multilayer non-noble metallic materials or precious metal alloys are formed, noble metal can be made to be uniformly dispersed in the material, reduce original
Interact between son, avoid its reunion, but when these powder noble metal catalysts are used as hydrogen-precipitating electrode need it is further molten
In liquid working process, such as the preparation process of commercialization Pt/C electrode first by catalyst fines be dispersed in containing isopropanol, water and
Masking liquid is formed in the solution of nafion, is then uniformly coated on electrode matrix and carries out drying again, preparation process is multiple
It is miscellaneous, operation possibility is poor, higher cost and uncontrollable.
The electrocatalysis characteristic of noble metal catalyst is related with many factors, including noble metal granule size, dispersibility, base
Bottom material and with the binding force of basis material etc..It is inexpensive preparation using conducting base original position carried noble metal elctro-catalyst
The effective ways of electrocatalytic hydrogen evolution electrode, Commercial foam nickel (NF) is from a wealth of sources, there is good electric conductivity, high porosity and machinery
Intensity is widely used as the electrode matrix of electro-catalysis water decomposition reaction.
However, using coating method on nickel foam substrate carried noble metal elctro-catalyst, not can be effectively controlled noble metal
Dispersibility of the catalyst on matrix also easily leads to active component and falls off from matrix during hydrogen release and weaken electrode
Electro-catalysis stability.Therefore a kind of method for developing simplicity is prepared with unique texture and high activity noble metal catalyst
There are still huge challenges for hydrogen-precipitating electrode.
Summary of the invention
The purpose of the present invention is to solve the above-mentioned problems and provides a kind of modified nickel foam supported precious metal catalyst
Hydrogen-precipitating electrode and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode, comprising the following steps:
(1) nickel foam is pre-processed；
It (2) is electrolysis with the alcohol water mixed solution of ammonium salt using platinized platinum as cathode using pretreated nickel foam as anode
Liquid carries out anodic oxidation reprocessing, obtains modified nickel foam matrix, obtains the modified matrix of nanoporous pattern；
(3) modified nickel foam matrix is placed in the presoma homogeneous phase solution containing precious metal element, is heated, it will
For precious metal element growth in situ behind modified nickel foam surface, cooling, washing, drying, i.e. your gold acquisition modified nickel foam loads
The hydrogen-precipitating electrode of metal particles.
Further, step (1) nickel foam pretreatment concrete mode is in hydrochloric acid solution, ethyl alcohol and to go nickel foam
It is ultrasonically treated respectively in ionized water, to remove the oxide and grease on surface, then is dried in thermostatic drying chamber, then sets
In tube furnace, H2Temperature programmed reduction processing is carried out under/Ar mixed atmosphere, is cooled to room temperature and is obtained pretreated foam
Nickel.
Further, the nickel foam is Commercial foam nickel, and with a thickness of 1.0mm~2.0mm, surface density is 200~500g/
m2。
Further, the H in gaseous mixture2Volume ratio with Ar is 1:5~40, and the reduction treatment temperature of nickel foam is 250
DEG C~500 DEG C, programmed rate is 2 DEG C~10 DEG C, and the reduction treatment time is 1~4h.
Further, the ammonium salt in step (2) described electrolyte is ammonium chloride, ammonium sulfate, ammonium fluoride, ammonium nitrate or carbonic acid
One or more of hydrogen ammonium, the molar concentration of ammonium salt are 0.0001~0.2mol/L；Alcohol in the electrolyte is methanol, second
One or more of alcohol, propyl alcohol, isopropanol, ethylene glycol or glycerine, the mass content of alcohol in the electrolytic solution are 5~99%；
The volume ratio of alcohol and water in the electrolyte is 1:0.02~2.
Further, step (2) carries out anodic oxidation reprocessing, DC power supply by the DC power supply that potentiostat generates
Voltage be 2V~30V, time of anodized is 10~300min.
Further, step (3) specific steps are as follows: the presoma homogeneous phase solution containing precious metal element is added to hydro-thermal
In kettle, modified nickel foam matrix is placed in solution, 100 DEG C~180 DEG C are heated to after sealing, 4~14h is kept the temperature, is cooled to
It is washed after room temperature with deionized water, dehydrated alcohol, then the modified foam of acquisition is dried at 40 DEG C in a vacuum drying oven
The electrode of nickel load noble metal granule.
Further, the presoma containing precious metal element described in step (3) is gold chloride, chloroplatinic acid, ruthenium hydrochloride ammonium, chlorine
One or more of rhodium acid ammonium or ammonium chloropalladate.
Further, the solvent of the precursor solution of step (3) containing precious metal element be water, methanol, ethyl alcohol, propyl alcohol,
One or more of isopropanol, ethylene glycol or glycerine, concentration of the precious metal element in precursor solution be 0.0001~
0.02mol/L。
Further, the hydrogen-precipitating electrode includes modified nickel foam, growth in situ in the noble metal on modified nickel foam surface
Elctro-catalyst and electrode for water decomposition evolving hydrogen reaction, the noble metal electrocatalyst are in Au, Pt, Ru, Rh, Pd
It is one or more of.
Further, the noble metal electrocatalyst is in granular form, and diameter is 2~50nm, and noble metal loads on matrix
Mass percent be 0.02~1.0%.
Compared with prior art, the present invention it is specific following the utility model has the advantages that
Nickel foam abundance used in the present invention, technology for preparing electrode is simple, controllable, and equipment requirement is lower.
The hydrogen-precipitating electrode of modified nickel foam carried noble metal elctro-catalyst provided by the invention, by Commercial foam nickel into
Row is modified, and realizes effective dispersion of the noble metal granule on modified nickel foam matrix surface；It is real by the carrying method of solvent heat
Existing low-load amount of the noble metal catalyst on modified nickel foam matrix, mass percent are no more than 1%, save raw material at
This；Noble metal electrocatalyst material and the binding force of modified nickel foam matrix are very strong on electrode, effectively prevent in water splitting processes
The problem that falls off of middle active component.
There is stronger association between noble metal electrocatalysis material and modified nickel foam matrix prepared by method provided by the invention
Same effect can significantly improve the electron transport ability during water decomposition evolving hydrogen reaction and the activation capacity to water, to moisture
Solution shows excellent electrocatalytic hydrogen evolution activity and stability, with important application prospects.
Present invention employs a kind of novel methods to be modified to Commercial foam nickel, i.e., carries out to pretreated nickel foam
Anodic oxidation can generate porous network shape nickel oxide on foam nickel skeleton, increase the active surface area of nickel foam substrate；
Modified nickel foam is heat-treated in noble metal precursor body alcohol solution, while generating noble metal nano point and porous structure
Nickel hydroxide hetero-junctions, the hydroxide that the noble metal active position of high dispersive is conducive to the absorption and reaction of hydrogen atom, and generates
Nickel be conducive to the decomposition of water and in active sites hydroxyl desorption, so as to effectively promote electrocatalytic hydrogen evolution rate.
Detailed description of the invention
Fig. 1 is X-ray electron spectrum (XPS) spectrogram of the modified nickel foam supporting Pt mosaic electrode prepared in embodiment 1.
Fig. 2 is Elemental redistribution (EELS) photo of the modified nickel foam supporting Pt mosaic electrode prepared in embodiment 1.
Fig. 3 is the continuous water decomposition evolving hydrogen reaction for 24 hours of the modified nickel foam supporting Pt mosaic electrode for preparing in embodiment 1
(HER) test result.
Fig. 4 is that the modified nickel foam prepared in embodiment 2 loads scanning electron microscope (SEM) photo of Au mosaic electrode.
Fig. 5 is that the modified nickel foam prepared in embodiment 2 loads X-ray diffraction (XRD) spectrogram of Au mosaic electrode.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
By Commercial foam nickel (with a thickness of 1.6mm, surface density 320g/m2) it is cut into 2 × 3cm2Size, be placed on 3mol/
The aqueous hydrochloric acid solution ultrasound 15min of L is placed sequentially in dehydrated alcohol and deionized water ultrasound respectively after being rinsed with water completely
20min, then be placed in thermostatic drying chamber and be dried at 60 DEG C to constant weight.Nickel foam after drying is placed in tube furnace, is used
H2The H that volume content is 15%2/ Ar gaseous mixture carries out temperature programmed reduction processing, and the reduction treatment temperature of nickel foam is 350 DEG C,
Programmed rate is 10 DEG C/min, and the control of reduction treatment time is cooled to room temperature and obtains pretreated nickel foam in 1h.
Prepare the NH of 0.005mol/L4F electrolyte, using ethylene glycol and water as mixed solvent, the volume ratio of ethylene glycol and water
For 1:0.1, using commercial platinized platinum as cathode, potentiostat will be used as directly by pretreated nickel foam as anode
Galvanic electricity source carries out anodized to nickel foam, and anodic oxidation voltage is controlled in 20V, and the anodized time is
120min.Nickel foam is washed with a large amount of deionized waters after processing, then is dried at 60 DEG C in thermostatic drying chamber, is obtained
Obtain modified nickel foam matrix.
The ethanol water (wherein the volume of second alcohol and water is 1:1) of the chloroplatinic acid of 0.003mol/L is added to 50mL's
In water heating kettle, modified nickel foam matrix is placed in solution, carries out being heated to 120 DEG C after sealing, keeps the temperature 6h, be cooled to room temperature
It is washed afterwards with deionized water, dehydrated alcohol, then is dried that obtain modified nickel foam negative at 40 DEG C in a vacuum drying oven
Carry the electrode of Pt particle.
Attached drawing 1 gives the XPS spectrum figure of the modified nickel foam supporting Pt mosaic electrode of the preparation of embodiment 1, it can be seen that Pt
Exist on modified nickel foam matrix with simple substance form；Attached drawing 2 gives the modified nickel foam supporting Pt particle of the preparation of embodiment 1
The EELS photo of electrode, it can be seen that Pt has preferable dispersibility on modified nickel foam matrix.
Electrode is monitored the performance of water decomposition evolving hydrogen reaction with CHI 660E electrochemical workstation, the environment temperature of test
Degree is 25 DEG C.It is carried out in 1.0M KOH aqueous solution (pH=13.7) using standard three electrode system, prepared electrode is work
Make electrode (1cm × 1cm × 1mm), platinum foil (1cm × 1cm) is as to electrode, and Hg/HgO is as reference electrode.The electrode of preparation
Excellent electrocatalytic hydrogen evolution activity, current density 10mA/cm are shown to water decomposition2Under overpotential be only 29mV, tower
Fei Er slope is 43.5mV/dec.Attached drawing 3 gives the modified nickel foam supporting Pt mosaic electrode of the preparation of embodiment 1 continuously for 24 hours
The test result of water decomposition evolving hydrogen reaction (HER), it can be seen that in the above system successive reaction for 24 hours after its overpotential variation compared with
It is small, show preferable stability.
Embodiment 2
By Commercial foam nickel (with a thickness of 1.2mm, surface density 300g/m2) it is cut into 2 × 3cm2Size, be placed on 3mol/
The aqueous hydrochloric acid solution ultrasound 15min of L is placed sequentially in dehydrated alcohol and deionized water ultrasound respectively after being rinsed with water completely
20min, then be placed in thermostatic drying chamber and be dried at 60 DEG C to constant weight.Nickel foam after drying is placed in tube furnace, is used
H2The H that volume content is 5%2/ Ar gaseous mixture carries out temperature programmed reduction processing, and the reduction treatment temperature of nickel foam is 300 DEG C,
Programmed rate is 5 DEG C/min, and the control of reduction treatment time is cooled to room temperature and obtains pretreated nickel foam in 1h.
Prepare the NH of 0.005mol/L4NO3Electrolyte, using second alcohol and water as mixed solvent, the volume ratio of ethyl alcohol and water is 1:
1, it will be used as anode by pretreated nickel foam, and using the platinized platinum of commercialization as cathode, use potentiostat as DC power supply,
Anodized is carried out to nickel foam, in 5V, the anodized time is 20min for anodic oxidation voltage control.After processing
Nickel foam is washed with a large amount of deionized waters, then is dried at 60 DEG C in thermostatic drying chamber, modified nickel foam is obtained
Matrix.
The aqueous solution of the gold chloride of 0.01mol/L is added in the water heating kettle of 50mL, modified nickel foam matrix is placed
It carries out being heated to 150 DEG C in solution, after sealing, keeps the temperature 4h, washed after being cooled to room temperature with deionized water, dehydrated alcohol
It washs, then the electrode for obtaining modified nickel foam load Au particle is dried at 40 DEG C in a vacuum drying oven.
Attached drawing 4 gives the SEM photograph of the modified nickel foam load Au mosaic electrode of the preparation of embodiment 2, it can be seen that Au
There is preferable dispersibility in nickel foam；Attached drawing 5 gives the modified nickel foam load Au mosaic electrode of the preparation of embodiment 2
XRD spectrum, it can be seen that the characteristic diffraction peak of Au is unobvious, shows that Au has lesser particle scale on the electrode of synthesis.
Electrode is monitored the performance of water decomposition evolving hydrogen reaction with CHI 660E electrochemical workstation, the environment temperature of test
Degree is 25 DEG C.It is carried out in 1.0M KOH aqueous solution (pH=13.7) using standard three electrode system, prepared electrode is work
Make electrode (1cm × 1cm × 1mm), platinum foil (1cm × 1cm) is as to electrode, and Hg/HgO is as reference electrode.The electrode of preparation
Excellent electrocatalytic hydrogen evolution activity, current density 10mA/cm are shown to water decomposition2Under overpotential be only 43mV, tower
Fei Er slope is 47.6mV/dec, and rear its overpotential variation is smaller for 24 hours for successive reaction in the above system for electrode, is shown preferably
Stability.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode, which is characterized in that including following step
It is rapid:
(1) nickel foam is pre-processed；
(2) using pretreated nickel foam as anode, using platinized platinum as cathode, using the alcohol water mixed solution of ammonium salt as electrolyte,
Anodic oxidation reprocessing is carried out, modified nickel foam matrix is obtained；
(3) modified nickel foam matrix is placed in the presoma homogeneous phase solution containing precious metal element, is heated, by your gold
Belong to element and be grown on modified nickel foam surface in situ, cooling after washing, being dry, that is, obtains modified nickel foam carried noble metal
The hydrogen-precipitating electrode of grain.
2. a kind of preparation method of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode according to claim 1,
It is characterized in that, step (1) nickel foam pretreatment concrete mode is, by nickel foam in hydrochloric acid solution, ethyl alcohol and deionized water
It is ultrasonically treated respectively, to remove the oxide and grease on surface, then is dried in thermostatic drying chamber, is subsequently placed in tube furnace
In, H2Temperature programmed reduction processing is carried out under/Ar mixed atmosphere, is cooled to room temperature and is obtained pretreated nickel foam.
3. a kind of preparation method of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode according to claim 2,
It is characterized in that, the nickel foam is Commercial foam nickel, and with a thickness of 1.0mm~2.0mm, surface density is 200~500g/m2。
4. a kind of preparation method of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode according to claim 2,
It is characterized in that, the H in gaseous mixture2Volume ratio with Ar is 1:5~40, and the reduction treatment temperature of nickel foam is 250 DEG C~500
DEG C, programmed rate is 2 DEG C~10 DEG C, and the reduction treatment time is 1~4h.
5. a kind of preparation method of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode according to claim 1,
It is characterized in that, the ammonium salt in step (2) described electrolyte is in ammonium chloride, ammonium sulfate, ammonium fluoride, ammonium nitrate or ammonium hydrogen carbonate
One or more, the molar concentration of ammonium salt are 0.0001~0.2mol/L；
Alcohol in the electrolyte is one or more of methanol, ethyl alcohol, propyl alcohol, isopropanol, ethylene glycol or glycerine, and alcohol exists
Mass content in electrolyte is 5~99%；
The volume ratio of alcohol and water in the electrolyte is 1:0.02~2.
6. a kind of preparation method of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode according to claim 1,
It is characterized in that, step (2) carries out anodic oxidation reprocessing by the DC power supply that potentiostat generates, and the voltage of DC power supply is
The V of 2 V~30, the time of anodized are 10~300min.
7. a kind of preparation method of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode according to claim 1,
Be characterized in that, the presoma containing precious metal element described in step (3) be gold chloride, chloroplatinic acid, ruthenium hydrochloride ammonium, chlorine rhodium acid ammonium or
One or more of ammonium chloropalladate.
8. a kind of preparation method of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode according to claim 7,
It is characterized in that, the solvent of the precursor solution of step (3) containing precious metal element is water, methanol, ethyl alcohol, propyl alcohol, isopropanol, second
One or more of glycol or glycerine, concentration of the precious metal element in precursor solution are 0.0001~0.02mol/L.
9. a kind of hydrogen-precipitating electrode that the preparation method as described in claim any one of 1-8 is prepared, which is characterized in that the analysis
Hydrogen electrode includes modified nickel foam, growth in situ in the noble metal electrocatalyst on modified nickel foam surface and for moisture parsing
The electrode of hydrogen reaction, the noble metal electrocatalyst are one or more of Au, Pt, Ru, Rh, Pd.
10. the hydrogen-precipitating electrode that preparation method is prepared according to claim 9, which is characterized in that the noble metal electricity is urged
Agent is in granular form, and diameter is 2~50nm, and the mass percent that noble metal loads on matrix is 0.02~1.0%.
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| CN112237927A (en) * | 2020-09-27 | 2021-01-19 | 东莞理工学院 | Catalyst for electrocatalytic reduction of nitrate and preparation method and application thereof |
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| CN113394030A (en) * | 2021-06-26 | 2021-09-14 | 南昌师范学院 | Nickel-based electrode material and preparation method and application thereof |
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| CN116510748B (en) * | 2023-07-04 | 2023-09-01 | 潍坊学院 | Catalyst for preparing formic acid by photocatalytic reduction of carbon dioxide as well as preparation method and application thereof |
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